Arihant CBSE Chemistry Term 2 C - Aditya Jangid

CBSE Term II
2022
Chemistry
Class XII
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CBSE Term II
2022
Chemistry
Class XII
Complete Theory Covering NCERT
Case Based Questions
Short/Long Answer Type Questions
3 Practice Papers with Explanations
Authors
Arshdeep Kaur
Aditya Jangid
ARIHANT PRAKASHAN (School Division Series)

ARIHANT PRAKASHAN (School Division Series)
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CBSE Term II
2022
Contents
CHAPTER
Electrochemistry -
CHAPTER
Chemical Kinetics -
CHAPTER
Surface Chemistry -
CHAPTER
The d-and f-Block Elements -
CHAPTER
Coordination Compounds -
CHAPTER
Aldehydes, Ketones and Carboxylic Acids -
CHAPTER
Amines -
Practice Papers - -
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Syllabus
CBSE Term II Class 12
S.No. Unit Periods Marks
. Electrochemistry
. Chemical Kinetics
. Surface Chemistry
. d-and f-Block Elements
. Coordination Compounds
. Aldehydes, Ketones and Carboxylic Acids
Amines
Total
. Electrochemistry : Redox reactions, EMF of a cell, standard electrode potential, Nernst equation
and its application to chemical cells, Relation between Gibbs energy change and EMF of a cell,
conductance in electrolytic solutions, specific and molar conductivity, variations of conductivity
with concentration, Kohlrausch s Law, electrolysis.
. Chemical Kinetics : Rate of a reaction Average and instantaneous , factors affecting rate of
reaction: concentration, temperature, catalyst; order and molecularity of a reaction, rate law and
specific rate constant, integrated rate equations and half-life only for zero and first order reactions .
. Surface Chemistry : Adsorption - physisorption and chemisorption, factors affecting adsorption of
gases on solids, colloidal state: distinction between true solutions, colloids and suspension;
lyophilic, lyophobic, multi-molecular and macromolecular colloids; properties of colloids; Tyndall
effect, Brownian movement, electrophoresis, coagulation.
. d-and f-Block Elements : General introduction, electronic configuration, occurrence and
characteristics of transition metals, general trends in properties of the first row transition metals
metallic character, ionization enthalpy, oxidation states, ionic radii, colour, catalytic property,
magnetic properties, interstitial compounds, alloy formation. Lanthanoids - Electronic
configuration, oxidation states and lanthanoid contraction and its consequences.
. Coordination Compounds : Coordination compounds - Introduction, ligands, coordination
number, colour, magnetic properties and shapes, IUPAC nomenclature of mononuclear
coordination compounds. Bonding, Werner s theory, VBT, and CFT.
. Aldehydes, Ketones and Carboxylic Acids : Aldehydes and Ketones: Nomenclature, nature of
carbonyl group, methods of preparation, physical and chemical properties, mechanism of
nucleophilic addition, reactivity of alpha hydrogen in aldehydes, uses. Carboxylic Acids:
Nomenclature, acidic nature, methods of preparation, physical and chemical properties; uses.
. Amines : Nomenclature, classification, structure, methods of preparation, physical and chemical
properties, uses, identification of primary, secondary and tertiary amines.
CBSE Term II
2022
CBSE Circular
Acad - 51/2021, 05 July 2021
Exam Scheme Term I & II
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Hkkjr CENTRAL BOARD OF SECONDARY EDUCATION

(An Autonomous Organisation under the Ministryof Education, Govt. of India)
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CENTRAL BOARD OF SECONDARY EDUCATION
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To cover this
situation, we
have given
both MCQs and
Subjective
Questions in
each Chapter.
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CHAPTER 01
Electrochemistry
In this Chapter...
l Cells
l Electrode Potential
l Electrochemical Series
l Nernst Equation
l Conductance of Electrolytic Solutions
Electrochemistry is the study of production of electricity from

energy released during spontaneous chemical reactions and the Electrode Potential
use of electrical energy to bring about non-spontaneous chemical l
Potential difference between the metal and the
transformations.
metal ion, in which electrode is dipped is called electrode
potential. At 1 atm pressure and 1M concentration of
Cells electrolyte, electrode potential is also known as standard
Cells are the devices that involves the interconversion of electrode potential (E°).
electrical energy and chemical energy. These are of two types l
According to the IUPAC convention, standard
(i) Electrochemical cell In this cell, chemical reactions are reduction potential of cell is now called standard
carried out that result in production of electricity. It is also electrode potential.
called as voltaic or galvanic cell. e.g. Daniell cell. l
The difference between electrode potentials (reduction
(ii) Electrolytic cell In this cell, electricity is used to produce potential) of the two half-cells of a cell is known as cell
non-spontaneous chemical changes. As there occur, breaking potential.
down of a molecule with the help of electricity, the process is E °cell = E °oxidation + E °reduction
called electrolysis. = E °cathode - E °anode
Electrolytic cell and Electrochemical cell = E °right - E °left
Electrochemical cell When switch is in on position, the flow of electrons is from
Electrolytic cell
(Galvanic or voltaic cell) negative electrode to the positive electrode and the
Non-spontaneous Gibbs energy of the spontaneous direction of current flow is opposite to that of electron
redox reaction is made to redox reaction is converted into flow.
occur. electrical work. e.g. Daniell cell l
Electromotive force (emf) of a cell is the potential
Occur in same electrolytic Occur in different electrolytic difference, when no current is drawn through the cell.
solution. solutions. It is measured in volts (V).
No salt-bridge is required. Salt-bridge is essential to It depends upon the following factors
maintain electroneutrality. (i) nature of metals and its ions.
Cathode is negative and Cathode is positive and anode is (ii) concentrations of electrolysis used.
anode is positive electrode. negative electrode.
(iii) temperature.
02 CBSE Term II Chemistry XII
Cell Representation Some metals like platinum or gold are used as inert
electrodes. They do not participate in the reaction but
While representing the galvanic cell, the anode is written on
provide their surface for oxidation or reduction and for the
the left and the cathode on the right. A vertical line separates
conduction of electrons.
the metal from the metal ion (electrolyte solution) and a
double vertical line indicates a salt bridge connecting the two
half-cells (two electrolytes). Electrochemical Series
The state of the metal and the solution is written with the The arrangement of various standard half cells in the order of
concentration of the electrolyte in parenthesis. their decreasing values of standard reduction potential is
called electrochemical series.
M1 ( s )| M1n + ( aq)|| M 2n + ( aq)|M 2 ( s )
Standard electrode potentials at 298K
Let us consider an example to understand the concept.
(Electrochemical series)
Step I Write the chemical reaction
¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾®
Cell reaction Reaction (oxidised form + ne - ¾® reduced form)
E- / V
Cu( s ) + 2Ag + ( aq) ¾® Cu 2+ ( aq) + 2Ag( s )
F2 ( g ) + 2e - ¾® 2F- 2.87
Step II Split the reaction into two half-cell reactions. -
Co 3+
+e ¾® Co2 + 1.81
Half-cell reactions
H2O 2 + 2H+ + 2e - ¾® 2H2O 1.78
At cathode (reduction)
MnO -4 + 8H+ + 5 e - ¾® Mn 2 + + 4H2O 1.51
2Ag + ( aq) + 2e - ¾® 2Ag( s ) 3+ -
Au + 3e ¾® Au ( s ) 1.40
At anode (oxidation)
Cl 2 (g ) + 2e - ¾® 2Cl - 1.36
Cu( s ) ¾® Cu 2+ ( aq) + 2e -
Cr2O 27 - + 14H + 6 e + -
¾® 2Cr 3+
+ 7H2O 1.33
Step III Represent the complete reaction according to the
conversion discussed above. O 2 ( g ) + 4H+ + 4 e - ¾® 2H2O 1.23
+ - 2+
MnO 2 ( s ) + 4H + 2e ¾® Mn + 2H2O 1.23
Cu( s )|Cu 2+ ( aq)|| Ag + ( aq)| Ag( s ).
Br2 + 2e – ¾® 2Br - 1.09
The EMF of the cell can be represented as
NO -3 + 4H + 3 e + -
¾® NO ( g ) + 2H2O 0.97
E cell = E right - E left 2+
2Hg + 2e - ¾® Hg22 + 0.92
For cell reaction;
Increasing strength of oxidising agent
+ -
Increasing strength of reducing agent

Cu( s ) + 2Ag + ( aq) ¾® Cu 2+ ( aq) + 2Ag( s ) Ag + e ¾® Ag(s ) 0.80
E cell = E Ag + /Ag - E Cu 2 + /Cu Fe3 + + e - ¾® Fe2 + 0.77

O 2 ( g ) + 2H+ + 2e - ¾® H2O 2 0.68
- -
Standard Hydrogen Electrode (SHE) I 2 + 2e ¾® 2l 0.54
The construction of the SHE is shown in the figure below Cu + + e - ¾® Cu(s ) 0.52
2+ -
Cu + 2e ¾® Cu ( s ) 0.34
AgCl ( s ) + e - ¾® Ag( s ) + Cl - 0.22
H2 (g) at
- -
1 bar AgBr (s ) + e ¾® Ag ( s ) + Br 0.10
2H+ + 2e - ¾® H2 ( g ) 0.00
2+ -
1.00 M H+ Pb + 2e ¾® Pb ( s ) -0.13
Sn 2 + + 2e - ¾® Sn ( s ) -0.14
2+ -
Finely divided platinum Ni + 2e ¾® Ni ( s ) -0.25
coated on platinum foil
Fe2 + + 2e - ¾® Fe( s ) -0.44
Standard Hydrogen Electrode (SHE) Cr 3 + + 3e - ¾® Cr (s ) -0.74
The standard hydrogen electrode consists of a platinum Zn 2 + + 2e - ¾® Zn ( s ) -0.76
- -
electrode coated with platinum black. The electrode is 2H2O + 2e ¾® H2 (g) + 2OH (aq) -0.83
dipped in an acidic solution and pure hydrogen gas is Al 3 + + 3 e - ¾® Al ( s ) -1.66
bubbled through it. Mg 2+
+ 2e -
¾® Mg( s ) -2.36
At 298K, the emf is measured by combining the SHE of the Na + + e - ¾® Na ( s ) -2.71
anode and another half-cell of the cathode, resulting in the
Ca 2 + + 2e – ¾® Ca (s ) -2.87
standard reduction potential of the other half-cell (cathode). + –
° = E° - E° K +e ¾® K ( s ) -2.93
¾
EMF of the cell = Ecell

Li + + e -
R L
¾® Li ( s ) -3.05
As E L° for SHE is zero, E ° = E R° - 0 = E R°
CBSE Term II Chemistry XII 03
Note Negative E° means that the redox couple is stronger reducing Relation between E cell and pH
agent than H + / H 2, e.g. Zn ( -0.76).
1
Positive E° means that the redox couple is a weaker reducing EH + / H = E °H + /H - 0.0591 log
agent than H + / H 2, e.g. Ag ( + 0.80). 2 2 [H + ]
From top to bottom in the table, the standard electrode = 0 - 0.0591 ( - log[ H + ]) = - 0.0591 pH
potential decreases and with this, decreases the oxidising [Q pH = - log[H + ]]
power of the species on the left and increases the reducing
power of the species on the right hand side of the reaction. Conductance of Electrolytic Solutions
Electrochemical series also helps to predict the feasibility of a
(i) The electrical resistance ( R) of any object is directly
redox reaction, thermal stability of metal oxides and
spontaneity of an electrochemical cell by choosing the proportional to its length l and inversely proportional to
its area of cross-section A.
half-cells with appropriate E° values. l l
If the standard electrode potential of an electrode is greater Thus, R µ or R = r .
A A
than zero, then its reduced form is more stable as compared
to hydrogen gas and vice-versa. where, r is resistivity (or specific resistance) of the object.
The standard electrode potential for flourine is highest which The SI unit of resistance is ohm (W) and it can be
indicates that fluorine gas (F2 ) has maximum tendency to get measured with the help of a Wheatstone bridge.
reduced to fluoride ion (F - ). In case of lithium, lithium ion is (ii) Resistivity (specific resistance) is defined as the
weakest oxidising agent while lithium metal is the most resistance offered by a substance of 1 m length with area
powerful reducing agent in an aqueous solution. of cross-section to 1 m 2 .
Its SI unit is ohm metre (W-m).
Nernst Equation l
l
For a general electrochemical reaction of the type The quantity is called the cell constant.
-
A
aA + bB ¾ne
¾® cC + dD It is denoted by the symbol G* .
Nerst equation is written as It will be given by,
2.303 RT [ C ] c [ D] d l
E cell = E cell
° - log G* = =R´ k
nF [ A] a [ B] b A
At 298 K, The unit of cell constant (G* ) is m - 1 .
c d
0.0591 [ C ] [ D] (iii) Conductance (G) is the reciprocal of resistance and
E cell = E cell
° - log
where,
n [ A] a [ B] b defined as the ease with which the electric current flows
1 A
E = electrode potential through the conductor, G = = .
E° = standard electrode potential R rl
Here, R = Resistance
R = gas constant, T = temperature, F = Faraday constant
SI unit of G = Siemen (S) or ohm -1
n = number of electrons involved in reaction
l
Nernst equation is used to find equilibrium constant and (iv) Conductivity or specific conductance (k) of an
electrolytic solution may be defined as the conductance
Gibb’s free energy change by using the formula’s
of a solution of 1 m length with its area of cross-section
°
(i) Ecell
0.0591
= log KC [QAt equilibrium , Ecell = 0] equal to 1 m 2 .
1
n k= ´ cell constant
where, K = equilibrium constant R
°
Its unit is Sm -1 or ohm -1 m -1 .
(ii) DGr° = - nFEcell
(v) Molar conductivity (L m ) is defined as the conducting
where, DG°= standard Gibbs free energy change power of all the ions produced by dissolving one mole of
(iii) DrG ° = - 2.303 RT log KC an electrolyte placed between two electrodes with area
of cross-section ‘A’ and at a distance of 1 cm.
If two half reactions having potentials E1° , E2° are combined
k
to give a third half reaction having a potential E3° , It is given by, L m = ,
C
n1 E1° + n2 E2° Here, k is expressed in Sm -1 and C in mol m -3 thus,
then, DG3° = DG1° + DG2° or E3° =
n3 unit of L m is Sm 2 mol -1 or ohm -1 m 2 mol -1 .
k ´ 1000 (ii) Dissociation constant can be determined as

or Lm =
M Ca2
where, M = molarity of solution Ka = (for weak electrolyte)
(1 - a )
If k is S cm -1 , then unit is W -1 cm 2 mol -1 or S cm 2 mol -1 . [C = concentration, a = degree of dissociation]
The molar conductivity can also be written as,
kA Products of Electrolysis
Lm = =k
l Products of electrolysis depend upon the nature of material
Since, l = 1 and A = V (volume containing 1 mole of being electrolysed, the type of electrodes being used,
electrolyte)
\ Lm = kV different oxidising and reducing species present in the
electrolytic cell and their standard electrode potentials,
Variation of Conductivity and Molar over voltage (kinetic barrier).
Conductivity with Concentration Some important examples of electrolysis are as follows :
l
Conductivity always decreases with decrease in l
Electrolysis of molten sodium chloride
concentration both for weak and strong electrolyte. This is At cathode Na + ( aq) + e - ¾® Na( s )
due to the fact that the number of ions that carry current in a
unit volume of solution always decreases with decrease in At anode 2Cl - ( aq) ¾® Cl 2 ( g ) + 2e -
concentration. l
Electrolysis of aqueous sodium chloride
l
Molar conductivity increases with decrease in concentration 1
because the total volume V of solution containing 1 mole of At cathode H 2O ( l ) + e - ¾® H 2 ( g ) + OH - ( aq)
electrolyte increases. When the concentration approaches 2
1
zero, the molar conductivity reaches a limiting value, known At anode Cl ( aq) ¾® Cl 2 ( g ) + e -
-
as limiting molar conductivity and is denoted by L°m . 2
l
For strong electrolytes, L m increases slowly with dilution. Net reaction NaCl( aq) + H 2 O( l ) ¾®
This can be represented by Debye-Huckel Onsager equation. 1 1
Na + ( aq) + OH - ( aq) + H 2 ( g ) + Cl 2 ( g )
Lm = L°m -A C 2 2
l
The value of constant ‘A’ depends upon the type of Note At cathode, H 2 is produced due to higher value of E ° and at
electrolyte, i.e. the charges on the cation and anion produced anode due to oxygen over potential, liberation of chlorine gas is
preferred.
on the dissociation of electrolyte in the solution. Therefore,
NaCl, CaCl 2 , MgSO 4 are known as 1 : 1, 2 : 1 and 2 : 2 l
Electrolysis of sulphuric acid
electrolytes, respectively. At anode
l
In case of weak electrolytes, like acetic acid, a lower value of 2H 2 O ( l ) ¾® O 2( g ) + 4H+ ( aq ) + 4 e - ; Ecell
°
= 1.23 V …(i)
degree of dissociation is observed at higher concentration and
2SO24 - ( aq ) ¾® S2 O28 - ( aq ) + 2e - ; °
Ecell = 1.96 V …(ii)
hence, there is a rapid increase in the value of L°m with dilution.
l
The limiting molar conductivity can be determined by using For dilute sulphuric acid, reaction (i) is preferred but at
Kohlrausch law of independent migration of ions. higher concentration of H 2 SO 4 , reaction (ii) is
Kohlrausch’s law states that limiting molar conductivity of an preferred.
1 ° = 0.00 V
electrolyte is the sum of individual contributions of At cathode H + + e - ¾® H 2 ( g ); E cell
conductivity of cation and anion of the electrolyte. 2
L°m = x l°m + y l°m l
Electrolysis of brine using, Hg as a cathode,
(x and y = number of cations and anions) At cathode Na + + e - ¾® Na
Some important applications of Kohlrausch law are as follows Na + Hg ¾® Na ¾ Hg
(i) Degree of dissociation of weak electrolyte can be 2Na ¾ Hg + 2H 2O ¾® 2NaOH + Hg + H 2 ( g )
L
determined as, a = m 1
L°m At anode Cl - ( aq) ¾® Cl 2 ( g ) + e - , E°cell = 1 . 36 V
2
[L m = molar conductivity at a given concentration,
2H 2O( l ) ¾® O 2 ( g ) + 4H + ( aq) + 4 e - ; E°cell = 1 . 23 V`
L°m = limiting molar conductivity].
Solved
Examples
Example 1. (i) Formulate the electrochemical cell Sol. Zn ( s )+Cu 2 + ( aq ) ¾¾® Zn 2 + ( aq ) + Cu( s )
representing the reaction
E° = + 1.1 V , DG° = ?
2Cr( s ) + 3Fe 2+ ( aq) ¾® 2Cr 3+ ( aq) + 3Fe ( s )
1F = 96500 C mol -1 , n = 2
° .
(ii) Calculate E cell DG° = - nFE° = - 2 ´ 96500 ´1.1
[Given, E°Cr 3+ /Cr = -0.74 V, E°Fe2+ / Fe = -0.44 V]. = -212300 J mol -1
Sol. (i) Representation of the given cell, Example 4. Calculate emf of the following cell at 25 °C.
Cr( s ) | Cr 3+ ( aq ) || Fe2 + ( aq ) | Fe( s ) Fe|Fe 2+ (0.001M)|| H + (0.01M)|H 2 ( g ) (1bar)|Pt( s )
° = Eright
(ii) Ecell ° - Eleft
° ° 2+ /Fe) = - 0.44 V; E°(H+ / H ) = 0.00V
E(Fe
° 3 + / Cr = -0.74 V ; E°Fe2 + / Fe = -0.44 V
As, ECr 2 (Delhi 2015)
= - 0.44 - (- 0.74) Sol. For the given cell representation, the cell reaction will be
= - 0.44 + 0.74 = 0.30 V Fe ( s ) + 2H+ ( aq ) ¾® Fe 2 + ( aq ) + H 2 ( g )
The standard emf of the cell will be,
Example 2. Calculate the potential for half-cell
° = E°H + /H - E°Fe 2 + /Fe , E°cell = 0 - ( - 0.44) = 0.44 V
Ecell
containing 0.10 M Cr 2O 2- 3+
7 ( aq), 0.20 M Cr ( aq) and
2
The Nernst equation for the cell reaction at 25°C,
1.0 ´ 10 -4 M H + (aq). 0.0591 [Fe 2 + ]
Ecell = Ecell
° - log + 2
The half-cell reaction is n [H ]
+ - 3+
Cr 2O 2–
7 ( aq) +14H ( aq) + 6e ¾® 2Cr ( aq) + 7H 2O( l ) 0.0591 [0.001]
= 0.44 - log
and the standard electrode potential is given as E° =1.33 V. 2 [0.01] 2
= 0.44 - 0.02955 (log10)
Sol. Given, [ Cr2O72- ] = 0.10 M, [Cr 3+ ] = 0.20 M and
= 0.44 - 0.02955 (1 ) [Q log10 = 1]
[ H+ ] = 1 ´ 10-4 M, Ecell
° = 1.33 V, n = 6 = 0.41045 V = 0.41 V
° -
0.0591 V [Cr 3+ ] 2 Example 5. Calculate the cell emf and D r G ° for the cell
Ecell = Ecell log
n [Cr2O 27 – ] [H+ ]14 reaction at 25° C.
0.0591 V (0.2) 2 Zn( s ) | Zn 2+ (0.1M)|| Cd 2+ (0.01M) |Cd(s )
= 1.33 V - log [Given, E°Zn 2+ / Zn = - 0.763 V, E°Cd 2+ /Cd = - 0.403 V
6 (0.1) (1.0 ´ 10-4 )14
0.0591 V 4 ´10-2
1 F = 96500 C mol -1 , R = 8.314 JK -1 mol -1 ]
= 1.33 V - log
6 1.0 ´ 10-57 ° = E°
Find E cell cathode - E° anode then, D r G° by using
= 1.33 V -
0.0591 V
log 4 ´ 1055 formula, D r G ° = - nFE cell
° .
6
Sol. E°cell = E°right - E °left = - 0.403 - (- 0.763) = 0.36 V
0.0591 V
= 1.33 V - ´ 55.6021
6 0.059 [Zn 2+ ( aq )]
Ecell = E°cell - log
= 1.33 V - 0.5477 V n [ Cd 2+ ( aq )]
= 0.7823 V 0.059 0.1
Ecell = 0.36 - log [ n = 2]
2 0.01
Example 3. The standard electrode potential (E°) for Ecell = 0.36 - 0.0295 log 10
Daniell cell is +1.1 V. Calculate the D G° for the reaction.
= 0.36 - 0.0295 ´ 1= 0.3305 V
Zn( s ) + Cu 2 + ( aq) ¾¾® Zn 2+ ( aq) + Cu( s )
D r G° = - nFEcell
° = - 2 ´ 96500 ´ 0.36
(1 F = 96500 C mol -1 ) = - 69480 J mol -1 = -69.48 kJ mol -1
Example 6. Conductivity of two electrolyte solutions A and Example 8. The electrical resistance of a column of
B each having a concentration of 0.1 M are 8.5 ´ 10 -2 S cm -1 0.05 M NaOH solution of diameter 1 cm and length 50 cm
and 4.1 ´ 10 -4 S cm -1 respectively. Which of the two offers is 5 .55 ´ 10 3 W. Calculate its resistivity, conductivity and
less resistance to the flow of current ? molar conductivity.
1
Sol. k µ
R (i) Calculate area from radius by using, A = pr 2
Hence, B will offer greater resistance. RA
(ii) Calculate resistivity from the formula, r =
Example 7. Conductivity of 0.00241 M acetic acid l
solution is 7.896 ´ 10 -5 S cm -1 . (iii) Calculate conductivity ( k ) from resistivity as k =1/ r
Calculate its molar conductivity in this solution. If L°m for (iv) Calculate molar conductivity, L m by using the formula
acetic acid be 390.5 S cm 2 mol -1 , what would be its k ´ 1000
Lm =
dissociation constant? (NCERT) M
2
(i) First, find molar conductivity using the formula, æ 1ö
Sol. Area, A = pr 2 = 3.14 ´ ç ÷ cm 2 = 0.785 cm 2
k ´ 1000 è 2ø
LCm = . RA
C Resistivity, r =
l
(ii) Then, find degree of dissociation (a) and
5.55 ´ 103W ´ 0.785 cm 2
dissociation constant (K a ) by using formula, =
50 cm
LCm Ca 2 = 87.135 W cm
a= and Ka = , respectively.
L°m 1-a 1 1
Conductivity, k = = W -1 cm -1
r 87.135
Sol. Given, k = 7.896 ´ 10 -5 S cm -1 ,
= 0.01148 W -1cm -1
L°m (CH COOH) = 390.5 S cm 2 mol -1
3
= 1.148 ´ 10–2 S cm –1
and Molarity (M) = 0.00241 M
k ´ 1000 Molar conductivity,
Molar conductivity, LCm = k ´ 1000
Molarity Lm =
M
7.896 ´ 10 -5 S cm -1 ´ 1000
= 1.148 ´ 10-2 ´ 1000
0.00241 M (mol cm -3 ) = = 229.6 S cm 2 mol -1
0.05
LCm = 32.76 S cm 2 mol -1
LCm 32.76 Example 9. Calculate L°m for acetic acid,
Degree of dissociation, a = = = 8.4 ´ 10 -2
L°m 390.5 Given that, L°m (HCl) = 426 S cm 2 mol -1
For dissociation constant of acetic acid, CH3 COOH L°m (NaCl) = 126 S cm 2 mol -1
CH3 COOH w CH3 COO - + H+ L°m = 91 S cm 2 mol -1
(CH 3COONa)
Initial conc. C 0 0
Sol. L°m (CH3 COOH) = L°H+ + L°CH
After time t, C - Ca Ca Ca 3 COO
–
Dissociation constant, = L°H+ + L°Cl – + L°CH – + L°Na+

3 COO
[CH3 COO -] [H+ ] Ca 2
Ka = = - L°Cl – - L°Na+ = L°m (HCl) + L°m (CH3 COONa) - L°m
[CH3 COOH] 1-a (NaCl )
-2 2 2 -1
0.00241 (8.4 ´ 10 ) = (426 + 91 - 126) S cm mol
Ka = = 1.86 ´ 10 -5
(1 - 0.084) = 391 S cm 2 mol -1
Chapter
Practice
PART 1 If half-cell potentials are :
Zn 2+ ( aq) + 2e - ¾® Zn( s ); E° = + 0.76 V
Objective Questions Ag 2O ( s ) + H 2O( l ) + 2e - ¾® 2Ag ( s ) + 2OH - ;
E° = 0.34V.
l Multiple Choice Questions
The cell potential will be
1. The electrode potential of a half-cell depends upon (a) 1.1 V (b) 0.42 V
(a) nature of metal (c) 0.84 V (d) 1. 34 V
(b) concentration of metal ions in solution
(c) temperature of the solution 6. Compounds XA, XB, XC are added into separate test
(d) All of the above tubes containing A, B, C solutions. XB react with A
and C. XA does not react with any of these. XC
2. For the electrochemical cell,
reacts with A.
Ag | AgCl| KCl || AgNO 3 | Ag + , the overall cell
Arrange the anion in the decreasing order of their
reaction is
oxidation.
(a) Ag+ + KCl ¾® AgCl(s ) + K+
(a) A- > B- > C -
1
(b) Ag + AgCl ¾® 2Ag + Cl 2 (b) B- > C - > A-
2 (c) C - > A- > B-
(c) AgCl(s ) ¾® Ag+ + Cl - (d) B- > A- > C -
(d) Ag+ + Cl – ¾® AgCl(s )
°
7. Using the data given below find out the strongest
3. For the cell, Cu |Cu 2+||Ag +|Ag, Ecell = + 0.46 V reducing agent.
2+ °
If concentration of Cu ions is doubled, then E cell E sCr2O27- /Cr 3+ = 1.33V; E sCl 2 /Cl - = 1.36V
will be E s MnO-4 / Mn 2+ = 1.51V; E sCr 3+ /Cr = - 0.74V
(a) halved
(a) Cl - (b) Cr
(b) doubled
(c) Cr 3+ (d) Mn 2 +
(c) four times
(d) remains the same 8. In the given reaction,
4. In the electrolysis of aqueous sodium chloride 2Cu + ( aq) s Cu 2+ ( aq) + Cu ( s )
solution, which of the half cell reaction will occur at ° °
ECu +
/Cu
= 0.6 V and ECu 2+
/Cu +
= 0.41 V
anode?
(a) Na + ( aq ) + e - ¾® Na ( s ); Escell = - 2.71 V The equilibrium constant for this reaction will be
+ -
(b) 2H2O ( l ) ¾® O 2 (g) + 4H ( aq ) + 4e ; Ecell = 1.23 V
s (a) 2.76 ´ 102
1 (b) 2.76 ´ 104
(c) H+ ( aq ) + e- ¾® H2 ( g ); Ecell ° = 0.00 V
(c) 2.76 ´ 106
2
1 (d) 2.76 ´ 108
(d) Cl - ( aq ) ¾® Cl 2 ( g ) + e - ; Escell = 1.36 V
2 9. Electrode potential for Mg electrode varies
5. A button cell used in watches, functions as following : according to the equation
Zn( s ) + Ag 2O ( s ) + H 2O( l ) 3 ° 0.059 1
E Mg 2+ / Mg = E Mg 2+
/ Mg
- log .
2Ag( s ) + Zn 2+ ( aq) + 2OH - ( aq) 2 [Mg 2+ ]
The graph of E Mg 2+ / Mg vs log [Mg 2+ ] is A B

(a) Weak electrolyte Strong electrolyte
(b) Strong electrolyte Weak electrolyte
EMg 2+/Mg
EMg 2+/Mg
(a) (b) (c) Weak electrolyte Weak electrolyte

(d) Strong electrolyte Strong electrolyte
log[Mg 2+]® log[Mg 2+]® 15. Consider the following graph,

149.8
EMg 2+/Mg
EMg 2+/Mg
149.4
(c) (d)
Lm /(S cm2 mol–1)

149.0
148.6
148.2
log[Mg 2+]® log[Mg 2+]®
147.8
10. Which of the following statement is correct? 147.4
(a) Ecell and D r G of cell reaction both are extensive properties 147.0
(b) Ecell and D r G of cell reaction both are intensive properties
O
(c) Ecell is an intensive property while D r G of cell reaction is 0.005 0.010 0.015 0.020
an extensive property ÖC
(d) Ecell is an extensive property while D r G of cell reaction is Here, the limiting molar conductivity is
an intensive property
(a) 148.6 (b) 150
11. The Gibbs energy for the decomposition of Al 2O 3 at (c) 87.46 (d) 147
500°C is as follows 16. At, 25°C the specific conductivity of N/50 KCl
2 4 solution is 0.002765 mho cm -1 , if the resistance of
Al 2O 3 ¾® Al + O 2 ; D r G = + 960 kJ mol -1
3 3 cell with solution is 400 W then the cell constant (G )
will be
The potential difference needed for the electrolytic
(a) 0.533 cm -1 (b) 1.106 cm -1
reduction of aluminium oxide (Al 2O 3 ) at 500°C is
(c) 2.212 cm -1 (d) None of these
atleast
(a) 4.5V (b) 3.0V (c) 2.5V (d) 5. 0V 17. L°m (NH 4OH) is equal to ......... . (NCERT Exemplar)
°
12. If the Ecell for a given reaction has a negative value, (a) L°m (NH4 OH) + L°m (NH4 Cl) - L°m (HCl )
then which of the following gives the correct (b) L°m (NH4 Cl) + L°m (NaOH) - L°m (NaCl )
relationships for the values of DG° and K eq ?
(a) DG°> 0; K eq < 1 (b) DG° > 0; K eq > 1 (c) L°m (NH4 Cl) + L°m (NaCl ) - L° m (NaOH)
(c) DG° < 0; K eq > 1 (d) DG° < 0; K eq < 1 (d) L°m (NaOH) + L°m (NaCl) - L°m (NH4 Cl )
13. Which of the following statements about solutions of
electrolytes is not correct? (NCERT Exemplar)
l
Assertion-Reasoning MCQs
(a) Conductivity of solution depends upon size of ions. Direction (Q. Nos. 18-22) Each of these questions
(b) Conductivity depends upon viscosity of solution. contains two statements Assertion (A) and Reason (R).
(c) Conductivity does not depend upon solvation of ions Each of these questions also has four alternative choices,
present in solution.
any one of which is the correct answer. You have to select
(d) Conductivity of solution increases with temperature.
one of the codes (a), (b), (c) and (d) given below.
14. The graph of molar conductivity ( L m ) versus root of (a) Both A and R are true and R is the correct
concentration C 1/ 2 is plotted. Which type of electrolyte explanation of A.
are used in A and B ? (b) Both A and R are true, but R is not the correct
400 explanation of A.
(c) A is true, but R is false.
Lm /(S cm2 mol–1)
(A) (d) A is false, but R is true.

18. Assertion Current stops flowing when Ecell = 0.
200
(B)
Reason Equilibrium of the cell reaction is attained.
(NCERT Exemplar)
19. Assertion Copper sulphate can be stored in zinc
0 vessel.
0 0.2 0.4 Reason Zinc is less reactive than copper.
C1/2/(mol/L)1/2 (NCERT Exemplar)
20. Assertion EAg + / Ag increases with increase in (ii) Molar conductivity of a solution is
+
concentration of Ag ions. 1.26 ´ 10 2 W -1cm 2mol -1 . Its molarity is 0.01.
Reason E Ag + / Ag has a positive value. Its specific conductivity will be
(NCERT Exemplar) (a) 1. 26 ´ 10-5 (b) 1.26 ´ 10-3
-4
21. Assertion Electrolysis of NaCl solution gives chlorine (c) 1. 26 ´ 10 (d) 12.6 ´ 10-3
at anode instead of O 2 . (iii) The increase in molar conductivity of HCl with
Reason Formation of oxygen at anode requires over dilution is due to
voltage. (NCERT Exemplar) (a) increase in self-ionisation of water
(b) hydrolysis of HCl
22. Assertion pH of brine solution increases during (c) decrease in self-ionisation of water
electrolysis. (d) decrease in interionic forces
Reason H 2 is liberated at cathode and Cl 2 is at anode
(iv) Which of the following is wrong about molar
during electrolysis of NaCl solution. conductivity ?
(a) The solution contains Avogadro number of
l Case Based MCQs molecules of the electrolyte
23. Read the following and answer the questions from (i) (b) It is the product of specific conductivity and
volume of solution in cc containing 1 mole of
to (iv) given below electrolyte
Molar conductivity of a solution is the conductance of (c) Its units are ohm -1 cm 2 mol -1
solution containing one mole of electrolyte, kept (d) Its value for 1 M NaCl is same as that of 1 M
between two electrodes having unit length between glucose solution
them and large cross-sectional area, so as to contain the Or
electrolyte. In other words, molar conductivity is the Highest molar conductivity will be exhibited by
conductance of the electrolytic solution kept between (a) 0.005 M NaCl (b) 0.1 M NaCl
the electrodes of a conductivity cell at unit distance (c) 0.5 M NaCl (d) 0.01 M NaCl
but having area of cross-section large enough to 24. Read the following and answer the questions from
accommodate sufficient volume of solution that (i) to (iv) given below
contains one mole of the electrolyte. It is denoted by
Lm . The potential difference between two half-cell is
called the cell-potential. The calculation of cell
The molar conductivity is related to conductivity as
potential for emf requires only the addition of the
1000 1000
Lm = k ´V = ´ k= k´ emf values for each half reaction, while the same
C Molarity cell potential calculation using standard potentials
Unity of L m (molar conductivity) shall be requires the usage of the following convention:
ohm -1 cm -1 mol -1 or Scm 2 mol -1 . °
E cell °
= E cathode °
- E anode
Thus, knowing molar concentration (C ) and Each half-cell reaction has a specific standard
conductivity ( k), L m can be calculated. L°m is called potential reported as the potential of the reduction
molar conductivity at infinite dilution. The molar reaction vs the normal hydrogen electrode (NHE).
conductivity of strong electrolytes is found to vary In an electrochemical cell, there is a half-cell
with concentration according to the equation, corresponding working electrode (WE), where the
LCm = L°m - A C reactions under study take place, and a reference
half-cell. Experimentally, the cell potential is
This equation is called Debye-Huckel Onsager
measured as the difference between the potentials
equation.
of the WE half-cell and the reference
Here, A is constant depending upon the type of electrode/reference half-cell. The archetypal
electrolyte taken and nature of solvent and reference electrode is the NHE, also known as the
temperature. standard hydrogen electrode (SHE) and is defined,
(i) If conductivity of 0.00241 M acetic acid is by convention, as 0 V for any temperature. The
7.896 ´ 10 -5 S cm -1 , the molar conductivity of arrangement of various standard half-cells in the
the solution shall be (in S cm -1 mol -1 ) order of their decreasing values of standard
(a) 3.276 (b) 0.3276
reduction potentials is called electrochemical
(c) 32.76 (d) 327.6
series.
(i) On which of the following, emf of a cell does 5. Write the Nernst equation and emf of the following cell
not depend? at 298 K.
(a) Temperature of electrolyte (i) Mg ( s ) | Mg 2+ (0.001 M) | | Cu 2+ (0.0001 M)|Cu ( s )
(b) Nature of electrolyte
(c) Concentration of electrolyte in two half-cells (ii) Fe ( s ) | Fe 2+ (0.001 M)| | H+ (1 M)| H2 ( g )
(d) Size of the plates (1 bar) | Pt ( s )
(ii) Electrical conductance increases with ........ Given that, E°Mg 2+ / Mg = - 2.36 V,
temperature. E°Cu2+ / Cu = 0.34 V, E°Fe2+ / Fe = -0.44 V
(a) increasing (b) decreasing
(c) constant (d) nullifies
6. Use the data to answer the following and also justify
giving reason
(iii) Which of the following is correct about a
salt-bridge? Cr Mn Fe Co
(a) It maintains the resistivity of both half-cells °
- 0.91 - 1.18 - 0.44 - 0.28
EM 2+
/M
(b) It maintains the electrical neutrality between
solutions of both the half-cells °
EM 3+ - 0.41 + 1.57 + 0.77 + 1.97
/ M 2+
(c) It maintains the electricity flow between both
half-cells
(i) Which is a stronger reducing agent in aqueous
(d) None of the above
medium, Cr 2+ or Fe 2+ and why?
(iv) The reduction of 1 mole of Zn 2 + to given 1 mole
(ii) Which is the most stable ion in +2 oxidation and why?
of Zn would need how many coulombs?
(a) 193000 C (b) 96500 C 7. Calculate the emf of the cell in which the following
(c) 56900 C (d) 487500 C reaction takes place.
Or Ni ( s ) + 2Ag + (0.002 M) ¾® Ni 2+ (0.160 M) + 2Ag ( s )
The equilibrium can be achieved in chemical Given that, E°cell = 1.05 V
reaction at what value of emf?
(a) + 1 (b) - 1 8. (i) The cell in which the following reaction occurs,
(c) 0.5 (d) Zero 2Fe 3+ ( aq) + 2I - ( aq) ¾® 2Fe 2+ ( aq) + I 2( s )
has E°cell = 0.236 V at 298 K. Calculate the standard
Gibbs energy of the cell reaction.
PART 2 (Given, 1 F = 96500 C mol -1 )
Subjective Questions (ii) How many electrons flow through a metallic wire, if
a current of 0.5 A is passed for 2 hours ?
l
Short Answer Type Questions (Given, 1 F = 96500 C mol -1 ) [All India 2017]
1. Define electrochemical cell. What happens if 9. Calculate D r G° and log K C for the following reaction
external potential applied becomes greater than Cd 2+ ( aq) + Zn( s ) ¾® Zn 2+ ( aq) + Cd ( s )
°
E cell of electrochemical cell? °
Given, E Cd 2+
/ Cd
= - 0.403 V
2. For a cell °
E Zn 2+ = - 0.763 V
Ag ( s )| AgNO 3 (0.01M)|| AgNO 3 (1.0M)| Ag( s) / Zn
(i) Calculate the emf of the cell at 25°C. 10. The resistance of a conductivity cell, when filled with
(ii) Write the net cell reaction. 0.05 M solution of an electrolyte x, is 100 W at 40°C.
(iii) Will the cell generate emf, when two The same conductivity cell when filled with 0.01 M
concentrations become equal? solution of electrolyte y, has a resistance of 50 W.
3. Write the cell reaction and Nernst equation for the The conductivity of 0.05 M solution of electrolyte x is
cell reaction in the Daniell cell. How will the E cell 1.0 ´ 10 -4 S cm -1 .
be affected when concentration of Zn 2+ ions is Calculate
increased?
(i) cell constant.
4. Calculate the potential of hydrogen electrode (ii) conductivity of 0.01 M y solution.
which is in contact with a solution whose pH is 10. (iii) molar conductivity of 0.01 M y solution.
11. What will be the limiting molar conductivity of 20. Following reactions can occur at cathode during the
CH 3COOH if the limiting molar conductivity of electrolysis of aqueous silver nitrate solution using Pt
CH 3COONa is 91 S cm 2 mol -1 ? Limiting molar electrodes: (Delhi 2015)
+ -
conductivity for individual ions are given in the Ag ( aq) + e ¾® Ag( s ); E° = 0.80 V
following table. 1
H + ( aq) + e - ¾® H 2 ( g ); E° = 0.00 V
S. No. Ions Limiting molar conductivity/S cm 2 mol -1 2
On the basis of their standard electrode potential
1 H+ 349.6
values, which reaction is feasible at cathode and why?
2 Na + 50.1
l Long Answer Type Questions
3 K+ 73.5
21. (i) Calculate E°cell for the following reaction at 298 K:
4 OH- 199.1
2Al( s ) + 3Cu2+ (0.01 M) ¾®
2Al3 + (0.01 M) +3Cu( s )
12. Suggest a way to determine the L°m for water.(NCERT)
Given, Ecell = 1.98 V
13. Calculate the degree of dissociation (a ) of acetic (ii) Using the E° values of A and B, predict which is better
acid, if its molar conductivity ( L m ) is 39.05 S cm 2 for coating the surface of iron
mol -1 . [E°(Fe2+/ Fe) = -0.44V] to prevent corrosion and
why?
Given : L° (H + ) = 349.6 S cm 2 mol –1
Given : E °( A2+ / A) = -2.37 V,
and L° (CH 3COO - ) = 40.9 S cm 2 mol -1
E °( B 2+ / B) = -0.14 V (Delhi 2016)
14. The conductivity of 0.20M solution of KCl at 298K
is 0.0248 S cm -1 . Calculate its molar conductivity.
22. (i) The emf of the following cell at 298 K is 0.1745 V.
Fe( s )|Fe 2+ (0.1 M)|| H + (x M)|| H 2 ( g )(1 bar)| Pt( s)
15. The conductivity of 0.001 M acetic acid is
Given, E Fe ° = - 0.44 V
4 ´ 10 -5 S /cm. Calculate the dissociation constant of 2+
/ Fe
acetic acid, if molar conductivity at infinite dilution Calculate the H + ions concentration of the
for acetic acid is 390 S cm2/mol. solution at the electrode where hydrogen is being
produced.
16. The molar conductivity of 0.025 mol L -1 methanoic
(ii) Why on dilution the L m of CH 3COOH increases
acid is 46.1 S cm 2 mol -1 . Calculate its degree of drastically, while that of CH 3COONa increases
dissociation and dissociation constant. gradually? (NCERT Exemplar)
Given, L° (H + ) = 349.6 S cm 2 mol -1
23. (i) State Kohlrausch law .
and L° (HCOO - ) = 54.6 S cm 2 mol -1 (ii) Calculate the emf of the following cell at 298 K:
17. Conductivity of 2.5 ´ 10 -4 M methanoic acid is Al ( s )|Al 3+ ( 015
. M)||Cu 2+ 0.025 M| Cu(s)
5.25 ´ 10 -5 S cm -1 . Calculate its molar conductivity (Given : E(°Al 3+ / Al ) = - 1.66 V, E(°Cu 3+ / Cu ) = 0.34 V,
and degree of dissociation.
Given: L°(H + ) = 349.5 S cm 2 mol - 1 and log 0.15 = - 0 . 8239, log 0.025 = -1.6020)
L°(HCOO - ) = 50.5 S cm 2 mol - 1 . (All India 2015)
24. (i) On the basis of E° values identify which amongst
the following is the strongest oxidising agent?
18. When acidulated water (dil. H 2SO 4 solution) is Cl 2 (g) + 2e - ¾® 2Cl - ; E° = +1.36 V
electrolysed, will the pH of the solution be affected?
MnO 4- + 8H+ + 5 e - ¾® Mn 2+ +4H2 O;
Justify your answer. (NCERT Exemplar)
E° =1.51V
19. Predict the products of electrolysis in each of the Cr2 O 72 - + 14H+ + 6e - ¾® 2Cr 3+ + 7H2 O;
following
E° = +1.33 V
(i) An aqueous solution AgNO 3 with silver
(ii) The following figure 2, represents variation of
electrodes.
(Lm ) vs C for an electrolyte. Here, L m is the
(ii) An aqueous solution AgNO 3 with platinum molar conductivity and C is the concentration of
electrodes. the electrolyte.
150.0 ° 2+
[Given: ECu ° +
= + 0.34; E Ag = + 0.80 V,
/Cu / Ag
148.8
° 3+
E Au / Au
= + 1.40 V]
149.4
(ii)
Lm/(S cm mol–1)
149.0
148.6
148.2 Zinc Silver
plate plate
147.8
Salt-bridge
147.4
147.0 Ag+(aq)
0 .005 .010 .015 .020 .025 .030 .035 Zn2+(aq)

C1/2/(mol/L)1/2
Consider the figure given above and answer the
(a) Define molar conductivity.
following questions:
(b) Identify the nature of electrolyte on the basis of
(a) What is the direction of flow of electrons?
the above plot. Justify your answer.
(b) Which one is anode and which one is cathode?
(c) Determine the value of L m for the electrolyte.
(c) What will happen if the salt bridge is removed?
(d) Show how to calculate the value of A for the
electrolyte using the above graph. (d) How will concentration of Zn 2+ and Ag + ions be
affected when the cell functions?
25. (i) Calculate emf of the following cell :
(e) How will concentration of these ions be affected
Zn( s ) / Zn 2 + (0.1 M) || (0.01 M) Ag + / Ag ( s ) when the cell becomes dead?
°
Given E Zn 2+ = - 0.76 V,
/ Zn lCase Based Questions
°
E Ag + = + 0.80 V
/ Ag 28. Read the following and answer the questions from (i)
[Given, log 10 = 1] to (iv) given below
(ii) X and Y are two electrolytes. On dilution molar Molar conductivity, L m is defined as the conducting
conductivity of ‘X’ increases 2.5 times, while that power of all the ions produced by dissolving one gram
of Y increases 25 times. Which of the two is a mole of an electrolyte in solution. It is related to
conductivity (or specific conductance), k as follows :
weak electrolyte and why? (All India 2020)
k
26. (i) The electrical resistance of a column of 0.05 M Molar conductivity, L m =
C
KOH solution of length 50 cm and area of
cross-section 0.625 cm 2 is 5 ´ 10 3 ohm. In the above equation, if k is expressed in S m -1 and
Calculate its resistivity, conductivity and molar the concentration C in mol m -3 then the units of L m
conductivity. are in Sm 2 mol -1
(ii) Predict the products of electrolysis of an aqueous Now, 1 mol m -3 = molarity (mol/L)´100 L / m 3
solution of CuCl 2 with platinum electrodes. Hence, L m (S m2 mol -1 )
°
(Given : ECu = + 0.34 V, E °(1/ 2 Cl = + 1.36 V
= k (S m -1 ) /molarity (mol L -1 ) ´1000 Lm -3
2+ -
/ Cu 2 /Cl )
°
EH = 0.00 V, E °(1/ 2 O2 / H 2 O) = + 1.23 V)
+
/H 2 ( g ), Pt If k is expressed in Scm -1 and C in mol cm -3 , then
(All India 2020) the units for L m are S cm 2 mol -1 . It can be
27. (i) When a bright silver object is placed in the calculated by using the equation
solution of gold chloride, it acquires a golden k (S cm -1 ) ´100 (cm 3 /L)
tinge but nothing happens when it is placed in a L( S cm 2 mol -1 ) =
molarity (mol/L)
solution of copper chloride. Explain this
behaviour of silver. Both type of units are used in literature and are
related to each other by the equations
1 S m 2 mol -1 = 10 4 S cm 2 mol -1 The standard potentials are always measured under

1 S cm 2 mol -1 = 10 -4 S cm 2 mol -1 standard conditions, i.e. when the pressure of a gas is
Equivalent conductance, L (lambda). It is defined as 1 atm, concentration of ions is 1 mol dm -3 and the
the conducting power of all the ions produced by temperature is 298 K. However, practically standard
dissolving one gram equivalent of an electrolyte in conditions are hardly achieved or used. The potential
solution. of the electrode whose reaction can be written (in the
form or reduction) as
(i) The molar conductivity of a 1.5 M solution of an
electrolyte is found to be 138.9 Scm 2 mol -1 . M n+ ( aq) + ne - ¾® M( s )
Calculate the conductivity of the solution. which is measured against standard hydrogen
electrode, is written as
(ii) How is the unit of molar conductivity arrived ?
RT [M]
(iii) Calculate the degree of dissociation (a) of E( M n+ / M ) = E(-M n+ / M ) - ln
nF [ M n+ ]
acetic acid if its molar conductivity( L m ) is
40.05 S cm2 mol -1 . This is known as the Nernst equation.
Given: l°(H + ) = 349.6 S cm2 mol -1 and (i) Write Nernst equation for the following cell
l°( A - ) = 50.9 S cm2 mol -1 reaction:
(iv) Why does the conductivity of a solution decrease Zn | Zn 2+ (aq)||Cu 2+ (aq)|Cu(s )
with dilution? (ii) What is the effect of increase in concentration of
Or zinc ions on the electrode potential of zinc
electrode for which E Zn 2+ / Zn equals - 0.76 V ?
What is the effect of decreasing concentration on
the molar conductivity of a weak electrolyte? (iii) How can the reduction potential of an electrode
be increased?
29. Read the following and answer the questions from (i)
to (iv) given below (iv) What does the standard electrode potential of a
metal being negative( E -Zn 2+ /Zn = - 0.7632)
Standard potentials are physical electrochemical indicate ?
quantities that represent essential properties of
Or
systems that involves metals and gases on the one
hand and ions in solution on the other. How does temperature affect Nernst equation?
EXPLANATIONS
Objective Questions 8. (c) Overall cell reaction,
1. (d) Electrode potential of any half-cell depends all of the 2Cu + (aq ) ¾® Cu (s ) + Cu 2+ ( aq )
given options, i.e. on nature of metal, concentration of metal ° ) = E° +
\ Cell potential ( Ecell ° 2+ +
- ECu
Cu / Cu / Cu
ions in the solution and temperature of solution. = 0.60 - 0.41 = 0.19 V
2. (c) For the electrochemical cell, As we know that,
Ag | AgCl | KCl || AgNO3 | Ag+ - nFE° = - RT ln K eq
The cell reaction is nE° 2 ´ 0.19 V
Þ log K eq = = = 6.44
AgCl (s)+ e - ¾® Ag + Cl – ( aq ) ( 2.303RT / F ) 0.059 V
Ag ¾® Ag+( aq ) + e – K eq = 106.44 = 2.76 ´ 106
Overall cell reaction, æ 0.059 ö
9. (b) EMg 2 + / Mg = ç ÷ log [ Mg2 + ] + EMg
°
AgCl(s ) ¾® Ag+ + Cl – è 2 ø
2+
/ Mg
° = Ecathode
3. (d) Ecell ° °
- Eanode This equation represents equation of straight line. It can be
i.e. it does not depend upon the concentration of ions. correlated as
Hence, if the concentration of Cu 2 + ions is doubled, then æ 0.059 ö
EMg 2+ /Mg = ç ÷ log [Mg2+ ] + EMg °
2+
° will remains the same.
Ecell è 2 ø /Mg
4. (d) In case of electrolysis of aqueous NaCl, oxidation

reaction occurs at anode as follows Y M X +C
1 °
Cl - ( aq ) ¾® Cl 2 ( g )+ e - ; Ecell = 1.36 V So, intercept (C) = E° 2+
Mg /Mg
2
0.059
2H2O (l) ¾® O 2 (g ) + 4H+ (aq ) +4 e - ; Ecell
°
= 1.23 V Slope =
2
°
But due to lower Ecell value, water should get oxidised in Thus, equation can be graphically represented as,
-
preference of Cl (aq).
However, the actual reaction taking place in the
EMg 2+/Mg
0.059
concentrated solution of NaCl is (d) and not (b), i.e. Cl 2 is Slope =
2
produced and not O 2 .
C = E Mg
° 2+/Mg
This unexpected result is explained on the basis of the
concept of ‘overvoltage’, i.e. water needs greater voltage for log[Mg 2+]®
oxidation to O 2 (as it is kinetically slow process) than that 10. (c) Ecell is an intensive property as it does not depend upon
needed for oxidation of Cl - ions to Cl 2 . mass of species (number of particles) but D r G of the cell
Thus, the correct option is (d) not (b). reaction is an extensive property because this depends upon
5. (a) Anode is always the site of oxidation and cathode is the mass of species (number of particles).
site of reduction. 11. (c) The half-cell reactions are
Thus, anode half-cell is 4Al 3+ ¾® 4Al + 12e - [Reduction]
Zn( s ) ¾® Zn 2+ (aq ) + 2e - ; E° = -0.76 V 12e - + 6O2 - ¾® 3O2 [Oxidation]
and cathode half-cell is
4 3+ 4
Ag2O(s ) + H2O( l ) + 2e - ¾® 2Ag ( s ) + 2OH- ( aq ) ; or Al ¾® Al + 4e - [Reduction]
3 3
E° = 0.34 V
4e - + 2O2- ¾® O2 [Oxidation]
° = E° °
Q Ecell cathode - Eanode
As we know that,
\ E° = 0.34 - ( - 0.76) = 1.1 V
cell DG° = - nFE°
1
6. (b) Oxidising tendency µ Given, DG = + 960 kJ mol -1 = 960 ´ 1000 J mol -1
electrode potential
XA ¾® No reaction n = 4F = 4 ´ 96500 C
XB ¾® A, C \ 960 ´ 1000 = - 4 ´ 96500 ´ E°
XC ¾® A 960000
Order of electrode potential is XB < XC < XA. E° = - = - 2.48 V
4 ´ 96500
Order of oxidation of anion B - > C - > A - . Potential difference » 2.5 V
7. (b) Here, out of given four options standard reduction 12. (a) The standard free energy ( DG° ) is related to standard
potential of chromium has highest negative value hence, electrode potential ( E° ) and equilibrium constant as
most powerful reducing agent is chromium.
DG° = - nFE° and DG° = - RT loge K eq
° is - ve, then DG° is + ve, i.e. DG° > 0.

Thus, if Ecell 1 ° = 1 .36V
At anode Cl -( aq ) ¾
¾® Cl 2 + e - ; Ecell
Hence, K eq would be negative and less than 1; K eq < 1. 2
13. (c) Solution consists of electrolytes is known as electrolytic 2H2O ( aq ) ¾ ¾® O 2 ( g ) + 4H+ ( aq ) + 4e - ; Ecell
° = 1.23 V
solution and conductivity of electrolytic solution depends °
Ecell for this reaction has lower value but formation of
upon the following factors oxygen at anode requires over potential.
(i) Size of ions As ion size increases, ion mobility 22. (b) Both A and R are true but R is not the correct explanation
decreases and conductivity decreases. of A. pH of brine solution increases due to formation of
(ii) Viscosity of solution Greater the viscosity of the NaOH at cathode during electrolysis.
solvent, lesser will be the conductivity of the solution. At cathode, 2Na ¾ Hg + 2H2O ¾® 2NaOH + Hg + H2( g )
(iii) Solvation of ions Greater the solvation of ions of an 23. (i) (c) Here, L = k ´ 1000
electrolyte, lesser will be the electrical conductivity of m
M
the solution.
7.896 ´ 10-5 ´ 1000
(iv) Temperature of medium Conductivity of solution =
increases with increase in temperature. 0.00241
14. (a) In the given graph, ‘A’ represents weak electrolyte like = 32.76 S cm -1 mol -1
CH3COOH as Lm is increasing steeply on dilution at low 1000 ´ k Lm ´ Molarity
concentration region and ‘B’ represents strong electrolyte (ii) (b) Lm = or k=
Molarity 1000
like NaCl as Lm is increasing slowly with dilution.
1. 26 ´ 10 -2 ´ 0.01
15. (b) When concentration approaches zero, the molar = = 1.26 ´ 10 -3
conductivity is known as limiting molar conductivity. 1000
So, here limiting molar conductivity is near about 150. (iii) (d) The increase in molar conductivity of any strong
16. (b) Given, k = 0.002765 electrolyte like HCl with dilution is due to decrease in
R = 400W the interionic forces.
[Here, R = resistance, k = specific conductivity] (iv) (d) Statement (d) is wrong about molar conductivity.
Glucose is a non-electrolyte and hence question of
Cell constant ( G) = R ´ k having molar conductivity does not arise.
= ( 400W ) ´ ( 0.002765 mho cm -1 ) = 1.106 cm -1 Or
17. (b) L°m (NH 4 Cl) = L°m (NH +) + L°m ( Cl - ) (a) Lm = k ´ V, where V is the volume of solution
4
L°m (NaOH) = L°m (Na+ ) + L°m (OH- ) containing 1 mole of the solute. Specific conductivity
( k ) decreases with dilution but volume increases much
L°m (NaCl) = L°m (Na+ ) + L°m (Cl - ) more on dilution. Hence, Lm increases with dilution.
As volume containing 1 mole of NaCl will be highest
- - - for 0.005 M NaCl solution, the product of k ´ V will be
L°m (NH4 Cl) + L°m (NaOH) - L°m (NaCl) = L°m (NH4 OH) highest and hence Lm will also be highest.
Hence, option (b) is correct choice. 24. (i) (d) Emf of a cell depends on the temperature of
electrode, concentration of electrolyte in two half-cells,
18. (a) Both A and R are true and R is the correct explanation of A. nature of the electrode and the distance of separation
Current stop flowing when Ecell = 0 between two electrodes. It does not depend on its
As at Ecell = 0, reaction reaches the equilibrium. shape and size.
19. (c) A is true, but R is false. (ii) (a) The electrical conductance increases with increasing
Copper sulphate can’t be stored in zinc vessel as zinc is more temperature. As the temperature increases, the
reactive than copper due to negative value of standard mobility of ions present in the solution increases and as
reduction potential of Zn. a result, conductance increases.
20. (b) Both A and R are true but R is not the correct explanation (iii) (b) A salt-bridge is used to connect the oxidation and
of A. reduction half-cells of a galvanic cell and it maintains
0.0591 1 the electrical neutrality between both half-cells. It
E = E- log completes the cycle of the charge flowing through the
1 [Ag+ ]
cell.
E = E° + 0.059 log [Ag+ ] (iv) (a) The reduction of Zn 2 + involves 2 electrons.
Thus, EAg + /Ag increases with increase in concentration of Ag+ . Zn 2 + + 2e - ¾® Zn( s )
21. (a) Both A and R are true and R is the correct explanation of A. So, 2 Faradays or 2 ´ 96500 = 193000 C charge is
required.
Explanation Electrolysis of NaCl is represented by
Or
following chemical reactions
(d) When the cell reaction attains equilibrium, then the
1
At cathode H+ ( aq ) + e- ¾¾® H 2 ( g ) value of emf of a cell becomes zero.
2
Subjective Questions (ii) Fe ( s )| Fe2 + (0.001 M) || H+ (1 M)| H2( g ) (1 bar) | Pt ( s )

1. The device through which chemical energy changes to The overall cell reaction will be
electrical energy is called electrochemical cell. The chemical
Fe(s ) + 2H+ ( aq ) ¾® Fe2 + ( aq ) + H2( g )
reaction of the cell is reversed and current flows in opposite
direction when opposing emf is greater than that of the cell. The Nernst equation is
2. Electrochemical reaction is ° 0.059 [ Fe2 + ]
Ecell = Ecell - log + 2
Ag + Ag+ ¾® Ag+ + Ag n [H ]
(1 M) ( 0. 01)
0.059 ( 0.001)
0.059 [ 0.01 ] = [ 0 - ( - 0.44)] - log
Ecell = Ecell
° - log 2 (1)2
n [1 ] 0.059
= 0.44 - log( 10- 3 )
= - 0.059 log10-2 [Q Ecell
° = EAg
° +
/ Ag
- EAg
° +
/ Ag
= 0] 2
= 0.44 - 0.0295 (- 3) = 0.44 + 0.0885
(i) Ecell = 2 ´ 0.059 = 01182. V
= 0.528 = 0.53 V (Approximately)
(ii) Net cell reaction is AgNO 3( 1M ) ¾® AgNO 3( 0.01 )M
6. (i) The ECr° °
value is - 0.41 V and EFe is 0.77 V.
(iii) The cell would not generate emf. 3+
/ Cr 3+
/ Fe
2+
If the concentrations are equal, then This means Cr can be easily oxidised to Cr 3+ than
Fe2 + as Fe2 + does not oxidised easily to Fe3+ . Cr 2 + is a
0.0591 [ Ag+ ]
Ecell = Ecell
° - log stronger reducing agent.
n [ Ag+ ]
(ii) Among the given ions, the ion with more (–) ve value of
0.0591
= 0- log 1 = 0 E° (red.) will loose the electron more easily, thus is
n more stable in (+) 2 oxidation state. Hence, Mn in
3. The cell reaction of Daniell cell is (+) 2 oxidation state is the most stable species.
Zn ( s ) + Cu 2 + ( aq ) ¾® Zn 2 + ( aq ) + Cu ( s ) 7. From the given cell reaction and Nernst equation,
The Nernst equation is 0.0591 [Ni 2 + ]
Ecell = Ecell
° – log
° 0.059 [ Zn 2 + ] n [Ag+ ] 2
Ecell = Ecell - log
2 [ Cu 2 + ] = 1.05 -
0.0591
log
(0.160)
According to above equation, Ecell decreases when 2 (0.002) 2
concentration of Zn 2 + ions is increased as Ecell is directly 0.0591
= 1.05 - log (4 ´ 104 )
dependent upon concentration of Cu 2 + and inversely 2
dependent upon the concentration of Zn 2 + ions. 0.0591
= 1.05 - (4.6021)
1 2
4. For hydrogen electrode, H+ + e - ¾® H2 = 1.05 - 0.135 = 0.915 V
2
Applying Nernst equation, = 0.915 V
°
0.0591 1 8. (i) Ecell = 0.236 V
E(H + /1/ 2 H ) = E(H
o
+
/1/ 2 H 2 )
- log + The standard Gibbs energy, DG = - nFEcell °
2 n [H ]
0.0591 1 = 2 ´ 96500 ´ 0.236
=0- log [pH = 10 ;[H+ ] = 10-10 M]
1 ( 10-10 ) = - 45.548 kJ
0.0591 (ii) Here, current ( i) = 0.5 A, t = 2 hours
=0- ´ ( 10 log10) = - 0591 . V
1 Quantity of current passed ( Q) = Current ´ Time
E(H + /1/ 2 H ) = - 0.591V = ( 0.5 A) ´ (2 ´ 60 ´ 60 sec)
2
= 3600 A sec = 3600 C
5. (i) For the given cell, the half-cell reactions will be given Now, Q = ne -
as below
where, n = number of electrons,
At anode Mg ¾® Mg 2 + + 2 e -
e - = charge on electron
At cathode Cu + 2e - ¾® Cu
2+
Therefore, the overall cell reaction will be Q 3600 C

n= -= = 2250 ´ 1019
Mg + Cu 2+ ¾® Mg2+ + Cu e 1.6 ´ 10- 19 C
The Nernst equation is \Number of electron flow = 2.250 ´ 1022
0.0591 [Mg2+ ] 9. Given, ° 2+
ECd = - 0.403 V
Ecell = E°cell - log / Cd
n [Cu 2+ ] ° 2+
EZn = - 0.763V
0.0591 (0.001) / Zn
\ Ecell = [0.34 - (- 2.36)] - log ° = - 0.403 - (-0.763)
2 (0.0001) \ Ecell
° = 0.36 V
Ecell
= 2.71 - 0.0295 log(10) = 2.7 - 0.0295
= 2.68 V Q °
D r G°`= - nFEcell
where, n = number of moles of electrons used 15. Concentration of acetic acid = 0.001 M
n = 2 (Here) k ´ 1000
Molar conductivity, Lm =
F = 96500 C mol -1 M
\ D r G° = - 2 ´ 96500 ´ 0.36 = 69480 J / mol 4 ´ 10- 5 ´ 1000
=
0.001
° = 0.0591 log K
Also, Ecell
n
C = 40 S cm 2 mol -1
°
n ´ Ecell 2 ´ 0.36 L°m ( CH3COOH) = 390 S cm 2 mol -1
\ log K C = = = 12.18
0.0591 0.0591 L 40
So, a = m = = 0.102
log K C = 12.18 L°m 390
10. (i) Cell constant, G* = resistance ( R ) ´ conductivity ( k) Ca 2
Now, dissociation constant ( K a ) for CH3COOH =
= 100 ´ 1.0 ´ 10-4 = 10-2 cm -1 1-a
(ii) Conductivity of solution y, 0.001(0.102)2
=
Cell constant 10-2 (1 - 0.120)
k= = = 2 ´ 10-4 S cm -1
Resistance 50 = 1.15 ´ 10- 5
(iii) Molar conductivity of solution y, 16. L°m (HCOOH) = L°m (HCOO- ) + L°m (H+ )
k ´ 1000 2 ´ 10-4 ´ 1000 = (54.6 + 349.6) S cm 2 mol -1
Lm = = = 20 S cm 2 mol –1
Molarity 0.01
= 404.2 S cm 2 mol -1
11. Given L°m (H+ ) 2
¾® 349.6 S cm mol -1
Lm (46.1) S cm 2 mol -1
a= = = 0.1140
L°m(Na+ ) ¾® 50.1 S cm 2 mol -1 L°m (404.2) S cm 2 mol -1
Water
Lm (K + ) ¾® 73.5 S cm 2 mol -1 HCOOH( aq ) s HCOO- ( aq ) + H + ( aq )
Lm(OH- ) ¾® 199.1 S cm 2 mol -1 Initial conc. C 0 0
Equilibrium conc. C (1 - a ) Ca Ca
L(CH3 COONa) ¾® 91 S cm 2 mol -1
Dissociation constant,
Complete reaction is as follows
[HCOO- ] [H+ ] C a ´ C a C a2
CH3COONa + HCl ¾® NaCl + CH3COOH Ka = = =
[HCOOH] C (1 - a ) (1 - a )
L°m (CH3COOH) =L°m (CH3COONa) - L°m (Na+ ) + L°m (H+ )
(0.025 mol L-1 ) ´ (0.114)2
= 91 - 50.1 + 349.6 Þ 390.5 S cm 2 mol -1 =
(1 - 0.114)
12. The molar conductance of water at infinite dilution can be
(3.249 ´ 10-4 mol L-1 )
obtained from the knowledge of molar conductances at = = 3.67 ´10-4 mol L-1
infinite dilution of sodium hydroxide, hydrochloric acid and (0.886)
sodium chloride (all strong electrolytes). This is in 17. Given, K = 5.25 ´ 10- 5 S cm -1
accordance with Kohlrausch’s law.
Molarity ( M ) = 2.5 ´ 10- 4 M
L°m ( H 2 O ) = L°m ( NaOH ) + L°m ( HCl ) - L°m (NaCl)
13. According to Kohlrausch’s law, L°(H+ ) = 349.5 S cm 2 mol -1
L°m (CH3 COOH) = L°(H+ ) + L° ( CH3 COO – ) L°( HCOO- ) = 50.5 S cm 2 mol -1
= 349.6 S cm 2 mol –1 + 40.9 S cm 2 mol -1 1000 ´ K
Molar conductivity, Lcm = S cm 2 mol -1
= 390.5 S cm 2 mol -1 Molarity
Lm 39.05 S cm 2 mol –1 1000 ´ 5.25 ´ 10- 5
a= = Þ a = 0.1 = S cm 2 mol -1
2
L°m 390.5 S cm mol
–1 2.5 ´ 10- 4
14. Conductivity ( k ) = 0.0248 S cm -1 = 0.0248 ohm -1 cm -1 = 210 S cm 2 mol -1

Molar concentration (C) = 0.20 mol L-1 L°m ( HCOOH) = l °( HCOO - ) + l°(H + )
=
(0.2 mol)
= 2.0 ´10-4 mol cm -3 = (50.5 + 349.5) S cm 2 mol -1
(1000 cm 3 ) = 400 S cm 2 mol -1
-1 -1
k (0.0248 ohm cm ) L°m
Molar conductivity ( Lm ) = = a=
C (2.0 ´ 10-4 mol cm -3 )
L°m
= 124 ohm -1 mol -1 cm 2 210
= = 0.525
or 124 S mol -1 cm 2 400
Molar conductivity = 124 S mol -1 cm 2
18. pH of the solution will not be affected as [ H+ ] remains = 1.98 +

0.0591
log100 = 1.98 +
0.0591
´2
constant. 6 6
At anode 2H2O ¾® O2 + 4H+ + 4e - [Q log100 = log 102 = 2 log 10 = 2 as log 10 = 1]
At cathode 4H+ + 4e - ¾® 2H2 = 1.9997 V » 2.0 V
19. (i) An aqueous solution of AgNO3 with silver electrodes. (ii) Coating the surface of iron with a more active metal
In aqueous solution, ionisation of AgNO3 and H2O prevents the iron from losing electrons and hence from
takes place. corrosion. As reduction potential of A is lower than that
( aq ) of iron, therefore A would be used for coating the
AgNO3( s ) s Ag+ ( aq ) + NO-3 ( aq ) surface of iron to prevent it from corrosion. This is
H2O (l ) s H+ ( aq ) + OH- ( aq ) because lower the reduction potential of an element,
more reactive is the element. Therefore, A would be
At cathode Ag+ ions has less discharge potential than more reactive than iron as well as B and hence, A
H+ ions so silver will be deposited at cathode. protects the iron metal from corrosion.
Ag+ ( aq ) + e - ¾® Ag( s ) 22. (i) Given, Ecell = 01745
. V
At anode An equivalent amount of silver will be EFe2+ / Fe = - 0.44
oxidised to Ag+ ions by releasing electrons.
[H+ ] = ?
Ag( s ) ¾® Ag+ ( aq ) + e -
The reaction for the given cell is written as,
Ag anode is attacked by NO-3 ions, so it will also
Fe( s ) + 2H+( aq ) ¾® H2 ( g ) + Fe2+( aq )
produce Ag+ in the solution.
Nernst equation for the above reaction is represented as,
(ii) An aqueous solution of AgNO3 with platinum electrodes. ° 2.303RT [Fe2 + ]
In aqueous solution ionisation of AgNO3 and H2 O Ecell = Ecell - log + 2 …(i)
nF [H ]
occurs ° ° °
( aq ) Also, Ecell = EH +
/H
- EFe 2+
/ Fe
+
AgNO3( s ) s Ag ( aq ) + NO3-( aq ) 2
= 0 - ( -0.44) = + 0.44 V
+ -
H2 O( l ) s H ( aq ) + OH ( aq ) °
Put Ecell value in Eq. (i),
As platinum electrodes are non-attackable electrodes, 0.0591 [ 01
. ]
they will not be reacted upon by NO-3 ions. \ 01745
. = 0.44 - log 2 [Q[ H+ ] = x (given)]
2 [ x]
At cathode Ag will be deposited at cathode. or log x = - 5
Ag+ ( aq ) + e - ¾® Ag( s ) log [H+ ] = - 5
At anode Out of NO -3 -
and OH ions, only OH ions will -
\ [H+ ] = 10-5
be oxidised (due to less discharge potential)
(ii) In the case of CH3COOH, which is a weak electrolyte,
preferentially and NO-3 ions will remain in the solution. the number of ions increases on dilution due to an
OH- ( aq ) ¾® OH + e - increase in degree of dissociation.
4 OH ¾® 2 H2 O( l ) + O2 ( g ) CH3COOH + H2 O s CH3COO- + H3O+
So, oxygen gas is produced at anode. The solution In case of strong electrolyte, the number of ions remains
remains acidic due to the presence of HNO3. the same but the inter ionic attraction decreases.
H+ ( aq ) + NO-3 ( aq ) ¾® HNO3 ( aq ) 23. (i) Kohlrausch law It states that limiting molar
20. Ag ( aq ) + e - ¾® Ag( s ); E° = 0.80 V.
+ conductivity of an electrolyte is the sum of the
individual contributions of the cation and the anion of
Reaction is feasible at cathode because it has higher
the electrolyte.
reduction potential.
Kohlrausch examined L°m values for a number of strong
21. (i) 2Al(s ) + 3Cu 2+ (0.01M) ¾® 2Al 3+ (0.01M) + 3Cu(s )
electrolytes and found certain regularities. Also,
E cell = 1.98 V Kohlrausch law of independent migration of ions is
Applying Nernst equation for the given cell reaction, used for determination of limiting molar conductivity
° - 0.0591 [Al 3+ ]2 for weak electrolyte.
Ecell = Ecell log
n [Cu 2+ ] 3 (ii) E° = E°
cell - E°
cathode anode
0.0591 [Al ] 3+ 2 = 0.34 - ( -1.66) = 2.00 V

° =E
Ecell cell + log According to Nernst equation,
n [Cu 2+ ] 3
3+ 2
Here, n = 6 (n = number of electrons transferred) ° = E°cell - 0.059 log [Al ]
Ecell
n [Cu 2+ ] 3
0.0591 (0.01)2
= 1.98 + log Here, n = 6
6 (0.01)3
0.059 . ]2
[ 015 10-1
Ecell = 2 - log = 1.56 - 0.0295 log
6 [ 0.025 ] 3 (10-2 ) 2
=2-
0.059
. - 3 log 0.025 )
( 2 log 015 = 1.56 - 0.0295 log 103
6 = 1.56 - 0.0295 ´ 3 log 10
059
.
=2- ( -1.6478 + 4.8062) = 1.56 - 0.0295 ´ 3
6
= 1.56 - 0.0885 = 1.4815 V
= 2 - 0.0311 = 1.9689 V
(ii) Y is a weak electrolyte. On dilution, complete
24. (i) MnO 4 is the strongest oxidising agent. Oxidising power dissociation of weak electrolyte occurs and thus a step
of metals decreases with a increase in their E° values. increase in molar conductivity. However, in case of
(ii) (a) Molar conducivity of a solution is the conductance of strong electrolyte it has already dissociated completely
that volume of solution containing one mole of therefore on dilution, the rise in conductivity is not
electrolyte, kept between two electrodes having unit significant.
length joining them and large cross sectional areas so
as to contain the electrolyte. For CH3COOH (weak electrolyte)
Lm (S cm2 mol–1)
(b) The nature the electrolyte on the basis of plot is
strong electrolyte. For strong electrolyte, L°m For KCl (strong electrolyte)
increases slowly with dilution.
(c) Using Debye-Huckel Onsager equation,
L m = L°m - A C 1/2
C (mol/L )
(d) L° value from graph is 150 S cm 2 mol -1.
150.0 26. (i) Given,
149.8 Molarity = 0.05 M
149.4
Length of column = 50 cm
Area of cross-section = 0.625 cm 2
Lm /(S cm mol–1)
149.0
Resistance = 5 ´ 103 W
148.6 rl A
We know, R = or r = R
148.2 A l
147.8 5 ´ 103 ´ 0.625
\ Resistivity = = 62.5 W cm
147.4 50
1 æ 1 ö
147.0 Conductivity ( k ) = = ç ÷ S cm = 0.016 S cm -1
r è 625. ø
k ´ 1000
0 .005 .010 .015 .020 .025 .030 .035 Molar conductivity, ( Lm ) =
C1/2/(mol/L)1/2 C
0.016 ´ 1000
æy -y ö =
(149 - 147.8) 0.05
A = - slope = çç 2 1 ÷÷ = -
x - x
è 2 1ø (0.010 - 0.022) = 320 S cm 2 mol -1
= 100 S cm 2 mol -1 / (mol / L-1 )1/ 2 °
(ii) Given : ECu 2+ = 0.34 V,
/ Cu
25. (i) Using Nernst equation, E°(1/ 2Cl - = + 1.36 V
0.059 2 / Cl )
Ecell = °
Ecell- log K °
EH + = 0.0 V, E1/° 2O2 / H2 O = + 1.23 V
n /H 2 ( g ), Pt
°
Ecell °
= EAg °
- EZn
+
/ Ag 2+
/ Zn The reaction with a higher value of E° takes place at the
cathode. Therefore, deposition of copper will take place
= 0.80 - ( - 0.76) at cathode.
= 0.80 + 0.76 = 1.56 V At cathode, following reduction reaction take place as:
At anode, Zn ¾® Zn 2 + + 2e - Cu 2 + + 2e - ¾® Cu( s ); E° = 0.34 V
At cathode, 2Ag+ + 2e - ¾® 2Ag 1
H+ ( aq ) + e - ¾® H2 ; E° = 0.0 V
On combining the net equation is 2
Zn( s ) + 2Ag+ ( aq ) ¾® Zn 2 + ( aq ) + 2Ag( s ) At anode, the reaction with a lower value of E° is
0.059 [Zn 2 + ] preferred. But due to over potential of oxygen, Cl - gets
Ecell = 1.56 - log oxidised at anode to produce Cl 2 gas. The reactions
2 [Ag+ ] 2 taking place at anode is
1
Cl - ¾® Cl 2 + e - ; E° = 1.36 V = 349.6 S cm 2 mol -1 + 50.9 S cm 2 mol -1
2 = 400.5 S cm 2 mol -1
2H2O ¾® O 2 + 4H+ + 4e - ; E° = +1.23 V L
a= m
27. (i) E° value of silver (E°Ag + / Ag = + 0.80 V) is lower L°m
than that of gold, hence silver displaces gold 40.05 S cm 2 mol -1
=
( E°Au 3 + / Au = + 1.40 V), which gets deposited on the 400.5 S cm 2 mol -1
silver object. Þ a = 0.1
E° value of copper ( E°Cu 2 + / Cu = +0.34) is lower than (iv) Conductivity of a electrolyte solution decreases with
that of silver, hence silver cannot displace copper from dilution because the number of ions per unit
its solution. volume furnished by an electrolyte decreases with
dilution.
(ii) (a) Electrons flow from Zn to Ag plate.
Or
(b) Zn acts as anode and Ag acts as cathode
On decreasing concentration, molar conductivity of a
(c) Cell will stop functioning
weak electrolyte increases.
(d) Concentration of Zn 2 + ions will increase and that of
29. (i) Zn | Zn 2 + (aq)||Cu 2+(aq )|Cu(s )
Ag + ions will decrease.
(e) No change 2.303RT [Zn 2+]
Ecell = Ecell - log
28. (i) Molar conductivity, Lm = 138.9 S cm 2 mol -1 2F [Cu 2+]
Molarity = 1.5 M; conductivity k = ? (ii) According to Nernst equation,
-
k ´ 1000 EZn2+ / Zn = EZn 2+ + 0.0591 log [Zn 2+ ]
Molar conductivity, Lm = / Zn
Molarity Hence, electrode potential will increase with increase
L ´ Molarity in concentration of Zn 2 + ions.
or k= m
1000 (iii) For the electrode reaction,
138.9 S cm2 mol -1 ´ 1.5 mol L-1 M n+ + ne - ¾® M
=
1000 cm3 L-1 - RT 1
EM n+ / M = EM n+ - ln n+
= 0.208 S cm-1 /M nF [M ]
100 ´ k 1000 1 l RT
(ii) Lm = = ´ ´ = E - n+ + ln [Mn+]
M M R a M /M nF
1000cm3 1 cm \Electrode potential can be increased either by
= ´ ´
mol -1 ohm cm2 increasing metal ion concentration, [ M n+ ] or
= ohm-1 cm2mol -1 temperature T.
= S cm2mol -1 (iv) E 2+ = -0.7632 V indicates that zinc electrode acts
Zn / Zn
2 -1 as anode when coupled to NHE. Since, oxidation takes
(iii) Given, Lm = 40.0.05 S cm mol
place at anode, therefore oxidation potential is positive
l°( H+ ) = 349.6 S cm 2 mol -1 but reduction potential is negative.
l°( A - ) = 50.9 S cm 2 mol -1 Or
L°m (H)( A ) = l °( H+ ) + l °( A - ) Temperature does not affect the Nernst equation.
Chapter Test 6. Assertion Conductivity decreases but molar
conductivity increases with increase in dilution.
Reason Molar conductivity is the conductance of
Multiple Choice Questions electrolytic solution which kept between the electrodes
1. The positive value of the standard electrode potential of conductivity cell at unit distance.
of Cu 2+ /Cu indicates that 7. Assertion KCl solution is generally used to determine
(a) this redox couple is a stronger reducing agent than the the cell constant.
H + /H 2 couple Reason The conductivity of KCl is known accurately at
(b) this redox couple is a stronger oxidising agent than H + /H 2 various concentration and different temperatures.
couple
(c) Cu can displace H 2 from acid Short Answer Type Questions
(d) Both (b) and (c) 8. Calculate the equilibrium constant for the reaction.
2. The electrode potentials for Fe( s) + Cd2 + ( aq ) Fe 2 + ( aq ) + Cd( s)
s
Cu 2+ ( aq ) + e- ¾® Cu + ( aq ) and [Given, E°Cd2+/Cd = - 0.40V, EFe° 2+/Fe = - 0.44 V]
[Ans. 22.70]
Cu + ( aq ) + e- ¾® Cu ( s) are + 0.15V and + 0.50V
°
respectively. The value of E°Cu 2+ /Cu will be 9. For a cell involving one electron, Ecell = 0.59 V at 298 K,
what will be the equilibrium constant for the cell
(a) 0.150 V (b) 0.50 V reaction? [Ans. 1.0 ´1010]
(c) 0.325 V (d) 0.650 V
10. Given the equilibrium constant ( KC ) of the reaction:
3. The cell constant of a conductivity cell Cu( s) + 2 Ag+ ( aq ) ¾® Cu 2 + ( aq ) + 2Ag( s)
(a) changes with change of electrolyte °
is 10 ´ 10 15 . Calculate the Ecell of this reaction at 298 K.
(b) changes with change of concentration of electrolyte [Ans. 0.473 V]
(c) changes with temperature of electrolyte
(d) remains constant for a cell 11. The resistance of 0.2 M solution of an electrolyte is 50 W.
The specific conductance of the solution is 1.3 S m - 1 . If
4. If the molar conductivity of Ca2 + and Cl- ions are resistance of 0.4 M solution of same electrolyte is 260 W,
119 and 71 S cm 2 mol-1 respectively, then the molar then what will be its molar conductivity?
[Ans. 6.25 ´ 10 -4 Sm2 mol -1]
conductivity of CaCl2 at infinite dilution is
(a) 215 S cm 2mol -1 Long Answer Type Questions
(b) 340 S cm 2mol -1 12. Using the standard electrode potentials, predict if the
(c) 126 S cm 2mol -1 reaction between the following is feasible.
(d) 261 S cm 2mol -1
(i) Fe 3+( aq ) and I -( aq ) (ii) Ag+( aq ) and Cu ( s)
Assertion-Reasoning MCQs (iii) Fe 3+( aq ) and Br - ( aq ) (iv) Ag( s) and Fe 3+( aq )
2+
Direction (Q. Nos. 5-7) Each of these questions (v) Br2 ( aq ) and Fe (aq)
contains two statements Assertion (A) and Reason (R). Given standard electrode potentials,
Each of these questions also has four alternative
E°1 /2 I 2 , I - = 0.541 V, E°Cu 2+, Cu = 0.34 V,
choices, any one of which is the correct answer. You
have to select one of the codes (a), (b), (c) and (d) E°1 /2 Br - = 1.09 V, E°Ag+, Ag = 0.80 V
2 , Br
given below. E°Fe 3+, Fe 2+ = 0.77 V
(a) Both A and R are true and R is the correct
13. (i) Calculate the degree of dissociation of 0.0024 M
explanation of A.
acetic acid if conductivity of this solution is
(b) Both A and R are true, but R is not the correct
8.0 ´ 10 -5 S cm -1 .
explanation of A.
(c) A is true, but R is false. Given : L°H+ = 349.6 S cm 2 mol-1 ;
(d) A is false, but R is true. L°CH3COO = 40.9 S cm 2mol-1 [Ans. 0.085]
5. Assertion Cu is oxidised to Cu 2+ in the reaction of (ii) Solutions of two electrolytes ‘A’ and ‘B’ are diluted.
copper with nitric acid. The limiting molar conductivity of ‘B’ increases to a
smaller extent, while that of ‘A’ increases to a much
Reason The oxidation of Cu to Cu 2+ ion is done by
larger extent comparatively. Which of the two is a
hydrogen ion.
strong electrolyte? Justify your answer.
Answers
Multiple Choice Questions For Detailed Solutions
1. (b) 2. (c) 3. (d) 4. (d)
Scan the code
5. (c) 6. (b) 7. (a)
22
CHAPTER 2
Chemical
Kinetics
In this Chapter...
l Chemical Reactions
l Rate Law and Rate Constant
l Order of Reaction
l Molecularity of Reaction
l Half-Life and Pseudo First Order Reaction
Chemical kinetics is the branch of chemistry which deals with (ii) Complex reactions When a sequence of elementary
the study of rates of the chemical reactions and their reactions (called mechanism) gives us the products,
mechanism. It also describes the conditions in which rates can the reactions are called complex reactions. Each step
be altered. in a complex reaction is called elementary step of a
reaction. The slowest step is called rate determining
Chemical Reactions step.
When one or more substances undergo a change which results
in the formation of a new product, it is called chemical reaction. Rate of a Chemical Reactions
On the basis of their speeds, chemical reactions are of three Rate of a chemical reaction is the change in molar
types which are as follows concentration of the species taking part in the chemical
(i) Very fast reactions Some reactions (such as ionic reactions) reaction per unit time.
occur very fast, e.g. precipitation of AgCl from AgNO3 and For the reaction, A ® B
NaCl. Rate of disappearance of A
(ii) Very slow reactions Some reactions are very slow, e.g. Decrease in concentration of A -D[ A]
= =
rusting of iron in the presence of air and moisture. Time taken Dt
(iii) Moderately slow reactions Some reactions occur at Rate of appearance of B
moderate speed, e.g. inversion of cane sugar and hydrolysis Increase in concentration of B D [ B]
= =
of starch. Time taken Dt
On the basis of number of steps, chemical reactions are of two and Rate may be expressed as
types as follows -D [ A] D [ B]
Rate = =
(i) Elementary reactions A balanced chemical equation does Dt Dt
not give a true picture of how a reaction takes place. It is very As D t ® 0, Instantaneous rate = Average rate
rare that the reaction gets completed in one step. The equations given above represent the average rate of
The reactions taking place in one step zare called the reaction (rav ).
elementary reactions. Units of rate = mol L-1 s -1 or atm s -1 (in gaseous state)
Instantaneous rate of reaction is the rate of change of Some enzyme catalysed reactions, reactions which occur on
concentration of any one of the species involved in the metal surfaces, decomposition of gaseous ammonia on a hot Pt
reaction at a particular instant of time. surface, thermal decomposition of HI on gold surface are the
For a general reaction, aA + bB ¾® cC + dD examples of zero order reaction.
1 d[ A] 1 d[ B] 1 d[C ] 1 d[ D] Hydrogenation of ethene, all natural and artificial
Instantaneous rate = - =- = = radioactive decay of unstable nuclei, decomposition of
a dt b dt c dt d dt
N 2 O5 and N 2 O are the examples of first order reaction.
At Dt ® 0, Instaneous rate = Average rate
Units of Rate Constant
Rate Law and Rate Constant The units of rate constant of different orders are different.
Rate law is the expression in which reaction rate is given in This can be easily illustrated below
terms of molar concentration of reactants with each terms For a general reaction,
raised to some power, which may or may not be same as
a A + bB ¾® cC + dD
the stoichiometric coefficient of the reacting species in a
balanced chemical equation. It is also called as rate equation Rate = k [ A] x [ B] y
or rate expression. where, x + y = n = order of the reaction
For a general reaction, aA + bB ¾® cC + dD Rate concentration 1
k= = ´
Rate = k[ A] x [ B] y , where x and y may or may not be equal to x
[ A] [ B] y time (concentration) n
the stoichiometric coefficients (a and b) of the reactants. = (concentration)1- n time -1 (where, [A] = [B])
d[ R]
- = k[ A] x [ B] y Considering SI units of concentration, mol L-1 and time s, the
dt
units of k = ( mol L-1 ) 1- n s -1 . Thus, the units of k for different
The above equation is known as differential rate equation,
order of reaction are given below
where k is a proportionality constant called rate constant.
Rate law for any reaction cannot be predicted by merely Units of rate constants
looking at the balanced chemical equation, i.e. theoretically Reaction in Gaseous
Reaction solutions reactions
but must be determined experimentally.
Zero order mol L-1s -1 atm s -1
Characteristics of Rate Constant
First order s -1 s -1
l
Rate constant is a measure of the rate of reaction. Greater
is the value of the rate constant, faster is the reaction. Second order mol -1L s -1 atm -1 s -1
l
Each reaction has a definite value of the rate constant at a nth order (mol L-1 )1- ns -1 (atm)1- n s -1
particular temperature and its value for the same reaction
changes with change in temperature.
l
Its value does not depend upon the concentrations of the Molecularity of a Reaction
reactant. It is the number of the reacting species taking part in an
l
The units of rate constant depend upon the order of reaction. elementary reaction, which must colloide simultaneously in
order to bring about a chemical reaction.e.g.
Order of Reaction Unimolecular reaction, NH4 NO 2 ¾® N 2 + 2H 2O
It is the sum of powers of the concentration of the reactants Bimolecular reaction, 2HI ¾® H 2 + I 2
in the rate law expression. Trimolecular reaction, 2NO + O 2 ¾® 2NO 2
Order of a reaction = x + y; if rate = k[ A] x [ B] y Note The probability that more than three molecules can collide and
For zero order, first order and second order reaction, value of react simultaneously is very small. Thus, reactions with the
n is 0, 1, 2. molecularity three are very rare and slow to proceed.
Characteristics of Order of Reaction Characteristics of Molecularity of a Reaction

Order of a reaction is an experimental quantity. It can be zero l
Molecularity cannot be zero or a non-integer.
and even a fraction. l
It is applicable only for elementary reactions.
Order is applicable to elementary as well as complex reactions. l
In case of complex reaction, molecularity of the slowest
For a complex reaction, order is given by the slowest step. step is same as the overall order of the reaction.
Difference between Molecularity and Order of Reaction

Molecularity Order of Reaction
The number of reacting species which collide simultaneously in The sum of powers of the concentrations of the reactants in the rate
order to carry out a chemical reaction is called molecularity of a law expression is called the order of that chemical reaction.
reaction.
Molecularity is always a whole number value (except zero), Order of reaction can be a whole number or even a fractional value.
i.e. 1, 2, 3 ....... .
Molecularity is a theoretical concept. Order of reaction is determined experimentally.
Molecularity is applicable to elementary reactions. For complex Order of reaction is applicable to elementary as well as complex
reactions, it has no meaning. reactions.
For simple reactions, molecularity can be obtained from the For simple reactions, order of reaction may not be equal to the number
stoichiometry of the equations. of molecules of the reactants as seen from the balanced equation.
Molecularity of a reaction cannot be zero. Order of a reaction can be zero.
Differential and Integrated Rate Equations

The differential and integrated rate equations for zero and first order reactions are tabulated below
Differential Unit of t 1/ 2
Reaction Order Integral equation Plot
equation k
(i) A ¾® Product dx
=k k=
x mol L-1s -1 a
( a)
a = initial dt t 2k
concentration of 0 x dx t1/2
dt
reactants
t (a–x) (a–x)
(ii) A ¾® P 1 dx
= k( a - x ) k =
2.303
log
a s-1 0.693
dt t a-x k
dx t1/2
log
(a–x) dt
t (a–x) (a–x)
Half-life of a Reaction Therefore, for zero order reaction t 1/ 2 µ [ R] 0 . For first order
The time in which the concentration of a reactant is reduced reaction, t 1/ 2 is independent of [ R 0 ] .
to one-half of its initial concentration is called the half-life of a 1
For second order reaction t 1/ 2 µ and so on.
reaction. It is represented as t 1/ 2 . [ R0 ]
l
For the first order reaction,
1 [ R] 0 2.303 [ R] 0 Pseudo First Order Reaction
k = ln = log
t [ R] t [ R] The reaction which is not actually of first order but behave
R0 so due to altered conditions is called pseudo first order
At t 1/ 2 , [ R] = reaction. In such a chemical reaction, between two
2
2.303 [ R] 0 substances, one reactant is present in large or excess
Therefore, k= log amounts.e.g.
t 1/ 2 [ R] 0 / 2 l
Acid hydrolysis of ethyl acetate
2.303 2.303 H+
or k= log 2 = ´ 0.301 CH 3COOC 2H5 + H 2O ¾® CH 3COOH + C 2H5 OH
t 1/ 2 t 1/ 2
0.693 Rate = k¢ [CH 3COOC 2H5 ] [H 2O], but [H 2O] can be taken
or t 1/ 2 = as constant.
k
Thus, for first order reaction, t 1/ 2 is independent of [ R] 0 \ Rate = k[CH 3COOC 2H5 ], where, k = k¢ [H 2O]
and hence, constant. l
Inversion of cane sugar
l
The half-life of a reaction with nth order is given as H+
1 C12H 22O 11 + H 2O ¾® C 6H12O 6 + C 6H12O 6
t 1/ 2 µ
[ R] n0 - 1 Rate = k [C12H 22O 11 ]
Chapter
Practice
PART 1 4. A graph of volume of hydrogen released vs time for
the reaction between zinc and dil. HCl is given in
Objective Questions figure. On the basis of this mark the correct option.
V5
l Multiple Choice Questions V4
1. The unit of rate and rate constant is same for which
order of reaction? V3
(a) Zero (b) First
V2
(c) Second (d) Third
V1
2. Which of the following expressions is correct for
the rate of reaction given below?
-
5 Br - ( aq) + BrO 3 ( aq) + 6 H + ( aq) ¾® 3 Br 2 ( aq) O
20 30 40 50
+ 3 H 2O( l ) (NCERT Exemplar)
- + V - V2
D[Br ] D[H ]
(a) =5 (NCERT Exemplar) (a) Average rate upto 40 s is 3
Dt Dt 40
D[Br- ] 6 D[H + ] V3 - V2
(b) = (b) Average rate upto 40 s is
Dt 5 Dt 40 - 30
V
D[Br- ] 5 D[H + ] (c) Average rate upto 40 s is 3
(c) = 40
Dt 6 Dt V3 - V1
(d) Average rate upto 40 s is
D[Br- ] D[H + ] 40 - 20
(d) =6
Dt Dt 5. Contact process is used in the formation of sulphur
3. Consider the reaction A ¾® B. The concentration trioxide,
of both the reactants and the products varies 2SO 2 ( g ) + O 2 ( g ) º2SO 3 ( g )
exponentially with time. Which of the following The rate of reaction can be expressed as
figures correctly describes the change in -D [O 2 ]
concentration of reactants and products with time? = 2.5 ´ 10 -4 mol L-1 s -1 .
(NCERT Exemplar) Dt
[B] Then rate of disappearance of [SO 2 ] will be
[B]
(a) 50.0 ´ 10 -5 mol L-1 s -1 (b) 3.75 ´ 10 -4 mol L-1 s -1
(c) 2.5 ´ 10 -4 mol L-1 s -1 (d) 4.12 ´ 10 -4 mol L-1 s -1
(a) (b)
[A ] [A ]
6. The rate law for a reaction between the substances
P and Q is given by rate = k[ P ] a [Q ] b . On doubling
Time Time
[B] the concentration of P and reducing the
[A ] concentration of Q to one-half, the ratio of the new
rate to the earlier rate of the reaction will be
(c) (d) 1
(a) (a + b)
(b) 2( a - b )
[A ] [B] 2
Time Time (c) ( a - b ) (d) ( a + b )
7. In acidic medium, the rate of reaction between 13. The reaction, 2N 2O5 º 4N O + O 2 2 is
- -
[BrO 3 ] and Br ions is given as (a) bimolecular and first order
– (b) unimolecular and second order
d[BrO 3 ]
- = k[BrO -3 ][Br - ][H + ]2 (c) bimolecular and second order
dt
(d) unimolecular and first order
It means that,
(a) the change in pH of the solution will not affect the rate 14. Which of the following statements is not correct
of reaction about order of a reaction? (NCERT Exemplar)
(b) rate constant of the reaction is 2s -1 (a) The order of a reaction can be a fractional number.
(c) the reaction rate increases by 4 times on doubling the (b) Order of a reaction is experimentally determined
concentration of H+ ions quantity.
(d) All of the above
(c) The order of a reaction is always equal to the sum of
8. Rate law for the reaction, A + 2B ¾® C is found to the stoichiometric coefficients of reactants in the
be Rate = k[ A][ B] balanced chemical equation for a reaction .
(d) The order of a reaction is the sum of the powers of
Concentration of reactant B is doubled, keeping the
molar concentration of the reactants in the rate law
concentration of A constant, the value of rate expression.
constant will be.......... . (NCERT Exemplar)
(a) the same (b) doubled 15. The half-life period for a zero order reaction is equal to
0.693 2k 2.303 [ R]0
(c) quadrupled (d) halved (a) (b) (c) (d)
k [ R]0 k 2k
9. Consider the following reactions, (All india 20201)
O 3 r O 2 + O (fast) …(i) (where, [ R ] 0 is initial concentration of reactant and
O + O 3 ¾® 2O 2 (slow) …(ii) k is rate constant.)
The rate law expression should be 16. The value of rate constant of a pseudo first order
(a) r = k¢ [O3 ]2 [O2 ]–1 reaction ......... . (NCERT Exemplar)
(b) r = k¢ [O3 ][O2 ] (a) depends on the concentration of reactants present in

small amount
(c) r = k¢ [O3 ]2 (b) depends on the concentration of reactants present in
(d) r = k¢ [O2 ]-1 excess
(c) is independent of the concentration of reactants
10. The unit of velocity constant for a zero order (d) depends only on temperature
reaction is
(a) L s -1 (b) L mol –1 17. In a first order reaction, the time taken to complete
half of the reaction
(c) mol L -1 s -1 (d) mol -1
(a) depends upon its initial concentration
11. For the reaction, I - + OCl - ¾® IO - + Cl - in (b) is inversely proportional to its initial concentration
aqueous medium, the rate of a reaction is given by (c) does not depend upon its initial concentration
d[IO - ] [I - ][OCl - ] (d) depends upon square root of its initial concentration
=k the overall order of the
dt [OH - ] 18. If a reaction obeys the following equation
reaction is 2.303 a
(a) -1 (b) 1 k= log 10
t ( a - x)
(c) 0 (d) 2
The order of reaction will be
12. The rate constant is numerically equal for three (a) zero (b) first
reactions of first, second and third order (c) second (d) third
respectively. Which of the following is true?
(a) If [ A] > 1 ; r3 > r2 > r1
19. The half-life period of a first order reaction is
4 min, the time after which 99.9% reaction gets
(b) If [ A] = 1 ; r1 = r2 = r3 completed is
(c) If [ A] < 1 ; r1 > r2 > r3 (a) 16 min (b) 8 min
(d) All of the above (c) 32 min (d) 40 min
20. Which of the following graph is correct for a zero 23. Assertion D [R ] is multiplied with - 1 to make the
order reaction? rate of the reaction a positive quantity.
Reason D[R ] is a negative quantity in the
- D [ R]
Concentration
Reaction rate
of reactant
expression, rate of disappearance of R = .
(a) (b) Dt
24. Assertion Zero order reactions are relatively
uncommon but these occur under special conditions.
Time Time
Reason Thermal decomposition of HI on gold
surface is a zero order reaction.
Concentration
Reaction rate
of reactant
(c) (d) 25. Assertion Order and molecularity are same.

Reason Order is determined experimentally and
molecularity is the sum of the stoichiometric
Time Time coefficient of rate determining elementary step.
21. Consider a first order gas phase decomposition (NCERT Exemplar)
reaction given below 26. Assertion Hydrolysis of ethyl acetate in the presence
A( g ) ¾® B( g ) + C( g ) of acid is a reaction of first order whereas in the
The initial pressure of the system before presence of alkali, it is a reaction of second order.
decomposition of A was p i . After lapse of time ‘t’ Reason Acid acts as catalyst only whereas alkali act
total pressure of the system increased by x units as one of the reaction.
and became ‘p t ’. The rate constant k for the 27. Assertion The t1/ 2 of zero order reaction depends
reaction is given as ......... . (NCERT Exemplar) on concentration of reactants.
2.303 pi 2.303 pi Reason t1/ 2 and rate constant of zero order reaction
(a) k = log (b) k = log
t pi - x t 2pi - pt [ R]
are related to each other as, t1/ 2 = ×
(c) k =
2.303 pi
(d) k =
2.303 pi 2k
log log
t 2pi + p t t pi + x
l Case Based MCQs
22. Some reactions alongwith the units of their rate
constants are given below 28. Read the following and answer the questions from
(i) to (iv) given below
S.No Reaction Unit of rate constant
The instantaneous rate can be measured by
1. SO2Cl 2 ¾® SO2 + Cl 2 s -1
determination of slope of the tangent at point ‘t’ in
2. NO + O3 ¾® NO2 + O2 L mol -1s -1 concentration vs time plot. This makes it difficult to
determine the rate law and hence the order of the
3. 2NO + Cl 2 ¾® 2NOCl L2 mol -2s -1
reaction.
Which of the following represents a third order reaction? In order to avoid this difficulty, we can integrate
(a) SO2 Cl 2 ¾® SO2 + Cl 2 (b) NO + O3 ¾® NO2 + O2 the differential rate equation to give a
(c) 2NO + Cl 2 ¾® 2NOCl (d) None of these relation between directly measured experimental
data, i.e. concentrations at different times and rate
l Assertion-Reasoning MCQs constant.
Direction (Q. Nos. 23-27) Each of these questions The integrated rate equations are different for the
contains two statements Assertion (A) and Reason (R). reactions of different reaction orders. We shall
Each of these questions also has four alternative choices, determine these equations only for zero and first
any one of which is the correct answer. You have to select order chemical reactions.
one of the codes (a), (b), (c) and (d) given below. Zero order reaction means that the rate of the
(a) Both A and R are true and R is the correct explanation reaction is proportional to zero power of the
of A.
concentration of reactants.
explanation of A. e.g. Consider the reaction,
(c) A is true, but R is false. d[ R]
R¾ ¾® P, Rate = = k[ R] 0
(d) A is false, but R is true. dt
First order reaction means that, the rate of the 29. Read the following and answer the questions from (i) to
reaction is proportional to the first power of the (iv) given below
concentration of reactions R. e.g. The zero order kinetics is an artifact of the conditions
d[ R ] under which the reaction is carried out. Therefore,
For the reaction, R ¾ ¾® P, Rate = = k[ R ]
dt reactions that follow zero-order kinetics are considered
1 [ R] 0 as pseudo-zero order reaction.
and the integrating rate equation is k = ln ,
t [ R] Zero-order systems provide an interesting opportunity
where [R] is final concentration and [ R ] 0 is initial for students to think about the underlying mechanism
concentration of reactant, respectively. behind the physical phenomena being modelled.
(i) For a hypothetical reaction, R ¾® products; Thirty-six general chemistry students, five physical
rate = - k[ R]. The negative sign used in the rate chemistry students, and three chemical engineering
expression indicates students were asked to think aloud as they responded to
(a) decrease in the concentration of reactants with time an interview prompt about the half-life of a
(b) decrease in the rate with time catalyst-driven zero-order reaction.
(c) reaction is reversible Our findings revealed that students often described
(d) None of the above zero-order in mathematical terms (i.e. the zero-order rate
(ii) For a reaction, P + Q ¾® R + S law, integrated rate law, and graphical representation),
The curve which depicts the variation of the but lacked a clear understanding of the particulate nature
concentration of products is of zero-order systems. Actually, zero-order reactions are
the curiosities of chemical kinetics.
P (i) For zero order reaction, the rate constant can be
Q
calculated from
Conc. (a) reactant concentration vs rate of reaction graph
(b) product concentration vs rate of reaction group
R (c) concentration vs time graph
S (d) reaction rate vs concentration graph
Time
(ii) Which of the following reactions is of zero order?
(a) P ((b) Q (c) R ((d) S (a) CH3Cl + H2O ¾® CH3OH + HCl
(iii) For the reaction, Hg( l ) + Cl 2 ( g ) ¾® HgCl 2 ( s ) hn
(b) H2 + Cl 2 ¾¾ ® 2HCl
The rate of reaction is given as 1
(c) N2O5 ¾® 2NO2 + O2
D [HgCl 2 ] D [Hg] 2
(a) (b) - (d) 2SO2 + O2 ¾® 2SO3
Dt Dt
D[Cl 2 ] (iii) The decomposition of ammonia gas on a hot platinum
(c) - (d) All of these
Dt surface is
(iv) For the reaction, 2X + Y ¾® X 2 Y (a) zero order reaction (b) first order reaction
(c) second order reaction (d) third order reaction
What will be the expression for instantaneous rate
of the reaction? (iv) Which of the following graph is correct for zero order
reaction?
-d[ X ] 1 d[ Y ]
(a) (b) +
2dt 2 dt
1 d[ X 2 Y ] (a)
Rate
(c) - (d) None of these (b) t1/2

2 dt
Or Contact process is used in the formation of sulphur
trioxide, Time [A ] 0
2SO 2 ( g ) + O 2 ( g ) º 2SO (g ) 3
The rate of reaction can be expressed as (c) t1/2 (d)
Rate
-D [O 2 ]
= 1.5 ´ 10 -4 mol L-1 s -1 .
Dt
Then rate of disappearance of [SO 2 ] will be [A ] 0 1/[A]0
-5 -1 -1 -4 -1 -1
(a) 30.0 ´ 10 mol L s (b) 3.75 ´ 10 mol L s Or The units of rate constant in zero order reaction is
(c) 2.5 ´ 10-4 mol L-1 s -1 (d) 50.0 ´ 10-4 mol L-1 s -1 (a) mol L-1 s -1 (b) mol -1 L s -1 (c) s -1 (d) mol 2L-2s -1
30. Read the following and answer the questions from (iii) The units of rate constant ‘k’ for n th order reaction is
(i) to (iv) given below (a) (mol L) 1-n (b) (mol s) + n
(c) (mol L -1s)1+ n (d) (mol L)1- n s -1
The rate of a reaction, which may also be called its
velocity or speed, can do defined with relation to (iv) Rate of reaction is also called ........
the concentration of any of the reacting substances, (a) rate law of reaction (b) speed of reaction
or to that of any product of the reaction. (c) momentum of reaction (d) concentration gradient
If the species chosen is a reactant which has a Or For gaseous reaction, the unit of rate constant for
dc which order reaction is atm -1s -1 ?
concentration c at time t the rate is , while the
dt (a) Zero order (b) First order
rate with reference to a product have a (c) Second order (d) nth
dx
concentration x at time t is .
dt
Any concentration units may be used for expression PART 2
the rate, thus if mole per litre are expressing the
rate; thus, if moles per litre are employed for Subjective Questions
concentration and seconds for the time, the units
for the rate are moles litre - 1 sec - 1 . l Short Answer Type Questions
For gas reactions pressure units are sometimes used
1. (i) Consider the following
to place of concentrations, so that units for the rate
would be (mm Hg) sec - 1 and atm sec - 1 . ln [ R ] vs time (min) plot.
Y
The order of a reaction concerns the dependence of
the rate upon the concentrations of reaching
substances thus, if the rate is found experimentally
to be proportional to the a th power of the
concentration of one of the reactants A, to the b th
ln [R]
power of the concentration of a second reactant B,
and so forth via., X
rate = kC AaC Bb ...(i) Time (min)
the overall order of the reaction is simply (a) What is the order of the reaction?
n=a+b+K ...(ii) (b) What are the units of rate constant, ( k ) for the
Such a reaction is said to be of the a th order with reaction?
respect to the substance A, the b th order with (ii) For the given reaction
respect to B. N2 (g) + 3H2 (g) ¾® 2NH3 (g)
(i) Which of the following statement is correct? If D [NH3 ] / Dt = 4 ´ 10 -8 mol L-1s -1 ,
(a) Rate of reaction is measure of change is concentration
of reactant only with respect to time
then what is the value of - D [H2 ] / Dt ?
(b) Rate of reaction is measure of change in 2. For a chemical reaction R ¾® P, the variation in the
concentration of reactant and product with respect to [ R] 0
time concentration of log vs time ‘ t ’ plot is given
[ R]
(c) Concentration of reactant increases with increase in here.
time
(d) Both (b) and (c) [R]0
log
[R]
(ii) For a reaction,
P + 2Q ¾® Products
The order of reaction depends on the t (s)
(a) concentration of products For this reaction

(b) rate constant (i) What is the order of the reaction?
(c) concentration of reactants (ii) What is the unit of rate constant?
(d) speed of the reaction
(iii) What is the slope of the curve?
3. For a reaction, the rate law expression is represented 9. The following data were obtained during the first
1
order thermal decomposition of SO 2 Cl 2 at a
as follows Rate = k[ A] [ B] 2 constant volume.
(i) Interpret whether the reaction is elementary or SO2 Cl2 (g) ¾® SO2 (g) + Cl2 (g)
complex. Give reason to support your answer.
(ii) Write the units of rate constant for this reaction, Experiment Time (s) -1 Total pressure (atm)
if concentration of A and B is expressed in moles/L.
I 0 0.5
4. The following results have been obtained during the II 100 0.6
kinetic studies of the reaction:
P + 2Q ¾® R + 2S Calculate the rate constant of the reaction when
Exp. Initial P Initial Q Initial rate of total pressure is 0.65 atm. (Delhi 2017) (NCERT)
(mol/L) (mol/L) formation of R 10. The rate constant for a first order reaction is 60 s - 1 .
(M min -1)
How much time will it take to reduce the
1 0.10 0.10 3.0 ´ 10- 4 initial concentration of the reactant to its 1/16th
2 0.30 0.30 9.0 ´ 10- 4 value? (NCERT)
3 0.10 0.30 3.0 ´ 10- 4 11. For the first order thermal decomposition reaction,
4 0.20 0.40 6.0 ´ 10 -4 the following data obtained
C 2 H 5 Cl(g ) ¾® C 2 H 4 (g ) + HCl(g )
Determine the rate law expression for the reaction.
Time/s Total pressure/atm
5. The chemical reaction, 2O 3 ¾® 3O 2 proceeds as
follows 0 0.30
O3 q O2 + O (Fast) 300 0.50
O + O 3 ¾® 2O 2 (Slow) Calculate the rate constant.
What should be the rate law expression? (Given log 2 = 0.3010, log 3 = 0.4771,
6. In a reaction between A and B, the initial rate of log 4 = 0.6021) (All India 2016)
reaction ( r0 ) was measured for different initial 12. A first order reaction has a rate constant
concentrations of A and B as given below
1.15 ´ 10 - 3 s -1 . How long will 5 g of this reactant
A/ mol L-1 0.20 0.20 0.40 take to reduce to 3 g?
-1
B/ mol L 0.30 0.10 0.05 13. The half-life period of a radioactive element is
r0 / mol L -1
s -1
5.07 ´ 10 -5
5.07 ´ 10 -5
1.43 ´ 10 -4 140 days. After 650 days, what amount of 1 g of the
element will be reduced ?
What is the order of the reaction with respect to
14. The half-life for radioactive decay of 14 C is 5730 yr.
A and B? (NCERT)
An archaeological artefact contained wood had
7. The reaction between A and B is of first order with only 80% of the 14 C found in a living tree.
respect to A and of zero order with respect to B. Fill Estimate the age of the sample. (NCERT)
in the blanks in the following table.
15. (i) The decomposition of dimethyl ether leads to the
Experiment [A]/M [B]/M Initial rate/M min - 1 formation of CH4 ,H2 and CO and the reaction
I. 0.1 0.1 2.0 ´ 10-2 rate is given by rate = k[CH3 OCH3 ]3/2 .
II. — 0.2 4.0 ´ 10-2 The rate of reaction is followed by increase in
III. 0.4 0.4 — pressure in a closed vessel, so the rate can also be
IV. — 0.2 2.0 ´ 10-2 expressed in terms of the partial pressure of
dimethyl ether, i.e. rate = k [ pCH 3 OCH 3 ]3/2 .
(NCERT)
If the pressure is measured in bar and time in
8. Consider a certain reaction, A ¾® products, with minutes, then what are the units of rate and rate
k = 2.0 ´ 10 - 2 s - 1 . Calculate the concentration of A constant?
remaining after 100 s, if the initial concentration of (ii) What is the order of a reaction that is 50%
A is 1.0 mol L - 1 . complete after 2h and 75% complete after 4h?
16. For a first order reaction, show that the time required 23. Consider the following reaction,
for 99% completion is twice the time required for the 2NO( g ) + Cl2 ( g ) ¾
¾® 2NOCl( g )
completion of 90% of reaction.
The rate of reaction becomes doubled when the
(NCERT; All India 2017C, Delhi 2013)
concentration of Cl2 is doubled. However, when the
17. A first order reaction is 25% complete in concentration of both the reactants are doubled, the
40 minutes. Calculate the value of rate rate becomes eight times. What is the order with
constant. In what time will the reaction be 80% respect to NO and with respect to reactant
completed? (Delhi 2020) chlorine? What is the overall order of reaction?
18. The rate of a first order reaction is 0.04 mol L-1s -1 24. For the decomposition of azoisopropane to hexane
at 10 min and 0.03 mol L-1s -1 at 20 min after and nitrogen at 543 K, the following data is obtained:
initiation. Find the half-life of reaction.
t (s) p(mm of Hg)
19. The conversion of molecules x to y follows second
order kinetics. If concentration of x is increased to 0 35.0
three times, how will it affect the rate of formation 360 54.0
of y ? (NCERT) 720 63.0
l Long Answer (LA) Type Questions Calculate the rate constant. (NCERT)
20. For the reaction, 25. (i) Following rate data were obtained at 300 K for the
2NO(g) + Cl2 (g) ¾® 2NOCl(g) reaction
2A + B ¾® C + D
The following data were collected at 270 K.
Initial rate of
Initial rate of Exp.
Initial [NO] Initial [Cl 2 ] [A] mol L -1 [B] mol L -1 formation of [C]
Exp. No. mol L-1 disappearance No. mol L -1 min -1
mol L-1
of Cl 2 (mol/min)
1 0.3 0.2 7.2 ´ 10-2
1 0.15 0.15 0.60
2 0.3 0.4 2.88 ´ 10-1
2 0.15 0.30 1.20
3 0.4 0.1 2.4 ´ 10-2
3 0.30 0.15 2.40
4 0.1 0.1 6.0 ´ 10-3
4 0.25 0.25 x
If the concentration of A = 0.5 mol L -1 and
(i) Write expression for rate law. B = 0.2 mol L -1 , then calculate the rate of formation
(ii) Calculate rate constant and write its unit.
of D.
(iii) Find initial rate of disappearance of Cl 2 in
(ii) Decomposition of NH3 on platinum surface is zero
experiment number (4).
order reaction. What are the rates of production of
21. (i) In a first order reaction, the reactant concentration N 2 and H2 , if k = 2.5 ´ 104 Ms -1 .
decreases from 0.8 M to 0.4 M in 15 min. What is
the time taken for the concentration to change from 26. (i) The decomposition of phosphine, PH3 proceeds
according to the following equation
0.1 M to 0.025 M?
(ii) A first order reaction takes 100 min for completion 4PH3 ( g ) ¾® P4 ( g ) + 6H2 ( g )
of 60% of the reaction. Find the time when 90% of It is found, that the reaction follows the following
the reaction will be completed. rate equation
Rate = k(PH3 )
22. (i) For a reaction A + B ¾® P, the rate is given by
Half-life of PH3 is 37.9 s at 120°C.
Rate = k[ A] [ B] 2
(a) How much time is required for 3/4th of PH 3 to
(a) How is the rate of reaction affected, if the decompose?
concentration of B is quadrupled? (b) What fraction of the original sample of PH 3
(b) What is the overall order of reaction, if A is remains behind after 1 minute?
present in large excess ? (ii) Consider a certain reaction,
(ii) A first order reaction takes 23.1 min for 50% A ® products with k = 2.0 ´ 10 -2 s -1 .
completion. Calculate the time required for 75% Calculate the concentration of A remaining after
completion of the reaction. 100 s, if the initial concentration of A is 1.0 mol L -1 .
27. During nuclear explosion, one of the products is Here, x and y, calculated experimentally, indicate
90 90
Sr with half-life of 28.1 yr. If 1 m g of Sr was how sensitive the rate is to the change in
absorbed in the bones of a newly born baby instead concentrations of A and B. Sum of these exponents,
of calcium, how much of it will remain after 10 yr i.e. x + y gives the overall order of a reaction
and 60 yr, if it is not lost metabolically? (NCERT) whereas, x and y represent the order with respect
to the reactants A and B, respectively.
l Case Based Questions Order of a reaction can be 0, 1, 2, 3 and even a
28. Read the following and answer the questions from fraction.
(i) to (iv) given below Molecularity is an another property of a reaction,
The rate of a chemical reaction at a given which helps in understanding its mechanism. The
temperature may depend on the concentration of number of reacting species (atoms, ions or
molecules) taking part in an elementary reaction,
one or more reactants and sometimes even on the
which must collide simultaneously in order to bring
concentration of products or some foreign
about a chemical reaction is called molecularity of
substances. The representation of rate of a reaction
the reaction.
in terms of the concentration of the reactants is
called rate law. e.g. If a reaction involves the decomposition of only
a single species, the molecularity is one and it is
The rate law for a given reaction has to be called unimolecular reaction.
established by experimental study of the rate of
Molecularity has no meaning for complex reactions
reaction over a wide range of concentration of the
as these reactions are supposed to take place in a
reactants and products. The rate law thus
sequence of a number of steps. It can be
established is also called differential rate equation determined only for the elementary reactions.
or rate expression.
KClO 3 + 6FeSO 4 + 3H 2SO 4 ¾®
(i) The reaction 2A + B + C ¾® 2E is found to be first
order in A , second order in B and zero order in C, KCl + 3Fe 2 (SO 4 ) 3 + 3H 2O
then write the rate expression. This reaction seems to be a tenth order reaction but
(ii) Express the rate of the following reaction actually it is a second order reaction. This indicates
H 2 + I2
- 2HI that the reaction takes place in several steps.
(iii) Why does the rate of a reaction not remain constant (i) Find the order of the reaction whose rate constant
throughout the reaction process? is 2.5 ´ 10 -2 min -1 .
(iv) The reaction A + B ¾® C has zero order. Write (ii) For which order of reaction, the units of rate
rate equation. constant and rate of the reaction are same?
Or (iii) For the given rate expression = k[ A] 3/ 2 [ B] -1 , the
Is there any reaction for which reaction rate does overall order of a reaction ?
not decrease with time? (iv) What will be the order of the reaction given
29. The sum of the exponents of the concentration of below?
2N2O5 º 2N O + O2 4 2
the reactants in the rate law expression is called the
Or
order of that chemical reaction.
A reaction is second order with respect to a
For a general reaction, reaction. How is the rate of reaction affected if the
aA + bB ¾® cC + dD ; Rate = k [ A] x [ B] y concentration of the reactant is doubled ?
EXPLANATIONS
Objective Questions 7. (c) Since, the rate law given is
- d[ A ] M - d[ BrO3 ] -
1. (a) Rate = = = mol L-1 s -1 = k[ BrO-3 ] [ Br - ] [ H+ ] 2
dt t dt
Thus, the reaction rate increases by 4 times on doubling the
k = (Conc.)1 - n s -1
concentration of H+ ions. Moreover, since it contains [ H+ ]
If n = 0, term, this means that, rate changes with variation in the
value of pH.
k = (mol L–1 )1 - 0 , s -1 = mol L-1 s -1
8. (b) Rate law for the given reaction, A + 2B ¾® C
Rate = k for zero order reaction. can be written as, Rate = k[ A ][ B ]
2. (c) Given, chemical reaction is Rate of reaction with respect to B is of first order.
5 Br - ( aq ) + BrO 3- ( aq ) + 6H+ ( aq ) ¾® 3Br2 ( aq ) + 3H2O( l ) R1 = k [ A ] [ B ]
When concentration of reactant ‘B’ is doubled then rate ( R 2 ).
Rate law expression for the above equation can be written as
R 2 = k [ A ] [ 2B ] = 2k [ A ] [ B ] = 2 R1
1 D[Br - ] D[BrO 3- ] -1 D[H+ ] +1 D[Br2 ]
- =- = = Therefore, as concentration of B is doubled keeping the
5 Dt Dt 6 Dt 3 Dt concentration of A constant, rate of reaction doubles.
D[Br - ] D[BrO 3- ] -5 D[ H+ ]
Þ - =- = 9. (a) Given,
Dt Dt 6 Dt O3 r O2 + O ( fast ) …(i)
D[Br - ] 5 D[ H+ ] O + O3 ¾® 2O2 (slow) …(ii)
Þ =
Dt 6 Dt [O2 ][O]
From Eq. (i), K eq =
3. (b) In the reaction, A ¾® B [O3 ]
Concentration of reactants and products varies exponentially K eq [ O 3 ]
w.r.t time.
or [O ] =
[O 2 ]
(i) Concentration of reactant (here, A) decreases
From Eq. (ii),
exponentially w.r.t time.
Rate = k[O3 ][O]
(ii) Concentration of product (here, B) increases
exponentially w.r.t time. Correct graph representing the k[O3 ][O3 ]
or r= K eq
above reaction is (b). [O2 ]
4. (c) Zn + Dil. HCl ¾® ZnCl 2 + H2 or r = k¢ [ O3 ] 2 [ O2 ] -1 [ k' = k ´ K eq ]
Change in concentration of H2
Average rate of reaction = 10. (c) Unit of rate constant = (mol L–1 )1- n s -1
Change in time
For zero order reaction, n = 0
V3 - 0 V3
= = \ Unit of rate constant = ( mol L-1 )1- 0 = mol L-1 s -1
40 - 0 40
11. (b) The rate of reaction is given by,
5. (a) For the reaction,
d[ IO- ] k[ I- ] [ OCl - ]
2SO2 ( g ) + O2 ( g ) r 2SO3( g ) = ×
the rate of reaction can be written as dt [ OH- ]
- D[SO2 ] æ D[O2 ]ö Therefore, overall order of reaction = 1 + 1 - 1 = 1
= 2 ç- ÷
Dt è Dt ø 12. (d) Consider a reaction A ¾® Products
- D[ O2 ] Let r1, r2 and r3 are the rate for first, second and third order
Q = 25. ´ 10-4 mol L -1 s -1 (Given)
Dt respectively.
- D[SO2 ] \ r1 = k[ A ]1 for 1st order …(i)
\ = 2 ´ 2.5 ´ 10-4 mol L-1 s -1
Dt r2 = k[ A ] 2 for 2nd order …(ii)
= 5.0 ´ 10-4 mol L-1 s -1 3
r3 = k[ A ] for 3rd order …(iii)
= 50.0 ´ 10-5 mol L-1 s -1
Q k is same in all the three cases.
6. (b)Q Rate = k[ P ] [ Q] b
a
b
Therefore, If [ A ] = 1, r1 = r 2 = r 3
é Qù [ Q] b If [ A] < 1, r1 > r 2 > r 3
\ New rate = k[ 2P ] a ê ú = k × 2a[ P ] a × b
ë 2û 2 If [ A ] > 1, r 3 > r 2 > r1
(a - b)
=2 × k[ P ] a[ Q] b = 2( a - b ) × rate 13. (a) The given reaction,
New rate 2N2O5 r 2N2O4 + O2; Rate = k[N 2O5 ] 2
Thus, = 2( a - b ) i.e.
Rate
The reaction occurs in two steps Slope (m) = - k (rate constant)

Step I
Slow
N 2O5 ¾¾® NO 2 + NO 3 Intercept (c) = [ R ] 0 (initial concentration)
Fast Thus, the graph between conc. of reactant and time is given
Step II N 2O5 + NO 2 ¾¾® 3NO 2 + O 2 as,
As the reaction, hence bimolecular reaction and the rate
determining step is the slowest step which is of first order. [R]0
Concentration
14. (c) Out of the given four statements, option (c) is not correct. Slope = – k
of reactant
Order of reaction is equal to the sum of powers of
concentration of the reactants in rate law expression.
For any chemical reaction
x A + yB ¾® Product Time
Rate = k [ A ] x[ B ] y Moreover, on rearranging Eq. (i)
Order = x + y [ R ] - [ R ]0
Order of reaction can be a fraction also. Order of reaction is = -k
t
not always equal to sum of the stoichiometric coefficients of [ R ] - [ R ]0
reactants in the balanced chemical equation. For a reaction, = - kt 0
t
it may or may not be equal to sum of stoichiometric
coefficient, of reactants. Rate µ t 0
[ R ]0 Therefore, the graph between reaction rate and time is
15. (d) For a zero order reaction, t1/ 2 = . given as,
2k
16. (a) Pseudo first order reaction is a chemical reaction in which
Reaction rate
rate of reaction depends upon concentration of one reactant
(present in small amount) while concentration of another
reactant has no effect on rate of reaction (present in excess).
Hence, (a) is the correct choice.
17. (c) Half-life period of a first order reaction is Time
0. 693 21. (b) A( g ) ¾® B( g ) + C( g )
t1/ 2 =
k Initially pi 0 0
At time, t pi - x x x
Equation of half-life period of a first order reaction does not
involve any concentration term. Thus, it is independent of p t = pi - x + x + x
initial concentration of reactants. = pi + x
For first order reaction x = p t - pi
18. (b) For a first order reaction, the integrated rate equation is
written as, 2.303 pi
2.303 a k= log
k= log t pi - x
t a-x
19. (d) Given, 2.303 pi
= log
t 1/ 2 = 4 min t pi - ( p t - p i)
a = 100; a - x = 01. 2.303 pi
0.693 = log
Now, t1/ 2 = [For first order reaction] t 2p i - p t
k
0.693 22. (c) The reaction 2NO + Cl 2 ¾® 2NOCl represents a third
\ k= ...(i)
4 order reaction as its unit of rate constant is L 2 mol - 2 s -1.
As we know that, 23. (a) Both A and R are true and R is the correct explanation of A.
2.303 a
k= log D[ R ]
t a-x Rate of disappearance of R = -
Dt
2.303 ´ 4 100
t= log [From Eq. (i)] Since, D[ R ] is a negative quantity, it is multiplied with -1 to
0.693 01.
make the reaction rate a positive quantity.
t = 39.88 min » 40 min
20. (d) For a zero order reaction, 24. (b) Both A and R are true but R is not the correct explanation
of A.
[ R ] = ( - k) t + [ R ] 0 …(i)
Zero order reactions are not so common and they occur
On comparing with equation of straight line; under special conditions, like some enzyme catalysed
y = mx + c reactions and reactions which occur on metal surfaces are a
y = [ R ] concentration few examples of zero order reactions. Moreover, thermal
decomposition of HI on gold surface is also zero order
x = t (time) reaction.
25. (d) A is false, but R is true. Thus, a plot of t1/ 2 vs [ A ] 0 will give a straight line graph
Order and molecularity may or may not be same as the order starting from the origin, i.e.
of reaction is sum of power of reactant which can be
determined experimentally. But molecularity is sum of
stoichiometric coefficient of rate determining elementary
step. t1/2
26. (a) Both A and R are true and R is the correct explanation of A.
Hydrolysis of ester in the presence of acid is pseudo first
order reaction. [A] 0
27. (a) Both A and R are true and R is the correct explanation of A. Or
t1/ 2 of zero order reaction is, t1/ 2 = [ R ] / 2k. (a) For a zero order reaction, units of k = molL-1s -1.
Therefore, t1/ 2 of zero order reaction depends on
30. (i) (b) Rate of reaction is measure of change in
concentration of reactants.
concentration of reactant and product with respect to
28. (i) (a) For a hypothetical reaction, R ® products; time. As concentration of product increases with
rate = - k[ R ]. The negative sign used in the rate increase in time, concentration of reactant deceases.
expression indicates decrease in the concentration of For reaction R ® P
reactants with time. - D[ R ] D[ P ]
(ii) (a) The curve P tells, that the gradual increase in Rate = =+
Dt Dt
concentration with the passage of time and
(ii) (c) Order of reaction depends on the concentration of
concentration of product increases in the course of
reacting substances. Thus, if the rate of reaction found
reaction.
experimentally proportional to the a th power of
(iii) (d) Rate of reaction concentration of one of the reactant A, to the b th power
D[Hg] D[ Cl 2 ] D[HgCl 2 ] of the concentration of a second reactant B. Then,
=- =- =
Dt Dt Dt Rate = kC AaC Bb
(iv) (a) Complete expression for instantaneous rate of Overall order of the reaction is simply
reaction is as follows
n=a+b
d[ X ] - d [ Y ] d[ X 2 Y ]
- = =+ (iii) (d) The unit of k depends on order of reaction and it is
2dt dt dt (mol L -1)1-n s -1, where n = order of reaction.
Or (iv) (b) Rate of reaction can be different for every reaction.
- D[ SO 2 ] æ D[ O 2 ] ö Rate of reaction is also known as speed of reaction or
(a) = 2ç- ÷ velocity of reaction.
Dt è Dt ø
Or
- D[SO 2 ]
\ = 2 ´ 1.5 ´ 10-4 mol L -1 s -1 (c) For second order reaction, the unit of k is atm -1s -1 in
Dt gaseous medium.
= 3.0 ´ 10-4 mol L -1 s -1
= 30.0 ´ 10-5 mol L -1 s -1 Subjective Questions
1. (i) (a) The given plot shows the first order reaction because
29. (i) (c) In case of zero order reaction, the slope of the according to integrated rate law of first order reaction,
concentration vs time graph is equal to negative of the
reaction constant. ln[ R ] = ln[ R ] 0 - kt
(ii) (b) Among the given reactions, the reaction between where, slope is -k which is represented in graph.
hydrogen and chlorine under influence of UV-light is an (b) Unit of k = (mol L- 1 )1 - n s - 1
example of zero-order reaction.
hn = (mol L- 1 )1 - 1 s - 1 = s -1
H2 + Cl 2 ¾¾ ® 2HCl
(ii) N 2 ( g ) + 3H2 ( g ) ¾® 2NH3( g )
(iii) (a) The decomposition of NH3 gas on a hot platinum
D[N 2 ] 1 D[H2 ]
surface is zero order reaction because the rate of this Rate of reaction = - =-
reaction is independent on the concentration of Dt 3 Dt
ammonia. 1 D[NH3 ]
=+
2 Dt
2NH3 ( g ) ¾1130
¾¾ K
® N2 ( g ) + 3H2 ( g )
Pt catalyst 1 D[H2 ] 1 D[NH3 ]
0
\ - =+
Rate = k[ NH3 ] 3 Dt 2 Dt
Hence, this reaction is a zero-order reaction. - D [H2 ] 3
= ´ 4 ´ 10- 8
[ A] 0 Dt 2
(iv) (b) For zero order reaction, t1/ 2 = = 6 ´ 10-8 mol L-1s -1
2k
2. (i) On substituting the above value of [ O ] in Eq. (i),

[ O ] [ O3 ]
r = k × K eq × 3
log
[R]0 [O2 ]
[R]
k ¢[ O 3 ] 2
= = k ¢[ O 3 ] 2 [ O 2 ] - 1
[ O2 ]
t (s)
where, k¢ = k × K eq
It is a first order reaction, log
[ R ]0
=
kt 6. Rate law states that rate = k [ A ] x[ B ] y
[ R] 2.303 (Rate)1 = k [0.20]x [ 0.30]y = 5.07 ´ 10 -5 …(i)
-1
(ii) Unit of rate constant k is s . x
(Rate) 2 = k [0.20] [ 010 y
. ] = 5.07 ´ 10 -5
…(ii)
k
(iii) Slope will be = (Rate) 3 = k [0.40]x[0.05]y = 1.43 ´ 10 - 4 …(iii)
2.303
3. (i) For an elementary reaction, order of reaction must be On dividing Eq. (i) by Eq. (ii), we get
equal to the molecularity but molecularity should be (Rate)1 k [ 0.20] x[ 0.30] y 5.07 ´10 -5
= = =1
integral. (Rate) 2 k [ 0.20] x[ 010. ] y 5.07 ´10 -5
For the given rate law, order of reaction comes out to
[ 3] y = [ 3] 0
3é 1ù
be ê1 + ú . As molecularity cannot be fractional, y=0
2ë 2û
therefore, order is not equal to molecularity. Hence, the Now, on dividing Eq. (iii) by Eq. (ii), we get
given rate law do not belong to an elementary reaction. (Rate) 3 k ( 0.40) x( 0.05 ) 0 1.43 ´ 10 - 4
= =
(ii) Units of rate constant are mol -1/ 2 L1/ 2 s -1. (Rate) 2 . ) 0 5.07 ´ 10 - 5
k ( 0.20) x( 010
4. For reaction, P + 2Q ¾® R + 2S æ1 ö
0
2.8205 = 2x ç ÷ = 2x
Let the rate law expression be è 2ø
log 2 . 8205 = x log 2
Rate = k[ P ] X [ Q] Y
0.4503
For experiment 1, x= = 1.5
0.3010
Rate 1 = 3.0 ´ 10- 4 = k( 010
. ) x( 010
. )y ...(i)
Thus, order of the reaction with respect to A and B are
For experiment 2, 1.5 and 0, respectively.
Rate 2 = 9.0 ´ 10- 4 = k( 0.30) x( 0.30) y ...(ii) 7. The rate law is,
For experiment 3, Rate = k[ A ]1[ B ] 0 = k[ A ]
Rate 3 = 3.0 ´ 10- 4 = k( 010
. ) x( 0.30) y ...(iii) Since, the reaction is of zero order w.r.t. B, hence any change
Equating (i) and (iii), in the concentration of B has no effect on the rate of
Rate (1) æ 1 ö
y
æ1 ö
y reaction.
=ç ÷ Þ1 = ç ÷ For experiment I,
Rate (3) è 3 ø è 3ø
Rate (2) 2.0 ´ 10- 2 M min -1 = k ´ (0.1 M)1
So, y= 0, and = (3) x Þ 3 = ( 3) x
Rate (3) 2.0 ´ 10- 2 M min -1
So, k= = 0.2 min -1
So, x = 1 0.1 M
\ Rate law = k[ P ] For experiment II,
5. The given reaction is, 2O 3 ¾® 3O 2 4.0 ´ 10-2 M min -1 = 0.2 min -1 ´[ A ]
The reaction proceeds as follows 4.0 ´ 10-2 M min -1
[ A] = = 0.2 M
O3 ® O2 + O (fast) 0.2 min -1
For experiment III,
O + O 3 ¾® 2O 2 (slow)
Rate = 0.2 min -1 ´ (0.4 M)1
As slowest step is rate determining step, rate of the reaction is
= 0.08 M min -1
r = k[ O ][ O 3 ] …(i) For experiment IV,
Fast step is in equilibrium, hence the concentration of [O] is
2.0 ´ 10-2 M min -1 = 0.2 min -1 ´ [A]
calculated from this step.
[ O 2 ][ O ] 2.0 ´ 10-2 M min -1
K eq = or [A] = = 0.1 M
[ O3] 0.2 min -1
8. k = 2.0 ´ 10- 2 s- 1; [ A ] 0 = 1.0 mol L- 1; t = 100 s
K eq [ O 3 ]
\ [ O] = 2.303 [ A] 0
[ O2 ] k= log
t [ A]
Therefore, 2.303
= ´ 4 ´ 0 . 3010
2.303 1.0 mol L -1
60 s -1
2.0 ´ 10- 2 s - 1 = log
100 s [ A] Time ( t ) = 4.62 ´ 10-2 s
-2 -1 2.303 11. C 2H5 Cl ( g ) ¾® C 2H4 ( g ) + HCl ( g )
2.0 ´ 10 s = (log 1 - log [ A ])
100 s
2.303 Initial pressure at t = 0 is 0.30 atm
2.0 ´ 10 - 2 s - 1 = ( 0 - log [ A ]) After 300s, ptotal = 0.30 - p + p + p atm
100 s
2.0 ´ 10- 2 s - 1 ´ 100 s = 0.30 + p atm
- log [ A ] = ptotal (given) = 0.50 = 0.30 + p
2.303
æ 2.0 ´ 10- 2 s -1 ´ 100 s ö Þ p = 0.50 - 0.30 = 0.20 atm
or [ A ] = antilog çç - ÷
÷ Pressure of C 2H5 Cl ( g ) after 300 sec
è 2.303 ø ( pC2 H5 Cl ) = 0.30 - 0.20 atm = 010
. atm
or [ A ] = 0.135 mol L- 1
2 .303 ( pC2 H5 Cl ) 0 2 .303 0.30 atm
9. SO 2Cl 2 ( g ) ¾® SO 2 ( g ) + Cl 2 ( g ) k= log = log
t ( pC2 H5 Cl ) 300 300 010
. atm
Initially pi 0 0
2 .303 2 .303
After time t, pi – p p p = log 3 = ´ 0.4771 = 3.66 ´ 10-3s -1
300 300
Total pressure after time t, i.e.
2.303 [ R ]0
p t = pi – p + p + p = pi + p 12. For a first order reaction, t = log
k [ R]
So, a = pi
2.303 (5 g)
a - x = pi - ( pt - pi ) = ´ log
(1.15 ´ 10- 3 s- 1 ) (3 g)
= pi – pt + pi = 2pi - p t 2.303
= (log 5 - log 3)
Substitutions of the value of a and ( a - x ) in first order (1.15 ´ 10- 3 s- 1 )
integrated rate equation gives. 2.303
2.303 pi = ( 0.6990 - 0.4771)
k= log (1.15 ´ 10- 3 s- 1 )
t ( 2pi – p t )
= 2.0 ´ 103 ´ 0.2219 s = 443.8 s
Calculation of rate constant, k or time = 444 s
Given, pi = 0.5 atm; pt = 0.6 atm 0.693 0.693
13. k= =
2.303 pi t1/ 2 140
k= log
t (2pi – pt ) 2.303 [ A] 0
\ t= log
2.303 0.5 atm 2.303 k [ A]
= log = log 1.25
(100 s) 0.4 atm (100 s) [ A] 0 t ´ k 650 ´ 0.693
Þ log = =
2.303 [ A] 2.303 2.303 ´ 140
= ´ 0.0969 = 2.23 ´ 10–3s –1
(100 s) [ A] 0
log = 1.397
Calculation of reaction rate when total pressure is 0.65 atm. [ A]
p SO2 Cl 2 = 0.50 - (0.65 - 0.50) [ A] 0
Þ = antilog 1.397
= (1 - 0.65) = 0.35 atm [ A]
k = 2.23 ´ 10-3s -1 [ A] 0
= 24.94 `
Rate = k ´ p SO2 Cl 2 [ A]
= (2.23 ´ 10-3s -1 ) ´ (0.35 atm) 1
Þ [ A] =
24.94
Rate = 7.8 ´ 10– 4 atm s –1
Þ [ A ] = 0.04 g `
10. For first order reaction,
2.303 a 14. t1/ 2 µ 5730 yr
t= log …(i)
k ( a - x) If a is the initial 14 C activity in a living tree, then
a 80
Given, ( a - x ) = ; k = 60 s -1 Activity in the dead wood, a t = á
16 100
On putting the values in Eq. (i) The nuclear l radioactive decays follow the first order
kinetics. So,
2.303 a ´ 16 2.303 2.303 a
t= log = log 16 t= log
60 s- 1 a 60 s- 1 k at
2.303 2.303 0.3693
= -1
´ log 24 = ´ 4 log 2 and k=
60s 60s -1 t1/ 2
Therefore, t =
2.303
log
a K = 0.0072 min -1
0.693 / t1/ 2 80 2.303 100
a t= log
100 0.0072 20
2.303 ´ 5730 100
= log = 223.6 min
0.693 80
18. For a first order reaction, A ¾® Products,
So, t = 1845.4 yr
15. (i) Given that, rate = k[CH3OCH3 ] 3/ 2 For concentration of the reactant at two different times, the
rate constant is
In this problem, pressure is in bar and time is in 2.303 [ A ]1
minutes. So, the unit of rate = bar min -1 k= log
t 2 - t1 [ A] 2
Also, unit of k = unit of rate/unit of [CH3OCH3 ] 3/ 2
But as rate = k [ A ],
\ Unit of k = bar min -1 / bar 3/ 2 = bar -1/ 2 min -1. (Rate)1 [ A ]1
(ii) It is a first order reaction because for 75% completion of We have, =
(Rate) 2 [ A ] 2
reaction two half-lives are required (as, t1/ 2 = 2 h), which
suggests that t1/ 2 is independent of initial concentration. 2.303 (Rate)1
Hence, k= log
-8 -1 -1 t 2 - t1 (Rate) 2
= 6 ´ 10 mol L s
2.303 0.04
16. Case I If a = 100 , ( a - x ) = ( 100 - 99) = 1 = log
( 20 - 10) min 0.03
For 99% completion of the reaction,
= 2.88 ´ 10-2 min -1
2.303 100
t 99% = log 0.693 0.693
k 1 t1/ 2 = =
2.303 2.303 ´ 2 k 2.88 ´ 10- 2 min - 1
= log 102 =
k k = 24.06 min or 1443.6 s
4.606 19. For the reaction, x ® y
t 99% = …(i)
k
Reaction rate, ( r ) = k [ x ] 2 (for II order) ...(i)
Case II If a = 100
If the concentration of x is increased three times, then
( a - x ) = ( 100 - 90) = 10 Reaction rate, ( r ¢) = k [ 3x ] 2 = k ´ [ 9x 2 ] …(ii)
For 90% completion of the reaction,
On dividing Eq. (ii) by Eq. (i), we get
2. 303 100
t 90% = log r ¢ k ´ [ 9x 2 ]
k 10 = =9
2. 303 2. 303 r k ´ [ x2 ]
= log10 = ...(ii)
k k It means that the rate of formation of y will increase by nine
On dividing Eq. (i) by Eq. (ii), we get times.
t 99% 4. 606 k 20. For the reaction,
= ´ =2
t 90% k 2. 303 2NO( g ) + Cl 2 ( g ) ¾® 2NOCl( g )
It means that time required for 99% completion of the r (rate) = k[NO ]x × [Cl 2 ] y
reaction is twice the time required to complete 90% of the (i) Comparing experiment number (1) and (2)
reaction.
17. For first order reaction, . ]x × [ 015
r1 = k[015 . ] y = 0.60 …(i)
x y
2.303 a r2 = k[ 015
. ] [ 0.30] = 1 . 20 …(ii)
k= log
t a-x On dividing Eq. (ii) by Eq. (i),
The given first order reaction completes 25% in 40 min. . ] x × [ 0.30] y 1 .20
r2 k[ 015
= =
Let, a = 100 r1 . ] x[ 015
k[ 015 . ]y 0.60
a - x = 100 - 25 Þ 2y = 21
a - x = 75
\ y=1 [On comparing the powers]
2.303 100
\ k= log Comparing experiment number (1) and (3)
40 75
2.303 . ] x × [ 015
r1 = k[ 015 . ] y = 0.60 …(i)
= (log 4 - log 3)
40 r3 = k[ 0.30] x × [ 015
. ] y = 2.40 …(iii)
k = 0.0072 min -1 On dividing Eq. (iii) by Eq. (i),
For 80% completion of reaction, r3 k[ 0.30] x × [ 015
. ] x 2.40
= x
=
a = 100 . ] × [ 015
r1 k[ 015 . ] y 0.60
a - x = 100 - 80 = 20 2x = 22
\ x=2 [On comparing the powers] 2.303 [ A] 0 2.303

= log = log 4
Hence, rate law, r = k × [NO] 2 × [Cl 2 ]1 t [ A] 0 / 4 t
(ii) From rate law, 0.693 2.303
= ´ 0.6020
Rate 0.60 231
. min t
k= =
[NO] 2 × [Cl 2 ] ( 015
. ) 2 ( 015
. ) 2.303 ´ 0.6020
t= ´ 231
. min Þ 46.2 min
k = 177.77 mol -2 L 2 min -1 0.693
(iii) Initial rate of disappearance of Cl 2 in experiment number 23. 2NO( g ) + Cl 2( g ) ¾
¾® 2NOCl ( g )
four. Let the rate of reaction be
r = k ×[0.25] 2 [0.25] r1 = k[ NO] a [ Cl 2 ] b ...(i)
= 177.77( 0. 25 ) 2 ( 0. 25 ) a
r2 = 2r1 = k[ NO] [ 2Cl 2 ] b
...(ii)
r = 2.78 mol/min a
r3 = 8r1 = k[ 2NO] [ 2Cl 2 ] b
...(iii)
21. (i ) Let, a = 0.8 M, a - x = 0.4 M, t = 15 min
On dividing Eq. (ii) by Eq. (i), we get
For first order reaction, r2 2r1 k[ NO] a [ 2Cl 2 ] b
2.303 a = =
k= log r1 r1 k[ NO] a [ Cl 2 ] b
t a-x
2.303 0.8 \ ( 2)1 = ( 2) b Þ b = 1
= log = 0.462 min -1
15 0.4 Similarly, on dividing Eq. (iii) by Eq. (i), we get
\ Time taken for 0.1 M to 0.025 M can be calculated as r3 8r1 k[ 2NO] a [ 2Cl 2 ] b
= =
t=
2.303
log
a r1 r1 k[ NO] a [ Cl 2 ] b
k a-x
8 = ( 2) a ( 2) b
2.303 01.
= log = 30 min 8 = ( 2) a ( 2)1 ; 4 = ( 2) a
0.0462 0.025
(ii ) If a first order reaction is 60% complete in 100 min. ( 2) 2 = ( 2) a ; a = 2
Let, [ x ] 0 = 100 M, [ x ] 60% = 100 - 60 = 40 M \ r = k[ NO] 2 [ Cl 2 ]1
and t = 100 min As, order with respect to NO = 2
2.303 x 2.303 100 Order with respect to Cl 2 = 1
k= log 0 = log
t x 100 40 Overall order of reaction = 2 + 1 = 3.
= 0.02303 log 25 . 24. Let the pressure of a azoisopropane decreases by x atm.
= 0.02303 ´ 0.397 = 0.009 min -1 As 1 mole of azoisopropane decompose to give 1 mole of N2
Time taken to complete 90% reaction = ? and 1 mole of hexane (C6H14 ), the pressure of N2 and hexane
increases by x atm.
[ x ] 0 = 100 M, [ x ] 90% = 100 - 90 = 10 M
(CH3 )2 CHN == NCH(CH3 )2 (g ) ¾® N2 (g ) + C6H14(g )
k = 0.009 min -1 Azoisopropane
2.303 x 2.303 100 At t = 0 35.0 atm 0 atm 0 atm
t= log 0 = log
k x 0.009 10 At time, t ( 35.0 - x ) atm x atm x atm
= 255.8 log10 = 255.8 min pt = pazoisopropane+ pN 2 + pC6 H14
22. (i) Rate = k[ A ] [ B ] 2 pt = 35.0 - x + x + x = 35 + x
Þ x = pt - 35
(a) When the concentration of B is quadrupled, then
\ p azoisopropane = 35.0 - ( pt - 35 ) = 70 - pt
Rate = k[ A ] [ 4( B )] 2
·Rate constant after 360 s = k1
= k[ A ] 16 × [ B ] 2 = 16 k [ A ] [ B ] 2 At t = 360 s, pi = 35 atm
The reaction rate increases sixteen times. pt = 54 atm
(b) If A is present in large excess, its concentration remains \ pazoisopropane = ( 70 - 54) atm = 16 atm
almost unchanged.
\Rate constant,
Hence, order with respect to A can be taken as zero. 2.303 35 2.303
Under these conditions, the overall order of the = log = log 2.187
360 16 360
reaction is two w.r.t B.
2.303 ´ 0.33984
0.693 = = 2.17 ´ 10-3s-1
(ii) For a first order reaction, t1/ 2 = = 231
. min 360
k
· Rate constant after 720s = k2
For 75% completion of the reaction, we can write
pi = 35 atm, pt = 63.0 atm
2.303 [ A] 0
k= log \ pazoisopropane = (70 - 63) atm = 7 atm
t [ A] t
\ Rate constant, 26. (i) (a) Decomposition of PH3 is a first order reaction
2.303 35 [PH3 ] 0 0.693 ´ t 0.3010 ´ t
k2 = log log = =
720 7 [PH3 ] t 2.303 ´ t1/ 2 t1/ 2
2.303 2.303 ´ 0.6990
= log5 = [PH3 ] 0 0.3010 ´ t
720 720 For t = t 3/ 4 , log =
-3 -1
[PH3 ] 0 / 4 37.9 s
= 2.24 ´ 10 s
37.9 s
(2.17 + 2.24) t= log 4 = 75.8 s
Average rate constant, k = ´ 10-3 0.3010
2
(b) If [ PH3 ] t is the concentration of PH3 left behind after
= 2.21 ´ 10-3 s-1
1 min, then
25. (i) Let, rate of formation of D = k[ A ] n[ B ] n [PH3 ] 0 kt 0.693 ´ 60 s
log = =- = - 0.476
Then, [PH3 ] t 2.303 2.303 ´ 37.9 s
Exp. 4 6.0 ´ 10-3 = k[ A ] n[ B ] m = k( 01
. ) n( 01
. )m …(a) [PH3 ] t 1
= 0.334 =
-2 n m n m [PH3 ] 0 3
Exp. 3 2.4 ´ 10 = k[ A ] [ B ] = k( 0.4) ( 01
. ) …(b)
Dividing Eq. (b) by Eq. (a) (ii) k = 2.0 ´ 10- 2 s - 1; [ A ] 0 = 1.0 mol L- 1; t = 100 s
2.4 ´ 10-2 k( 0.4) n ( 01. ) m ( 0.4) n 2.303 [ A] 0
-3
= n
= = 4n k= log
6.0 ´ 10 k( 01 . ) m ( 01
. ) ( 01 . )n t [ A]
4 = 4n Þ n = 1 Therefore,
Similarly, from 2.303 1.0 mol L- 1
2.0 ´ 10- 2s - 1 = log
Exp. 1 7. 2 ´ 10-2 = k( 0.3) n( 0. 2) m …(c) 100 s [ A]
-1 2.303
2.0 ´ 10- 2 s - 1 =
n m
Exp. 2 2.88 ´ 10 = k( 0.3) ( 0.4) …(d) (log 1 - log [ A ])
100 s
Dividing Eq. (d) by Eq. (c)
2.303
2.88 ´ 10-1 k( 0.3) n ( 0.4) m 2.0 ´ 10- 2 s - 1 = ( 0 - log [ A ])
= = 2m 100 s
7.2 ´ 10-2 k( 0.3) n( 0. 2) m
4 = 2m 2.0 ´ 10- 2 s - 1 ´ 100 s
- log [ A ] =
Þ m=2 2.303
\Rate of formation of D = k[ A ]1[ B ] 2 = k[ A ] [ B ] 2 æ 2.0 ´ 10- 2 s -1 ´ 100 s ö
-1 -1 2
or [ A ] = antilog çç - ÷
÷
= k( 05
. mol L ) (0.2 mol L ) …(e) è 2.303 ø
Using data of exp. 4 or [ A ] = 0.135 mol L- 1
6.0 ´ 10-3 mol L -1 min -1 = k( 01 . )2
. ) ( 01 …(f) 0.693 0.693 -1
27. t1/ 2 =28.1 yr, k = = yr
Dividing Eq. (e) by Eq. (f) t1/ 2 28.1
Rate of formation of D . ) ( 0.2) 2
k( 05 For first order reaction,
-3 -1 -1
=
6.0 ´ 10 mol L min k( 01 . )2
. ) ( 01 2.303 a
t= log
Þ 5 ´ ( 2) 2 Þ 20 k ( a - x)
Rate of formation of D = 6 ´ 10- 3 mol L -1 min -1 ´ 20 Case I a = 1 m g, t = 10 yr, k =
0.693 -1
yr
= 0.12 mol L min -1 -1 28.1
2.303 a
(ii) For reaction, 10 yr = ´ 28.1 yr log
2NH3 ¾® N 2 + 3H2 0.693 ( a - x)
a 10 yr ´ 0.693
Reaction rate = k[NH3 ] 0 = k log = = 0.107
( a - x ) 2.303 ´ 28.1
Rate of production of N 2
a
d[N 2 ] = antilog (0.107) = 1.279
= . ´ 10-4 Ms -1
= k = 25 ( a - x)
dt
a ( 1 mg )
Rate of production of H2 ( a - x) = = = 0.7819 mg
1.279 1.279
d[H2 ]
= = 3k Amount left after 10 yr = 0.7819 mg
dt
Case II a = 1 mg, t = 60 yr
. ´ 10-4 Ms -1
= 3 ´ 25
0.693 -1
. ´ 10-4 Ms -1
= 75 k= yr
28.1
60 yr =
2.303
´ log
a 29. (i) The value of k = 2.5 ´ 10 -2 min -1 carries the unit of
-1
0.693 /28.1 yr ( a - x) time alone and therefore, it is a first order reaction.
a ( 60 yr ) ´ 0.693 /28.1 yr -1 (ii) The units of rate constant and rate of a reaction are
log = = 0.642 same for zero order reaction, i.e. molL-1s -1.
( a - x) 2.303
a (iii) Rate = k[ A ] x [ B ] y
= antilog 0.642 = 4.385
( a - x) Order = x + y
a ( 1 mg ) æ 3ö
( a - x) = = = 0.2280 mg \Order is ç ÷ + ( -1 ) = 1 / 2 , i.e. half-order.
4.385 4.385 è 2ø
Amount left after 60 yr = 0.2280 mg (iv) 2N 2 O5 r 2N 2 O 4 + O 2 is a first order reaction.
28. (i) Rate = k[ A ]1 [ B ] 2 [ C ] 0 Rate = k[ N2O5 ] 2
d[ H2 ] d[ I2 ] 1 d[ HI] This reaction occurs in two steps as
(ii) Rate = - =- =+
dt dt 2 dt Step I N2O5 ¾Slow
¾¾® NO2 + NO
change in concentration
(iii) Rate µ Step II N2O5 + NO3 ¾Fast
¾® 3NO2 + O2
time
The rate of a reaction decreases as time progresses as it The slow step is unimolecular which is rate determining
is inversely proportional to time. steps. Hence, it is first order reaction.
(iv) For the zero order reaction, rate equation = k[ A ] 0 [ B ] 0 Or
A reaction is second order with respect to a reaction.
Or
Rate = k[ A ] 2
For a zero order reaction, the reaction rate does not
decrease with time because it is independent of If the concentration of the reactant is doubled, the rate of
concentration of the reactants. reaction becomes 4 times.
Chapter Test 7. Assertion In the reaction, N2 + 3H2 ¾® 2NH3 , the rate of
reaction is different in terms of N2 , H2 and NH3 .
Reason Rate of reaction is equal to the rate of
disappearance or formation divided by the stoichiometric
Multiple Choice Questions coefficient.
1. For the given rate expression= k[ A ] 1 [B] 1 , units of rate 8. Assertion The reaction, H2 + Br2 ¾® 2HBr
constant is has molecularity of two.
(a) mol -1 Ls -1 (b) mol -1 Ls Reason Order of the given reaction is 2.
(c) mol -1 L-1 (d) None of these
Short Answer Type Questions
2. For the given rate expression = k[ A ] 3 / 2 [B] -1 , the
overall order of a reaction is 9. For the reaction, 2 A + B ¾® A2B ;
(a) zero (b) half (c) one (d) two The rate = k [ A ] [B] 2 with k = 2.0 ´ 10 -6 mol-2 L2 s -1 .
3. In a first order reaction, reactant concentration ‘ C’ (i) Calculate the initial rate of reaction when
varies with time ‘ t’ as [ A] = 0.1 mol L-1 , [B] = 0.2 mol L-1
(a) C decreases with
1
(b) log C decreases with
1 [Ans. 8.0 ´ 10 -9mol L-1s -1]
t t
1 (ii) Calculate the rate of reaction after [ A] is reduced to
(c)
C
increases linearly with t 0.06 mol L- 1 . [Ans. 3.89 ´ 10 -9mol L-1s -1]
(d) log C decrease linearly with t 10. In a pseudo first order hydrolysis of an ester in water, the
4. Which of the following represents the expression following results were obtained :
5 t /s 0 30 60 90
for life of a first order reaction?
6 -1
[Ester]/mol L 0.55 0.31 0.17 0.085
k 6 2.303 4
(a) log (b) log (i) Calculate the average rate of reaction between the time
2.303 5 k 6
interval 30 to 60 s. [Ans. 4.67 ´ 10 -3mol L-1s -1]
2.303 2.303
(c) log 6 (d) log 5 (ii) Calculate the pseudo first order rate constant for the
k k
hydrolysis of an ester. [Ans. 1.98 ´ 10 -2s -1]
5. The rate constant ‘k’ for pseudo first order reaction
is 11. For a first order reaction, calculate the ratio between
2.303 2.303 C time taken to complete three fourth of the reaction and
(a) log C0 - C (b) log time taken to complete half of the reaction. [Ans. 2]
t t C0
2.303 2.303 C 12. A reaction is of second order with respect to a reactant.
(c) log C0 + C (d) log 0
t t C How is the rate of reaction affected, if the concentration
of the reactant is reduced to half? What is the unit of rate
Assertion-Reasoning MCQs constant for such a reaction?
Direction (Q. Nos. 6-8) Each of these questions Long Answer Type Questions
contain two statements Assertion (A) and Reason (R).
13. (i) A first order reaction is 25% complete in 40 minutes.
Each of these questions also has four alternative
Calculate the value of rate constant. In what time will
choices, any one of which is the correct answer. You the reaction be80% completed?
have to select one of the codes (a), (b), (c) and (d) [Ans. 0.0072 min-1, 223.6 min]]
given below.
(ii) Define order of reaction. Write the condition under
(a) Both A and R are true and R is the correct explanation which a bimolecular reaction follows first order kinetics.
of A.
(b) Both A and R are true, but R is not the correct 14. (i) In a reaction, if the concentration of the reactant R is
explanation of A. quadrupled, the rate of reaction becomes sixty four
(c) A is true, but R is false. times. What is the order of reaction? [Ans. 3]
(d) A is false, but R is true. (ii) A first order reaction has a rate constant of 0.0051 min -1 .
6. Assertion Rate of reaction can be expressed as rate If we begin with 0.10 M concentration of reactant, what
of change in partial pressure of the gaseous concentration of reactant will remain in solution after 3
reactants or products. hours? [Ans. 0.04 mol L-1 ]
Reason Partial pressure of a gas is equal to its
concentration.
Answers
1. (a) 2. (b) 3. (d) 4. (c) 5. (d) Scan the code
6. (c) 7. (d) 8. (c)
CHAPTER 03
Surface
Chemistry
In this Chapter...
l Adsorption
l Adsorption Isotherms
l Colloidal State
Surface chemistry deals with phenomena which occurs at the

If DH = -ve and DS = -ve
surfaces or interfaces. It is represented by separating the bulk
phases by a hyphen or a slash. \ DG = -ve - [ T( -ve)] = -ve + T
i.e. DG is negative only when DH has sufficiently high
Adsorption negative value, and temperature is not very high.
l
It is the phenomenon of attracting and retaining the
l
DG value is negative means, Gibb’s free energy decreases
molecules of a substance on the surface of a solid resulting and when DG becomes zero, a state of adsorption
into a higher concentration on the surface than in the bulk. equilibrium is established.
e.g. water vapour on silica gel. Distinction between Absorption and Adsorption
l
Adsorbent is a material on the surface of which, adsorption Absorption Adsorption
takes place. Absorbate is the species which is adsorbed on
the surface of adsorbent.
l
It is a bulk phenomenon, l
It is a surface phenomenon,
e.g. water vapours are e.g. water vapours are
l
Adsorption arises due to the fact that the surface particles of absorbed by anhydrous adsorbed by silica gel on its
the adsorbent are not in the same environment as the calcium chloride. surface.
particles inside the bulk. l
The concentration of solute l
The concentration of
l
The unbalanced or residual attractive forces of absorbent is uniform throughout the substance (adsorbate) is only
molecules are responsible for attracting the adsorbate bulk of the solid, e.g. when at the surface and it does not
particles on is surface. cotton is dipped in blue penetrate to the bulk,
ink, it gets blue throughout. e.g. when a chalk stick
Thermodynamics of Adsorption is dipped in ink, it is blue
on the surface and white in
During adsorption, following thermodynamical changes occur bulk.
l
Heat is evolved, i.e. adsorption is an exothermic process and l
The concentration of the
that’s why it’s, DH value is negative. is uniform throughout the adsorbate increases only at
l
When adsorbate is adsorbed, freedom of movement of its bulk of the solid. the surface of the adsorbent.
molecules gets restricted. It results in decrease in entropy of
adsorbate, i.e. DSis negative for adsorption. Note l When adsorption and absorption occur side by side it is known
as sorption.
l
From Gibbs-Helmholtz equation, l Desorption is the process of removing an adsorbed substance,
DG = DH - TDS i.e. adsorbate from the surface of adsorbent.
Types of Adsorption divided metals (Pt, Ni) and porous substance (charcoal, silica
gel) are best solid adsorbents.
There are two types of adsorption of gases on solids, l
Temperature Adsorption is an exothermic process (taking
i.e. physisorption and chemisorption.
place with evolution of heat), therefore in accordance with
Difference between Physisorption and Chemisorption Le-Chatelier’s principle, the magnitude of adsorption
should increase with fall in temperature. This actually
Physisorption Chemisorption
happens except in chemisorption where extent of adsorption
l
It arises because of van der l
It is caused by chemical bond first increases and then decreases with increases in
Waals’ forces. formation, covalent or ionic.
temperature.
l
It is non-specific in nature. l
It is highly specific in nature. l
Pressure of the Adsorbate Gas Since, adsorption of a gas
l
It is reversible in nature. l
It is irreversible in nature leads to decrease of pressure, the magnitude of adsorption
l
It depends on the nature of l
It also depends on the nature increases with increase in pressure. At low temperature, the
gas. More easily liquefiable of gas. Gases which can react extent of adsorption increases very rapidly with pressure.
gases are adsorbed readily. with the adsorbent show Over a small range of pressure, the extent of adsorption is
chemisorption. found to be directly proportional to the pressure.
l
Enthalpy of adsorption is low l
Enthalpy of adsorption is However, at higher pressures (closer to the saturation
(20-40 kJ mol -1) high. (80-240 kJ mol -1) point of the vapour pressure of the gas), the adsorption
l
Low temperature is l
This type of adsorption first tends to achieve a limiting value. At this point, formation
favourable for this increases with increase of of multilayers starts and a stage of desorption may be
adsorption. It decreases with temperature and then
increases of temperature. decreases. observed.
l
Activation of Adsorbent Activation of an adsorbent refers to
l
No appreciable activation l
High activation energy is
energy is needed. sometimes needed. increasing the adsorbing capacity of the adsorbent through
different methods. For instance making the surface of solid
l
No compound formation l
Surface compounds are
rough or breaking it into small pieces increases surface area
takes place. formed.
hence the extent of adsorption.
l
It results into formation of l
It result into the formation of
multimolecular layers on unimolecular layer.
adsorbent surface under high Adsorption Isotherms
pressure. The relationship between extent of adsorption (x/m) and
pressure of the gas at constant temperature is known as
l
Similarity between chemisorption and physisorption adsorption isotherm.
Both are directly depends on the surface area,
It is generally represented in the form of a curve as shown below
i.e. increase with an increase in surface of the adsorbent.
195 K
Factors Affecting the Adsorption
of Gases on Solids
x 244 K
The extent of adsorption is affected by the following factors m
l
Nature of Adsorbent A gas is adsorbed in different 273 K
amounts on different adsorbents. e.g. Hydrogen is
strongly adsorbed on nickel surface, while it is weakly O p
adsorbed on alumina surface under identical conditions. Adsorption isotherm
l
Nature of the Gas In general, the more liquefiable a gas
is, the more readily will it be adsorbed. Easily liquefiable Freundlich Adsorption Isotherm
gases such as NH 3, HCl , Cl 2, SO 2, CO 2 , etc., are
readily adsorbed than the permanent gases, such as In 1909, Freundlich gave the relationship between x / m and p
O 2, N 2, H 2, etc. Higher the critical temperature of the at particular temperature as :
x
gas, greater is the extent of adsorption. = kp1/ n ( n > 1 ) ...(i)
m
Thus, the amount of adsorption of gas on same mass of
charcoal follows the order where, m = mass of adsorbent
SO 2 ( Tc = 157 ° C) > CH4 ( Tc = 83 °C ) > H 2 (Tc = -120 ° C). x = mass of the gas adsorbed
l
Surface Area Increase in the surface area of the p = pressure
adsorbent, increases the total amount of the gas adsorbed k = constant
because number of adsorbing sites increases. Thus, finely n = constant/integer
Taking logarithm of whole Eq. (i), we get (ii) Colloidal solution Here, the size of dispersed
x 1 particles range between 1nm and 1000 nm
log = log k + log p ( i. e. 10 -9 m -10 -6 m ). The dispersed particles of
m n
colloids could be macromolecular or association of
It now becomes similar to straight line equation as many molecules. e.g. Protein globules in blood
y = mx + c plasma, fat droplets in milk.
x
A graph of log is plotted against log p as shown below (iii) Suspension It has size of dispersed particles greater
m than 1000 nm (i. e. >10 -6 m), which are aggregates of
Y
millions of molecules. e.g. Soil particles in water, soot
particles in smoke.
b
log
x Q
a Slope =
1 Classification of Colloids
m n l
Depending upon the phases of dispersed phase and
} log k=intercept
X
dispersion medium, colloids are of following types
O
log p Dispersed Dispersion Types of
medium Examples
phase colloid
The slope of line and its y-axis intercept correspond to 1 / n and
Solid Solid Solid sol Some coloured glasses,
log k respectively. gem stones
1
The factor can have values between 0 and 1. Solid Liquid Sol Paints, cell fluids
n
1 x Solid Gas Aerosol Smoke, dust
When = 0, = k, adsorption is independent of pressure.
n m Liquid Solid Gel Cheese, butter, jellies
1 x Liquid Liquid Emulsion Milk, hair cream
When = 1, = kp, adsorption varies directly with pressure.
n m Liquid Gas Aerosol Fog, mist, cloud,
insecticide sprays
Adsorption from Solution Phase
Gas Solid Solid sol Pumice stone, foam
Freundlich adsorption isotherm gives approximate idea about rubber
the adsorption from solution. Here, in place of pressure, the Gas Liquid Foam Froth, whipped cream,
concentration of adsorbate in solution are used. soap lather
x
= kC 1/ n ( n > 1 ) Out of the various types of colloids given above on the
m
table, the most common are sols, gels and emulsions.
Here, C is the equilibrium concentration, i.e. when adsorption l
Based on the nature of interaction between dispersed
is complete.
phase and dispersion medium, colloidal sols are divided
Applications of Adsorption into following two categories
The adsorption phenomena finds a number of applications such Lyophilic colloid Lyophobic colloid
as in production of high vacuum, in controlling humidity, in A colloidal solution in which A colloidal solution in which
heterogeneous catalysis, chromatographic analysis, froth floatation dispersed phase and dispersion dispersed phase and dispersion
process, in removal of colouring matter from solutions, in curing medium attract each other. medium repel each other.
diseases, separation of noble gases, in making gas masks etc. It is prepared by simple mixing It is prepared by special
of the dispersed phase and methods.
dispersion medium.
Colloidal State
It is reversible sol. It is irreversible sol.
l
A colloid is a heterogeneous system in which one substance is
dispersed (dispersed phase) as very fine particles in another No stabilising agent is required. Stabilising agent is required.
substance (dispersion medium). Viscosity increases. Viscosity remains same.
l
Colloids are sometimes also referred to as solutions. But essential Surface tension decreases. Surface tension remains same.
difference between a solution and a colloid is that of particle size
Quite stable and cannot be Not stable and can be easily
(dispersed phase). Thus, on the basis of the size of the dispersed easily coagulated. coagulated by heating, shaking,
phase, solutions are divided into following three classes e.g. Starch sol, albumin sol. etc. e.g. Gold sol.
(i) True solution It has dispersed particles with size less than Note Lyophilic means solvent attracting and lyophobic means
1 nm (i.e. < 10 -9 m). Here, the dispersed particles constitute solvent repelling. If water is the dispersion medium, the terms
single molecules or ions. e.g. Sugar in water or salt in water. used are hydrophilic and hydrophobic.
l
Based on the type of particles of the dispersed phase colloids Double
As 2 O 3 + 3H 2 S ¾¾¾¾® As 2 S 3 (sol) + 3H 2 O
are classified as decomposition
Multimolecular Macromolecular Associated colloids (ii) Electrical disintegration method (Bredig’s arc
colloids colloids (micelles) method) It involves dispersion as well as
Aggregates of atoms These particles are These colloids are condensation. By this method, colloidal solutions of
or molecules with large molecules of produced by the metals like gold, silver, etc., are obtained.
diameter less than colloidal range. aggregates of a large (iii) Peptisation is defined as the process of converting
1 nm is called e.g. Starch, number of ions because of freshly prepared precipitate into colloidal sol by
multimolecular cellulose, nylon, the attraction towards shaking it with dispersion medium in the presence of
colloids. proteins, oppositely charged ions in
concentrated solution.
small amount of electrolyte. The electrolyte added is
e.g. Sulphur sol, polythene, etc. called peptising agent.
e.g. Soap solution,
gold sol. detergent.
Purification of Colloidal Solution
They have generally They have These molecules
lyophilic character. lyophobic contain both lyophilic and The process used for reducing the amount of impurities to
character. lyophobic group. the required extent is known as purification of colloidal
solution. It is carried out by the following methods
These particles are Due to long chain, Greater van der Waals’
held together by van der Waals’ forces are observed at l
Dialysis is a process of removing small molecules or
weak van der forces are higher concentration of ions from a colloidal solution by diffusion through a
Waals’ forces. comparatively ions/molecules. semipermeable membrane. The apparatus used for this
stronger.
purpose is known as dialyser.
l
Electro-dialysis is a dialysis process carried out under
Micelle Formation the influence of an electric field. It speeds up the
l The formation of micelles takes place only above a particular migration of ions to the opposite electrodes.
temperature known as Kraft temperature(Tk ) and above a l
Ultra filtration is a process of separation of
particular concentration known as Critical Micelle colloidal particles from the solvent and soluble
Concentration (CMC).
solutes present in the colloidal solution through an
l The hydrophilicCOO - group (also called polar-ionic ‘head’) ultrafilter paper.
interacts with water molecule while the hydrophobic long
non-polar hydrocarbon chain R (also called non-polar ‘tail’) does Note The pores of the filter paper can be reduced in size by
not interact. impregnating with colloidion solution to stop the flow of
colloidal particles.
l At CMC, the anions are pulled into the bulk of the solution and
aggregate to form a spherical shape in which carboxylate groups
forms a negatively charged spherical surface with the hydrocarbon Properties of Colloidal Solution
chains inside the sphere. Thus, the aggregate formed is known as The important properties of colloidal solutions are given
‘ionic micelle’. below
l The cleansing action of soap is due to the fact that soap l
The value of colligative properties (osmotic pressure,
molecules form micelle around the oil droplet in such a way that
its hydrophobic part is in the oil and the hydrophilic part project lowering in vapour pressure, depression in freezing
outside the grease due to which it interacts water with the point and elevation in boiling point) are of small order
molecules present which is around the oil droplet is pulled from as compared to values shown by true solutions at same
the surface of cloth into water. concentrations.
l
When light passes through a colloidal sol, its path
Preparation of Colloids become visible due to scattering of light by particles. It
is called Tyndall effect and the illuminated path of the
A few important methods for the preparation of colloids are as
beam is called Tyndall cone.
follows
l
Movement of colloidal particles at random in zig-zag
(i) Chemical methods includes double decomposition, motion is known as Brownian movement. This
oxidation reduction or hydrolysis reactions.
movement is due to the bombardment of dispersion
Oxidation
2H 2S + SO 2 ¾¾¾® 2S + 2H 2O medium particles over dispersed phase particles. It helps
(Sol) in providing stability to colloidal sol by not allowing
Reduction
2 AuCl 3 + 3 HCHO + 3H 2O ¾¾® 2 Au + 3 HCOOH + 6 HCl them to settle down.
(Sol) l
Colloidal particles always carry an electric charge. The
Hydrolysis
FeCl 3 + 3 H 2O ¾¾¾® Fe(OH) 3 + 3 HCl nature of this charge (either +ve or -ve) is the same on
Red sol all the particles in a given colloidal solution.
l
The presence of charge is due to preferential adsorption of Note l The coagulating power of electrolyte is governed by Hardy-Schulze
ions present in the dispersion medium. rule. It state that ‘‘greater the valency of the flocculating ion added
the greater is its power to cause precipitation.’’
l
The combination of the two layers (i.e. fixed layer and l The coagulating power of an electrolyte is directly proportional to
diffused layer) of opposite charges around the sol particles the valency of the effective ion.
is called Helmholtz electrical double layer. l
The minimum concentration of the electrolyte in millimoles
l
The potential difference between fixed layer and that must be added to one litre of the colloidal sol. So, as to
diffused layer is called the zeta potential or electrokinetic bring about complete coagulation is called the coagulation
potential. value of flocculation value of the electrolyte.
l
The presence of equal and similar charges on colloidal l
The smaller the coagulation or flocculating value of the
particles is largely responsible in giving stability to the electrolyte, greater is its coagulating power.
system, as the repulsive forces between charged particles
having same charge prevent them from coalescing or
l
Stability of lyophillic sols depends upon the two factors,
aggregating when they come closer to one another. i.e. charge and solvation of the colloidal particles. When
these two factors are removed, lyophillic sols can be
Following are the significance of charge. coagulated. This can be done by (i) adding a suitable solvent
(i) Electrophoresis (Cataphoresis) The existence of charge to lyophilic solution, (ii) adding an electrolyte.
on colloidal particle is confirmed by electrophoresis
experiment. The migration of colloidal particles toward Protection of Colloids
the oppositely charged electrodes under the influence of Lyophillic sols are more stable than lyophobic sols because
applied electric field.
lyophillic sols are extensively solvated. They have a unique
(ii) When electrophoresis is prevented by some suitable property of protecting lyophobic colloids and thus are called
means, it is seen that the dispersion medium begins to as protective colloids.
move in an electric field. This phenomenon is called
electroosmosis. The protecting power of lyophillic sols are expressed in
terms of gold number. Gold number of a protective colloid
(iii) The process of settlings of colloidal particles is called
is the minimum weight in milligrams which must be
coagulation or precipitation of the sol. Coagulation of a
lyophobic sols can be carried by electrophoresis, by added to 10 mL of a standard red gold sol, so that no
mixing two oppositely charged sols, by boiling, coagulation of gold sol takes place when 1 mL of 10% NaCl is
persistent dialysis and by addition of electrolytes. added to it.
48
Chapter
Practice
6 The correct option representing a Freundlich
PART 1 adsorption isotherm is
x
Objective Questions (a)
m
= k p0. 3
x
(b) = k p2.5
l Multiple Choice Questions m
x
1. Which of the following is an example of absorption? (c) = k p-0.5
m
(a) Water on silica gel (NCERT Exemplar) x
(b) Water on calcium chloride (d) = k p-1
m
(c) Hydrogen on finely divided nickel
(d) Oxygen on metal surface 7. Which of the following curves is in according with
Freundlich adsorption isotherm?
2. At the equilibrium position in the process of
adsorption ......... . (NCERT Exemplar)
(a) D H > 0 (b) D H = TDS
log x/m
log x/m
(c) D H > TDS (d) D H < TDS (a) (b)
3. Activation of adsorbent means its adsorbing power is

increased by log p log p
(a) making the surface rough
(b) dipping the surface in acid to make it smooth
(c) dissolving in water
log x/m
log x/m
(c) (d)
4. On the basis of data given below predict which of the
following gases shows least adsorption on a definite log p log p
amount of charcoal? (NCERT Exemplar)
Gas CO 2 SO 2 CH4 H2
8. Butter is a colloidal solution of
(a) solid-solid
Critical temp./K 304 630 190 33 (b) liquid-solid
(a) CO 2 (b) SO 2 (c) CH4 (d) H2 (c) solid-liquid
(d) gas-solid
5. Freundlich adsorption isotherm is represented at
9. An example of solid sol is
temperature T1 , T2 and T3 . (a) gem stones
T1 (b) hair cream
(c) butter
T2
x/m (d) paint
T3
10. Among the colloids cheese (C ), milk ( M ) and smoke
(S), the correct combination of the dispersed phase
p and dispersion medium, respectively is
Arrange the temperature in the increasing order. (a) C : liquid in solid; M : liquid in liquid; S : solid in gas
(NCERT Exemplar) (b) C : solid in liquid; M : liquid in liquid; S : gas in solid
(a) T1 < T2 < T3 (b) T3 < T2 < T1 (c) C : liquid in solid; M : liquid in solid; S : solid in gas
(c) T2 < T3 < T1 (d) T3 < T1 < T2 (d) C : solid in liquid; M : solid in liquid; S : solid in gas
11. Method of formation of solution is given in Column I. 15. What is the reason of Brownian movement ?
Match it with the type of solution given in Column II. (a) Variation of temperature in liquid state
(b) Attraction and repulsion of colloidal particles due to
Column I Column II presence of charge on it
A. Sulphur vapours passed 1. Normal electrolyte (c) Impact of dispersion medium particles on colloidal particles
through cold water. solution (d) Size of particles
B. Soap mixed with water 2. Molecular colloids 16. Freshly prepared precipitate sometimes gets
above critical micelle converted to colloidal solution by ......... .
concentration. (NCERT Exemplar)
C. White of egg whipped 3. Associated colloid (a) coagulation (b) electrolysis
with water. (c) diffusion (d) peptisation
D. Soap mixed with water 4. Macromolecular 17. Which of the following processes is involved in
below critical micelle colloids Bredig’s arc method?
concentration.
(a) Only dispersion
Choose the correct code that are given below. (b) Only condensation
Codes (NCERT Exemplar) (c) Dispersion as well as condensation
A B C D A B C D (d) Diffusion
(a) 2 3 4 1 (b) 1 2 3 4 18 Haemoglobin and gold sol are examples of
(c) 3 2 4 1 (c) 2 3 1 4 (a) negatively and positively charged sols, respectively
12. Select the method by which lyophobic sol can be (b) negatively charged sols
(c) positively charged sols
protected.
(d) positively and negatively charged sols, respectively
(a) By addition of oppositely charged sol (NCERT Exemplar)
(b) By addition of an electrolyte 19. On which of the following properties does the
(c) By addition of lyophilic sol coagulation power of an ion depend?
(d) By boiling (a) Both magnitude and sign of the charge on the ion
13. Match the statement given in Column I with the (b) Size of the ion alone
phenomenon given in Column II. (c) The magnitude of the charge on the ion alone
(d) The sign of charge on the ion alone
Column I Column II
A. Dispersion medium moves in an 1. Osmosis
20. Which of the following electrolytes will have
electric field. maximum coagulating value for Ag/Ag + sol?
(NCERT Exemplar)
B. Solvent molecules pass through 2. Electrophoresis
semipermeable membrane (a) Na 2S (b) Na 3PO 4
towards solvent side. (c) Na 2SO 4 (d) NaCl
C. Movement of charged colloidal 3. Electroosmosis 21. Gold number of A, B, C and D sol is respectively
particles under the influence of 0.001, 0.15, 20 and 25, most effective protective
applied electric potential towards colloidal is
oppositely charged electrodes. (a) A (b) B
D. Solvent molecules pass through 4. Reverse-osmosis (c) C (d) D
semipermeable membranes
towards solution side. l
Choose the correct code that are given below. Direction (Q. Nos. 22-26) Each of these questions
Codes (NCERT Exemplar) contains two statements Assertion (A) and Reason (R).
A B C D Each of these questions also has four alternative choices,
(a) 3 4 2 1 any one of which is the correct answer. You have to
(b) 4 3 2 1 select one of the codes (a), (b), (c) and (d) given below.
(c) 1 2 3 4 (a) Both A and R are true and R is the correct
(c) 2 1 4 3 explanation of A.
14. Which property of colloidal solution is independent (b) Both A and R are true, but R is not the correct
of charge on the colloidal particle? explanation of A.
(a) Coagulation (b) Electrophoresis (c) A is true, but R is false.
(c) Electroosmosis (d) Tyndall effect (d) A is false, but R is true.
22. Assertion Chemical adsorption of molecules on represented RCOO - Na + (e.g. sodium stearate
surface requires activation energy. CH 3 (CH 2 )16 COO - Na + or sodium palmitate
Reason Because the bonds of the adsorbed CH 3 (CH 2 )14 COO - Na + ). When soap is dissolved in
molecules are broken. water, it dissociates into RCOO - and Na + ions. The
23. Assertion The vegetable tanning materials have RCOO - ions consist of two parts hydrocarbon chain
smaller surface areas. R (non-polar tail) which is hydrophobic
Reason The capillaries present in leather are (water-repelling), and a polar group COO (polar
reduced to smaller diameters. ionic) which is hydrophilic (water-loving).
(i) A large number of atoms or molecules of a substance
24. Assertion Fe 3+ can be used for coagulation of As 2S 3
aggregate together to form species having size in the
sol.
colloidal range, these species are called
Reason Fe 3+ reacts with As 2S 3 to give Fe 2S 3 . (a) multimolecular colloids
25. Assertion Aqueous gold colloidal soultion is red in (b) macromolecular colloids
colour. (c) solid sol
(d) emulsion
Reason The colour arises due to scattering of light by
colloidal gold particles. (ii) Gold sols and sulphur sols are the examples of
(a) multimolecular colloids
26. Assertion Micelles are formed by surfactant (b) macromolecular colloids
molecules above the critical micellar concentration (c) associated colloids
(CMC). (d) All of the above
Reason The conductivity of a solution having (iii) Which of the following colloids resemble to the true
surfactant molecules decreases sharply at the CMC. solutions?
(a) Micelles
l Case Based MCQs (b) Macromolecular colloids
(c) Lyophobic colloids
27. Read the following and answer the questions from (d) All of the above
Or
The state of the substance in which dispersed phase
The formation of micelles takes place above the
(solute) and dispersion medium (solvent) floats with
particular range of temperature termed as
each other is called colloidal state.
(a) critical temperature (b) Kraft temperature
Depending on the size of particles of the dispersed (c) CMC (d) Micelles temperature
phase, colloids are classified as multimolecular. (iv) Soaps and synthetic detergents belong to the class of
macromolecular and associated colloids. Associated (a) macromolecular colloids
colloids are very important in our day-to-day life. (b) associated colloids
There are some substances which at low (c) multimolecular colloids
concentrations behave as normal strong (d) Both (b) and (c)
electrolytes, but at higher concentrations exhibit 28. Read the following and answer the questions from
colloidal behaviour due to the formation of (i) to (iv) given below
aggregates. The aggregated particles thus formed
are called micelles. These are also known as A colloid is one of the three primary types of mixtures,
associated colloids. with the other two being a solution and suspensions. A
colloid is a mixture that has particles ranging between
The formation of micelles takes place only above a 1 to 1000 nanometers in diameter, yet are still able to
particular temperature and above a particular remain evenly distributed throughout the solution.
concentration. On dilution, these colloids revert These are also known as colloidal dispersions because
back to individual ions. Surface active agents such the substances remain dispersed and do not settle to
as soaps and synthetic detergents belong to this the bottom of the container. In colloids, one substance
class. For soaps, the CMC is 10 -4 to 10 -3 mol L-1 . is evenly dispersed in another. The substance being
These colloids have both lyophobic and lyophilic dispersed is referred to as being in the dispersed
parts. Micelles may contain as many as 100 phase, while the substance in the dispersed phase
molecules more. must be larger than the size of a molecule but smaller
Taking an example of soap solution in which soap is than what can be seen with the naked eye . This can be
sodium salt of higher fatty acid and may be more precisely quantified as one or more of the
substance’s dimensions must be between 1 and 5. Write the differences between physisorption and
1000 nanometers. chemisorption with respect to the following.
If the dimensions are smaller than this substance is (i) Specificity
considered a solution and if they are larger than the (ii) Temperature dependence
substance is a suspension. A common method of (iii) Reversibility and
classifying colloids is based on the phase of the
(iv) Enthalpy change
dispersed substance and what phase it is dispersed
in. The types of colloids includes sol, emulsion, 6. What are the three factors which influence the
foam and aerosol. adsorption of the gas on a solid?
(i) The disperse phase, dispersion medium and nature of 7. What do you understand by activation of adsorbent?
colloidal solution (lyophilic or lyophobic) of ‘Gold sol’ How is it achieved? Give one example.
respectively are
(a) solid, solid, lyophobic (b) liquid, liquid, lyophobic 8. What is an adsorption isotherm? Describe Freundlich
(c) solid, liquid, lyophobic (d) solid, liquid, lyophilic adsorption isotherm.
(ii) Which of the following make the lyophilic solution 9. Comment on the statement that colloid is not a
unstable? substance but a state of substance. (NCERT)
(a) Dialysis
10. (i) What type of colloid is formed when a gas is
(b) Addition of electrolyte
dispersed in a solid ? (All India, 2017)
(c) Addition of alcohol
(d) Addition of alcohol and electrolyte both
(ii) Based on the type of dispersed phase, what type of
colloid is micelles ?
(iii) The colloidal solution of mercury in water can be
easily obtained by 11. Define the following terms by giving an example of
(a) mechanical precipitation (b) Bredig’s Arc method each.
(c) repeated washing (d) ultrasonic dispersion (i) Hydrosol (ii) Aerosol
(iv) Foam is a type of colloidal of 12. Write the dispersed phase and dispersion medium of
(a) liquid in gas (b) liquid in liquid the following colloidal systems.
(c) gas in liquid (d) solid in gas (i) Smoke (ii) Milk
Or 13. Write one difference in each of the following:
Which property of colloidal solutions is (i) Lyophobic sol and lyophilic sol.
independent of charge on the colloidal particles ?
(ii) Solution and colloid. (Delhi, 2017)
(a) Coagulation (b) Electrophoresis
(c) Electroosmosis (d) Tyndall effect (iii) Multimolecular colloid and associated colloid
(All India, 2020; Delhi, 2017)
14. How are the following colloidal solutions prepared?
PART 2 (i) Sulphur in water (ii) Gold in water
15. What is meant by coagulation of a colloidal
Subjective Questions solution? Describe briefly any three methods by which
coagulation of lyophobic sols can be carried out.
l
16. Explain the cleaning action of soap. Why do soaps not
1. Distinguish between the meaning of the terms work in hard water?
adsorption and absorption. Give one example of
17. Explain what is observed,
each. (NCERT)
(i) when a beam of light is passed through a colloidal
2. Why do physisorption and chemisorption behave solution? (All India)
differently with rise in temperature? (ii) when an electrolyte, NaCl, is added to hydrated ferric
(NCERT Exemplar)
oxide solution?
3. Why physisorption forms multimolecular layers (iii) electric current is passed through a colloidal
whereas chemisorption forms unimolecular layers? solution?
4. Why are substances like platinum and palladium 18. What modification can you suggest in the
often used for carrying out electrolysis of aqueous Hardy-Schulze rule? (NCERT)
solutions ?
19. Give reasons for the following observations: (c) Artificial rain is caused by spraying salt over
(i) Leather gets hardened after tanning. clouds.
(ii) Lyophilic sol is more stable than lyophobic sol. (ii) Define the following terms with an example in each
(Delhi 2015) case
(a) Macromolecular colloids
20. How are colloids classified on the basis of
(b) Peptisation
(i) physical state of components?
(ii) nature of dispersed phase? 25. (i) What happens, when
(iii) interaction between dispersed phase and dispersion (a) a freshly prepared precipitate of Fe(OH) 3 is
medium? (NCERT)
shaken with a small amount of FeCl 3 solution?
(b) persistent dialysis of a colloidal solution is
lLong Answer Type Questions carried out? (CBSE 2018)
21. Answer the following (ii) How can a colloidal solution and true solution of the
same colour be distinguished from each other?
(i) Out of NH3 and N 2 , which gas will be adsorbed
more readily on the surface of charcoal and why? (iii) Distinguish between micelles and colloidal
particles.
(ii) Give reason why a finely divided substance is more
effective as an adsorbent? 26. (i) What type of forces is responsible for the occurrence
(iii) What is the role of activated charcoal in gas masks of physisorption?
used in coal mines? (ii) What is aquasol and alcosol?
(iv) Why does the white precipitate of silver (iii) What are the dispersed phase and dispersion
halide becomes coloured in the presence of the dye medium in milk?
eosin? (iv) Give one example of sol and gel.
(v) Write one example of best semipermeable (v) Why is a colloidal sol stable? (Delhi 2017)
membrane.
l Case Based Questions
22. (i) Write one similarity between physisorption and
chemisorption. (Delhi 2017) 27. Read the following and answer the questions from (i)
(ii) In physisorption or chemisorption, which has a to (iv) given below
higher enthalpy of adsorption? A colloid is a heterogeneous system in which one
(iii) Give reason for the following substance is dispersed (dispersed phase) as very fine
(a) Alum can be used to purify water. particle in another substance (dispersion medium)
(b) Bleeding can be stop by rubbing moit alum. colloids are sometimes also referred to as solutions.
(c) A delta is formed at the meeting point of sea But the essential difference between a solution and a
water and river water. (All India 2015) colloid is that of particle size.
23. (i) Out of MgCl 2 and AlCl 3 , which is more effective In a true solution, the constituent particles are ions or
in causing coagulation of negatively charged small molecules while in a colloid, the dispersed
solution and why? phase may consist of particle of single macromolecule
(ii) Out of sulphur sol and proteins, which one forms or an aggregate of many ions, atoms or molecules.
multimolecular colloidal. (Delhi 2016) Thus, on the basis of the size of dispersed phase,
(iii) Define the following terms solutions are divided as: true solution, colloidal and
(a) Desorption suspension.
(b) Critical micelle concentration (i) What is the diameter of colloidal particles?
(c) Dialysis (ii) What type of colloid is formed when a liquid is
dispersed in a solid? Give an example.
24. (i) Give reason for the following
(iii) What type of colloid is formed when a gas is
(a) It is essential to wash the precipitate with water
before estimating it quantitatively. dispersed in a liquid? Give an example.
(b) Same substance can acts as colloids and (iv) What is collodion?
crystalloids Or What is the reason for stability of colloidal sols?
28. Read the following and answer the questions from (i) (ii) Adsorption of a gas on surface of solid is generally
to (iv) given below accompanied by a decrease in entropy, still it is a
The boundary which separates the two bulk phases spontaneous process. Explain.
(may be compounds or solutions) is called surface or (iii) Describe the application of adsorption in
interface. controlling humidity.
The interface or surface is represented by separating (iv) Why is adsorption always exothermic?
the bulk phases by a hyphen or a slash, e.g. Or
solid-solid, solid-liquid interface etc. Name two type of adsorption phenomenon.
The interface is usually few molecules thick but it 29. Read the following and answer the questions from (i)
area depends on the size of the particles of bulk to (iv) given below
phases. As gases are completely miscible, no Colloidal particles always carry an electric charge
interfaces exists between them. which may be either positive or negative. For
Many important phenomenon like corrosion example, when AgNO 3 solution is added to KI
electrode processes, dissolution and solution, a negatively charged colloidal sol is
crystallisation occur at interfaces. Surface chemistry obtained. The presence of equal and similar charges
deals which such phenomenon occuring at an on colloidal particles provide stability to the colloidal
interface. sol and if, somehow, charge is removed, coagulation
Solid surface has the tendency to attract and retain to of sol occurs. Lyophobic sols are readily coagulated
attract and attain the molecules of the phase with as compare to lyophilic sols. (All India, 2020)
which it comes in contact. Those molecules (i) What is the reason for the charge on sol particles ?
remain only at the surface and do not go deeper into
the bulk. (ii) Why the presence of equal and similar charges on
colloidal particles provide stability ?
The process in which molecular species are
accumulated at the surface rather than in the bulk of (iii) Why a negatively charged sol is obtained on adding
a solid or liquid phase is termed as adsorption. AgNO 3 solution to KI solution ?
Whereas, the process in which molecular species are (iv) Name one method by which coagulation of lyophobic
go deeper into the bulk of a solid or liquid phase is sol can be carried out.
termed as absorption. Or
(i) Out of NH 3 and CO 2 , which gas will be adsorbed Out of KI or K 2SO 4 , which electrolyte is better in
more readily on the surface of activated charcoal the coagulation of positive sol ?
and why?
EXPLANATIONS
Objective Questions So, the value of 1/ n lies between 0 and 1 in all cases.
1. (b) Absorption means penetration of adsorbate
molecules into the bulk of the adsorbent.
From the given option (b) is an example of absorption
because, when water is spread over calcium chloride,
log x/m
Slope = 1/n
water gets penetrated into bulk of the calcium chloride.
2. (b) As we know that, at equilibrium DG = 0 log k (intercept)
DH - TDS = 0 log p
D H = TD S 8. (b) Butter is a colloidal solution of liquid-solid,
Hence, at equilibrium enthalpy change is equal to i.e. the dispersed phase is liquid and dispersion medium is solid.
product of temperature and entropy change. This type of colloid is called gel.
3. (a) Activation of an adsorption refers to increasing the 9. (a) Solid sol consists of solid as both dispersed phase and
absorbing capacity of the adsorbent through different dispersion medium. In gemstones, metal crystals (salt and
methods. oxides of metals) are dispersed in solid (stone) medium. Hair
For instance, breaking it into small pieces increases the cream is an emulsion (liquid in liquid). Butter is a colloidal
surface area, hence, increases the extent of adsorption. solution of liquid in solid. Paint is also sol (solid in liquid).
4. (d) Lesser the value of critical temperature of gases 10. (a)
lesser will be the extent of adsorption. Here, H2 has Dispersed Dispersion Type of
lowest value of critical temperature, i.e. 33. phase Examples
medium colloid
Hence, hydrogen gas shows least adsorption on a
definite amount of charcoal. Liquid Solid Gel Cheese (C),
butter, jellies
x
5. (a) shows the extent of adsorption. Liquid Liquid Emulsion Milk (M), hair
m
cream
Extent of adsorption increases by decrease of
temperature. Solid Gas Aerosol Smoke (S), dust
Therefore, the order of temperature is T1 < T2 < T3.
Thus, option (a) is correct, i.e. C : liquid in solid, M : liquid in
6. (a) According to Freundlich adsorption isotherm. liquid and S : solid in gas.
x 11. (a) A® (2); B ® (3); C ® (4); D ® (1)
= k × p1/ n
m A. When sulphur vapours passed through cold water it leads to
x
where, = amount of the gas adsorbed per unit mass of formation of molecular colloids.
m
adsorbent, p = pressure, k and n are the constants. B. When soap is mixed with water above critical micelle
concentration it lead to formation of associated colloids.
The value of n lies in between 0 to 1.
C. White of egg whipped with water is an example of
x macromolecular colloids in which proteneous molecule,
Thus, = k × p0. 3 is the correct option.
m having high molecular mass, acts as a colloidal particle.
7. (c) According to the Freundlich adsorption isotherm D. Soap mixed with water below critical micelle concentration
x
1 is known as normal electrolyte solution.
= kp n 12. (c) Lyophobic sol can be protected by addition of lyophilic sol. As
m
lyophobic sols are readily precipitated on addition of small amount
x æ1 ö
Taking log on both side log = ç ÷ log p + log k of electrolytes or shaking, or heating hence they are made stable by
m è nø adding lyophillic sol which stabilises the lyophobic sols.
13. (a) A ® (3); B ® (4); C ® (2); D ® (1)
Y = m X + C A. Dispersion medium moves in an electric field is known as
electroosmosis.
On comparing it with equation of straight line and drawing
x B. Solvent molecules pass through semipermeable membrane
the graph log versus log p , we get a straight line with towards solvent side is known as reverse-osmosis.
m
C. Movement of charged colloidal particles under the
intercept log k and slope of the straight line gives the value
1 influence of applied electric potential towards oppositely
of . charge electrodes is known as electrophoresis.
n D. Solvent molecules pass through semipermeable membranes
The value of n is always greater than 1. towards solution side is known as osmosis.
14. (d) Tyndall effect is the scatttering of light by sol particles, So, both A and R are true and R is the correct explanation
which cannot be affected by charge on them. of A.
Other given options such as coagulation, electrophoresis and 24. (c) When oppositely charged sols are mixed in almost equal
electroosmosis depend on charge particles. proportions, their charges are neutralised. Both sols may be
Thus, option (d) is correct. partially or completely precipitated.
15. (c) The molecules of dispersion medium due to their kinetic When negatively charged As 2S 3 sol is added to positively
motion strike against the colloidal particles from all sides charged Fe(OH) 3 sol in suitable amounts, precipitation of
with different forces causing them to move. both the sols take place simultaneously. Thus, A is true but R
is false.
16. (d) Freshly prepared precipitate sometimes gets converted
to colloidal solution by peptisation. 25. (a) Both A and R are true and R is the correct explanation of A.
Peptisation is a process in which precipitate gets converted The colour of colloidal solution depends on the wavelength
of light scattered by the dispersed particles. The wavelength
into colloidal solution by addition of a suitable peptising
of light further depends on the size and nature of the
agent.
particles.
17. (c) Bredig’s arc method involves the process of both Finest gold sol in red in colour. As size of the particles
dispersion as well as condensation. Colloidal sols of metals increases, it becomes purple, then blue and finally golden
such as gold, silver, platinum etc., can be prepared by this yellow.
method. 26. (b) At a certain concentration, surfactant molecules start to
18. (d) Haemoglobin and gold sol both are colloids and always aggregate and from micelle. This concentration is called
carry an electric charge. Haemoglobin is a positively critical micellar concentration (CMC).
charged sol, because in haemoglobin, Fe2+ ion is the central Moreover, the conductivity of a solution having surfactant
metal ion of the octahedral complex. molecules decreases sharply at the CMC.
All metal sols like, Au-sol, Ag-sol etc; are negatively charged Thus, both A and R are true but R is not the correct
sols. explanation of A.
19. (a) Coagulation power of an ion depends both on magnitude 27. (i) (b) A large number of atoms or molecules of a substance
and sign of the charge (positive or negative) on the ion. This aggregates together to form species having size in the
fact can be explained by Hardy-Schulze rule. According to colloidal range. These species are called
this rule “greater the valency of the coagulation macromolecular colloids.
ion/flocculating ion (appositively charged ion) added, the (ii) (a) Gold sols and sulphur sols are the examples of
greater is its power to coagulation. multimolecular colloids.
20. (b) According to Hardy-Schulze law, greater the charge on (iii) (b) Macromolecular colloids are quite stable and
resemble to the true solutions in many respects.
anion greater will be its coagulating power.
Or
Electrolytes Anionic part Charge on anion (b) The formation of micelles takes place above the
Na 2S S2 - 2 particular range of temperature termed as Kraft
temperature.
Na 3PO 4 PO 3-
4 3
(iv) (b) Soaps and synthetic detergent belongs to the class of
Na 2SO 4 SO 24 - 2 association colloids.
28. (i) (c) In gold sol, gold particles (solid) are dispersed in
NaCl Cl - 1 water (liquid). Gold sol cannot be prepared directly by
Here, PO 3- 3- shaking with water as it is a lyophobic sol.
4 have highest charge. Hence, PO 4 have highest
coagulating power. (ii) (d) Addition of alcohol is similar to replacement of the
dispersion medium and addition of electrolyte may
1
21. (a) As Protective power µ cause coagulation. Hence, both these make lyophilic
Gold number solution unstable.
Therefore, sol A is most effective protective colloidal. (iii) (d) Colloidal solution of mercury in water is easily
22. (a) Both A and R are true and R is the correct explanation of A. obtained by ultrasonic dispersion.
Enthalpy of chemisorption is high as it involves chemical (iv) (c) When gas is dispersed in liquid medium then foam
bond formation. is formed.
Or
23. (a) The vegetable tanning materials have smaller surface (d) Tyndall effect is the scattering of light by sol
areas because the capillaries are reduced to smaller particles, which cannot be affected by charge on them.
diameters.
Subjective Questions 6. (i) Effect of pressure on adsorption of gases on solids At

1. Distinction between Absorption and Adsorption constant temperature, the adsorption of gases increases
with increase of pressure. (This is further explained by
Absorption Adsorption Freundlich’s adsorption isotherm.)
l
It is a bulk phenomenon, l
It is a surface phenomenon, (ii) Effect of temperature Adsorption is an exothermic
e.g. water vapours are e.g. water vapours are process. Therefore, in accordance with Le-Chatelier’s
absorbed by anhydrous adsorbed by silica gel on its principle, the magnitude of adsorption increases with
calcium chloride. surface. decrease in temperature. Actually, physisorption
l
The concentration of increases with decrease in temperature but
is uniform throughout the substance (adsorbate) is chemisorption first increases and then decreases with
bulk of the solid, e.g. when only at the surface and it increase in temperature.
cotton is dipped in blue does not penetrate to the
ink, it gets blue bulk, e.g. when a chalk
throughout. stick is dipped in ink, it is
Adsorption
Adsorption
blue on the surface and p-constant
white in bulk.
l
The concentration of the
is uniform throughout the adsorbate increases only
bulk of the solid. at the surface of the T T
Physisorption Chemisorption
adsorbent.
(iii) Nature of adsorbent A gas is adsorbed in different
2. Behaviour of physisorption and chemisorption on increase in amounts on different adsorbents.
temperature can be explained on the basis of nature of forces 7. Activation of an adsorbent refers to increasing the adsorbing
present to bind their particles. capacity of the adsorbent through different methods. For
Physisorption involves weak van der Waals’ forces which instance making the surface of solid rough or breaking it into
weakens with increase in temperature. Chemisorption small pieces increases surface area hence the extent of
involves formation of chemical bond which requires activation adsorption. That is why, metals in finely divided state act as
energy. good adsorbents. Certain specific treatment also activate an
adsorbent. e.g. Heating wood charcoal between 600 - 1200°C
3. Chemisorption occurs when reactant molecules form
activate it.
covalent or ionic bonds with the surface of adsorbent.
Once the layer of reactant molecules has been formed 8. Adsorption isotherm The variation in the amount of gas
on the surface of adsorbent, no other active site is available adsorbed by the adsorbent with pressure at constant
for bonding of reactant-adsorbent to form further layers. temperature can be expressed by means of a curve called
adsorption isotherm.
Physisorption is simply driven by van der Waals' forces of 195 K
attraction. So, number of layers may be formed one over the
other on the surface of the adsorbent.
4. Due to the following features
(i) Chemical inertness Both form chemically inert
electrodes. x
244 K
(ii) Adsorption capacity Platinum and palladium both have m
good adsorptive capacity for hydrogen. 273 K
5.
Properties Physisorption Chemisorption
p
(i) Specificity l
It is non-specific l
It is highly Adsorption isotherm
in nature. specific in nature. These curves indicated that at a fixed pressure, there is a
(ii) Temperature l
Low temperature l
High temperature decrease in physical adsorption with increase in temperature.
dependence is favourable for is favourable for Freundlich’s adsorption isotherm It is an empirical
adsorption. adsorption. It relationship between the quantity of gas adsorbed by unit mass
It decreases with increases with the of solid adsorbent and pressure at a particular. temperature.
increase of increase in x
temperature. temperature and = kp1/ n ( n > 1 ) …(i)
then decreases. m
x x
(iii) Reversibility l
It is reversible in l
It is irreversible when n = 1, = kp or µp
m m
nature. in nature.
where, x is the mass of gas adsorbed on mass m of the
(iv) Enthalpy l
Enthalpy of l
Enthalpy of adsorbent at pressure p, k and n are constants which depend
change adsorption is low adsorption is high on the nature of the adsorbent and the gas at a particular
(20-40 kJ mol -1 ). (80-240 kJ mol -1). temperature.
Taking log in Eq. (i), gives (iii) Multimolecular colloid These are aggregates of atoms
x 1 or molecules with diameter less than 1 nm.
log = log k + log p
m n Associated colloid These colloids are produced by the
The validity of Freundlich isotherm can be verified by aggregates of a large number of ions because of the
x attraction towards oppositely charged ions in
plotting log on Y-axis and log p on X-axis.
m concentrated solution.
If it comes to be a straight line, the Freundlich isotherm is 14. (i) Sulphur sol is prepared by the oxidation of H 2 S with SO 2 .
valid. Oxidation
SO 2 + 2 H 2 S ¾¾¾® 3S + 2H 2 O
(Sol)
(ii) Gold sol is prepared by Bredig’s arc process or by the
x
log reduction of AuCl 3 with HCHO.
m 1
Slope = Reduction
n e.g. 2AuCl 3 + 3HCHO + 3H2O ¾¾¾® 2Au
(Sol)
log p +3HCOOH + 6HCl
Freundlich isotherm 15. The process of settling of colloidal particles is called
9. Colloid is not a substance but a state of substance is a coagulation of the sol. It is also known as precipitation.
true statement because some substances which are Following are the three methods by which coagulation of
crystalloids under certain conditions can be colloids under lyophobic sols can be carried out:
the other, e.g. NaCl is a crystalloid in aqueous medium, but (i) Electrophoresis In this process, the colloidal particles
when mixed with benzene, it behaves as a colloid. It is the size move towards oppositely charged electrodes and get
of the particles of that matter, i.e. the state in which the discharged resulting in coagulation.
substance exists. If size lies in range of 1-1000 nm, it is in the (ii) Mixing of two oppositely charged sols (or mutual
colloidal state. So, above statement is true. coagulation) When equal proportions of oppositely
10. (i) Foam chaged sols are mixed, they neutralise each other
Example : Shaving cream. resulting in coagulation.
(ii) Associated colloids from micelles There are some (iii) Prolonged dialysis By this method, electrolytes present
substances which at low concentration behave as normal in sol are removed completely and colloid becomes
strong electrolyte but at higher concentration exhibit unstable resulting in coagulation.
colloidal behaviour due to the formation of aggregates. 16. The cleansing action of soap is due to the fact that soap
The aggregated particles thus formed are called molecules form micelle around the oil droplet in such a way
micelles. that hydrophobic part of the stearate ions [ C17H35 COO - ] is in
11. (i) Hydrosol When solid is dispresed in water, it is called the oil droplet and hydrophilic part interact with water, the
hydrosol, e.g. starch sol. oil droplet surrounded by stearate ions is now pulled in water
(ii) Aerosol It is a type of colloidal system in which and removed from the dirty surface.
dispersion medium is gas and dispersed phase is either
Thus, soap helps in emulsification and washing away of oils
solid or liquid, e.g. fog, smoke, mist, etc. Colloidal
and fats. The negatively charged sheath around the globules
suspensions in the air are also called aerosols.
prevents them from coming together and forming aggregates.
12. (i) Dispersed phase of smoke = Solid
Dispersion medium of smoke = Gas
(ii) Dispersed phase of milk = Liquid
Dispersion medium of milk = Water (liquid)
13. (i) Lyophilic sol The colloidal solution in which the (a) (b) (c)
particles of the dispersed phase have a great affinity for Stearate on cloth Stearate ions
Grease droplet
the dispersion medium is called lyophilic sol. e.g. gum, arranging around the
surrounded by
geletin, starch etc. grease droplets
stearate ions
Lyophobic sol The colloidal solution in which there is (micelle formed)
no affinity between particles of the dispersed phase Hard water contains calcium and magnesium ions. These ions
and the dispersion medium is called lyophobic sol. form insoluble calcium and magnesium when sodium or
Lyophobic sols need stabilising agents for their potassium soaps are disoolved in hard water. These insoluble
preservation. soaps separate as scum in water and are useless as cleansing
(ii) Solution It contains small solute particles dispersed agent.
throughout the solvent. The particle size is less than 1 nm. 17. (i) When a beam of light is passed through a sol, scattering
Colloid It contain particles of intermediate size. It is a of light takes place and the path of light becomes visible
heterogeneous solution. The particles of colloid have (Tyndall effect).
diameters between 1 to 1000 nm.
(ii) Charge on ferric ion is neutralised by chloride ions. Thus, 21. (i) NH3, adsorbed more readily than N 2 on the surface of
coagulation takes place. charcoal because, it is more easily liquefiable as
(iii) When electric current is passed through a sol, the compared to N 2 and has a greater molecular size too.
colloidal particles move towards the oppositely charged (ii) A finely divided substance is more effective as an
electrode and the phenomenon is called electrophoresis. adsorbent because of the availability of its greater
surface area per unit mass of the adsorbent leading to
18. According to Hardy-Schulze rule, greater the valency of greater adsorption.
flocculating ion, greater is its power to cause precipitation.
(iii) It adsorbs poisonous gases present in coal mines.
This rule takes into consideration only the charge not the size
of an ion. Since, both the size and the charge of an ion (iv) Eosin dye gets adsorbed on the surface of white
precipitate of silver halide, making it coloured.
determine polarising power hence, this rule can be modified
as greater the polarising power of flocculating ion, greater is (v) Cellophane.
its power to cause precipitation. 22. (i) Both physisorption and chemisorption directly
19. (i) The process of hardening of leather is known as tanning. depends on the surface area i.e. increases with an
Animal skin is colloidal in nature and has positively increase in surface area of the adsorbent.
charged particles. When they are soaked in tannin, their (ii) Chemisorption has higher enthalpy of adsorption, i.e.
mutual coagulation takes place and, thus leather becomes 80-240 kJ mol -1 as it involves chemical bond formation
hard after tanning. (in case of physisorption, it is 20- 40 kJ mol -1).
Note Tannin, which is obtained from a mixture of
polyhydroxy benzoic acids and contains negatively (iii) (a) We add alum to purify water as, it coagulates the
charged colloidal particles. colloidal impurities present in water so that these
(ii) Lyophilic sols are more stable than lyophobic sols. This is impurities settle down and get removed by
due to the fact that lyophilic colloids are extensively decantation or filtration.
solvated, i.e. colloidal particles are covered by a sheath of (b) Blood is a colloidal sol. When we rub the injured
the liquid in which they are dispersed. part with moist alum then coagulation of blood
20. (i) Depending on the basis of the physical states of the takes place. Hence, clot is formed, which stops
dispersed phase and dispersion medium, eight types of the bleeding.
colloidal systems are formed. These are as follow (c) River water is colloidal solution of clay and sea
water contains a number of electrolytes. When
Dispersed Dispersion Type of river water meets the sea water, the electrolytes
Examples
phase medium colloid present in sea water coagulates the colloidal
Solid Solid Solid Some coloured solution of clay resulting in its deposition with
glasses, gem the formation of delta.
stones 23. (i) According to Hardy-Schulze rule, ‘‘greater the
Solid Liquid Sol Paints, cell fluids valency of the flocculating ion added, the greater is its
power to cause precipitation.’’
Solid Gas Aerosol Smoke, dust
As Al 3+ ion due to greater valency has more
Liquid Solid Gel Cheese, buter, flocculating power than Mg2 + ion. Therefore, AlCl 3 is
jellies more effective than MgCl 2 in causing coagulation of
Liquid Liquid Emulsion Milk, hair cream negatively charged sol.
Liquid Gas Aerosol Fog, mis, cloud, (ii) Sulphur sol forms multimolecular colloids. It consists
insecticide sprays of particles containing a thousand or more S 8 sulphur
molecules which associate together to form a
Gas Solid Solid sol Pumice stone, multimolecular colloid.
foam rubber.
(iii) (a) Desorption is the process of removing an
Gas Liquid Foam Froth, whipped adsorbed substance from the surface to which it is
cream, soap lather. adsorbed.
(b) Critical micelle concentration (or CMC) is the
Note Ninth possibility, i.e. a gas mixed with another gas is a minimum concentration required for the
homogeneous system and not a colloid.
formation of micelle.
(ii) On the basis of nature of dispersed phase, collids are (c) It is a process of removing a dissolved substance
classified as: from a colloidal solution by means of diffusion
(a) Multimolecular collids, e.g. gold sol, sulphur etc. through a suitable membrane. For dialysis
(b) Macromolecular colloids, e.g. cellulose, starch, etc. process, colloidal solution is taken in a parchment
(c) Associated colloids, e.g. soaps, synthtic detergents. paper or cellophane membrane and this bag is
(iii) On the basis of interaction between dispersed phase and suspended in water. Impurities (molecules or ions
dispersion medium, colloids are of two types: as small as solute of true solution) diffuse in water
(a) Lyophilic colloids, e.g. gum, gelatin etc. through the membrane and colloids become pure.
The apparatus as shown in figure, used for this
(b) Lyophobic colloids, e.g. metals, their sulphides etc. purpose is called dialyser.
24. (i) (a) Some of the reactant ions may be adsorbed or may (iv) Sol - paints Gel - butter
adhere to the surface of the particles of the precipitate (v) Following method can be used to stabilised the
formed during an ionic reaction. In order to remove colloidal sol.
these reactant ions, the precipitate should be washed l
Solvation-colloidal particles are covered by a
with water. If this is not done, an error may be sheath of liquid in which they are extensively
produced during quantitative analysis.
solvated, thereby providing stability.
(b) The nature of the substance whether colloid or l
Electrostatic stabilisation-presence of equal and
crystalloid depend upon size of the solute particles. similar charges on the colloidal particles prevents
When size of solute particles lies between 1 to
coagulation of the colloidal sol.
1000 nm, it behaves as a colloid and when the size is
less than 1 nm it behaves as crystalloid. 27. (i) Diameter of colloidal particles vary between
(c) As we know rainfall occurs when oppositely charged 1-1000 nm, i.e. 10-9 - 10-6 m.
clouds meet, since, clouds are colloidal in nature and (ii) The colloid which is formed when a liquid is dispersed
carry charge. Spray of silver iodide, an electrolyte, in a solid is gel, e.g. butter.
leads to artificial rain. Sometimes electrified sand is (iii) Foam is the colloid that the colloid that obtained when
also used for this purpose. gas is dispersed in liquid, e.g. whipped cream.
(ii) (a) Macromolecular colloids When substances which (iv) 4% solution of nitrocellulose in a mixture of alcohol
possess very high molecular masses are dispersed in and ether is called collodion.
suitable dispersion medium, the colloidal solution,
thus, formed are called macromolecular colloids. Or
These colloids are quite stable, e.g. cellulose, starch The presence of equal and similar charges on colloidal
etc. particles is largely responsible in providing stability to
the colloidal solution because having same charge
(b) The process of conversion of a fress precipitate present them from coalescing or aggregating or
into colloidal sol by shaking it with dispersion coagulating when they come to one another.
medium in the presence of electrolyte is called
peptisation. 28. (i) Easily liquefiable gases, i.e. with higher critical
temperatures are readily adsorbed as van der Waals’
25. (i) (a) When a freshly prepared precipitate of Fe(OH) 3 is forces are stronger near the critical temperature.
shaken with a small amount of FeCl 3 solution, sol Therefore, out of NH3 and CO 2 gas, NH3 gas will be
formation takes place. It is due to the preferential adsorbed more readily on the surface due to its high
adsorption of Fe 3 + of FeCl 3 over Fe(OH) 3 . critical temperature than CO 2 gas.
The resultant particles formed after adsorption are (ii) Adsorption is an exothermic proces, i.e. energy factor
of colloidal size. Thus, forming sol with remaining favours the process. As, DG = DH - TDS, in adsorption,
dispersion medium. The complete reaction can be through DS is negative but DH is also negative and
seen as DH > TDS in magnitude so that DG is negative. Hence,
Fe (OH) 3 + x Fe 3 + ¾® Fe(OH) 3 xFe 3+ the process is spontaneous.
Colloidal sol (iii) Application of adsorption in controlling humidity
(b) Persistent and prolonged dialysis of colloidal sol Silica and aluminium gels are used as adsorbents for
remove even traces of electrolytes completely and removing moisture and controlling humidity.
colloids become unstable and ultimately coagulate. (iv) During adsorption, there is always a decrease in
(ii) When a beam of light is passed through true and residual or unbalanced forces of the surface. This
colloidal solutions each kept in a different glass vessel, results in decrease in sufrace energy which appears
colloidal solution exhibits Tyndall effect whereas true as heat, therefore adsorption in an exothermic process.
solution does not. Or Physisorption and chemisorption.
(iii) Micelles Some substances (like soap) at higher 29. (i) Origin of charge on colloidal particles is due to
concentrations (10-4 to 10-3 mol/L in case of soap) show preferential adsorption of ions from the solution.
colloidal behaviour due to the formation of aggregates.
(ii) The presence of equal and similar charges on colloidal
These aggregates particles are called micelles or
particles is largely responsible for providing stability to
associated colloids.
the collodial solution, as the repulsive force between
Colloidal solution Those are the solution in which the charged particles having same charge prevent them
diameter of dispersed phase particles may range from 1
from coalescing or aggregating when they come close
to 100 nm. These are intermediate of true solution and
to one another.
suspensions. The colloidal particles do not settle down
under the force of gravity even on long standing. (iii) When AgNO 3 is added to KI solution, the precipitated
AgI adsorbs iodide ions from the dispersion medium
26. (i) van der Waals’ forces. and negatively charged colloidal sol results.
(ii) If the dispersion medium is water, the sol is called (iv) Electrophoresis
aquasol and if it is alcohol then called as alcosol.
Or Out of KI and K 2SO 4 , latter one is a better electrolyte
(iii) Dispersed phase - liquid
for coagulation of positive sol according to
Dispersion medium - liquid Hardy-Schulze rule.
Chapter Test 6. Assertion Most of the medicines are more effective
in the colloidal form.
Reason Colloidal form exhibit large surface area and
Multiple Choice Questions medicines are easily assimilated in this form.
1. Adsorption of oxalic acid can be takes place on activated 7. Assertion Coagulation power of Al3+ is more than
charcoal. It this case, the activated charcoal is act as Na+ .
(a) adsorbed (b) adsorbate
Reason Greater the valency of the flocculating ion
(c) adsorbent (d) occlusion
added, greater is its power to cause precipitation
2. Which of the following process is responsible for the (Hardy-Schulze rule).
formation of delta at a place where rivers meet the sea? 8. Assertion Substances whose solutions cannot pass
(a) Colloid formation (b) Coagulation throughout filter paper are called as colloids.
(c) Peptisation (d) None of these
Reason The size of colloidal particles are smaller
3. Choose the incorrect statement with respect to than the size of suspension particles.
physisorption.
(a) It is not specific in nature Short Answer Type Questions
(b) It arises because of van der Waals’ forces 9. (i) Explain the following terms with suitable examples:
(c) It is reversible in nature
(a) Aerosol
(d) Enthalpy of adsorption is in range 80-240 kJ mol -1
(b) Hydrosol
4. The protecting power of lyophilic colloidal sol is expressed (ii) Why the colour of water is blue?
in terms of
(a) coagulating value 10. (i) What is especially observed when a beam of light is
(b) gold number passed through a colloidal solution?
(c) critical micelle concentration (ii) What is Helmholtz electrical double layer?
(d) oxidation number
11. (i) Explain the electrophoresis.
5. Match the items of Column I and Column II. (ii) What happens when dialysis is prolonged?
Column I Column II (iii) Why is Fe(OH) 3 colloid positively charged, when
A. Butter 1. Dispersion of liquid in liquid prepared by addingFe(OH) 3 to hot water?
12. (i) Write an important characteristic of lyophilic sols.
B. Pumice stone 2. Dispersion of solid in liquid
(ii) Based on the type of particles of dispersed phase,
C. Milk 3. Dispersion of gas in solid give one example each of associated colloid and
multimolecular colloid.
D. Paint 4. Dispersion of liquid in solid
13. (i) How can a colloidal solution and true solution
Choose the correct code that are given below of the same colour be distinguished from each
Codes other?
A B C D A B C D
(a) 4 3 1 2 (b) 2 3 1 4 (ii) Why is water alone not very effective for removing
(c) 1 4 2 3 (d) 3 2 1 4 dirt from clothes?
Assertion-Reasoning MCQs Long Answer Type Questions
Direction (Q. Nos. 6-8) Each of these questions contains 14. Write any three methods for preparation of colloid
two statements Assertion (A) and Reason (R). Each of and explain the various methods used in the
these questions also has four alternative choices, any one purification of colloid.
of which is the correct answer. You have to select one of 15. (i) What are the factors which influence the
the codes (a), (b), (c) and (d) given below. adsorption of a gas on a solid?
(a) Both A and R are true and R is the correct explanation of A. (ii) What is meant by critical micelle concentration?
(b) Both A and R are true, but R is not the correct explanation (iii) Which will be adsorbed more readily on the surface
of A. of charcoalNH3 orO 2 and why?
(c) A is true, but R is false. (iv) What is common in aqua and solid sols?
(d) A is false, but R is true. (v) How is adsorption of a gas related to its critical
temperature?
Answers
1. (c) 2. (b) 3. (d) 4. (b) 5. (a) Scan the code
6. (a) 7. (a) 8. (d)
CHAPTER 04
The d - and f- Block

Elements
In this Chapter...
l d -Block Elements
l f-Block Elements
The d-block of the periodic table includes the elements of Electronic Configuration
the groups 3 to12, in which the d-orbitals are In general, the electronic configuration of outer orbitals of these
progressively filled in each of the four long periods.
elements is ( n - 1 )d 1 - 10 ns 1 - 2 . Half and completely filled sets of
The elements constituting the f- block are those in which orbitals are relatively more stable.
the 4 f- and 5 f- orbitals are progressively filled in the latter
two long periods. e.g. Cr ( 3 d 5 4 s 1 ) and Cu ( 3 d 10 4 s 1 ).
Exception
d-Block Elements l
Last members of different series such as Zn, Cd and Hg have
(Transition Elements) completely filled d-orbitals ( n -1 ) d 10 ns 2 in the ground state as
well as in their common oxidation states. These do not show
l
The elements in which the differentiating electron any characteristic properties of transition elements except
enters in ( n -1 ) d-sub level are called d-block complex formation. Hence, these elements are not considered
elements (group 3-12). as transition elements.
l
The d-block elements in which the atoms or ions l
Some of the exceptions are observed in electronic
have incomplete d-orbitals are called transition configuration due to very little energy difference between
elements. ( n -1 )d and ns-orbitals such as
l
There are mainly four series of the transition metals, Cr : 3 d 5 , 4 s 1 instead of 3 d 4 , 4 s 2
3d-series (Sc to Zn), 4d- series (Y to Cd), 5 d-series Cu : 3 d 10 , 4 s 1 instead of 3 d 9 , 4 s 2
(La and Hf to Hg) and 6d-series which has Ac and
elements from Rf to Cn. General Properties of Transition Elements
l
Zn, Cd and Hg have completely filled ( n - 1 ) d-orbitals, The general properties of transition elements are as follows
so they do not show much resemblance with other Physical Properties
transition elements. l
Nearly, all the transition elements (except Zn, Cd, Hg and Mn)
l
The d-block occupies the large middle section of the display typical metallic properties such as high tensile strength,
periodic table flanked between s and p -blocks in the ductility, malleability, high thermal and electrical conductivity
periodic table. and metallic lustre.
l
The transition metals (except Zn, Cd and Hg) are very hard l
The ability of fluorine to stabilise the highest oxidation
and have low volatility. state is due to either higher lattice enthalpy or higher
bond enthalpy for higher covalent compounds.
Melting and Boiling Points
l
Cu 2+ is more stable than Cu + due to lower reduction
Their melting and boiling points are high due to involvement of
potential and highly negative hydration lattice energy of
greater number of electrons from ( n -1 ) d in addition to ns
Cu 2+ compounds.
electrons in the interatomic metallic bonding.
l
The highest oxidation number in the oxides coincide
In any row, the melting point of these metals rise to a maximum
with the group number and is attained in Sc 2 O 3 to
at d 5 except for anomalous values of Mn and Tc and fall regularly
Mn 2 O 7 . Beyond group 7, no higher oxides of Fe above
as the atomic number increases.
Fe 2 O 3 are known.
Enthalpies of Atomisation l
Besides the oxides, oxocations stabilise V v as VO+2 ,
They have high enthalpies of atomisation. The metals of the V iv as VO2+ and Ti iv as TiO 2+ .
second and third series have greater enthalpies of atomisation l
The ability of oxygen to stabilise these high
than the corresponding elements of the first series. oxidation states exceeds that of fluorine. Thus, the
Atomic and Ionic Radii highest Mn fluoride is MnF4 , whereas the highest oxide
is Mn 2O 7 .
l
In general, ions of the same charge in a given series show
progressive decrease in radius with increasing atomic number. M 2+ /M Standard Electrode Potential
l
The shielding effect of a d-electron is not that effective, l
There is no regular trend for M 2+ /M standard electrode
hence, the net electrostatic attraction between the nuclear potential due to the irregularities in ionisation
charge and the outermost electron increases and the ionic enthalpies and enthalpy of atomisation.
radius decreases. l
The general trend towards less negative E° values
l
The filling of 4 f -orbitals before 5 d-orbitals result in a regular across the series is related to the general increase in the
decrease in atomic radii called lanthanoid contraction which sum of the first and second ionisation enthalpies.
essentially compensates for the expected increase in atomic size l
The unique behaviour of Cu having a positive E° is due
with increasing atomic number. to its inability to liberate H 2 from acids.
l
Density The decrease in metallic radius coupled with increase l
The value of E° for Mn, Ni and Zn are more negative
in atomic mass results in a general increase in the density of than expected from the trend.
these elements.
M 3+ / M 2+ Standard Electrode Potential
Ionisation Enthalpies l
There is no regular trend for M 3+ / M 2+ standard
l
There is an increase in ionisation enthalpy along each series of electrode potential.
the transition elements from left to right due to an increase in ° 3+ 2+
nuclear charge which accompanies the filling of inner d-orbitals.
l
The highest EM /M for Zn is due to the removal of
an electron from the stable d 10 configuration of Zn 2+ .
l
The first ionisation enthalpy, in general increases, but the
magnitude of the increase in the second and third ionisation Similarly, low value for Sc reflects the stability of Sc 3+ ,
enthalpies for the successive elements is much higher along a which has a noble gas configuration.
series. Zn, Cd and Hg have highest ionisation energy. l
The comparatively high value for Mn shows that M 2+
l
The trend of steady increase in second and third ionisation ( d 5 ) is stable, whereas low value of Fe shows the extra
enthalpy breaks for the formation of Mn 2+ and Fe 3+ stability of Fe 3+ ( d 5 ). The low value for V is related to
respectively. the stability of V 2+ ( half-filled t 2 g level).
Oxidation States
Chemical Reactivity and E ° Values
l
The transition elements show variety of oxidation states due to l
The metals of the first series with the exception of
very small difference between ( n -1 ) d and ns-orbitals.
copper are relatively more reactive and are oxidised
l
The elements which give the greatest number of oxidation by 1M H + .
states occur in or near the middle of the series.
e.g. Mn show +2 to +7 oxidation state. l
The E° values for M 2+ / M decreases to form divalent
cations across the series. An examination of the E° values
l
Low oxidation states are found when a complex compound has
ligands capable of p-acceptor character in addition to for the redox couple M 3+ / M 2+ shows that Mn 3+ and
s -bonding. e.g. Ni(CO) 4 and Fe(CO) 5 . Co 3+ ions are the strongest oxidising agents in aqueous
solutions.
l
The highest oxidation numbers are achieved in TiX 4 , VF5 and
CrF6 . Beyond Mn, no metal has a trihalide except FeX 3 and l
The ions Ti 2+ , V 2+ and Cr 2+ are strong reducing
CoF3 . agents and will liberate hydrogen from dilute acid.
Magnetic Properties Alloy Formation

l
Diamagnetic substances are repelled by the applied l
Alloys are homogeneous solid solutions in which the atoms of
field, while the paramagnetic substances are attracted. one metal are distributed randomly among the atoms of the
Substances which are attracted very strongly by the other.
applied field are said to be ferromagnetic. Many of the l
Because of similar radii and other characteristics of transition
transition metal ions are paramagnetic. metals, alloys are readily formed by these metals. Alloys so
l
The magnetic moment is determined by, m = n( n + 2) formed are hard and often have high melting points.
where, n = number of unpaired electrons and m is the l
Some alloys of Cu,
magnetic moment in units of Bohr Magneton (BM). Brass – 70-80% Cu + 30-20% Zn
l
The magnetic moment increases with the increasing Bronze – 80-90% Cu + 20-10% Sn
number of unpaired electrons. Bell metal – 72-80% Cu + 28-20% Zn
Gun metal – 85% Cu + 5% Sn + 10% Zn
Formation of Coloured Ions
Monel metal – 70% Cu + 30% Ni
l
If unpaired electron is present, complex is coloured due
to d-d transition and also, paramagnetic in nature. f-block Elements
l
If unpaired electron is absent, complex or compound is
colourless due to the absence of d-d transition and
(Inner Transition Elements)
diamagnetic in nature. l
The f -block consists of elements in which 4 f -and 5 f -orbitals
Note Few compounds in which transition metal has d 0 are progressively filled. They are placed in a separate panel at
configuration, may also exhibit colour due to charge transfer. the bottom of the periodic table. They are known as inner
e.g. CrO 3 has transition elements.
d 0 configuration of Cr and shows orange colour due to charge l
The two series of the inner transition metals are 4 f (Cl to Lu)
transfer.
and 5 f (Th to Lr) are known as lanthanoids and actinoids
Formation of Complex Compounds respectively.
l
Transition metals due to their small size, high charge l
Lanthanum and actinium does not belong to f -block
density,presence of vacant d-orbital for bond formation elements as they do not have any electron in 4 f and
can form complex. 5 f - subshell respectively. However, their properties resemble
l
Transition elements and their compounds show catalytic with elements of 4 f and 5 f -series.
properties, due to variable oxidation states and ability to
form complex. Lanthanoids
Catalytic Properties Some important properties of lanthanoids are discussed below.
Transition metals have ability to adopt multiple oxidation Electronic Configuration
states and to form complexes. The lanthanoids include Ce to Lu and have electronic
For example, Vanadium (V) oxide (in contact process), configuration with 6 s 2 common but with variable occupancy of 4
finely divided iron (in Haber’s process) and nickel (in f level.
catalytic hydrogenation).
Atomic and Ionic Radii
They can change their oxidation states and act as effective
catalysts. e.g. The atomic and ionic radii decrease from lanthanum to lutetium.
This is due to the unique property of lanthanoids which is known
2Fe 3+ + 2I - ¾® 2Fe 2+ + I 2
as lanthanoid contraction.
2Fe 2+ + S 2O 28- ¾® 2Fe 3+ + 2SO 42-
Lanthanoid Contraction
Formation of Interstitial Compounds The filling of 4f-orbital before 5d-orbital results in a regular
l
Transition metals also have a tendency to form decrease in atomic radii called lanthanoid contraction. The
interstitial compounds with H, C, B or N-atoms. factor responsible for the lanthanoid contraction is similar to that
l
They are usually non-stoichiometric and are neither of ordinary transition series, i.e. the imperfect shielding of one
typically ionic nor covalent. e.g. TiC, Mn 4 N, Fe 3 N, electron by another in the same set of orbitals.
VH 0.56 and TiH1 .7 etc. However, the shielding of one 4f-electron by another is less than
l
The interstitial compounds are very hard, retain metallic that of one d-electron by another and as the nuclear charge
conductivity have high melting points and are increases along the series, there is fairly regular decrease in the
chemically inert. size of the entire 4 f n orbitals.
The decrease in atomic radii is not regular but the decrease Consequences of Lanthanoid Contraction
in ionic radii of their M 3 + ions are quite regular as (i) Basic character of oxides and hydroxides Due to the
represented by the following graph. lanthanoid contraction, the covalent nature of
Ln¾OH bond increases as the basic character of oxides
110 Sm2+ and hydroxides decreases from La(OH) 3 to Lu(OH) 3 .
Eu2+ (ii) Separation of lanthanoids Due to lanthanoid contraction,
La3+ there is a small difference in the size of lanthanoids. There
is the difference in some properties of lanthanoids
Ce3+ likesolubility, degree of hydration and complex formation.
Pr3+ These differences enable the separation of lanthanoids by
100 Nd3+ ion exchange method.
Pm3+
Oxidation States
Ionic radii/pm
Sm3+
Eu3+ l
In the lanthanoids, La (II) and Ln (III) compounds are
Gd3+ Tm2+ predominant species. However, occasionally +2 and +4 ions
4+ Tb 3+ Yb2+ in solution or in solid compounds are also obtained. This
Ce
Dy3+
irregularity arises mainly from the extra stability of empty,
90 Pr4+ Ho3+ half-filled or fully-filled f -subshell.
Er3+
Tm3+
e.g. Ce 4 + acts as an oxidising agent by converting into Ce 3+ ,
Tb 4+
Yb3+ whereas Eu 2+ and Yb 2+ acts as reducing agent by
Lu3+ converting into Eu 3+ and Yb 3+ respectively.
57 59 61 63 65 67 69 71
l
Pr, Nd, Tb and Dy also exhibit +4 state but only in oxides,
Atomic number MO 2 . The behaviour of samarium is very much like
Trends in ionic radii of lanthanoids europium exhibiting both +2 and +3 oxidation states.
65
Chapter
Practice
6. Although zirconium belongs to 4d-transition series
PART 1 and hafniun to 5 d-transition series even then they
show similar physical and chemical properties
Objective Questions because ............. . (NCERT Exemplar)
(a) both belong to d-block
l
Multiple Choice Questions (b) both have same number of electrons
(c) both have similar atomic radius
1. The electronic configuration of Cu(II) is 3d 9 where
(d) both belong to the same group of the periodic table
as that of Cu(I) is 3d 10 . Which of the following is
correct? (NCERT Exemplar)
7. Which of the following is a paramagnetic ion?
(a) Cu(II) is more stable (a) Zn 2+ (b) Ni 2+
(b) Cu(II) is less stable (c) Cu + (d) Ag +
(c) Cu(I) and Cu(II) are equally stable 8. Identify the configuration of transition element,
(d) Stability of Cu(I) and Cu(II) depends on nature of which shows highest magnetic moment.
copper salts
(a) 3 d 7 (b) 3 d5 (NCERT Exemplar)
2. Transition element which does not show variable (c) 3 d 8 (d) 3 d 2
oxidation state is
(a) Ti (b) V 9. Arrange the following in increasing order of number
(c) Fe (d) Zn of unpaired electrons.
3. Highest oxidation state of manganese in fluoride is I. Cu 2+ II. Cr 3+ III. Ni 2+ IV. Fe 3+
(a) I > III > II > IV (b) III > I > IV > II
+4 (MnF4 ) but highest oxidation state in oxides is
+7(Mn 2O 7 ) because (NCERT Exemplar)
(c) IV > II > III > I (d) II > IV > III > I
(a) fluorine is more electronegative than oxygen 10. The ‘spin-only’ magnetic moment [in units of Bohr
(b) fluorine does not possess d-orbitals magneton, ( m b )] of Ni 2+ in aqueous solution would
(c) fluorine stabilises lower oxidation state be (atomic number of Ni = 28)
(d) in covalent compounds, fluorine can form single bond (a) 2.84 (b) 4.90
only while oxygen forms double bond (c) 0 (d) 1.73
4. Metallic radii of some transition elements are given 11. Generally, transition elements form coloured salts
below. Which of these elements will have highest due to the presence of unpaired electrons. Which
density? (NCERT Exemplar) of the following compounds will be coloured in
Element Fe Co Ni Cu solid state? (NCERT Exemplar)
126 125 125 128 (a) Ag 2 SO4 (b) CuF2

Metallic radii/pm
(c) ZnF2 (d) Cu 2 Cl 2
(a) Fe (b) Ni (c) Co (d) Cu
12. Out of TiF62- , CoF63- , Cu 2Cl 2 and NiCl 2-
4 (at. no. of
5. Which one of the following does not correctly Ti = 22, Co = 27, Cu = 29 and Ni = 28 ), the colourless
represent the correct order of the property indicated species are
against it? (a) TiF62- and CoF63–
(a) Ti < V < Cr < Mn, increasing number of oxidation states
(b) Cu 2 Cl 2 and NiCl42-
(b) Ti 3+ < V3+ < Cr 3+ < Mn 3+ , increasing magnetic moment
(c) TiF62- and Cu 2 Cl 2
(c) Ti < V < Cr > Mn, increasing melting points
(d) Ti < V < Mn < Cr, increasing 2nd ionisation enthalpy (d) CoF63– and NiCl42-
13. Which of the following is not the characteristic 22. Assertion Separation of Zr and Hf is difficult.
property of interstitial compounds? (NCERT Exemplar) Reason Because Zr and Hf lie in the same group of
(a) They have high melting points in comparison to pure the periodic table. (NCERT Exemplar)
metals
23. Assertion La(OH) 3 is more basic than Lu(OH) 3 .
(b) They are very hard
(c) They retain metallic conductivity Reason Size of Lu 3 + ions increases along the
(d) They are chemically very reactive lanthanide series shows less covalent character.
14. Outermost electronic configuration of lanthanide is l
Case Based MCQs
(a) 4 f 1 - 14 , 5 d 0 , 6 s 2 (b) 4 f 1 - 14 , 5 d 0 - 1 , 6 s 2
(c) 4 f 0 -14 , 5 d 0 - 2 , 6 s 2 (d) 4 f 0 - 14 , 5 d1 , 6 s 2
24. Read the following and answer the questions from
15. Lanthanoid for which + II and + III oxidation states “The elements in which the last differentiating
are common
electrons enters into d-orbital of the penultimate
(a) La (b) Nd (c) Ce (d) Eu
shell, i.e. ( n - 1)d where, n is the last shell are
16. Which of the following oxidation state is common for called d-block elements”.
all lanthanoids? (NCERT Exemplar)
A transition element may also be defined as the
(a) +2 (b) +3 (c) +4 (d) +5
element which has partially filled d-orbital in their
17. Although +3 is the characteristic oxidation state for ground state or most stable oxidation state.
lanthanoids but cerium also shows +4 oxidation state
because The properties of these elements are intermediate
between the properties of s- and p-block elements.
I. it has variable ionisation enthalpy
The atomic radii of the transition metals lie in
II. it has a tendency to attain noble gas configuration
between those of s- and p-block elements. Except
III. it has a tendency to attain f 0 configuration mercury, all the transition elements have typical
IV. it resembles Pb 4+ metallic structure. They have high melting point.
(a) Only II (b) II and III (c) I and IV (d) II and IV Their first ionisation enthalpies lies between
18. As the atomic number of lanthanoid increases, the s-block and p-block elements.
atomic radius decreases, but exception is They are higher than those of s-block and are lesser
(a) Ga and Eu (b) Eu and Yb than those of p-block elements with exception of
(c) Nd and Ho (d) Dy and Ho few elements, most of the d-block elements shows
more than one oxidation state.
l
Assertion-Reasoning MCQs Thermodynamic stability of the compounds of
Direction (Q. Nos. 19-23) Each of these questions transition elements can be evaluated in terms of
contains two statements Assertion (A) and Reason (R). the magnitude of ionisation enthalpies of the
Each of these questions also has four alternative choices, metals. Most of these transition elements and their
any one of which is the correct answer. You have to select compounds have good catalytic properties. Their
one of the codes (a), (b), (c) and (d) given below. ions forms a large number of complex compounds.
(a) Both A and R are true and R is the correct (i) The atomic radii decreases less rapidly in case of
explanation of A. 3d-series because
(b) Both A and R are true, but R is not the correct (a) 4s-electrons shield 3d-electrons more effectively
explanation of A. than the other outershell electrons
(c) A is true, but R is false. (b) 3d-electrons shield 4s-electrons more effectively
(d) A is false, but R is true. than the other outershell electrons
19. Assertion Cr and Cu are extra stable elements in the (c) 3d-electrons shield 4s-electrons less effectively than
the other outershell electrons
3d-series.
(d) 4s-electrons shield 3d-electrons less effectively than
Reason Half and completely filled set of orbitals are the other outershell electrons
relatively more stable. (ii) The third ionisation enthalpy is minimum for
2+
20. Assertion Cu iodide is not known. (a) Mn (b) Ni (c) Co (d) Fe
Reason Cu 2+
oxidises I - to iodine. (NCERT Exemplar) (iii) Four successive members of the first series of the
transition metals are listed below. For which one
21. Assertion The highest oxidation state of osmium is +8 . of them, the standard potential (E M°
2+ ) value
/M
Reason Osmium is a 5d-series element.(NCERT Exemplar) has a positive sign?
(a) Co (Z = 27) (b) Ni ( Z = 28) Or E ° ° 3+ 2 +

> E Cr
Mn 3+ / Mn 2 + / Cr
(c) Cu ( Z = 29) (d) Fe ( Z = 26)
This trend is found because
(iv) Cuprous ion is colourless, while cupric ion is
(a) Mn 2 + can be easily oxidised to Mn 3+ due to low
coloured because ionisation enthalpy
(a) both have unpaired electrons in the d-subshell (b) third IE of Mn is much larger due to its stable
(b) cuprous ion has a complete d-subshell and cupric configuration
ion has an incomplete d-subshell (c) Mn 3+ is more stable than Mn 2 + due to its higher
(c) both have half-filled p- and d-subshell oxidation state
(d) cuprous ion has incomplete d-subshell and cupric (d) second IE of Mn is higher than its third IE
ion has a complete d-subshell
Or
The value of EM° 2+ / M for which of the following PART 2
transition elements are more negative than
expected?
Subjective Questions
(a) Cr, Mn and Zn (b) Mn, Ni and Zn
(c) V, Mn and Cu (d) Fe, Co and Ni
l
25. Read the following and answer the questions from (i) 1. Name the two transition elements which have
to (iv) given below abnormal electronic configuration and explain why?
The elements which have incompletely filled d-orbitals 2. Explain, why density of transition elements increases
in its ground state or in any of its oxidation state are from left to right in a period?
called d-block elements. (transition elements). 3. Why do transition elements show variable oxidation
As zinc (Zn), cadmium (Cd), mercury (Hg) of group 12 states?
have full d 10 -configuration it their ground state as well (i) Name the element showing maximum number of
as in their common oxidation states, thus they are not oxidation states among the first series of transition
regarded as transition metals, but they are studied metals from Sc ( Z = 21) to Zn ( Z = 30 ).
along with the chemistry of the transition metals. (ii) Name the element which shows only +3 oxidation
state. (Delhi 2020)
Various precious metals like silver, gold and platinum
and industrially important metals like iron, copper and
4. Explain briefly how + 2 state becomes more and more
stable in the first half of the first row transition
titanium form part of the transition metals.
elements with increasing atomic number?
(i) Ground state configuration of element having atomic (NCERT Exemplar)
number = 24 is 3d 5 4s 1 . This is because,
(a) the energy of 3d and 4 s-orbitals is very low
5. Why E° values for Mn, Ni and Zn are more negative
than expected?
(b) 3d and 4s-orbitals are of comparable energy
(c) energy of 3d-orbital is lower than the energy of 6. Explain the following
4s-orbital (i) The second and third rows of transition elements
(d) Energy gap between third and fourth shell is very small resemble each other much more than they resemble
(ii) The filling of 4 f before 5 d-orbital results in a the first row. (NCERT Exemplar)
regular decrease in atomic radii called (ii) Copper can not replace hydrogen from acids.
(a) lanthanoid contraction (NCERT Exemplar)
(b) shielding effect 7. Observed and calculated values for the standard
(c) actinoids contraction electrode potentials of elements from Ti to Zn in the
(d) None of the above first reactivity series are depicted in figure
(iii) The transition element which does not exhibit 0.5
Standard electrode potential/V
variable oxidation states is

0
(a) titanium (b) scandium
(c) copper (d) zinc –0.5
(iv) Which of the following ions will exhibit colour in
–1
aqueous solutions?
3+
(a) Sc ( Z = 21 ) –1.5
(b) La 3+ ( Z = 57)
–2
(c) Ti 3+( Z = 22) Ti V Cr Mn Fe Co Ni Cu Zn
(d) La 3+ ( Z = 71 ) Observed values Calculated values
Explain the following observations (iii) Zn, Cd and hg are quite soft and have low melting
(i) The general trend towards less negative E° values points. (Delhi 2020)
across the series. 17. (i) Consider the hydrated ions of Ti 2+ , V 2+ , Ti 3+ and
(ii) The unique behaviour of copper. Sc 3+ . Write the correct order of their spin-only
(iii) More negative E° values of Mn and Zn. magnetic moment
(ii) What are misch metal?
8. Explain the following observations.
(i) Copper atom has completely filled d-orbitals ( 3 d 10 ) 18. Give reasons for the following
in ground state, yet it is regarded as a transition (i) Transition metals form alloys.
element. (ii) Eu 2+ is a strong reducing agent.
(ii) Cr 2+ is a stronger reducing agent than Fe 2+ in
19. What are inner-transition elements? Describe which
aqueous solution .
of the following are the atomic numbers of the
9. Calculate the number of unpaired electrons in the inner-transition elements : 29, 59, 74 ?
following gaseous ions Mn 3+ , Cr 3+ , V 3+ and Ti 3+.
20. Given reason
Which one of these is the most stable in aqueous
(i) Although Zr belongs to 4d and Hf belongs to 5 d
solution? (NCERT Exemplar)
transition series but it is quite difficult to separate
10. Use Hund’s rule to derive the electronic them. (NCERT Exemplar)
configuration of Ce 3+ ion and calculate its magnetic (ii) Although +3 oxidation states is the characteristic
moment on the basis of ‘spin only’ formula. oxidation state of lanthanoids but cerium shows +4
(NCERT Exemplar) oxidation state also. Why? (NCERT Exemplar)
11. Calculate the ‘spin only’ magnetic moment of
M 2+ ( aq) ion. ( Z = 27) (NCERT Exemplar)
l
Long Answer (LA) Type Questions
12. (i) Calculate the magnetic moment of a divalent ion in 21. Account for the following.
aqueous solution [Fe(H 2O) 6 ] 2+, if atomic number (i) Mn 2+ is more stable than Fe 2+ towards oxidation to
of Fe is 26. +3 state.
(ii) Although fluorine is more electronegative than (ii) The enthalpy of atomisation is lowest for Zn in
oxygen, but the ability of oxygen to stabilise higher 3d-series of the transition elements.
oxidation states exceeds that of fluorine. Why? (iii) Identify the metal in MO 3 F and justify your answer.
(iii) Although Cr 3+ and Co 2+ ions have same number of (iv) The E° value for the Mn 3+ / Mn 2+ couple is much
unpaired electrons but the magnetic moment of more positive than that for Cr 3+ / Cr 2+ couple.
Cr 3+ is 3.87 BM and that of Co 2+ is 4.87 BM. Give (v) Transition metals form a large number of complexes.
reason.
22. (i) Answer the following questions
13. Give reasons (a) Which element of the first transition series has
(i) E° value for Mn 3 + / Mn 2 + couple is much more highest second ionisation enthalpy?
positive than that for Fe 3 + / Fe 2 + . (b) Which element of the first transition series has
(ii) Iron has higher enthalpy of atomisation than that of highest third ionisation enthalpy?
copper. (c) Which element of the first transition series has
(iii) Sc 3 + is colourless in aqueous solution whereas lowest enthalpy of atomisation?
Ti 3 + is colured. (CBSE 2018) (ii) Identify the metal and justify your answer.
14. Predict which of the following will be coloured in Carbonyl M(CO)5
aqueous solution? (iii) Although F is more electronegative than O, the
highest fluoride of Mn is MnF4 , whereas the
Ti 3+ , V 3+ , Cu + , Sc 3+ , Mn 2+ , Fe 3+ and Co 2+. Give highest oxide is Mn 2O 7 . Give reason.
reasons for each. (NCERT Exemplar)
15. (i) Why Zn 2+ salts are white while Ni 2+ salts are blue? 23. Explain giving reasons.
(i) The enthalpies of atomisation of the transition
(ii) Out of [Sc(H 2O) 6 ] 3+ and [Ti(H 2O) 6 ] 3+ ions, which
metals are high.
is coloured and why? (ii) Transition metals and many of their compounds
16. Give reasons for the following show paramagnetic behaviour.
(i) Iron is a transition metal while sodium is not. (iii) The transition metals generally form coloured
(ii) Cd 2+ salts are white. compounds.
(iv) Transition metals and their many compounds act as Cd, Hg and Mn, they have one or more typical
good catalyst. metallic structures at normal temperature.
(v) Ni 2 + is more stable than Pt 2 + whereas Pt 4 + is Transition metals shows a great variety of oxidation
more stable than Ni4 + . (NCERT Exemplar) (Delhi 2020) states in its compounds, except few elements. The
24. (i) Name a compound of elements, which give the greatest number of
(a) transition metal which is used in the oxidation states occur in or near the middle of the
manufacture of sulphuric acid. series. Stability of higher oxidation states increases in
(b) transition metal which is used in Haber’s
a group form top to bottom due to increase in the
process for the manufacture of ammonia. distance from the outermost shell.
(c) transition metal that has light sensitive (i) Why are Mn 2+ compounds more stable than Fe 2+
properties and act as valuable source in towards oxidation to their +3 state?
photographic industry. (ii) Why is the highest oxidation state of a metal
(ii) Reactivity of transition elements decreases almost exhibited in its oxide or fluoride only?
regularly from Sc to Cu. Explain. (NCERT Exemplar) (iii) Explain, why Cu + ion is not stable in aqueous
25. Mention the type of compounds formed when small solution?
atoms like H, C and N get trapped inside the crystal (iv) Which metal in the first series of transition metals
lattice of transition metals. Also give physical and exhibit + 1 oxidation state most frequently and why?
chemical characteristics of these compounds. Or
(NCERT Exemplar) 3+
Explain why Mn is a good oxidising agent?
26. (i) (a) Which transition element in 3d series has positive 29. Read the following and answer the questions from (i)
E °M 2 + / M value and why?
to (iv) given below
(b) Name a member of lanthanoid series which is well
known to exhibit +4 oxidation state and why? The d-block occupies the large middle section
(ii) Given reason for the following observations. flanked between s- and p-blocks in the periodic table.
(a) The highest oxidation state is exhibited in oxonions The name ‘transition’ given to the elements of
of transition metals. d-block is only because of their position between s-
(b) Transition elements show high melting points. and p-block elements.
(c) First ionisation enthalpy of Cr is lower than that of The d-orbitals of the penultimate energy level in
Zn? their atoms receive electrons giving rise to the three
27. On the basis of lanthanoid contraction, explain the rows of the transition metals, i.e. 3d, 4d, and 5d. The
following fourth row of 6d is still incomplete. First transition
(i) Nature of bonding in La 2O 3 and Lu 2O 3 . series or 3d-series: Scandium (Sc) to Zinc (Zn).
(ii) Trends in the stability of oxo salts of lanthanoids Second transition series or d-series: to cadmium (Cd).
from La to Lu. Third transition series or 5d-series: Lanthanum (La).
(iii) Stability of the complexes of lanthanoids. to Mercury (Hg). Excluding Ce to Lu
(iv) Radii of 4d and 5 d-block elements. Fourth transition series or 6d-series: Actinium (Ac)
(v) Trends in acidic character of lanthanoid oxides. to Copernicium (Cu) excluding Th to Lr.
(i) Name the element which shows outer electronic
l
Case Based Questions configuration 3 d 2 4 s 2 .
28. Read the following and answer the questions from (i) (ii) Silver atom has completely filled d-orbitals ( 4 d 10 ) in
to (iv) given below its ground state. How can you say that it is a
transition element?
General electronic configuration of transition metals
is ( n - 1)d 1 - 10 n 1 s - 2 , where n the outermost shell (iii) In the series Sc (Z = 21) to Zn (Z = 30 ), the enthalpy
which may have one or two electrons, whereas ( n - 1) of atomisation of zinc is lowest, i.e. 126 kJ mol -1 .
stands for the inner d-orbitals which may have one to Why?
ten electrons. (iv) Which transition metal of the 3d-series exhibits the
Transition elements display typically metallic largest number of oxidation states and why?
property such as high tensile strength, ductility, Or
The E Mo value of copper is positive (+ 0.34 V).
malleability and lustre. With the exceptions of Zn, 2+
/M
What is the possible reason for this?
EXPLANATIONS
Objective Questions 10. (a) Ni 2+ = [Ar] 3d 8
1. (a) Cu(II) is more stable than Cu(I). As it is known that,
Cu(I) has 3 d10 stable configuration while Cu(II) has 3 d 9 Number of unpaired electrons = 2
configuration. But Cu(II) is more stable due to greater
effective nuclear charge, i.e. it holds 17 electrons instead of Hence, magnetic moment of Ni 2 + in aqueous solution
18 in Cu(I). m = n( n + 2) = 8 = 2.84 BM
2. (d) Due to completely filled d-orbital Zn shows only + 2 11. (b) Transition elements form coloured salt due to the
oxidation state. presence of unpaired electrons. In CuF2 , Cu(II) contain one
3. (d) Highest oxidation state of manganese in fluoride is unpaired electron hence, CuF2 is coloured in solid state.
+4 (MnF4 ) but highest oxidation state in oxides is +7(Mn 2O 7 ). 12. (c) Oxidation state of Ti in TiF62- = Ti +4
The reason is that in covalent compounds fluorine can form
= [Ne]3 s 2 3p6 (no unpaired electrons)
single bond while oxygen forms double bond.
4. (d) On moving left to right along period, metallic radius Oxidation state of Cu in Cu 2Cl 2 = Cu +
decreases while mass increases. Decrease in metallic radius = [ Ar ] 3d10 (no unpaired electron)
coupled with increase in atomic mass results in increase in
density of metal. \ Both are colourless species as they do not have unpaired
electrons.
Hence, among the given four choices Cu belongs to right
side of periodic table in transition metal, and it has highest 13. (d) Interstitial compounds are formed when small atoms are
density (89 g/cm 3). trapped inside the crystal lattice of metals. Some of their
important characteristics are as follows
5. (c) The correct order of melting point is Ti < V < Cr > Mn.
(i) They are very hard and rigid.
The melting point of transition elements first increases to a (ii) They have melting point which are even higher than
maximum extent and then fall as atomic number those of the pure metals.
increases. Mn, however, has abnormally low melting
point, due to stable configuration and weak intermetallic (iii) They show conductivity like that of the pure metal.
bonding. (iv) They acquire chemical inertness.
6. (c) Due to lanthanoid contraction, Zr and Hf possess 14. (b) Lanthanoids exhibit 4 f 1 - 14 , 5 d 0 - 1, 6s 2 electronic
nearly same atomic and ionic radii, i.e. Zr = 160 pm and configuration.
Hf = 159 pm, Zr 4+ = 79 pm and Hf 4+ = 78 pm. Therefore, 15. (d) Lanthanoids are f -block elements starting from Ce(58) to
these two elements show similar properties (physical and
Lu(71).
chemical properties).
7. (b) Elements Atomic number Oxidation state
Zn2+ = [Ar] 3d10 (0 unpaired electron) La 57 +3
Ce 58 + 3, + 4
Ni2+ = [Ar] 3d8 (2 unpaired electrons)
Nd 60 + 2, + 3, + 4
Cu+ = [Ar] 3d10 (0 unpaired electron) Eu 63 + 2, + 3
Thus, for Eu common oxidation states are + 2 and + 3. Nd

Ag+ = [Kr] 4d10 (0 unpaired electron) also exhibits + 2 and + 3 oxidation state but + 3 is its
common oxidation state.
Thus, due to presence of two unpaired electrons Ni2 + is
paramagnetic ion. 16. (b) Lanthanoids show common oxidation state of +3. Some of
which also show +2 and +4 stable oxidation state alongwith
8. (b) Greater the number of unpaired electron, higher will be +3 oxidation state.These are shown by those elements which
the value of magnetic moment. on losing 2 or 4 electrons acquire a stable configuration of
2+ 7 2+ 14 4+
Since, 3 d 5 has 5 unpaired electrons hence highest magnetic f 0 , f 7 or f 14 . e.g. Eu is [Xe] 4 f , Yb is [ Xe] 4 f , Ce is
moment. 0 4+ 7
[Xe]4 f and Tb is [Xe]4 f .
m = 5( 5 + 2) = 35 = 5.95 BM
17. (b) Electronic configuration of 58Ce = 54 [Xe] 4 f 2 5 d 0 6 s 2 .
9. (c) I. Cu 2+ - 3d 9 4 s0 (Number of unpaired electrons 1)
II. Cr 3+ - 3d 3 (Number of unpaired electrons 3) Therefore, electronic configuration of Ce4+ = 54 [Xe] 4 f 0 .
III. Ni 2 + - 3d 8 (Number of unpaired electrons 2) Thus, it has a tendency to attain noble gas configuration and
IV. Fe3+ - 3d5 (Number of unpaired electrons 5) attain f 0 configuration.
So, the correct order of number of unpaired electrons is 18. (b) In Eu and Yb as atomic number increases atomic radius
IV > II > III > I. increases, which is an exception.
19. (a) Both A and R are true and R is the correct explanation of A. Therefore, it must have positive sign for standard
Half and completely filled set of orbitals are relatively more potential [EM° 2+ /M ].
stable. Thus, electronic configuration of Cr is 3 d5 4s1 instead
of 3 d 4 4s 2, the energy gap between the two sets (3d and 4s ) of (iv) (b) Cu (Z = 29) : [Ar]18 4s1 3 d10
orbitals is small enough to prevent electron entering the Cu + (cupric ion) = [Ar]18 3 d 10
3d-orbitals. Similarly, in the case of Cu, the configuration is Cu 2+ (cuprous ion) = [Ar]18 3d 9
3 d10 4s1 and not 3 d 9 4s 2 .
Cu + has completely filled d-subshell, while Cu 2+ has
20. (a) Both A and R are true and R is the correct explanation of A.
Copper (II) iodide (CuI2 ) is not known because Cu 2+ oxidises incomplete d-subshell. Thus, Cu + (cuprous) is
I- to iodine. colourless and Cu 2+ (cupric) is blue.
21. (a) Both A and R are true but R is not the correct explanation Or
of A. (b) The value of E° for Mn, Ni and Zn are more
The highest oxidation state of osmium is +8 due to its ability negative than expected from the trend. The stability of
to expand their octet by using all its 8 electrons (2 from 6s the half-filled d-subshell in Mn 2 + and the completely
and 6 from 5 d). filled d10 -configuration in Zn 2 + are related to their E°
values, whereas E° for Ni is related to the highest
22. (b) Both A and R are true but R is not the correct
negative D hyd H °.
explanation of A.
Separation of Zr and Hf is difficult; it is not because of they 25. (i) (b) One electron in case of atomic number 24, moves
lie in the same group of periodic table. It is due to from 4s to 3d-orbital to achieve more stability. This is
lanthanoid contraction which causes almost similar radii of because, energy of 3d and 4s-orbitals are of comparable
both of them. energy.
23. (c) A is true, but R is false. (ii) (a) The filling of 4 f -orbital before 5 d-orbital results in a
regular decrease in atomic radii called lanthanoid
Due to lanthanoid contraction, the size of Lu 3 + is decreases, contraction which essentially compensates for the
then covalent character of hydroxides increases and hence expected increase in atomic size with increasing atomic
the basic strength decreases. Thus, La(OH)3 is more ionic number.
and thus, more basic.
(iii) (b) Among the given elements, Sc and Zn do not show
24. (i) (b) As we move along the period in a 3d-series, nuclear variable oxidation state but Zn is not a transition
charge increases from Sc to Zn but electrons are added element.
to the orbital of inner subshell, i.e. 3d-orbitals. These
(iv) (c) Electronic configuration of Ti 3+ is 3d 1 , thus, Ti 3+
3d-electrons shield the 4s-electrons from the increasing
contains an unpaired electron, so it will exhibit colour
nuclear charge more effectively than the outershell
in aqueous solution due to d -d transition.
electrons can shield one another.
Therefore, the atomic radii decreases less rapidly in Or
case of 3d-series. (b) Third ionisation enthalpy of Mn is much larger
(ii) (d) Fe has minimum value of third ionisation enthalpy. because configuration of Mn 2+ (3d 5 ) is stable and a
Ground state electronic configuration of Fe is large amount of energy is required to convert it into
[Ar]3d 6 4s 2 . less stable Mn 3+ (3d 4 ).
Fe2 + has [Ar ]3d 6 configuration, whereas Fe3+ has Subjective Questions
[Ar ]3d5 . The latter is a stable configuration and easier 1. Some of the exceptions are observed in electronic
to ionise Fe2 + to Fe3+ than expected. Hence possess least configuration due to very little energy difference between
value. ( n - 1 ) d and ns orbitals such as
Ni has highest value of third ionisation enthalpy due to Cr : 3d 5 4s1 instead of 3d 4 4s 2
its greater nuclear charge and smaller size. Cu : 3d10 4s1 instead of 3d 9 4s 2
Due to the same reason, Co > Fe > Mn should be the
order for the remaining elements, but the anomalous This can be explained on the basis of electronic repulsion
order is due to greater stability of Mn 2 + having [Ar ]3d5 and energy exchange which proves that half-filled and
completely filled d-orbital are more stable configuration.
configuration than Mn 3+ with [Ar ]3d 4 .
In the transition elements, the d-orbitals project to the
Whereas for Co2 + , the electronic configuration is
periphery of an atom more than the other orbitals (i.e. s and p).
[Ar ]3d 7 , Thus, ionisation enthalpy needed to Thus, they are more influenced by the surroundings as well as
remove third electron is less as compared to that affecting the atoms or molecules surrounding them.
of Mn 2+ .
2. While going from left to right in a period, the radii of
(iii) (c) In electrochemical series, metals with positive
transition metals remains similar but their atomic masses
standard potential are placed below hydrogen. Out of
increases gradually. As a result their density increases
given transition metals, only Cu is placed below
correspondingly.
hydrogen in electrochemical series.
3. Transition elements show variable oxidation state due to

their ability of utilising single or multiple 4s and 3d V3+ ( Z = 23) = [ Ar] 3d 2
electrons.
(i) Mn (manganese) shows the maximum number of
oxidation states. Ti 3+ ( Z = 22) = [Ar] 3d1
(ii) Scandium shows only +3 oxidation state. Cr 3 + is the most stable among these in aqueous solution
4. Elements (+ 2 state) 21 Sc
2+
, 22 Ti 2+
, 23 V 2+
, 24 Cr 2+ because it has half-filled t 2 g level ( = t 23 g ).
2+
and 25 Mn have more stable +2 oxidation state and the
10. Ce ( Z = 58) = [ Xe] 4 f 1 5 d16s 2
outer electronic configuration are 3d1, 3d 2 , 3d 3, 3d 4 and 3d5
Ce3 + = 54[Xe] 4 f 1(only one unpaired electron), i.e. n = 1
respectively. In all the elements listed, the removal of two 4s
electrons (in Cr 2 + , 1 e - from 4s and 1 e - from 3d), the According to ‘spin-only’ formula,
3d-orbitals get gradually occupied. Since, the number of Magnetic moment of Ce3+ (m ) = n ( n + 2) BM
empty d-orbitals decreases or the number of unpaired
electrons in 3d-orbitals increases with increase in atomic = 1 (1 + 2) BM = 3 BM = 1.73 BM
number of cations, so the stability of the cations (M 2+ ) 11. Magnetic moment ( m ) = n( n + 2) BM
increases from Sc 2 + to Mn 2 +.
of M (27) =[ Ar ] 3d 7 4s 2
2+ 2+
5. Negative values of Mn and Zn are related to stabilities
Fe2 + =[ Ar ] 3d 7 4s 0
of half-filled and completely filled configuration
respectively. But for Ni 2+, E° value is related to the highest m = n( n + 2)
negative enthalpy of hydration. = 3( 3 + 2) = 15
Hence, E s values for Mn, Ni and Zn are more negative than
= 3.8 BM
expected.
12. (i) Magentic moment ( m ) = n( n + 2) BM
6. (i) Due to lanthanoid contraction, the atomic radii of the
second and third rows of transition elements is almost Atomic number of Fe = 25 =[Ar] 3d 6 4s 2
same. Fe2 + = [Ar] 3d 6 4s 0
So, they resemble each other much more as
compared to first row elements and show similar
characteristics. So, m = n( n + 2) = 4( 4 + 2) = 24 = 4.89 BM
(ii) Copper cannot replace hydrogen from acids because
(ii) Oxygen can form multiple bonds with metals, while
Cu has positive E° value, i.e. less reactive than
fluorine can not form multiple bond with metals. Hence,
hydrogen which has electrode potential 0.00V.
oxygen has more ability to stabilize higher oxidation state
7. (i) The general trend towards less negative E°V values rather than fluorine.
across the series is related to the general increase in the (iii) Magnetic moment of any metal ion can be decided on
sum of the first and second ionisation enthalpies. the basis of spin as well as orbital contribution of
(ii) The high energy to transform Cu(s) to Cu 2 + (aq) is not electron. Due to symmetrical electronic configuration,
balanced by its hydration enthalpy. there is no orbital contribution in Cr 3+ ion. However,
Most of Cu (I) compound are unstable in aqueous appreciable orbital contribution takes place in Co2+ ion.
solution and undergo disproportionation. 13. (i) Mn 2 + compounds are more stable due to half-filled
2Cu+ ¾® Cu 2+ + Cu d-orbitals. Fe 2 + compounds are comparatively less stable
(iii) The stability of the half-filled d-subshell in Mn 2 + and as they have six electrons in their orbitals. So, they
the completely filled d10 configuration in Zn 2 + are tend to lose one electron from Fe 2 + and get stable 3d 5
related to their more negative E° V values. configuration in Fe 3 + .
8. (i) Because it has incompletely filled d-orbitals in one of Therefore, comparatively high positive value of E° for
its oxidation states, i.e. Cu 2 + ([ Ar ] 3d 9 ). Mn 3 + / Mn 2 + indicates the stability of Mn 2 + ( d5 ) whereas
comparatively low value for Fe 3 + / Fe 2 + indicates the extra
(ii) Cr 2 + ([Ar] 3d 4 ) changes to Cr 3+ ([ Ar ] 3d 3 ) while Fe2 +
stability of Fe 3 + ( d5 ).
([ Ar ] 3d 6 ) changes to Fe3+ ([Ar] 3d 5 ).
(ii) Energy required to convert metallic crystal into individual
In aqueous medium, the configuration [Ar] 3d 3 is more atom is enthalpy of atomisation. In transition row
stable than the configuration [Ar] 3d5 . Hence, Cr 2 + is a elements, it first increases and reaches to maximum upto
stronger reducing agent. middle element and then decreases. This is because of
strong inter atomic interaction due to unpaired electron.
9. Mn 3 + ( Z = 25 ) = [ Ar] 3d 4 Greater the number of unpaired electron, stronger will
be bonding and thus enthalpy of atomisation will also be
more. Since iron has more unpaired electron than copper
Cr 3 + (Z = 24) = [Ar] 3d 3
therefore its enthalpy of atomisation is more.
(iii) The metal ions with partially or incomplete Z n M Nature

Metal ion
filled d-orbitals will be coloured in aqueous (for metal ion) (BM)
solution. While the metal ions having either empty
or completely filled d-orbitals are colourless. Ti 2 + 22 2 (3d 2 ) 8 Paramagnetic
The colour will be due to d-d transition of electrons. V2 + 23 3 ( 3d 3 ) 15 Paramagnetic
Thus, the outer electronic configuration of metal ions
3+ 1
are Sc 3 + : 3d 0 , Ti 3 + : 3d1 Ti 22 1 ( 3d ) 3 Paramagnetic
Hence, among the given ions, Ti 3 + will exhibit colour Sc3+ 21 0 ( 3d 0 ) 0 Diamagnetic
in aqueous solution while Sc 3 + will be colourless.
14. Only those ions will be coloured which have incomplete Thus, the correct order of spin only magnetic moments
d-orbitals. Ions which has complete or vacant d-orbitals are of given hydrated ions will be
colourless. Sc3+ < Ti 3+ < Ti 2 + < V2 + V2 +
Ti 3 + = [Ar] 3d 1 Purple (ii) Misch metal is an alloy which consists of a lanthanoid
3+ 2 metal (~ 95%) iron (~5%) and traces of S, C, Ca and Al.
V = [Ar] 3d Green
It is used in Mg based alloy to produce bullets, shell
+ 10
Cu = [Ar] 3d Colourless and lighter-flint.
3+ 18. (i) Atoms of transition metal can easily take place in the
Sc = [Ar] Colourless
crystal lattice of another metal in the molten state and
Mn 2 + = [Ar] 3d 5 Pink are miscible with each other and thus forms alloys.
Fe 3+
= [Ar] d 5
Brown (ii) Eu 2 + having electronic configuration [Xe]4 f 7 is a
2+ 7 strong reducing agent because in the aqueous solution,
Co = [Ar] 3d Pink
it events back to the most stable +3 oxidation.
As Sc 3+ and Cu + have 3d 0 and 3d 0 configuration in their 19. Inner-transition elements inner transition elements (or
valence shell so their aqueous solutions are colourles. All f -block elements) include lanthanoids (Z = 58 to 71) and
other, i.e. Ti 3+ , V 3+ , Mn 2 + , Fe3+ and Co2+ are coloured in actinoids ( Z = 90 to 103). These elements have incomplete
aqueous medium. f -orbital in penultimate shell of their atoms.
The electronic configuration of given atomic number are as
15. (i) Electronic configuration of Zn 2 + = 3d10 4s 0
¼ ¼ ¼ ¼ ¼ 29 = [Ar] 4s1 3d10 (d-block element or transition element).
¼ ¼ ¼ ¼ ¼
59 = [Ar] 6s1 4 f 3 (d-block element or inner transition element).
Electronic configuration of Ni 2 + = 3d 8 4s 0
¼ ¼ ¼ 74 = [ Xe] 6s 2 4 f 1 3d 3 (d-block element or inner transition
¼ ¼ ¼ ¼ ¼ element).
Compounds that contains unpaired electrons are 20. (i) Separation of Zr and Hf are quite difficult because of
coloured. lanthanoid contraction. Due to lanthanoid contraction,
(ii) Out of [Ti(H2O) 6 ] 3 + and [Sc(H2O) 6 ] 3+ , latter is they have almost same size (Zr = 160 pm and
colourless because it cannot undergo d-d transition as Hf = 159 pm) and thus, similar chemical properties.
do not have unpaired electrons. [Ti(H2O) 6 ] 3 + has That’s why it is very difficult to separate them by
unpaired electron for d-d transition which is chemical methods.
responsible of colourness of a complex. (ii) It is due to the fact that after losing one more electron
16. (i) This is because iron has unpaired electrons in the Ce acquires stable 4 f 0 electronic configuration. So, Ce
d-subshell while sodium does not. shows +4 oxidation state along with +3 oxidation state.
(ii) This is because Cd 2 + ion has completely filled 21. (i) Electronic configuration of Mn 2 + = [ Ar ]18 3d5
d-orbitals ( 4d10 ). Hence, in the absence of d-d
Electronic configuration of Fe 2 + = [ Ar ]18 3d 6
transition, they show only white colour.
(iii) Zn, Cd, Hg metals have completely filled d-orbitals Mn 2 + having half-filled d-orbitals will be more stable
( d10 ). It means that d-electrons are not readily available than Fe 2 + , as it has partially filled d-orbitals.
for metallic bond formation. Since, the metallic bonds (ii) Zinc has completely filled d-orbitals, which limits its
are weak. Therefore, these metals are quite soft and tendency to form metallic bonds. Thus, it requires least
also have low melting points. enthalpy to get atomised.
(iii) MO3F is MnO 3 F.
17. (i) The spin only magnetic moment ( m ) of each ion can be
calculated as In MO3F,
m = n ( n + 2) BM Let the oxidation state of M in x.
[Q n = No. of unpaired electron(s)] Þ m µ n, i.e. higher x + 3 ´ ( - 2) + ( - 1 ) = 0
the number of unpaired electron, higher will be the or, x = + 7, i.e. M is in oxidation state of +7. Hence, the
value of m. given compound is MnO 3 F.
(iv) E°Cr 3 + / Cr 2 + is negative (–0.4 V). It shows the stability (v) Ni 2 + compounds have the sum of first two ionisation
enthalpies to be lower than that of Pt 2 + compounds and
of Cr 3+ ions i.e. Cr 3+ in solution cannot be reduced to are thermodynamically stable. However, the sum of
Cr 2 + ions. Mn 3+ has high positive value of E° due to first four IEs of Pt 4 + is lower than that of first four IEs
extra stability of half-filled electronic configuration. of Ni 4 + and is relatively stable.
Thus, Cr 3+ is the most stable, Mn 3+ is least stable.
24. (i) (a) Vanadium, (b) Iron, (c) Silver
(v) Transition elements form a large number of complexes
due to the comparatively smaller sizes of the metal ions, (ii) Reactivity of transition elements depends mostly upon
their high conic charges and the availability of their ionisation enthalpies. As we move from left to
d-orbitals for bond formation. right in the periodic table (Sc to Cu), ionisation
enthalpies increase almost regularly.
22. (i) (a) Cu, because the electronic configuration of Cu is
Hence, their reactivity decreases almost regularly from
3d10 4s1. So, second electron needs to be removed
Sc to Cu.
from completely filled d-orbital which is very
difficult. 25. When small atoms like H, C and N get trapped inside the
crystal lattice of transition metals.
(b) Zinc, because of electronic configuration of
Zn = 3 d10 4s 2 and Zn 2 + = 3 d10 which is fully filled (i) Such compounds are called interstitial compounds.
and hence is very stable. Removal of third electron (ii) Their characteristic properties are
requires very high energy. (a) They have high melting points, higher than those of
pure metals.
(c) Zinc, because of it has completely filled 3d subshell
(b) They are very hard.
and no unpaired electron is available for metallic
bonding. (c) They retain metallic conductivity.
(d) They are chemically inert.
(ii) Carbonyl M(CO)5 is Fe(CO)5 .
According to EAN rule, the effective number of a metal 26. (i) (a) Copper; Due to high D aH ° and low D hyd H °
in a metal carbonyl is equal to the atomic number of (b) Cerium; Due to stable 4 f 0 configuration/Tb; Due
nearest inert gas EAN is calculated as
to stable 4 f 7 configuration
EAN = number of electrons in metal +2 ´ (CO)
(ii) (a) Due to ability of oxygen to form multiple bond to
= atomic number of nearest inert gas
metal.)
In M(CO)5 = x + 2 ´ ( 5 ) = 36 (Kr is the nearest inert (b) Transition elements show high melting point, due
gas) to involvement of greater number of electrons in
x = 26 (atomic number of metal) the interatomic bonding from ( n - 1 ) d-orbitals in
So, the metal is Fe(iron). addition to ns electrons in forming metallic bond.
Thus, large number of electrons participate
(iii) It is because oxygen can form multiple bonds, whereas
forming large number of metallic bond.
fluorine can only form single bonds with metals.
(c) Ionisation enthalpy of Cr is less than that of Zn
23. (i) Energy required to convert metallic crystal into
because Cr has stable d 5 configuration. In case of
individual atom is known as enthalpy of atomisation. The
zinc, electron comes out from completely filled
transition metals have high enthalpy of atomisation.
4s-orbital. So, removal of electron from zinc requires
It first increases, reaches to the maximum in the more energy as compared to the chromium.
middle of each series and then decreases. It can be
explained on the basis of strong interatomic interaction 27. (i) As the size decreases covalent character increases.
due to unpaired electrons. Greater the number of Therefore, La 2O 3 is more ionic and Lu 2O 3 is more
unpaired electrons, stronger is the resultant bonding. covalent.
(ii) Paramagnetic behaviour arises due to presence of (ii) As the size decreases from La to Lu, stability of oxo
unpaired electrons in d-subshell. salts also decreases.
(iii) Most of the compounds of transition metals are (iii) Stability of complexes increases as the size of
lanthanoids decreases.
coloured due to d-d transition. Transition metal ions
having d 0 configuration are colourless. When ligand has (iv) Radii of 4d and 5 d-block elements will be almost same.
free electrons, the transfer of electron from atom to (v) Acidic character of oxides increases from La to Lu.
cation takes place. In this case, energy is absorbed 28. (i) Mn 2 + compounds are more stable due to half-filled
during this process which is responsible for colour. d-orbitals. Fe 2 + compounds are comparatively less
(iv) Catalytic activity of transition metal is due to their stable as they have six electrons in their orbitals. So,
ability to adopt multiple oxidation states and to form they tend to lose one electron from Fe 2 + and get stable
complexes. Transition metals because of their variable 3d5 configuration.
valencies sometimes form unstable intermediate (ii) Oxygen and fluorine both have small size and high
compounds and provide a new path with lower value of electronegativity. So, they can oxidise the metal
activation energy for the reaction. to their highest oxidation states.
(iii) In aqueous solution, copper (I) undergoes 29. (i) Titanium

disproportionation reaction. (ii) Silver in its + 1 oxidation state, exhibits 4d 10 5 s 0
2Cu + ( aq ) ¾® Cu 2 + + Cu (s ) configuration. But in some compounds, it also shows
+2 oxidation state, so the configuration becomes 4d 9 5 s 0 .
The highest stability of Cu 2 + ion in aqueous solution is
Here, d-orbital is not completely filled. Therefore, silver
due to negative enthalpy of hydration.
is a transition element.
Hence, Cu + is not known (or unstable) in aqueous
solution. (iii) Zinc has stable ground state due to its completely filled
d-orbitals. It therefore, has least tendency to form
(iv) Electronic configuration of Cu is [Ar] 3d 10 4s1. When metallic bonds, in the series, thus requires least enthalpy
copper atom loses 1 electron, it exhibits + 1 oxidation of atomisation to get atomised.
state and forms Cu + ion with stable 3d10 configuration. (iv) Manganese shows maximum number of oxidation states
So, copper metal in the first transition series tends to ( EC : 3d 5 , 4s 2 ), i.e. + 2, + 3, + 4, + 5, + 6, + 7 in its
have + 1 oxidation state to achieve a stable compounds due to maximum number of unpaired
configuration. electrons.
Or Or
3+ 2+
Mn /Mn has large positive E° value. Hence, o
EM 2+ value of copper is positive as value of hydration
Mn 3+ can be easily reduced to Mn 2 + because Mn 2 +
/M
has half-filled electronic configuration, so it is stable enthalpy is less than the sum of values of ionisation
enthalpy and enthalpy of ionisation.
and Mn 3 + is least stable. Therefore, it is a good
oxidising agent.
Chapter Test
Multiple Choice Questions 7. Assertion Cr 2+ is reducing, while Mn 3+ is oxidising even
1. Which of the following elements does not have though both have d 4 -configuration.
( n - 1 ) d 10 ns2 electronic configuration? Reason Configuration of Cr changes from d 3 to d 4 .
(a) Zn (b) Cd
(c) Hg (d) Cu Short Answer Type Questions
2. Which element can have oxidation state from 4 to 6? 8. Why there is striking similarities (horizontal and vertical)
(a) Fe among successive members of the transition series?
(b) Mg 9. The E (oM 2+ / M ) value for copper is positive (+0.34 V). What
(c) Co is the possible reason for this?
(d) Cr
10. (i) The second and third rows of transition elements
3. Which one of the following ions is the most stable in
aqueous solution?[Atomic number of Ti = 22, V = 23, resemble each other much more than they resemble the
Cr = 24 and Mn = 25] first row.
(a) Cr 3+ (b) V 3+ (ii) Identify the metal MO 3F and justify your answer.
(c) Ti 3+ (d) Mn 3+ 11. How would you account for the following?
4. The highest value of the calculated spin only (i) Of the d 4 species,Cr 2+ is strongly reducing agent while
magnetic moment (in BM) among all the transition manganese (III) is strongly oxidising agent.
metal complexes is (ii) Cobalt (II) is stable in aqueous solution but in the
(a) 5.92 (b) 3.87 presence of complexing reagents, it is easily oxidised.
(c) 6.93 (d) 4.90 (iii) The d 1 configuration is very unstable in ions.
Assertion-Reasoning MCQs Long Answer Type Questions
Direction (Q. Nos. 5-7) Each of these questions contains 12. (i) Transition metals can act as catalysts because these
two statements Assertion (A) and Reason (R). Each of can change their oxidation state. How does Fe (III)
these questions also has four alternative choices, any catalyse the reaction between iodide and persulphate
one of which is the correct answer. You have to select ions?
one of the codes (a), (b), (c) and (d) given below. (ii) Mention any three processes where transition metals
(a) Both A and R are true and R is the correct explanation of A. act as catalysts.
(b) Both A and R are true, but R is not the correct 13. (i) Explain the following observation.
explanation of A. (a) Which element of the first transition series has
(c) A is true, but R is false. highest second ionisation enthalpy?
(d) A is false, but R is true.
(b) Write down the electronic configuration of
5. Assertion Radii of the members of the third gadolinium (Gd). Its atomic number is 64.
transition series is very similar to those of the
(c) What are the different oxidation states exhibited
corresponding members of the second series.
by lanthanoids?
Reason It is due to lanthanoid contraction.
(ii) What is meant by disproportionation? Give two
6. Assertion First ionisation enthalpy of Cr is lower than examples of disproportionation reaction in aqueous
that of Zn. solution.
Reason I.E. of Cr is lower due to it’s stable half-filled
configuration.
Answers
Multiple Choice Questions
1. (d) 2. (d) 3. (a) 4. (a)
For Detailed Solutions
Assertion-Reasoning MCQs Scan the code
5. (a) 6. (a) 7. (c)
CHAPTER 05
Coordination
Compounds
In this Chapter...
l Double Salt and Complex Compounds
l Werner’s Theory of Coordination Compounds
l Terms Used in Coordination Compounds
l Nomenclature of Coordination Compounds
l Bonding in Coordination Compounds
Transition metals form a large number of complex compounds in l

Every metal atom must satisfy both of its valencies.
which the metal atoms are bound to a number of anions or neutral l
Primary valencies are satisfied by negative ions
molecules by sharing of electrons. Such compounds are known as
whereas secondary valencies are satisfied by neutral
coordination compounds.
molecules or negative ions.
Coordination compounds are those in which a central metal atom l
Primary valencies are non-directional. Secondary
or ion is attached with a fixed number of groups or molecules valencies are directed in space towards fixed
(ligands) through coordinate bonds. position giving a definite shape to the complex.
The ions or groups bound by the secondary linkages
Double Salts and Complex Compounds
l
to the metal have characteristic spatial

Double salts These are the addition compounds which are stable arrangements corresponding to coordination
inthe solid state but when dissolved in water they dissociate numbers. In modern formulations such spatial
completely into ions, arrangements is called coordination polyhedra.
e.g. Mohr’s salt : [FeSO 4 (NH 4 ) 2 SO 4 × 6H 2 O].
Coordination compounds They do not dissociate completely into Terms Used in Coordination
simple ions and do not completely lose their identity in solution. Compounds
e.g. K 4 [Fe(CN) 6 ].
Definitions of some important terms used in
Werner’s Theory of Coordination coordination compounds are as follows
(i) Coordination entity It constitutes a central metal
Compounds atom or ion bonded to a fixed number of ions or
(i) Alfred Werner, a Swiss chemist was the first to formulate his idea molecules.
about the structures of coordination compounds. He proposed (ii) Central metal atom or ion In a coordination entity,
the concept of primary valence and secondary valence. the atom or ion around which a fixed number of ions
(ii) Postulates of Werner’s Theory or groups are bound in a definite geometrical
arrangement is called the central atom or ion. In
l
Metals possess two types of valencies, called primary or complex compounds, the central metal atom or
ionisable valency (oxidation number) and secondary or ion can act as Lewis acid and ligands act as Lewis
non-ionisable valency (coordination number). base.
(iii) Ligands Ions or molecules which can donate a lone pair of l

The central atom is listed first.
electron to the central atom or ion are called ligands. l
The ligands are then listed in alphabetical order. The
l
When a ligand is bound to a metal ion through a single placement of a ligand in the list does not depend on its
donor atoms (e.g. Cl - , H 2O), the ligand is said to be charge.
unidentate. l
Polydentate ligands are also listed alphabetically.
l
When a ligand can bind through two donor atoms as in In case of abbreviated ligand, the first letter of the
oxalate, the ligand is said to be didentate and when abbreviation is used to determine the position of the
several donor atoms are present in a single ligand as in ligand in the alphabetical order.
N(CH 2CH 2NH 2 ) 3 , the ligand is said to be polydentate. l
The formula for the entire coordination entity, whether
l
When a di or polydentate ligand uses its two or more charged or not is enclosed in square brackets. When
donor atoms simultaneously to bind a single metal ion, it is ligands are polyatomic, their formulae are enclosed in
said to be a chelating ligand. parenthesis. Ligand abbreviations are also enclosed in
parenthesis.
l
The number of such ligating groups is called the
denticity of the ligand.
l
There should be no space between the ligands and the
metal within a coordination sphere.
l
Chelating ligand is a neutral molecule, free radical or ion
with two or more lone pairs of electrons on different atoms.
l
When the formula of a charged coordination entity is to
l
Ligand which has two different donor atoms and either of be written without that of the counter ion, the charge is
the two ligates in the complex is called ambidentate indicated outside the square brackets as a right
ligands. Examples are NO -2 and SCN - ion. superscript with the number before the sign. e.g.
[Co(CN) 6 ] 3- , [Cr(H 2O) 6 ] 3+ etc.
(iv) Coordination number For a metal ion in a complex it can
be defined as the number of ligand donor atoms to which
l
The charge of the cation(s) is balanced by the charge of
the metal is directly bonded. the anion(s).
(v) Counter ions The part of the coordination which is present 2. Naming of Mononuclear Coordination Compounds
outside the square brackets is known as ionisation sphere. The following rules are used while naming the
These are also known as counter ions. coordination compounds
(vi) Coordination sphere The central atom/ion and the l
The cation is named first in both positively and
ligands attached to it are enclosed in the square brackets negatively charged coordination entities.
are collectively known as coordination sphere. l
The ligands are named in an alphabetical order before
(vii) Coordination polyhedron The spatial arrangement of the the name of the central atom or ion. (This procedure is
ligand atoms which are directly attached to the central reversed from writing formula).
atom/ion defines a coordination polyhedron about the l
Name of the anionic ligands end in -‘o’, those of neutral
central atom. and cationic ligands are the same except aqua for H 2 O,
(viii) Oxidation number The charge present on central metal ammine for NH3 , carbonyl for CO and nitrosyl for NO.
atom or ion, if all the ligands are removed alongwith the These are placed within enclosing marks ( ).
electron pairs that are shared with it is called oxidation If ambidentate ligand is present, then it is named by
number of central atom. placing the symbol of donor atom or by using different
(ix) Charge on the complex ion The charge carried by a names. e.g. ONO (nitrito-O), ¾NO 2 (nitrito-N).
complex ion is the algebraic sum of the charges carried by l
Prefixes mono, di, tri, etc. are used to indicate the number
the central metal ion and the total ligands attached to the of the individual ligands in the coordination entity. When
central metal ion. the names of the ligands include a numerical prefix, then
the terms, bis, tris, tetrakis are used, the ligand to which
Homoleptic Complexes and Heteroleptic Complexes they refer is placed in parenthesis.
l Complexes in which metal is bound to only one kind of donor l
Oxidation state of the metal in cation, anion or neutral
groups are known as homoleptic complexes. e.g. [Co(NH 3 ) 6] 3+ .
coordination entity is indicated by Roman numeral in
l Complexes in which a metal is bound to more than one
parenthesis.
kind of donor groups are known as heteroleptic complexes.
e.g. [Co(NH 3 ) 4 Cl 2 ] + . l
If the complex ion is a cation, the metal is named same
as the element, e.g. Co in a complex cation is called
cobalt and Pt is called platinum.
Nomenclature of Coordination l
If the complex ion is an anion, the name of the metal
Compounds ends with the suffix—‘ate’, e.g. Co in a complex anion,
The rules for the nomenclature of coordination compounds are [Co(SCN)4 ] 2- is called cobaltate. For some metals, the
as follows Latin names are used in the complex anions, e.g. ferrate
for F.
1. Formulae of Mononuclear Coordination Compounds l
The neutral complex molecule is named similar to that
The following rules are applied, while writing the formulae of the complex cation.
Bonding in Coordination Compounds

Many approaches have been put to explain, the nature of bonding in coordination compounds. These are valence bond theory
(VBT), crystal field theory (CFT) etc.
Valence Bond Theory

According to valence bond theory (VBT), the metal atom or ion under the influence of ligands can use ( n - 1 ) d, ns, np, nd
orbitals for hybridisation to yield square planar, tetrahedral or octahedral geometry. These hybridised orbitals overlap with
ligand orbitals which can donate an electron pair for bonding.
Hybridisation and Geometry of Complexes
Type of sp sp 2 sp 3 dsp 2 dsp 3 sp 3 d d 2 sp 3 sp3d 2

hybridisation
Coordination
number 2 3 4 4 5 5 6 6
Geometry Linear Trigonal Tetrahedral Square Square Trigonal Octahedral Octahedral

planar planar pyramidal bipyramidal (inner orbital) (outer orbital)
Examples [Ag(NH3 ) 2 ] + [HgI 3 ] - Ni[(CO) 4 ] [Ni(CN) 4 ] 2- Fe(CO) 5 , [SbF5 ] 2- [Cr(NH3 ) 6 ] 3+ [FeF6 ] 3–

- 2- 3–
[Ag(CN) 2 ] [NiX 4 ] [Cu(NH3 ) 4 ] 2+ [CuCl 5 ] [Fe(CN) 6 ] 3- [Fe(H2 O) 6 ] 2+
[ZnCl 4 ]2-
[Ni(NH3 ) 4 ] 2+ [Ni(NH3 ) 6 ] 2–
[CuX 4 ] 2-
Octahedral Complexes e.g. [NiCl 4 ] 2-

Octahedral complexes involve one s, three p and two Oxidation state of Ni is +2 and its valence shell configuration
d-orbitals. is [ Ar ] 3 d 8 .
3d 4s 4p
e.g. [Co(NH 3 ) 6 ] 3 + Ni-atom ¼¼¼ ¼
(Z = 28) ¼¼¼ ¼¼ ¼
l
Oxidation state of cobalt is +3 and electronic configuration Orbitals of Ni2+ ¼¼¼
of Co 3+ ion is [ Ar ]18 3d 6 . ion ¼¼¼ ¼¼
sp3-hybridised ¼¼¼
l
Its hybridisation scheme can be shown as orbitals of Ni 2+ ¼¼¼ ¼¼
sp3
3d 4s 4p 2–
[NiCl 4 ] ´´´´ ´´ ´´
Co-atom
¼¼ ¼
Z = 27 ¼¿ ¼¿ ¼ ¼ ¼ ¼¿ (high spin
¼ ¼¼ ¼¼ – – – –
Cl Cl Cl Cl
complex)
Orbitals of sp3-hybridised
Co3+ ion ¼¿ ¼ ¼ ¼ ¼
d 2sp3-hybridised
¼¿ ¼¿ ¼¿ Square Planar Complexes
orbitals of Co3+
Square planar complexes involve one d, one s and two
ì
ï
ï
ï
ï
í
ï
ï
ï
ï
î
Six empty orbitals = two 3d, one p-orbitals for bonding. The hybridisation involved is dsp 2.
4s and three 4p orbitals ( d 2sp3)
[Ni(CN) 4 ] 2– has square planar shape.
[Co(NH3)6]3+= ´´ ´´ ´´ ´´ ´´ ´´
¼¿ ¼¿ ¼¿ Ni atom (ground state) = [Ar] 3d 8 , 4s 2 , 4p 0
(inner orbital or 3d Six pairs of e - from
low spin complex) 6 NH3 molecule 3d 4s 4p
Ni atom
(Z = 28) ¼¿ ¼¿ ¼¿ ¼ ¼ ¼¿
l
Six pairs of electrons one from each NH3 molecule, occupy 3d 4p
the six hybrid orbitals. dsp2-hybridised
orbitals of Ni2+ ¼¿ ¼¿ ¼¿ ¼¿
Complex has octahedral ( d 2 sp 3 ) geometry.
ì
ï
ï
í
ï
ï
î
dsp2-hybrid
3d dsp 2 4p
Tetrahedral Complexes 2-
[Ni(CN)4] = ¼¿ ¼¿ ¼¿ ¼¿ ´´ ´´ ´ ´ ´´
l
In tetrahedral complexes, one s and three p-orbitals are (low spin
complex) 4e- pairs from
hybridised to form four equivalent orbitals oriented 4 CN- ions
tetrahedrally.
Inner and Outer Orbital Complexes The splitting of d-orbitals in an octahedral crystal field can be
A complex compound may be inner orbital complex or seen in following diagram.
outer orbital complex depending upon whether d-orbitals L
of the inner shell or outer shell are involved in
hybridisation. Inner orbital complex is generally low spin M
L
M
L
M
complex, while outer orbital complex is generally high
L L
spin complex.
Energy L
Magnetic Properties of Z
dx2–y2 dz2 eg
Coordination Compounds Y
3/5Do
If no unpaired electron is present, the complex is X
diamagnetic. If unpaired electron(s) is/are present, Bary centre
Do
complex is paramagnetic. Metal 2/5Do
Its magnetic moment m can be calculate of as d-orbitals dxy dxz dyz
t2g
m = n( n + 2)BM where, n is the number of unpaired dx2–y2 dz2 dxy dxz dyz Average energy Splitting of d-orbitals
electrons present. Free metal ion of the d-orbitals in in octahedral
spherical crystal field crystal field
Limitations of Valence Bond Theory d-orbital splitting in an octahedral crystal field
Although, valence bond theory is advantageous to explain
formation, structures and magnetic properties of Here, CFSE can be calculated as,
coordination compounds but it suffers with few limitations, CFSE = [ - 0.4 x + 0.6 y ] D0
listed as follows
where, D0 = CFSE in octahedral complex
l
It is based on a number of assumptions.
l
It does not distinguish between weak and strong ligands. x = number of electrons in t 2 g -orbitals
l
It does not give quantitative interpretations of magnetic y = number of unpaired electrons in eg - orbitals.
data. l
The extent of crystal field splitting depends on the strength of
l
It does not give a quantitative interpretation of the ligand and charge on metal ion.
thermodynamic or kinetic stabilities of coordination l
A strong ligand causes greater splitting, while a weak ligand
compounds. causes smaller splitting.
l
It fails to explain relative energies of different shapes. l
Ligands can be arranged in a series in the order of increasing
l
It does not explain the colour and spectral properties of field strength as given below
the 4-coordination compounds. I - < Br - < SCN - < Cl - < S 2- < F - < OH - < C 2 O 2–
4
l
It fails to predict the exact tetrahedral and square planar < H 2 O < NCS - < NH 3 < en < NO 2- < CN - < CO
structures of 4-coordinate complexes. This series is called spectrochemical series.
l
The single d-electron of metal ion in octahedral coordination
Crystal Field Theory (CFT) entities occupies one of the lower energy t 2 g -orbitals. In
It is an electrostatic model which considers the d 2 and d 3 coordination entities, the d-electrons occupy the
metal-ligand bond to be ionic arising purely from single t 2 g - orbitals in accordance with the Hund’s rule.
electrostatic interactions between the metal ion and the l
For metal ion complex, d 4 configuration, d-orbital occupancy
ligand. depends on the relative magnitude of the crystal field
l
Ligands are treated as point charges in case of anions or splitting, D o and the pairing energy, P (P represents the
point dipoles in case of neutral molecules. energy required for electron pairing in a single orbital).
l
According to CFT, under the influence of ligand field, l
If D o < P, the fourth electron enters one of the eg - orbitals giving
degeneracy of the d-orbital is disturbed and it splits into the configuration t 23g e1g . Ligands for which D o < P are known as
two or more energy levels. weak field ligands and form high spin complexes.
l
Octahedral complexes yield three orbitals of lower l
If D o > P, it becomes more energetically favourable for the
energy, t 2 g set and two orbitals of higher energy, e g set.
This splitting of degenerate levels due to the presence of fourth electron to occupy t 2 g orbital with configuration t 42 g e g0 .
Ligands which produce this effect are known as strong field
ligands in a definite geometry is termed as crystal field
splitting and the energy separation is denoted by D o . ligands and form low spin complexes.
l
Calculations show that d 4 to d 7 coordination entities are l
The orbital splitting energies are not sufficiently large to
more stable for strong field as compared to weak field force pairing and therefore low spin are rarely observed in
cases. tetrahedral complexes.
l
In tetrahedral coordination entity formation, the d-orbital
Limitations of Crystal Field Theory
splitting is inverted and is smaller as compared to the
octahedral field splitting. It can be easily illustrated from CFT has the following limitations :
the given figure. l
As the ligands are point charges, the anionic ligands should
dxy , dxz , dyz exert the greatest splitting effect. Actually,
t2
the anionic ligands are found at the low end of the
Energy 2D
— spectrochemical series.
5 t
Dt l
CFT treats the metal-ligand bond as purely ionic and it does
3D
—
not take into account the covalent character of bonding
5 t between the ligand and the central atom.
Average energy e Note Valence bond theory consider the M—L bond as covalent while
d-orbitals of the d-orbitals dx –y dz
2 2 2
crystal field theory consider the M—L bond to be ionic.
free ion in spherical Splitting of
crystal field d-orbital in
tetrahedral Colour of Coordination Compounds
crystal field l
In complex compounds, d-orbitals split into two sets t 2 g and
d-orbital splitting in a tetrahedral crystal field e g . These have different energies. The difference in energies
Here, CFSE can be calculated as, lies in visible region and electron jump from ground state t 2 g
level to higher state e g level.
CFSE = [ - 0.61 + 0.4y ] Dt l
This is known as d - d transition and is responsible for colour
Dt = CFSE in tetrahedral in e-orbitals of coordination compounds. d - d transition takes place in d 1
x = number of electrons in e-orbitals to d 9 ions, so the ions having d 1 to d 9 configuration are
y = number of electrons in t 2 -orbitals coloured.
l
For the same metal, the same ligands and metal ligand l
On the other hand, the ions with d 0 and d 10 configuration do
distances, it can be shown as D t = 4 / 9 D o . not show d-d transition.
Chapter
Practice
7. The correct structure of ethylenediamminetetraacetic
acid (EDTA) is
PART 1 HOOCCH2 CH2COOH

Objective Questions (a)
HOOCCH2

N — CH == CH — N

CH2COOH
HOOC COOH
l
Multiple Choice Questions (MCQs) (b)

N — CH2 — CH2 — N

1. Primary valency of binary compound CrCl 3 , CoCl 2 HOOC COOH
and PdCl 2 are HOOCCH2

CH2COOH
(a) 2, 2 and 3 respectively (b) 2, 3 and 2 respectively (c) N — CH2 — CH2 — N

(c) 3, 3 and 2 respectively (d) 3, 2 and 2 respectively HOOCCH2 CH2COOH
2. When 1 mole of CrCl 3 × 6H 2O is treated with excess of H2C ¾ COOH
AgNO 3 , 3 moles of AgCl are obtained.` The formula HOOC ¾ H2C ½ H

of the complex is (d) N— CH— CH— N

H ½ CH COOH
(a) [CrCl 3 (H2O)3 ]× 3H2O CH2COOH 2
(b) [CrCl 2 (H2O)4 ]Cl × 2H2O
(c) [CrCl(H2O)5 ]Cl 2 × H2O 8. IUPAC name of [Pt(NH 3 ) 2 Cl(NO 2 )] is
(a) platinum diamminechloronitrite (NCERT Exemplar)
(d) [Cr(H2O)6 ]Cl 3
(b) chloronitrito-N-ammineplatinum (II)
3. When 0.1 mole of CoCl 3 (NH 3 ) 5 is treated with (c) diamminechloridonitrito-N-platinum (II)
excess of AgNO 3 , 0.2 mole of AgCl are obtained. The (d) diamminechloronitrito-N-platinate (II)
conductivity of solution will correspond to 9. The correct IUPAC name of [Pt(NH 3 ) 2 Cl 2 ] is
(a) 1 : 3 electrolyte (b) 1 : 2 electrolyte (a) diamminedichloridoplatinum (II) (NCERT Exemplar)
(c) 1 : 1 electrolyte (d) 3 : 1 electrolyte (b) diamminedichloridoplatinum (IV)
4. The oxidation number of the central atom in a (c) diamminedichloridoplatinum (0)
complex is defined as the charge it would carry (d) dichloridodiammineplatinum (IV)
(a) if all the ligands are removed along with the electron 10. Write the formula for coordination compound
pairs that are donated by the central atom diamminesilver (I) dicyanoargentate (I).
(b) if all the ligands are removed along with the electron (a) [Ag(NH3 )2 ][Ag(CN)2 ] (b) [Ag(NH3 )3 ][Ag(CN)2 ]
pairs that are shared with the central atom (c) [Ag(NH3 )2 ][Ag(CN)3 ] (d) [Ag(NH2 )2 ][Ag(CN)2 ]
(c) if all the ligands are removed from the central metal atom
(d) if all the electrons pairs are shared with the central atom 11. Match the complex ions given in Column I with the
hybridisation and number of unpaired electrons
5. Coordination number of Co in [Co(en) 2 Cl 2 ]Cl is
(a) 3 (b) 4 (c) 5 (d) 6
given in Column II and assign the correct code.
3+ +
6. [Co(NH 3 ) 6 ] and [Co(NH 3 ) 4 Cl 2 ] are the Column II
Column I
(Hybridisation, number
examples of (Complex ion)
of unpaired electrons)
(a) homoleptic complexes
(b) heteroleptic complexes A. [Cr(H2O) 6 ] 3+ 1. dsp2 , 1
(c) [Co(NH3 )6 ]3+ homoleptic complex, [Co(NH3 )4 Cl 2 ]+ B. [Co(CN) 4 ] 2 - 2. sp3d 2 , 5
heteroleptic complex
C. [Ni(NH3 ) 6 ] 2+ 3. d 2 sp3, 3
(d) [Co(NH3 )6 ]3+ heteroleptic complex, [Co(NH3 )4 Cl 2 ]+
homoleptic complex D. [MnF6 ] 4 - 4. sp3 d 2 , 2
Codes Reason Unpaired electrons are present in their

A B C D A B C D d-orbitals. (NCERT Exemplar)
(a) 3 1 4 2 (b) 4 3 2 1 3-
(c) 3 2 4 1 (d) 4 1 2 3 20. Assertion [Fe(CN) 6 ] ion shows magnetic moment
corresponding to two unpaired electrons.
12. Which of the following complex ions is diamagnetic
in nature? Reason Because it has d 2 sp 3 type hybridisation.
(NCERT Exemplar)
(a) [CoF 6 ] 3- (b) [NiCl 4 ] 2 - (c) [Ni(CN) 4 ] 2 - (d) [CuCl 2 ] 2 -
-
21. Assertion [CuCl 2 ] has linear shape with sp
13. Which one of the following is an outer orbital hybridisation.
complex and exhibits paramagnetic behaviour?
(a) [Ni(NH3 ) 6 ] 2 + (b) [Zn(NH3 ) 6 ] 2 +
Reason [CuCl 2 ] - has zero unpaired electrons.
(c) [Cr(NH3 ) 6 ] 3+
(d) [Co(NH3 ) 6 ] 3+ 22. Assertion d 4 and d 7 configuration is more stable in
high spin state.
14. For d 4 ions, the fourth electron enters one of the Reason High spin are stable when D o < P.
eg -orbitals giving the configuration t 23g e1g , when
(a) D o > P (b) D o < P (c) D o = P (d) D o ³ P l
Case Based MCQs
15. What is the correct electronic configuration of the
central atom in K 4 [Fe(CN ) 6 ] based on crystal field 23. Read the following and answer the questions from (i)
theory? to (iv) given below
(a) t62g e g0 (b) e 3t 23 (c) e 4 t 22 (d) t 24 g e g2 The crystal field theory (CFT) is an electrostatic
model which considers the metal-ligand bond as
16. Colourless complex ion in the following is ionic arising purely from electrostatic interactions
(a) [Cu(NH3 ) 4 ] 2+ (b) [Zn(NH3 ) 4 ] 2+ between the metal ion and the ligand.
(c) [Fe(H 2 O) 6 ] 3+
(d) [Fe(CN) 6 ]3 - In an octahedral coordination entity with six ligands
surrounding the metal atom or ion, there will be
l Assertion-Reasoning MCQs repulsion between the electrons in metal d-orbitals
Direction (Q. Nos. 17-22) Each of these questions and the electrons (or negative charges) of the ligands.
contains two statements Assertion (A) and Reason (R). Such a repulsion is more when the metal d-orbital is
Each of these questions also has four alternative directed towards the ligand than when it is away
choices, any one of which is the correct answer. You from the ligand.
have to select one of the codes (a), (b), (c) and (d) given Thus, the dx 2 -y 2 and dz 2 orbitals, which point
below. towards the axes along the direction of the ligand will
(a) Both A and R are true and R is the correct experience more repulsion and will be raised in
explanation of A.
energy and the dxy , dz x and dyz orbitals which are
explanation of A.
directed between the axes will be lowered in energy
(c) A is true, but R is false. relative to the average energy in the spherical crystal
(d) A is false, but R is true. field.
Thus, the degeneracy of the d-orbitals has been
17. Assertion In the coordination compound removed due to ligand-metal electron repulsions in
[Co ( H 2 NCH 2CH 2 NH 2 ) 3 ]2 , ethane-1,2-diammine is
the octahedral complex to yield three orbitals of
a neutral molecule.
lower energy, t 2g set and two orbitals of higher
Reason Oxidation number of Co in the complex ion energy, eg set. This splitting of the degenerate levels
is +3. due to the presence of ligands in a definite geometry
18. Assertion When EDTA solution is added to Mg 2+ is termed as crystal field splitting.
ion solution then four coordinate site of Mg 2+ are The difference of energy between the two sets of
occupied by EDTA and remaining two sites are degenerate orbitals as a result of crystal field splitting
occupied by water molecules. is known as Crystal Field Stabilisation Energy
(CFSE), it is denoted by D o (the subscript o is for
Reason EDTA is a hexadentate ligand.
octahedral). Thus, the energy of the two e g orbitals
19. Assertion [Cr(H 2O) 6 ]Cl 2 and [Fe(H 2O) 6 ]Cl 2 are will increase by (3/5) D o and that of the three t 2g will
reducing in nature. decrease by (2/5)D o .
(i) Which one of these statements about [Co(CN) 6 ] 3- Secondary valency is equal to the coordination
is correct? number of central atom or ion. It is directional and
(a) [Co(CN)6 ]3- has no unpaired electrons and will be in a non-ionisable. It is commonly satisfied by neutral
low-spin configuration molecules or negative ions and is always fixed for a
(b) [Co(CN)6 ]3- has four unpaired electrons and will be in metal. Each metal ion has a fixed number of
a low-spin configuration secondary valency.
(c) [Co(CN)6 ]3- has four unpaired electrons and will be (i) When 1 mole of CrCl 3 × 6H2 O is treated with excess
in a high-spin configuration of AgNO3 , 3 moles of AgCl are obtained. The
(d) [Co(CN)6 ]3- has no unpaired electrons and will be in formula of the complex is
a high-spin configuration (a) [CrCl 3 (H 2 O) 3 ] × 3H 2 O
(ii) Among the ligands NH 3 , en, CN - and CO, the (b) [CrCl 2 (H 2 O) 4 ]Cl × 2H 2 O
correct order of their increasing field strength, is (c) [CrCl(H 2 O) 5 ]Cl 2 × H 2 O
(a) CO < NH3 < en < CN - (d) [Cr(H 2 O) 6 ]Cl 3
(b) NH3 < en < CN - < CO
(ii) The primary and secondary valencies of chromium
(c) CN - < NH3 < CO < en
in the complex ion, dichlorodioxalato chromium
(d) en < CN - < NH3 < CO (III) respectively are
(iii) Identify the correct trend given below : (Atomic (a) 3 and 4 (b) 4 and 3
number, Ti= 22, Cr = 24 and Mo = 42) (c) 6 and 3 (d) 3 and 6
(a) D o of [Cr(H2O)6 ]2+ < [Mo(H2O)6 ]2+ (iii) Which one of the following complexes will consume
and D o of [Ti(H2O)6 ]3+ < [Ti(H2O)6 ]2+ more equivalents of aqueous solution of AgNO3 ?
(b) D o of [Cr(H2O)6 ]2 + > [Mo(H2O)6 ]2+ (a) Na 2[CrCl6 ] (b) [Cr(H2O)5 Cl] Cl 2
and D o of [Ti(H2O)6 ]2+ > [Mo(H2O)6 ]2+ (c) [Cr(H2O)6 ] Cl 3 (d) Na 2[CrCl 5 (H2O)]
(c) D o of [Cr(H2O)6 ]2+ > [Mo(H2O)6 ]2+ (iv) How many ions are obtained after dissociation of
and D o of [Ti(H2O)6 ]2+ < [Mo(H2O)6 ]2+ the complex [ Co(NH3 ) 6 Cl 3 ?
(d) D o of [Cr(H2O)6 ]2+ < [Mo(H2O)6 ]2+ (a) 3 (b) 2 (c) 5 (d) 4
and D o of [Ti(H2O)6 ]3+ > [Ti(H2O)6 ]2+ Or Consider the formula [Co(NH3 ) 6 ] (3Cl – ). In this
3+
formula the species within the square bracket and the

Or Crystal field stabilisation energy for high spin d 4
ions outside the square bracket respectively
octahedral complex is (a) Coordination entity and counter ions
(a) -0.6D o (b) -1.8D o
(b) Counter ions and coordination entity
(c) -1.6 D o + P (d) -1.2 D o
(c) Counter ions and counter entity
(iv) The CFSE for octahedral [CoCl 6 ] 4- is 18,000 cm -1 . (d) Coordinated ions and counter entity
The CFSE for tetrahedral [CoCl 4 ] 2- will be
(a) 18000 cm -1 (b) 16000 cm -1
(c) 8000 cm -1 (d) 20000 cm -1 PART 2
to (iv) given below Subjective Questions
Alfred Werner (1866-1919), a Swiss chemist was the
first to formulate his ideas about the structures of l
coordination compounds in 1898. He proposed the
concept of a primary valence and a secondary
1. Write the IUPAC name of the following coordination
compounds. (Delhi 2017)
valence for a metal ion.
(i) [Cr(NH 3 )3 Cl 3 ] (ii) K 3 [Fe(CN)6 ]
Binary compounds such as CrCl 3 , CoCl 2 and PdCl 2
have primary valence of 3, 2 and 2 respectively. In a (iii) [Co(NH 3 ) 5 (CO 3 )]Cl
series of compounds of cobalt (III) chloride with 2. Using IUPAC norms, write the formulae for the
ammonia, it was found that some of the chloride ions following
could be precipitated as AgCl on adding excess (i) Tetrahydroxozincate(II)
AgNO 3 solution in cold but some remained in the (ii) Potassium tetrachloridopalladate(II)
solution.
(iii) Diamminedichloridoplatinum(II)
Primary valency is equal to the oxidation number of (iv) Potassium tetracyanonickelate(II)
central ion. It is non-directional and ionisable. It is
satisfied by negative ions, e.g. in CrCl 3 , the primary (v) Pentaamminenitrito-O-cobalt(III)
valency is three. (vi) Hexaamminecobalt(III) sulphate (NCERT)
3. (i) Write the electronic configuration of iron ion in the 14. What is meant by crystal field splitting energy?
following complex ion and predict its magnetic How does the magnitude of splitting decide the
behaviour : [Fe(H2 O) 6 ] 2+ . actual configuration of d-orbitals in an octahedral
(ii) Write the IUPAC name of the coordination complex: field for a coordination entity?
[CoCl 2 (en) 2 ]NO3 . 15. Using crystal field theory, draw energy level
4. Specify the oxidation number of metal in the following diagram, write electronic configuration of central
coordination entities. atom or ion and determine the magnetic moment
(i) [Co(H 2O)(CN)(en) 2 ] 2 + (ii) [CoBr2 (en) 2 ] + (i) [FeF6 ] 3- (ii) [Fe(H 2O) 6 ] 2+ (iii) [Fe(CN) 6 ]4 -
(iii) [PtCl 4 ] 2 - (NCERT)
16. Account for the following :
5. (i) Write the systematic names of the following : (i) Which of the two K4 [Fe(CN)6 ] or K3 [Fe(CN)6 ]
(a) [Co(NH 3 ) 6 ] Cl 3 is more stable and why ?
(b) [Pt(NH 3 ) 2 Cl (NH 2CH 3 )] Cl (ii) What are the various factors affecting crystal field
(ii) Write the formula of the following compounds: splitting?
(a) Sodium hexanitrito-N-cobaltate (III) 17. Answer the following
(b) Tetraaquadichlorochromium (III) chloride (i) Why Co 2+ is easily oxidised to Co 3+ in presence
(iii) Calculate the oxidation state of Cu in of a strong field ligand.
[Cu(NH 3 )4 ] SO 4 . (All India 2017) (ii) Arrange the following complex ions in increasing
6. Give the oxidation state, d-orbital occupation and order of crystal field splitting energy ( D o ).
coordination number of the central metal ion in the [CrCl 6 ] 3- , [ Cr(CN)6 ] 3- , [Cr (NH3 ) 6 ] 3+
following complexes:
18. Account for the following
(i) K 3 [Co(C 2O 4 ) 3 ] (ii) (NH4 ) 2 [CoF4 ]
Co(III) forms paramagnetic octahedral complex
(iii) cis-[Cr(en) 2 Cl 2 ]Cl (iv) [Mn(H 2O) 6 ]SO 4 with weak field ligands, whereas it forms
7. (i) Write the IUPAC nomenclature of [Cr(NH 3 )4 Cl 2 ] + diamagnetic octahedral complex with strong field
and [Co( en ) 3 ] 3+ complexes. ligands.
(ii) Magnetic moment of [MnCl4 ] 2- is 5.92 BM. Give 19. Both [Co(NH 3 ) 6 ] 3+ and [CoF6 ] 3- are octahedral
reason.
8. Discuss the nature of bonding in the coordination complexes. Predict the magnetic nature of the two
3-
entity, [Co(C 2 O 4 ) 3 ] on the basis of valence bond complexes using CFT.
theory. Also, comment on the hybridisation and 20. A solution of [Ni(H2 O)6 ]2 + is green but a solution
magnetic behaviour of the given entity. of [Ni(CN)4 ]2 - is colourless. Explain. (Delhi 2017)
9. [Cr(NH3 )6 ]3 + is paramagnetic while[Ni(CN)4 ]2 - is l
Long Answer (LA) Type Questions
diamagnetic. Explain, why?
10. Explain, why [Co(NH3 )6 ]3 + is an inner orbital 21. Discuss the nature of bonding in the following
2+ coordination entities on the basis of valence bond
complex, whereas[Ni(NH3 )6 ] is an outer orbital
theory. (NCERT)
complex. (NCERT)
(i) [Fe(CN) 6 ]4 - (ii) [FeF6 ] 3-
11. Why are different colours observed in octahedral and
tetrahedral complexes for the same metal and same (iii) [Co(C 2O 4 ) 3 ] 3-
ligands ? (iv) [CoF6 ] 3-
12. Why do compounds having similar geometry have 22. Write the important postulates and the limitations
different magnetic moment? (NCERT Exemplar) of valence bond theory.
13. (i) Arrange the following complexes in the increasing 23. Using valence bond theory, explain the following in
order of conducting nature of their solution. relation to the complexes given below
[Co(NH3 )3 Cl3 ],[Co(NH3 )4 Cl2 ]Cl,
[Mn(CN) 6 ]3- , [Co(NH 3 ) 6 ]3+ , [Cr(H 2O) 6 ]3+
[Co(NH3 )6 ]Cl3 ,[Co(NH3 )5 Cl]Cl2
(i) Type of hybridisation.
(ii) Explain, why [Fe(H2 O)6 ]3+ has magnetic moment (ii) Inner or outer orbital complex.
value of 5.92 BM, whereas [Fe(CN)6 ]3- has a value (iii) Magnetic behaviour.
of only 1.73 BM? (iv) Spin only magnetic moment value. (CBSE 2019)
24. (i) On the basis of crystal field theory explain why (i) Write the state of hybridisation, shape and the
Co (III) forms paramagnetic octahedral complex with magnetic behaviour of the [Cr(H 2O) 2 (C2O 4 ) 2 ] - .
weak field ligands whereas it forms diamagnetic
octahedral complex with strong field ligands. (ii) Why s- orbital does not show preference to any
direction?
(ii) Give the electronic configuration of the following
complexes on the basis of crystal field splitting theory (iii) Why is [CoF6 ]3- is paramagnetic but
[CoF6 ] 3- , [Fe(CN) 6 ] 4- and [Cu(NH3 ) 6 ] 2+ . [Co(NH 3 ) 6 ]3+ is diamagnetic in nature?
25. The hexaaquamanganese (II) ion contains five (iv) Describe the type of hybridisation, shape and
unpaired electrons, while the hexacyano ion contains magnetic properites of [Co(NH3 ) 4 Cl 2 ] Cl
only one paired electron. Explain using crystal field [Given : Atomic number of Co = 27]
Or
theory. (NCERT)
Explain the geometry and magnetic character of
26. Using crystal field theory, draw energy level diagram, complex [Cr(NH3 ) 6 ]3+ .
write electronic configuration of the central metal
atom or ion and determine the magnetic moment value 29. Read the following and answer the questions from
in the following. (NCERT Exemplar) (i) to (iv) given below
3- 2+ 3- The properties of coordination compounds are
(i) [CoF6 ] , [Co(H2 O) 6 ] and [Co(CN) 6 ]
3- 2+ different from their constituents. In coordination
(ii) [FeF6 ] , [Fe(H2 O) 6 ] and [Fe(CN) 6 ]4 -
compounds, the central metal atom or ion is linked
27. (i) [Cr(NH3 ) 6 ] 3+ is paramagnetic while [Ni(CN) 4 ] 2- is to a number of ions or neutral molecules, called
diamagnetic. Explain, why? ligands, by coordinate bonds. For example,
dimethyl glyoxime (dmg) is a bidendate ligand
(ii) [Fe(CN) 6 ] 4- and [Fe(H2 O) 6 ] 2+ are of different chelating large amounts of metals.
colours in dilute solutions. Why? (NCERT) The ligands which contains three or more donor
atoms, are called polydentate ligands. When a di-or
l
Case Based MCQs polydentate ligand uses its two or more donor sites
28. Read the following and answer the questions from (i) to bind a single metal ion, it is called a chelating
to (iv) given below ligand.
The number of such liganting groups is called the
Valence bond theory describes the bonding in
denticity of the ligand.
complexes in terms of coordinate covalent bonds
resulting from overlap of filled ligand orbitals with (i) What is the structure of [ Pt(en)Cl 2 ]?
vacant metal hybrid orbitals. This theory explains (ii) Give an example of a coordination complexes
magnetic behaviour and geometrical shape of where central metal atom has coordination
number 8.
coordination compounds.
(iii) Name any one bidentate ligand.
Magnetic moment of a complex, compound can be
(iv) Categorised ethylenediamminetetra-acetate on
determined experimentally and theoretically by using
the basis of denticity.
spin only formula.
Or
Magnetic moment n( n + 2) BM Categorise (ethylene diammine) on the basis of
(where, n = no. of unpaired electrons) denticity.
87
EXPLANATIONS
1. (d) Primary valency corresponds to the oxidation state of Hence, correct IUPAC name of [Pt (NH3 ) 2 Cl 2 ] is
metal. Thus, in the given binary compounds CrCl 3, CoCl 2 Diammine dichloridoplatinum (II).
and PdCl 2 , the primary valencies are 3, 2 and 2 respectively. So, (a) option is correct.
2. (d) 1 mole of AgNO 3 precipitates one free chloride ion (Cl - ). 10. (a) The formula of compound diammine silver (I)
Here, 3 moles of AgCl are precipitated by excess of AgNO 3. dicyanoargentate (I) is [Ag(NH3 )2 ][Ag(CN)2 ].
Hence, there must be three free Cl - ions. x + 0=1 x - 2= -1
So, the formula of the complex can be [Cr(H2O) 6 ]Cl 3. x =1 x =1
3. (b) One mole of AgNO 3 precipitates one mole of chloride And oxidation state of silver in both is + 1.
ion. In the given reaction, when 0.1 mole CoCl 3(NH3 )5 is 11. (a) A ® (3); B ® (1); C ® (4); D ® (2)
treated with excess of AgNO 3, 0.2 mole of AgCl are obtained Formation of inner orbital complex and outer orbital complex
thus, there must be two free chloride ions in the solution of determines hybridisation of molecule which inturn depends
electrolyte. upon field strength of ligand and number of vacant d-orbitals.
So, molecular formula of complex will be [Co(NH3 )5 Cl] Cl 2 (i) Strong field ligand forms inner orbital complex with
and electrolytic solution must contain [Co(NH3 )5 Cl] 2+ and hybridisation d 2 sp3.
two Cl - as constituent ions. Thus, it is 1 : 2 electrolyte. (ii) Weak field ligand forms outer orbital complex with
[Co(NH3 )5 Cl]Cl 2 ¾® [Co(NH3 )5 Cl] 2 Å (aq ) + 2Cl - ( aq ) hybridisation sp3d 2 .
Hence, option (b) is the correct. According to VBT, hybridisation and number of unpaired
4. (b) The O.N. of central atom in complex is the charge it electrons of coordination compounds can be calculated as :
would carry if all ligands are removed along with electron
A. [Cr(H2O) 6 ] 3+
pairs that are shared with central atom.
5. (d) Coordination number of Co in [Co(en)2Cl2]Cl is 6, MOEC (Molecular orbital electronic configuration) of Cr 3+
because it is comprise of 2 en ligands (bidentate ligands) and in [Cr(H2O) 6 ] 3+is
2 Cl (unidentate ligand). 3d 4s 4p
6. (c) Homoleptic complexes are those complexes which have ×× ×× ×× ×× ×× ××
one type of ligands. e.g. [Co(NH3 )6 ]3+ , whereas heteroleptic
complexes are those which have more than one kind of H2O H2O H2O H2O H2O H2O
ligand, e.g. [Co(NH3 )4 Cl 2 ]+ . Hybridisation = d sp 2 3
7. (c) The correct structure of ethylenediaminetetracetic acid is n (number of unpaired electrons) = 3

as follows: 12. (c) Ni has dsp2 -hybridisation where CN- is a strong field
HOOCCH2 CH2COOH ligand.
N — CH2 — CH2 — N dsp 2 -hybridisation
HOOCCH2 CH2COOH
8. (c) Correct IUPAC name can be written as
The ligands present in the given coordination compound are:
(i) (NH3 ) represented as ammine CN – CN – CN – CN –
(ii) Cl s represented as chlorido Since, all the electrons are paired, thus it is diamagnetic.
(iii) NO s2 represented as nitrito-N 13. (a) Outer orbital complex utilises d-orbitals for bonding and
According to IUPAC rule, ligands are named in an exhibit paramagnetic behaviour, only if there are unpaired
alphabetical order before central atom. Prefex di-will be electrons.
used to indicate the number of NH 3 ligands present. In [Ni(NH3 ) 6 ] 2 + , Ni 2+ = [Ar] 3d 8 4s 0
Oxidation state of metal is indicated by Roman numeral in [Ni(NH3 ) 6 ] 2 + =
parenthesis.
3d 4s 4p 4d
So, IUPAC name will be
diamminechloridonitrito-N-platinum (II).
®
Hence, option (c) is correct.

Two unpaired sp 3d 2 -hybridisation
9. (a) The complex compound is [Pt(NH3 ) 2 Cl 2 ] . electrons
The ligands present in the compound are So, this is an outer orbital complex having paramagnetic
(i) NH3 - neutral ligand represented as amine. character.
(ii) Cl - anion ligand (ending with-o-) represented as 14. (b) The fourth electron enters one of the e g orbitals giving the
chlorido and di prefixed is added to represent two ligands. configuration t 23 g e1g when D o < P.
The oxidation number of platinum in the compound is 2.
15. (a) In K4[Fe(CN)6 ], Fe is present as Fe2+ = [Ar]3 d 6 4s 0
CN- is a strong field ligand and as it approaches the metal 22. (d) A is false, but R is true.
ion, the electrons must pair up. d 4 and d 7 are stable in low spin state. When D 0 > P, pairing
The splitting of the d-orbitals in two sets orbitals in an is not favoured and electron excite to e g level forming high
octahedral complex, K4[Fe(CN)6 ] may be represented as spin complex.
dx2–y2 dz2 23. (i) (a) Statement (a) is correct. [Co(CN) 6 ] 3-
eg
Co 3+=1 s 2 , 2s 2 2p6 , 3s 2 3p6 3d 6
dxy dxz dyz -
CN is a strong field ligand and as it approaches the metal
Average energy of the t2g
d-orbitals in spherical ion, the electron must pair up. The splitting of the d-orbitals
crystal field Splitting of d-orbitals into two sets of orbitals in as octahedral complex. Splitting
d-orbitals in octahedral
free ion crystal field of [Co(CN) 6 ] 3- can be shown as
Hence, the electronic configuration of the central atom in dx2– y2,dz2
K4[Fe(CN)6 ] is t 26 g e g0 . 3d eg -orbitals
2+ 2+
16. (b) [Zn(NH3 ) 4 ] is a colourless complex as, Zn ion has no ×× ×× Do
unpaired electron. t2g -orbitals
Zn = 3d 10 , 4 s 2 dxy dyz dxz
i.e. Zn 2+ = 3 d 10 6
Here, for d ions, three electrons first enter orbitals with
3d parallel spin. The remaining may pair up in t 2 g -orbital
»
»
»
»
»
giving rise to low spin complex (strong ligand).

(no unpaired electron) \ [Co(CN) 6 ] 3- has no unpaired electrons and will be in low
spin configuration.
17. (b) Both A and R are true but R is not the correct explanation (ii) (b) Based on spectrochemical series, ligands arranged in
of A. increasing order of crystal field strength are as
Ethane-1, 2-diammine is a neutral molecule. As it NH 3 < en < CN - < CO
carries no charge. (iii) (b) For [Cr(H2O) 6 ] 2 +
Oxidation number of Co in the complex ion is +3.
18. (d) A is false, but R is true. Outer configuration of Cr 2 + = [Ar], 3 d 4
When EDTA solution is added to Mg 2 + ion solution, then eg
six coordinate site of Mg 2 + are occupied by EDTA.
0.6 Do
EDTA has a hexadentate ligand. Energy
19. (b) Both A and R are true but R is not the correct explanation
Average energy of –0.4 Do
of A. Correct R is; [Cr(H2O 6 )]Cl 2 and [Fe(H2O) 6 ]Cl 2 are d-orbitals in symmetrical
reducing in nature due to formation of more stable complex crystal field
ion after gaining of electron. t2g
Splitting in an
20. (d) A is false, but R is true. octahedral crystal field
According to VBT, MOEC (Molecular Orbital Electronic
Configuration) of Fe3+ in [Fe(CN) 6 ] 3- is As H2O is a weak field ligand, so pairing of electrons does
not occur.
3d 4s 4p CFSE for [Cr(H2O) 6 ] 2 + = 3( -0.4D o ) + 1(0.6D o ) = -0.6D o
[Ar] ×× ×× ×× ×× ×× ×× D o depends on Zeff and for 3d-series, Zeff is less than
4d-series.
CN CN CN CN CN CN Hence, D o of [Cr(H2O) 6 ] 2 + > [Mo(H2O) 6 ] 2 +
Hybridisation = d sp 2 3 D a charge on metal ion
The crystal field splitting energy, o
n =1 size of metal ion
Hence, correct A is; [Fe(CN) 6 ] 3- ion shows magnetic \ D o of [Ti(H2O) 6 ] > D o of [Ti(H2O) 6 ] 2 +
3+
moment corresponding to one unpaired electron. Or

i.e. m = n( n + 2) (a) CFSE = 3 ( - 0.4) + 1 (0.6) = - 0.6D o
(iv) (c) CFSE for octahedral and tetrahedral complexes are
= 1( 1 + 2) 4
closely related to each other by formula D t = D o.
= 3 = 1.73 BM 9
21. (d) A is false, but R is true. where, D o = CFSE for octahedral complex,
[ CuCl 2 ] - has d10 configuration so zero unpaired electron but D t = CFSE for tetrahedral complex
exist in tetrahedral geometry with sp3-hybridisation. According to question, D o = 18000 cm -1
4 4 4. Coordination entities Oxidation state

\ Dt = D o = ´ 18000 cm -1
9 9 (i) [ Co( H2O )( CN )( en ) 2 ] 2 + +3
= 4 ´ 2000 cm -1 (ii) [ CoBr2 ( en ) 2 ] + +3
= 8000 cm -1 (iii) [ PtCl 4 ] 2 - +2
Hence, correct choice is option (c). 5. (i) (a) Hexaammine cobalt (III) chloride.
24. (i) (d) 1 mole of AgNO 3 precipitates one free chloride ion (Cl - ). (b) Diammine chloro (methylamine) platinum (II)
Here, 3 moles of AgCl are precipitated by excess of AgNO 3 . chloride.
Hence, there must be three free Cl - ions. (ii) (a) Na[Co(NO 2 ) 6 ]
So, the formula of the complex can be [Cr(H 2 O) 6 ]Cl 3 and (b) [CrCl 2 (H2O) 4 ] Cl
correct choice is (d). (iii) Oxidation state of Cu in [Cu(NH3 ) 4 ] SO 4 is calculated as,
(ii) (d) The primary and secondary valencies of chromium in the
Let oxidation state of Cu = x
complex ion, dichlorodioxalatochromium (III)
[ CrCl 2( Ox ) 2 ] 3 - are 3 and 6 respectively. x + ( 0 ´ 4) ´ - 2 = 0
x=+2
(iii) (c) 6. (i) Oxidation state Co
Dissociation in aqueous
Complex In K 3[Co(C 2O 4 ) 3 ] , is calculated as,
solution of AgNO 3
Let oxidation state of Co = x
(a) Na 3[CrCl6 ] 3Na + + [CrCl6 ]3-
( + 1 ) 3 + x + ( - 2) 3 = 0
(b) [Cr(H2O)5 Cl] Cl 2 [Cr(H2O)5 Cl]2+ + 2Cl - Þ x=+3
(c) [Cr(H2O)6 ]Cl 3 [Cr(H2O)6 ]3+ + 3Cl - Thus, Co is present as Co3+.
7 2
(d) Na 2[CrCl 5( H2O)] 2Na + + [CrCl 5 (H2O)]2- 27 Co = [Ar] 3d , 3s
\ Co3+ = [Ar] 3d6

[Cr(H2O)6 ]Cl 3 contains maximum number of ionisable anion
(3Cl - ). So, d-orbital occupation is d 6 or t 62 g e g0.
Hence, it will consume more equivalents of aqueous solution (As C 2O 42 - is strong field ligand)
of AgNO3 and form three mole of AgCl (white ppt.). C.N. of Co = 3 ´ denticity of C 2O 4 = 3 ´ 2 = 6
(iv) (d) Primary valency of coordination compounds are
(ii) (NH4 ) 2 [CoF4 ]
ionisable. Thus, dissociation of the complex, [Co(NH3 )6 ] Cl 3
takes place as follows ( + 1) 2 + x + ( - 1) 4 = 0 Þ x = + 2
[Co(NH3 )6 ] Cl 3 ¾® [Co(NH3 ) 6 ] 3+ + 3Cl - Thus, Co is present as Co2+.
Co2 + = [ Ar] 3d 7
Therefore, total number of ions obtained after dissociation
are 4. So, the configuration is d 7 or t52 g e g2.
Or As F- is a weak field ligand.
(a) In the complex, [Co(NH3 )6 ]3+ (3Cl - ) the species within C.N. of Co = 4
the square bracket is coordination entity and the ions (iii) cis- [Cr(en) 2 Cl 2 ]Cl
outside the square bracket is counter ions.
x + (0) 2 + ( -1)2 + ( -1) = 0Þ x = +3
Subjective Questions Thus, Cr is present as Cr 3+.
1. (i) Triamminetrichloridochromium(III) Cr 3+ = [Ar] 3d 3
(ii) Potassium hexacyanoferrate(III) 3
So, the configuration is d 3 or t 2 g e g0.
(iii) Pentamine carbonatocobalt (III) chloride
2. (i) [Zn(OH) 4 ] 2 - (ii) K 2 [PdCl 4 ] C.N. of Cr = 2 ´ 2 + 2 = 6 (as en is didentate.)
(iii) [Pt(NH3 ) 2 Cl 2 ] (iv) K 2 [Ni(CN) 4 ] (iv) [Mn(H2O) 6 ]SO 4
(v) [Co(NH3 ) 5 (ONO)] 2 + (vi) [Co(NH3 ) 6 ] 2 (SO 4 ) 3 x + ( 0) 6 + ( - 2) = 0Þ x = + 2
2+
3. (i) In [Fe(H2O) 6 ] , the oxidation state of Fe is + 2 . Thus, Mn is present as Mn 2 +.
Electronic configuration of Fe(26) = 3 d 6 4s 2 and Mn 2 + = [Ar] 3d5 or t 23 g e g2.
Fe2 + = 3 d 6 4s 0 or Fe2 + = t 24 g e g 2 C.N. of Mn = 6
The number of unpaired electrons are four. 7. (i) (a) [ Cr ( NH3 ) 4 Cl 2 ] +
Hence, it is paramagnetic. IUPAC name Tetraammine dichlorido chromium (III) ion.
(ii) The IUPAC name of the coordination complex (b) [ Co( en ) 3 ] 3+
[CoCl 2 (en) 2 ]NO 3 is dichlorido-bis (ethane - 1,
IUPAC name tris-(ethan-1,2-diamine) cobalt (III) ion.
2-diamine) cobalt (III) nitrate.
3d 4s 4p
(ii) The magnetic moment 5.92 BM shows that there are Co-atom
five unpaired electrons present in the d-orbitals of Z=27
Mn 2 + ion. As a result, the hybridisation involved is sp3
3d 4s 4p
rather than dsp2 . Thus, tetrahedral structure of Orbitals of
[MnCl 4 ] 2 - shows 5.92 BM magnetic moment value. Co 3+ ion
8. [Co(C 2O4 )3 ] 3- [Co(NH3)6] 3+ ´´ ´´ ´´ ´´ ´´ ´´

In this complex, the oxidation state of Co is +3.
3d
Outer configuration of Co = 3 d 7 4s 2 d 2sp 3
2 3
Co3+ = 3 d 6 4s 0 Complex has octahedral ( d sp ) geometry and is diamagnetic.
3d6 3s0 Since, ( n-1 ) d orbitals are available so forms inner orbital
Co3+= complex.
Oxalate ion being a strong field ligand pairs up the In [Ni(NH3 ) 6 ] 2 + ,

3d-electrons, thus two out of the five 3d-orbitals are 3d 4d
available for oxalate ions. ´´ ´´ ´´ ´´ ´´ ´´
[Co(C 2O4 )3 ]3- =
3d sp 3d 2
×× ×× ×× ×× ××
Since, ( n - 1 ) d-orbitals are not available so, the nd-orbitals
d 2sp3
are used in bond formation and form outer orbital complex.
Thus, the hybridisation of given entity is d 2 sp3. Since, all the
æ 4ö
electrons are paired, the complex is diamagnetic. 11. D t = ç ÷ D o
9. Hexaammine chromium (III) ion, [Cr(NH3 ) 6 ] 3 + ion è 9ø
Oxidation state of Cr = + 3 So, higher wavelength of light is absorbed in octahedral

complexes than tetrahedral complexes for same metal and
24 Cr = [Ar] 3 d5 4s1 ligands. Thus, different colours are observed.
Cr 3 + = [Ar] 3 d 3 12. Compounds having similar geometry may have different
3+ magnetic moment it is due to presence of weak or strong
Cr provides six empty orbitals to accommodate six
electron pairs from six NH3 molecules. It involves field ligands in complexes. e.g. [CoF6 ] 3 - and [Co(NH3 ) 6 ] 3 + ,
d 2 sp3-hybridisation and hence, octahedral. the former is paramagnetic, and the latter is diamagnetic
because F- is a weak field ligand and NH3 is a strong field
It is paramagnetic due to the presence of three unpaired
ligand while both have similar geometry.
electrons.
3d 4s 4p F 3– NH3 3+
3+ F F NH3 NH3
Cr =
Co and Co
[Cr(NH3 )6 ] 3+= F F NH3 NH3
3d 4s 4p F NH3
´´ ´´ ´´ ´´ ´´ ´´
13. (i) The increasing order of conducting nature of given
NH3 NH3 NH3 NH3 NH3 NH3 complexes in their solution is
Three unpaired
electron d 2sp 3-hybridisation [Co(NH3 ) 3Cl 3 ] < [Co(NH3 ) 4 Cl 2 ] Cl <
[Co(NH3 )5 Cl] Cl 2 < [Co(NH3 ) 6 ]Cl 3
Tetracyanonickelate (II) ion, [Ni(CN) 4 ] 2 -
This is because ions produced from these complexes
Ni = [Ar] 3 d 8 4s 2 , Ni 2 + = [Ar] 3 d 8 are 0, 2, 3 and 4 respectively.
3d 4s 4p
(ii) In both the complex, Fe is in +3 oxidation state with
2+
Ni = configuration 3d5 ,i.e. it has five unpaired electrons. In
the presence of weak H2O ligand, the unpaired
(CN - being strong field ligand causes pairing of 3d electrons electrons do not pair up but in the presence of strong
thus, one of the 3d- orbital becomes empty for CN - ion.)
ligand, i.e. CN - , they get paired up.
Unpaired electron is not present, so it is diamagnetic. 3d 5
3d 4s 4p
[Fe (CN)6]3– = ×× ×× ×× ×× ×× ××
´´ ´´ ´´ ´´
CN– CN– CN– CN– CN– CN–
2 3
All electrons dsp 2-hybridisation d sp -hybridisation
are paired (Square planar structure)
10. In [Co(NH3 ) 6 ] 3 + , cobalt is in + 3 oxidation state having Magnetic moment ( m ) = n( n + 2)

electronic configuration [Ar]18 3d 6 . = 3 = 1.73 BM
3d 5 16. (i) In K 4 [Fe(CN) 6 ], oxidation state of Fe is + 2.

[Fe(H2O)6]3+ = ×× ×× ×× ×× ×× ×× In K 3 [Fe(CN) 6 ], oxidation state of Fe is + 3.
3 2 Therefore, outer electronic configuration of
sp d -hybridisation
Fe2 + = 3 d 6 = t 26 g and of
Magnetic moment ( m ) = n( n + 2)
Fe3+ = 3 d5 = t52 g
= 5( 5 + 2)
= 35 = 5.92 BM C.F.S.E of K 4 [Fe(CN) 6 ] = - 0.4 ´ 6D o = -2.4D o
14. In complexes, the splitting of degenerate orbitals into C.F.S.E of K 3 [Fe(CN) 6 ] = - 0.4 ´ 5D o = -2.0D o
two sets, t 2 g and eg occurs due to the presence of ligands More is the C.F.S.E, more is the stability of the complex.
in a definite geometry. This is known as crystal field Therefore, K 4 [Fe(CN) 6 ] is more stable than K 3 [Fe(CN) 6 ].
splitting and in case of octahedral complexes, the energy
separation is known as crystal field splitting energy (ii) The crystal field splitting, D o depends upon the field
(C.F.S.E). It is denoted by D o. produced by the ligand and charge on the metal ion.
The magnitude of splitting decides the actual Some ligands are able to produce strong fields in that
configuration of d-orbitals in an octahedral field for a case, the splitting will be large, whereas others produce
coordination entity. weak field and consequently results in small splitting of
d-orbitals.
If D o < P ( P is the energy required for pairing of electrons)
then fourth electron enters in one of the e g orbitals 17. (i) Co2 + is a 3 d 7 species. In the presence of a strong field
( t 23 g e1g ). It means first five orbitals are individually ligand, the distribution of these electrons is t 26 g e1g . For
occupied and then pairing will take place. It is the case of greater stability thus Co2 + can lose one unpaired
weak field ligand and a high spin complex.
electron from higher ( e g ) energy level.
If D o > P, t 2 g set will have d 1 to d 6 -electrons (because (ii) Crystal field splitting energy (C.F.S.E) is higher
pairing occurs in t 2 g ), whereas e g level orbitals remain when the complex contains strong field ligand
unoccupied upto d 6 . It is the case of strong field ligand and The order of field strength of given ligand is
low spin complex.
Cl - < NH3 < CN -
15. We know that magnetic moment, Therefore, crystal field splitting energy increases in the order
m = n( n + 2) [CrCl 6 ] 3 - < [Cr(NH3 ) 6 ] 3 + < [Cr(CN) 6 ] 3 -
where, n is the unpaired electrons. 18. With weak field ligands, D o < P, (pairing energy) so, pairing
does not occurs the electronic configuration of Co (III) will be
eg
dz2 dx2–y2 t 24 g e g2 , i.e. it has 4 unpaired electrons and is paramagnetic.
(i) [FeF6]3–
eg
Fe3+= 3d 5 d5 t2g
dx 2–y 2 dz 2
dxy dyz yzx
Do
Number of unpaired electrons = 5
Degenerate
m = 5( 5 + 2) = 35 = 5.92 BM d-orbital t2g
dxy dyz d zx
eg
dz2 dx2–y2 With strong field ligands D o > P (pairing energy), so pairing
(ii) [Fe(H2O)6]2+ occurs thus, the electronic configuration will be t 26 g e g0 . It has
Fe2+= 3d 6 dxy dyz dzx
t2g
no unpaired electrons and is diamagnetic.
6
Number of unpaired electrons = 4 3d 4s0
3+
Co Þ
Magnetic moment = 4( 4 + 2) = 24 = 4.9 BM (Do > P)
No unpaired electron
dz 2 dx2– y2
eg 19. In [ Co( NH3 ) 6 ] 3+ , Co has oxidation state + 3 and its outer
(iii) [Fe(CN)6]4– outer electronic configuration is 3 d 6 . Since, NH3 is a strong
Fe2+= 3d 6 t2g field ligand and D o > P, the pairing of electrons occur and
dx dy dz electronic configuration is t 26 g e 0g .
No unpaired electrons, so diamagnetic.
Thus, all electrons are paired and the complex is (ii) [FeF6 ]3- In this complex, the oxidation state of Fe is
diamagnetic. + 3.
eg
Outer configuration of Fe 3+ = 3d 5 4s 0
dz 2 dx 2 – y 2 3d 5 4s 4p 4d
Do Fe3+ =
Degenerate F - is a weak field ligand, so no pairing occurs. Thus,
3d-orbital t 2g 3d-orbitals are not available to take part in bonding.
dxy dyz dzx
[FeF6 ]3- =
3-
In [CoF6 ] , the oxidation state of Co is + 3 and outer 3d 4d
electronic configuration is 3 d 6 . Since, F- is a weak field ´´ ´´ ´´ ´´ ´´ ´´
ligand and D o < P, so pairing up of electrons does not take
place and electronic configuration is t 24 g e g2 . Since, there are sp 3d 2 -hybridised
four unpaired electrons, the complex is paramagnetic. Because of the presence of five unpaired electrons, the
complex is paramagnetic.
eg Moreover, nd-orbitals are involved in bonding, so it is
dz 2 dx 2 – y 2 an outer orbital or high spin complex.
(iii) [Co(C 2O4 )3 ]3- In this complex, the oxidation state of Co
Degenerate is +3.
3d-orbital t 2g Outer configuration of Co = 3d 7 4s 2
dxy dyz dzx and for Co 3 + = 3d 6 4 s 0
3d 6 4s 0
20. The configuration of Ni 2 + ion is [Ar] 3 d 8 4s 0 .
3d 4s 4p
\ Co3+ =
2+
Ni = Oxalate ion being a strong field ligand pair up the
2+ 3d-electrons, thus, two out of the five 3d-orbitals are
In [Ni(H2O) 6 ] , H2O molecules are weak field ligands, they
available for oxalate ions.
do not cause electron pairing. As a result, the complex has 3d
two unpaired electrons. 3–
[Co(C2 O4 )3 ] = ´´ ´´ ´´´´ ´´ ´´
Thus, d-d transition takes place due to absorption of
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radiation corresponding to red light and the emission of d 2sp3-hybridised
complementary green colour occurs.
Since, all the electrons are paired, hence this complex
Hence, it is green. is diamagnetic. It is an inner orbital complex because of
In [Ni(CN) 4 ] 2 - , CN - are strong field ligands so in the the involvement of ( n - 1 ) d-orbital for bonding.
presence of CN - ions, the two unpaired electrons in the (iv) [CoF6 ]3- In this complex, the oxidation state of Co is + 3.
3d-orbital pair up. Hence, there is no unpaired electron and
Outer configuration of Co3+ = 3 d 6
no transition. Therefore, it is colourless.
21. (i) [Fe(CN)6 ]4- : In this complex, Fe is present as Fe2 +. \ Co3+ =
Outer configuration of Fe = [ Ar ] 3d 6 4s2 F- is a weak field ligand, thus it does not pair up the
Outer configuration of Fe2+ = 3d 6 4 s 0 3d electrons,
3d 6 [CoF6]3– = ´´ ´ ´ ´´ ´´ ´´ ´´
=
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sp3 d 2-hybridised
CN - being strong field ligand, pair up the unpaired
d-electrons. Thus, vacant two 3d-orbitals are now l This complex is paramagnetic, due to the presence of
available for CN - ions. 4 unpaired electrons.
3d 4p l Since, nd-orbitals are involve for bonding thus, it is a
3d 6 4s
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´´ ´´ ´´ ´´ ´´ ´´ outer orbital complex.

[Fe(CN)6 ]4- = CN- CN- CN- CN- CN- CN- 22. The main points of valence bond theory are as follows
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No unpaired (i) Central atom or ion makes available required number

electron d 2sp3-hybridised
of empty orbitals.
Since, all the electrons are paired, the complex is
(ii) These orbitals undergo hybridisation by using ( n - 1 ) d,
diamagnetic. Moreover, ( n - 1 ) d-orbitals are involved
ns, np or ns, np, nd orbitals of central atom/ion under
in bonding. So, it is an inner orbital or low spin
the influence of ligands to give same number of hybrid
complex.
orbitals of equal energy and definite geometry, such as [Cr(H 2O)6 ]3+
linear, tetrahedral, square planar and octahedral shapes.
Outer configuration of
These hybridised orbitals are allowed to overlap with
3d3 4s0
ligand orbitals that can donate electron pairs for
bonding. [Cr3+=3d3 4s0=
(iii) Ligands must have one sigma orbital containing lone
pair of electrons. 3d 4s 4p
The limitations of valence bond theory are as follows [Cr(H2O)6]3+= ´´ ´´ ´´ ´´ ´´ ´´
(i) It is based on a number of assumptions.
(ii) It does not distinguish between weak and strong d2sp3
ligands. (i) d 2 sp3-hybridisation
(iii) It does not give quantitative interpretations of (ii) Inner orbital complex [as ( n -1 ) d-orbital take part.]
magnetic data. (iii) Paramagnetic (as three unpaired electrons are
(iv) It does not give a quantitative interpretation of the present.)
thermodynamic or kinetic stabilities of coordination
(iv) m = n ( n + 2) = 3 ( 3 + 2) = 15 = 3.87 BM
compounds.
(v) It fails to explain relative energies of different shapes. 24. (i) With weak field ligands; D o < P, (pairing energy) so, the
(vi) It does not explain the colour and spectral properties of electronic configuration of Co (III) will be t 24 g e g2 , i.e. it
the compounds with C.N. = 4. has 4 unpaired electrons and is paramagnetic.
(vii) It fails to predict the exact tetrahedral and square eg
planar structures of complexes with C.N. = 4.
23. [Mn(CN)6 ]3-
Outer configuration of Mn 3+ = 3d 4
Degenerate t2g
3d d-orbital
= With strong field ligands, D o > P (pairing energy),
3d 4s 4p so pairing occurs thus, the electronic configuration
will be t 26 g e g0 . It has no unpaired electrons and is
[Mn(CN)6]3– = ´´ ´´ ´´ ´´ ´´ ´´
diamagnetic.
CN– CN– CN– CN– CN– CN–
eg
d2sp3-hybridisation
(i) d 2 sp3-hybridisation
(ii) Inner orbital complex because ( n - 1 ) d-orbitals are Degenerate t2g
used. d-orbital
(iii) Paramagnetic, as two unpaired electrons are present.
(ii) CN - and NH 3 being strong field ligand pair up the t 2 g
(iv) Spin only magnetic moment
electrons before filling e g set.
( m ) = 2 ( 2 + 2) = 8 = 2.82 BM
But this is not the case with F- ligand as it is a weak
[Co(NH 3 )6 ]3+ field ligand.
Outer configuration of Co3+ = 3d 6 4s 0 [CoF6 ]3- ; Electronic configuration Co3+ =( d 6 ) t 24 g e g2
6
3d
eg
=
3d 4s 4p
[Co(NH3)6]3+ = ´´ ´´ ´´ ´´ ´´ ´´ Degenerate d-orbitals
t2g
d2sp3
[Fe(CN)6 ]4- ; Electronic configuration Fe2 + = ( d 6 ) t 26 g e g0
(NH 3 pair up the unpaired 3d-electrons.) eg
(i) d 2 sp3-hybridisation
(ii) Inner orbital complex because of the involvement of
( n - 1 ) d-orbital in bonding.
Degenerate d-orbitals
(iii) Diamagnetic, as no unpaired electron is present. t2g
(iv) m = n ( n + 2) = 0 ( 0 + 2) = 0 (Zero)
[Cu(NH3 )6 ]2+ ; Electronic configuration Cu 2 + = ( d 9 ) t 36g e g3 eg

eg
Degenerate
d-orbitals t2g
Degenerate
t2g
d-orbitals Number of unpaired electrons ( n ) = 3
25. Because of the presence of six ligands the complex is m = 3 ( 3 + 2) = 15 = 3.87 BM
octahedral and thus, d-orbital split up into lower energy [Co(CN)6 ] , i.e. Co 3 +
3-
t 2 g -orbitals and higher energy eg- orbitals.
Electronic configuration of Co3+ = 3d6( or t 26 g e g0 )
CN - is a strong field ligand (thus, causes pairing) and H2O is
a weak field ligand. Mn (II) ion has 3d5 configuration. In the eg
presence of H2O molecules (acting as weak field ligand), the
distribution of these five electrons is t 23 g , e g2 , i.e. all the
electrons remain unpaired to form a high spin complex. Degenerate
d-orbitals t2g
eg
d x2 _ y2 d z2
There is no unpaired electron, so it is diamagnetic.
(ii) [FeF6 ] 3-
Do
Electronic configuration of Fe3+ = 3 d5 ( or t 23 g e g2 )
Degenerate
d-orbitals
eg
t 2g
dxy dyz dzx
Splitting in the presence of
octahedral weak field Degenerate
d-orbitals t2g
However, in the presence of CN - (acting as strong field
Number of unpaired electrons, n = 5
ligands), the distribution of these electrons is t52 g , e g0 , i.e. two
t 2 g orbitals contain paired electrons, while the third t 2 g m = 5 ( 5 + 2) = 35 = 5.92 BM
orbital contains one unpaired electron.The complex formed [Fe(H 2O)6 ] 2+
is a low spin complex.
eg Electronic configuration of Fe2+ = 3 d 6 ( or t 24 g e g2 )
Degenerate eg
d-orbitals
Do
Degenerate
Splitting in the t 2g d-orbitals t2g
presence of strong
field ligand
Number of unpaired electrons, n = 4
26. (i) [CoF6 ]3- , i.e. Co 3 + m = 4 ( 4 + 2)
Configuration of Co3+ = 3d 6 (or t 24g e g2 ) Z = 24 = 4.98 BM
eg [Fe(CN)6 ]4-
Electronic configuration of Fe2+ = 3 d 6 ( or t 26 g e g0 )
eg
Degenerate
d-orbitals t2g
Number of unpaired electrons ( n ) = 4 Degenerate

Magnetic moment ( m ) = n ( n + 2) d-orbitals t2g
= 4 ( 4 + 2) Since, CN- is a strong field ligand, all the electrons get
= 24 = 4. 9 BM paired. Hence, there is no unpaired electron, so it is
2+ 2+ diamagnetic in nature.
[Co(H 2O)6 ] , i.e. Co
27. (i) Hexaammine chromium (III) ion, [Cr(NH 3) 6] 3+ ion
Configuration of Co2+ = 3d 7 ( or t52 g e g2 )
Oxidation state of Cr = +3
Outer electronic configuration of 24 Cr = [ Ar] 3d5 4s1 28. (i) [Cr(H2O)2(C 2O 4)2]-
Outer electronic configuration of Cr 3+ = [ Ar] 3d 3 In this complex, Cr is present as Cr 3+
3d 4s 4p
Cr 3+ = [Ar] 3 d 3 4s 0
Cr3+ = Hybridisation d 2 sp2

Shape Octahedral
3d 4s 4p
Magnetic property Paramagnetic
3+ ´´ ´´ ´´ ´´ ´´ ´´
[Cr(NH3)6] = (ii) The s - orbtial is spherically symmetric in shape so it
NH3 NH3 NH3 NH3 NH3 NH3 does not show preference to any direction.
Three unpaired 2 3
d sp -hybridisation
It is the same from all the directions.
electron (iii) In[CoF6]3- unpaired electrons are present in sp3d 2
Cr 3+ provides six empty orbitals to accommodate six configuration but in[Co(NH3 )6]3+ , all electrons are
electron pairs from six NH 3 molecules. It involves paired in d 2 sp3-configuration.
d 2 sp3 hybridisation and hence, octahedral. [Co(NH 3 )4 Cl 2 ] Cl
It is paramagnetic due to the presence of three In this complex, Co is present as Co3+
unpaired electrons.
Outer configuration of Co3+ = [ Ar ] 3d 6 4s 0
Tetracyanonickelate (II) ion, [Ni(CN) 4 ]2-
Electronic configuration of Ni = [ Ar] 3d 8 4s 2 and for (iv) Hybridisation d 2 sp3
Ni2 + = [ Ar] 3d 8 Shape Octahedral
Magnetic properites Diamagnetic [as is a strong field
3d8 4s 4p
ligand]
Ni2+ = Or
(CN - being strong field ligand causes pairing of 3d [ Cr(NH3 ) 6 ] 3+ is a octahedral complex including
electrons thus, one of the 3d-orbital becomes empty for d 2 sp2 -hybridisation. It is paramagnetic due to the
CN - ion.) presence of three unpaired electrons.
3d 4s 4p 29. (i) The correct structure of [Pt(en)Cl 2 ] is
2– ´´ ´´ ´´ ´´
[Ni(CN)4] = H2
CH2 N Cl
All electrons ds p2-hybridisation Pt
are paired CH2 N Cl
H2
Unpaired electron is not present so it is diamagnetic.
(ii) In both the complex compounds, Fe is in +2 oxidation (ii) In Cu 2[ZnF8], coordination number of Zn is 8 as it
state with configuration 3d 6 , i.e. it has four unpaired attached to 8-fluorine atoms.
electrons. In the presence of weak H2O ligands, the (iii) Oxalate (C 2O 24 - ) is bidentate ligand as it can bonded
unpaired electrons do not pair up. But in the presence through two donor sites to central metal atom/ion.
of strong ligand CN - , they get paired up. Then no (iv) Ethylene diaminetetraacetate ion (EDTA 4 - ) is
unpaired electron is left. Due to this difference in the hexadentate ligand and classified in polydentate ligand.
number of unpaired electrons, both complex ions have Or
different colours. [ Fe(CN) 6 ] 4 - is colourless and en (ethylenediamine) is a bidentate ligand.
[ Fe(H2O) 6 ] 2 + is coloured.
Chapter Test 7. Assertion Removal of water from [ Ti(H2O) 6 ] Cl3 on
heating renders it colourless.
Multiple Choice Questions Reason In the absence of ligand, crystal field
splitting does not occur.
1. According to postulates of Werner’s theory for
coordination compounds, which of the following is true? Short Answer Type Questions
(a) Primary valencies are ionisable. 8. For the complex [Fe(en) 2 Cl2 ]Cl, identify the
(b) Secondary valencies are ionisable.
following :
(c) Only primary valencies are non-ionisable
(d) Both primary and secondary valencies are non-ionisable. (i) Name of the complex and oxidation number of iron
(ii) Hybrid orbitals and shape of the complex
2. A complex compound in which the oxidation number of a
(iii) Magnetic behaviour of the complex
metal is zero, is
(a) [Ni(CO) 4 ] 9. Predict the number of unpaired electrons and
(b) [Pt(NH 3 ) 4 ]Cl 2 magnetic nature in the square planar [Pt (CN) 4 ]2-
(c) K 3[Fe(CN) 6 ] ion.
(d) K 4 [Fe(CN) 6 ] 10. On the basis of crystal field theory, explain why
3. Which among the following will be named Co(III) forms paramagnetic octahedral complex with
as dibromidobis (ethylenediammine) weak field ligands whereas it forms diamagnetic
chromium (III) bromide ? octahedral complex with strong field ligands.
(a) [Cr(en) 3 ] Br3 11. What is the relationship between observed colour
(b) [Cr(en) 2Br2 ]Br of the complex and the wavelength of light
(c) [Cr(en)Br4 ]- absorbed by the complex?
(d) [Cr(en)Br2 ]Br
4. For d 4 ions, the fourth electron enters in one of the eg Long Answer Type Questions
orbitals giving the configuration t 23g eg1 , when 12. PtCl4 and NH3 may form five complexes,
(a) D o > P (b) D o < P A (PtCl4 ×6NH3 ), B (PtCl4 ×5NH3 ) , C (PtCl4 × 4NH3 ),
(c) D o = P (d) D o ³ P D (PtCl4 × 3NH3 ) and E(PtCl4 × 2NH3 ). One mole of
each A , B, C , D and E reacts with excess of AgNO 3 to
Assertion Reason
yield 4, 3, 2 and 1 mole(s) of AgCl respectively, while E
Direction (Q. Nos. 5-7) Each of these questions contains
gives, no AgCl. The conductance of their solutions are
two statements Assertion (A) and Reason (R). Each of
in the order A > B > C > D > E. On the basis of
these questions also has four alternative choices, any one
of which is the correct answer. You have to select one of Werner’s theory, write their structure and give the
the codes (a), (b), (c) and (d) given below. total number of ions given by one complex.
(a) Both A and R are true and R is the correct explanation of A. 13. Write down the IUPAC name for each of the
(b) Both A and R are true, but R is not the correct explanation following complexes and indicate the oxidation
of A. state, electronic configuration and coordination
number. Also give stereochemistry and magnetic
(d) A is false, but R is true.
moment of the complex.
5. Assertion The ligands of nitro and nitrito are called
ambidentate ligands. (i) K [Cr(H2O) 2 (C 2O 4) 2 ] × 3H2O
Reason These ligands give linkage isomer. (ii) [Co(NH3 )5 Cl]Cl2
3-
6. Assertion [Fe(CN) 6 ]ion shows magnetic moment (iii) [CrCl3 (py) 3 ]
corresponding to two unpaired electrons. (iv) Cs[FeCl4 ]
Reason [Fe(CN) 6 ] 3- has d 2 sp 3 type hybridisation.
(v) K 4 [Mn(CN) 6 ]
Answers
1. (a) 2. (a) 3. (b) 4. (b)
5. (a) 6. (d) 7. (a)
97
CHAPTER 06
Aldehydes, Ketones
and Carboxylic Acids
In this Chapter...
l Nomenclature and Structure of Carbonyl Group
l Preparation of Aldehydes and Ketones
l Chemical Reaction of Aldehydes and Ketones
l Carboxylic Acid
l
The organic compounds containing carbon-oxygen l
The common names of ketones are derived by naming two alkyl
double bond ( C == O ), called carbonyl group, are or aryl groups bonded to the carbonyl group.
known as carbonyl compounds. Their general formula l
The locations of substituents are indicated by Greek letters
is C n H 2 n O . aa ¢, bb¢ and so on and beginning with the carbon atoms next to
l
In aldehydes, the carbonyl group is bonded to a the carbonyl group, indicated as aa ¢.
carbon and a hydrogen, while in ketones, it is bonded l
The IUPAC names of open chain aliphatic aldehydes and ketones
to two carbon atoms.
are derived from the names of the corresponding alkanes by
O O
replacing the ending -‘e’ with -‘al’ and -‘one’, respectively.
R H R R´ l
The substituents are prefixed in alphabetical order along with
Aldehyde Ketone numerals indicating their positions in the carbon chain. When an
l
The carbonyl compounds in which carbonyl group is aldehyde group is attached to a ring, the suffix carbaldehyde is
bonded to an oxygen atom of hydroxyl moiety ( ¾ OH) added after the full name of the cycloalkane. The numbering of
are known as carboxylic acids. the ring carbon atoms start from the carbon atom attached to the
l
In compounds, where carbonyl carbon is attached to a aldehyde group.
nitrogen and to halogens, are called amides and acyl Structure
halides respectively.
The C-atom of carbonyl group is sp 2 -hybridised with bond angle
Nomenclature and Structure 120° and possessing trigonal co-planar structure.
The carbonyl carbon and the three atoms attached to it lie in the
of Carbonyl Group same plane and the p-electron cloud lies above and below this plane.
Nomenclature p-bond 120°
s-bond sp2
120°
Common names of aldehydes are derived from sp2

l
C O C O C O
corresponding carboxylic acids by replacing the sp2 sp2
ending -ic of acid with aldehyde. The location of 120°
substituent in the carbon chain is indicated by Greek Orbital diagram for the formation of carbonyl group
letters a, b, g, etc.
Preparation of Aldehydes and Ketones

Some important preparation of aldehydes and ketones are discussed below
Preparation of Aldehydes
O Aromatic aldehydes Aliphatic aldehydes
C Cl O
Pd/BaSO4
H2, Pd-BaSO4 RC—Cl + H 2
(Reduction (Rosenmund reduction)
Rosenmund reduction of acid
derivatives)
CH3
(i) Dry ether
(i) (CH3CO)2O RCN + SnCl2 + HCl
(ii) H3O+
CrO3 +
(ii) H3O+/D (Stephen reduction)
(i) CrO2Cl2,CS2 ALDEHYDES

CH3
(ii) H O+
3
(Etard reaction) K2Cr2O7 + H2SO4
(Oxidation) 1° alcohols
Anhy.AlCl3
+ CO + HCl
(Gattermann-Koch reaction) Cu/573 K
(Dehydrogenation) 1° alcohols
CH3
Cl2/hn CHCl3 or CCl4
(Ozonolysis)
RCH CHR + O3
H2O/373 K
(Side chain chlorination
followed by hydrolysis)
Preparation of Ketones The solubility of aldehydes and ketones decreases rapidly on
Dry ether increasing the length of alkyl chain. All aldehydes and ketones
R' CCl + R2Cd are fairly soluble in organic solvents.
O l
Odour Lower aldehydes have sharp pungent smell. The
KETONES odour becomes less pungent with increase in molecular
Ag or Cu
2° alcohols size. Many naturally occurring aldehydes and ketones are
(Dehydrogenation)
used in blending of perfumes and flavouring agents.
(i) Ether
R' Mg + RC N Chemical Properties
(ii) H3O+
Br l
Polar nature of carbonyl group The polarity of carbonyl group
(Friedel-Craft's
arises due to high electronegativity of O-atom. The carbonyl
O carbon acts as an electrophilic centre (Lewis acid) and carbonyl
acylation)
Anhyd.AlCl3 oxygen acts as a nucleophilic centre (Lewis base).
Ar/RCCl + C6H6
(Oppenauer oxidation)
l
Acidity of a-hydrogen atom The strong electron
Al [(CH3)3CO]3
withdrawing effect of carbonyl group and resonance
R2CHOH + (CH3)2C O stabilisation of the conjugate base are responsible for the
CrO3
2° alcohols acidity of a-hydrogen atom.
[O] O O O
Physical Properties —C—C— —C—C— —

—C—C—
l
Physical state Lower member of aldehydes and ketones
H B
upto C10 are colourless, volatile liquid, while
formaldehyde is a gas at ordinary temperature. Higher l
Nucleophilic addition reactions In nucleophilic addition
members of both are solids with fruity odour. reactions, the reactivity of aldehydes is more than that of
l
Boiling points Boiling points of carbonyl compounds are ketones due to the following reasons
higher than those of non-polar compounds, hydrocarbons (i) Steric reason The attack of nucleophile on carbonyl carbon
and ethers due to dipole-dipole interactions. But their is hindered by the presence of large substituents in ketones.
boiling points are lower than those of corresponding alcohols. (ii) Electronic reason The presence of two alkyl groups in
l
Solubility Lower members of aldehydes and ketones are ketones reduce the electrophilicity of carbonyl carbon
soluble in water because of H-bonding. more effectively than in aldehydes.
Chemical Reactions of Aldehydes and Ketones

Some important chemical reactions of aldehydes and ketones are discussed below
Reduction Oxidation
K2 Cr2 O7/H+
NaBH4 RCOOH 9.
1. alcohols
or LiAlH4
– 2[Ag(NH3) 2] +
2Ag ¯ + RCOO 10.
Tollen’s test
Zn-Hg/HCl (Only aldehydes)
2. CH2
Clemmensen
Alkane
reduction Chemical reactions – 2Cu2++ 5OH– 11.
Cu2 O¯ +RCOO
NH2 ¾NH2/OH– of aldehydes (Only aldehydes) Fehling’s test
3. CH2 and ketones
Wolff-Kishner Alkane – + NaOX
reduction CHX3¯ +RCOONa 12.
(Only carbonyl group having
atleast one methyl give this
Nucleophilic addition reaction)
reaction
with CN Reactions due to

4. C
HCN/OH– a -hydrogens
OH
Cyanohydrin
Aldol condensation
NaHSO3 SO3 Na 13.
5. C Dil.
2CH3CHO CH3CH¾ CH2CHO
OH NaOH
Bisulphite addition
product OH
–H2O
R OH OR ROH OR
6. C C CH3 ¾CH ¾ CH—CHO
Dry HCl Dry HCl
OH OR
Hemiacetal Acetal
CH2OH Cannizzaro reaction
14.
CH2OH OCH2
7. C
Dry HCl C6H5CHO + HCHO
OCH2 D conc.
Ketal NaOH
H2N— Z –+
8. C==N¾Z C6 H5CH2OH + HCOONa
Z=OH,–NH2
C6 H5NH2 Imine
Uses of Aldehydes and Ketones For naming compounds containing more than one
l
These are used as solvents in chemical industry. carboxyl group, the alkyl chain leaving carboxyl groups is
numbered and number of carboxyl groups are indicated by
l
Formalin (40% solution of formaldehyde) is used to preserve
adding multiplicative prefix to the name of parent alkyl
biological specimens and to prepare bakelite. chain.
l
Benzaldehyde is used in perfumery and in dye industries.
Structure
Carboxylic Acids
In carboxylic acids, the bonds to the carboxyl carbon lie in
The carboxyl group, consists of a carbonyl group attached to a
one plane and are separated by about 120°.
hydroxyl group. They may be aliphatic (RCOOH) or aromatic
(ArCOOH) depending on the group, alkyl or aryl, attached to The entire molecule is planar with sp 2 -hybridised carbon
carboxylic carbon. Their general formula is Cn H2 n O2 . atom and trigonal planar geometry. The carboxylic carbon
is less electrophilic than carbonyl carbon because of
Nomenclature and Structure possible structures
of Carboxyl Group O O
– –
O
In IUPAC system, aliphatic carboxylic acids are named by –C –C + –C
replacing the ending ‘-e’ in the name of the corresponding O¾H O¾H O¾H
+
alkane with ‘-oic’ acid.
Preparation of Carboxylic Acids l Esterification

H+
(i) Alkaline KMnO4
RCH2OH RCOOH + R¢ OH RCOOR¢ + H2 O
w
(ii) H3O+
[O]
(1°) l Reaction with PCl 5 , PCl 3 and SOCl 2
RCOOH
RCHO
PCl5
H2O RCOCl + POCl3 + HCl
(RCO)2O H3O+/D PCl3
Ar/RCOZ R—COOH 3RCOCl + H3PO3
SOCl2
(Z = NH2, —X, OR', etc.) RCOCl + SO2 + HCl
H+/OH–
Ar/RCOOR' + H2O
Hydrolysis of ester H+ or OH–
l Reaction with ammonia
RCN – + D
H2O, D RCOOH + NH3 —® RCO O N H 4 —® RCONH2
- H 2O
Dry ether
CO2 + RMgX
l
Reactions involving —COOH group
H3O+ l Reduction
(i) LiAlH 4 / ether or B2 H 6
Physical Properties RCOOH ¾¾¾¾¾¾¾® RCH2 OH
(ii) H 3 O+
l
Colour These are colourless liquids upto nine carbon
atoms at room temperature. l Decarboxylation
– + NaOH + CaO
l
Boiling points Monocarboxylic acid have higher boiling
RCO O Na ¾¾¾¾® R — H + Na 2 CO3
points as compared to the alcohols of comparable molecular Heat
masses due to the presence of strong intermolecular l
Substitution reactions in the hydrocarbon part
hydrogen bonding. l Hell-Volhard Zelinsky reaction
l
They exist in dimeric forms due to intermolecular hydrogen (i) X 2 / Red P
bonding. Carboxylic acids have high melting points. RCH2 COOH ———® R — CH COOH
(ii) H 2O
l
Solubility Simple aliphatic carboxylic acids having upto ½
four carbon atoms are soluble in water due to H-bonding. X
Solubility decreases with increase in number of C-atoms.
Higher carboxylic acids are practically insoluble in water. Electrophilic Ring Substitution
Aromatic carboxylic acids undergo electrophilic substitution
Chemical Properties reactions in which the carboxyl group acts as a deactivating
and meta-directing group.
l
Reactions involving cleavage of O—H bond
They do not undergo Friedel-Crafts reaction because
l Acidity of carboxylic acids carboxyl group is deactivating group and catalyst AlCl 3 (Lewis
2Na – +
2RCOO Na + H2 acid) gets bonded to the carboxyl group.
NaOH – + COOH COOH COOH
R—COOH RCOO Na + H2O
NaHCO3 – +
RCOO Na + H2O + CO2 Br2 Conc. HNO3
FeBr3, D Conc. H2SO4, D
l Carboxylic acids are stronger acids than alcohols Br NO2
and many simple phenols but weaker than mineral
acids.
Uses of Carboxylic Acids
l Electron withdrawing group stabilises the carboxylate
anion and strengthen the acid, whereas electron l
HCOOH is used in rubber, textile, dyeing, leather and
donating group destabilises the carboxylate anion and electroplating industries.
weakens the acid. l
CH3 COOH is used as a solvent, hexanedioic acid is used in
l
Reactions involving cleavage of C—OH bond the manufacture of nylon-6, 6. Sodium benzoate is used as
l Formation of anhydride a food preservative.
Note Phenol and carboxylic acid can be distinguished by their reaction
O O
+ with NaHCO 3. Carboxylic acid gives effervescence of CO2 with
H D
2R—COOH R—C C—R NaHCO3 gas, whereas phenol does not undergo any reaction
or P2O5, D with it.
O
Chapter
Practice
6. Alcohol vapours are passed over which of the
PART 1 following catalysts to give aldehydes and ketones?
(a) S or Pd (b) Ag or Cu
Objective Questions (c) F or Cl (d) Li or K
1. The bond angle and structure of carbonyl 7. Consider the following reaction,
compounds respectively are CHC6H5 (i) O3
(a) 120° and trigonal planar
(ii) Zn / H2O
(b) 109°28¢ and tetrahedral
(c) 120° and tetrahedral O
(d) 109°28¢ and trigonal planar +X
2. The orbital diagram for the formation of carbonyl
group is given as follows The compound X is
CHO CHO
sp I sp II 120° III (a) (b)
2 2
sp 2 C O sp 2 C O 120° C O
120° OH COOH
(c) (d)
(A) (B) (C)
Which type of bond is involved in I and II? 8. Rosenmund reduction gives
I II I II (a) aldehyde (b) ether
(a) s p (b) p p (c) carboxylic acid (d) hydrocarbon
(c) s s (d) p s 9. In the reaction,
3. The most suitable reagent for the conversion of H 3C ¾ CH == CH ¾ CH 2 ¾ CH 2 ¾ CN
R ¾ CH 2 ¾ OH ¾® R ¾ CHO is (i) AlH(i —Bu)2
(a) KMnO4 ¾¾¾¾¾¾®
(ii) H 2 O
(b) K2Cr2O7
Identify the product formed in the given reaction.
(c) H2 SO4
(a) H3C ¾ CH2CH2CH2CH2CN
(d) PCC (Pyridinium Chlorochromate)
(b) H3C ¾ CH == CH ¾ CH2CH2CHO
4. The reaction that does not give benzoic acid as the
major product is (c) H3CCH2CH2CH2CH2CHO
CH2OH COCH3 (d) None of the above
K2Cr2O7 (i) NaOCl
(a) (b) 10. Select the structure of chromium complex formed
(ii) H3O+
when toluene reacts with chromyl chloride to give
CH2OH CH2OH benzaldehyde on hydrolysis.
PCC KMnO4/H+ CH(OCrCl2)2 CH2(OCrOHCl2)
(c) (d)
(Pyridinium
chlorochromate) (a) (b)
5. Which of the following compounds will give

butanone on oxidation with alkaline KMnO 4 CH(OCrOHCl2)2 CH(OCrOH2Cl)2
solution? (NCERT Exemplar)
(c) (d)
(a) Butan-1-ol (b) Butan-2-ol
(c) Both (a) and (b) (d) None of these
11. The reagent which does not react with both, acetone 18. The carboxylic carbon is less electrophilic than
and benzaldehyde ? (NCERT) carbonyl carbon because of
(a) Sodium hydrogen sulphite (a) the possible resonating structure
(b) Phenyl hydrazine (b) Lewis structure
(c) Fehling's solution (c) the possible hyperconjugative structure
(d) Grignard reagent (d) Both (a) and (b)
12. The most polar compound among the given carbonyl 19. Which of the following types of hydrolysis of esters
compounds is give directly carboxylic acids and carboxylates
(a) propanone respectively?
(b) formaldehyde (a) Acidic hydrolysis and basic hydrolysis
(c) propanal (b) Basic hydrolysis and acidic hydrolysis
(d) hexan-3-one (c) Acidic hydrolysis and acidic hydrolysis
(d) Basic hydrolysis and basic hydrolysis
13. Arrange the following compounds in the increasing
20. The following steps are given for the mechanism of
order of their boiling points.
esterification of carboxylic acids.
CH 3CH 2CH 2CHO, CH 3CH 2CH 2CH 2OH,
(I) (II)
I. The protonated esters loses a proton to give the
ester.
H 5C 2O — C 2 H 5 , CH 3CH 2CH 2CH 2CH 3 II. Protonation of the carbonyl oxygen activates the
(III) (IV)
carbonyl group towards nucleophilic addition of
(a) IV < I < II < III (b) IV < III < II < I
the alcohol.
(c) IV < III < I < II (d) IV < II < III < I
III. Proton transfer in the tetrahedral intermediate
14. Which of the following compounds is most reactive occurs.
towards nucleophilic addition reactions?
Arrange the following steps in their correct sequence.
(NCERT Exemplar)
(a) I, II and III (b) I, III and II
O O
|| || (c) II, III and I (d) III, II and I
(a) CH 3 ¾ C ¾ H (b) CH 3 ¾ C ¾ CH 3 21. Name the product formed during the
decarboxylation of malonic acid.
O O
(c) (d) (a) Acetic acid (b) Ethanone
C H C CH3 (c) Propanone (d) Formic acid
22. The product formed during Hell-Volhard-Zelinsky
reaction is
15. Which of the following compound does not reduce
(a) R ¾ CH— COOH (b) R — CH2 ¾ COX
Fehling solution? ½
(a) CH 3COOH (b) HCOOH X
(c) HCHO (d) CH 3CHO X
½
16. Which of the following compounds do not undergo (c) R ¾ C — COOH (d) R ¾ CH— CH2 ¾ COOH
aldol condensation? ½ ½
CH3 X X
½
(a) CH3 ¾ C ¾ CHO (b) CH3 ¾ CHO
l
½ Direction (Q. Nos. 23-29) Each of these questions
CH3 contains two statements Assertion (A) and Reason (R).
O Each of these questions also has four alternative
½½ choices, any one of which is the correct answer. You
(c) CH3 ¾ C ¾ CH3 (d) CH3CH2 CHO have to select one of the codes (a), (b), (c) and (d) given
17. Which one of the following aldehydes does not give below.
Cannizzaro reaction? (NCERT) (a) Both A and R are true and R is the correct
(a) Formaldehyde explanation of A.
(b) Acetaldehyde
explanation of A.
(c) Trimethyl acetaldehyde (c) A is true, but R is false.
(d) Benzaldehyde (d) A is false, but R is true.
23. Assertion IUPAC name of However, on heating with only mineral acids,
HOOC — ( CH 2 — ) 2 COOH is butane - dioic acid. carboxylic acids gives corresponding anhydride. Acid
Reason In compounds containing more than one anhydrides are obtained by the elimination of water
carboxyl group, ‘-e’ of the alkane is retained, and molecules.
O
prefix ‘di’ is added to the term-‘oic’. O
24. Assertion The boiling points of aldehydes and ½½ H+ , D R C
ketones are greater than hydrocarbons and ethers of 2R ¾ C ¾ OH ¾ ¾¾® O + H 2O
or P2O5 , D R C
comparable masses.
Reason It is due to weak molecular association in O
aldehydes and ketones arising out of the (i) Which of the following is the strongest acid?
dipole-dipole interactions. (a) CH3COOH (b) ClCH2COOH
25. Assertion Cross aldol condensation of ethanol and (c) Cl 2CHCOOH (d) Cl 3C ¾ COOH
propanal gives a mixture of four products. (ii) Which of the following reagents is/are used for the
Reason Ethanal and propanal both contain conversion of ethanoic acid to ethanoic anhydride?
(a) SOCl 2, D (b) PCl 3, D
a-hydrogen atom. (c) P2O5, D (d) All of these
26. Assertion Oxidation of ketones is easier than (iii) Identify the ‘X’ and ‘Y’ from following reaction.
aldehydes. CH3 COOH + CH3 OH WX+Y
Reason C ¾ C bond of ketones is stronger than (a) X = CH3COOCH3, Y = H2O
C ¾ H bond of aldehydes.
(b) X = CH3CH2OH, Y = CO2
27. Assertion Carboxylic acids have higher boiling (c) X = CH3CH2COOH, Y = H2
liquids than aldehydes, ketones and even alcohols of
(d) X = CH3COCH3, Y = CO2
comparable molecular masses.
(iv) What is the name of the above reaction?
Reason More extensive association of carboxylic (a) Saponification
acid molecules through intermolecular hydrogen (b) Hell-Volhard-Zelinsky reaction
bonding is responsible for the high boiling point of (c) Kolbe’s reaction
carboxylic acid. (d) Esterification
28. Assertion Nitration of benzoic acid gives Or
m-nitrobenzoic acid. What will be the by products of the following
Reason Carboxyl group increases the electron reaction?
density at the meta-position. R ¾ COOH + SOCl 2 ¾® RCOCl + ? + ?
29. Assertion Benzoic acid does not undergo (a) CO 2 , HCl (b) SO 2 , H2O
Friedal-Crafts reaction.
(c) SO 2 , HCl (d) CO 2 , H2
Reason The carboxyl group is activating and undergo
electrophilic substitution reaction.
to (iv) given below
l
Case Based MCQs Nucleophilic addition reactions are encountered in
compounds containing polar functional groups
(C==O, CººN, C==S). In the first step, a nucleophile
to (iv) given below
with its pair of electrons attacks the carbon atom of a
Carboxylic acids are organic acids identified by a double or triple bond, forming a carbanion. It is
carboxyl group (—COOH). They are widespread in followed by a second step in which this carbanion
nature and are typically weak acids, meaning they reacts with a positive species.
can only dissociate into H + cations and RCOO - Y
anions in aqueous solutions. The presence of
C C + Y s
C Cs
electronegative groups (such as OH - or Cl - ) next to Step I
be carboxylic acid increases the acidity through Y Y

inductive effects. The carboxylic acids react with Step II C Cs + Wr C C W
alcohols or phenols in the presence of a mineral acid
such as conc. H 2SO 4 or HCl gas (as a catalyst) to form
an ester. When the olefin contains a good leaving group (as
defined for nucleophilic substitution), substitution is
a side reaction, (i.e. a nucleophilic substitution at a (iv) Which of the following alternative is correct for the
vinylic substrate). treatment of ketones with ethylene glycol in the
Addition of HCN to carbonyl group and addition of presence of dry HCl?
(a) The product obtained is ethylene glycol hemi-ketal
alcohol to carbonyl group is a nucleophilic addition
(b) In this reaction, electrophilicity of carbonyl carbon
reaction. decreases
Addition of HCN to carbonyl group In this reaction (c) HCl protonates the oxygen of the carbonyl group
cyanide ion (CN - ) acts as a nucleophile which (d) The product thus obtained is cyanohydrin
attacks the carbon of carbonyl group, the Or
carbon-oxygen double bond breaks followed by Consider the following reaction,
capture of proton and a cyanohydrins is formed .
é OH ù
r NC s r
C == O + H 2 N — Z s ê C ú ¾®
O O H
NC ê ú
êë NH Z ú
û
Addition of alcohol to carbonyl compounds
Aldehydes or ketones react with one mole of alcohol C == N — Z + H 2O

to form hemiacetal or hemiketal, respectively.
Which of the following statements is/are true about
Reaction with second mole of alcohol gives acetal or
the above reaction?
ketal. In this reaction, the alcohol with lone pair of
(a) H2N— Z tends to add to the carbon of carbonyl group of
electrons of oxygen atom acts as a nucleophile. aldehydes and ketones
O HO OR RO OR (b) The reaction is reversible and catalysed by acid
R OH ROH
(c) The equilibrium favours the product formation due to
Catalysed by Catalysed by rapid dehydration of the intermediate
R R acid or base R R acid only R R
Ketone Hemiacetal Acetal
(i) Identify the example in which both nucleophilic

addition and nucleophilic addition elimination PART 2
reaction occur respectively in the carbonyl
compound.
(a) Addition of Grignard reagent
(b) Addition of sodium sulphide
(c) Addition of HCN
l
(d) Addition of NH3 1. Write the IUPAC names of the following ketones
(ii) Arrange the following carbonyl compounds in and aldehydes. Wherever possible, give their
increasing order of their reactivity in nucleophilic common names. (NCERT)
addition reaction. (i) CH3 CO(CH 2 ) 4 CH3
(a) Butanone < propanone < propanal < ethanal
(ii) CH3 CH 2CHBrCH 2CH(CH3 )CHO
(b) Butanone < propanal < propanone < ethanal
(iii) CH3 (CH 2 )5 CHO
(c) Butanone < ethanal < propanone < propanal
(d) Butanone < ethanal < propanal < propanone (iv) Ph ¾ CH == CH ¾ CHO
(iii) Consider the following reaction, CHO
(v)
SO2H Proton transfer
C O + NaHSO3 qC – +
ONa
q SO3Na
(vi) PhCOPh
C 2. Write the structure of major product(s) in the
OH following
Bisulphite addition
compound (crystalline) (a) H2 N ¾NH2
(i) CH 3 ¾ CH 2 ¾ C ¾ H ¾¾¾¾¾¾¾®
|| (b) KOH, Glycol /heat
In the given reaction, equilibrium lies largely to
the right hand side for most aldehydes and the O
left for most ketones due to CH 3
(a) electronic reasons | Conc. NaOH
(b) steric reasons (ii) CH 3 ¾ C ¾ CHO ¾¾¾¾®
(c) bonding reasons |
(d) Both (a) and (b)
CH 3
3. Draw the structures of the following derivatives. 11. How do you convert the following?
(i) 2,4-dinitrophenylhydrazone of benzaldehyde (i) Ethanal to propanone
(ii) Cyclopropanone oxime (ii) Toluene to benzoic acid (CBSE 2018)
(iii) Acetaldehyde dimethylacetal 12. Identify the compounds A, B and C in the following
(iv) Semicarbazone of cyclobutanone
reaction
(v) Ethylene ketal of hexan-3-one
Mg / Ether
2 (i) CO
(vi) Methyl hemiacetal of formaldehyde CH 3 ¾ Br ¾¾¾® [ A] ¾¾¾® [ B]
(ii) Water
4. Name the electrophile produced in the reaction of CH3OH / H +
benzene with benzoyl chloride in the presence of ¾¾¾¾® [ C ]
anhydrous AlCl3 . Name the reaction also. (NCERT Exemplar)
(NCERT Exemplar) 13. Account for the following
5. Arrange the following compounds in the increasing
(i) Aromatic carboxylic acids do not undergo
order of their reactivity towards nucleophilic Friedel-Craft’s reaction.
addition reactions.
(ii) pK a value of 4-nitrobenzoic acid is lower than that of
(i) Ethanal, propanal, propanone, butanone benzoic acid. (CBSE 2018)
(ii) Benzaldehyde, p-tolualdehyde,
14. Account for the following.
p-nitrobenzaldehyde, acetophenone (NCERT)
(i) Cl ¾ CH 2COOH is a stronger acid than CH 3COOH .
6. Complete the following reaction sequence.
O (ii) Carboxylic acids do not give reactions of carbonyl
group.
(i) CH MgBr
Na metal CH3 — Br
CH3 ¾ C ¾ CH3 ¾¾¾¾
3
® A ¾¾¾®
Ether
B ¾¾¾® C 15. Write the products of the following reactions:
(ii) H2O
(NCERT Exemplar) O
+
7. An organic compound with molecular formula H
== O + NH2 ¾ NH ¾ C ¾ NH2 ¾®
(i)
C 9H10O, forms 2,4-DNP derivative, reduces Tollen’s
reagent and undergoes Cannizzaro reaction. Dry ether
On vigorous oxidation, it gives 1,2-benzene (ii) CH 3MgBr + CO 2 ¾ ¾ ¾ ¾®
H 3 O+
dicarboxylic acid. Identify the compound. (NCERT)
Red phosphorus
8. An organic compound contains 69.77% carbon, (iii) CH 3CH 2COOH + Br2 ¾¾¾¾¾® (Delhi 2017C)
11.63% hydrogen and rest oxygen. The molecular
mass of the compound is 86. It does not reduce l
Long Answer Type Questions
Tollen’s reagent but forms an addition compound 16. (i) An organic compound (A) having molecular formula
with sodium hydrogen sulphite and gives positive C4 H 8O gives orange red precipitate with 2, 4-DNP
iodoform test. reagent. It does not reduce Tollen’s reagent but gives
On vigorous oxidation, it gives ethanoic acid and yellow precipitate of iodoform on heating with
propanoic acid. Write the possible structure of the NaOH and I 2 . Compound (A) on reduction with
compound. (NCERT) NaBH 4 gives compound (B) which undergoes
9. A, B and C are three non-cyclic functional isomers dehydration reaction on heating with conc. H 2SO 4
of a carbonyl compound with molecular formula to form compound (C). Compound (C) on ozonolysis
C 4 H 8O. gives two molecules of ethanol.
Isomers A and C give positive Tollens’ test whereas Identify (A), (B) and (C) and write their structures.
isomer B does not give Tollens’ test, but gives Write the reactions of compound( A) with (i)
positive iodoform test. Isomers A and B on NaOH / I 2 and (ii) NaBH4 .
reduction with Zn-Hg/conc. HCl give the same (ii) Give reasons
product D. (a) Oxidation of propanal is easier than propanone.
(a) Write the structures of A, B, C and D. (b) a-hydrogen of aldehydes and ketones is acidic in
(b) Out of A, B and C isomers, which one is least nature.
reactive towards addition of HCN? (CBSE 2018) 17. An aldehyde A (C11H 8 O) which does not undergo self
10. Write the equations involved in the following aldol condensation but gives benzaldehyde and two
reactions moles of B on ozonolysis. Compound B on oxidation
(i) Wolf-Kishner reduction with silver ions gives oxalic acid. Identify the
(ii) Etard reaction (Delhi 2017) compounds A and B.
18. (i) Draw structures of the following derivatives formula C 3 H 6 O. E neither gives Tollen’s test nor
(a) Cyanohydrin of cyclobutanone reduces
(b) Hemiacetal of ethanal Fehling’s solution but forms 2,4-dinitrophenyl
(ii) Write a major product(s) in the following hydrazone. Identify A,B,C,D and E.
(i) DIBAL - H 23. (i) Write the products of the following reactions
(a) CH 3 ¾ CH == CH ¾ CH 2 ¾ CN ¾¾¾¾¾®
(ii) H 3 O+ +
H
CrO3 (a) == O + H2N ¾ OH ¾®
(b) CH 3 ¾ CH 2 ¾ OH ¾¾®
(iii) How can you distinguish between propanal and (b) 2 C 6H5 CHO + Conc. NaOH ¾®
propanone? (c) CH 3COOH ¾Cl 2 /P®
¾¾
19. A ketone A (CH 4 H 8O) which undergoes a haloform
(ii) Give simple chemical tests to distinguish between
reaction gives compound B on reduction, heating
the following pairs of compounds.
with sulphuric acid gives a compound C which forms
mono-ozonide D. D on hydrolysis with zinc dust (a) Benzaldehyde and benzoic acid.
gives only E. Identify A, B, C, D and E write the (b) Propanal and propanone.
reactions involved. l Case Based Questions
How does compound A gives iodoform reaction?
20. (i) Write the final products in the following
to (iv) given below
CH3
Zn/Hg
The reduction of aldehydes and ketones can be
(a) C O carried out under different conditions. Aldehydes
Conc. HCl
CH3 and ketones are reduced to primary and secondary
alcohols respectively by NaBH 4 or LiAlH 4 as well as
NaOH/CaO
(b) —COONa catalytic hydrogenation.
D
The carbonyl group of aldehydes and ketones is
I. DIBAL-H reduced to CH2 group on treatment with Zn-Hg
(c) CH2 CH—CH2—CN
II. H3O+ and concentrated HCl or with hydrazine followed by
(ii) Arrange the following in the increasing order of NaOH or KOH in highly boiling solvent such as
their reactivity towards nucleophilic addition, ethylene glycol.
reaction
The aldehydes and ketones can be differ by oxidation
CH3COCH3,HCHO, CH3CHO, —COCH3 reactions. Aldehydes are easily oxidised to carboxylic
acids on treatment with HNO 2 , KMnO 4 , K 2Cr 2O 7 ,
etc. Even mild oxidising agents mainly Tollen’s
(iii) Draw the structure of 2, 4-DNP derivative of
reagent and Fehling’s solution also oxidise aldehydes
acetaldehyde.
whereas ketones are generally oxidised under
21. (i) Write the products formed when benzaldehyde vigorous conditions, i.e. strong oxidising agents and
reacts with the following reagents at elevated temperatures, to give mixture of
(a) CH 3CHO in presence of dilute NaOH carboxylic acids having lesser number of C-atom
than the parent ketone. Benedict’s solution reacts in
(b) H2N—NH— the same way as Fehling’s solution.
O
(c) Conc. NaOH
(i) What will be the products if is oxidised by
(ii) Distinguish between following
acidified K 2 Cr2 O7 ?
(a) CH 3 ¾ CH == CH ¾ CO ¾ CH 3 and
CH 3 ¾ CH 2 ¾ CO ¾ CH == CH 2 (ii) Name the appropriate reagents for the following
(b) Benzaldehyde and benzoic acid. transformation.
O
22. An organic compound A on treatment with ethyl
CH2 CH3
alcohol gives carboxylic acid B and compound C. CH3 ?
Hydrolysis of C under acidic conditions gives B
and D. Oxidation of D with KMnO 4 also gives B. HO HO
B on heating with Ca(OH) 2 gives E with molecular Or
Or
Give the simple chemical test to distinguish between neutral, acidic or alkaline medium or by potassium
ethanal and propanal. dichormate ( K 2Cr 2O 7 ) and chromium trioxide
(iii) Complete the following reaction (CrO 3 ) in acidic medium.
O Carboxylic acids are also prepared from aldehydes
½½ by the use of mild oxidising agents like Tollen’s
CH3 ¾ C ¾ CH3 ¾LiAlH
¾¾ ¾ 4
® reagent.
(iv) The compound ‘X’ on treating with conc. H2 SO4 (i) What happens when methyl benzene is oxidised
gives C4 H8 and water. What is the compound ‘X’? with alkaline KMnO4 ?
25. Read the following and answer the questions from (i) (ii) Complete the following reaction
to (iv) given below CH3 ( CH2 )4 CH2 OH ¾CrO¾¾ 3®
H2SO4
The preparation of carboxylic acids can be done by the
oxidation of a number of functional groups using a (iii) Name the oxidising agent which is used in the
conversion of toluene to potassium benzoate.
wide variety of reagents.
(iv) When acetaldehyde is treated with Tollen’s
The preparation of carboxylic acids is primarily reagent, then the compound ‘X’ is formed. Write
characterised by the structure of the acid produced, the name and formula of ‘X ’.
the functionality of the starting material and finally, by
the oxidising agent used. Or
Write the reagents required in the following
Primary alcohols and aldehydes are readily oxidised to
reaction.
corresponding carboxylic acids with common oxidising
agents such as potassium permanganate ( KMnO 4 ) in CH 3COOH ¾ ¾? ® CH 3CONH 2
EXPLANATIONS
Objective Questions 8. (a) Acyl chloride is hydrogenated over catalyst, palladium
1. (a) The bond angles are approximately 120° with trigonal barium sulphate to give aldehyde. This reaction is called
planar structure in the carbonyl compounds. Rosenmund reaction.
O COCl CHO
H2
1 20
C
°
Pd-BaSO4
R R´/ H Benzoyl chloride Benzaldehyde
Trigonal planar 9. (b) Diisobutylaluminium hydride is used to selectively
2. (a) The type of bond involved in I and II are as follows reduce nitriles aldehydes complete reaction is as follows :
I ® Sigma (s) II ®Pi ( p) (i) AlH( i - Bu) 2
CH3 ¾ CH === CH ¾ CH2 ¾ CH2 ¾ CN ¾¾¾¾®
It can be explained as (ii) H 2O
In I, the carbonyl carbon is sp2 -hybridised and forms CH3 ¾ CH === CH ¾ CH2 ¾ CH2 ¾ CHO
3s -bonds. 10. (c) Chromyl chloride oxidises methyl group to a chromium
In II, the fourth valence electron of carbon remains in its complex, which on hydrolysis gives corresponding
p-orbital and forms a p-bond with oxygen by overlap with benzaldehyde.
p-orbital of an oxygen atom. The complete reaction is shown below
3. (d) The most suitable reagent for the conversion of alcohol CH3 CH(OCrOHCl2)2
( RCH2 ¾ OH) to aldehyde (R—CHO) is PCC
R ¾ CH2OH ¾¾® R ¾ CHO
PCC CS2 H3 O +
+ CrO2Cl2
Pyridinium chlorochromate (PCC) is a mild oxidising
agent which causes the conversion of alcohol to aldehyde CHO
Chromium
and not carboxylic acid. complex
Whereas, K2Cr2O7 and KMnO4 are strong oxidising agents
which cause conversion of alcohol directly to acid and H2SO4
acts as a dehydrating agent. Benzaldehyde
Thus, they cannot be used for the conversion. This reaction is called Etard reaction.
4. (c) Primary aromatic alcohols on reaction with pyridinium 11. (c) Acetone and benzaldehyde both do not react with
chlorochromate (PCC), which is a mild oxidising agent, form Fehling’s solution. Fehling’s solution do not react with
aromatic aldehydes. ketone as acetone is a ketone while benzaldehyde is an
Thus, this reaction will not give benzoic acid. aromatic aldehyde having absence of a-hydrogen.
CH2OH CHO 12. (b) Among the given compounds, formaldehyde is the most
PCC
polar due to lowest electron density on C of carbonyl group,
(Pyridinium whereas in all other cases, the electron density on C is high
chlorochromate)
Benzyl alcohol Benzaldehyde due to +I effect of alkyl groups.
5. (b) Butan-2-ol on oxidation with alkaline KMnO4 solution 13. (c) The boiling point of butan-1-ol (II) would be the highest,
produces butanone complete reaction is as follows due to extensive intermolecular hydrogen bonding. Butanal
CH3 [O] CH3 (I) is more polar than ethoxyethane (III). So, the
Alkaline KMnO4 intermolecular dipole-dipole attraction is stronger in butanal
OH O and will have higher boiling point than ethoxy ethane.
Butan-2-ol Butan-2-one n-pentane (IV) have only weak van der Waals’ forces and
6. (b) Alcohol vapours are passed over heavy metal catalysts (Ag thus will have the lowest boiling point.
or Cu) to give aldehydes and ketones. Primary and
Therefore, the increasing order of boiling point of the given
secondary alcohols give aldehydes and ketones respectively.
compounds are
7. (a)
CHC6H5 O IV < III < I < II
(i) O3
CHC6H5
14. (a) Reactivity of carbonyl compounds can be decided by two
O O factors.
Ozonide
(i) Steric factor Lesser the steric factor, greater will be its
O CHO reactivity.
(ii) Zn / H2O
+ (ii) Electronic factor Greater the number of alkyl group,
lesser will be its electrophilicity.
Cyclohexanone X Hence, CH3 ¾ CHO is most reactive towards
Benzaldehyde
nucleophilic addition reaction.
Here, x is benzaldehyde.
15. (a) Only compounds having —CHO group can reduce 25. (a) Both A and R are true but R is the correct explanation of A.
Fehling solution. Thus, CH3COOH does not react with 26. (d) A is false, but R is true. Oxidation of ketones is rather
Fehling solution. difficult than aldehydes because C ¾ C bond of ketones is
HCOOH have —CHO group present in it. Thus, it also stronger than C ¾ H bond of aldehydes. Therefore, ketones
reduces Fehling solution. cannot be oxidised by weak oxidising agent.
16. (a) The necessary condition for aldol condensation is the 27. (a) Both A and R are true and R is the correct explanation of
presence of atleast one a-H atom in aldehydes and ketones. A. Carboxylic acids are higher boiling liquids than
CH3 aldehydes, ketones and even alcohols of comparable
| molecular masses. This is due to more extensive association
Thus, among the given options, CH3 — C — CHO does not of carboxylic acid molecules through intermolecular
| hydrogen bonding.
CH3
28. (c) A is true, but R is false. Carboxyl group only marginally
undergo aldol condensation as it does not contains any decreases the electron density at m-position relative to o-
a-hydrogen atom. and p-positions.
17. (b) Cannizzaro reaction is given by the aldehydes that do not 29. (c) A is true, but R is false.
contain a-H-atom. The aldehydes like acetaldehyde, Benzoic acid do not undergo Friedel-Crafts reaction because
CH3CHO possess a-H-atom and hence, does not undergo the carboxyl group is deactivating and the catalyst
Cannizaro reaction. aluminium chloride (Lewis acid) gets bonded to the carboxyl
18. (a) The carboxylic carbon is less electrophilic than carbonyl group.
carbon because of the possible resonating structures as 30. (i) (d) Cl 3C ¾ COOH is the strongest acid due to presence
shown below : ]
of three electron withdrawing chlorine group ( ¾ Cl ),
–
O O next to ¾COOH group.
—C —C (ii) (c) Carboxylic acids on heating with mineral acids such
O—H O —H as H2SO4 or P2O5 give corresponding anhydride.
+
(iii) (a) CH3COOH + CH3OH e CH3COOCH3 + H2O
19. (a) Acidic hydrolysis of esters directly give carboxylic acids (X) ( Y)
while basic hydrolysis of esters gives carboxylates, which on
acidification give corresponding carboxylic acids. In the given reactions X = CH3COOCH3 and Y = H2O
COOC2H5 (iv) (d) The reaction given in previous question, i.e.
CH3COOH + CH3OH e CH3COOCH3 + H2O
COOH Acetic acid Methanol Methyl acetate Water
+
H3O
+ C2H5OH This is an esterification reaction.
Or
20. (c) The correct arrangement of steps given in the (c) In the given reaction,
esterification of carboxylic acid is II, III and I. RCOOH + SOCl 2 ¾® RCOCl + SO 2 + HCl
21. (a) The decarboxylation of malonic acid is shown below The byproducts formed are SO 2 and HCl.
b a
D 31. (i) (d) The addition of NH3 to carbonyl compound is an
HO — C — CH2 — COOH ¾® H3C— COOH + CO2
½½ Acetic acid example in which nucleophilic addition is followed by
O elimination reaction occur respectively.
Malonic acid
(i) NH3
Therefore, acetic acid is formed by the decarboxylation of C ==O ¾¾¾® C ==NH+H2O
(ii) D
malonic acid.
i.e. ammonia is added to carbonyl group and water
22. (a) Carboxylic acids having an a-hydrogen are halogenated molecules gets eliminated.
at the a-position on treatment with chlorine or bromine in (ii) (a) In ethanal ® propanal ® propanone ® butanone,
the presence of small amount of red phosphorus to give
the electron density on the carbon atom of the carbonyl
a-halocarboxylic acids. This reaction is known as
group increases due to the increase of +I-effect of the
Hell-Volhard-Zelinsky reaction.
alkyl group.
23. (a) Both A and R is true and R is the correct explanation of A. Thus, the attack by the nucleophile becomes slower
IUPAC name of HOOC — ( CH2—)2 COOH is butane-dioic and slower. The reactivity increases in the reverse
acid. For compounds containing more than one carboxyl order
group, the ending ‘-e’ of the alkane is retained. The number
Butanone <propanone < propanal < ethanal
of carboxyl groups are indicated by adding the multiplicative
prefix, di, tri etc., to the term ‘oic’. (iii) (b) The position of the equilibrium lies largely to the
right hand side for most aldehydes and to the left for
24. (a) Both A and R are true and R is the correct explanation of
most ketones due to steric reasons.
A. The boiling points of aldehydes and ketones are greater
than hydrocarbons and ethers of comparable molecular (iv) (c) Ketones react with ethylene glycol in the presence
masses. It is due to weak molecular association in aldehydes of dry HCl to form cyclic products known as ethylene
and ketones arising out of the dipole-dipole interactions. glycol ketals.
O OH O O NO2
HCl
+
OH Ethylene glycol 3.
Ketone Ethylene glycol
ketal
(i) CH NNH NO2
Or
N—OH
(d) Nucleophiles, such as ammonia and its derivatives (H2N — Z )
add to the carbonyl group of aldehydes and ketones. The reaction is (ii)
reversible and catalysed by acid.
The equilibrium favours the product formation due to rapid
OCH3
dehydration of the intermediate C OH . H3C
NHZ (iii) C
H OCH3
Structure IUPAC name Common name
1. O
CH3CO(CH2 ) 4 CH3 Heptan- 2-one Methyl n-pentyl
ketone (iv) NNH—C—NH2
CH3CH2CHBrCH2 4-bromo-2- g-bromo-
CH(CH3 )CHO methylhexanal a-methyl H2C —CH2
caproaldehyde
(v) O O
CH3(CH2 )5 CHO Heptanal Heptanaldehyde
CH3—CH2—C——CH2—CH2—CH3
Ph ¾ CH == CH ¾ CHO 3-phenylprop-2-enal b-phenylacrolein
H OH
CHO Cyclopentane Cyclopentane (vi) C
carbaldehyde carbaldehyde
H OCH3
PhCOPh Diphenylmethanone Benzophenone 4. Benzene, on reaction with benzoyl chloride gives
benzophenone through an intermediate benzoylinium cation.
2. Structure of major product O
(a) H2N —NH2
(i) CH3 ¾ CH2 ¾ C ¾ H ¾¾¾¾¾¾¾¾® ¾ C ¾ Cl + AlCl3 (anhydrous) ¾®
½½ (b) KOH, glycol or heat O
O
O
+
H H H ¾ C ¾¾¾®
½ ½ ½
CH3 ¾ CH2 ¾ CH3 Or H ¾ C ¾ C ¾ C ¾ H Benzoylinium Benzophenone
Propane ½ ½ ½ cation
H H H This is an example of Friedel-Craft’s acylation reaction.
CH3 5. The electron density on the carbon atom of the carbonyl
½ Conc. NaOH - + group increases due to increase + I effect of alkyl group.
(ii) CH3 ¾ C ¾ CHO ¾¾¾¾® (CH3 )3 COONa + H2O
½ (i) Butanone < propanone < propanal < ethanal
CH3 (ii) Acetophenone < p-tolualdehyde < benzaldehyde
H < p-nitrobenzaldehyde
H H C H 6.
O OH
s Å
Or H C C O Na + H2 O (i) CH3MgBr Na metal
CH3 ¾ C ¾ CH3 ¾¾¾® CH3 ¾ C ¾ CH3 Ether
(ii) H2O
H H C H
CH3
H (A)
–+ Since, it does not give Tollen’s test but gives positive

ONa O ¾ CH3
iodoform test, hence it is a methyl ketone, i.e. have
CH Br ¾ COCH3 group. Since, it gives ethanoic acid and
CH3 ¾ C ¾ CH3 ¾¾¾®3
CH3 ¾ C ¾ CH3
-NaBr propanoic acid on oxidation, it is pentan-2-one.
CH3 CH2 [O]
CH3 ¾ C ¾ CH2 CH2CH3 ¾® CH3COOH+ CH3CH2COOH
(B) (C ) ½½ Acetic acid Propenoic acid
2-methyl-2-methoxy O
propane Pentan -2-one
Hence, the compound is pentan-2-one.
7. l
As the given compound with molecular formula C9 H10O,
forms a 2,4-DNP derivative and reduces Tollen’s reagent, 9. The possible functional isomers of carbonyl compound with
thus it must be an aldehyde. molecular formula, C4H8 O are
l
As it undergoes Cannizzaro reaction, hence ¾CHO CH 3 O
group is directly attached to the benzene ring. ½ ½½
l
On vigorous oxidation, it gives 1,2-benzenedicarboxylic CH3 ¾ CH ¾ CHO, CH3CH2CH2CHO, CH3CH2 ¾ C ¾ CH3
acid. Isomers (A) and (C) gives positive Tollen’s test, thus they
l
Therefore, it must be an ortho-substituted benzaldehyde must be aldehydes.
and the only o-substituted aromatic aldehyde which have D
C 9 H10O molecular formula is o-ethyl benzaldehyde. RCHO + 2[Ag(NH3 )2 ]+ + 3 OH- ¾® RCOO-
Aldehyde Tollen's reagent
Reactions involved
+ 2Ag ¯ + 2H2O + 4NH3
CHO –
COO– Silver mirror
[Ag(NH3)2]+OH
¾¾¾¾®
Tollen’s reagent
+ Ag ¯ RCHO = CH3 ¾ CH ¾ CHO and CH3CH2CH2CHO
C2H5 C2H5 Silver ½
2-ethylbenzoate mirror CH3
o-ethyl benzaldehyde
10. (i) Wolff-Kishner reduction Carbonyl group are easily reduce
CHO COOH by hydrazine followed by heating with strong base like alkali to
[O]
¾¾® CH .
2
C2H5 COOH
1, 2-benzene NH2NH2
dicarboxylic acid C O ¾¾¾®
–H O
C N—NH2
2
Ketone
NO2
or aldehyde
KOH
¾¾¾®
Ethylene
CH2 + N2
H2NNH ¾ ¾ NO2
glycol
CHO
2,4-DNP (ii) Etard reaction Toluene reacts with chromyl chloride in
¾¾¾¾¾¾¾¾¾®
presence of CS 2 followed by hydrolysis produces
C2H5 benzaldehyde.
O2N CH3 CH(OCrOHCl2)2 CHO
CH==NNH ¾ ¾ NO2 + H2O CS2 H O+

+ CrO2Cl2 ¾® ¾¾®
3
2,4-DNP derivative Chromyl

Chromium
C2H5 Toluene chloride
complex
Benzaldehyde
8. C = 69.77%, H = 11.63%, O = 100 - (69.77 + 11.63) = 18.6% 11. (i) Ethanal to propanone
– +
Percentage Molar mass Moles Simple OMgBr
Element
—
(x) (y) (x/ y) ratio CH3CHO

CH3MgBr
CH3CH—CH3
Hydrolysis
Ethanal
C 69.77 12 5.81 5 OH O
—
—
—
H 11.63 1 11.63 10 CH3—CH—CH3

Oxidation
CH3—C—CH3
K2Cr2O7 /H2 SO4 Propanone
O 18.60 16 1.16 1 Propan-2-ol
(ii) Toluene to benzoic acid

Empirical formula of given compound = C5H10O CH3 COOH
Empirical formula mass = 5 ´ 12 + 10 ´ 1 + 1 ´ 16 = 86 ½ ½
86 K2Cr2O7+H2SO4
n= =1
86 Oxidation
\ Molecular formula = (C5H10O)1 = C5H10O Toluene Benzoic acid

12. Complete chemical conversion can be done as Dry ether

(ii) CH3MgBr + CO2 ¾¾¾¾® +
CH3COOH
Mg / Ether (i) CO 2 H 3O
CH3 ¾ Br ¾¾® CH3MgBr ¾¾®
(ii) Water
Bromomethane (A) Red
Methyl magnesium phosphorus
bromide (iii) CH3CH2COOH + Br2 ¾¾¾® CH3 — CH—COOH
|
3 CH OH/ H+ Br
CH3COOH ¾¾¾¾® CH3COOCH3
( B) (C ) 16. (i) A forms 2, 4-DNP derivative. Therefore, it is an
Ethanoic acid Methyl ethanoate aldehyde or a ketone. Since, it does not reduce Tollen’s
Hence, A = CH3MgBr, B = CH3COOH, reagent. Therefore, it should be a ketone. Given,
O compound also gives yellow precipitate of iodoform on
½½ heating with NaOH and I2. So, it must be methyl
C = CH3 ¾ C ¾ O ¾ CH3 ketone.
NO2
13. (i) The ¾ COOH group attached to benzene ring is electron O
withdrawing in nature and thus deactivates ring. Secondly,
the catalyst used in the reaction, i.e. AlCl 3 is a Lewis acid CH3 ¾ CH2 ¾ C ¾ CH3 + H2NHN NO2
which has the tendency to make bond with carboxyl group. (A)
That’s why aromatic carboxylic acid does not undergo Butanone
NO2
Friedel-Craft’s reaction.
(ii) Lower pK a value means stronger acid. pK a value of –H2O
4-nitro benzoic acid is lower than benzoic acid due to ¾ N ¾ NH
CH3 ¾ CH ¾ CH¾ NO2
following reasons:
CH3
(a) Due to – I and – R effect of ¾ NO2 group, electron
2, 4-DNP derivative
density in O ¾ H bond decreases, thus it becomes
weak and easily loses a proton and therefore it is O O
more acidic. NaOH/I2
CH3CH2¾C¾ CH3 CHI3 ¯ + CH3CH2¾ C¾ O–Na+
Haloform
(b) Due to – I and – R effect of ¾ NO2 group, test Iodoform
delocalisation of -ve charge occurs and NaBH4 (yellow ppt.)
p-nitrobenzoate ion becomes more stable than
OH
benzoate ion. H3C H
Conc. H2SO4
14. (i) Cl ¾ CH2COOH is a stronger acid than CH3COOH. This CH3¾CH2¾CH¾ CH3 C¾C
is because ¾ Cl group exhibits -I-effect which makes the Butan-2-ol H CH3
carboxylate ion more stable. (C)
But-2-ene
Higher the stability of carboxylate ion, easier is the O3
removal of proton from the carboxylic acid and stronger is 2CH3CHO
Zn—CH3COOH
the acid.
(ii) (a) The C ==O bond present in carbonyl compounds
In CH3COOH, ¾ CH3 group has + I-effect which have electron withdrawing nature. The C ¾ H bond
destabilised it. Hence, CH3COOH is a weaker acid. in aldehyde is weak and thus it can be easily
(ii) Carboxylic acids contain carbonyl group but do not show oxidised to corresponding carboxylic acid.
the reactions of carbonyl group such as nucleophilic
The C ¾ C bond in ketone is stronger than C ¾ H
addition reaction which are shown by aldehydes
bond of aldehyde. Hence, oxidation is easier in
and ketones.
propanal than propanone.
It is because of the presence of lone pair of electrons on
(b) The acidity of a-hydrogen atom of carbonyl carbon
the O-atom of ¾OH group, the electrophilic character of
is due to the strong withdrawing effect of the
carbonyl carbon by resonance decreases, hence the
carbonyl group and resonance stabilisation of the
partial positive charge on carbonyl carbon atom is
conjugate base.
reduced and therefore, they do not show nucleophilic s
addition reactions. O O O
O O-
¾C¾C¾ ¾C¾C¾ ¾ C == C ¾
+ s
¾ C ¾ O ¾ H ¬® ¾ C == O ¾ H H:B
O 17. As the compound A (C11 H8O) gives benzaldehyde as one of
15. (i) O + NH2 — NH — C—NH2 H+ the products on ozonolysis, it must have a benzene nucleus
or phenyl group ( C 6H5 ).
NNHCONH2 Since, the compound ‘A’ gives ozonolysis products, it is an
aldehyde with C ==C attaches with the ring.
Therefore, the side chain should be C 4H2CHO. The reactions involved are
\ Compound A = C 6H5 —(C 4H2CHO) [H]
CH3COCH2CH3 ¾¾® CH3 ¾ CH ¾ CH2CH3
LiAlH4
As one mole of A on ozonolysis gives two moles of B, this means Butan-2-one
½
that the side chain must have unsaturation at two places, one of (A )
OH
these should be a triple bond, based on formula. Compound A Butan-2-ol
does not undergo aldol condensation, so no a -H atom is present. (B )
So, compound A is C 6H5 ¾ CH==CH ¾ C ºº C ¾ CHO. Conc. H2SO4 3 O
¾¾¾¾¾® CH3 ¾ CH==CH ¾ CH3 ¾¾¾¾®
The reactions involved are as follows –H2O 2-butene Ozonolysis
CH== CH—C ºº CCHO CHO (C )
CHO O Zn/H2O
(i) O3 CH3 ¾ CH CH ¾ CH3 ¾¾¾® 2CH3CHO
+2 Acetaldehyde
(ii) Zn/H2O
COOH O O (E )
Benzaldehyde Mono-ozonide
C11H8O Formyl (D)
(A) methanoic acid
(B)
5-phenylpent-4-en-2-yn-al A gives iodoform reaction as
COOH
Ag+ CH3COCH2CH3 + 3I2 + 4NaOH ¾®
2
COOH Oxidation CHI3 ¯ + C 2H5 COONa + 3NaI + 3H2O
Oxalic acid 20. CH 3 Zn/Hg
or ethanedioic acid (i) (a) C O CH3—CH2—CH3
Conc. HCl
NaOH/I2
CH3 Propane
18. (i) (a) Propan-2-one
OH
O CN NaOH/CaO
Cyclobutanone (b) —COO–Na+ D
Cyanohydrin
(Sodium salt of (Benzene)

CH3 H3C OH benzoic acid)
CH3OH + Na2CO3
(b) C¾O C
HCl gas
DIBAL-H
H H OCH3 (c) CH2 == CH ¾ CH2 ¾ CN ¾I.¾ ¾ ¾¾®
Ethanal Hemiacetal of II. H 3O+
ethanal
CH 2 == CH ¾ CHO
(ii) (a) Product is CH3 ¾ CH == CH ¾ CH2 ¾ CHO
(Prop -2-en -1-al)
(b) Product is CH3 ¾ CH2 ¾ CHO
(iii) Propanal and propanone (ii) As the number and size of the substituted group increases,
the hindrance to the attack of nucleophile also increases.
These compounds can be distinguished by using Tollen’s Nucleophilic attack is difficult when number of attached
test. Propanal being an aldehyde reduces Tollen’s group increases. Hence, the order of nucleophilic addition
reagent to shining silver mirror and propanone being a
ketone does not. C 6H5 COCH3 < CH3COCH3 < CH3CHO < HCHO
CH3CH2CHO + 2[ Ag( NH3 ) 2 ] + + 3OH- —NO2
Propanal
(iii) CH3—CH N—NH
Tollen’s reagent
¾® CH3CH2COO - + 2 Ag ¯
Propanoate ion Silver mirror O2N
Tollen’s
CH3COCH3 ¾¾¾® No silver mirror Acetaldehyde-2, 4-dinitrophenylhydrazone.
Propanone reagent
19. Since, A gives haloform test, it must contain ¾ COCH3 group. CH—CHO
Thus, its possible formula is C 2H5 COCH3. CHO CH
On reduction, it gives butan-2-ol, i.e. compound B which on
dehydration with sulphuric acid gives but-2-ene ( C ). Dil. NaOH
Ozonolysis of but-2-ene gives only acetaldehyde (E). 21. (i) (a) + CH3CHO
D
(3-phenyl prop-2-ene-1-al)
H O+
H—C O III. C ¾ ¾
3
¾® B + D
Hydrolysis
H + Thus, C is CH3COOC 2H5 , (Ethyl ethanoate) as esters

(b) + H2N—NH— upon hydrolysis gives alcohol and carboxylic acid.
3 2 CH CH OH
IV. A ¾¾¾¾® B+C
—C N—NH— Thus, A is (CH3CO) 2 O, acetic anhydride as anhydrides
reacts with alcohol to give an acid and an ester.
H The reactions involved are :
CHO
(CH3CO) 2 O + CH3 CH2 OH ¾®
(A) Ethanol
(c) 2 + Conc. NaOH —CH2OH+ CH3 COOH + CH3COOC 2H5
( B) ( C)
(Benzyl alcohol)
H2 O
CH3COOC 2H5 ¾¾®
+
CH3 COOH + CH3CH2OH
H
—COO–Na+ ( C) ( B) (D)
KMnO4
(Sodium benzoate)
CH3CH2OH ¾¾¾® CH3 — COOH
(D) [O] ( B)
(ii) (a) Iodoform test is used to distinguish CH3 ¾ CO ¾ (i) Ca(OH) 2

group containing compound from other. CH3 — COOH ¾¾¾¾® CH3 COCH3
( B) (ii) Distillation (E)
O
23. (i)
½½
H+
CH3 ¾ CH == CH ¾ C ¾ CH3 + 4NaOH + 3I2 (a) O + H2N— OH
¯
CHI3 ¯ + H3C ¾ CH == CH ¾ COO -Na + +
(Yellow ppt. ) N—OH + H2O
3NaI + H2O
O (b) 2C 6H5 CHO + Conc. NaOH ¾®
½½ -+
CH3 ¾ CH2 ¾ C ¾ CH == CH2 + 4NaOH + 3I2 C 6H5 CH2OH+ C 6H5 COON a
¯ Benzyl Sodium
alcohol benzoate
No reaction
(b) Benzaldehyde and Benzoic acid Cl / P Cl 2 / P
(c) CH3COOH ¾®
2 ClCH2COOH ¾®
Both can be distinguished by using sodium bicarbonate Acetic acid Monochloroacetic acid
(NaHCO 3) test. Benzoic acid being an acid reacts with
Cl 2 / P
NaHCO 3 solution to produce brish efferversence due to Cl 2CHCOOH ¾® Cl 3CCOOH
evolution of CO 2 gas while benzaldehyde does not. Dichloroacetic acid Trichloroacetic acid
C 6H5 COOH+ NaHCO 3 ¾® (ii) (a) Benzaldehyde and benzoic acid NaHCO test
3
Benzoic acid - +
C 6H5 COONa+CO 2 + H2O Benzoic acid being an acid reacts with NaHCO3
solution, to produce brisk effervescence due to
evolution of CO2 while benzaldehyde does not give
C 6H5 CHO + NaHCO 3 ¾® No effeversence due to
Benzaldehyde evolution of CO 2 gas. this test.
C6H5COOH + NaHCO3 ¾®
22. E, (C 3H6O) forms 2,4-dinitrophenyl hydrazone. Thus, it is a - +
carbonyl compound (aldehyde or ketone). But it does not C6H5CO O Na + CO2 + H2O
reduce Tollen’s reagent or Fehling’s solution, so it is a ketone. NaHCO 3 solution
Thus, E is CH3COCH3, propanone. E is obtained when B is C6H5CHO ¾¾¾¾¾® No effervescence
heated with Ca(OH) 2 , so B is acetic acid CH3COOH. (b) Propanal and propanone Propanone responds to
I. CH3COOH + Ca(OH) 2 ¾
¾D
® CH3COCH3 iodoform test whereas propanal (CH3CH2CHO),
does not due to the absence of CH3CO ¾ group.
( B) ( E)
KMnO NaOH, I 2
II. D ¾ ¾ ¾
¾4
®B CH3COCH3 + 3NaOI ¾¾¾® CHI3 ¯
Oxidation Sodium Heat (Yellow ppt.)
Propanone
hypoiodite Iodoform
Thus, D is CH3CH2OH.
- +
Ethanol as alcohols undergoes oxidation to give + CH3CO O Na + 2NaOH
carboxylic acid. Sodium
acetate
O O
24. (i) 25. (i) Benzoic acid is obtained.
[O]
CH3 COOH
CH3 CH3 2–
Cr2O7 /H+ CH3 OH
Pentan-2-one Ethanoic acid Alkaline KMnO4
+ 3 [O] + H 2O
+ CH3— CH2—COOH KOH, heat
Propanoic acid Methylbenzene Benzoic acid
(ii) The given reaction is Wolff-Kishner reduction. The CrO ,H SO

reagents used for this reduction are NH2× NH2/KOH. (ii) CH3( CH2 ) 4 CH2OH ¾ ¾ ¾
3 ¾
2 ¾4® CH ( CH ) COOH
3 2 4
Or Iodoform test is used to identify whether a compound is –+

ethanal or propanal. Ethanal, because of the presence of CH3 COOK
CH3CO — skeleton gives iodoform test whereas propanal
due to the absence of such a skeleton does not. (iii) KMnO4 /KOH
D -+
CH3CHO + 3NaOI ¾® CH3COONa Toluene
Heat
Potassium
Ethanal
+ 2NaOH + CHI3 ¯ benzoate
NaOI
CH3CH2CHO ¾¾® NO ppts. of CHI3 The reagent used in the conversion of toluene to
D
O OH potassium benzoate is KMnO4 or KOH.

½½ ½ (iv) CH3CHO
[O]
¾ ¾® CH3COOH
LiAlH4
(iii) CH3 ¾ C ¾ CH3 ¾ ¾ ¾¾® CH3 ¾ CH ¾ CH3 Acetaldehyde Tollen's reagent Acetic acid
Propan -2-one Propan -2-ol (X)
OH The compound ‘X’ is acetic acid ( CH3COOH).
½
Conc. H2SO4
(iv) CH3 ¾ CH ¾ CH2 CH3 ¾ ¾ ¾ ¾ ¾
¾® Or
NH / Heat
(C4 H10 O) CH3COOH ¾ ¾3¾¾® CH3CONH2
Butan -2-ol ( X ) - H2 O
CH3 ¾ CH == CH ¾ CH3 + H2O
But-2-ene In this reaction, NH3 is used as a reagent.
(C4 H8 )
The compound ‘X’ is butan-2-ol.
Chapter Test 7. Assertion Compounds containing — CHO group
are easily oxidised to corresponding carboxylic
acids.
Reason Carboxylic acids can be reduced to
alcohols by treatment with LiAlH 4 .
Multiple Choice Questions (MCQs)
1. The hydrogenation of benzoyl chloride in the presence of
Pd/BaSO 4 produces 8. Identify the missing compounds in the following
(a) benzyl alcohol (b) benzaldehyde reaction sequence :
(c) benzoic acid (d) phenol COOH
2. Consider the reaction given below. (i) NaBH4

? Conc. HNO3 SOCl2 (ii) H3O+
CH2 == CH ¾ CHO ¾¾® CH2 == CH ¾ CH2 ¾ OH A B C
Conc. H2SO4
Which of the following is the suitable reagent for the
conversion of above reaction?
(a) NaBH 4 (b) Ni / H 2 9. Write down the IUPAC and common name for the
(c) Zn-Hg / HCl (d) Red P + HI following.
3. The Clemmensen reduction of ketones is carried out in the CHO
presence of (i)
(a) Zn-Hg with HCl CHO
(b) LiAlH 4
O
(c) H 2 and Pt as a catalyst (ii)
(d) glycol with KOH
CH3
4. Cannizzaro’s reaction is not given by ........ .
CHO (iii) CH2 == CHCHO
(a) (b) CHO 10. Convert
CH3
(i) Acetaldehyde to formaldehyde
(c) HCHO (d) CH3CHO (ii) Propanal to butanone.
11. (i) Give chemical tests to distinguish between the
Assertion-Reasoning MCQs following pairs of compounds.
Direction (Q. Nos. 5-7) Each of these questions contains two (a) Propanal and propanone
statements Assertion (A) and Reason (R). Each of these (b) Acetophenone and benzophenone.
questions also has four alternative choices, any one of (ii) Arrange the following compounds in increasing
which is the correct answer. You have to select one of the order of reactivity towards HCN.
codes (a), (b), (c) and (d) given below. Acetaldehyde, acetone, di- tert- butylketone,
(a) Both A and R are true and R is the correct explanation of A. methyl-tert-butylketone.
(b) Both A and R are true, but R is not the correct explanation of A.
Long Answer Type Question
(d) A is false, but R is true. 12. A compound A (C2H4O) on oxidation gives B
5. Assertion Carboxylic acids are more acidic than phenols. (C2H4O2 ) . A undergoes iodoform reaction. On
treatment with HCN, A forms a product C which
Reason The carboxylate ion is less stabilised than phenoxide
on hydrolysis gives 2-hydroxy propanoic acid.
ion.
(i) Identify A, B and C.
6. Assertion Formaldehyde is a planar molecule.
(ii) Write down the equations for the
Reason Formaldehyde contains sp 2 hybridised carbon atom. reactions involved.
(iii) Name the product when A reacts with dil. NaOH.
Answers
1. (b) 2. (a) 3. (a) 4. (d) Scan the code
5. (c) 6. (a) 7. (b)
CHAPTER 07
Amines
In this Chapter...
l Structure of Amines
l Classification of Amines
l Nomenclature of Amines
l Identification of Amines
l Uses of Amines
Amines are the derivatives of ammonia obtained by replacing

either one, two or three H-atoms by alkyl or aryl groups. Classification of Amines
For example, CH 3 ¾ NH 2 , C 6 H5 ¾ NH 2 , Depending upon the number of hydrogen atoms replaced by
CH 3 alkyl or aryl groups in ammonia molecule.
CH 3 ¾ NH ¾ CH 3 , CH 3 ¾ N Amines are classified as primary (1° ), secondary ( 2° ) and
CH
3
tertiary ( 3° ).
Structure of Amines Replacement Replacement R
3 NH 3 ¾¾¾¾® RNH 2 ¾¾¾¾® N¾ H
l
Nitrogen orbitals in amines are sp -hybridised and geometry Ammonia of H by R
(1 ° )
of H by R¢ R¢
is pyramidal. (2 ° )
The ground state electronic configuration of N is 1 s 2 ,

Replacement R
l
¾¾¾¾® N ¾ R¢¢
2 s 2 , 2p1x 2p1y 2p1z . Here, one 2s-orbital and three 2p-orbitals of H by R¢¢ R¢
(3 °)
are hybridised to form four sp 3 -hybridised orbitals, three
of them have one electron and the fourth orbital has one Degree and Functional Group of Various Amines
lone pair of electrons. Amine
n (no. of H-atoms Type of Functional
attached to N) amine group
l
Each of the three sp 3 -hybridised orbitals of nitrogen overlap
with orbitals of hydrogen or carbon depending upon the H
| 2 1° (primary) ¾ NH2
composition of amines. The fourth orbital of nitrogen in all R ¾ N¾ H
amines contain an unshared pair of electrons.
R
Unshared NH 1 2° (secondary) -- NH --
electron pair R
N sp3-hybridised R

108°
H R¾N 0 3° (tertiary) ¾N
H
H R
Pyramidal
Nomenclature of Amines
l
In common system of nomenclature, an aliphatic amine is named by prefixing alkyl group to amine, i.e. alkyl amine.
l
In secondary and tertiary amines, when two or more groups are same, the prefix di or tri is added before the name of alkyl group.
l
In IUPAC system, amines are named as alkanamines.
l
To name 2° and 3° amines, we use locant ‘N’ to designate substituent attached to a nitrogen atom while, naming aryl amines,
suffix ‘e’ of arene is replaced by ‘amine’.
Methods of Preparation of Amines
Following methods can be used for the preparation of amines
Methods Reactions involved Important points regarding reaction
By reduction of RCH 2NH 2
l Reaction is used for ascent of amine series,
lH 4 i.e. for preparation of amines containing
(i) Alkyl nitrile LiA
RCN one C-atom more than starting amine.
Eth Na
ano
l RCH 2NH 2
(ii) Nitroalkane Raney Ni / 250°C or l Reduction with Fe scrap and HCl is

R / ArNO2 + 3H2 ¾¾¾¾¾¾® R / ArNH2 preferred because FeCl 2 formed get
Fe/ HCl or H 2 / Pt
hydrolysed to release HCl during reaction.
(iii) Amides O l Reduction of amides give amine with same
½½ LiAlH 4
number of carbons.
R C NH2 ¾¾® RCH2NH2 + H2O
NH 3 / 393K ·· ·· · · RX ·· It yields a mixture of 1°, 2° and 3° amines
Hofmann ammonolysis l RX ¾¾¾® R N H2 ¾® R2 NH ¾® R3 N ¾® [ R4 N] X -
RX RX l
method (1°)
and also quaternary ammonium salt.
( 2 °) ( 3°)
l 1° amine is obtained as major product,
l Order of reactivity of halides with amines when excess of NH 3 is taken.
RI > RBr > RCl
Gabriel phthalimide O
l Only 1° amines can be synthesised by this
synthesis method. Exception : t-butyl amine cannot
C COOH be prepared by this method as in this case,
(i) KOH elimination takes place.
NH
(ii) RX l Aromatic 1° amines cannot be prepared by
C (iii) H 2O/OH – COOH this method as aryl halides do not undergo
+ RNH 2 nucleophilic substitution reaction with
O
potassium phthalimide.
D Amine formed contains one carbon less
Hofmann-bromamide RCONH2 + Br2 + 4NaOH ¾® RNH2 + 2NaBr l
degradation + Na 2CO3 + 2H2O than that present in the amide.
Physical Properties Chemical Properties and Reactions

Physical state The lower aliphatic amines are gases with fishy Basic Character of Amines
odour. 1° amines with three or more carbon atoms are liquid The reaction of amines with mineral acids to form ammonium
and the higher ones are solids. salts show that, they are basic in nature. Their basicity is due
Colour Aniline and other arylamines are usually colourless to lone pair of electrons on N atom. Basic character can be
but get coloured on storage due to atmospheric oxidation. better understood by their K b and pK b values. Larger the
Solubility It decreases with increase in molar mass of amines. value of K b or smaller the value of pK b , stronger is the base.
Amines are soluble in organic solvents like alcohol, ether and
benzene. Structure-Basicity Relationship of Amines
Boiling point Primary and secondary amines are engaged in 1. Alkanamines vs Ammonia
intermolecular association due to hydrogen bonding, while
tertiary amines do not have intermolecular association (due to
l
Alkyl amines are stronger bases than NH 3 .
absence of H-atom). l
Basic nature of aliphatic amines increases with increase in
Therefore, the order of boiling points of isomeric amines is as the number of alkyl groups, i.e. +I-effect of alkyl group
follows increases their basicity.
1 ° > 2°> 3 °
l
The order of basicity of amines in gaseous phase is 2. Alkyl Amines vs Ammonia
3° amine > 2° amine > 1° amine > NH 3 . l
Aniline is more stable than anilinium ion. Hence,
l
In aqueous phase, solvation effect and steric hindrance, besides the proton acceptability (basic nature) of aniline or
inductive effect of alkyl group decides the basic strength of alkyl aryl amines would be less than that of ammonia.
amines. l
The less basicity of aniline as compared to NH 3 is
l
The order of basicity of amines, when alkyl group is ethyl group is, attributed to - I-effect of benzene (sp 2 -hybridised)
Amines : (C 2 H5 ) 2 NH > (C 2 H5 ) 3 N > C 2 H5 NH 2 > NH 3 ring and delocalisation of lone pair of N.
pK b : 3.00 3.25 3.29 4.75 l
In substituted aniline, ERGs ( ¾ OCH 3 , ¾ CH 3 )
l
The order of basicity of amines, when alkyl group is methyl group, is, increase basic strength, whereas EWG
Amines : (CH 3 ) 2 NH > CH 3 NH 2 > (CH 3 ) 3 N > NH 3 ( ¾ NO 2 , ¾ SO 3 H) decrease basic strength.
pK b : 3.27 3.38 4.22 4.75
Important Chemical Reactions of Amines

Method Reaction involved Important points related to reaction
Aliphatic amines
Alkylation HX RX l It yields a mixture of 1°, 2° and 3° amines
R ¾ X + R ¢ NH2 ¾® R ¾ NHR ¢ ¾® and also quaternary ammonium salt.
(1°) ( 2 °) - HX
RY + l Major product is obtained when amine is

R 2 NR ¢ ¾® R 3 N R ¢ X - taken in excess.
( 3°) Quaternary
ammonium salt
·· ·· The reaction is carried out in presence of a
Acylation CH 3 COCl or l
R / Ar ¾ N ¾ H ¾¾¾¾® R / Ar ¾ N ¾ C CH3 base stronger than amine (e.g. pyridine)
½ (CH 3 CO 2 )O
Base
½ ½½ which removes HCl so formed and shifts
H H O equilibrium to right side.
N -alkyl/arylethanamide
+ CH3COOH
Benzoylation RNH2 + C6H5COCl ¾® RNHCOC6 H5 + HCl l Substituted aryl amides are obtained by this
method.
Carbylamine reaction D l Secondary and tertiary amines do not show
RNH2 + CHCl 3 + 3KOH ¾® R ¾ NC+3KCl + 3H2O this reaction.
l It is used as a test for 1° amines.
Reaction with nitrous HNO 2 l Reaction is used to distinguish three classes
RNH2 ¾¾® ROH + H2 + HCl of amines, i.e. 1°, 2° and 3° amines.
acid (1°)
HNO2
R 2 NH ¾¾® R 2 N ¾ N == O + H2O
( 2 °)
HNO 2 D
R 3N ¾® [ R 3NH]+ NO-2 ¾® ROH + R 2N ¾ N == O
( 3°)
Reaction with aryl RNH2 + C6H5SO2Cl ¾® C6H5SO2NH ¾ R l Reaction is used to distinguish three classes
sulphonyl chloride (1°) - HCl (Soluble in alkali) of amines, i.e. 1°, 2° and 3° amines.
(Hinsberg’s reagent,
C6H5SO2Cl) R 2 NH + C6H5SO2Cl ¾® C6H5SO2NR 2
( 2 °) - HCl (Insoluble in alkali)
R 3N + C6H5SO2Cl ¾® No reaction
( 3°)
Aromatic amines
Electrophilic substitution l NH 2 group is ortho and para directing and powerful activating group.
reactions l Activating effect of —NH 2 group in aniline can be controlled by protecting the —NH 2 group by
acetylation with acetic anhydride and then carrying out the desired substitution followed by hydrolysis.
O
(CH 3 CO) 2 O ½½
C6H5NH2 ¾¾¾® C6H5NH C CH3
Aniline Pyridine Acetanilide
Method Reaction involved Important points related to reaction

(i) Bromination NH 2 NH 2 To get monosubstituted aniline derivative, path II is
Br Br followed.
Br 2/H 2O
+ 3Br 2 + 3HBr
Br
O
NHCCH 3 NH 2
O
Br 2 3OH – or H +
C 6H 5NHCCH 3
CH 3COOH
Br Br
(ii) Nitration NH 2 NH 2 NH 2 NH 2 To get monosubstituted p-nitro derivatives, path II

NO 2 is followed.
HNO 3, H 2SO 4
+ +
288 K
NO 2
(47%) (2%)
NO 2
(51%)
NHCOCH 3 NH 2
HNO 3, H 2SO 4 OH –
C 6H 5NHCOCH 3
288 K or OH +
NO 2 NO 2
(iii) Sulphonation + –
Å l p-aminobenzene sulphonic acid is the major product
NH 2 NH 3HSO 4 NH 2 NH 3 because distance between —NH 2 and —SO 3H is
maximum.
H 2SO 4 453-473 K l Sulphanilic acid exist in Zwitter ion form as shown a
side.
SO 3H SO –3
Zwitter ion
Identification of Amines
1°, 2° and 3° amines can be identified by the following tests
(i) Carbylamine test Only 1° amines give foul smelling isocyanide whereas 2° and 3° amine do not give this test.
(ii) Reaction with nitrous acid Aliphatic 1° amine gives alcohol, aromatic 1° amine gives diazonium salt while 2° amine gives
a yellow green oily layer of N-nitrosoamine.
(iii) Hinsberg test Primary amine gives monoalkyl sulphonamide which is soluble in alkali 2° amine gives dialkyl
sulphonamide which is insoluble in KOH whereas 3° and aromatic amines does not give this test.
Uses of Amines
l
Aliphatic amines are used as solvents and intermediates in the manufacture of drugs.
l
They are used as reagents in organic synthesis.
l
Aromatic amines are used for the formation of polymers, dyes and drugs.
l
Quaternary salts of amines are formed from long chain tertiary amines which are used as detergents,
e.g. n-hexadecyl trimethylammonium chloride.
l
N, N-dimethylaniline (DMA) is used in the preparation of dyes.
Chapter
Practice
PART 1 4. How many primary amines are possible for the
formula C 4 H11N ? (CBSE 2018)
Objective Questions (a) 4

(c) 3
(b) 2
(d) 5
l Multiple Choice Questions 5. Which of the following reagent is required for the
following conversion ?
1. The correct IUPAC name for
CH 2 == CHCH 2 NHCH 3 is C 6H5 CH 2Cl ¾® C 6H5 CH 2 ¾ N ¾ CH 3
(NCERT Exemplar)
½
(a) allyl methylamine CH 3
(b) 2-amino-4-pentene (a) CH3 NH 2 , CH3 Cl
(c) 4-aminopent-1-ene (b) CH3 Cl, RNH 2
(d) N-methylprop-2-en-1-amine (c) NH3 , CH3 Cl
2. The IUPAC name of the compound (d) CH3 CH 2 NH 2
N(CH3)2 6. Which of the following reagents is/are used in the

given reaction?
is NO2 NH2
?
(a) N-phenyl-N-propene
(a) H2 /Pd, ethanol (b) Sn + HCl
(b) N, N-methyl benzene
(c) Fe + HCl (d) All of these
(c) N, N-dimethyl benzenamine
(d) N, N-dimethyl benzene 7. The source of nitrogen in Gabriel synthesis of amines
3. Match the amines given in Column I with their is ......... .
(a) sodium azide, NaN3
classification in the Column II and choose the
(b) sodium nitrite, NaNO2
correct option from the codes given below. (c) potassium cyanide, KCN
Column I Column II (d) potassium phthalimide C6H4 (CO2 )N- K+
NH2 8. Which of the following can be prepared using
Gabriel phthalimide synthesis?
A. 1. Primary amine (a) Primary aromatic amines (b) Secondary amines
(c) Primary aliphatic amines (d) Tertiary amines
N(CH3)2 9. Which of the following reagents would not be a good

choice for reducing an aryl nitro compound to an
B. 2. Secondary amine amine?
(a) H2 (excess)/Pt (b) LiAlH4 in ether
(c) Fe and HCl (d) Sn and HCl
C. (C2 H5 )2 NH 3. Tertiary amine 10. The most suitable reagent used for the conversion of
2-phenyl propanamide into 2-phenyl propanamine is
Codes
(a) LiAlH4 /ether (NCERT Exemplar)
A B C A B C
(b) Br2 in aqueous NaOH
(a) 1 2 3 (b) 1 3 2
(c) 2 1 3 (d) 2 3 1 (c) excess H2
(d) I2 , red P
11. The correct order of increasing boiling points for 18. Consider the following reaction :
the bases, CH 3 NH 2 , (CH 3 ) 2 NH, (CH 3 ) 3 N is O O
(a) CH3NH2 < (CH3 )2 NH < (CH3 )3 N S—Cl + 'X' S—N—C2H5 + HCl
(b) CH3NH2 < (CH3 )3 N < (CH3 )2 NH
(c) (CH3 )3 N < (CH3 )2 NH < CH3NH2 O O H
(d) (CH3 )3 N < CH3NH2 < (CH3 )2 NH Here, substance ‘X’ is
(a) C2H5NH2 (b) (C2H5 )2 NH
12. Amongst the following, the strongest base in
(c) (C2H5 )3 N (d) (C2H5 )4 N+
aqueous medium is ......... .
(a) CH3 NH 2 (b) NCCH 2 NH 2
(c) (CH3 ) 2 NH (d) C 6 H5 NHCH3
l Assertion-Reasoning MCQs
Direction (Q. Nos. 19-23) Each of these questions
13. The most reactive amine towards dilute contains two statements Assertion (A) and Reason (R).
hydrochloric acid is ......... . Each of these questions also has four alternative choices, any
(a) CH3 — NH2 CH3
(b) NH one of which is the correct answer. You have to select one of
CH3
the codes (a), (b), (c) and (d) given below.
NH2 (a) Both A and R are true and R is the correct explanation of A
CH3 explanation of A
(c) NH ¾ CH3 (d) (c) A is true, but R is false
CH3
(NCERT Exemplar) (d) A is false, but R is true
14. Hofmann bromamide degradation reaction is 19. Assertion The angle of C—N—C in trimethylamine is
shown by ......... . 108°.
(a) ArNH2 (b) ArCONH2 (c) ArNO2 (d) ArCH2NH2 Reason There is unshared pair of electron in
15. Benzylamine may be alkylated as shown in the trimethylamine which makes the angle less than 109.5°.
following equation, 20. Assertion In order to convert R ¾Cl to pure
C 6 H 5CH 2 NH 2 + R — X ¾® C 6 H 5CH 2 NHR R ¾ NH 2 . Gabriel phthalimide synthesis can be used.
Which of the following alkyl halides is best suited Reason With proper choice of alkyl halides, phthalimide
for this reaction through S N 1 mechanism ? synthesis can be used to prepare 1°, 2° or 3° amines.
(a) CH3Br (b) C6H5Br (c) C6H5CH2Br (d) C2H5Br 21. Assertion MeNH 2 is the weaker base than MeOH.
Reason N is less electronegative than O, lone pair of
16. In the nitration of benzene using a mixture of conc.
electrons on N is more easily available for donation in
H 2SO 4 and conc. HNO 3 , the species which
MeNH 2 .
initiates the reaction is ......... .
(a) NO2 (b) NO+ (c) NO+2 (d) NO-2 22. Assertion In Hofmann bromamide reaction, the amine
formed has one carbon atom less than the parent 1° amide.
17. Match the reactions given in Column I with the
statements given in Column II and mark the Reason N-methyl acetamide undergoes Hofmann
correct code that are give below. bromamide reaction.
Column I Column II 23. Assertion N-ethyl benzene sulphonamide is soluble in
alkali.
A. Ammonolysis 1. Amine with lesser number of
carbon atoms
Reason Hydrogen attached to nitrogen in sulphonamide
is strongly acidic. (NCERT Exemplar)
B. Gabriel phthalimide 2. Detection test for primary
synthesis amines. l
Case Based MCQs
C. Hofmann 3. Reaction of phthalimide with 24. Read the following and answer the questions from (i) to
bromamide reaction KOH and R—X (iv) given below
D. Carbylamine 4. Reaction of alkyl halides with Amines are the derivatives of ammonia, obtained by the
reaction NH3 replacement of one, two or three hydrogen atoms by
Codes alkyl/aryl group. These are classified as primary,
A B C D A B C D secondary and tertiary depending upon the number of
(a) 1 4 3 2 (b) 2 3 1 4 hydrogen atoms in ammonia molecule replaced by alkyl
(c) 4 3 1 2 (d) 2 3 4 1 or aryl groups.
Amines are prepared by the reduction of nitro replacement of one, two or three hydrogen atoms by
compounds, Hofmann bromamide degradation alkyl/aryl groups. Amines are very reactive due to the
reaction and ammonolysis of alkyl halide. Amines are difference in electronegativity between nitrogen and
basic in nature. Aniline show electrophilic hydrogen atoms and due to the presence of unshared
substitution reactions at o and p-position. pair of electrons over N-atom.
Halogenation, nitration and sulphonation are some The number of hydrogen atoms attached to the
common reaction that are shown by aniline. N-atom decides the course of reactions of amine, that
(i) Acid anhydrides on reaction with primary amines is why amines differ in many reactions. In aromatic
give ......... . amines like aniline, electron density at ortho and
(a) amide (b) imide
(c) secondary amine (d) imine para-positions with respect to —NH 2 group is high.
(ii) Which of the following should be most volatile? Therefore, this group is ortho or para directing and a
powerful activating group
I. CH 3CH 2CH 2 NH 2 II. (CH 3 ) 3 N
(i) Carbylamine test is done for
CH 3CH 2 (a) detection of NO 2 group
III. NH IV. CH 3CH 2CH 3
(b) confirming the presence of secondary amine
CH 3
(c) confirming the presence of primary amine
Choose the correct option (d) for confirming the basic nature of ¾NH2 group
(a) II (b) IV (c) I (d) III
(ii) Aniline will not show which of the following
(iii) Which of the following species are involved in reaction?
the carbylamine test? (a) Isocyanide test
I. R—NC II. CHCl 3 (b) Diazotisation
III. COCl 2 IV. NaNO2 + HCl (c) Schotten Baumann reaction
(a) I and II (b) I and IV (c) II and IV (d) III and IV (d) Friedel-Crafts reaction
(iv) Which of the following arenium ion is not involve (iii) The solubility of water for C 6 H5 NH2 (I),
in the bromination of aniline ? (C 2 H5 )2 NH(II) and C 2 H5 NH2 (III) increases in
+
NH2 NH2 the order.
(a) II < III < I (b) I < II < III
H H
(c) III < II < I (d) II < I < III
(a) Br (b) Br
+
(iv) Which of the following on reduction with lithium
aluminium hydride yields secondary amine?
+
NH2 NH2 (a) Methyl cyanide (b) Nitroethane
(c) Methyl isocyanide (d) Acetamide
+
(c) (d) H
Or
Br Which of the following amines cannot be prepared
H Br
by Gabriel phthalimide synthesis?
(a) Ethylamine (b) Isopropyl amine
Or Under which of the following reaction conditions, (c) Propylamine (d) Ethyl methyl amine
aniline gives p-nitro derivative as the major
product ?
I. Acetyl chloride/pyridine followed by reaction with
conc. H2SO4 + conc. HNO3.
PART 2
II. Acetic anhydride/pyridine followed by conc.
H2SO4 + conc. HNO3.
III. Dil. HCl followed by reaction with conc.
H2SO4 + conc. HNO3.
l
IV. Reaction with conc. HNO3 + conc. H2SO4. 1. Classify the following amines as primary, secondary
(a) I and II (b) II and III or tertiary.
(c) III and IV (d) II and IV NH2 N(CH3)2
to (iv) given below (i) (ii)
Amines constitute one of the most important class of
organic compounds. In nature, they occur among
(iii) (C 2H5 ) 2 CHNH2
vitamins, proteins, alkaloids and hormones. These are
the derivatives of ammonia, obtained by the (iv) (C 2H5 ) 2 NH
2. How will you convert the following? (ii) In the increasing order of basic strength
(i) Nitrobenzene into aniline C 6H5 NH 2 , C 6H5 N(CH 3 ) 2 , (C 2H5 ) 2 NH and
(ii) Ethanoic acid into methanamine (NCERT) CH 3NH 2 .
3. (i) Which type of reagent is a good choice for (iii) In the increasing order of basic strength.
reducing an aryl nitro compound to an amine ? (a)Aniline, p-nitroaniline and p-toluidine
(ii) In the reduction of nitro compounds, why (b) C 6H5 NH 2 , C 6H5 NHCH 3 , C 6H5 CH 2NH 2
Fe scrap and HCl is preferred over other 12. Give reasons for the following. (NCERT)
metals ? (i) Aniline does not undergo Friedel-Crafts reaction.
4. Give the structures of A, B and C in the following (ii) (CH 3 ) 2 NH is more basic than (CH 3 ) 3 N in an
reaction.
NaCN OH - aqueous solution.
CH 3CH 2I ¾¾® A ¾¾¾¾¾¾® B
Partial hydrolysis (iii) Primary amines have higher boiling point than
NaOH + Br
¾¾¾¾®
2
C tertiary amines. (All India, 2016)
13. Why is —NH 2 group of aniline acetylated before
5. (i) Name the reagent used in the following reactions. carrying out nitration?
¾A ® RCH 2NH 2
(a) R -- C ºº N ¾
14. Account for the following.
¾C® C 6 H5 NH 2 + 2H 2O
(b) C 6 H5 NO 2 + 3H 2 ¾ (i) Diazonium salts of aromatic amines are more
(ii) Complete the following reaction. stable than those of aliphatic amines.
CH3 CH2 NH 2 + CHCl 3 + alc. 3KOH ¾® (ii) Gabriel phthalimide synthesis is preferred for
synthesising primary amines. (NCERT)
6. Give the structures of A, B and C in the following
reactions. 15. Give reasons for the following.
KCN LiAlH 4 HNO 2
(i) CH3 CH2 Br ¾¾® A ¾¾® B ¾¾® C (i) Acetylation of aniline reduces its activation effect.
0 °C
NaNO 2 / HCl
(ii) CH 3NH 2 is more basic than C 6H5 NH 2 .
3 NH NaOBr
(ii) CH 3COOH ¾¾® A ¾¾® B ¾¾¾¾® C (iii) Although, ¾NH 2 is o/p-directing group, yet
D (NCERT) aniline on nitration gives a significant amount of
7. C5 H13N reacts with HNO 2 to give an optically active m-nitroaniline. (All India, 2017)
alcohol. What is this compound? Give its IUPAC
16. Identify A and B in the following reaction.
name.
8. Write an isomer of C 3H 9N which gives foul smell of O
isocyanide when treated with chloroform and Cl
ethanolic NaOH. (All India, 2020) KCN H2/Pd
A B
9. Arrange the following.
(i) In the decreasing order of basic strength in gas 17. How will you convert
phase (i) ethanamine into methanamine?
C 2H5 NH 2 , (C 2H5 ) 2 NH , (C 2H5 ) 3 N and NH3 . (ii) methanamine into ethanamine? (NCERT)
(ii) In the increasing order of boiling point C 2H5 OH , 18. Give one chemical test to distinguish between the
(CH 3 ) 2 NH , C 2H5 NH2 . following pairs of compounds.
(iii) In the increasing order of solubility in water (i) Aniline and benzylamine
C 6H5 NH 2 , (C 2H5 ) 2 NH , C 2H5 NH 2 .(All India, 2015) (ii) Aniline and N-methyl aniline (All India, 2015)
10. Complete the following acid-base reactions and 19. (i) What is Hinsberg reagent?
name the products. (ii) In the following reaction,
(i) CH 3 ¾ CH 2 ¾ CH 2 ¾ NH2 + HCl ¾® O
(ii) (C 2H5 ) 3 N + HCl ¾®
N Conc. HNO +
11. Arrange the following. H ¾¾¾¾
Conc. H SO
®
3
X
2 4
(i) In the decreasing order of pK b values
C 2H5 NH 2 , C 6H5 NHCH 3 , (C 2H5 ) 2 NH and What is the structure of product X ?
C 6H5 NH2 . (iii) What is the role of pyridine in the acylation
reaction of amines?
20. (i) Give a chemical test to distinguish between 25. A hydrocarbon ‘A’ (C 4 H 8 ) on reaction with HCl
N-methylethanamine and N,N-dimethyl ethanamine. gives a compound ‘B,’ (C 4 H 9Cl), which on
(ii) Write the reaction for catalytic reduction of reaction with 1 mol of NH 3 gives compound ‘C,’
nitrobenzene followed by reaction of product so (C 4 H11N). On reacting with NaNO 2 and HCl
formed with bromine water. followed by treatment with water, compound ‘C’
(iii) Out of butan-1-ol and butan-1-amine, which will be yields an optically active alcohol, ‘D’.
more soluble in water and why? (CBSE Sample Paper) Ozonolysis of ‘A’ gives 2 moles of acetaldehyde.
l Long Answer Type Questions Identify compounds ‘A’ to ‘D’. Explain the
reactions involved. (NCERT Exemplar)
21. (i) Draw the structures of different isomers
corresponding to the molecular formula, C 3H 9N. 26. An aromatic compound ‘A’ of molecular formula
Write the IUPAC names of the isomers which will C 7H 6O 2 , undergoes a series of reactions as shown
liberate nitrogen gas on treatment with nitrous acid. below. Write the structures of A, B, C, D and E in
(ii) Complete the following reactions. the following reactions.
(a) Aniline + 3Br2 (aq ) ¾® D
(b) C 6H5 NH2 + (CH3CO) 2 O ¾® LiAlH4/Ether
NH3/Heat
22. (i) Suggest a route by which the following conversion (C7H6O2) ¾¾¾® C6H5CONH2
can be accomplished. A Br2 (CH3CO)2O
O ¾¾¾® B ¾¾¾¾¾®C
+ NaOH
NH2 NH ¾ CH3 Br2/(aq)

¾¾®
E
27. (i) Write the main products of the following
(ii) Arrange the following in the increasing order of reactions.
their basic strength.
2 HNO
(a) C2 H5 NH2 , C 6H5 NH2 , NH3 , C 6H5 CH2NH2 and (a) CH 3 —C H 2 —NH 2 ¾¾¾®
(C 2H5 ) 2 NH (0° C)
O
(b) C 2H5 NH2 , (C 2H5 ) 2 NH, (C 2H5 ) 3N, C 6H5 NH2
(c) CH3NH2 , (CH3 ) 2NH, (CH3 ) 3N, C 6H5 NH2 , (b) —S—Cl + H—N—C2H5
C 6H5 CH2NH2
O H
23. (i) Write the structure of main products when aniline O
reacts with the following reagents :
(a) Br2 water CH3 —C—Cl
N—H
Base
(b) HCl (c)
(c) (CH 3CO) 2 O /pyridine H
(ii) Arrange the following in the increasing order of (ii) Accomplish the following conversions.
their boiling point : (a) Benzyl chloride to 2-phenylethanamine
C 2H5 NH2 , C 2H5 OH, (CH 3 ) 3 N (b) Chlorobenzene to p-chloroaniline
(iii) Give a simple chemical test to distinguish between l
Case Based Questions
the following pair of compounds (CH 3 ) 2 NH and
(CH 3 ) 3 N. (Delhi, 2015) 28. Read the following and answer the questions from
24. (i) Account for the following. Amines are the derivatives of ammonia, obtained
(a) Methylamine in water reacts with ferric chloride to
precipitate hydrated ferric oxide.
by the replacement of one, two or three hydrogen
atom by alkyl/aryl group. Pure amines are
(b) Aniline does not undergo Friedel-Crafts reaction.
colourless but develop colour on exposure to air
(ii) How will you convert (All India, 2019) or on storage due to atmospheric oxidation. Lower
(a) ethanoic acid into methanamine? aliphatic amines can form hydrogen bonds with
(b) hexane nitrile into 1-aminopentane? water molecules and hence, are soluble in water.
(c) methanol into ethanoic acid? They have high boiling points.
Amines are very reactive due to the difference in the ephedrine, both containing secondary amino group
electronegativity between nitrogen and hydrogen are used to increase the blood pressure.
atoms. Most of the amines are basic, their basic Amines are the derivatives of ammonia obtained by
character depends upon the ease for the formation of the replacement of one, two or three hydrogen
cation by accepting a proton from acid. atoms by alkyl/aryl groups. Like ammonia, nitrogen
Identification of 1°, 2° and 3° amines are done by atom of amines is trivalent and carries an unshared
the reaction with nitrous acid and aryl sulphonyl pair of electrons. Amines are classified as primary
chloride. secondary and tertiary amine, depending upon
(i) Consider the following statement in considering the number of hydrogen atoms in ammonia
whether amine is 1°, 2° or 3°. “The amine is molecule which get replaced by alkyl (B) or aryl (Ar)
gaseous and smells like ammonia”. groups.
(ii) Why are the higher aliphatic amines not soluble in Amines can be prepared by the reduction of nitro
water ? compounds, by the hofmann bromamide
(iii) Give reason why amines are reactive? degradation, by Gabriel phthalimide synthesis etc.
(iv) Give the chemical test to distinguish between the (i) Give the name of any two naturally occurring
following pair of compounds: ethylamine and amines.
dimethylamine. (ii) Draw the structure of N-methylethanamine.
Or (iii) Write the IUPAC name of the following
Arrange the following compounds in the compound and classify it into primary, secondary
increasing order of dipole moment. and tertiary amine.
CH 3 CH 2CH 3 , CH 3 CH 2NH 2 , CH 3 CH 2OH m -BrC 6H 4 NH 2
(iv) Write the main product of the following reaction.
Br2 + NaOH
to (iv) given below CH 3 ¾ C ¾ NH 2 ¾¾¾¾®
Amines constitute one of the most important class of ½½
organic compounds. In nature they occur among O
Or
vitamins, proteins, alkaloids and hormones. Synthetic What is the best reagent to convert nitrile to
examples includes drugs, polymers and dyestuffs. primary amine?
Biologically active compounds such as adrenaline and
EXPLANATIONS
Objective Questions
3 2 1 NO2 NH2
1. (d) IUPAC name of CH2 == CH CH2NHCH3 is H2/Pd
Ethanol
N-methylprop-2-en-1-amine.
2. (c) The IUPAC name of the compound NO2 NH2
Sn + HCl or
Methyl groups
Fe + HCl
H 3C CH3 attached to nitrogen atom
N
7. (d) Source of nitrogen in Gabriel phthalimide synthesis is
potassium phthalimide.
is N, N-dimethylbenzenamine O
||
C CO
3. (b) A–1, B–3, C–2 –H2O –+ RI, D
NH2 NH + KOH (alc.) NK –KI
C CO
||
A. (Primary amine) O
Phthalimide
CO H+/H2O, D COOH
N(CH3)2 or
N—R –
HO /H2O, D
+ RNH2
1° amine
CO COOH
B. (Tertiary amine) Phthalic acid
8. (c) Primary aliphatic amines can be prepared by Gabriel
phthalimide synthesis. Secondary and tertiary amines cannot be
C. (C2H5)2 NH (Secondary amine) prepared by this method due to steric hindrance. Aromatic
4. (a) The given formula shows the following primary primary amines cannot be prepared because aryl halides do not
amines undergo nucleophilic substitution with the anion formed by
(i) C4H9 — NH2 phthalimide.
CH3 9. (b) Aryl nitro compound can’t be converted into amine using
½ LiAlH4 in ether.
(ii) CH3 ¾ C ¾ NH2 NH2
½ H2(excess)/Pt
CH3 Option (a)
(iii) CH3 — CH — CH2 — NH2 NO2 NH2

½ Fe/HCl
CH3 Option (c)
(iv) H3C — CH — CH2 — CH3 Nitrobenzene NH2

Sn/HCl
½ (aryl nitro compound)
NH2 Option (d)
5. (a) LiAlH4/ether
CH2Cl CH2—N—CH3 No reaction
Option (b)
+CH3NH2
–HCl
Hence, option (b) is the correct choice.
10. (a) Amides can be converted into amines with same number of
CH2NHCH3 CH2N(CH3)2 carbon atoms by LiAlH 4 / ether.
+CH3Cl
–HCl 11. (c) The correct order of increasing boiling point is
(CH3 )3 N < (CH3 )2 NH < CH3 NH2 .
6. (d) The reagents used to reduce nitro compounds to
corresponding amines are hydrogen gas in the This is due to the presence of hydrogen bonding. It occur more in
presence of finely divided nickel, palladium or 1° amines than in 2° amines. There are two hydrogen atoms
platinum and also by reduction with metals in acidic available for H-bond formation in 1° amine.
medium. The reactions are as follows : H-bonding does not occur in 3° amines.
12. (c) 17. (c) A ® (4), B ® (3), C ® (1), D ® (2)

Compound Factors responsible for Reaction Statements
basic character are A. Ammonolysis Reaction of alkyl halide with NH3.
(a) CH3 ¾ NH2 Inductive effect ( + I) R — X + NH3 ¾® RNH2 + HCl.
(b) NC ¾ CH2 ¾ NH2 Inductive effect ( - I) B. Gabriel Reaction of phthalimide with KOH and
(c) (CH3 ) 2 NH Inductive effect ( + I)and solvation phthalimide R—X.
H
synthesis O O
(d) N - I-effect and resonance. OH

KOH
CH3 NH
R—X OH
Since, + I effect and solvation increases basic character while
-I effect and resonance decreases basic character. Hence, O O
correct choice is (c). C. Hofmann Amine with lesser number of carbon atoms.
13. (b) Greater the strength of base, greater will have its bromamide NaOX
reactivity towards dilute HCl. reaction RCONH2 ¾ ¾ ¾ ¾® RNH2
Hence, (CH3 ) 2 NH will have highest basic strength due to
highest reactivity. D. Carbylamine Detection test for primary amines.
reaction
H3C H3C H
HCl
N—H N Cl 18. (a) The reaction of benzene sulphonyl chloride with primary
H3C H3C H amine yields N-ethyl benzene sulphonamide.
14. (b) Hofmann-bromamide degradation is shown by O
O
½½ —S—Cl + C2H5NH2
Ar — C— NH2 by which amide is converted into amine (X)
O O
via intramolecular migration of phenyl group.
—S—N—C2H5 + HCl
O NH2
O H
NH2 Br2/NaOH N-ethyl benzene sulphonamide
+ K2CO3 + KBr + 2H2O (Soluble in alkali)
Benzamide Aniline
19. (a) Both A and R are true and R is the correct explanation
of A.
15. (c) S N1 reaction proceeds through formation of carbocation. The angle of C—N¾ C in trimethyl amine is less than
Hence, more stable be the carbocation, more is the 109.5°, i.e. 108° due to the presence of unshared pair of
reactivity towards SN 1 mechanism. electrons.
Alkyl halides Intermediate 20. (c) A is true but R is false.
¾¾¾® CH3Å Only primary aliphatic amines can be prepared by Gabriel
(a) CH3Br
phthalimide reaction.
(b) C 6H5 Br ¾¾¾® C 6H5 Å
21. (d) A is false but R is true
(c) C 6H5 CH2Br ¾¾¾® C 6H5 — CH2 Å ( more stable )
MeNH2 is a stronger base than MeOH because N is less
(d) C 2H5 Br ¾¾¾® C 2H5 Å electronegative than O and lone pair of electrons on N is
Hence, the reaction will proceed through S N 1 mechanism more easily available for the donation in MeNH2.
when, C6H5CH2Br is the substrate. because on ionisation it 22. (c) A is true but R is false.
gives a resonance stabilised carbocation (C6H5CH2). Only primary amines can be prepared from amides
16. (c) Nitration of benzene using a mixture of conc. H2SO 4 and (RCONH2 ) by treating with Br2 and KOH.
conc. HNO 3 proceeds as, Thus, N-methyl acetamide, i.e. CH3CONHCH3 does not
undergo Hofmann bromamide reaction.
O
HO—N + H2SO4 H3O + NO2 + 2H2O +SO2 23. (a) Both A and R are true and R is the correct explanation
O—H of A.
Å
NO2 N-ethylbenzene sulphonamide is soluble in alkali
NO2
because hydrogen attached to nitrogen in sulphonamide is
strongly acidic and forms a salt during reaction between
these two.
This reaction is known as electrophilic substitution reaction.
24. (i) (a) Acid anhydride on reaction with primary amine H COCH3
produces amide as : NH2 N
R
CH3COCl or
(CH3CO)2O
O O O NH2 O
RNH2
R O R R O R Acetanilide Conc. HNO3 +
Aniline conc. H2SO4
N
O O
H COCH3
N
R—N R + RCOOH R—N R + R—COO
H H H
Amide + o-isomer
(major)
(ii) (b) 1 o and 2o amines have higher boiling points due to
intermolecular H-bonding but less volatile than
3o amines and hydrocarbons of comparable molecular mass. NO2
Further, because of polar C¾N bonds, 3o amines are more p-nitroaniline
(major)
polar than hydrocarbons which are almost non-polar.
Hence, due to weak dipole-dipole interactions, 25. (i) (c) Carbylamine test is used to distinguish 1° amines
3o amines have higher boiling point (i.e. less volatile) than (both aliphatic and aromatic) from 2° and 3°
hydrocarbons. amines by the following reaction.
In other words, hydrocarbons are more volatile among D
R ¾ NH2 + CHCl 3 + 3KOH(alc.) ¾®
given compounds as amine are less volatile than
R ¾ N ºº C + 3KCl + 3HOH
hydrocarbon.
(iii) (a) Carbylamine reaction Amine on reaction with a mixture (ii) (d) Aniline does not show Friedel-Crafts reaction
of CHCl 3 and KOH produces alkyl isocyanate. due to salt formation with anhydrous AlCl 3 which
R— NH2 + CHCl 3 + 3KOH ¾ ¾® RNC+ 3KCl+ 3H2O is used as a catalyst. Here nitrogen of aniline will
acquire positive charge and hence acts as a strong
Only RNC and CHCl 3 are involved in carbylamine reaction. deactivating group.
(iv) (d) Arenium ion involved in the bromination of aniline are (iii) (c) Solubility in water decreases as the extent of
as follows H-bonding decreases. So, solubility in water
follows the order III < II > I.
NH2 NH2 (iv) (c) Methyl isocyanide on reduction with lithium
Br aluminium hydride will yield secondary amine.
Br LiAlH
(i) H CH3 ¾ N ºº C ¾¾®
4
CH3NHCH3
ortho
attack Methyl isocyanide (2 ° amine)
NH2 NH2 Or
(d) Ethyl methyl amine being secondary amine
Br Br
cannot be prepared by Gabriel phthalimide
H H
synthesis, while others are primary amines which
+ can be prepared by this process.
NH2 NH2
1. (i) Primary (ii) Tertiary (iii) Primary (iv) Secondary
Br 2. (i) Nitrobenzene into aniline
(ii) Sn + HCl
C6H5 NO 2 + 3H 2 ¾¾¾® C6H5 NH 2 + 2H 2O
Nitrobenzene or Fe + HCl Aniline
H Br (ii) Ethanoic acid into methanamine
Or SOCl NH 3(excess)
CH3COOH ¾¾®
2
CH3COCl ¾¾¾¾¾®
(a) Aniline on reaction with acetyl chloride or acetic Ethanoic acid Ethanoyl
anhydride in the presence of pyridine productes N-acetyl chloride
aniline which is an ortho, para directing group which on Br / KOH
further reaction with nitrating mixture (conc. HNO 3 + conc. CH3CONH2 ¾(Hofmann
¾¾¾¾¾¾®
2
bromamide
CH3NH2
Ethanamide reaction) Methanamine
H2SO 4 ) produces p-nitroaniline preferentially as shown
below.
3. (i) Following reagent are good choice for reducing an aryl 8. CH3CH2CH2NH2 (1° amine)
nitro compound to an amine. CHCl 3
CH3CH2CH2NH2 ¾¾¾® CH3CH3CH2N ºº C
Alc. NaOH
NH2 Propylamine Propylisocyanide
H2(excess)/Pt
NO2 The foul smell is due to formation of isocyanide.
NH2 9. (i) (C 2 H5 ) 3 N > (C 2 H5 ) 2 NH > C 2 H5 NH 2 > NH3
Fe/HCl
(ii) (CH3 ) 2 NH < C 2 H5 NH 2 < C 2 H5 OH
NH2 (iii) C 6 H5 NH 2 < C 2 H5 NH 2 < (C 2 H5 ) 2 NH
Sn/HCl · ·
10.
(i) CH3 ¾ CH2 ¾ CH2 ¾ N H2 + H ¾ Cl ¾®
n-propylamine +
-
(ii) Reduction with Fe scrap and HCl is preferred because CH3 ¾ CH2 ¾ CH2 ¾ NH3Cl
FeCl 2 formed gets hydrolysed to release HCl during the n-propyl ammonium chloride
reaction. ·· +
(ii) (C2H5 )3 N + H ¾ Cl ¾® (C2H5 )3 N HCl -
Therefore, only a small amount of HCl is needed to Triethylamine Triethylammonium
initiate the reaction. chloride
-
4. CH3CH2 I ¾¾®
NaCN
CH3CH2CN ¾¾®
OH 11. (i) C 6 H5 NH 2 > C 6 H5 NHCH3 > C 2 H5 NH 2
Ethyl iodide Ethyl cyanide Partial > (C 2 H5 ) 2 NH
(A) hydrolysis
NaOH + Br2 (ii) C 6 H5 NH 2 < C 6 H5 N(CH3 ) 2 < CH3 NH 2
CH3CH2CONH2 ¾¾¾¾® CH3CH2NH2 < (C 2 H5 ) 2 NH
Propionamide Ethyl amine
(B) (C) (iii) (a) p-nitroaniline < aniline < p-toluidine
5. (i) (a) Reduction of nitriles with lithium aluminium NH2 NH2 NH2
hydride (LiAlH4 ) or catalytic hydrogenation
produces primary amines. This method is used to
< <
prepare amines containing one carbon atom more
than the starting amine.
Raney Ni / H2
R ¾ C ºº N ¾¾¾¾¾¾¾¾¾¾¾® R ¾ CH 2 ¾ NH2 NO2 CH3
LiAlH4 or Na (Hg) / C2 H5 OH
(b) C 6 H5 NH 2 < C 6 H5 NHCH3 < C 6 H5 CH 2 NH 2
(b) C 6H5NO 2 + 3H2 ¾ ¾+ ¾
Sn HCl
¾® C 6H5NH2 + 2H2O
Nitrobenzene Or Fe + HCl Aniline 12. (i) Aniline being a Lewis base, react with the Lewis acid
D
AlCl 3 used in Friedel-Crafts reaction and produce a
(ii) CH3CH2 NH2 + CHCl 3 + 3KOH (alc.)¾® salt, hence does not show Friedel-Crafts reaction.
+
CH3CH2 ¾ N ºº C + 3KCl + 3H2O C6H5NH2 + AlCl 3 ¾® C6H5 N H2AlCl -3 (Salt)
Ethyl isocyanide
6. KCN 4 LiAlH (ii) In aqueous solution, basic nature depends on
(i) CH3CH2Br ¾¾® CH3CH2 CN ¾¾®
Ethyl bromide Ethyl cyanide
+ I-effect, H-bonding and steric-effect.
(A) The combined effect shows that (CH3 )2 NH is more
HNO basic than (CH3 )3 N as H-bonding is more in case of
CH3CH2CH2NH2 ¾¾®
2
CH3CH2CH2OH
n-propylamine 0°C n-propyl alcohol
(CH3 )2 NH than in (CH3 )3 N, which predominates over
(B) (C) the stability due to + I- effect of three ¾ CH3 groups.
NH 3 NaOBr
(ii) CH3COOH ¾¾®
Heat
CH 3CONH 2 ¾¾® (iii) Primary amines (1°) show two-hydrogen bonds whereas
Acetic acid Acetamide tertiary amines (3°) show no hydrogen bonding. Thus,
A
( )
the net attractive force in case of primary amines is more
NaNO 2 / HCl
CH3NH2 ¾¾¾¾¾® CH3OH than that of tertiary amines. Hence, primary amines have
Methyl amine Methanol higher boiling point than that of tertiary amines.
(B) (C )
13. In order to get mono derivative, the activating effect of
7. HNO 2 reacts with C 5 H13 N to give an alcohol, means the
¾NH2 group was controlled by acetylation with acetic
compound is primary amine. C 5 H13 N means C 5 H11 NH 2 anhydride or acetyl chloride in the presence of pyridine to
(primary amine).
form acetanilide which can be further nitrated easily by
Optically active alcohol means C 5 H11 OH segment contain a nitrating mixture.
chiral carbon.
H After nitration, the acetyl group is removed by hydrolysis.
5 4 3 2½ 14. (i) Diazonium salts of aromatic amines are more stable
CH3 ¾ CH2 ¾ CH2 ¾ C ¾ OH than those of aliphatic amines because these are
½ resonance stabilised while no such resonance
1
CH3
stabilisation is possible in the corresponding diazonium
Pentan-2-ol salts of aliphatic amines.
Å Å
s Å
s Å s 16.
N N N N N N N N O O
Å Å
Cl CN
KCN
¾¾®
SN2
Å
(A)
(ii) Gabriel phthalimide synthesis produces primary amines O
only without the traces of secondary or tertiary amines. So,
this method is preferred for the synthesis of primary amines. CH2NH2
15. (i) Due to electron withdrawing effect of the acetyl group, the H2/Pd
lone pair of electrons on N-atom is attracted by group. Reduction
As a result, lone pair of electrons on N-atom is not exclusively (B)
available for donation to the benzene ring and hence,
activating effect of the ¾ NH 2 group is reduced. 17. (i) Ethanamine into methanamine
[O]
(ii) In aniline (C 6 H5 NH 2 ), the electron pair on nitrogen atom is CH3CH2NH2 ¾HONO
¾¾® CH3CH2OH ¾ ¾¾®
–N 2 , –H 2O K 2 Cr2 O 7
involved in conjugation with ring and is less available for Ethanamine Ethanol
/H2 SO 4
protonation because electrons get delocalised in the ring [O]
due to resonance than that in methylamine (CH3 NH 2 ). CH3CHO ¾ ¾ ¾ ¾
¾® CH3COOH
K 2 Cr2 O 7 /H2 SO 4
Therefore, aniline is less basic than methylamine. NH 3 Br2 / KOH
Following are the resonance structures of aniline ¾Heat
¾¾® CH3CONH2 ¾¾¾® CH3NH2
Ethanamide Methanamine
NH2 + NH + NH
2 2
(ii) Methanamine into ethanamine
Red P / I
CH3NH2 ¾ HONO
¾ ¾® CH3OH ¾¾¾®
2
Methanamine - N 2 , - H 2O Methanol
Na / C2H 5OH /
KCN(alc.) Reduction
CH3I ¾¾¾® CH3CN ¾¾¾¾®
4[H]
NH2 NH2 Methyl iodide Ethane nitrile
CH3CH2 NH2
Ethanamine
18. (i) Nitrous acid test Aniline with HNO 2 (from
NaNO 2 + HCl ) gives benzene diazonium chloride
which is stable at 273-278 K and hence, does not
(iii) Nitration is usually carried out with a mixture of decompose to give N 2 gas.
conc. HNO 3 and conc. H 2 SO 4 . So, in the presence of these
acids, aniline gets protonated to form anilinium ion. NaNO 2 , HCl
Therefore, the reaction mixture consists of aniline and NH2 273 - 278 K
anilinium ion. ¾ NH 2 group in aniline is o, p-directing and
activating, whereas the NH3 group in anilinium is Aniline + –
m -directing and deactivating. Now, nitration of aniline N NCl
mainly gives p-nitroaniline due to steric hindrance at
Benzene diazonium chloride
o-position and the nitration of anilinium ion gives m
-nitroaniline. + NaCl + 2H2O
NH2 NH2 NH2 While benzylamine reacts with HNO 2 , it give
NO2 diazonium salt which being unstable at low
+
+NO2 temperature decomposes and gives N 2 gas.
¾¾®
+
+ +
–H NaNO 2 / HCl
C6H5CH2NH2 ¾¾¾® [C6H5CH2 ¾ N ºº NCl - ]
Aniline o-nitroaniline Benzylamine (Unstable)
NO2 (2%) H 2O
p-nitroaniline ¾¾® C6 H5CH2OH + N2 + HCl
(51%) Benzyl alcohol
+ + (ii) Aniline is a primary aromatic amine while
NH3 NH3 NH2
N-methyl aniline is a secondary aromatic amine.
+ So, they can be distinguished by carbylamine test.
+NO2 NH OH
¾¾®
+
¾¾®
4
Secondary and tertiary amines (both aliphatic and
–H
NO2 NO2 aromatic) do not give this test.
Anilinium ion m-nitroaniline Hence, this test is used to distinguish 1° amine
(47%) from 2° and 3° amine.
19. (i) Benzene sulphonyl chloride (C 6 H5 SO 2 Cl) is known as H3 C

Hinsberg reagent. It is used to distinguish between CH ¾ NH + HONO ¾®
2
primary, secondary and tertiary amines. H3 C Propan -2-amine
(ii)
NO2 O H3 C
CH ¾ OH + N + H O
2 2
N H3 C
Propan -2-ol
(Major product)
H
(ii)
(iii) Pyridine being a base, is used to remove the side NH2 NH2
product, i.e. HCl from reaction mixture.
Br Br
NH2 NHCOCH3 Br2 (aq.)
(a) +3HBr
CH3COCl
¾¾¾¾® + HCl
Br
2,4,6– tribromoaniline
N O
+ HCl ¾® Cl– NH2 NH—C— CH3
N N
½ (CH3 CO)2O
H (b) Pyridine
20. (i) N-methylethanamine is secondary amine.
Aniline
When it reacts with benzene sulphonyl chloride, it
forms N-ethyl-N-methyl sulphonamide while 22. (i) Complete conversion can be performed as,
N, N-dimethylethanamine is a tertiary amine, it does not O
react with benzene sulphonyl chloride. NH2 CHCl /KOH
NH Br /KOH2 ¾¾¾¾® 3
(ii) NO 2
¾¾¾¾®
2 NH 2 NH 2 Hofmann Carbylamine
bromamide reaction
Br Br Cyclohexyl reaction Cyclohexyl
amide amine
H2/Ni Br2/H2O
+ –
N ºº C H /Pd NH ¾ CH3
2
¾¾®
Br
(iii) Butan-1-ol is more soluble in water. Alcohol forms Cyclohexyl Cyclohexyl
isocyanide methylamine
stronger hydrogen bonds with water than formed by
amine due to higher electronegativity of O in alcohol (ii) (a) C 2 H5 NH 2 < NH3 < C 6 H5 CH 2 NH 2 < C 2 H5 NH 2
than N in amine. < (C 2 H5 ) 2 NH
R Od–—H
(b) C 6 H5 NH 2 < C 2 H5 NH 2 < (C 2 H5 ) 3 N < (C 2 H5 ) 2 NH
Hd+— O—R (c) C 6 H5 NH 2 < C 6 H5 CH 2 NH 2 < (CH3 ) 3 N
H—Od– < CH3 NH 2 < (CH3 ) 2 NH
R NH2 NH2
21. (i) Four structural isomers are possible. ½ Br ½
Br2/H2O Br
CH3 ¾ CH 2 ¾ CH 2 ¾ NH 2 , N( CH3 ) 3, 23. (i) (a) ¾¾¾® + 3HBr
Propan -1-amine Trimethylamine
(1 ° amine) (3 ° amine)
Aniline ½
CH3 ¾ NH ¾ C 2 H5 , CH3 ¾ C H ¾ CH3 Br
N -methyl ethanamine ½ 2, 4, 6-tribromoaniline
(2 ° amine) NH2
+
Propan -2-amine
(1 ° amine) NH2 NH3Cl–
Only 1° amines react with HNO 2 to give N 2 gas, i.e. ½ ½
(b) + HCl
CH3 ¾ CH2 ¾ CH2 ¾ NH2 + HONO ¾®
Propan -1-amine
Anilinium
chloride
CH3 ¾ CH 2 ¾ CH 2 OH + N 2 + H 2 O
Propan -l -ol (Major product)
NH2 NHCOCH3
(b) Hexane nitrile into 1-aminopentane
½ ½
(CH3CO)2O H 3 O+
(c) ¾¾¾¾® CH3 (CH 2 ) 4 CN ¾¾¾®
Partial
CH3(CH 2 ) 4 CONH 2
Pyridine Hexane nitrile hydrolysis Hexanamide
Acetanilide Br2 /KOH
¾¾¾¾¾¾¾¾¾¾® CH3 (CH 2) 4 NH 2
(ii) Alcohols have higher boiling point as compared to that Hofmann -bromamide reaction
1-aminopentane
of amines, because oxygen being more electronegative
(c) Methanol into ethanoic acid
atom, forms strong hydrogen bond as compared to that
of nitrogen. PCl 5 KCN(alc.)
CH3 OH ¾¾® CH3 Cl ¾¾¾¾®
In tertiary amine, there is no hydrogen bond formation
H 3 O+
Methanol Chloromethane
due to the absence of H-atoms and hence, has the CH3 CN ¾ ¾ ¾® CH3 COOH
lowest boiling point. Ethane nitrile Ethanoic acid
Therefore, increasing order of boiling point 25. l
Addition of HCl to compound ‘A’ shows that compound ‘A’
(CH3 ) 3 N < C 2 H5 NH 2 < C 2 H5 OH is alkene. Compound ‘ B ’ is C 4H9Cl.
(iii) (CH3 ) 2 NH and (CH3 ) 3 N are secondary and tertiary l
Compound ‘ B ’ reacts with NH3, it forms amine ‘C’.
amines respectively. These are distinguished by HCl NH
Hinsberg’s reagent which gives sulphonamide with C4H8 ¾ ¾¾® C4H9 Cl ¾ ¾¾3® C4H11N or C4H9 NH2
[ A] [ B] [ C]
secondary amines and no reaction carried out with
tertiary amines. (CH3 ) 2 NH reacts with benzene ‘C ’ gives diazonium salt on reaction with NaNO 2 /HCl,
l
sulphonyl chloride as follows: which on hydrolysis yields an optically active alcohol. So, ‘
O C’ is aliphatic amine.
== ==
‘A’ on ozonolysis produces 2 moles of CH3CHO. So, ‘A’ is

l
¾ S ¾ Cl + H ¾ N ¾ CH3 ¾®
CH3 — CH == CH — CH3 (But-2-ene).
½
O Reactions
CH3
O 4 3 2 1 HCl
(i) CH3 —CH == CH —CH3 ¾ ¾ ¾®
== ==
But-2 -ene
¾ S ¾ N ¾ CH3 + HCl [ A]
½ [C4 H8 ] 4 3 2 1
O CH3 —CH2 —CH—CH3
CH3 ½
N, N-dimethyl benzene sulphonamide Cl
2 -chorobutane
24. (i) (a) Methylamine being more basic than water, accepts [ B]
a proton from water and OH- ions are produced Cl [C4 H9 Cl]
which further reacts with ferric ion to give brown ½ NH3

ppt. of hydrated ferric oxide. (ii) CH3 — CH2 —CH—CH3 ¾®
2 -chlorobutane
[ B]
+ CH3 —CH2 — CH — CH3
CH3NH2 + H—OH ¾® CH3NH3 + OH – ½
Methylamine NH2
2 -amino butane
FeCl 3 ¾® Fe 3+ + 3 Cl - [ C]
[C4 H11 N]
2Fe3+ + 6 OH- ¾® 2Fe(OH)3 or Fe2O3 ×3 H2O 3 4
Hydrated ferric CH2 C H3
oxide
(Brown ppt.) ½
NaNO2 / HCl 1 2
(b) Aniline does not undergo Friedel-Craft’s reaction (iii) CH3 —CH2 — CH — CH3 ¾¾¾® CH3 —C — H
H2 O
because the reagent AlCl 3 being electron deficient acts ½ ½
as a Lewis base and attacks on the lone pair of nitrogen NH2 OH
Butan -2 -ol
present in aniline to form insoluble precipitate and 2 -amino butane
[ D]
[ C]
reaction does not proceeds. [C4 H11 N] (Optically active)
··
C6H5 NH2 + AlCl 3 ¾® [C6H5NH2 ]+ [AlCl 3 ]- O
Aniline (Lewis acid) (Complex)
(Lewis base)
(iv) CH3 ¾ CH==CH ¾ CH3 + O3 CH3—CH CH—CH
(ii) (a) Ethanoic acid into methanamine But-2-ene
SOCl 2
3 NH (excess) [A] O O
CH3 COOH ¾¾® CH3 COCl ¾¾¾¾® Ozonide
Ethanoic Ethanoyl Zn+H2O
acid chloride
Br / KOH CH3CHO + CH3CHO
CH3 CONH 2 ¾¾¾¾¾¾¾®
2
CH3 NH 2
Ethanamide Hofmann bromamide Methanamine 2 moles of acetaldehyde
reaction
26. The reaction is given as O

N—H
Base
NHCOCH3 (c) + CH3—C—Cl
Acetanilide
H
O
(C ) Aniline
NH—C—CH3
(CH3CO)2O Acetylation
+ HCl
NH3/Heat Br2 + NaOH
C7H6O2 ¾¾¾® C6H5CONH2 ¾¾¾¾® C6H5NH2 N-phenyl ethanamide
Hofmann Aniline (Acetanilide)
(A) Benzamide
bromamide (B)
Reduction
CH2Cl CH2CN
degradation
Bromination
LiAlH4/ether
C6H5CH2NH2 Br2 (aq) KCN (alc.), D
(ii) (a)
Benzylamine – KCl
(D)
Benzyl Phenyl ethane
NH2 nitrile
chloride
Br Br
CH2CH2NH2
LiAlH4
Br
2, 4, 6-tribromo aniline (Reduction)
(E )
2-phenylethanamine
COOH NH2 Cl Cl Cl
Conc. HNO3+ Sn/HCl

A is ; B is ; (b)
conc. H2SO4, D (Reduction)
Benzoic acid Aniline Chlorobenzene
NO2 NH2
p-nitrochlorobenzene p-chloroaniline
C is ¾ NHCOCH3 ; (Major product)
D is C6H5CH2NH2
N-phenylethanamide Benzylamine 28. (i) Primary amine is gaseous and smells like ammonia.
(Acetanilide) (ii) Because they have no hydrogen bond.
NH2 (iii) Amines are reactive due to the difference in
Br Br electronegativity between hydrogen and nitrogen atom.
E is (iv) Ethylamine gives carbylamine test, i.e. on treatment with
alcoholic KOH and chloroform, followed by heating, it
Br gives offensive odour of ethyl isocyanide. Dimethylamine
2, 4, 6-tribromoaniline does not give this test.
Or As the bond polarity increases, dipole moment increases
27. (i) (a)
and hence, order is
0° C
CH3 CH2 NH2 + HNO2 ¾¾® CH3CH2OH+ N 2 + H 2 O CH3CH2CH3 < CH3CH2NH2 < CH3CH2OH
Ethylamine Ethyl alcohol
29. (i) Alkaloids and proteins.
O H 2 1
(ii) C H3 ¾ C H 2 ¾ NH ¾ CH3
(b) S Cl + H—N—C2H5 (iii) N -methylethanamine
Br
O
Benzene sulphonyl
chloride
NH2
3-bromobenzenamine
O Br + NaOH
(iv) CH3 ¾ C ¾ NH2 ¾¾¾¾®
2
CH3NH2 + Na 2 CO 3
S N— C2H5 + HCl
½½ Hofmann
bromamide + 2NaBr + 2H 2 O
O reaction
O H
Or
N-ethylbenzene sulphonamide
(Soluble in alkali) The best reagent to reduce nitriles is sodium/alcohol or
LiAlH4 and the product of this reduction is primary amine.
Chapter Test
8. (i) Why amines are basic substances while amides are
1. The IUPAC name of C 2H5 ¾ N ¾ (CH2 ) 3 ¾ CH3 is neutral?
½
C 2H5 (ii) Draw the structure fo N, N-bis (1-bromo ethyl)
ethanamine.
(a) N-ethylbutan-2-amine (b) N-diethylbutan-1-amine
(c) N, N-diethylbutan-1-amine (d) N, N-diethylbutan-2-amine 9. Explain the following observations.
2. N-methylbenzamide is formed when methanamine reacts (i) Electrophilic substitution in case of aromatic
with benzoyl chloride. This reaction is known as amines
(a) benzoylation (b) Hinsberg test take place more readily than benzene.
(c) Schmidt reaction (d) Curtius reaction (ii) Tertiary amines do not undergo acylation.
3. The best reagent for converting 2-phenylpropanamide 10. (i) How will you convert the following? Aniline into
into 2-phenylpropanamine is ......... . N-phenylethanamide (write the chemical
(a) excess H 2 equations involved)
(b) Br2 in aqueous NaOH (ii) Complete the following reaction.
(c) iodine in the presence of red phosphorus C 6H5NH2 + H2SO 4 (conc. ) ¾®
(d) LiAlH 4 in ether
11. A compound Z with molecular formula C 3H9N reacts
4. What would be the side products formed with primary with C 6H5SO 2Cl to give a solid, insoluble in alkali.
amine in the Hofmann bromamide degradation reaction? Identify Z.
(a) Na 2CO 3 + NaBr (b) NaBr + H 2O + NaOH
(c) NaBr + H 2O + Na 2CO 3 (d) Br2 + H 2O + Na 2CO 3 Long Answer Type Questions
12. (i) Write the chemical reaction of aniline with
Assertion-Reasoning MCQs benzoyl-chloride and also write the name of the
Direction (Q. Nos. 5-7) Each of these questions contains product obtained.
two statements Assertion (A) and Reason (R). Each of (ii) Complete the following reactions.
these questions also has four alternative choices, any (a)C 6H5 NH2 + CHCl3 + alc. 3KOH ¾®
one of which is the correct answer. You have to select Fe/HCl
(b)C 6H5 NO 2 ¾¾® A ¾ ¾¾
2
®B
HNO
273 K
one of the codes (a), (b), (c) and (d) given below.
(a) Both A and R are true and R is the correct explanation of A. (iii) Arrange the following compounds in the
(b) Both A and R are true, but R is not the correct explanation increasing order of basic strength.
of A. C 6H5NH2 , C 6H5NHCH3 , C 6H5CH2 NH2
(c) A is true, but R is false. 13. Predict the reagent or the product in the following
(d) A is false, but R is true. reaction sequence.
5. Assertion Ammonloysis of alkyl halides involves the CH3 CH3 CH3
reaction between aryl halides and alcoholic ammonia.
Reason Reaction can be used to form 1°, 2°, 3° amines 1 (CH3CO2)2O HNO3
2
and finally quaternary ammonium salts. pyridine H2SO4
6. Assertion p-fluoro anilinium ion is more acidic than

NO2 NH2 NHCOCH3 3
anilinium ion.
Reason Electron density in the N—H bond of
p-fluoroanilinium ion decreases and release of a proton CH3 CH3
from p-fluoroanilinium ion is much easier than from
anilinium ion.
5 NaNO2/HCl
7. Assertion N, N-diethylbenzene sulphonamide is insoluble 4
in aklali. NO2 NO2
Reason Sulphonyl gorup attached to nitrogen atom is NH2
strong electron withdrawing group.
Answers
1. (c) 2. (a) 3. (d) 4. (c)
5. (a) 6. (a) 7. (b)
Chemistry
Class 12t h ( Term II)
Practice Paper 1 *
(Solved)
General Instructions Time : 2 Hours
Max. Marks : 35
1. There are 9 questions inthe questionpaper. All questions are compulsory.
2. Questionno. 1is a Case BasedQuestions, whichhas four MCQs. Eachquestioncarries one mark.
3. Questionno. 2 to 6 are Short Answer Type Questions. Eachquestioncarries 3 marks.
4. Questionno. 7to 9 are Long Answer Type Questions. Eachquestioncarries 5 marks.
5. There is no overall choice. However, internal choices have beenprovidedinsome questions. Students have to attempt
onlyone of the alternatives insuchquestions.
* As exact Blue-print and Pattern for CBSE Term II exams is not released yet. So the pattern of this
paper is designed by the author on the basis of trend of past CBSE Papers. Students are advised
not to consider the pattern of this paper as official, it is just for practice purpose.
1. Read the following and answer the questions from (i) to (v) given below
Reductive alkylation is the term applied to the process of introducing alkyl groups into ammonia or a
primary or secondary amine by means of an aldehyde or ketone in the presence of a reducing agent. The
present discussion is limited to those reductive alkylations in which the reducing agent is hydrogen and a
catalyst or “nascent” hydrogen, usually from a metalacid combination; most of these reductive alkylations
have been carried out with hydrogen and a catalyst.
The principal variation excluded is that in which the reducing agent is formic acid or one of its derivatives;
this modification is known as the Leuckart reaction. The process of reductive alkylation of ammonia consists
in the addition of ammonia to a carbonyl compound and reduction of the addition compound or its
dehydration product.
The reaction usually is carried out in ethanol solution when the reduction is to be effected catalytically.
2[H]
RCHO + NH3 RCHOHNH2 RCH2NH2
2[H]
RCH NH
Since, the primary amine is formed in the presence of the aldehyde it may react in the same way as
ammonia, yielding an addition compound, a Schiff ’s base ( RCH == NCH 2 R ) and finally, a secondary amine.
Similarly, the primary amine may react with the imine, forming an addition product which also is reduced to
a secondary amine.
Finally, the secondary amine may react with either the aldehyde or the imine to give products which are
reduced to tertiary amines.
2[H]
RCH == NH + RCH 2 NH 2 a RCHNHCH 2 R ¾® ( RCH 2 ) 2 NH + NH 3
½
NH 2
( RCH 2 ) 2 NH + RCHO a ( RCH 2 ) 2 NCHR 3. Give the reasons for the following.
½ (i) Aniline does not undergo Friedel-Crafts reaction.
OH
2[H] (ii) (CH3 ) 2 NH is more basic than (CH3 ) 3 ×N in an
¾® ( RCH 2 ) 3 N + H 3O
aqueous solution.
( RCH 2 ) 2 N + RCH == NH a (iii) Primary amines have higher boiling point than
2[H] tertiary amines.
( RCH 2 ) 2 NCHR ¾® ( RCH 2 ) 3 N + NH 3
½ 4. (i) Predict the products of electrolysis in each of the
NH 2 following
(a) An aqueous solution of H2 SO4 with platinum
Similar reactions may occur when the carbonyl electrodes.
compound employed is a ketone.
(b) An aqueous solution of AgNO3 with
(i) Ethanal on reaction with ammonia forms an imine
platinum electrodes.
(X) which on reaction with nascent hydrogen gives
(Y). Identify ‘X’ and ‘Y’ . (ii) Estimate the minimum potential difference
(a) X is CH3CH == NH and Y is CH3NH2 needed to reduce Al 2O 3 at 500°C. The Gibbs
(b) X is CH3CHOHNH2 and Y is CH3CH2 NH2 energy change for the decomposition reaction
2 4
(c) X is CH3CHOHNH2 and Y is CH3NH2 Al 2O3 ¾® Al + O 2 is 960 kJ.
(d) X is CH3CH == NH and Y is CH3CH2 NH2 3 3
Or ( F = 96500 C mol -1 )
(ii) Acetaldehyde is reacted with ammonia followed by
reduction in presence of hydrogen as a catalyst. The (i) Calculate D rG° and log K C for the following
primary amine so formed further reacts with reaction at 298 K.
acetaldehyde. The Schiff ’s base formed during the 2Cr( s ) + 3Cd 2+ ( aq) ¾® 2Cr 3+ ( aq) + 3Cd( s )
reaction is
(a) CH3CH == NHCH3 (b) CH3CH == NHCH2 CH3 ° = + 0.34 V, F = 96500 C mol -1 ]
[Given, E cell
(c) CH3 == NHCH2 CH3 (d) CH3CH2 CH == NHCH3 (ii) Resistance of a conductivity cell filled with
(iii) The reaction of ammonia and its derivatives with 0.1 mol L-1 KCl solution is 100 W. If the
aldehydes is called resistance of the same cell when filled with
(a) nucleophilic substitution reaction 0.02 mol L-1 KCl solution is 520 W, calculate
(b) electrophilic substitution reaction
the conductivity and molar conductivity of
(c) nucleophilic addition reaction 0.02 mol L-1 KCl solution.
(d) electrophilic addition reaction
2[ H ]
The conductivity of 0.1 mol L-1 KCl solution is
(iv) ( CH3 CH2 CH2 ) 2 NH + CH3 CH2 CHO ¾® P ¾® Q 1.29 ´ 10 -2 W -1 cm -1.
The compound Q is
(a) ( CH3CH2 CH2 ) 3 N
5. What can be inferred from the magnetic moment
values of the following complex species?
(b) ( CH3CH2 CH2 ) 2 N(CH2 CH3 )
(c) ( CH3CH2 ) 3 N Examples Magnetic moment (BM)
(d) ( CH3CH2 ) 2 NH
K 4 [Mn(CN) 6 ] 2.2
Or Reductive alkylation of ammonia by means of an
[Fe(H2O) 6 ] 2 + 5.3
aldehyde in presence of hydrogen as reducing
agents results in formation of Or
(a) primary amines
Write down the number of 3d-electron in each of
(b) secondary amines
the following ions; Ti 2+ , V 2+ , Cr 3+ , Mn 2+ , Fe 2+ ,
(c) tertiary amines
Fe 3+ , Co 2+ , Ni 2+ and Cu 2+ . Indicate how would
(d) mixture of all three amines
you expect the five 3d-orbitals to be occupied for
2. Write structures of compounds A, B and C in each of these hydrated ions (octahedral)?
the following reactions
6. (i) Assign reason for
(g )
(i) C6H5 Br ¾Mg/
¾¾ ¾ ¾® A ¾(a)
dry ether
¾CO¾2¾¾® B ¾PCl
¾¾ 5
®C (a) amines are less acidic than alcohols of
(b) H3 O+
comparable molecular masses.
D
(ii) CH3 CN ¾(a)
¾SnCl
¾¾ 2/ HCl
¾¾® A ¾Dil.NaOH
¾ ¾ ¾® B ¾¾ ®C (b) aliphatic amines are stronger bases than
(b) H3 O+
aromatic amines.
(ii) Give the structures of A, B and C in the following (ii) Calculate the value of rate constant for the
reactions reaction.
KCN 4 LiAlH HNO2 (iii) Which of the following possible reaction
(a) CH3 Br ¾¾® A ¾¾® B ¾¾¾® C
273 K mechanisms is consistent with the rate law?
NH 2 Br + KOH
3 CHCl + NaOH I. A + B ¾® C + E (slow)
(b) CH3 COOH ¾®
3
A ¾¾¾® B ¾¾¾¾® C A + E ¾® D (fast)
D
Or II. B ¾® C + E (slow)
An aromatic compound ‘A’ of molecular formula A + E ¾® F (fast)
C 7 H 6 O2 undergoes a series of reactions as shown A + F ¾® D (fast)
below. Write the structures of A, B, C, D and E in the 8. What is the difference between multimolecular
following reactions. and macromolecular colloids? Give one
D example of each.
LiAlH4/Ether Or
NH /Heat
(C7H6O2)A ¾¾¾®
3
C6H5CONH2 Differentiate among a homogeneous solution,
NaOH Br2 (CH CO) O a suspension and a colloidal solution, give a
¾® B ¾¾¾¾®
3 2
C suitable example of each.
Br2(aq)
9. Account for the following
E
(i) The enthalpies of atomisation of the transition
7. A reaction is second order w.r.t A and first order w.r.t. B. metals are high.
(i) Write the differential rate equation. (ii) The lowest oxide of a transition metal is basic,
the highest is amphoteric or acidic.
(ii) How is the rate affected on increasing the concentration
of A three times? (iii) Cobalt (II) is stable in aqueous solution but in
the presence of complexing agents, it is easily
(iii) How is the rate affected when the concentrations of
oxidised.
both A and B are doubled?
Or
Or
From the given data of E° values, answer the
Consider the reaction, 2A + B ¾® C + D
following questions
Following results were obtained from experiments
designed to study the rate of reactions. Cr Mn Fe Co Ni Cu
E (°M 2 + / M )
-0.91 -1.18 -0.44 -0.28 -0.25 +0.34
Initial concentration (mol L -1 ) Initial rate of formation
Exp.
No. [A ] [B ] [ D ] (M/min)
° 2+
(i) Why is E Cu value exceptionally
-3 / Cu
1. 0.10 0.10 1 .5 ´ 10
positive?
2. 0.20 0.20 3.0 ´ 10-3 (ii) Why is E (°Mn 2 + / Mn ) value highly negative as
-3
3. 0.20 0.40 6.0 ´ 10 compared to other elements?
(iii) Which is a stronger reducing agent Cr 2+ or
(i) Write the rate law for the reaction.
Fe 2+ ? Give reason.
Solutions
1. (i) (d) CH3CHO + NH3 H2N CH CH3 OH
–H2O
(Ethanal) (Ammonia) ½ D
OH HN CH CH3 CH3 ¾ CH ¾ CH2 ¾ CHO ¾®
(Imine) ( X)
(B)
3-hydroxy butanal
+2(H) CH3 ¾ CH == CH ¾ CHO
(C)
but -2-nal
CH3CH2NH2
(Y) 3. (i) Aniline being a Lewis base react with the Lewis acid
(Ethanamine) AlCl 3 used in Friedel-Crafts reaction and produce a
(ii) (b) CH3CHO + NH3 H2N CH CH3 salt, hence does not show Friedel-Crafts reaction.
–H2O +
C6H5 × NH2 + AlCl 3 ¾® C6H5 × N H2 × AlCl 3- (Salt)
OH
HN CH CH3 (ii) In aqueous solution, basic nature depends on
Imine
+ I-effect, H-bonding and steric-effect.
+2(H) The combined effect shows that (CH3 )2 × NH is more
CH3CH2NH2 basic than (CH3 )3 × N as H-bonding is more in case of
Amine (CH3 )2 × NH than in (CH3 )3 N, which predominates over
+CH3CHO the stability due to + I- effect of three ¾ CH3 groups.
(iii) Primary amines (1°) show two-hydrogen bonds whereas
H3C CH2N CH CH3 + H2O tertiary amines (3°)show no hydrogen bonding. Thus,
(Schiff's base) the net attractive force in case of primary amines is
(iii) (c) The reaction of ammonia and its derivatives with more than that of tertiary amines. Hence, primary
aldehydes is called nucleophilic addition reaction. amines have higher boiling point than that of tertiary
Complete reaction is as follows amines.
O O– OH 4. (i) (a) A dilute solution of H2 SO4 with platinum elections.
C + NH2
r
H C +H
r
C Both H2 SO4 and water ionise in the solution.
+ 2-
H CH3 H CH3
NH2
H CH3
NH2
E 2H ( aq ) + SO ( aq )
H2 SO4 ( aq ) 4
+ -
H O( l ) E 2H ( aq ) + OH ( aq )
2
(iv) (a) (CH3CH2CH2)2NH + CH3CH2CHO
At cathode H+ ions will be reduced and hydrogen gas
(CH3CH2CH2)2N CHCH2CH3 is produced at cathode.
(P)
OH H+ ( aq ) + e - ¾® H( g )
+2(H) H( g ) + H( g ) ¾® H2 ( g )
(CH3CH2CH2)3 N + H2O
At anode OH- ions will be released preferentially and
(Q) not SO-4 ions due to less discharge potential.
Or (a) Reductive alkylation of ammonia by means of an OH- ( aq ) ¾® OH + e -
aldehyde in presence of hydrogen as reducing agent 4 OH ¾® 2H2O( l ) + O2 ( g )
result in formation of primary amine.
Oxygen gas is produced at anode.
OH
Solution will be acidic and will contain H2 SO4
CH3CHO + NH3 CH3CH NH2
–H2O (b) An aqueous solution of CuCl 2 with platinum electrodes.
CH3 — CH==NH
Both CuCl 2 and water ionise as usual.
+2(H) ( aq )
2+ -
CuCl 2 E Cu ( aq ) + 2Cl ( aq )
CH3CH2NH2 + -
H O( l ) E 2H ( aq ) + OH ( aq )
2
(Primary amine)
At cathode Cu 2 + ions will be reduced preferentially
2. (i) MgBr COOH COCl
due to less discharge potential than H+ ions.
Mg/dry ether
C6H5Br ¾¾¾®
(a) CO (g)
¾¾¾®
2 PCl
¾®
5 Cu 2 + ( aq ) + 2e - ¾® Cu( s )
+
(b) H3O
Copper metal is deposited at cathode.
(A )
Phenyl magnesium
(B) (C)
Benzoic acid Benzoyl chloride At anode Cl - ions will be discharged in preference to
bromide OH- ions and chlorine gas is produced at anode.
(a) SnCl 2 / HCl dil. NaOH Cl - ( aq ) ¾® Cl ( g ) + e -
(ii) CH3CN ¾¾¾¾® CH3CHO ¾¾®
(b) H 3 O+ (A) Cl ( g ) + Cl( g ) ¾® Cl 2 ( g )
Acetaldehyde
(ii) Reaction involved In [Fe(H2O)6 ]2+ , Fe is in +2 oxidation state. Given, m = 5.3

2 4 BM ( » 5 ), shows that there are four unpaired electrons.
Al 2O3 ¾® Al + O2
3 3 Since, H2O is a weak ligand. Hence, the electrons in 3d do
Here, n = 4 not pair up when the ligands, i.e. H2O molecules, approach.
Given, DG = 960 k J To accommodate the electrons donated by H2O molecules,
the hybridisation is sp3d 2 . Hence, it will be an outer orbital
DG = - nFE°
octahedral complex.
-960 kJ = -4 ´ 96500 ´ E° 3d 4s
960000 J
E° = = 2.48 V » 25
. V Fe =
4 ´ 96500 J 26
3d 4s
Or
(i) °
D r G° = - nFEcell , n = 6 Fe2+ =
3d
= - 6 ´ 96500 C/mol ´ 0.34 V 2+
= - 196860 J/mol or - 196.860 kJ / mol [Fe(H2O)6] =
° = 0.059 V/ n ´ log K C
\ Ecell Four unpaired
electrons
0.34 V ´ 6 4d
log K C = = 34.5762
0.059 V ´´´´ ´´´´ ´´´´
(ii) (a) Cell constant, Six pairs of electrons in
G*= conductivity ´ resistance sp 3d 2 -hybrid from six H2 O
= 1.29 S m -1 ´ 100W = 129 m -1 = 1.29 cm -1
Or
(b) Conductivity of 0.02 M KCl solution, All the ions form complex of the type [ M (H2O)6 ] n+ . As water
Cell constant 1.29 cm -1 is a weak field ligand, therefore, in case of octahedal
k= =
Resistance 520 W complex, pairing takes place, when each t 2 g and eg orbital is
-3 -1 singly occupied [ t 2g ( dxy , dyz , dzx ) set is of lower energy and
= 2.48 ´ 10 S cm
k ´ 1000 eg ( dz 2 , dx2 - y 2 ) is of higher energy].
(c) Molar conductivity, Lm =
M Number
2.48 ´ 10-3 ´ 1000 Number Occupancy
= = 124 S cm 2 mol -1 of
Ions Configuration of of
0.02 unpaired
3d electrons 3d-orbitals
5. Magnetic moment ( m ) = n ( n + 2) BM electrons
For n = 1, m = 1 ( 1 + 2) = 3 = 1.73 BM » 2 Ti 2+ 3 d2 2 2 t 22g
For n = 2, m = 2( 2 + 2) = 8 = 2.83 BM » 3
V 2+ 3 d3 3 3 t 23g
For n = 3, m = 3( 3 + 2) = 15 = 3.87 BM » 4
For n = 4, m = 4( 4 + 2) = 24 = 4.90 BM » 5 Cr 3+ 3 d3 3 3 t 23g
For n = 5, m = 5 ( 5 + 2) = 35 = 5.92 BM » 6 Mn 2+ 3 d5 5 5 t 23g e g2
In K4[Mn(CN)6 ] , Mn is in +2 oxidation state, i.e. given
Fe 2+ 3 d6 6 4 t 42 g e g2
value of m (2.2 BM » 2) indicates the presence of one
unpaired electron. Since, CN– is a strong field ligand.
Fe 3+ 3 d5 5 5 t 23g e g2
Hence, when CN– ligands approach Mn 2 + ion, the
electrons in 3d pair up. Hybridisation involved is d 2 sp3 Co 2+ 3 d7 7 3 t 52 g e g2
forming inner orbital octahedral complex.
3d 4s Ni 2+ 3 d8 8 2 t 26g e g2
25 Mn = Cu 2+ 3 d9 9 1 t 26g e g3
3d 4s
Mn2+ = 6. (i) (a) Loss of proton from amines give RNH- ion whereas
loss of proton from alcohol forms alkoxide ion. Since, O
3d
is more electronegative than N therefore, RO- can
[Mn(CN)6 ] 4- = ´´ ´´ ´´ ´ ´ ´ ´ ´ ´ accommodate the negative charge more easily than
RNH- . Further, O—H bond is more polar than N—H bond
One unpaired Six pairs of electrons
as O is more electronegative than N. Hence, amines are less
electron in d 2 sp 3 -hybrid
– acidic than alcohol.
from six CN
(b) In aromatic amines, the lone pair of electrons present on nitrogen takes part in resonance and hence, not available for
donation. However, in aliphatic amines, the lone pair is easily available for donation. That’s why, aliphatic amines are more
basic than aromatic amines.
LiAlH HNO 2
(ii) (a) CH3Br ¾KCN ¾¾® CH3CN ¾ ¾¾4 ® CH3CH2NH2 ¾273 ¾¾ K
® CH3CH2OH + N2 + H2O
(A) (B)
NH Br2 + KOH CHCl 3 + NaOH

(b) CH3COOH ¾ ¾
¾3 ® CH3CONH2 ¾¾¾® CH3NH2 ¾ ¾ ¾ ¾ ¾
¾® CH3NC + 3NaCl + 3H2O
D (A) (B) D (C)
Or
COOH NH2
A is benzoic acid, B is aniline, C is ¾ NHCOCH3
NH2 N-phenylethanamide
(Acetanilide)
Br Br
D is C6H5CH2NH2 , E is
Benzylamine
Br
2, 4, 6-tribromoaniline
NHCOCH3
(C)
Acetanilide NH2
(CH3CO)2O Acetylation Br Br
Br2 (aq)
NH3/Heat Br2 + NaOH
C7H6O2 (A) ¾¾¾® C6H5CONH2 ¾¾¾¾® Hofmann
C6H5NH2
Benzamide Aniline Bromination
bromamide
Reduction degradation (B) Br
LiAlH4 /ether 2, 4, 6-tribromo
aniline
C6H5CH2NH2
Benzylamine (E )
( D)
7. A reaction is second order w.r.t. A and first order w.r.t B. (Rate)3 k (0.2)p (0.4)q 6 ´ 10-3
= =
-d[ R ] (Rate)2 k (0.2)p (0.2)q 3 ´ 10-3
(i) Differential rate equation = (Rate)1 = = k[ A ] 2 [ B ]
dt
or 2q=2 , q = 1
(ii) When the concentration of A is increased three times,
i.e. 3A then Comparing experiments (i) and (ii)
(Rate) 2 = k [3 A ] 2 [ B ] = 9k[ A ] 2 [ B ] = 9 ( Rate )1 (Rate)1 = k (0.1)p (0.1)q = 1.5 ´ 10-3 …(iii)
p q -3
This shows that rate will be increased 9 times to the (Rate)2 = k (0. 2) (0. 2) = 3 . 0 ´ 10 …(iv)
initial rate. Dividing Eq. (iv) by Eq. (iii), we get
(iii) When concentrations of both A and B are doubled then, 3 ´ 10-3 k (0.2)p (0.2)q
=
(Rate) 3 = k [2 A ] 2 [ 2B ] = k 8[ A ] 2 [ B ] 1.5 ´ 10-3 k (0.1)p (0.1)q
= 8k [ A ] 2 [ B ] = 8 (Rate)1 2 = (2)p (2)q
This shows that rate will be increased 8 times to the where, q = 1, 1 = 2 p, 2 0 = 2 p
initial rate. p=0
Or (i) Thus, the rate law is
Rate law may be written as, Rate = k [ A ] p [ B ] q rate = k [ A ] 0 [ B ] = k [ B ]
Comparing experiments (ii) and (iii), we get (ii) Rate = k [ B ]
(Rate)2 = k (0.2)p (0. 2)q = 3 ´ 10-3 …(i) Rate 3 ´ 10-3
k= = = 15 ´ 10-3 min -1
(Rate)3 = k (0.2)p (0.4)q = 6 ´ 10- 3 …(ii) [ B] 0. 2
Dividing Eq. (ii) by Eq. (i), we get (iii) B ¾® C + E (slow) is the possible reaction which is
consistent with the rate law, rate = k [ B ].
8. Differences between multimolecular and macromolecular colloids 9. (i) Transition metals have high enthalpies of
atomisation due to strong metallic bonding and
Multimolecular colloids Macromolecular colloids additional covalent bonding. Metallic bonding is
When substances which possess due to their smaller size while covalent bonding is
When a large number of small
very high molecular masses are due to d-d overlapping.
molecules or atoms (diameter <
1 nm) of a substance combine dispersed in suitable dispersion (ii) In lower oxidation states, transition metals behave
together in a dispersion medium to medium, the colloidal solutions, like metals and metal oxides are basic in nature.
thus formed, are called Thus, in lower oxidation states, transition metal
form aggregates, which have size in macromolecular colloids.
the colloidal range, the colloidal oxides are basic. As the oxidation state increases,
solutions, thus formed, are known its metallic character decreases due to decrease in
as multimolecular colloids. size, thus, it becomes less metallic or more
non-metallic.
These colloids are not very much These colloids are quite stable.
Oxides of a non-metal may be acidic or neutral.
stable.
Thus, in higher oxidation states, transition metal
e.g. gold sol, sulphur sol, etc. e.g. Cellulose, starch, etc. oxides are amphoteric or acidic.
(iii) In the presence of complexing agents, cobalt gets
Or oxidised from + 2 to + 3 state because it provides
energy to remove an electron from Co2 + .
Homogeneous Moreover, Co (III) is more stable than Co (II).
Colloidal solution Suspension
solution Or
Particle size < 1 nm. Particle size between 1 Particle size > 1000 (i) Sum of enthalphy of atomisation and ionisation is
to 1000 nm. nm. greater than enthalphy of hydration. Thus,
E°M 2 + / M is positive for copper.
Constituent particles Constituent Constituent particles (ii) Ionisation enthalpy is lower than hydration
are ions or small particles are single are molecules. enthalphy due to stable 3d5 configuration. Thus,
molecules. macromolecule or E°Mn 2 + /Mn is more negative.
aggregates of many
atoms, ions or (iii) Cr 2 + is a stronger reducing agent because it can
molecules. lose electron to form Cr 3+ which has stable 3d 3
configuration (half-filled t 23 g ). Further is more
e.g. Sugar solution e.g. Paint e.g. Sand solution
negative than Fe2 + .
Chemistry
Practice Paper 2 *
(Unsolved)

Max. Marks : 35
1. Read the following and answer the questions from (i) to (v) given below.
Some colloids are stable by their nature, i.e. gels, alloys, and solid foams. Gelatin and jellies are two
common examples of a gel. The solid and liquid phases in a gel are interdispersed with both phases being
continuous.
In most systems, the major factor influencing the stability is the charge on the colloidal particles. If a
particular ion is preferentially adsorbed on the surface of the particles, the particles in suspension will repel
each other, thereby preventing the formation of aggregates that are larger than colloidal dimensions.
The ion can be either positive or negative depending on the particular colloidal system, i.e. air bubbles
accumulate negative ions, sulphur particles have a net negative charge in a sulphur sol, and the particles in a
metal hydroxide sol are positively charged. Accumulation of charge on a surface is not an unusual
phenomenon-dust is attracted to furniture surfaces by electrostatic forces.
When salts are added to lyophobic colloidal systems the colloidal particles begin to form larger aggregates
and a sediment forms as they settle. This phenomenon is called flocculation, and the suspension can be
referred to as flocculated, or colloidally unstable. If the salt is removed, the suspension can usually be
restored to its original state; this process is called deflocculation or peptisation. The original and restored
colloidal systems are called deflocculated, peptised, or stable sols.
Why does a small amount of salt have such a dramatic effect on the stability of a lyophobic colloidal system?
The answer lies in an understanding of the attractive and repulsive forces that exist between colloidal
particles. van der Waals’ forces are responsible for the attractions, while the repulsive forces are due to the
surface charge on the particles. In a stable colloid, the repulsive forces are of greater magnitude than the
attractive forces.
The magnitude of the electrical repulsion is diminished by addition of ionised salt, which allows the
dispersed particles to aggregate and flocculate. River deltas provide an example of this behaviour. A delta is
formed at the mouth of a river because the colloidal clay particles are flocculated when the freshwater mixes
with the salt water of the ocean.
(i) Gelatin is a ………… colloidal system. 4. (i) For a chemical reaction R ® P, the variation in the
(a) solid in solid concentration, ln [R] vs time(s) plot is given as
(b) solid in gas
(c) liquid in solid
(d) liquid in gas
(ii) Colloidal solutions are stable due to In [R]
(a) presence of charges on the colloidal particles
(b) formation of aggregates by colloidal particles
t(s)
(c) preferential adsorption on the surface
(d) preferential absorption on the surface (a) Predict the order of the reaction.
(iii) Settling down of colloidal particles to form a (b) What is the slope of curve?
suspension is called (c) Write the unit of rate constant for this reaction.
(a) flocculation (ii) Show that the time required for 99% completion is
(b) peptisation double of the time required for the completion of
(c) aggregation 90% reaction.
(d) deflocculation
Or
(iv) When van der Waals’ forces are greater than other
The data given below is for the reaction,
forces due to the surface charge on the particles,
(a) flocculation occurs. 2N 2O5 ( g ) ¾® 4NO2 ( g ) + O2 ( g )
(b) the colloid is stable.
(c) peptisation takes place. Rate of disappearance
S. No. N 2O5 (mol L-1 ) of N 2O5 (mol L-1 min -1 )
(d) deflocculation occurs.
Or 1. 1.13 ´ 10-2 34 ´ 10-5
The particles in suspension will repel each other, 2. 0.84 ´ 10-2 25 ´ 10-5
thereby preventing the formation of aggregates 3. 0.62 ´ 10-2 18 ´ 10-5
that are larger than colloidal dimensions. This
statement explains: Determine for this reaction,
(a) formation of delta
(i) order of reaction (ii) rate law
(b) river water is a colloidal of clay particles
(iii) rate constant
(c) effect of salt on lyphobic colloid
(d) phenomenon of flocculation (ii) A first order reaction takes 10 min for 25%
decomposition. Calculate t 1/ 2 for the reaction.
2. (i) Write the structures of A and B in the following
(Given : log 2 = 0.3010, log 3 = 0.4771,
reactions
H 2, Pd -BaSO 4 H 2 N -OH
log 4 = 0.6021)
(a) CH3 COCl ¾¾® A ¾¾® B 5. (i) Draw the structures of the following derivatives
(i) CO2 PCl 5
(b) CH3 MgBr ¾® A ¾® B (a) Propanone oxime
+
(ii) H 3O (b) Semicarbazone of CH3 CHO
(ii) Distinguish between (ii) How will you convert ethanal into the following
(a) C6 H5 ¾ COCH3 and C6 H5 ¾ CHO compounds? Give the chemical equations involved:
(b) CH3 ¾ COOH and HCOOH (a) CH3 ¾ CH3
Or (b) CH3 ¾ CH ¾ CH 2 ¾ CHO
Write the structures of A, B, C, D and E in the ½
OH
following reactions.
CH3COCl Zn-Hg/Conc. HCl (c) CH3 CH 2 OH
C6H6 A B
Anhyd. AlCl3 Or
NaOI (i) KMnO4-KOH, D
C A ketone A(C4 H 8 O) which undergoes a haloform
(ii) H O+
3
D+E reaction and gives compound B on reduction. B on
heating with sulphuric acid gives a compound C
3. Why does bromination of aniline, even under very which forms mono-ozonide D. D on hydrolysis with
mild conditions, gives 2, 4, 6- tribromoaniline zinc dust gives only E. Identify A, B, C, D and E.
instantaneously? Write the reactions involved.
° = 0. 236 V at 298 K. Calculate the standard

has E cell
6. (i) Why aniline does not undergo Friedel-Crafts
reaction? Gibbs energy of the cell reaction. (Given, 1 F = 96500
(ii) Why can primary aromatic amines be not C mol -1 )
prepared by Gabriel phthalimide synthesis? (ii) How many electrons flow through a metallic wire if a
Write the main products of the following current of 0.5 A is passed for 2 h? (given, 1 F =
reactions 96500 C mol -1 )
HNO2 Or
(i) CH3 CH 2NH 2 ¾¾¾¾®
0°C Calculate emf of the following cell at 298 K.
(ii) O Mg( s )|Mg 2 + (0.1 M)||Cu 2 + (0.01)|Cu( s )
—S—Cl + H—N—C2H5 ¾®
Given, E°cell = +2.71 V, 1F = 96500 C mol -1
O
8. The first few members of the series are quite reactive.
H
They usually form oxides and hydroxides. Complete
(iii) the following reactions of lanthanoids.
O
Heated with N
CH ¾ C ¾ Cl (i) Ln ¾¾¾¾®
N—H ¾¾¾¾¾®
3
With halogens
(ii) Ln ¾¾¾¾®
H
Burns in O
(iii) Ln ¾¾¾¾®
2
Or 9. Give the formula of each of the following coordination

An aromatic compound ‘A’ of molecular formula entities.
C 7 H 7 ON undergoes a series of reactions as (i) Co 3+ ion is bound to one Cl - , one NH molecule and
shown below. Write the structures of A, B, C, D two bidentate ethylenediamine (en) molecules.
and E in the following reactions
(ii) Ni 2+ ion is bound to two water molecules and two
D oxalate ions.
CHCl3 + NaOH Write the name and magnetic behaviour of each of the
Br2 + KOH CH3 COCl
(C7H7ON)A C6H5NH2 above coordination entities.
Anhyd. AlCl3
NaNO2 + HCl (Atomic number of Co= 27, Ni= 28)
273 K
E Or
Br2
B C Explain the following.
H 2O
(i) Low spin octahedral complexes of nickel are not
7. (i) The cell in which the following reaction occurs known.
2Fe3+ ( aq) + 2I - ( aq) ¾® 2Fe2+ ( aq) + I 2 ( s ) (ii) CO is a stronger ligand than NH 3 for many metals.
Answers
1. (i) - (c); (ii) - (a); (iii) - (a); (iv) - (d, b)
Chemistry
Practice Paper 3 *
(Unsolved)

Max. Marks : 35
1. Read the following and answer the questions from (i) to (iv) given below.
Molar conductivity of a solution is the conductance of solution containing one mole of electrolyte, kept
between two electrodes having unit length between them and large cross- sectional area, so as to contain the
electrolyte. In other words, molar conductivity is the conductance of the electrolytic solution kept between
the electrodes of a conductivity cell at unit distance but having area of cross-section large enough to
accommodate sufficient volume of solution that contains one mole of the electrolyte. It is denoted by L m .
The molar conductivity is related to conductivity as
1000 1000
Lm = k ´V = ´ k= k´
C Molarity
Unity of L m (molar conductivity) shall be ohm -1cm -1 mol -1 or S cm 2 mol -1 .
Thus, knowing molar concentration (C ) and conductivity ( k), L m can be calculated. L°m is called molar
conductivity at infinite dilution. The molar conductivity of strong electrolytes is found to vary with
concentration according to the equation,
LCm = L°m - A C
This equation is called Debye-Huckel Onsager equation.
Here, A is constant depending upon the type of electrolyte taken and nature of solvent and temperature.
(i) If conductivity of 0.00241 M acetic acid is 7.896 ´ 10 -5 S cm -1 , the molar conductivity of the solution shall be (in
S cm -1 mol -1 )
(a) 3.276 (b) 0.3276 (c) 32.76 (d) 327.6
(ii) Molar conductivity of a solution is 1.26 ´ 10 2 W -1cm 2 mol -1 . Its molarity is 0.01. Its specific conductivity will
be
(a) 1. 26 ´ 10-5 (b) 1.26 ´ 10-3 (c) 1. 26 ´ 10-4 (d) 12.6 ´ 10-3
(iii) The increase in molar conductivity of HCl with Or

dilution is due to (i) Convert
(a) increase in self-ionisation of water
(a) Benzoic acid to benzaldehyde
(b) hydrolysis of HCl
(c) decrease in self-ionisation of water (b) Propanone to propane
(d) decrease in interionic forces (ii) Arrange the following comopunds in the
Or decreasing order of their acidic strength.
Highest molar conductivity will be exhibited by CH3 CH2 COOH, CH3 CH2 CH(F)COOH,
(a) 0.005 M NaCl (b) 0.1 M NaCl
CH3 CH(F)CH2 COOH, ( CH3 ) 2 CHCOOH
(c) 0.5 M NaCl (d) 0.01 M NaCl 6. Electrophilic substitution in case of aromatic
(iv) Which of the following is wrong about molar amines takes place more readily than benzene.
conductivity ? Identify A and B in the following reactions.
(a) The solution contains Avogadro number of molecules of Br × NaOH
the electrolyte.
(i) CH3 ¾ CH2 ¾ CHNH2 ¾ ¾2 ¾ ¾¾®
(b) It is the product of specific conductivity and volume of ½
solution in cc containing 1 mole of electrolyte. CH3
(c) Its units are ohm -1 cm 2 mol -1. A ¾HNO
¾¾ 2
®B
(d) Its value for 1 M NaCl is same as that of 1 M glucose
solution. 3+
¾2 /¾
(ii) C6 H5 NO2 ¾Br Fe
¾® A ¾HNO
¾ ¾¾ 2®B
2. Write down the IUPAC and common name for the +
following. (iii) CH3 CN ¾H¾/H
¾2¾O
® A ¾LiAlH
¾¾ ¾ 4®B
CHO O Or
(i) (ii) Answer the following questions
CHO CH3 (i) The compound of A( C3 H9 N) reacts with benzene
(iii) CH 2 == CHCHO sulphonyl chloride to give a solid, insoluble in
alkali. Identify ‘A’.
Or
(ii) Outline a synthesis of p-bromonitrobenzene from
Give names of the reagents to bring about the benzene in two steps.
following transformations
(i) Benzoyl chloride to benzaldehyde 7. Following data are obtained for the reaction
1
(ii) Benzene to benzaldehyde N 2 O 5 ¾® 2NO 2 + O 2
(iii) Benzene to acetophenone 2
3. What happens when t/s 0 300 600

-1 -2 -2
(i) toluence is treated with conc. HNO3 and conc. [N 2O5 ] /mol L 1 .6 ´ 10 0.8 ´ 10 0.4 ´ 10-2
H2 SO4 at 293 K?
(ii) nitrobenzene is treated with conc. HNO3 and conc. (i) Show that it follows first order reaction.
H2 SO4 at 363 K? (ii) Calculate the half-life.
4. Although Cu + does not exist in solution state, but (Given: log 2 = 0 .3010 , log 4 = 0 .6021)
CuCl( s ) is formed in the presence of Cl - ions in Or
aqueous solution of Cu(s) and Cu 2+ . Explain. For the first order thermal decomposition reaction,
the following data obtained:
5. (i) Write the chemical equations when acetic acid C 2H5 Cl ( g ) ¾® C 2H 4 ( g ) + HCl( g )
reacts with
(a) Br2 in the presence of phosphorus. Time/s Total pressure/atm
(b) Cl 2 in the presence of phosphorus. 0 0.30
(ii) Give two reactions in which aliphatic aldehydes 300 0.50
differ from aromatic aldehydes? Calculate the rate constant. (Given : log 2 = 0.3010,
log 3 = 0.4771, log 4 = 0.6021)
8. Write one difference in each of the following (ii) Predict the number of unpaired electrons, the
magnetic moments for each of the following
(i) Lyophobic sol and lyophilic sol.
complex.
(ii) Solution and colloid.
(i) [Fe(CN) 6 ]4 -
(iii) Homogeneous catalysis and heterogeneous
catalysis. (ii) [ Cr(NH3 ) 6 ] 2 +
Or (iii) [ Sc(H2 O) 6 ] 3 +
What happen, when Or
(i) a freshly prepared precipitate of Fe(OH) 3 is PtCl 4 and NH 3 may form five complexes,
shaken with a small amount of FeCl 3 solution?
A(PtCl 4 × 6NH 3 ), B(PtCl 4 × 5NH 3 ), C(PtCl 4 × 4NH 3 ),
(ii) presistent dialysis of a colloidal solution is carried D( PtCl 4 × 3NH 3 ) and E( PtCl 4 × 2NH 3 ). One mole of
out?
each A, B, C, D and E reacts with excess of AgNO 3
(iii) an emulsion is centrifuged? to yield 4, 3, 2 and 1 mole(s) of AgCl respectively,
9. (i) [Ti(H2 O) 6 ] 3 + absorbs light of wavelength 500 nm. while E gives, no AgCl. The conductance of their
Name one ligand which would form Ti(III) solutions are in the order A > B > C > D > E. On
complex absorbing light of lower wavelength than the basis of Werner’s theory, write their structure
500 nm and one ligand which would form a and give the total number of ions given by one
complex absorbing light of wavelength higher than complex.
500 nm.
Answers
1. (i) - (c); (ii) - (b); (iii) - (b, a); (iv) - (d)

Arihant CBSE Chemistry Term 2 C - Aditya Jangid

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Exam Scheme Term I & II

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Electrochemistry is the study of production of electricity from

Increasing strength of reducing agent

E cell = E Ag + /Ag - E Cu 2 + /Cu Fe3 + + e - ¾® Fe2 + 0.77

EMF of the cell = Ecell

k ´ 1000 (ii) Dissociation constant can be determined as

Dissociation constant, = L°H+ + L°Cl – + L°CH – + L°Na+

The graph of E Mg 2+ / Mg vs log [Mg 2+ ] is A B

(a) (b) (c) Weak electrolyte Weak electrolyte

log[Mg 2+]® log[Mg 2+]® 15. Consider the following graph,

Lm /(S cm2 mol–1)

(A) (d) A is false, but R is true.

0 .005 .010 .015 .020 .025 .030 .035 Zn2+(aq)

1 S m 2 mol -1 = 10 4 S cm 2 mol -1 The standard potentials are always measured under

4. (d) In case of electrolysis of aqueous NaCl, oxidation ­ ­ ­ ­

° is - ve, then DG° is + ve, i.e. DG° > 0.

Subjective Questions (ii) Fe ( s )| Fe2 + (0.001 M) || H+ (1 M)| H2( g ) (1 bar) | Pt ( s )

Therefore, the overall cell reaction will be Q 3600 C

14. Conductivity ( k ) = 0.0248 S cm -1 = 0.0248 ohm -1 cm -1 = 210 S cm 2 mol -1

18. pH of the solution will not be affected as [ H+ ] remains = 1.98 +

0.0591 [Al ] 3+ 2 = 0.34 - ( -1.66) = 2.00 V

Characteristics of Order of Reaction Characteristics of Molecularity of a Reaction

Difference between Molecularity and Order of Reaction

Differential and Integrated Rate Equations

(b) r = k¢ [O3 ][O2 ] (a) depends on the concentration of reactants present in

(c) (d) 25. Assertion Order and molecularity are same.

(c) - (d) None of these (b) t1/2

(a) concentration of products For this reaction

The reaction occurs in two steps Slope (m) = - k (rate constant)

2. (i) On substituting the above value of [ O ] in Eq. (i),

\ x=2 [On comparing the powers] 2.303 [ A] 0 2.303

Surface chemistry deals with phenomena which occurs at the

3. Activation of adsorbent means its adsorbing power is

Subjective Questions 6. (i) Effect of pressure on adsorption of gases on solids At

The d - and f- Block

Magnetic Properties Alloy Formation

126 125 125 128 (a) Ag 2 SO4 (b) CuF2

(a) Co (Z = 27) (b) Ni ( Z = 28) Or E ° ° 3+ 2 +

variable oxidation states is

Cu+ = [Ar] 3d10 (0 unpaired electron) Eu 63 + 2, + 3

Thus, for Eu common oxidation states are + 2 and + 3. Nd

3. Transition elements show variable oxidation state due to

(iii) The metal ions with partially or incomplete Z n M Nature

(iii) In aqueous solution, copper (I) undergoes 29. (i) Titanium

Transition metals form a large number of complex compounds in l

to the metal have characteristic spatial

(iii) Ligands Ions or molecules which can donate a lone pair of l

Bonding in Coordination Compounds

4. (d) In case of electrolysis of aqueous NaCl, oxidation