Chemistry 5 Chapters Active Site
Chemistry 5 Chapters Active Site
ATOM
THEORY
NCERT SOLUTIONS
STRUCTURE OF ATOM
John Dalton coined the term atom. The atom is the fundamental particle of matter and
considered to be indivisible and indestructible.
In fact, the atom as the whole is electrically neutral as
number of protons in it is equal to number of electrons.
Glowing is due to the bombardment of glass wall by the cathode rays. It may be noted that
when the gas pressure in the tube is 1 atm, no electric current flows through the tube. This
is because the gases are poor conductor of electricity.
Origin of Cathode rays:
Cathode rays are first produced in cathode due to bombardment of the gas molecules by the
high-speed electrons emitted first from the cathode.
vi. They produce X-rays when they strike against the surface
vii. They produce green fluorescence on the glass walls of the discharge tube exp: ZnS.
ix. They possess penetrating effect (i.e., they can easily pass-through thin foils of metals).
x. The nature of the cathode rays does not depend upon the nature of the gas, taken in
xi. For each cathode rays, the ratio of charge (e) to mass (m) is constant
Fundamental particles:
1) Electron: Electron is a universal constituent discovered by the J.J. Thomson.
Charge: It was determined by Mullikan by oil drop experiment as -1.602x10-19coulombs
or 4.803x10-10 e.s.u.
Mass:9.11x10-28g (nearly equal to 1/1837th of mass of hydrogen atom).
Specific charge:e/m ratio is called specific charge & is equal to 1.76x108 coulombs/gm.
Mass of one mole of electrons: It is 0.55 mg.
Charge on one mole of electron is 96500 coulombs or 1 faraday.
Density: 2.17x1017 g/cc.
3. Neutron (0n1)
* It was discovered by Chadwick by bombarding Be atom with high speed -particles.
𝟒𝐁𝐞𝟗 + 𝟐 𝐇𝐞𝟒 → 𝟔𝐂
𝟏𝟐
+𝟎 𝐧 𝟏
* Charge: Charge less or neutral particle.
* Mass:1.675x10-24 g or 1.675x10-27 kg.
* Density:1.5x1014 g/cm3 and is heavier than proton by 0.18%.
* Specific charge: It is zero.
* Among all the elementary particles neutron is the heaviest and least stable.
Important Features
• It shows the electrical neutrality of the atom.
• The mass of the atom is assumed to be uniformly distributed over the atom.
The model was rejected as it was not consistent with the results of the alpha
scattering experiment.
Limitation: It is failed explain the results of scattering experiment of Rutherford and the
stability of atom.
i. Most of the -particles passed through the gold foil without any deflection from their
original path.
Bcz atom has largely empty space as most of the -particles passed through the foil
undeflected.
ii. A few of the alpha particles are deflected fairly at large angles while some are
deflected through small angles.
Bcz there is heavy positive charge at the center of the atom which causes repulsions.
The entire mass of the atom is concentrated in the nucleus.
iii. A very few -particles are deflected back along their path.
According to Rutherford,
1. Atom is spherical & mostly hollow with lot of empty space in it.
2. It has a small +ly charged part at its center known as nucleus.
3. The nucleus is surrounded by electrons. Electrons revolve round
the nucleus with very high speeds in circular paths called orbits.
4. The number of extra nuclear electrons is equal to the number of
units of positive charge in the nucleus. Therefore, the atom is electrically neutral.
Electrons and the nucleus are held together by electrostatic forces of attraction.
5. Rutherford’s model has resemblances with solar system. Hence, it’s also known as
planetary model of the atom.
6. There is an empty space around the nucleus called extra nuclear part. In this part
electrons are present. As the nucleus of the atom is responsible for the mass of the
atom, the extra nuclear part is responsible for its volume.
Drawbacks:
1. According to the electromagnetic theory of Maxwell, when a charged
particle moves under the influence of attractive force it loses energy
continuously in the form of electromagnetic radiation. Therefore, an
electron in an orbit will emit radiation.
As a result of this, the electron should lose energy at every turn and
move closer and closer to the nucleus following a spiral path. Ultimate result is that it
will fall into the nucleus thereby making the atom unstable.
i.e., Rutherford’s model cannot explain the stability of the atom.
Atomic number(Z): Atomic number denotes the number of protons or the number of
electrons in the neutral atom.
Atomic number (Z) = Number of protons in the nucleus of an atom or ion
= Number of electrons in a neutral atom.
Each element has a different atomic number.
A The atomic number of sulfur (S) is 16.
B The atomic number of iron (Fe) is 26.
C The atomic number of silver (Ag) is 47.
Mass number (A): The mass number is the total number of protons and neutrons
present in the nucleus of an atom of an element and indicated as A.
Protons and neutrons present in the nucleus of an atom are collectively known as nucleons.
Therefore, the mass number is also known as nucleon number.
Mass number (A) = Number of protons (Z) + Number of neutrons (n)
The number of neutrons (n) in an atom is equal to the difference between the mass
number and the atomic number. n = A – Z
Mass Number
Atomic Number
A
Z X OR
Z XA
Symbol of Element
1 electron 1 electron
1 electron
Isotopes of an element differ in the number of neutrons present in the nucleus. But they
have the same number of protons and electrons.
Because of same number of electrons, they show same chemical properties. They,
have different number of neutrons, so they will have different masses and hence
different physical properties.
Isobars: The atoms of different elements which have the same mass number but
different atomic numbers are called isobars.
Exp: 18 Ar 40 , 19 K 40 , 20 Ca40
They have same number of nucleons. But they are differed chemically because the chemical
characteristics depend upon the number of electrons which is determined by the atomic
number.
Isotones: Isotones are the atoms of different elements which have the same number of
neutrons.
Eg: 6 C14 , 7 N15 , 8 O16 (n = 8)
14 Si30 , 15 P31, 16 S32 (n = 16)
Isotones show different physical and chemical properties.
1. Wave length:
The distance between two successive crests, troughs or between any two consecutive
identical points in the same phase of a wave is called wave length. It is denoted by the
letter (lambda).
The wave length is measured in terms of meters (m), centimeters (cm), angstrom units
(A0) nanometers (nm), picometers (pm) and also in millimicrons (m).
The S.I. unit of wavelength is meter, m
0 –10 –8
1A = 10 m or 10 cm
–9 –7
1nm = 10 m or 10 cm = 10A0
–12 –10
1pm = 10 m or 10 cm =10−2 A0
2.Frequency:
The number of waves that pass-through a given point in one second is known as
frequency of radiation. It is denoted by the ‘v’ (nue).
Crest Crest
a
a
Trough Trough
SI unit of frequency is per second(s–1) or Hertz (Hz). A cycle is said to be completed when
a wave consisting of a crest and a trough passes through a point.
3.Velocity:
Distance travelled by the wave in one second is called velocity or speed of the wave (C).
Wave length, wave number𝝂̅ , frequency 𝝂 and velocity c are related as follows
.
⇒ 𝑪 = 𝜐𝜆
5.Amplitude:
The height of the crest or the depth of the trough of the wave is called amplitude of
the wave. It is denoted by A.
The amplitude determines the strength or intensity or brightness of radiation.
6.Time period:
It is the time taken by the wave for one complete cycle or vibrations. It is denoted by
T. It is expressed in second per cycle.
1 1
T= ( where = frequency)
𝑉
Electromagnetic spectrum:
The arrangement of different types of electromagnetic radiations in the order of
increasing wavelengths or decreasing frequencies is known as electromagnetic spectrum.
3. Energy of each quantum of light is directly proportional to the frequency of the radiation.
E or E = h
Where ‘h’ is known as Planck’s constant.
The value of ‘h’, 6.6256 × 10–34 Jsec- or 6.6256 × 10–27ergs sec-
4. In case of light, the quantum of energy is called a photon.
Total amount of energy emitted or absorbed by a body is some whole number multiple of
quantum,
E = nh , where n is an integer such as 1,2,3 . . . . .
This means that a body can emit or absorb energy equal to hv, 2hv, 3hv . . . . . Or any other
integral multiple of h. This is called quantization of energy.
Photoelectric Effect:
When radiations with certain minimum frequency (ν0 ) strike the surface of a metal, the
electrons are ejected from the surface of the metal. It is called photoelectric effect,
electrons emitted are called photoelectron.
For each metal a certain minimum frequency is needed to eject the electrons called as
K.E. constant
o
It was explained by Einstein. When light of suitable frequency falls on a metal surface, the
light photon gives its energy to the electron of metal atom and the electron is ejected from
metal surface by absorbing this energy. The minimum energy of a photon required to
eject an electron from a metal is called work function () of the metal. The remaining part
of the energy (h - ) of photon is used to increase the kinetic energy of the ejected
electron. If o is the threshold frequency and , the frequency of incident light then
Work function, = h o .
According to Einstein, E = h
ATOMIC SPECTRA
Spectrum is the impression produced on a screen when radiations of a particular
wavelengths are analyzed through a prism or diffraction grating. Spectra are broadly
classified into two types.
1. Emission Spectrum: When the radiation emitted from some source, e.g., from the sun or
by-passing electric discharge through a gas at low pressure or by heating some substance to
high temperature etc. is passed directly through the prism and then received on the
photographic plate, the spectrum obtained is called ‘Emission spectrum’.
Spectrum of radiation emitted by a substance in its excited state is an emission spectrum.
Emission Spectrum is of two types:
a. Continuous Spectrum: When white light from any source such as sun, a bulb or any hot
glowing body is analyzed by passing through a prism, it is observed that it splits up into
seven different colors from violet to red, (like rainbow), as shown in fig.
These colors are so continuous that each of them merges into the next. Hence, the spectrum
is called continuous spectrum.
It may be noted that on passing through the prism, red colour with the longest wavelength is
dedicated least while violet colour with shortest wavelength is deviated the most.
1. The line spectrum has sharp, distinct well- 1. The band spectrum has many closed lines.
defined lines.
2. The line spectrum is the characteristic of 2. The band spectrum is characteristic of
atoms and is also called atomic spectrum. molecules and is also called molecular
spectrum.
3. The line spectrum is due to transition of 3. The band spectrum is due to vibrations and
electrons in an atom. rotations of atoms in a molecule
4. The line spectrum is given by inert gases, 4. The band spectrum is given by hot metals
metal vapors and atomized nonmetals. and molecular nonmetals.
2. Absorption spectra: When white light from any source is first passed through the solution
or vapours of a chemical substance and then analyzed by the spectroscope, it is observed that
some dark lines are obtained. Further, it is observed that the dark lines are at the same place
where coloured lines are obtained in the emission spectra for the same substance.
Wave numbers of all the lines in all the series can be calculated by the Rydberg equation.
1 1 1
ν̅ = = RZ2 ( 2 − 2 )
λ n1 n2
For one electron species like He+, Li2+ and Be3+, the value of R is 109677 cm–1× Z2, where Z
is the atomic number of the species.
ELECTRONIC TRANSITIONS
n1=2, n2=3,4,5,6----
υ
n=2 Near
Balmer series Visible region
Infra-red region
n1=1, n2=2,3,4,5----
n=1 Lyman series U.V region
To overcome the objections of Rutherford model and to explain the hydrogen spectrum,
Bohr proposed a quantum mechanical model.
• The centrifugal force of the revolving electron in a stationary orbit is balanced by the
electrostatic attraction between the electron and the nucleus.
• Electron can revolve only in orbits whose angular momentum are an integral multiple of the
factor h/2 π.
nh
mvr = 2π
Where m = mass of electron,
v = velocity of electron,
r = radius of the orbit and
‘n’ is the integral number like, 1, 2, 3, 4 . . . , is called principal quantum number and h =
Planck’s constant
• The energy of an electron changes only when it moves from one orbit to another. Outer
orbits have higher energies while inner orbits have lower energies.
The energy is absorbed when an electron moves from inner orbit to outer orbit. The
energy is emitted when the electron jumps from outer orbit to inner orbit.
• The energy emitted or absorbed in a transition is equal to the difference between the
energies of the two orbits (E2 – E1). Energy emitted or absorbed is in the form of quanta.
E=E2 – E1 = hv
Here E1 and E2 are the lower and higher allowed energy states.
Consider an electron of mass ‘m’ and charge ‘e–’ revolving round the nucleus of charge ‘Ze’ in a
circular orbit of radius ‘r’.
Let ‘v’ be the tangential velocity of the electron. As per coulomb’s law, the electrostatic
force of attraction between the moving electron andthenucleus is –Ze2/r.
For the atom to be stable an equal centrifugal force must act away
from the nucleus. This centrifugal force is equal to –mv2/r, where
‘m’ is the mass of electron and ‘r’ is the radius of the orbit.
In a stationary orbit
–Ze2 −mv2 Ze2
= or = mv2
r2 r r
𝑛ℎ
As per Bohr’s quantum condition, mvr = 2𝜋
nh 𝑛2 ℎ 2
∴v= 2πmror v2= 4𝜋2𝑚2 𝑟 2
The radius of the first orbit of hydrogen is 0.529 A0 or 0.0529 nm or 52.9 pm. This value
is known as Bohr’s radius. As the value of n increases, the radius of the orbit will increase.
n2 h2
In S.I units, rn = 4π2mKZe2
1
Where,K = 4π∈ (ϵ0 = permitivity of air = 8.854 × 10−12 Farad Metre)
0
Ze2 Ze2
K.E = 2mv2 =
1
∵ mv 2 =
2r 2r
−Ze2
P.E of electron = 𝑟
−313.6×𝑍 2
or En = k cal mol–1
𝑛2
−1312×Z2 –1
or En = kJ mol
n2
−2.18×10−11 𝑍 2
or En = erg per atom
𝑛2
−2.18×10−18 𝑍 2
orEn = j/atom
𝑛2
2π2 mK2 Z2 e4
In S.I units: En = − n 2 h2
–1
WhereK = 4𝜋𝜖 and 𝜀𝑜 beingpermittivity of air and is equal to 8.854 × 10–12 Farad metre
1
0
If the numbers of the higher and lower energy states are n2 and n1 respectively, En2 =
−2π2 mZe4 1
. n2
h2 2
−2π2 mZe4 1
En1 = . n2
h2 1
−2π2 mZe4 1 1
En2 − E n1 = [n2 − n2 ]
h2 1 2
En2 − En1
But En2 − En1 = hcν̅ and ν̅ = ch
1 −2π2 mZe4 1 1
ν̅ = λ = [n2 − n2 ]
ch2 1 2
1 1 1
This equation is similar to Rydberg equation. [ν̅ = λ = R × (n2 − n2)]
1 2
2π2 mZ e4
Rydberg constant R should be equal to R = ch3
Substituting the values, we get RH= 1,09,681cm-1.This value is almost equal to Rydberg’s
constant 1,09,677 cm–1.
The frequencies of the spectral lines in the hydrogen spectrum calculated by using Bohr’s
equation are in excellent agreement with the experimental values. This is a concrete
proof of the validity of Bohr’s theory of hydrogen atom.
2πZe2
v= cms −1
n
• Pfund series are obtained in far infrared region when electron returns to the fifth energy
level from higher energy levels 6, 7…….
The maximum number of lines produced when electrons jumps from nth level to ground level
𝑛(𝑛−1)
is equal to, Or ∑(𝑛2 − 𝑛1 )
2
3. This theory not only explains hydrogen spectrum but also explains the spectra of one
2+ 3+
electron species such as He+, Li and Be etc.
4. The experimentally determined frequencies of spectral lines are in close agreement with
those calculated by Bohr’s theory.
5. The value of Rydberg constant for hydrogen calculated from Bohr’s equation tallies with
the value determined experimentally.
ii) The nucleus is one of the foci for all these orbits.
iii) The angular momentum of electron in closed elliptical
paths is also quantized i.e. k (h/2), where k is another integer except zero.
n length of major axis
iv) The ratio = length of suggests for the possible number of subshells in a shell.
k min or axis
Possible values of k for n = 4 are 1, 2, 3, 4 respectively. For any given value of n, k cannot be
zero as in that case, the ellipse would degenerate into a straight line passing through the
nucleus. When n = k, path becomes circular.
hc
Einstein’s generalization of Planck’s theory is given as, E = hν = λ
2
Einstein’s mass energy relationship is E = mc
hc 2 h h
Equating above two equations, we get, = mc or = mc or λ = mc
λ λ
h
Where ‘c’ is the velocity of light. If the velocity of micro particle is ‘v’ then, λ = mV
This is de Broglie’s equation,
Where ‘λ’ is the de Broglie’s wave length, ‘m’ is the mass of the moving particle and ‘h’ is
Planck’s constant.
h
P = mv or λ = P
Here 𝜆 signifies wave nature and P signifies particle nature.
It is applicable to microparticles like electron, proton, etc., and not applicable for macro-
bodies like cricket ball, bullet etc.
The electron moving with high speed possesses both the particle nature and the wave nature.
The waves associated with material particles are known as matter waves or particle waves.
“It is impossible to determine simultaneously and accurately the exact position and
momentum or velocity of a sub-atomic particle like electron in an atom”.
One can determine the position of a particle very accurately, and then the determination of
its velocity becomes less accurate. Similarly, one can determine the velocity of a particle
very accurately, and then the determination of its position becomes less accurate. The
certainty in one factor introduces the uncertainty in another factor.
If the uncertainty in the determination of the position of a small particle is given by Δx and
uncertainty in its momentum is Δp, then
ℎ
(Δx) (Δp) ≥ 𝑛𝜋, Where n = 1,2,3,4.........
For an electron revolving around the nucleus in an atom the value of n is nearly 4.
Thus Heisenberg’s principle can also be stated as the product of uncertainty in position and
momentum of an electron like micro particle moving with high speed cannot be less than h/4.
ℎ
Heisenberg’s equation can also be written as, (Δx) (Δv) ≥ 4𝜋𝑚
If the position of the particle is known exactly (Δx = 0), Δv becomes infinity (∞) and vice
versa. Heisenberg's uncertainty principle is not applicable to those objects which cannot
change their position by themselves when a light falls on them. It is applicable for micro
particles like electrons.
Thus, the product of Δx and Δ𝜐 is extremely small. For particles of mass greater than 1 mg,
the product will still smaller. Hence, these values are negligible.
For a microscopic particle like an electron, we have
ℎ 6.625×10−34 𝑘𝑔𝑚2 𝑠−1
Δx.Δ𝜐 = 4𝜋𝑚 = 4×3.1416×(9×10−31 𝑘𝑔) ≈ 10−4 𝑚2 𝑠 −1
Classical mechanics, based on Newton’s laws of motion, was successful in explaining the
motion of macroscopic bodies like falling stones or motion of planets around the sun etc. But
it failed when applied to microscopic particles like electrons, atoms, molecules etc. Hence,
new branch introduced called as ‘Quantum mechanics.
The intensity of light is proportional to the square of amplitude (ψ2). Just as 𝛙2 indicates
the density of photons in space, 𝛙2 in case of electron wave denotes the probability of
finding an electron in the space or probability of finding the electron is also maximum.
QUANTUM NUMBERS
The behavior of an electron in an atom is described mathematically by a wave function or
orbital. They are principal quantum number, azimuthal quantum number, magnetic quantum
number and spin quantum number.
‘Set of numbers used to describe energy, size, shape of orbitals in an atom’ called as
quantum numbers.
1.Principal quantum number(n):
• ‘n’ can be any whole number value such as 1,2,3,4, etc. The energy shells corresponding to
these numbers are K, L, M, N, etc.
• Principal Quantum no. indicates the main energy level to which the electron belongs. It also
indicates the average distance of an electron from nucleus and also the speed of the
atomic electron.
• As the ‘n’ value increases the distance of electron from the nucleus increases and its energy
also increases.
• The maximum no. of electrons that can be present in an orbit is given by 2𝑛2 . The maximum
no. of electron in K, L, M, and N shells are 2,8,18 and 32 respectively.
0.529×𝑛2
• The radius of the orbit is given by the expression: rn = Ao.
𝑍
• The energy of the electron/orbit is given by the expression.
−13.6×𝑍 2
En= cm/sec
𝑛
2.18×108 ×𝑍
• The velocity of the electron is given by the expression. Vn= cm /sec.
𝑛
2 0 (2s), 1 (2p)
Atomic Orbital:
The three-dimensional space around the nucleus where the probability of finding the
electron is maximum is called an atomic orbital.
Node- The three-dimensional space around the nucleus where the probability of
finding the electron is minimum or zero.
Types of Nodes:
Nodes are of two types: a) Radial Node b) Angular Node
A radial node is the spherical region around then nucleus, where the probability if finding
the electron is zero (Ψ2 = 0).
Shapes of Orbitals:
• s –Orbitals: s- Orbital can accommodate electrons with l = 0 and these orbitals are
present in every orbit starting from 1st orbit.
• p – Orbitals:
p- Sublevel begins from 2nd orbit. For p -
sublevel l = 1, indicates that each p - sub
level contains three orbitals with ‘m’
values –1, 0, +1. These are designated as
px, py and pz, depending on the axis in
which electron density is present.
In px-orbital, electron density is concentrated along the x-axis.
p-Orbitals have dumb-bell shape. Each p -orbital has two lobes separated by one nodal plane.
The probability density function is zero on the plane where the two lobes touch each other.
The nodal planes for px, py and pz - orbitals are YZ, ZX and XY - planes respectively.
The three orbitals present in a given p - sublevel will have same shape, size and energy but
different orientations (differ in m value). These three orbitals are perpendicular to each
other and the angle between any two p - orbitals is 90o.
• d - Orbitals:begins from 3rd orbit (n = 3). For d- sub level l= 2, indicates that each d -
sublevel contains five orbitals with ‘m’ values –2, –1, 0, +1, +2. These are designated as
dxy,dyz,dzx, 𝑑𝑥 2 −𝑦 2 and d𝑧 2 .
All the d-orbitals (except d𝑧 2 ) have double dumb-bell shape. Each d-orbital has four lobes
separated by two nodal planes.
In case of dxy, dyz and dzxorbitals, lobes are present in between the corresponding axes.
i.e., between x and y axis in case of dxy orbital. Where as in d𝑥 2−𝑦 2 and d𝑧 2 orbitals lobes are
present along the axes. dxy Orbital contains yz and zx as nodal planes. dyz and dzx contain
(xy, zx) and (xy, yz) planes respectively. d𝑥 2−𝑦 2 orbital contains two nodal planes perpendicular
to each other and which make an angle of 45o with respect to x and y axes. 𝑑𝑧 2 orbital does
not contain nodal planes.
5d orbitals present in a given d- sublevel will have same energy in the ground state.
ENERGY OF ORBITALS
The energy of an electron in a hydrogen atom is determined only by the principal quantum
number. Within a shell, all hydrogen orbitals have the same energy, independent of the other
quantum numbers.
1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p = 4d = 4f
Although the shapes of 2s and 2p orbitals are different, an electron has the same energy
when it is in 2s orbital or 2p orbital. The energy of an electron in a multielectron atom
depends, not only on its principal quantum number, but also on its azimuthal quantum number.
The s, p, d and f orbitals within a given shell have slightly different energies in a multi
electron atom.
The (n + l) value of 3d = 3 + 2 = 5
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s and so on.
The sequence in which the electrons occupy various orbitals can be easily remembered with
the help of Moeller’s diagram as shown in above Fig
• Pauli’s Exclusion principle:stated as “No two electrons in an atom can have the same
set of values for all the four quantum numbers”. This means that two electrons in an
orbital may have the same n, same l and same m but differ in spin quantum number. In an
orbital if one electron has clockwise spin, the other has anticlockwise spin. It follows that
an orbital can hold a maximum of two electrons with opposite spins.
Exp- helium atom has two electrons in its 1s orbital. Quantum numbers for first electron are
n =1, l = 0, m = 0 and s = +1/2. Quantum numbers for second electron are:
The two electrons have the same value for n, same value for l and same value for m but
differ in s.
Thus in s, p, d and f subshells, pairing starts from 2nd, 4th, 6th and 8th electrons respectively.
The electrons in 2p subshell are occupied sing ally. i.e., 1s2 2s2 2𝑝𝑥1 2𝑝𝑦1 2𝑝𝑧1
22 Ti 1s2 2s2 2p6 3s2 3p6 3d2 4s2 [Ar] 3d2 4s2
23 V 1s2 2s2 2p6 3s2 3p6 3d3 4s2 [Ar] 3d3 4s2
24 Cr 1s2 2s2 2p6 3s2 3p6 3d5 4s1 [Ar] 3d5 4s1
25 Mn 1s2 2s2 2p6 3s2 3p6 3d5 4s2 [Ar] 3d5 4s2
26 Fe 1s2 2s2 2p6 3s2 3p6 3d6 4s2 [Ar] 3d6 4s2
27 Co 1s2 2s2 2p6 3s2 3p6 3d7 4s2 [Ar] 3d7 4s2
28 Ni 1s2 2s2 2p6 3s2 3p6 3d8 4s2 [Ar] 3d8 4s2
29 Cu 1s2 2s2 2p6 3s2 3p6 3d10 4s1 [Ar] 3d10 4s1
30 Zn 1s2 2s2 2p6 3s2 3p6 3d10 4s2 [Ar] 3d10 4s2
Stability of atoms
Extra stability is associated with atoms in which degenerate orbitals are either half-filled
or completely filled due to
(1) Symmetrical distribution of electrons
(2) Exchange energy. Greater the exchange energy greater is the stability.
The presence of half-filled and completely filled degenerate orbitals gives greater
stability to atoms.
1
It is for this reason the electronic configurations of Cr and Cu are represented as [Ar] 4s
5 1 10
3d and [Ar] 4s 3d respectively.
NCERT SOLUTIONS
Q. 1.
(i) Calculate the number of electrons which will together weigh one gram.
(ii) Calculate the mass and charge of one mole of electrons.
Ans. (i) Mass of one electron = 9.10939 × 10 –31 kg
Number of electrons that weigh 9.10939 × 10 –31 kg = 1
1
Number of electrons that will weigh 1 g = (1 × 10 –3 kg) = 9.10939×10−31 𝑘𝑔 × (1 × 10−3 𝑘𝑔)
= 0.1098 × 10 –3 + 31 = 0.1098 × 10 28 = 1.098 × 10 27
(ii) Mass of one electron = 9.10939 × 10 –31 kg
Mass of one mole of electron = (6.022 × 10 23) × (9.10939 ×10 –31 kg) = 5.48 × 10 –7 kg
Charge on one electron = 1.6022 × 10 –19 coulomb
Charge on one mole of electron = (1.6022 × 10 –19 C) (6.022 × 1023) = 9.65 × 10 4 C
Q. 2.
(i) Calculate the total number of electrons present in one mole of methane.
(ii) Find (a) the total number and (b) the total mass of neutrons in 7 mg of 14C. (Assume that mass of
a neutron = 1.675 × 10 –27 kg).
(iii) Find (a) the total number and (b) the total mass of protons in 34 mg of NH 3 at STP.
Will the answer change if the temperature and pressure are changed?
Ans.
(i) Number of electrons present in 1 molecule of methane (CH4)
{1(6) + 4(1)} = 10
Number of electrons present in 1 mole i.e., 6.023 × 10 23 molecules of methane
= 6.022 × 10 23 × 10 = 6.022 × 10 24
(ii) (a) Number of atoms of 14C in 1 mole= 6.023 × 1023
Since 1 atom of 14C contains (14 – 6) i.e., 8 neutrons, the number of neutrons in 14 g of 14C is (6.023 ×
1023) ×8.
Or, 14 g of 14C contains (6.022 × 10 23 × 8) neutrons.
6.023 × 1023 × 8 × 7mg
Number of neutrons in 7 mg: = = 2.4092 × 10 21
1400mg
(b) Mass of one neutron = 1.67493 × 10 –27 kg
Mass of total neutrons in 7 g of 14C
= (2.4092 × 10 21) (1.67493 × 10 –27 kg)
= 4.0352 × 10 –6 kg
(iii) (a) 1 mole of NH3 = {1(14) + 3(1)} g of NH 3
= 17 g of NH3
= 6.022× 10 23 molecules of NH 3
Total number of protons present in 1 molecule of NH 3
= {1(7) + 3(1)} = 10
Number of protons in 6.023 × 10 23 molecules of NH 3
= (6.023 × 10 23) (10)
= 6.023 × 10 24
⇒ 17 g of NH3 contains (6.023 × 10 24) protons.
6.022 × 1024 × 34mg
Number of protons in 34 mg of NH 3 = = 1.2046 × 1022
17000mg
(b) Mass of one proton = 1.67493 × 10 –27 kg
Total mass of protons in 34 mg of NH 3
Thus, frequency of yellow light emitted from the sodium lamp = 5.17 × 10 14 s–1
Q.7. Calculate the wavelength,frequency & wave number of a light wave whose period is 2.0×10 –10s.
1
Ans. Frequency (ν) of light =
𝑝𝑒𝑟𝑖𝑜𝑑
𝑐
Wavelength (λ) of light =
𝑣
Where, c = velocity of light in vacuum = 3×10 8 m/s
Substituting the value in the given expression of λ:
Q.8. What is the number of photons of light with a wavelength of 4000 pm that p rovide 1 J of
energy?
Ans. Energy (E) of a photon = hν
Energy (En) of ‘n’ photons = nhν
Where,
λ = wavelength of light = 4000 pm = 4000 ×10 –12 m
c = velocity of light in vacuum = 3 × 10 8 m/s
h = Planck’s constant = 6.626 × 10 –34 Js
Substituting the values in the given expression of n:
Hence, the number of photons with a wavelength of 4000 pm and energy of 1 J are 2.012 × 10 16.
Q.9. A photon of wavelength 4 × 10 –7 m strikes on metal surface, the work function of the metal
being 2.13 eV. Calculate
(i) the energy of the photon (eV),
(ii) the kinetic energy of the emission, and
(iii) the velocity of the photo electron (1 eV= 1.6020 × 10 –19 J).
Ans.
(i) Energy (E) of a photon = hν = hc/λ
Where,
h = Planck’s constant = 6.626 × 10 –34 Js
c = velocity of light in vacuum = 3 × 10 8 m/s
λ = wavelength of photon = 4 × 10 –7 m
Substituting the values in the given expression of E:
Where, is the kinetic energy of emission in Joules and ‘m’ is the mass of the photoelectron.
Substituting the values in the given expression of v:
v = 5.84 × 10 5 ms–1
Hence, the velocity of the photoelectron is 5.84 × 10 5 ms–1.
Q.10. Electromagnetic radiation of wavelength 242 nm is just sufficient to
ionise the sodium atom. Calculate the ionisation energy of sodium in kJ mol –1.
𝑁𝐴 ℎ𝑐
Ans. Energy of sodium (E)=
𝜆
= 4.947 × 10 5 J mol–1
= 494.7 × 10 3 J mol–1 = 494 kJ mol –1
Q.11. A 25watt bulb emits monochromatic yellow light of wavelength of 0.57μm. Calculate the rate
of emission of quanta per second.
Ans. Power of bulb, P = 25 Watt = 25 Js –1
Energy of one photon, E = hν = hc/λ
Substituting the values in the given expression of E:
E = 34.87 × 10 –20 J
Rate of emission of quanta per second
Q.12. Electrons are emitted with zero velocity from a metal surface when it is exposed to radiation
of wavelength 6800 Å. Calculate threshold frequency (𝒗𝟎 ) and work function (W0) of the metal.
Ans. Threshold wavelength of radian = 6800 × 10 –10 m
Threshold frequency(𝒗𝟎 )of the metal
= 4.41 × 10 14 s–1
Thus, the threshold frequency of the metal is 4.41 × 1014 s–1.
Hence, work function (W0) of the metal = hν0
= (6.626 × 10 –34 Js) (4.41 × 1014 s–1)
= 2.922 × 10 –19 J
Q.13. What is the wavelength of light emitted when the electron in a hydrogen atom undergoes
transition from an energy level with n = 4 to an energy level with n = 2?
Ans. The ni = 4 to nf = 2 transition will give rise to a spectral line of the Balmer series. The energy
involved in the transition is given by the relation,
E = – (4.0875 × 10–19 J)
The negative sign indicates the energy of emission.
Q.14. How much energy is required to ionise a H atom if the electron occupies n = 5 orbit? Compare
your answer with the ionization enthalpy of H atom (energy required to remove the electron from n
= 1 orbit).
Ans. The expression of energy is given by,
Where,
Z = atomic number of the atom
n = principal quantum number
For ionization from n1 = 5 to ,
Hence, less energy is required to ionize an electron in the 5 th orbital of hydrogen atom as compared
to that in the ground state.
Q.15. What is the maximum number of emission lines when the excited electron of an H atom in n =
6 drops to the ground state?
Ans. When the excited electron of an H atom in n = 6 drops to the ground state, the following
transitions are possible:
E5 = –8.72 × 10 –20 J
(ii) Radius of Bohr’s nth orbit for hydrogen atom is given by,
rn = (0.0529 nm) n2
For, n = 5
r5 = (0.0529 nm) (5) 2
r5 = 1.3225 nm
Q.17. Calculate the wave number for the longest wavelength transition in the Balmer series of
atomic hydrogen.
Ans. For the Balmer series, ni = 2. Thus, the expression of wave number is given by,
Wave number is inversely proportional to wavelength of transition. Hence, for the longest
wavelength transition, has to be the smallest.
For to be minimum, nf should be minimum. For the Balmer series, a transition from ni = 2 to nf = 3 is
allowed. Hence, taking nf = 3, we get:
Q.18. What is the energy in joules, required to shift the electron of the hydrogen atom from the
first Bohr orbit to the fifth Bohr orbit and what is the wavelength of the light emitted when the
electron returns to the ground state? The ground state electron energy is –2.18 × 10 –11 ergs.
Ans. Energy (E) of the nth Bohr orbit of an atom is given by,
Where,
Z = atomic number of the atom
Ground state energy = – 2.18 × 10 –11 ergs
= –2.18 × 10 –11 × 10–7 J
= – 2.18 × 10 –18 J
Energy required to shift the electron from n = 1 to n = 5 is given as: ΔE = E5 – E1
Q.19. The electron energy in hydrogen atom is given by E n = (–2.18 × 10 –18)/n2 J. Calculate the
energy required to remove an electron completely from the n = 2 orbit. What is the longest
ΔE = 0.545 × 10 –18 J
= 5.45 × 10 –19 J
= 3647 × 10 –10 m
= 3647 Å
Q.20. Calculate the wavelength of an electron moving with a velocity of 2.05 × 10 7 ms–1.
Ans. According to de Broglie’s equation,
Where,
λ = wavelength of moving particle
m = mass of particle
v = velocity of particle
h = Planck’s constant
Substituting the values in the expression of λ:
Q.21. The mass of an electron is 9.1 × 10 –31 kg. If its K.E. is 3.0 × 10 –25 J, calculate its wavelength.
Ans. From De Broglie’s equation,
λ = h/mv
Given,
Kinetic energy (K.E) of the electron = 3.0 × 10 –25 J
Q.22. Which of the following are isoelectronic species i.e., those having the same number of
electrons?
Na+ , K+ , Mg2+ , Ca2+ , S2–, Ar
Ans. Isoelectronic species have the same number of electrons.
Number of electrons in sodium (Na +) = 11
Number of electrons in (Na + ) = 10
A positive charge denotes the loss of an electron.
Similarly,
Number of electrons in K + = 18
Number of electrons in Mg 2+ = 10
Number of electrons in Ca 2+ = 18
A negative charge denotes the gain of an electron by a species.
Number of electrons in sulphur (S) = 16
∴ Number of electrons in S 2- = 18
Number of electrons in argon (Ar) = 18
Hence, the following are isoelectronic species:
1) Na+ and Mg2+ (10 electrons each)
2) K+ , Ca2+ , S2– and Ar (18 electrons each)
Q.23
(i) Write the electronic configurations of the following ions:
(a) H–
(b) Na+
(c) O2–
(d) F–
(ii) What are the atomic numbers of elements whose outermost electrons are represented by:
(a) 3s1
(b) 2p3
(c) 3p5?
(iii) Which atoms are indicated by the following configurations?
(a) [He] 2s1
(a) n = 0, l = 0, ml = 0,
(b) n = 1, l = 0, ml = 0,
(c) n = 1, l = 1, ml = 0,
(d) n = 2, l = 1, ml = 0,
(e) n = 3, l = 3, ml = – 3,
(f) n = 3, l = 1, ml = 0,
Ans:-
(a) The given set of quantum numbers is not possible because the value of the principal quantum
number (n) cannot be zero.
(b) The given set of quantum numbers is possible.
(c) The given set of quantum numbers is not possible.
For a given value of n, ‘l’ can have values from zero to (n – 1).
For n = 1, l = 0 and not 1.
(d) The given set of quantum numbers is possible.
(e) The given set of quantum numbers is not possible.
For n = 3,
l = 0 to (3 – 1)
l = 0 to 2 i.e., 0, 1, 2
(f) The given set of quantum numbers is possible.
Q.31: How many electrons in an atom may have the following quantum numbers?
(a) n = 4,
(b) n = 3, l = 0
Ans:-
(a) Total number of electrons in an atom for a value of n = 2n2
∴ For n = 4,
Total number of electrons = 2 (4) 2 = 32
The given element has a fully filled orbital as
1s2 2s2 2p6 3s2 3p6 4s2 3d10.
Hence, all the electrons are paired.
Where, n = 1, 2, 3, …
According to de Broglie’s equation:
Since ‘2πr’ represents the circumference of the Bohr orbit (r), it is proved by equation (3) that the
circumference of the Bohr orbit of the hydrogen atom is an integral multiple of de Broglie’s
wavelength associated with the electron revolving around the orbit.
Q.33: What transition in the hydrogen spectrum would have the same wavelength as the Balmer
transition n = 4 to n = 2 of He spectrum?
Ans:- For He+ ion, the wave number associated with the Balmer transition, n = 4 to n = 2 is given by:
Where,
n1 = 2, n2 = 4
According to the question, the desired transition for hydrogen will have the same wavelength as that
of He+ .
By hit and trail method, the equality given by equation (1) is true only when n1 = 1and n2 = 2.
∴ The transition for n2 = 2 to n = 1 in hydrogen spectrum would have the same wavelength as Balmer
transition n = 4 to n = 2 of He + spectrum.
Q.34: Calculate the energy required for the process He+(g)→ He+(g) + e- The ionization energy for
the H atom in the ground state is 2.18 ×10 –18 J atom–1
Ans:- Energy associated with hydrogen-like species is given by,
Q.36: 2 × 10 8 atoms of carbon are arranged side by side. Calculate the radius of carbon atom if the
length of this arrangement is 2.4 cm.
Ans:- Length of the given arrangement = 2.4 cm
Number of carbon atoms present = 2 × 10 8
∴ Diameter of carbon atom
Q.37: The diameter of zinc atom is .Calculate (a) radius of zinc atom in pm and (b) number of
atoms present in a length of 1.6 cm if the zinc atoms are arranged side by side lengthwise.
Ans:- (a) Radius of zinc atom = diameter/2
Q.38: A certain particle carries 2.5 × 10 –16C of static electric charge. Calculate the number of
electrons present in it.
Ans:- Charge on one electron = 1.6022 × 10–19 C
⇒ 1.6022 × 10 –19C charge is carried by 1 electron.
∴ Number of electrons carrying a charge of 2.5 × 10 –16 C
Q.39: In Milikan’s experiment, static electric charge on the oil drops has been obtained by shining
X-rays. If the static electric charge on the oil drop is –1.282 × 10 –18C, calculate the number of
electrons present on it.
Ans:- Charge on the oil drop = 1.282 ×10 –18C
Charge on one electron = 1.6022 × 10–19C
∴Number of electrons present on the oil drop
Q.40: In Rutherford’s experiment, generally the thin foil of heavy atoms, like gold, platinum etc.
have been used to be bombarded by the α-particles. If the thin foil of light atoms like aluminium
etc. is used, what difference would be observed from the above results?
Ans:- A thin foil of lighter atoms will not give the same results as given with the foil of heavier atoms.
Lighter atoms would be able to carry very little positive charge. Hence, they will not cause enough
deflection of α-particles (positively charged).
Q.41: Symbols 𝟕𝟗 79 𝟑𝟓 35
𝟑𝟓𝑩𝒓 and Br can be written, whereas symbols 𝟕𝟗𝑩𝒓 and Br are not acceptable.
Answer briefly.
Ans:- The general convention of representing an element along with its atomic mass (A) and atomic
number (Z) is
Hence, is acceptable but is not acceptable.
can be written but cannot be written because the atomic number of an element is constant,
but the atomic mass of an element depends upon the relative abundance of its isotopes. Hence, it is
necessary to mention the atomic mass of an element
Q.42: An element with mass number 81 contains 31.7% more neutrons as compared to protons.
Assign the atomic symbol.
Ans:- Let the number of protons in the element be x.
∴ Number of neutrons in the element
= x + 31.7% of x
= x + 0.317 x
= 1.317 x
According to the question,
Mass number of the element = 81
∴ (Number of protons number of neutrons) = 81
Q.43: An ion with mass number 37 possesses one unit of negative charge. If the ion contains 11.1%
more neutrons than the electrons, find the symbol of the ion.
Ans:- Let the number of electrons in the ion carrying a negative charge be x.
Then, Number of neutrons present = x + 11.1% of x
= x + 0.111 x
= 1.111 x
Number of electrons in the neutral atom = (x – 1)
(When an ion carries a negative charge, it carries an extra electron)
∴ Number of protons in the neutral atom = x – 1
Given, Mass number of the ion = 37
∴ (x – 1) + 1.111x = 37
2.111x = 38
x = 18
∴The symbol of the ion is
Q.44: An ion with mass number 56 contains 3 units of positive charge and 30.4% more neutrons
than electrons. Assign the symbol to this ion.
Ans:- Let the number of electrons present in ion
∴ Number of neutrons in it = x + 30.4% of x = 1.304 x
Since the ion is tri-positive,
⇒ Number of electrons in neutral atom = x + 3
∴ Number of protons in neutral atom = x + 3
Given, Mass number of the ion = 56
∴ Number of protons = x + 3 = 23 + 3 = 26
∴ The symbol of the ion
Q.45: Arrange the following type of radiations in increasing order of frequency:
(a) radiation from microwave oven
(b) amber light from traffic signal
(c) radiation from FM radio
(d) cosmic rays from outer space and
(e) X-rays.
Ans:- The increasing order of frequency is as follows:
Radiation from FM radio < amber light < radiation from microwave oven < X- rays < cosmic rays
The increasing order of wavelength is as follows:
Cosmic rays < X-rays < radiation from microwave ovens < amber light < radiation of FM radio
Q.46: Nitrogen laser produces a radiation at a wavelength of 337.1 nm. If the number of photons
emitted is 5.6 × 10 24, calculate the power of this laser.
Ans:- Power of laser = Energy with which it emits photons
Power
Where,
N = number of photons emitted
h = Planck’s constant
c = velocity of radiation
λ = wavelength of radiation
Substituting the values in the given expression of Energy (E):
E = 0.3302 × 107 J
= 3.33 × 106 J
Hence, the power of the laser is 3.33 × 10 6 J.
Q.47: Neon gas is generally used in the sign boards. If it emits strongly at 616 nm, calculate
(a) the frequency of emission,
(b) distance traveled by this radiation in 30 s
(c) energy of quantum and
(d) number of quanta present if it produces 2 J of energy.
Ans:- Wavelength of radiation emitted = 616 nm
= 616 × 10 –9 m (Given)
(a) Frequency of emission
Where,
c = velocity of radiation
λ = wavelength of radiation
Substituting the values in the given expression of :
= 6.19 ×10 18
= 6.2 ×1018
Q.48: In astronomical observations, signals observed from the distant stars are generally weak. If
the photon detector receives a total of 3.15 × 10 –18 J from the radiations of 600 nm, calculate the
number of photons received by the detector.
Ans:- From the expression of energy of one photon (E),
E = hc / λ
Where,
λ = wavelength of radiation
h = Planck’s constant
c = velocity of radiation
Substituting the values in the given expression of E:
E
E = 3.313 × 10 –19 J
Energy of one photon = 3.313 × 10 –19 J
Number of photons received with 3.15 × 10 –18 J energy
= 9.5 ≈ 10
Q.49: Lifetimes of the molecules in the excited states are often measured by using pulsed radiation
source of duration nearly in the nano second range. If the radiation source has the duration of 2 ns
and the number of photons emitted during the pulse source is 2.5 × 10 15, calculate the energy of the
source.
Ans:- Frequency of radiation (ν),
= 5.093 × 10 14 s–1
Similarly, for λ2 = 589.6 nm
Frequency of transition
=5.088 × 10 14 s–1
Energy difference (ΔE) between excited states = E1 – E2
Where,
E2 = energy associated with λ2
E1 = energy associated with λ1
ΔE = hν1 – hν2
= h(ν1 – ν2)
= (6.626 × 10 –34 Js) (5.093 × 10 14 – 5.088 × 1014)s–1
= (6.626 × 10 –34 J) (5.0 × 10 –3 × 1014)
ΔE = 3.31 × 10 –22 J.
Q.51: The work function for caesium atom is 1.9 eV. Calculate
(a) the threshold wavelength and
(b) the threshold frequency of the radiation. If the caesium element is irradiated with a wavelength
500 nm, calculate the kinetic energy and the velocity of the ejected photoelectron .
Ans:- It is given that the work function (W 0) for caesium atom is 1.9 eV.
Where,
λ0 = threshold wavelength
h = Planck’s constant
c = velocity of radiation
Substituting the values in the given expression of (λ0):
6.53 × 10 –7 m
Hence, the threshold wavelength is 653 nm.
(b) From the expression, , we get:
Vo = W0/h
Where, ν0 = threshold frequency
h = Planck’s constant
Substituting the values in the given expression of ν0:
(1 eV = 1.602 × 10 –19 J)
ν0 = 4.593 × 10 14 s–1
Hence, the threshold frequency of radiation (ν0) is 4.593 × 10 14 s–1.
(c) According to the question:
Wavelength used in irradiation (λ) = 500 nm
Kinetic energy = h (ν – ν0)
= 9.3149 × 10 –20 J
Kinetic energy of the ejected photoelectron = 9.3149 × 10 –20J
Since K.E
= 4.52 × 10 5 ms–1
Hence, the velocity of the ejected photoelectron (v) is 4.52 × 10 5 ms–1.
Q.52: Following results are observed when sodium metal is irradiated with different wavelengths.
Calculate (a) threshold wavelength and, (b) Planck’s constant.
Ans:- (a) Assuming the threshold wavelength to be , the kinetic energy of the
radiation is given as:
Similarly,
Q.53 The ejection of the photoelectron from the silver metal in the photoelectric effect experiment
can be stopped by applying the voltage of 0.35 V when the radiation 256.7 nm is used. Calculate the
work function for silver metal.
Ans. From the principle of conservation of energy, the energy of an incident photon ( E) is equal to the
sum of the work function (W 0) of radiation and its kinetic energy (K.E) i.e.,
E = W0 K.E
⇒ W0 = E – K.E
Energy of incident photon (E)
Where,
c = velocity of radiation
h = Planck’s constant
λ = wavelength of radiation
Substituting the values in the given expression of E:
E = 4.83 eV
The potential applied to silver metal changes to kinetic energy (K.E) of the photoelectron. Hence,
K.E = 0.35 V
K.E= 0.35 eV
Work function, W 0 = E – K.E
= 4.83 eV – 0.35 eV
= 4.48 eV
Q.54 If the photon of the wavelength 150 pm strikes an atom and one of its inner bound electrons is
ejected out with a velocity of 1.5 × 10 7 ms–1, calculate the energy with which it is bound to the
nucleus.
Ans. Energy of incident photon (E) is given by,
E = hc / λ
Q.55 Emission transitions in the Paschen series end at orbit n = 3 and start from orbit n and can be
represented as v = 3.29 × 10 15 (Hz) [1/32 – 1/n2] . Calculate the value of n if the transition is
observed at 1285 nm. Find the region of the spectrum.
Ans. Wavelength of transition = 1285 nm
= 1285 × 10–9 m (Given)
(Given)
Since v = c/λ
n = 4.98 ≈ 5
Hence, for the transition to be observed at 1285 nm, n = 5.
The spectrum lies in the infra-red region.
Q.56 Calculate the wavelength for the emission transition if it starts from the orbit having radius
1.3225 nm & ends at 211.6 pm. Name the series to which this transition belongs & the region of the
spectrum.
Ans. The radius of the nth orbit of hydrogen-like particles is given by,
Thus, the transition is from the 5 th orbit to the 2 nd orbit. It belongs to the Balmer series.
Wave number for the transition is given by,
1.097 × 10 7 m–1
= 2.303 × 10 6 m–1
Wavelength (λ) associated with the emission transition is given by,
= 0.434 ×10 –6 m
λ = 434 nm
Q.57 Dual behaviour of matter proposed by de Broglie led to the discovery of electron microscope
often used for the highly magnified images of biological molecules & other type of material. If the
velocity of the electron in this microscope is 1.6×10 6 ms–1, calculate de Broglie wavelength
associated with this electron.
Ans. From de Broglie’s equation,
Where,
v = velocity of particle (neutron)
h = Planck’s constant
m = mass of particle (neutron)
λ = wavelength
Substituting the values in the expression of velocity (v),
= 4.94 × 10 2 ms–1
v = 494 ms–1
Velocity associated with the neutron = 494 ms –1
Q.59 If the velocity of the electron in Bohr’s first orbit is 2.19 × 10 6 ms–1, calculate the de Broglie
wavelength associated with it.
Ans. According to de Broglie’s equation,
Where,
λ = wavelength associated with the electron
h = Planck’s constant
m = mass of electron
v = velocity of electron
Substituting the values in the expression of λ:
λ = 332 pm
Wavelength associated with the electron = 332 pm
Q.60 The velocity associated with a proton moving in a potential difference of 1000 V is 4.37 ×
105 ms–1. If the hockey ball of mass 0.1 kg is moving with this velocity, calculate the wavelength
associated with this velocity.
Ans. According to De Broglie’s expression,
λ = h/mv
Substituting the values in the expression,
Q.61 If the position of the electron is measured within an accuracy of 0.002 nm, calculate the
uncertainty in the momentum of the electron. Suppose the momentum of the electron is h/4π m ×
0.05 nm, is there any problem in defining this value.
Ans. From Heisenberg’s uncertainty principle,
Where,
Δx = uncertainty in position of the electron
Δp = uncertainty in momentum of the electron
Substituting the values in the expression of Δp:
Actual momentum =
Hence, the six electrons i.e., 1, 2, 3, 4, 5, and 6 are present in the 4d, 3d, 4p, 3d, 3p, and 4p orbitals
respectively.
Therefore, the increasing order of energies is 5(3p) < 2(3d) = 4(3d) < 3(4p) = 6(4p) < 1 (4d).
Q.63 The bromine atom possesses 35 electrons.It contains 6 electrons in 2p orbital,6 electrons in
3p orbital & 5 electrons in 4p orbital. Which of these electron experiences the lowest effective
nuclear charge?
Ans. Nuclear charge experienced by an electron (present in a multi-electron atom) is dependant upon
the distance between the nucleus and the orbital, in which the electron is present. As the distance
increases, the effective nuclear charge also decreases.
Among p-orbitals, 4p orbitals are farthest from the nucleus of bromine atom with ( 35) charge. Hence,
the electrons in the 4p orbital will experience the lowest effective nuclear charge. These electrons are
shielded by electrons present in the 2p and 3p orbitals along with the s-orbitals. Therefore, they will
experience the lowest nuclear charge.
Q.64 Among the following pairs of orbitals which orbital will experience the larger effective nuclear
charge?
(i) 2s and 3s,
(ii) 4d and 4f,
(iii) 3d and 3p
Ans. Nuclear charge is defined as the net positive charge experienced by an electron in the orbital of
a multi-electron atom. The closer the orbital, the greater is the nuclear charge experienced by the
electron (s) in it.
(i) The electron(s) present in the 2s orbital will experience greater nuclear charge (being closer to the
nucleus) than the electron(s) in the 3s orbital.
(ii) 4d will experience greater nuclear charge than 4f since 4d is closer to the nucleus.
(iii) 3p will experience greater nuclear charge since it is closer to the nucleus than 3f.
Q.65 The unpaired electrons in Al and Si are present in 3p orbital. Which electrons will experience
more effective nuclear charge from the nucleus?
Ans. Nuclear charge is defined as the net positive charge experienced by an electron in a multi-electron
atom.The higher the atomic number,the higher is the nuclear charge. Silicon has 14 protons while
aluminium has 13 protons. Hence, silicon has a larger nuclear charge of ( 14) than aluminium, which has
a nuclear charge of ( 13) Thus, the electrons in the 3p orbital of silicon will experience a more effective
nuclear charge than aluminium.
Q.66 Indicate the number of unpaired electrons in:
(a) P,
(b) Si,
(c) Cr,
(d) Fe
(e) Kr.
Ans. (a) Phosphorus (P):
Atomic number = 15
The electronic configuration of P is:
1s2 2s2 2p6 3s2 3p3
The orbital picture of P can be represented as:
Since all orbitals are fully occupied, there are no unpaired electrons in krypton.
Q.67
(a) How many sub-shells are associated with n = 4?
(b) How many electrons will be present in the sub-shells having ms value of –1/2 for n = 4?
Ans. (a) n = 4 (Given)
For a given value of ‘n’, ‘l’ can have values from zero to (n – 1).
∴ l = 0, 1, 2, 3
Thus, four sub-shells are associated with n = 4, which are s, p, d and f.
(b) Number of orbitals in the nth shell = n2
For n = 4
Number of orbitals = 16
If each orbital is taken fully, then it will have 1 electron with ms value of - ½.
∴ Number of electrons with ms value of (- ½ ) is 16.
EXEMPLER PROBLEMS
Q1. Which of the following conclusions could not be derived from Rutherford’s α-
particle scattering experiment?
(a) Most of the space in the atom is empty.
(b) The radius of the atom is about 10 -10 m while that of nucleus is 10 -15
(c) Electrons move in a circular path of fixed energy called orbits.
(d) Electrons and the nucleus are held together by electrostatic forces of attraction.
Sol: (c) The concept of circular paths of fixed energy was proposed by Bohr and not derived
from Rutherford’s scattering experiment.
Q2. Which of the following options does not represent ground state electronic
configuration of an atom?
(i) 1s2 2s2 2p6 3s2 3p6 3d8 4s2
(ii) 1s2 2s2 2p6 3s2 3p6 3d9 4s2
(iii) 1s2 2s2 2p6 3s2 3p6 3d10 4s1
(iv) 1s2 2s2 2p6 3s2 3p6 3d5 4s1
Sol: (b) Correct configuration in ground state should be 1 s2 2s2 2p6 3s2 3pb3d104s1
Q3. The probability density plots of Is and 2s orbitals are given in the following
figures.
The density of dots in a region represents the probability density of finding electrons in
the region. On the basis of the above diagram, which of the following statements is
incorrect?
(a) 1s and 2s orbitals are spherical in shape.
(b) The probability of finding the electron is maximum near the nucleus.
(c) The probability of finding the electron at a given distance is equal in all directions.
(d) The probability density of electrons for 2s orbital decreases uniformly as distance
from the nucleus increases.
Sol: (d) The probability density of electrons for 2s orbital first increases then decreases
and after that it begins to increase again.
Q4. Which of the following statements is not correct about the characteristics of
cathode rays?
(a) They start from the cathode and move towards the anode.
(b) They travel in straight line in the absence of an external electrical or magnetic
field.
(c) Characteristics of cathode rays do not depend upon the material of electrodes in
Q6. Which of the following properties of atom could be explained correctly by Thomson
Model of atom?
(a) Overall neutrality of atom.
(b) Spectra of hydrogen atom.
(c) Position of electrons, protons and neutrons in atom.
(d) Stability of atom.
Sol: (a) According to Thomson model of atom, the mass of the atom is assumed to be
uniformly distributed over the atom. This model was able to explain the overall neutrality of
the atom.
Q10. Which of the following is responsible to rule out the existence of definite paths
or trajectories of electrons?
(a) Pauli’s exclusion principle
(b) Heisenberg’s uncertainty principle
(c) Hund’s rule of maximum multiplicity
(d) Aufbau principle
Sol: (b) According to Heisenberg’s uncertainty principle, the position and velocity of an
electron cannot be determined simultaneously with accuracy which rules out the existence of
fixed paths.
Q11. Total number of orbitals associated with third shell will be _______.
(a) 2 (b) 4 (c) 9 (d) 3
Sol: (c) No of orbitals in 3 shell (n = 3) = n2 = 32 = 9.
rd
Q13. Cl exists in two isotopic forms, Cl-37 and Cl-35, but its atomic mass is 35.5.
This indicates the ratio of Cl-37 and Cl-35 is approximately
(a) 1 : 2 (b) 1 : 1 (c) 1:3 (d) 3:1
Q15. For the electrons of oxygen atom, which of the following statements is correct?
(a) Zeff for an electron in a 2s orbital is the same as Zeff for an electron in a 2p
(b) An electron in the 2s orbital has the same energy as an electron in the 2p
(c) Zeff for an electron in Is orbital is the same as Zeff for an electron in a 2s orbital.
(d) The two electrons present in the? s orbital have spin quantum numbers ms but of
opposite sign.
Q16. If traveling at same speeds, which of the following matter waves have the
shortest wavelength?
(a) Electron
(b) Alpha particle (He2- )
(c) Neutron
(d) Proton
Q18. Out of the following pairs of electrons, identify the pairs of electrons present in
degenerate orbitals:
(a) (i) n = 3, l = 2, ml = -2, ms = -1/2, (ii) n = 3, l= 2, ml = -1, ms = -1/2
(b) (i) n = 3, l = 1, ml = 1, ms = +1/2, (ii) n = 3, l = 2, ml = 1, ms = +1/2
(c) (i) n = 4, l = 1, ml = 1, ms = +1/2 (ii) n = 3, l = 2, ml = 1, ms = +1/2
(d) (i) n = 3, l = 2, ml = +2, ms = -1/2 (ii)n = 3, l = 2, ml = +2, ms = +1/2
Sol: (a, d) Degenerate orbitals mean the orbitals of the same sub-shell of the same main shell,
i.e., their n and l values are the same. Other two pairs have different values of n and l
hence, cannot be having the same energy.
Q19. Which of the following sets of quantum numbers are correct?
Q21. Which of the following statements concerning the quantum numbers are correct?
(a) Angular quantum number determines the three dimensional shape of the orbital.
(b) The principal quantum number determines the orientation and energy of the orbital.
(c) Magnetic quantum number determines the size of the orbital.
(d) Spin quantum number of an electron determines the orientation of the spin of
electron relative to the chosen axis.
Sol: (a, d)
(a) Azimuthal quantum number l is also known as orbital angular momentum or subsidiary
quantum number. It determines three-dimensional shape of the orbital.
(b) The principal quantum number determines the size of the orbit.
(c) Magnetic quantum number determines the orientation of the electron cloud in a subshell.
(d) An electron spins around its own’ axis, much in a similar way as earth spins around its own
axis while revolving around the sun. In other words, an electron has, besides charge and
mass, intrinsic spin angular quantum number.
Q24. Show the distribution of electrons in oxygen atom (atomic number 8) using orbital
diagram.
Sol: Ni (28): ls2 2s2 2p6 Is2 3p6 3d8 4s2
Ni2+ (26): Is2 2s2 2p6 3s2 3p6 3d8
Hence, to form Ni2+ ion, it will lose 2 electrons from 4s orbital.
Q26. Calculate the total number of angular nodes and radial nodes present in 3p
orbital.
Sol: For 3p orbital, n = 3,l= 1
Number of angular nodes = 1=1
Number of radial nodes = n — l —1 = 3—1 — 1 = 1
Q27. The arrangement of orbitals on the basis of energy is based upon their (n +l)
value. Lower the value of (n + l), lower is the energy. For orbitals having the same
values of (n + I), the orbital with lower value of n will have lower energy.
I. Based upon the above information, arrange the following orbitals in the increasing
order of energy.
(a) 1s, 2s, 3s, 2p (b) 4s, 3s , 3p, 4d
(c) 5p, 4d, 5d, 4f, 6s (d) 5f, 6d , 7s , 7p
II. Based upon the above information, solve the questions given below:
(a) Which of the following orbitals has the lowest energy?
4d, 4f, 5s, 5p
(b) Which of the following orbitals has the highest energy?
5p, 5d, 5f 6s, 6p
Q28. Which of the following will not show deflection from the path on passing through
an electric field?
Proton, cathode rays, electron, neutron.
Sol: Neutron, since it is neutral and cannot be deflected by an electric field.
Q29. An atom having atomic mass number 13 has 7 neutrons. What is the atomic
number of the atom?
Sol: Atomic mass number = A = 13. n = 7
As A = n + p p = A — n= 13 —7 = 6
Hence Z = p = 6
Q31. The electronic configuration of valence shell of Cu is 3d10 4s 1 and not 3d94s2. How
is this configuration explained?
Sol: Configuration with completely filled and half-filled orbitals have extra stability. In
3d104s1, d-orbitals are completely filled and s-orbital is half- filled. Hence, it is a more stable
configuration.
Q32. The Balmer series in the hydrogen spectrum corresponds to the transition from
n1 = 2 to n2 = 3, 4,……… This series lies in the visible region. Calculate the wave number
of line associated with the transition in Balmer series when the electron moves to n = 4
orbit. (RH = 109677 cm-1).
Q33. According to de Broglie, matter should exhibit dual behaviour, that is both
particle and wave like properties. However, a cricket ball of mass 100 g does not move
like a wave when it is thrown by a bowler at a speed of 100 km/h. Calculate the
wavelength of the ball and explain why it does not show wave nature.
Since the wavelength is very small, the wave nature cannot be detected.
IMPORTANT QUESTIONS
1 Marks Questions
Question 1. How many total electrons are present in nitrate ion?
Answer:
No. of electrons in NO3– ion
= No. of electrons on N + No. of electrons on 3 oxygen atom + one ē = 7 + 3 × 8 + 1 = 32 e-
Question 2. The nucleus of the atom of an element does not contain a neutron. Name the
element and what does its nucleus consists of.
Answer:
The nucleus of hydrogen. It contains only one proton.
Question 5. Which of the following has the smallest de-Broglie wavelength? O2, H2, a proton,
an electron.
Answer:
According to the de-Broglie equation λ = hm×v for same value of velocity λ ∝1m
∴ O2 molecule has shortest wavelength.
Question 6. How many unpaired electrons are there is a carbon atom in the ground state?
Answer:
C = 6 = 1s2, 2s2, 2p1x 2p1y. There are only two unpaired electrons.
Question 7. What type of spectrum is obtained when light emitted from the discharge tube
containing hydrogen gas is analyzed?
Answer:
Emission line spectrum.
Question 8. What is the maximum number of e-s in an atom having n = 3, l = 1 and s = + 12?
Answer:
Three electrons (one each in 3px’ 3py’, 3pz’ ).
Question 9. Name the spectral line in the spectrum of H-atom obtained when an electron
jumps from n = 4 to n = 2.
Answer:
Balmer Series.
Question 10. Give some examples of electromagnetic radiation.
Answer:
Y-rays, X-rays, UV-rays, visible rays, radio waves, etc.
Question 11. State two properties of electromagnetic radiation.
Answer:
Electromagnetic radiation shows the phenomenon of:
1. Interference,
2. Diffraction.
Question 12. What is meant by the quantization of electron energy?
Answer:
It means that an electron in an atom has a certain, specific, discrete amount of energy.
Question 13. What does a principal quantity number denote?
Answer:
It denotes a specific stationary state.
Question 14. Why Bohr’s orbits are also called ‘energy levels’?
Answer:
Because they are associated with a certain definite amount of energy.
Question 15. How many spherical nodal surfaces are there in a 3s- sub-shell?
Answer:
Two.
Question 16. Out of 6s and 4f orbitals, which has higher energy and why?
Answer:
4forbital has higher energy, ((n + l) value of 4f is 7 while that of 6s is 6). The higher the (n +
l) value of an orbital higher is the energy.
Question 17. List the value/values of quantum numbers n and l for 4f electrons.
Answer:
n = 4, l = 3.
Question 18. Out of 4s and 3d orbitals, which will have higher energy and why?
Answer:
3d orbital has higher energy as it has a higher value of (n + l).
Question 19. Which of the following orbitals are not possible?
1p, 2p, 2d, 3f, 4f?
Answer:
1p, 2d, 3f is not possible.
Question 20. Which orbital does not have directional characteristics?
Answer:
s-orbital.
Question 21. An electron is in 3p-orbital. What are the permitted values of n, l, and m?
Answer:
n = 3, l = 1, m = – 1, 0, + 1.
Question 22. Write designation of an orbital having n = 5,1 = 3.
Answer:
5f -orbital.
Question 23. Consider the electronic configuration 1s° 2s° 2p° 3s1.
Name the element having this configuration. Is it in an excited state or ground state?
Answer:
It is the configuration of the H-atom. It is in an excited state.
Question 24. Which quantum number determines the
(i) size, Principal
(ii) orientation, Magnetic
(in) the shape of orbital, Azimuthal quantum number.
Question 25. Which energy level does not have a p-orbital?
Answer:
First energy level (i.e., n – 1, K-shell).
Question 26. Name an element that has only one d-electron.
Answer:
Scandium (atomic no. = 21).
Question 27. Given an isotone of C-13 atom.
Answer:
Isotones are the atoms of different elements which have the same number of neutrons. N-
14 is an isotone of a C-13 atom.
Question 28. Which of the following orbitals does not make sense? 5s, 4f, 3p, 2d.
Answer:
2d orbital does not exist and thus makes no sense.
Question 29. Name the famous experiment which showed for the first time that an atom has
a nucleus.
Answer:
Rutherford experiment of scattering of a-particles.
Question 30. Write the value of four quantum numbers for the valence electron of the
sodium atom.
Answer:
Na atom has 11 electrons and its valence electron is 3s1 (as configuration is 1s2, 2s2p6, 3s1)
∴ The value are: n = 3, l = 0, m = 0, s = + 12
Question 31. What is the relationship between velocity, wavelength, and frequency of
radiation?
Answer: These three characteristics of wave motion are related to each other as frequency
= Velocity Wavelength
In terms of symbols v = cλ.
Question 32. How wave number (v⃗ ) and wave length (λ) are related?
Answer:
v⃗ = 1λ . Wave number is the reciprocal of wavelength.
Question 33.Which series of hydrogen spectrum lies in the visible spectrum?
Answer:
Balmer series.
Question 34.How do you distinguish the two electrons present in the same orbital?
Answer:
By their spin quantum no. s which has + 12 and – 12 values.
Question 35. Name the principle which establishes that two electrons cannot have the same
values for all the 4 quantum numbers.
Answer:
Pauli exclusion principle.
Question 36. Write down the electronic configuration of Cu (= 29) in the ground state.
Answer:
Cu = 29 = 1s2, 2s2 2p6, 3s2 3p6, 3d10 4s1.
Question 37. What is the lowest value of n that allows g orbitals to exists?
Answer:
n = 5.
Question 38. Why do an atom M and its ion M2+ have the same mass?
Answer:
Both have the same no. of neutrons and protons which are responsible for the mass of an
atom.
Question 39. The nucleus of an atom has 6 protons and 8 neutrons. What are its atomic
number and mass number? What is this element1?
Answer:
At. No. = 6; Mass No. = 6 + 8 = 14; Element is Carbon.
Question 40. What is the number of electrons having l = 0 in an atom with an atomic number
29?
Answer:
7. [1s2, 2s2, 3s2, 4s1, i.e., 2 + 2 + 1 = 7]
Question 53. What is observed when an opaque object is placed in the path of cathode rays?
Answer:
A shadow of an opaque object is observed on the wall opposite to cathode.
Question 54. What happens when a very light paddle wheel is placed? in the path of cathode
rays?
Answer:
It begins to undergo a rotatory motion.
Question 55. What name was given to the particles which constitute cathode rays?
Answer:
Electron.
Question 56. Arrange the following orbitals in the order in which electrons may be normally
expected to fill them.
3s, 2p, 3p, 2s, 3d, 4s.
Answer: According to the Aufbau principle, the given orbitals will be filled in the order: 2s,
2p, 3s, 3p, 4s, 3d.
Question 57. Which fundamental property of an atom is not understood if we assume that an
atom consists of a nucleus containing protons only and an extranuclear part containing an
equal number of electrons?
Answer:
The mass number of atoms and stability of the nucleus cannot be explained.
Question 58. The following ions are isoelectronic: F–, Mg2+, O2-. Write the common electronic
configuration.
Answer: Each given ion contains 10 electrons. The common configuration is that of the Neon
atom, i.e., 1s2, 2s2 p6.
Question 59. What is the atomic number of an element whose mass number is 23 and
contains 12 neutrons in its nucleus? What is the symbol of an element?
Answer:
Atomic number = No. of protons in the nucleus
= Mass no. – No. of neutrons
= 23 – 12 = 11
The element is sodium and its symbol is Na.
Question 60. An atom has 2 K, 8 L, and 5 M electrons. Write the electronic configuration of
the atom. How many unpaired electrons are there in the atom?
Answer:
Electronic configuration of atom is: 1s2, 2s2p6, 3s2, 3p1x, 3p1y, 3p1z. It has three unpaired
electrons.
Question 61. Write the various possible quantum numbers for unpaired electron of Aluminium
atom?
Answer:
Al = 13 = 1s2, 2s2 2p6 3s2 3p1x
n = 3; l = 1; m = – 1, 0, + 1; s = 12 or – 12 .
Question 62. Give the values of quantum numbers for the electron with the highest energy in
sodium atom.
Answer:
n = 3; l = 0; m = 0; s = + 12 or – 12 .
Question 63. What do you observe in the spectrum of NaCl?
Answer:
Two yellow lines with a wavelength of 5890 Å and 5896 Å
Question 64. What do you mean by saying that the energy of the electron is quantized?
Answer:
This means that the electrons in an atom have only definite values of energy.
Question 65. Why are Bohr’s orbits called stationary states?
Answer:
This is because the energies of the orbits in which the electrons revolve are fixed.
Question 66. What is the difference between a quantum and a photon?
Answer:
The smallest packet of energy of any radiation is called a quantum whereas that of light is
called a photon.
Question 67. Which quantum number does not follow from the solution of the Schrodinger
wave equation?
Answer:
Spin quantum number.
Question 68. How many orbitals will be possible in a g-subshell?
Answer:
For g-subsheil l = 4; m = 2l + 1; – 4, – 3, – 2, – 1, 0, + 1, + 2, + 3, + 4; 9 orbitals.
2 Marks Questions
Question 1. Enumerate the important characteristics of anode-rays (or positive rays). How
this study led to the discovery of proton?
1) The mass of positive particles which constitute these rays depend upon the nature of
the gas in the tube.
2) The charge/mass (e/m) ratio of anode-rays is not constant but depends upon the
nature of gas in the tube. The value of e/m is greatest for the lightest gas, hydrogen
the electric charge on a lightest positively charged particle from hydrogen gas was
found to be exactly equal in magnitude but opposite in sign to that of the electron.
This lightest positively charged particle from hydrogen gas was named the proton. The
mass of a proton is almost 1836 times that of the electron.
Question 2. What are anode-rays? Illustrate their formation by a diagram.
Answer: Anode-rays. If a perforated cathode is used in the discharge tube experiment, it is
found that a certain type of radiation also travels from anode to cathode. These are called
anode rays or positive rays.
Question 3. Describe the important properties of cathode-rays. What is concluded about the
nature of these rays?
Answer: The cathode rays possess the following properties:
1) Travel in straight lines perpendicular to the surface of the cathode.
2) Consists of material particles.
3) Have got the heating effect.
4) Consists of negatively charged particles.
5) Produce X-rays when they strike against hard metals like copper, tungsten, platinum,
etc.
6) Produce fluorescence when they strike glass or certain other materials like zinc
sulfide.
7) Penetrate through thin aluminum foils and other metals.
8) Affect the photographic plates.
Question 4. What are the main features of Rutherford’s model of an atom?
Answer: The main features of this model are:
1) Atom is spherical and consists of two parts: Nucleus and extra-nuclear part.
2) The entire mass and entire positive charge are concentrated in a very small region at
the center known as the nucleus.
3) The space surrounding the nucleus known as the extra-nuclear part is negatively
charged so an atom as a whole is neutral.
4) Most of the extra-nuclear part is empty.
5) The electrons are not stationary but are revolving around the nucleus at very high
speeds like planets revolving around the Sun.
Question 5. What is meant by the dual nature of radiation?
Answer: The fact that light energy is carried in terms of packets of energy (i.e., photons) as
suggested by Planck’s theory means that light has a particle character. At the same time,
the fact light has a wave character. These experimental facts led Einstein to suggest that
light has a dual character, i.e., it behaves both like a wave and like a particle.
Question 6. Describe the drawback to Rutherford’s model of the atom.
Answer: The main drawback is that it could not explain the stability of an atom. Maxwell has
shown that when electric charge is subjected to acceleration, it emits energy in the form of
radiations. In Rutherford’s model of the atom, electrons are orbiting the nucleus and hence
the direction of their velocity is constantly changing, i.e., electrons are accelerating.
This will cause the electrons will have lesser and lesser energy and will
get closer and closer to the nucleus until at last, it spirals into the
nucleus and thus does not provide a stable model of the atom.
Question 7. What is the value of (i) charge to mass ratio (e/m) of electrons,
Answer: J. Thomson determined the value of e/m for electron by the study of deflection of
electron beam under the simultaneous influence of electric and magnetic field perpendicular
to each other, the e/m value is 1.76 × 108 coulomb per gram of electrons.
(ii) charge of electrons,
Answer: The charge of electrons was measured by Millikan in 1909 by his famous ‘oil drop’
experiment. It was found to be 1.60 × 10-19 coulombs.
(iii) mass of an electron?
Answer: The mass of electrons is 9.1 × 10-28 g.
Question 8. How is it concluded that electrons are a universal constituent of all matter?
Answer: The charge/mass (e/m) ratio for the particles in the cathode rays (i.e., electron) is
found to be the same irrespective of the nature of the cathode or the nature of the gas
taken in the discharge tube. This shows that electrons are universal constituents of all
matter.
Question 9. Distinguish between an Emission spectrum and an Absorption spectrum.
Answer: The important differences between the emission and absorption spectra are given in
the following table:
Emission Spectrum Absorption Spectrum
the electron cannot lose energy at all, i.e., an atom does not collapse. In other words, it is
quite stable.
Question 12.What are the main achievements of Bohr’s theory of the atom?
Answer:The main achievements of Bohr’s theory of atom are:
1) It can explain the stability of the atom.
2) It successfully explains the line spectrum of hydrogen.
3) It explains the line spectra of single-electron ions like He+ and Li2+.
Question 13.Write a short note on de-Broglie relation (or de-Borglie) equation.
Answer: A moving material particle, like an electron, proton, etc. having mass m and velocity v
is associated with wavelength X related by:
λ = hmv=hp
where p stands for the momentum of the particle and h is Planck’s constant. This relation is
known as a de-Broglie equation.
Question 14. Do atomic orbitals have sharp boundaries? Explain why or why not?
Or
Why don’t we draw a boundary surface diagram within the probability of finding the electron
is 100%?
Answer: No, atomic orbitals do not have sharp boundaries because the probability of finding
the electron even at large distances may become very small, but not equal to zero.
Question 15. What is the difference between the angular momentum of an electron present
in 3p and that present in 4p?
Answer: No difference, because angular momentum is given by = h2πl(l+1)−−−−−−√, i.e., it
depends only on the value of l and not the principal quantum no. n.
Question 16. Why splitting of spectral lines takes place when the source giving the spectrum
is placed in a magnetic field?
Answer: In the presence of a magnetic field, the orbitals present in a subshell (which were
degenerate) take up different orientations.
Question 17. How many electrons in Sulphur (Z = 16) can have n + l = 3?
Answer: 16S = 1s2, 2s2 2p6 3s2 3p4
• For 1s2, n + l = l+ 0 = l
• For 1s2, n + l = 2 + 0 = 2
• For 2p6, n + 1 = 2 + 1= 3
• For 3s2, n + l = 3 + 0 = 3
• For 3p4, n + l = 3 + l = 4.
Thus n + l = 3 for 2p6 and 3s2 electrons, i.e. for 8 electrons.
Question 18. Why Pauli Exclusion principle is called the exclusion principle?
Answer: This is because according to the principle, if one electron in an atom has some
particular values for the four quantum numbers, then all the other electrons in that atom are
excluded from having the same set of values.
Question 19. Why Hund’s rule is called the rule of maximum multiplicity?
Answer: This is because out of the various possible electronic configurations, only that
Configuration is correct for which the total spin value is maximum.
3 Marks Questions
Question 1. How many nucleons are present in an atom Nobelium, No? How many electrons are
present in the atom? How many nucleons may be considered neutrons?
Answer: Nucleons = 254, electrons = 102 and neutrons 254 – 102 = 152.
Question 2. Complete the following table:
Answer:
Answer:
Question 9. Calculate the wave number of radiations having a frequency of 4 × 1014 Hz.
Answer:
v = 4 × 1014 Hz = 4 × 1014 sec-1
Wave lemgth v̅ = 1λ=vc
= 4×1014sec−13×108msec−1
= 1.33 × 106 m-1
= 1.33 × 104 cm-1.
Question 10. A photon of wave length 4 × 10-7 m strikes on metal surface, the work function
of the metal being 2.13 eV. Calculate
(i) the energy of the photon (eV)
Answer: Energy of the photon = E = hv
Question 11. Electromagnetic radiation of wavelength 242 nm is just sufficient to ionize the
sodium atom. Calculate the Ionisation energy of solution in kJ mol-1
Question 12. The wavelength of the first line in the Balmer Series is 656 nm. Calculate the
wavelength of the second line and limiting line in the Balmer series.
Answer: According to Rydberg’s formula
Question 13. Calculate the wavelength of the spherical line in the Lyman series corresponding
to n2 = 3.
Answer: For the Lyman series n1 = 1
∴ v̅ = R[112−132]
= 109577 × 89 = 97490.7 m-1
λ = 1v=197490.7 cm-1
= 102.6 × 10-7cm
= 102.6 nm
Question 14. Calculate the velocity of electrons in the first Bohr orbit of the hydrogen atom.
Given that Bohr’s radius = 0,529 A. Planck’s constant h = 6.626 × 10-34 Js mass of electron =
9.11 × 10-31 kg and 1 J = 1 kg m2 s-1.
Question 15. The electron energy in a hydrogen atom is given by EH = (- 2.18 × 10-18)/n2 J.
Calculate the energy required to, remove the electron completely from n = 2 orbit. What is
the longest wavelength of light in cm that can be used to cause this transition?
Question 16. Give the values of the quantum numbers for the electron with the highest
energy in the sodium atom.
Answer: Electronic configuration of riNa = 1s2, 2s22p6 3s1
The electron with the highest energy is 3s1 for which n = 3 and l = 0
Question 17. Find the number of unpaired electrons in Fe2+ and Fe3+. At.No. of Fe = 26.
Answer: Electronic configuration of 26Fe = 1s2, 2s22p6, 3s2 3p6 3d6 4s2
Fe2+ = 1s2, 2s2 2p6, 3s2 3p6 3d6 It has 4 unpaired electrons
Fe3+ = 1s2, 1s2 2p6, 3s2 3p6 3d5 It has 5 unpaired electrons.
Question 18. What atoms are indicated by the following electronic cofigurations?
(i) 1s2, 2s22p1,
Answer: Total no. of electrons = 2 + 2 + 1 = 5
∴ At. no. of element is 5.
Hence the element is Boron (B).
(ii) [Ar] 4s2 3d1
Answer: Total no. of electrons in [Ar] 4s2 3d1 = 18 + 2 + 1 = 21
∴ At. no. of element is 21.
Hence the element is Scandium (Sc).
Question 19. Give the electronic configuration of N-3, K+, P-3, O2-.
• N = 7 = 1s2,2s2 2p3
• N3- = 10e = 1s2, 2s2 2p6
• K = 19 = 1s2, 2s2 2p6, 3s2 3p6 4s1
• K+ = 18e = 1s2, 2s2 2p6, 3s2 3p6
• P = 15 = 1s2, 2s2 2p6, 3s2 3p3
• p3- = 18e– = 1s2, 2s2 2p6, 3s2 3p6
• O = 8 = 1s2, 2s2 2p4
• O2- = 10e– = 1s2, 2s2 2p6
Question 20. Which out of Cu2+, Fe2+, Cr3+ has the highest paramagnetism and why?
Answer: Paramagnetism is a property of unpaired electrons. More the no. of unpaired
electrons, more the paramagnetism.
Cu2+ = 1s2, 2s2 2p6, 3s2 3p6 3d9
∴ It has only one unpaired electron.
Fe2+ = 1s2, 2s2 2p6, 3s2 3p6 3d6
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Q1 -Find the wavelength of radiation emitted when an electron from infinity falls to stationary state 1 in
a hydrogen atom. (RH = 1.09 x 107 m-1)
(3 Marks)
Q2 - Explain Hund’s rule with the help of example of nitrogen.
(3 Marks)
Q4 - The frequency of a radiation is 6 x 1014 cycles / sec. Find out the wavelength of radiation in
nanometer.
(2 Marks)
Q5 - An isotope of atomic mass 27 has 14 neutrons in the nucleus. What is the atomic number, name
and symbol of element.
(2 Marks)
Q1 - The uncertainty in momentum of an electron is 1.0 x 10-5 Kg ms-1 . What is the uncertainty in its
position?
(2 Marks)
Q2 - Find the de Broglie wavelength in Å of a particle with mass 1g and velocity 100m/s.
(2 Marks)
(2 Marks)
Q4 - What will be the uncertainty in velocity of an electron (mass of electron = 9.1 x 10-28 g) moving
with a velocity of 3.0 x 104 ms-1 accurate up to 0.011%?
(3 Marks)
Q4 - If the largest value of m for an electron is +2, then the electron may be present in what type of sub
shell?
(2 Marks)
Q5 - Point out the differences and similarities in the orbitals represented by following sets of quantum
numbers-
n l m
(i) 3 2 +2
(ii) 3 2 –1
(2 Marks)
Q6 - The work function of a metal is 4.2 eV. If radiations of 2000 A0 fall on the metal , then find the
kinetic energy of fastest photon electron.
(3 Marks)
NCERT SOLUTIONS
Chemistry is the branch of Science which deals with the study of composition of matter,
its properties and structure. It also deals with the relation between changes in composition
and changes in energy.
But now chemistry is a science, not an Art. Chemistry is an experimental science which
concerns itself with the study of matter. Due to its abnormal development, chemistry has been
divided into a number of branches. Important branches of chemistry are:
CLASSIFICATION OF MATTER:
Anything that has mass and occupies space is called matter.
It exists in three physical states, e.g., Solid, Liquid and Gas. It also has two others, states
namely Bose-Eistein condensite and Plasma
(A) Physical classification of matter: Depending upon the physical state of matter, it can be
classified into solid, liquid and gaseous state.
(B) Chemical classification of matter: Based on chemical composition, matter classified into
three types: elements, compounds and mixtures
Gold is an element
made up of only gold
atoms.
Carbon is an element
made up of only carbon
atoms.
The properties of the compound are totally different from the elements from which these are
formed: A compound can be organic or inorganic.
(b) Heterogeneous mixtures: These consist of two or more phases which have different
compositions.
The 11th general conference of weights and measures in 1960 recommended the use of
international system of units. Abbreviated as SI Units (after the French expression La
System International de units).
S.I OR BASE UNITS has seven basic units from which all other units are derived.
DERIVED UNITS: -Units of different physical quantities can be derived from the seven
basic units are called derived units because these are derived from the basic units.
For deriving these units, we can multiply or divide the symbols for units as if they are algebraic
quantities.
2
• Area = Length x Breadth = mx m = m
Mass 𝐊𝐠
• Density= =
Volume 𝐦𝟑
Velocity m.s−1 -2
• Acceleration= = = m.s
Time s
-2
• Force = Mass x acceleration = Kg. m.s
Kg.m.s−2 -1 -2
• Pressure=
Force
= =Kg.m .s
Area m2
-2 2 -2
• Energy, work = Force x distance = Kg.m.s x m = Kg.m .s = Joule
• Electric charge = current x time = A. S = Coulomb
Energy kg.m2 .s−2 -1 -1
• Electric potential= = = Joule. A .s = Volt
Charge A.S
PREFIXES: The SI units of some of the physical quantities are either too small or too large.
To change the order of magnitude, these are expressed by using prefixes before the names
of the basic units.
These equalities are called unit conversion factor or conversion factor or simply unit factor.
Examples
10−10 m -10
0.74A° = 0.74A°x = 0.74 x 10 m
1 Ao
-12 1 pm
1pm = 10 m or 1 =10−12 m
10−3 m3 -3 3
1L atm = 1 L atm x = 10 m atm
1L
101,325 pa
1atm = 101, 325 Pa or 1 = 1 atm
3 -3 3 3
10-3m atm=10 m atmx =101, 325Pa10-3m3= 101.325Pa.m
101,325 pa
1 atm
N
But, Pa =m2
3 3N
101.325Pa.m =101.325.m =101.325N.m = 101.325 J (Q 1 J = N.m)
m2
• It is a measure of the difference between the experimental value and the true value.
Small difference between the experimental value and the true value, larger is the accuracy.
Accuracy expresses the correctness of measurement.
• Precision is the difference between a measured value and the arithmetic mean value for
a series of measurements.
Precision refers for the closeness of the set of values obtained from identical measurement
of a quantity.
Example: Three students were asked to determine the mass of piece of metal where mass is
known to be0.520g. Data obtained by each student are recorded as follows.
Measurements(g) Average(g)
(1) (2) (3)
Student A 0.521 0.515 0.509 0.515
Student B 0.516 0.515 0.514 0.515
Student C 0.521 0.520 0.520 0.520
Data of student A are neither very precise nor accurate. The individual values differ widely
from one another and the average value is not accurate.
Student B was able to determine the mass more precisely. The values deviate, but little from
one another. However, the average mass is still not accurate. The data for student C is both
precise and accurate.
2) 0.00013842 = 1.3842×10-4
1.To transform a number larger than 9.999... to scientific rotation, the decimal point there
is only one non-zero digit before the decimal point. If the decimal point is moved x
places to the left, then exponent n = x
1395.2 = 1.3952×103
21.654 = 2.1654×101
2.To transform a number smaller than 1 to scientific notation, the decimal point is moved to
the right until there is one nonzero digit before the decimal point. If the decimal point is
moved ‘y’ places to the right, the exponent, n = -y
0.00549 = 5.49×10-3
0.1641 = 1.641×10-1
SIGNIFICANT FIGURES
To express the results in an accurate way, we express generally those digits which are known
with certainty. This is done is terms of significant figures.
The significant figures in a number are all the certain digits plus one doubtful digit. The
digits in a properly recorded measurement are knows as significant figures.
The greater the number of significant figures in a reported result, smaller is the uncertainty
and greater than precision.
2. When a number is greater than 1, all the zeros to the right of the decimal point are
significant
3. For a number less than 1, only zeros to the right of the first significant digit at
significant. But the zeros to the left of the first significant digit are not significant
Ex: The number of significant figures in 0.4960 = 4
The number of significant figures in 0.0013 = 2
5. When adding or subtracting, the number of decimal places in the answer should be equal
to the number of decimal places in the number with the least number of decimal places.
Since the term 1.5 involved in addition, has only one decimal place, the overall answer of
26.112 should be reported as 26.1.
6. In multiplication and division, the number of significant figures in the answer should be
same as that in the number with least number of significant figures.
Ex:Since the term3.376 has 4 and1.25 has3 significant figures, the multiplied answer
should be 4.22
Ex: 12.696,18.35 and 13.93 are reported as 12.7, 18.4, 13.9 respectively when rounded off
to three significant figures
1) Law of conservation of mass: It states that “matter is neither created nor destroyed
during any physical or chemical change”
• When matter undergoes a physical change: A piece of ice (solid water) is taken in a
small conical flask. It is well corked and weighed. The flask is now heated gently to melt
Heat
the ice (solid) into water (liquid).Ice → Water
The flask is again weighed. It is found that there is no change in the Weight though a
physical change has taken place.
• When matter undergoes a chemical change: The following chemical changes illustrate
the law.
Ex. 1-5.2g of CaCO3heated produced 1.99g of Carbon dioxide and the residue (CaO)
left behind weighs 3.2g. Show that these results illustrate the law of
conservation of mass.
Difference between the wt. of the reactant and the total wt. of the products is
Ex. 2: When 20g of NaHCO3 is heated, 12.62g of Na2CO3 and 5.24g of CO2 is
produced. How many grams of H2O is produced?
2) Law of definite proportion (Law of constant proportion)states that “Any pure compound
however made contains the same elements in the fixed ratio of their weights”, or
‘A pure chemical compound always contains the same elements combined together
in the fixed ratio of their weights whatever its methods of preparation may be’.
Ex.1:Pure water contains 2gm of hydrogen and 16gm of oxygen i.e., the ratio of hydrogen and
oxygen in pure water is 1: 8.
Ex.2: A sample of CO2 may be prepared in the laboratory by (a) heating lime stone (CaCO3),
(b) by burning coal in air, (c) by the action of dilute hydrochloric acid on marble, (d) by heating
sodium bicarbonate. In each case, it is found that CO2 is made up of the same elements. i.e.,
carbon and oxygen, combined together in the same fixed ratio of 12: 32 or 3: 8 by mass.
For example, in theformation of the compound CO2, if C-12isotope combines, the ratio of C:O
is 12: 32, but if C-14 isotopes combines, the ratio ofC:O is 14 : 32.
Problem 1.6.488g of lead combine directly with 1.002g of oxygen to form lead peroxide
(PbO2).Itis also produced by heating lead nitrate and it was found that the percentage of
oxygen present in lead peroxide is 13.38 percent. Use these data to illustrate the law of
constant composition.
Solution: Step1. To calculate the percentage of oxygen in first experiment.
Mass of peroxide formed = 6.488 + 1.002 = 7.490g.
Problem 2. Ammonia contains 82.65% N 2 and 17.65% H2. If the law of constant proportions
is true, then the mass of zinc required to give 10g Ammonia will be:
Problem 3. Irrespective of the source, pure sample of water always yields 88.89% mass of
oxygen and 11.11% mass of hydrogen. This is explained by the law of:
8
So, oxygen = 8+1 × 100 = 88.89%
1
Hydrogen = 8+1 × 100 = 11.11%
(a) In one case, 1.75g of the metal were dissolved in nitric acid and igniting the residual copper
nitrate yielded 2.19g of copper oxide.
(b)In the second case, 1.14g of metal dissolved in nitric acid was precipitated as copper
hydroxide by adding caustic alkali solution. The precipitated copper hydroxide after washing,
drying and heating yielded 1.43g of copper oxide.
(c)In the third case, 1.45g of copper when strongly heated in a current of air yielded 1.83g of
copper oxide. Show that the given data illustrate the law of constant composition.
Thus the percentage of copper in copper oxide derived from all the three experiments is nearly
the same. Hence, the above data illustrate the law of constant composition.
Ex: The weight of Oxygen that will combine with 32gm of sulphur in SO2 and SO3 is the
ratio of 2: 3
Problem 2. Carbon is found to form two oxides, which contain 42.9% and 27.3% carbon
respectively. Show that these figures illustrate the law of multiple proportions.
Solution: Step1. To calculate the percentage composition of carbon and oxygen in each of the
two oxides
Step2. To calculate the masses of carbon which combine with a fixed mass, i.e., one part
by mass of oxygen in each of the two oxides:
Step3. To compare the masses of carbon which combine with the same mass of oxygen in
both the oxides:
The ratio of the masses of carbon that combine with the same mass of oxygen (1 part) is
0.751: 0.376 or2: 1
Since this is a simple whole number ratio, of the above data illustrate the law of multiple
proportions.
The ratio of the masses of two elements A and B which combine separately with a fixed
mass of the third element C is either the same or some simple multiple of the ratio of the
masses in which A and B combine directly with each other.
“when two elements combine separately with fixed mass of third element then ratio of
their masses in which they do so is either the same or some whole number multiple of the
ratio in which they combine with each other”.
This law may be illustrated with the help of the following examples:
(1) Elements C and O combine separately with the third element H to form CH4 and H2O
and they combine directly with each other to form CO2, as shown below
O
CO2 H2O
C H
CH4
In H2O, 2 parts by mass of H combine with 16parts by masses of oxygen. Thus, the masses of
C and O which combine with fixed mass of hydrogen(say 4parts by mass) are 12 and 32,
i.e., they are in the ratio 12 : 32 or 3 : 8.Now, in CO2, 12parts by mass of carbon combine
directly with 32parts by mass of oxygen, i.e. they combine directly in the ratio 12: 32 or 3:
8 which is the same as the first ratio.
(2) The elements H and O combine separately with the third
element S to form H2S and SO2 and they combine directly with
each other to from H2O, the masses of H and O which combine
with the fixed mass of S, viz, 32parts are 2 and 32,
88.90
In H2O, 11.10gof H combine with O=88.90g 1g of H combine withO =11.10 g = 8.01g
∴ Ratio of the masses of NandO which combine with fixed mass (=1g) of H =4.67:8.01=1: 1.72
In N2O3, ratio of masses of N and O which combine with each other = 36.85: 63.15 = 1: 1.71
4) Gay - Lussac’s law of combining volumes: Under same conditions of temperature and
pressure, whenever gases react together, the volumes of the reacting gases as well
as products are in a simple whole number ratio.
‘at the same temperature and pressure, the volumes of gaseous reactants reacted and
the volumes of gaseous products formed bear a simple ratio.’
5) Avogadro’s Law: Equal volumes of all gases under similar conditions of temperature
and pressure contains equal number of molecules
Molecular weight
or Vapour density = 2
(iii) It helps in the determination of mass of fixed volume or molar volume of a gas.
Mass of 1 ml gas = V.D. 0.0000897gm.
• It failed to explain how and why atoms of elements combine with each other to form
compound atoms or molecules.
• It failed to explain the nature of forces that bind together different atoms in
molecules.
• It failed to explain Gay Lussac’s law of combining volumes.
• It did not make any distinction between ultimate particle of an element that takes part
in reaction (atoms) and the ultimate particle that has independent existence (molecules).
Atom: The smallest particles of an element that can take part in chemical
bonding but generallyCannot exist freely as such.
• Atomic Mass: The number which indicates how many times the mass
1 th 12 1 th
of one atom of the element a heavier than12 of the mass of C mass of an atom of
12
12
C is knows as atomic mass unit (amu).
When equivalent weight scale was altered from H =1 to O =16 the definition of atomic weight
changes to
Weight of 1 atom of the element
Atomic weight of an element = 1
×weight of 1 atom of oxygen
16
Modern reference standard for atomic weights is carbon isotope of mass number 12.
Weight of 1 atom of the element
Atomic weight of an element = 1
×weight of 1C12
12
1
Unit of atomic weight: The modern unit of atomic weight is of the mass of one atom of C–
12
12. Unit of atomic weight representation as a.m.u.
1
1a.m.u. =12× mass of C—12 atom.
Gram atomic mass: The atomic mass of an element expressed in grams is called its gram
atomic mass.Itis also called gram atom.
AVERAGE ATOMIC MASS- Elements are found in different isotopic forms (atoms of same
elements having different atomic mass), so the atomic mass of any element is the average of
all the isotopic mass within a given sample.
Exp- 1 Use the date given in the following table to calculate the molar mass of naturally
occurring argon.
Isotope Isotopic molar mass Abundance
36 −1
Ar 35.96755 g mol 7.1%
38
Ar 37.96272gmol−1 16.3%
40 −1
Ar 39.9624 g mol 76.6%
Solution: Molar mass of Ar
= 35.96755 0.071 + 37.96272 0.163 + 39.96924 0.766
= 39.352gmol−1
Exp-2 Carbon occurs in nature as a mixture of carbon 12 and carbon 13. The average atomic
mass of carbon is 12.011. What is the percentage abundance of carbon 12 in nature?
∑ %abundance×atomicmass
Solution: Average atomic mass= 100
𝑥×12+(100−𝑥)13
i.e.12.011 = 100
1201.1 = 12x + 1300 – 13x
x = 1300 – 1201.1 = 98.9%
• Molecular Mass: is number which indicates how many times the mass of one molecule of
1 th
a substance is heavier than12 part of mass of C12.
weight of one molecule of a substance
Molecular weight = 1
×weight of one atom of C–12
12
Gram molecular mass or Gram molecule: The molecular mass of an element or compound
expressed in grams is called its gram molecular mass.
Ex:The molecular mass of Oxygen = 32amu
The gram molecular mass of Oxygen = 32gm
One-gram molecule of Oxygen = 32gm of Oxygen
Calculation of Molecular Mass:
Molar volume-Volume occupied by one mole of any gas at STP is called Gram molar volume.
The value of gram molar volume is 22.4litres. Volume of 1mole of any gas at STP = 22.4litres
• Equivalent mass: The number of parts by mass of a substance that combines with or
displaces 1.008parts by mass of hydrogen or 8.0parts of oxygen or 35.5parts of chlorine
is called equivalent mass (EM). On the other hand, quantity of a substance in grams
numerically equal to its equivalent mass is called its gram equivalent mass (GEM) or gram
equivalent.
Mass of the substance in grams
Number of GEM =
GEM of the substance
Expressions for equivalent mass (EM)
Atomic mass
(i) EM of an element = Valency
Molecular mass
(ii)EM of an acid = Basicity
(Basicity of acid is the number of replaceable H- atoms in one molecule of the acid).
Molecular mass
(iii)EM of a base= Acidity
Equivalent mass of common oxidising agent changes with the medium of the reaction.
MOLE CONCEPT
Mole: The amount of substance that contains the same number of chemical
entities (atoms, molecules, ions), as the number of atoms present in 12gm of
12
C isotope.
Avogadro number: The number of atoms present in one-gram atom of an element or the
number of molecules present in one-gram molecule (1mole) of a substance is
called Avogadro number. It is equal to 6.023 x 1023. Thus, a mole contains
6.023x1023 units. These units can be atoms, molecules, ions, electron or
anything else.
1mole of hydrogen atoms means 6.023x1023 hydrogen atoms.
1mole of H2molecules means 6.023x1023 hydrogen molecules
1mole of potassium ions means 6.023x1023 potassium ions
1mole of electron ions means 6.023x1023 electrons.
Avogadro Number (NA). The number of carbon atoms present in one gram-atom (1 mole
atom) of C–12 isotope.
One gram-atom (12grams) of C–12 contains 6.02 × 1023atoms. Thus the numerical value
of Avogadro’s number (NA) is 6.02 × 1023 per mol. It should be noted that
th of mass of a C12 atom
1
1 a.m.u.=
12
i.e. (i)6.023 × 1023 atoms of Na constitute one mole atom of Na.
(ii) 6.023×1023molecules of oxygen constitutes 1mole of oxygen molecules.
(iii) 6.023 × 1023 electrons constitute one mole of electrons.
Number of particles
(iv) No. of moles = 6.023×1023
Standard Temperature and Pressure (STP OR NTP): The temperature of 273K and a
pressure of 1atm are taken as STP conditions
Formula weight: The formula weight of a substance is the total mass of all atoms present in
the chemical formula of the substance.
Molar Mass: The mass of one mole of a substance is called its molar mass. The units of
molar mass are gm/mole or Kg/mole.
Therefore, molar mass is equal to atomic mass or molecular mass expressed in grams depends
on whether the substance contains atoms or molecules.
• 1mole atom = 6.02x1023atoms =Gram Atomic weight =22.4litres at STP (only for
gas) (or 1 gram atom)
23
Ex:1mole He =6.02x10 atoms = 4gram = 22.4 litres at STP
23
• 1mole molecule=6.02x10 molecules=Gram Molecular weight=22.4 lit at STP (Only
for gas)
Problem 2: Calculate the number of atoms of the constituent elements in 53g of Na2CO3.
Solution: By mole concept.
1mole of Na2CO3=Gram formula mass of Na2CO3=2x23+12+16x3=106 g
Now, 106g of Na2CO3=1mole
53g of Na2CO3= 0.5mole of Na2CO3
But 1mole Na2CO3 contains 2moles of Na+ ion or 2x6.022x1023 Na+ ions.
0.5mole of Na2CO3 contain 2x6.022x1023x0.5Na+ ions=6.022x1023Na+ ions
Again, 1mole Na2CO3 contains 1mole of carbon atoms=6.022x1023Na+ ions
23 23
∴0.5mole of Na2CO3contain=6.022x10 x0.5 carbon atoms=3.011x 10 carbon atoms.
Further, 1mole Na2CO3 contains 3moles of oxygen atoms
or 3x6.022x 1023oxygen atoms.
23 23
∴0.5 mole of Na2CO3 will contain = 3 x 6.022 x 10 x 0.5 oxygen atoms = 9.033 x 10 oxygen
atoms.
Sample Problem 3: Calculate the number of molecules present in 350cm3 of NH3 gas at
273Kand 2atmosphere pressures.
Solution: First of all, we have to determine the volume of the gas at STP.
V1 = 350cm3 V2=?
T1 = 273K T2 = 273K
P1 = 2atmospheres P2 = 1atm
𝑃1 𝑉1 𝑃2 𝑉2
Applying gas equation: =
𝑇1 𝑇2
350×2 1×𝑉2 350×2 273
Weget = orV2 = × = 700𝑐𝑚3
273 273 273 1
Sample Problem 4:(i) Assuming the density of water to be 1g/cm3, calculate the volume
occupied by one molecule of water.
(ii)Assuming the water molecule to be spherical, calculate the diameter of the water molecule.
Approximately the diameter of the oxygen atom.
(ii)As water molecules is assumed to be spherical. If R is its radius, then its volume will
4
be πR3 = 2.989 × 10−23 cm3 orR3 = 7.1336 x 10-24 or R = (7.133) 1/3
x 10-8= 1.925 x 10-8 cm
3
1 1
Take n=(7.133)1/3logn= 3 log 7.122 =3 × 0.8533 = 0.2844
(iii)As oxygen atom occupies half of the volume occupied by water molecule, hence if r is
4
theradius of oxygen atom, then 3 πr 3 = 2.989 × 10−23 cm3 or
1. From 200mg of CO2, 1021molecules are removed. How many moles of CO2 are left?
Mass in gram 0.2
Solution: Total no. of moles of CO2 = = = 0.00454
Gram molecular mass 44
1021
No. of moles removed = = 0.00166
6.022×1023
11.2 1
=22.4 = 2 = 0.5
=3.011 1023
= 2 12 = 24g.
= 1 100 = 100
Step1. Calculate the molecular mass of the compound from its formula its formula by adding
the atomic masses of the elements present.
Step2.Calculate the percentage of the element or the constituent by supplying the following
relation:
𝑁𝑜. 𝑜𝑓𝑝𝑎𝑟𝑡𝑠𝑏𝑦𝑚𝑎𝑠𝑠𝑜𝑓𝑡ℎ𝑒𝑒𝑙𝑒𝑚𝑒𝑛𝑡𝑠𝑜𝑟𝑐𝑜𝑛𝑠𝑡𝑖𝑡𝑢𝑒𝑛𝑡
% of the element = × 100
𝑀𝑜𝑙.𝑚𝑎𝑠𝑠𝑜𝑓𝑡ℎ𝑒𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
Sample Problem 1: Calculate the percentage compositions of the various elements in MgSO4.
Sample Problem 2: Calculate the percentage of water of crystallisation in the sample of blue
vitriol (CuSO4.5H2O).
The formula which gives the relative number of atoms of various elements in one molecule
of the compound is called empirical formula.
Ex: Molecular formula of benzene is C6H6. It means that one molecule of benzene has six
carbon atoms and six hydrogen atoms.
Empirical formula of benzene is CH. It means that carbon and hydrogen are present in the
ratio of 1:1 in benzene.
1. Compound contains C = 71.23%, H = 12.95% and O = 15.81%. What is the empirical formula
of the compound?
Element Atomic Weight % in Relative no, of atom Simplest atomic Empirical
mass compound ratio formula
2. The simplest formula of a compound containing 50% of element X (Atomic mass=10) and
50% of the element Y (Atomic mass=20) is
(A) XY (B)X2Y (C) XY2 (D)X2Y3
3. A compound of carbon, hydrogen and nitrogen contains these elements in the ratio
9:1:3.5. Calculate the empirical formula. If its molecular mass is 108, what is the
molecular formula?
Element Element ratio Atomic mass Relative number of atoms Simplest ratio
C 9 12 9 0.75
= 0.75 =3
12 0.25
H 1 1 1 1
=1 =4
1 0.25
N 3.5 14 3.5 0.25
= 0.25 =1
14 0.25
Empirical formula = C3H4N
Empirical formula mass = (3 12) + (4 1) + 14 = 54
mol. mass 108
n= = =2
Emp. mass 54
Thus, molecular formula of the compound = 2 empirical formula
= 2 C3H4N = C6H8N2
4. 2.38 gm of uranium was heated strongly in a current of air. The resulting oxide weighed
2.806g. Determine the empirical formula of the oxide. (At. mass U =238; O=16).
Step1: To calculate the percentage of uranium and oxygen in the oxide.
Relative no. of
no.
At. mass of
atomic ratio
atomic ratio
of elements
Percentage
atoms
elements
Element
Simplest
Simplest
Percentage
=
whole
At. mass
6. The empirical formula of a compound is𝐶𝐻2 𝑂. Its molecular weight is 90. Calculate the
molecular formula of the compound.
(Atomic weights C=12, H=1, O=16)
Solution: Empirical formula = CH2 O
Empirical formula weight = (12 + 2 + 16) = 30
molecular weight 90
n = empirical formula weight ∴ n = 30 = 3
7. A substance, on analysis, gave the following percentage composition: Na= 43. 4%,
C= 11.3%, O= 45.3%. Calculate its empirical formula. {Na= 23, C= 12,O= 16]
Simple ratio of Simplest whole no.
SYMBOL % age Atomic Mass Relative number of moles
moles ratio
43 .4 1.88
Na 43.4 23 = 1.88 =2 2
23 0.94
11 .3 0.94
C 11.3 12 = 0.94 =1 1
12 0.94
45 .3 2.83
O 45.3 16 = 2.83 =3 3
16 0.94
Therefore, the empirical formula is Na2CO3.
9.76 0.406
Mg 9.76 24 = 0.406 =1 1
24 0.406
13 .01 0.406
S 13.01 32 = 0.406 =1 1
32 0.406
26 .01 1.625
O 26.01 16 = 1.625 =4 4
16 0.406
51 .22 2.846
H2O 51.22 18 = 2.846 =7 7
18 0.406
9. What is the simplest formula of the compound which has the following percentage
composition. Carbon 80%, Hydrogen 20%. If the molecular mass is 30, calculate
its molecular formula.
Relative number of Simple ratio of Simples whole
Element % age At. Mass
moles moles no.ratio
80 6.66
C 80 12 = 6.66 =1 1
12 6.66
20 20
H 20 1 = 20 =3 3
1 6.66
Empirical formula is CH3
Molecular mass 30
Empirical mass = 12 1 + 1 3 = 15 n = = =2
Emprical formula mass 15
Molecular mass 88
n= = =2
Empirical formula mass 44
11. An organic compound on analysis gave the following data: C = 57.82%, H = 3.6%,
and the rest is oxygen. Its vapour density is 83. Find its empirical and molecular
formula.
Simple ratio of Simplest whole no.
Element % age At. Mass Relative number of moles
moles ratio
57 .82 4 .8
C 57.82 12 = 4.80 =2 4
12 2 .4
3.60 3 .6
H 3.60 1 = 3.60 = 1 .5 3
1 2 .3
38 .58 2 .4
O 38.58 16 = 2.40 =1 2
16 2 .4
1.94
Silver = 100 = 70.65%
2.746
0.268
Sulphur = 100 = 9.75 %
2.746
0.538
Oxygen = 100 = 19.6%
2.746
9.75 0.305
S 9.75 32 = 0.305 =1 1
32 0.305
19 .6 1.22
O 19.6 16 = 1.22 =4 4
16 0.305
• For every 16gms of CH4 , 64gms of O2 will be required to produce 44gms of CO2 and 36gms
of H2O this signifies Mass – Mass relation
• Ratio of moles of CO2 : H2O at any time = 1 : 2
• There will be no change in total mass of all reactants and products at any time for any
chemical reaction.
The quantitative information conveyed by a chemical equation helps in a number of calculations.
The problems involving these calculations may be classified into the following different types:
(1)Mass-Mass Relationships, i.e., mass of one of the reactants or products is given and the
mass of some other reactant or product is to be calculated.
(3)Volume-Volume Relationship, i.e, volume of one of the reactants or the products is given and
the volume of the other is to be calculated.
The general method of calculations for all the problems of the above types consists of the
following steps:
Sample Problem 1: Calculate the mass of iron which will be converted into its oxide (Fe3O4)by
the action of 18g of steam on it.
Sample Problem 2: What mass of slaked lime would be required to decompose completely
4grams of ammonium chloride and what would be the mass of each product?
Solution: The equation representing the decomposition of NH4CI by slaked lime, i.e.Ca (OH)2is:
Ca(OH)2+ 2NH4Cl → CaCl2 + 2NH3 + 2H2O
40+2(1+16) 2(14+4+35.5) 40+2×35.5 2(14+3×1) 2(2×1+16)
=74g =107g =111g =34g =36g
Sample Problem 3:1.5g of an impure sample of sodium sulphate dissolvedin water was treated
with excess of barium chloride solution when 1.74 g of BaSO4was obtained as dry
precipitate. Calculate the percentage purity of the sample.
Solution: The chemical equation representing the reaction is:
Na2SO4+BaCl2→BaSO4+ 2NaCl
2×23+32+4×16=142g 137+32+4×16=233g
Step1.To calculates the mass of Na2SO4which produces 1.74g of BaSO4? From the chemical
equation, 233g of BaSO4 are produced from Na2SO4=142g
142
∴1.74g of it would be obtained from NaSO4= 233 × 1.74 = 1.06g
This is the mass of pure Na2SO4 present in 1.5g of impure sample.
Step2. To calculate the percentage purity of impure sample.
1.5g impure sample contains pure Na2SO4= 1.06g
1.06
∴100g of impure sample will contain pure Na2SO4= 1.5
× 100 = 70.67 g
Sample Problem 4: Current market prices of Al, Zn and Fe scraps per kg are Rs.20, Rs.16 and
Rs.3 respectively. If H2 is to be prepared by the reaction of one of these metals with
H2SO4, which would be the cheapest metal to use? Which would most expensive?
Solution: The various chemical reactions involved are given below:
(i) 2Al + 3H2SO4→ Al2(SO4)3 + 3H2
2×27=57g 3×2=6g
(ii) Zn + H2SO4→ ZnSO4 +H2
65g 2g
(iii) Fe + H2SO4→ FeSO4 +H2
56g 2g
Let us suppose that the amount of hydrogen to be prepared = 100g.
Step1. To calculate the cost of preparation of 100g of H2 from Al
Thus, Fe is the cheapest and Zn is the most expensive metal to use of the preparation of H2.
Sample Problem5: Calculate the amount of lime, Ca(OH)2, required to remove hardness of
50,000litres of well water which has been found to contain 1.62g of calcium bicarbonate
per 10litre.
(i)Calculation of total Ca(HCO3)2 present.
1.62
50,000L of water will contain Ca(HCO3)2= 10 × 50000g = 8100 g
(ii)Calculation of lime required. The balanced equation for the reaction involved is:
1 mole 1 mole
Sample Problem 6:1.0g of a mixture of carbonates of calcium and magnesium gave 240cm3 of
CO2 at STP. Calculate the percentage composition of the mixture.
MgCO3 →MgO+CO2
∴Percentage of MgCO3=100–62.5=37.5
Limiting Reagent
In single-reactant reactions, the calculations are carried out with only that amount of the
reactant which has converted to the product. This is done in all the methods mentioned above.
• Reactions proceed until one of the reactants is used up and one is left in excess.
• The limiting reactant limits the extent of the reaction and, thereby, determines the
amount of product formed.
• The excess reactants are all the leftover unused reactants.
• Determining the limiting reactant is important because the amount of the product
formed depends on this reactant.
In the reactions where more than one reactant is involved, one has to first identify the limiting
reactant, i.e., the reactant which is completely consumed or runs out first. All calculations
are to be carried out with the amount of the limiting reactant only. Now the question is how
to identify the limiting reactant? The procedure is simple analogy as illustrated below:
(1) Syrup is a limiting Reagent
A + 2B → 4C
The reactant producing the least number of moles of the product is the limiting
reactant and hence A is the limiting reactant.
Experimental Conditions
Reactants Products
Before reaction
2 molecules N2 3 molecules H2 0 molecules NH3
After reaction
1 molecule N2 0 molecules H2 2 molecules NH3
N 2 + 3H 2 ⎯⎯
→ 2NH 3
Initial mole 5 12 −
Ex.1: How much magnesium sulphide can be obtained from 2.00 g of magnesium and
2.00 g of sulphur by the reaction Mg + S⎯⎯→MgS? Which is the limiting reagent?
Calculate the amount of the reactants which remains unreacted.
Solution: First of all, each of these masses are converted into moles:
2.00
2.00 g of Mg = = 0.0824 moles of Mg
24 .3
2.00
2.00 g of S = = 0.0624 moles of S
32 .1
From the equation, Mg + S ⎯⎯→MgS, it follows that one mole of Mg reacts with one mole of
S. We are given more moles of Mg than of S. Therefore, Mg is in excess and some of it will
remain unreacted when the reaction is over. S is the limiting reagent and will control the
amount of product. From the equation we note that one mole of S gives one mole of MgS, so
0.0624 mole of S will react with 0.0624 mole of Mg to form 0.0624 mole of MgS.
= 0.0200 moles of Mg
Ex.2: 4 mole of MgCO3 is reacted with 6 moles of HCl solution. Find the volume of
CO 2 gas produced at STP. The reaction is MgCO3 + 2HCl → MgCl2 + CO2 + H 2O
Solution: From the reaction MgCO3 + 2HCl → MgCl2 + CO2 + H 2O
Given moles 4 mole 6 mole
Given mole ratio 2 : 3
Stoichiometric
Coefficient ratio 1 : 2
There should be one limiting reagent.
To find the limiting reagent, divide the given moles by stoichiometric coefficient.
MgCO3 HCl
4 6
=4 =3
1 2
HCl is limiting reagent.
moles of HCl moles of CO2 produced
Q =
2 1
moles of CO 2 produced = 3 moles
volumes of CO 2 produced at S.T.P, = 3 22.4 = 67.2L
Ex. 3: What weight of AgCl will be precipitated when a solution containing 4.77 g NaCl
is added to a solution of 5.77g of AgNO3 ?
Solution: AgNO3 + NaCl ⎯⎯→ AgCl + NaNO3
5.77 4.77
moles. Mixed = 1000 1000
170 58.5
= 33.94 = 81.54 0 0
moles. left 0 47.60 33.94 33.94
w
moles of AgCl formed = 33.94, 1000 = 33.94 WAgCl = 4.87g
143.5
Mass (amu) 44.09 amu C3H8 + 160.00 amu O2 → 132.03 amu CO2 + 72.06 amu H2O
1mole 1mole
24gram 71grams
71-gram Cl2 → 24gram Mg
4 mole 3 mole
4 x 27gram 3 x 32 gram
3 x 32gram O2 → 4 x 27gram Al
4×27
8gram O2 → x8 = 9gram Al
3×32
27 𝐴.𝑤
E.W. of Al = 9 = =
3 𝑉𝑎𝑙𝑒𝑛𝑐𝑦
1mole 2mole
98gram
1mole H+
98
→ = 32.66
3
98 𝑀.𝑊
E.W. of H3PO4= 32.66 = = 𝐵𝑎𝑠𝑖𝑐𝑖𝑡𝑦
3
• Equivalent weight of base:It is the weight of base that gives one mole OH − . or reacts
with 1mole H+
Molecular mass
Equivalent mass of a base =
Acidity(OH − )
Acidity: The number of hydroxyl groups present in a molecule of the base “is known as
acidity of the base.
Eg. Ca (OH) 2
→ Ca2+ + 2OH-
1 mole 2 mole
74gram
1mole
133.5gram
133.5gram AlCl3→3mole positive & 3mole negative charge
• Gram equivalent weight: When equivalent weight is expressed in grams, it is called gram
equivalent weight.
𝑤𝑒𝑖𝑔ℎ𝑡𝑜𝑓𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒
Number of gram equivalents = 𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑤𝑒𝑖𝑔ℎ𝑡
𝐸𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡𝑠 𝑤 𝐺.𝑀.𝑊
=𝐺.𝑀.𝑊/𝑥 × =𝑥
𝑀𝑜𝑙𝑒𝑠 𝑤
(ii) Oxide formation or reduction of the oxide method: Calculate the mass of metal
which combines with or displaces 8parts by mass of oxygen.
mass of element mass of element
Eq.mass = × 8 = Vol(ml)of O × 5600
mass of oxygen 2 displaced at STP
(iii) Chloride formation method: Calculate the mass of the element which combines with
or displaces 35.5parts by mass of chlorine
mass of element
Eq.mass = mass of chlorine × 35.5
(iv)Metal displacement method: When a more electropositive metal is added to displace a less
electropositive metal from its salt
(e.g Zn +CuSO4→ZnSO4+Cu)
Mass of metal added Eq.Mass of metal added
=
Mass of metal displaced Eq.Mass of metal displaced
Eq. mass of acid (RCOOH) = Eq. mass of RCOOAg – Eq. mass of Ag+ Eq. mass of H
= Eq. mass of RCOOAg – 107
Solution made up of; two components are called binary solutions, three components are
ternary solutions, four components are quaternary solutions.
The componet which is major ingredient and whose physical state is the same as that of
solution is called solvent.
CONCENTRATION TERMS
• The concentration of a solution is defined as the amount of solute present in the given
quantity of the solution (or solvent).
• Solutions containing relatively high concentration of solute are called concentrated
solutions, while those of relatively low concentrations of solute are called dilute
solutions
• Volume Percentage:isthe volume of the solute present per 100 parts by volume of
solution.
volume of solute
Volume percentage= volume of solution × 100
6
• Parts per million (ppm): It is the amount of the solute in grams present in 10 grams
of the solution.
𝑚𝑎𝑠𝑠𝑜𝑓𝑥
ppm of ‘x’=𝑚𝑎𝑠𝑠𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 × 106
• Molarity: Molarity is the number of moles of the solute present in one litre of the
solution. It is denoted by ‘M’. The units of molarity are moles/litre.
When one mole of the solute is dissolved in 1litre solution, the solution is called one
molar(or 1M) solution.
Mathematical Relations:
𝑛𝑜.𝑜𝑓𝑚𝑜𝑙𝑒𝑠𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑒 wt.of solute 1
• Molarity = = ×
𝑣𝑜𝑙𝑢𝑚𝑒𝑜𝑓𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛(𝑙𝑖𝑡𝑟𝑒𝑠) G.M.W. volume of solution (litres)
• Calculation of resultant molarity, when two or more solutions of the same substance are
mixed.
𝐌𝟏 𝐕𝟏 + 𝐌𝟐 𝐕𝟐 + 𝐌𝟑 𝐕𝟑 + … … … .
𝐌=
𝐕𝐟𝐢𝐧𝐚𝐥
M1 and V1, M2 and V2, M3 and V3 are the molarities and volumes of the individual solutions.
• When two solutions of different substance are mixed together (titrated against each
other), then
M1V1 M2V2
=
n1 n2
M1, V1, and M2, V2, are molarities and volumes of the two solutions n1 and n2 are the no. of
moles of the two substances involved.
149gm
Moles of KCl = =2
74.5gm
2
Molarity of the solution = = 0.2M
10
Ex.2: What volume of a 3.0 M HCl solution be mixed with 500 mL of a 7 M HCl
solution to prepare a HCl solution whose molarity will be 4.0?
Ex. 4: What volume of a 5.00 M H 2SO4 solution should be added to a 150 mL 1.0 M
H 2SO4 solution to obtain a solution of sulphuric acid of molarity 2.5?
Solution: It is again a case of mixing of two solutions. Let us assume that V mL of the
stock solution of H 2SO4 is added.
2.5 V = 225
225
V= = 90 mL
2.5
Ex.5: A 150 mL 0.25 M NaCl solution, 250 mL 0.45 M CaCl2 solution and a 100 mL
0.60 M AlCl3 solution are mixed together and diluted to a final volume of 750
mL by adding enough water. Determine molarity of chloride ion Cl− ( ) in solution
assuming that all three salts are completely soluble as well as completely
dissociated.
−
Solution: First we need to calculate total mmoles of Cl from the three salt solutions:
−
mmoles of Cl ion from NaCl = 37.5
−
mmoles of Cl ion from CaCl2 = 2 × mmoles of CaCl2
= 2 × 112.5 = 225
−
mmoles of Cl ion from AlCl3 = 3 × mmoles of AlCl3
= 3 60 = 180
−
Total mmoles of Cl in final solution
mmoles of Cl – 442.5
Molarity of Cl – = = = 0.59 M
mL of solution 750
Normality: It is the number of gram equivalents of the solute present in one litre of the
solution. It is denoted by ‘N’. The units of normality are gram equivalents/litre. When one gram
equivalent weight of a solute is dissolved in 1litre solution, the solution is called one normal
(1N) solution.
Mathematical Relations:
no.of moles of solute
Normality =
volume of solution (litres)
• When a solution of Normality N1 and volume V1 is diluted with a solvent to get a solution
of Normality N2 and volume V2, then, N1V1 = N2V2
• Calculation of resultant Normality, when two or more solutions of the same substance
are mixed.
N1 V1 + N2 V2 + N3 V3 + ……….
N= Vfinal
• When two solutions of different substance are mixed together (titrated against each
wt
other), then, N1V1 = N2V2 (or)G.E.W = N. V. (lit)
x -factor is basicity for acids, acidity for bases, total +ve or –ve charges for salts, change
in oxidation no. for oxidant & reductant.
5
Number of moles of urea = = 0.083
60
Ex.2: The molarity and molality of a solution are M and m respectively. If the
molecular weight of the solute is M , calculate the density of the solution in
terms of M, m and M .
Sol: Let weight of solute be w g and weight of solvent is W g and volume of solution is V mL.
w 1000
M= … (1)
M V
w 1000
m= … (2)
M W
w+W
D= … (3)
V
MMV
By Eq. (1) w = … (4)
1000
MV
W= … (5)
m
MV MMV
+ M
1
By Eq. (3) D = m 1000 D = M +
V m 1000
Where, wA and wB are the weights of A and B in grams respectively and MA and MB are the
molecular masses of A and B respectively.
The sum of the mole fractions of the components of a solution is equal to unity. In a binary
solution, mole fraction of solute + mole fraction of solvent = 1
• Formality: It is the number of formula masses in grams of the solute dissolved per litre
of the solution. It is denoted by ‘F’. It is used for ionic compounds in which there is no
existence of molecule.
Number of gram formula units of solute
Formality(F) =
Volume of solution in litres
Mass of ionic solute (g)
Formality(F) =
gram formula unit mass of solute × Volume of solution (l)
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NCERT SOLUTIONS
(c) CH4
The molecular mass of methane, CH 4:
= (1 × Atomic mass of carbon) + (4 × Atomic mass of hydrogen)
= [1(12.011 u) + 4 (1.008 u)]
= 12.011 u + 4.032 u = 16.043 u
Question 1.2: Calculate the mass per cent of different elements present in sodium
sulphate (Na2SO4).
The molecular formula of sodium sulphate is Na 2SO4
Molar mass of Na2SO4 = [(2 × 23.0) + (32.066) + 4 (16.00)] = 142.066 g
𝑚𝑎𝑠𝑠 𝑖𝑓 𝑡ℎ𝑎𝑡 𝑒𝑙𝑒𝑚𝑒𝑛𝑡 𝑖𝑛 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
Mass percent of an element = × 100
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑑
46.0𝑔
∴ Mass percent of sodium: = × 100 = 32.379 = 32.4%
142.066𝑔
32.066𝑔
Mass percent of sulphur:= × 100 = 22.57 = 22.6 %
142.066𝑔
64.0𝑔
Mass percent of oxygen: = × 100 = 45.049 = 45.05%
142.066𝑔
Question 1.3: Determine the empirical formula of an oxide of iron that has 69.9%
iron & 30.1% dioxygen by mass.
Given:
% of iron by mass = 69.9 %
% of oxygen by mass = 30.1 %
𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑖𝑟𝑜𝑛 𝑏𝑦 𝑚𝑎𝑠𝑠 69.9
Relative moles of iron in iron oxide: = = = 1.25
𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑟𝑜𝑛 55.85
𝑝𝑒𝑟𝑐𝑒𝑛𝑡𝑎𝑔𝑒 𝑜𝑓 𝑜𝑥𝑦𝑔𝑒𝑛 𝑏𝑦 𝑚𝑎𝑠𝑠 30.1
Relative moles of oxygen in iron oxide: = = = 1.88
𝑎𝑡𝑜𝑚𝑖𝑐 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑖𝑟𝑜𝑛 16.0
The simplest molar ratio of iron to oxygen: = 1.25: 1.88 = 1:1.5 = 2:3
∴ The empirical formula of the iron oxide is Fe2O3.
Question 1.4: Calculate the amount of carbon dioxide that could be produced when
(a) 1 mole of carbon is burnt in the air.
(b) 1 mole of carbon is burnt in 16 g of dioxygen.
(c) 2 moles of carbon are burnt in 16 g of dioxygen.
(a) As per the balanced equation, 1 mole of carbon burns in 1 mole of dioxygen (air) to
produce 1 mole of carbon dioxide.
(b) According to the question, only 16 g (0.5 mol) of dioxygen is available. Hence, it will
react with 0.5 moles of carbon to give 22 g of carbon dioxide. Hence, it is a limiting
reactant.
(c) Since oxygen is the limiting reactant here, the 16g (0.5 mol) of O 2 will react with 6 g of
carbon (0.5 mol) to form 22 g of carbon dioxide. The remaining 18 g of carbon (1.5 mol) will
not undergo combustion.
Question 1.5: Calculate the mass of sodium acetate (CH 3COONa) required to make
500 mL of 0.375 molars aqueous solution. The molar mass of sodium acetate is
82.0245 g mol–1.
0.375 M aqueous solution of sodium acetate ≡ 1000 mL of a solution containing 0.375 moles
of sodium acetate.
∴ A number of moles of sodium acetate in 500 mL. = 0.375/1000 x 500 = 0.1875 mole
Molar mass of sodium acetate = 82.0245 g mol–1 (Given)
∴ Required mass of sodium acetate = (82.0245 g mol –1) (0.1875 mole) = 15.38 g
Question 1.6: Calculate the concentration of nitric acid in moles per litre in a
sample that has a density, 1.41 g mL –1, and the mass percent of nitric acid in it
being 69%.
The mass percent of nitric acid in the sample = 69 % (Given)
Thus, 100 g of nitric acid contains 69 g of nitric acid by mass.
Molar mass of nitric acid (HNO 3): = [1 +14 + 3(16)] g mol–1 = 1 +14 + 48 = 63 g mol–1
69𝑔
∴ Number of moles in 69 g of HNO 3 = = 1.095 mol
63𝑔𝑚𝑜𝑙 −1
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 100𝑔
The volume of 100 g of nitric acid solution = =
𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1.41𝑔𝑚𝑜𝑙−1
= 70.92 mL ≡ 70.92 x 10-3 L
1.095 𝑚𝑜𝑙𝑒
The concentration of nitric acid:= 𝐿 = 15.44 mol/L
70.92 × 10−3
∴ Concentration of nitric acid = 15.44 mol/L
Question 1.7: How much copper can be obtained from 100 g of copper sulphate
(CuSO4)?
1 mole of CuSO4 contains 1 mole of copper.
Molar mass of CuSO4 = (63.5) + (32.00) + 4(16.00) = 63.5 +32.00 + 64.00 = 159.5 g
159.5 g of CuSO4 contains 63.5 g of copper.
63.5 ×100𝑔
⇒ 100 g of CuSO4 will contain of copper.
159.5
63.5 ×100𝑔
∴ Amount of copper that can be obtained from 100 g CuSO 4 = = 39.81
159.5
Question 1.8: Determine the molecular formula of an oxide of iron in which the mass
per cent of iron and oxygen are 69.9 and 30.1, respectively. Given that the molar
mass of the oxide is 159.69 g mol –1.
► Mass percent of iron (Fe) = 69.9% (Given)
► Mass percent of oxygen (O) = 30.1% (Given)
► Number of moles of iron present in the oxide = 69.90/55.85 = 1.25
► Number of moles of oxygen present in the oxide = 30.1/16.0 = 1.88
► The ratio of iron to oxygen in the oxide: 1.25 : 1.88
1.25 1.88
= ∶ = 1: 15 = 2 ∶ 3
1.25 1.25
The empirical formula of the oxide is Fe 2O3.
Empirical formula mass of Fe 2O3 = [2(55.85) + 3(16.00)] g
Molar mass of Fe2O3 = 159.69 g
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 159.69𝑔
So, 𝑛 = 𝑒𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑚𝑎𝑠𝑠 = = 0.999 = 1(𝑎𝑝𝑝𝑟𝑜𝑥)
159.7𝑔
Molecular formula of a compound is obtained by multiplying the empirical formula with n.
Thus, the empirical formula of the given oxide is Fe 2O3 and n is 1.
Hence, the molecular formula of the oxide is Fe 2O3.
Question 1.9: Calculate the atomic mass (average) of chlorine using the
following data:
% Natural Abundance Molar Mass
35
Cl 75.77 34.9689
37
Cl 24.23 36.9659
Question 1.11: What is the concentration of sugar (C 12H22O11) in mol L–1 if its 20 g
are dissolved in enough water to make a final volume up to 2 L?
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑢𝑔𝑎𝑟/𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑢𝑔𝑎𝑟
Molarity (M) of a solution is given by: = =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒𝑠 2𝐿
Question 1.13: The pressure is determined as force per unit area of the surface.
an SI unit of pressure, Pascal is as shown below:
• 1 Pa = 1 N m –2
If the mass of air at sea level is 1034 g cm –2, calculate the pressure in Pascals.
The pressure is defined as a force acting per unit area of the surface.
P = F/A
1034𝑔×9.8 𝑚𝑠−1 1𝐾𝑔 (100)2 𝑐𝑚2
= × 1000𝑔 × = 1.01332 × 105 kg m-1 s-2
𝑐𝑚2 1𝑚2
We know, 1 N = 1 kg ms–2
Then,
1 Pa = 1 N m–2 = 1 kg m–2s–2
1 Pa = 1 kg m1–s2–
Question 1.19: How many significant figures are present in the following?
(a) 0.0025
(b) 208
(c) 5005
(d) 126,000
(e) 500.0
(f) 2.0034
(a) 0.0025, there are 2 significant figures.
(b) 208, there are 3 significant figures.
(c) 5005, there are 4 significant figures.
(d) 126,000, there are 3 significant figures.
(e) 500.0, there are 4 significant figures.
(f) 2.0034, there are 5 significant figures.
Question 1.21: The following data are obtained when dinitrogen and dioxygen react
together to form different compounds:
Mass of dinitrogen Mass of dioxygen
(i) 14 g 16 g
(ii) 14 g 32 g
(iii) 28 g 32 g
(iv) 28 g 80 g
(a) Which law of chemical combination is obeyed by the above experimental data?
Give its statement.
(b) Fill in the blanks in the following conversions:
(i) 1 km = ........... mm = ........... pm
(ii) 1 mg = ........... kg = ........... ng
(iii) 1 ml = ........... l = ........... dm3
(a) If we fix the mass of dinitrogen at 28 g, then the masses of dioxygen that will combine
with the fixed mass of dinitrogen are 32 g, 64 g, 32 g, and 80 g.
The masses of dioxygen bear a whole number ratio of 1:2:2:5. Hence, the given
experimental data obeys the law of multiple proportions.
The law states that if two elements combine to form more than one compound, then the
masses of one element that combines with the fixed mass of another element are in the
ratio of small whole numbers.
(b) (i) 1 km = 1 km × 1000 m/1 km × 100 cm/1m × 10 mm/1cm
⇒ 1 km = 106 mm
⇒ 1 km = 1 km × 1000 m/1 km × 1 pm/10-12 m
⇒ 1 km = 1015 pm
Hence, 1 km = 106 mm = 1015 pm
(ii) 1 mg = 1 mg × 1 g/1000 mg × 1 kg/1000 g
⇒ 1 mg = 10-6 kg
⇒ 1 mg = 1 mg × 1 g/ 1000 mg × 1 mg/ 10-9 g 1
⇒ 1 mg = 106 ng
Hence, 1 mg = 10–6 kg = 106 ng
(iii) 1 mL = 1 mL × 1 L/1000 mL
⇒ 1 mL = 10–3 L
⇒ 1 mL = 1 cm3
1𝑑𝑚 × 1𝑑𝑚 × 1𝑑𝑚
= 1𝑐𝑚3 × = 1𝑚𝑙 = 10−3 𝑑𝑚3
10𝑐𝑚 × 10𝑐𝑚 × 10𝑐𝑚
= 1𝑚𝑙 = 10−3 𝐿 = 10−3 𝑑𝑚3
Question 1.22: If the speed of light is 3.0 × 10 8 ms-1, calculate the distance
covered by light in 2.00 ns.
According to the question:
Time taken to cover the distance = 2.00 ns = 2.00 × 10 –9 s
Speed of light = 3.0 × 10 8 ms–1
Distance travelled by light in 2.00 ns:
= Speed of light × Time taken
= (3.0 × 108 ms –1) (2.00 × 10–9 s)
= 6.00 × 10–1 m = 0.600 m
Question 1.24: Dinitrogen and dihydrogen react with each other to produce ammonia
according to the following chemical equation:
N2(g) + H2(g) → 2NH3(g)
(a) Calculate the mass of ammonia produced if 2.00 × 10 3 g dinitrogen reacts with
1.00 × 103 g of dihydrogen.
(b) Will any of the two reactants remain unreacted?
(c) If yes, which one and what would be its mass?
(a) Balancing the given chemical equation, N2(g) + H2(g) → 2NH3(g)
From the equation, 1 mole (28 g) of dinitrogen reacts with 3 mole (6 g) of dihydrogen to
give 2 mole (34 g) of ammonia.
⇒ 2.00 × 103 g of dinitrogen will react with 6 g/28 g × 2.00 x 103 g dihydrogen i.e., 2.00 ×
103 g of dinitrogen will react with 428.6 g of dihydrogen.
Given,
Amount of dihydrogen = 1.00 × 10 3 g
Hence, N2 is the limiting reagent. 28 g of N 2 produces 34 g of NH3.
Hence, mass of ammonia produced by: 2000 g of N2 = 34 g/28 g × 2000g = 2428.57 g
(b) N2 is the limiting reagent and H 2 is the excess reagent. Hence, H 2 will remain
unreacted.
Question 1.25: How are 0.50 mol Na 2CO3 and 0.50 M Na 2CO3 different?
Molar mass of Na2CO3 = (2 × 23) +12.00 + (3 × 16) = 106 g mol –1
Now, 1 mole of Na2CO3 means 106 g of Na2CO3.
106𝑔
⇒ 0.5 mol of Na2CO3 = × 0.5 𝑚𝑜𝑙𝑒 𝑜𝑓 𝑁𝑎2 𝐶𝑂3 = 53 g Na2CO3
1 𝑚𝑜𝑙𝑒
⇒ 0.50 M of Na2CO3 = 0.50 mol/L Na2CO3
Hence, 0.50 mol of Na2CO3 is present in 1 L of water or 53 g of Na 2CO3 is present in 1 L of
water.
Question 1.26: If ten volumes of dihydrogen gas react with five volumes of dioxygen
gas, how many volumes of water vapour would be produced?
Reaction of dihydrogen with dioxygen can be written as: 2H2(g) + O2(g) → 2H2O(g)
Now, two volumes of dihydrogen react with one volume of dihydrogen to produce two
volumes of water vapour.
Hence, ten volumes of dihydrogen will react with five volumes of dioxygen to produce ten
volumes of water vapour.
Question 1.28: Which one of the following will have largest number of atoms?
(a) 1 g Au (s)
(b) 1 g Na (s)
(c) 1 g Li (s)
(d) 1 g of Cl2(g)
Question 1.29: Calculate the molarity of a solution of ethanol in water in which the
mole fraction of ethanol is 0.040 (assume the density of water to be one).
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶 𝐻 𝑂𝐻
Mole fraction of C2H5OH = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
2 5
𝐶𝐶2𝐻5 𝑂𝐻
0.040 = … … … … … … . . (1)
𝑛𝐶2𝐻5 𝑂𝐻 + 𝑛𝐻2 𝑂
1000𝑔
Number of moles present in 1 L water:𝑛𝐻2 𝑂 = 18𝑔 𝑚𝑜𝑙−1 = 55.55 𝑚𝑜𝑙
Substituting the value of 𝑛𝐻2 𝑂 in equation (1)
𝑛𝐶2𝐻5 𝑂𝐻
= 0.040
𝑛𝐶2 𝐻5 𝑂𝐻 + 55.55
0.96𝑛𝐶2𝐻5 𝑂𝐻 = 2.222𝑚𝑜𝑙
2.222
𝑛𝐶2 𝐻5 𝑂𝐻 = 𝑚𝑜𝑙 = 2.314𝑚𝑜𝑙
0.96
2.314𝑚𝑜𝑙
∴ 𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = = 2.214𝑀
1𝐿
Question 1.30: What will be the mass of one 12C atom in g?
1 mole of carbon atoms = 6.023 × 10 23 atoms of carbon = 12 g of carbon
Mass of one 12C atom = 12 g/6.022 × 10 23 = 1.993 × 10–23 g.
Question 1.31: How many significant figures should be present in the of the
following calculations?
𝟎.𝟎𝟐𝟖𝟓𝟔×𝟐𝟗𝟖.𝟏𝟓×𝟎.𝟏𝟏𝟐
(a)
𝟎.𝟓𝟕𝟖𝟓
(b) 5 × 5.364
(c) 0.0125 + 0.7864 + 0.0215
𝟎.𝟎𝟐𝟖𝟓𝟔×𝟐𝟗𝟖.𝟏𝟓×𝟎.𝟏𝟏𝟐
(a)
𝟎.𝟓𝟕𝟖𝟓
Least precise number of calculations = 0.112
Number of significant figures in the Ans = Number of significant figures in the least
precise number = 3
(b) 5 × 5.364
Least precise number of calculations = 5.364
Number of significant figures in the Ans = Number of significant figures in 5.364 = 4
(c) 0.0125 + 0.7864 + 0.0215
Since the least number of decimal places in each term is four, the number of significant
figures in the Ans: is also 4.
Question 1.32: Use the data given in the following table to calculate the molar mass
of naturally occurring argon isotopes:
Isotope Isotopic molar mass Abundance
36
Ar 35.96755 gmol–1 0.337%
38
Ar 37.96272 gmol–1 0.063%
40
Ar 39.9624 gmol–1 99.600%
0.337 0.063 90.60
Molar mass of argon: = [(35.96755 × ) + (37.96272 × ) + (39.9624 × )]
100 100 100
= [0.121 + 0.024 + 39.802] 𝑔𝑚𝑜𝑙 −1 = 39.947 g mol–1
6.022×1023 ×52
52𝑔 𝑜𝑓 𝐻𝑒 = 𝑎𝑡𝑜𝑚𝑠 𝑜𝑓 𝐻𝑒 = 7.8286 × 1024 atoms of He.
4
Question 1.34: A welding fuel gas contains carbon and hydrogen only. Burning a
small sample of it in oxygen gives 3.38 g carbon dioxide, 0.690 g of water and no
other products. A volume of 10.0 L (measured at STP) of this welding gas is found
to weigh 11.6 g.
Calculate:
(a) Empirical formula
(b) Molar mass of the gas
(c) Molecular formula
a) 1 mole (44 g) of CO2 contains 12 g of carbon.
3.38 g of CO2 will contain carbon = 12 g/44 g × 3.38 g = 0.9217 g
18 g of water contains 2 g of hydrogen. = 2 g/18 g × 0.690
0.690 g of water will contain hydrogen = 0.0767 g
Since carbon and hydrogen are the only constituents of the compound, the total mass of
the compound is: = 0.9217 g + 0.0767 g = 0.9984 g
Percent of C in the compound = 0.9217 g/0.9984 × 100 = 92.32%
Percent of H in the compound = 0.0767 g/0.9984 × 100 = 7.68%
Moles of carbon in the compound = 92.32/12.00 = 7.69
Moles of hydrogen in the compound = 7.68
∴ Ratio of carbon to hydrogen in the compound = 7.69 : 7.68 = 1: 1
Hence, the empirical formula of the gas is CH.
(b) Given,
Weight of 10.0 L of the gas (at S.T.P) = 11.6 g
11.6𝑔
∴ Weight of 22.4 L of gas at STP = × 22.4𝐿 = 25.984 g≈ 26 g.
10.0𝐿
Hence, the molar mass of the gas is 26 g.
(c) Empirical formula mass of CH = 12 + 1 = 13 g
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑔𝑎𝑠
𝑛 = 𝑒𝑚𝑝𝑖𝑟𝑖𝑐𝑎𝑙 𝑓𝑜𝑟𝑚𝑢𝑙𝑎 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑔𝑎𝑠 = 26 g/13 gn = 2
Molecular formula of gas = (CH) = C 2H2
Question 1.35: Calcium carbonate reacts with aqueous HCl to give CaCl 2 and
CO2 according to the reaction,
CaCO3(s) + 2HCl(aq) → CaCl2(aq) + CO2(g) + H2O(l)
What mass of CaCO3 is required to react completely with 25 mL of 0.75 M HCl?
0.75 M of HCl ≡ 0.75 mol of HCl are present in 1 L of water
≡ [(0.75 mol) × (36.5 g mol–1)] HCl is present in 1 L of water
≡ 27.375 g of HCl is present in 1 L of water
Thus, 1000 mL of solution contains 27.375 g of HCl.
Amount of HCl present in 25 mL of solution = 27.375 g/1000 mL × 25 mL = 0.6844 g
EXEMPLER PROBLEMS
(i) Results of both the students are neither accurate nor precise.
(ii) Results of student A are both precise and accurate.
(iii) Results of student B are neither precise nor accurate.
(iv) Results of student B are both precise and accurate.
Solution:
For both the students, average value is close to the correct value. Hence, readings of both
are accurate. But readings of student A are also close to each other (differ only by 0.02)
and also close to the average value, hence readings of A are also precise. But readings of B
are not close to each other (differ by 0.1) and hence are not precise. Thus, results of
student A are both precise and accurate.
2. A measured temperature on Fahrenheit scale is 200 °F. What will this reading be on
Celsius scale?
(i) 40 °C (ii) 94 °C (iii) 93.3 °C (iv) 30 °C
Solution:
3. What will be the molarity of a solution, which contains 5.85 g of NaCl(s) per 500 mL?
(i) 4 mol L–1
(ii) 20 mol L–1
(iii) 0.2 mol L–1
(iv) 2 mol L–1
Solution:
5. The number of atoms present in one mole of an element is equal to Avogadro number.
Which of the following element contains the greatest number of atoms?
(i) 4g He (ii) 46g Na (iii) 0.40g Ca (iv) 12g He
7. What will be the molality of the solution containing 18.25 g of HCl gas in 500 g of
water?
(i) 0.1 m
(ii) 1 M
(iii) 0.5 m
(iv) 1 m
11. If the density of a solution is 3.12 g mL-1, the mass of 1.5 mL solution in significant
figures is _______.
(i) 4.7g
(ii) 4680 × 10-3 g
(iii) 4.680g
(iv) 46.80g
Sol: (a) Density of solution = 3.12 g mL-1
Volume of solution =1.5 mL
Mass of solution = Volume x Density
= 1.5 mL x 3.12 g mL-1 = 4.68 g = 4.7 g (up to 2 significant figures)
32 : 16 or 2 : 1 to each other.
This is an example of law of multiple proportion.
2. How many significant figures should be present in the answer of the following
2.5×1.25×3.5
calculations?
2.01
6. 45.4 L of dinitrogen reacted with 22.7 L of dioxygen and 45.4 L of nitrous oxide was
formed. The reaction is given below:
2N2(g) + O2(g) → 2N2O(g)
Which law is being obeyed in this experiment? Write the statement of the law?
Sol: Gases are reacting together to form gaseous products. Ratio of volumes of gases:
N2: 02: N20 = 45.4 : 22.7 : 45.4 =2:1:2
Which is a simple whole number ratio. Hence the experiment proves Gay- Lussac’s law
of gaseous volumes. This law states that gases combine or are produced in a chemical
reaction in a simple whole number ratio by volume provided that all gases are at the
same temperature and pressure.
7. If two elements can combine to form more than one compound, the masses of one
element that combine with a fixed mass of the other element, are in whole number
ratio.
Masses of oxygen (16 and 32) which combine with fixed mass of hydrogen (2) are in
the ratio of 16 : 32 or 1 : 2
8. Calculate the average atomic mass of hydrogen using the following data:
9. Hydrogen gas is prepared in the laboratory by reacting dilute HCl with granulated zinc.
Following reaction takes place.
Zn + 2HCl → ZnCl2 + H2
Calculate the volume of hydrogen gas liberated at STP when 32.65 g of zinc reacts
with HCl. 1 mol of a gas occupies 22.7 L volume at STP; atomic mass of Zn = 65.3 u.
Sol: Given that, mass of Zn = 32.65 g
1 mole of gas occupies = 22.7 L volume at STP Atomic mass of Zn = 65.3u
The given equation is
10. Density of 3 molal solution of NaOH is 1.110 g mL-1. Calculate the molarity of solution.
Sol: 3 molal solution of NaOH means 3 moles of NaOH is dissolved in 1000 g of water.
But 3 moles of NaOH = 3 x 40 g = 120 g
120 g = 1120 g
11. Volume of a solution changes with change in temperature, then, will the molality of
the solution be affected by temperature? Give reason for your answer.
Sol: No, molality of a solution does not change with temperature since mass remains
unaffected by temperature.
13. The reactant which is entirely consumed in reaction is known as limiting reagent. In
the reaction 2A + 4B → 3C + 4D, when 5 moles of A react with 6 moles of B, then
(i) which is the limiting reagent?
(ii) calculate the amount of C formed?
2. Assertion (A) : One atomic mass unit is defined as one twelfth of the mass of one
carbon-12 atom.
Reason (R) : Carbon-12 isotope is the most abundunt isotope of carbon and has been
chosen as standard.
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) Both A and R are false.
Sol: (b) 1 amu = —1/12 Mass of one C12 atom
C12 isotope is considered as standard for defining the atomic and molecular mass.
2. Calcium carbonate reacts with aqueous HCl to give CaCl2 and CO2 according to the
reaction given below:
CaCO3 (s) + 2HCl (aq) → CaCl2(aq) + CO2(g) + H2O(l)
What mass of CaCl2 will be formed when 250 mL of 0.76 M HCl reacts with 1000 g of
CaCO3 ? Name the limiting reagent. Calculate the number of moles of CaCl2 formed in
the reaction.
Since HCl on complete consumption gives lesser amount of product hence HC1 will be
limiting reagent and the number of moles of CaCl2 formed will be 0.095 mol.
3. Define the law of multiple proportions. Explain it with two examples. How does this law
point to the existence of atoms?
Sol: Law of multiple proportions: When two elements combine to form two or more
chemical compounds, then the masses of one of the elements which combine with a
fixed mass of the other, bear a simple ratio to one another, e.g., carbon combines with
oxygen to form two compounds, namely, carbon dioxide and carbon monoxide.
The masses of oxygen which combine with a fixed mass of carbon in C02 and CO are 32
and 16 respectively. These masses of oxygen bear a simple ratio of 32 : 16 or 2 : 1 to
each other. For example, sulphur combines with oxygen to form two compounds,
namely, sulphur trioxide and sulphur dioxide.
The masses of oxygen which combine with a fixed mass of sulphur in S03 and S02 are
48 and 32 respectively. These masses of oxygen bear a simple ratio of 48 : 32 or 3 : 2
to each other. This law shows that there are constituents which combine in a definite
proportion. These constituents may be atoms. Thus, the law of multiple proportions
shows the existence of atoms which combine to form molecules.
4. A box contains some identical red coloured balls, labelled as A, each weighing 2 grams.
Another box contains identical blue coloured balls, labelled as B, each weighing 5
grams. Consider the combinations AB, AB2, A2B and A2B3 and show that law of multiple
proportions is applicable.
Sol:
Combination of A and B AB ab2 A, B A2B3
Mass of A (in g) 2 2 4 4
Mass of B (in g) 5 10 5 15
Q.4. Why do we regard the gaseous state of water as vapours while that of
ammonia as gas?
Ans. Only the gaseous states of those substances are regarded as vapours which are
liquid at room temperature. Since water is a liquid, its gaseous state is called vapours.
However, the gaseous state of ammonia is called gas because it is not a liquid at room
temperature.
Q.6. Mixture of salt & water is a solution while that of oil & water is not. Explain.
Ans. Solution is a homogeneous mixture of two or more components. The mixture of salt
and water is generally homogeneous. Therefore, it is a solution. Oil and water on the
other hand, form a heterogeneous or immiscible mixture. Therefore, it is not a solution.
Q.11. What is the difference between the mass of a molecule and molecular mass?
Ans. Mass of a molecule is that of a single molecule also known as its actual mass. But
molecular mass is the mass of Avogadro's number (6.022 × 10 23) of molecules.
Q.13. Does one gram mole of a gas occupy 22.4 L under all conditions of
temperature and pressure?
Ans. No, one gram mole of a gas occupies 22.4 L only under N.T.P. or S.T.P. conditions,
i.e. at 273 K temperature and under 760 mm pressure. If these conditions are not used,
then the volume is not 22.4 L.
Q.14. What is the basic difference between empirical and molecular formulae?
Ans. Empirical formula gives the simplest ratio of the atoms of different elements in
the molecule of a substance but the molecular formula gives their actual ratio.
Q.15. The percentages of all the elements present in a compound are 92. What
does it indicate?
Ans. This indicates that the compound contains in it oxygen also and its percentage is
(100 - 92) = 8.
Q.19. Classify the following substances into elements, compounds and mixtures : (i)
Milk (ii) 22-carat gold (iii) Iodized table salt (iv) Diamond (v) Smoke (vi) Steel (vii)
Brass (viii) Dry ice (ix) Mercury (x) Air (xi) Aerated drinks (xii) Glucose (xiii)
Petrol/Diesel/Kerosene oil (xiv) Steam (xv) Cloud.
Ans. Elements - (iv), (ix) Compounds - (viii), (xii), (xiv), (xv) Mixtures - (i), (ii), (iii), (v),
(vi), (vii), (x), (xi), (xiii).
Q.21. What physical quantities are represented by the following units and what are
their most common names?
(i) kgms −2
(ii) kgm 2s−2
(iii) dm 3
Ans.
(i) Force (newton)
(ii) Work (joule)
(iii) Volume (no special name).
Q.23. Given that density of water is 1gmL −1. What is its density in kgm −3?
Ans.
= 1000 kg m -3
Q.24. What is the difference between the following?
(i) 2⋅5 × 103 g and 2⋅50 × 103g
(ii) 160 cm and 160.0 cm.
Ans.
(i) 2⋅5 × 103g has two significant figures while 2⋅50 × 103g has three significant figures.
Hence, 2⋅50×103g represents greater accuracy than 2⋅5×103.
(ii) 160 has three significant figures while 160.0 has four significant figures. Hence,
160.0 represents greater accuracy.
Q.26. Is the law of constant composition true for all types of compounds? Explain
why or why not.
Ans. No, law of constant composition is not true for all types of compounds. It is true
only for the compounds obtained from one isotope. For example, carbon exists in two
common isotopes, 12C and 14C. When it forms CO 2 from 12C, the ratio of masses is 12 : 32
= 3 : 8 but from 14C, the ratio will be 14 : 32 = 7 : 16 which is not same as in the first
case.
Q.27. 1 L of a gas at S.T.P. weighs 1.97 g. What is the vapour density of the
gas?
Ans. 22.4 L of the gas at S.T.P. will weigh = 1.97 × 22.4g = 44.1 g , i.e., molecular mass =
44.1. Hence, vapour density = 44.1/2 = 22.05.
Q.28. What is the difference in the molar volume of a gas if S.T.P. conditions are
(i) 1 atm,0 ∘ C
(ii)1 bar,0 ∘ C?
Ans.
(i) If S.T.P. conditions are 1 atm, 0 ∘C molar volume = 22400 cm 3
(ii) If S.T.P. conditions are 1 bar, 0 ∘C, molar volume = 22700 cm 3
Q.30. Why are the atomic masses of most of the elements fractional?
Ans. This is because atomic masses are the relative masses of atoms as compared with
an atom of C-12 isotope taken as 12.
Q.31. What is die difference between the mass of a molecule and gram molecular
mass?
Ans. Mass of a molecule is the actual mass of a single molecule expressed in grams
whereas gram molecular mass is the mass in gram of Avogadro's number of molecules.
Q.33. Write the formulae and names of three compounds containing same
percentage composition of C, H and O.
Ans. Compounds with the same percentage composition of C, H and O will have the same
empirical formula. The compounds with the empirical formula CH 2O can be
Q.34. Determine the equivalent weight of each of the following compounds assuming
the formula weights of these compounds are x, y and z respectively.
(i) Na 2SO4
(ii) Na 3PO4.12H2O
(iii) Ca 3(PO4)2
Ans.
Eq wt = Mol. wt/Total positive valency of metal atoms
(i) x/2
(ii) y/3
(iii) z/6
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Q2 - Calculate the molar volume of water at 273 K (density of water = 1.00 g/cm3).
(1 Mark)
(5 Marks)
Q4 - A solution is prepared by dissolving 5.85g of NaCl in 90g of H2O. Find mole fraction of NaCl and
H2O.
(3 Marks)
Q5 - Find the molarity of solution prepared by dissolving 7.1g of Na2SO4 in 100ml of aqueous solution.
(3 Marks)
(2 Marks)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -03 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.
(2 Marks)
Q3 - On complete combustion 0.858 g of compound (x) gives 2.63 g of CO2 and 1.27g of H2O. Calculate
the empirical formula of the compound.
(5 Marks)
13
Q5 - Solve the following and express the answer in standard exponential form (2.0 x 10 ) +
(1.5 x 10 14).
(1 Mark)
Q6 - (i) How many moles of sulphur will be produced when 2 moles of H2S reacts with 11.2L of SO2 at
NTP.
(ii) Name the limiting reagent in the above reaction.
(2 Marks)
(1 Mark)
Q8 -A car consumes 30 moles per gallon of gasoline and drives 12000 miles per year. Calculate the
amount of oxygen required to run the car for one year.
[Assume that octane (C8H18) is the main component of the gasoline.]
(3 Marks)
Q9 -The mass of an empty beaker is 50.55g. The mass of a same beaker when filled completely with a
liquid is 150.457g. If the volume of the empty glass is 100.2ml, calculate the density of the liquid.
Express the answer in appropriate significant figures.
(3 Marks)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -03 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.
(2 Marks)
Q3 - On complete combustion 0.858 g of compound (x) gives 2.63 g of CO2 and 1.27g of H2O. Calculate
the empirical formula of the compound.
(5 Marks)
13
Q5 - Solve the following and express the answer in standard exponential form (2.0 x 10 ) +
(1.5 x 10 14).
(1 Mark)
Q6 - (i) How many moles of sulphur will be produced when 2 moles of H2S reacts with 11.2L of SO2 at
NTP.
(ii) Name the limiting reagent in the above reaction.
(2 Marks)
(1 Mark)
Q8 -A car consumes 30 moles per gallon of gasoline and drives 12000 miles per year. Calculate the
amount of oxygen required to run the car for one year.
[Assume that octane (C8H18) is the main component of the gasoline.]
(3 Marks)
Q9 -The mass of an empty beaker is 50.55g. The mass of a same beaker when filled completely with a
liquid is 150.457g. If the volume of the empty glass is 100.2ml, calculate the density of the liquid.
Express the answer in appropriate significant figures.
(3 Marks)
2011-2012
……………………………………………………………………………………………………..
Q3. What is the length in centimeters of a glass rod 7.82 inches long ? 1M
Q11. Carbon and oxygen are known to form two compounds. The carbon content in
one of these is 42.9% while in the other it is 27.3%. Show that this data is in
Q12. A fluoride of oxygen was prepared by mixing oxygen and fluorine in the proper
ratio at 60K. This compound contains 32.1 % F and 67.9 % O. What is the
Q14. Calculate the molarity of a solution of ethanol in water in which the mole
Q15. Define the following (i) Molarity (ii) Molality (iii) Molefraction 3M
Q17. (a) How many significant figures are there in (i) 202.50 (ii) 9.78 x 10-24
(iii) 29.6 ?
Q18. Calculate (i) the molality of the solution (ii) the mole fraction of sugar. 3M
Q2 -Calculate the mass of CaCO3 which is required to react with 25 ml of 0.75 M HCl.
(5 Marks)
Q3 - During preparation of ammonia by Haber’s process 30 L of H2 and 30 L of N2 are mixed. The yield
of NH3was 50%. Find the composition of gaseous mixtures.
(3 Marks)
Q4 -Potassium bromide (KBr) contains 32.9% potassium by mass. If 6.40 g of Br2 is made to react with
3.60 g of potassium, find the actual mass of potassium which reacts with bromine.
(2 Marks)
-22
Q5 - One atom of an element weighs 1.8 x 10 g . What is the atomic mass of element?
(1 Mark)
Q6 -Chlorophyll contains 2.7% of Magnesium by mass.The number of magnesium atoms present in
4.00g of chlorophyll is
(3 Marks)
(1 Mark)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -01 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.
Q2 -Calculate the mass of CaCO3 which is required to react with 25 ml of 0.75 M HCl.
(5 Marks)
Q3 - During preparation of ammonia by Haber’s process 30 L of H2 and 30 L of N2 are mixed. The yield
of NH3was 50%. Find the composition of gaseous mixtures.
(3 Marks)
Q4 -Potassium bromide (KBr) contains 32.9% potassium by mass. If 6.40 g of Br2 is made to react with
3.60 g of potassium, find the actual mass of potassium which reacts with bromine.
(2 Marks)
-22
Q5 - One atom of an element weighs 1.8 x 10 g . What is the atomic mass of element?
(1 Mark)
Q6 -Chlorophyll contains 2.7% of Magnesium by mass.The number of magnesium atoms present in
4.00g of chlorophyll is
(3 Marks)
(1 Mark)
XI Chemistry Worksheet
Time: 30 min Ch#1 : Some Basic Concepts of Chemistry -02 Full Marks: 20
Instructions:
1. All questions are compulsory.
2. Please give the explanation for the answer where applicable.
Q2 - Calculate the molar volume of water at 273 K (density of water = 1.00 g/cm3).
(1 Mark)
(5 Marks)
Q4 - A solution is prepared by dissolving 5.85g of NaCl in 90g of H2O. Find mole fraction of NaCl and
H2O.
(3 Marks)
Q5 - Find the molarity of solution prepared by dissolving 7.1g of Na2SO4 in 100ml of aqueous solution.
(3 Marks)
(2 Marks)
CHEMICAL EQUILIBRIUM
INTRODUCTION:
Equilibrium is a state in which there are no observable changes as time goes by.
When a chemical reaction has reached the equilibrium state, the concentrations of
reactants and products remain constant over time and there are no visible changes
in the system.However, there is much activity at the
molecular level because reactant molecules continue to from
product molecules while product molecules react to yield
reactant molecules. This dynamic situation is the subject of this chapter.
Some examples for equilibrium systems are
N2 + 3H2 2NH3 + 23 k cal
2SO2 + O2 2SO3 + 45 k cal
N2 + O2 + 43.2 k cal 2NO
PCl5 + 10 k cal PCl3 + Cl2
2HI + 5 k cal H2 + I2
1. Irreversible Reactions:
The chemical reactions in which the products formed do not combine to give back the
reactants are known as irreversible reaction.
Properties of irreversible reactions
• Reactions in which reactant react to form product only.
• Reactions proceed in one single direction.
• Always proceed to completion.
• In this type of reactions, if product is gaseous in state, then they can escape
from reacting site and if they are solid in state they will precipitate.
• Reaction in which one of product is a gas,
e.g.2 H+ (aq) + Mg (s) ⎯→ Mg2+ (aq) + H2 (g)
• Reaction in which one of product is a precipitate,
CHEMICAL EQUILIBRIUM (FULLY SOLVED) FOR CBSE (IIT-JEE) EXAMS (2021 - 2022)
e.g.Ag+ (aq) + Cl− (aq) ⎯→ AgCl (s)
• Reaction in which one of the product is a weak electrolyte,
e.g.H+ (aq) + OH− (aq) ⎯→ H2O (l)
• Reaction in which a large amount of energy is released,
e.g. CH4 (g) + 2 O2 (g) ⎯→ CO2 (g) + 2 H2O (l)
Examples:
a. Thermal decomposition in open vessel. 2KClO3 ⟶ 2KCl + 3O2
b. All the neutralization reaction of strong acid and strong base.
NaOH + HCl ⟶ NaCl + H2 O
c. Ionic precipitation reaction. AgNO3 + NaCl ⟶ AgCl + NaNO3
d. Oxidation-reduction reactionSnCl2 + 2FeCl2 ⟶ SnCl4 + 2FeCl2
2. Reversible Reactions:
The reactions in which the products can react with one another to give back the
reactants again under suitable conditions called as reversible reaction.
R1 + R2 P1 + P2
Re ac tan ts Pr oducts
3 Do not attain equilibrium state. 3 Attain the equilibrium state and never go to completion.
4 Such reactions are represented by single arrow {→} 4 Represented by double arrow ( ) or ( )
5 Examples – 5 Examples :–
(a) Precipitation reactions e.g. (a) Homogeneous reactions- only one phase is present
NaCl(aq) + AgNO3(aq) → NaNO3(aq) + AgCl (i) Gaseous phase–
(b) Neutralization reactions e.g H2(g) + I2(g) 2HI(g)
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O N2(g) + O2(g) 2NO(g) [Birkland eyde process (HNO3)]
(c) 2KClO3 (s) ⎯⎯→ 2KCl(s) + 3O2(g) N2(g) + 3H2(g) 2NH3(g) (Haber’s process)
(d) Reactions in open vessel :– (ii) Liquid phase
Even a reversible reaction will become irreversible if it is CH3 COOH(l) + C2H5OH(l) CH3COOC2H5(l)+ H2O(l)
carried out in open vessel. Ex. Heterogeneous reactions– More than one phases are present
CaCO3(s) CaO(s) + CO2(g) Open CaCO 3 (s) CaO(s) + CO 2 (g)
NH4HS(s) NH3(g) + H2S(g) vessel (b) NH4HS(s) NH3(g) + H2S(g) Closed
vessel
State of Equilibrium
In general, reactions (physical and chemical) do not proceed to completion when they
are carried out in a closed container. Consider vaporization of water, in closed
vessel
𝐋𝐢𝐪𝐮𝐢𝐝 𝐰𝐚𝐭𝐞𝐫 ⇌ 𝐖𝐚𝐭𝐞𝐫 𝐯𝐚𝐩𝐨𝐮𝐫
• At any temperature, vaporization of water takes place, initially the concentration
of water is much greater than the concentration of vapour, but with the progress
of time, concentration of vapour increases whereas that of water remains constant
or
So, state of chemical equilibrium in a reversible reaction at which both forward and
backward reactions occur of the same speed.
Classification of equilibrium:
A. Equilibrium in Physical Process:
1. Solid Liquid equilibrium: Some amount of ice& water are taken in a thermo flask.
Exp- H2 O(s) ⇌ H2 O(L)
When temperature remains constant, the mass of ice & water remains constant.
Some liquid molecules adhere to ice and simultaneously some molecules of ice enter
into liquid. The no. of molecules of water forming ice &no. of molecules of ice
forming water are same i.e., equilibrium is attained.So, no change in mass of ice &
water.
The temperature at which the solid & the liquid phase are at equilibrium at
atmospheric pressure is called freezing point.
2. Liquid Vapour equilibrium:-Liquid water is taken in closed vessel at room temp, it
starts evaporating.
Equilibrium Constant(K)
aA + bB cC + dD
we have
rf = Rate of forward reaction [A]a [B]b
rb = Rate of backward reaction [C]c [D]d.
Let k f be the rate constant for the forward reaction and kb be that for the
backwardreaction. Then,
rf = k f [A]a [B]b; rb = kb [C]c [D]d.
At equilibrium, rf = rb
k
K = f =
Cc Dd .
kb A a Bb
This expression is the law of chemical equilibrium.
kf
K = , is the equilibrium constant.
kb
When the active masses of reactants & products are expressed in molar
concentration, the equilibrium constant is represented as Kc. On other hand, when
the active masses are expressed as partial pressures, it is represented as Kp.
EX.3: Determine the active mass of NaOH in a solution containing 4gm of NaOH in
500ml.
no.of moles 4 1
Solution-Active mass = Vol.of solution inL = 40 × 0.5 = 0.2mL−1
EX.4:Calculate the active masses of ethanol and carbon tetrachloride taking their
densities to be 0.8and 1.58g per ml respectively.
Problem.1: When alcohol and acetic acid are mixed together in equimolecular
proportions, 66.5% areconverted into ester. Calculate the equilibrium constant of
the reaction.
Solution- The concerned reaction is, CH3COOH + C2H5OH ⇌ CH3COOC2H5 + H2O
Problem.2: 1.1mol of A is mixed with 2.2mol of B and the mixture is kept in a one
litre flask till theequilibrium,A + 2B ⇌ 2C + Dis reached. At equilibrium 0.2mol of C
is formed. Calculate the equilibrium constant for the above reaction.
Solution
[SO 2 ] 2 [O 2 ] 2
p SO 2
. p O2
[PCl 3 ][Cl 2 ] p PCl3 . p Cl2
4. PCl5(g) PCl3(g) + Cl2(g), K c = ; Kp =
[PCl 5 ] p PCl5
[ NO] 2 p 2NO
5. N2(g) + O2(g) 2NO(g), K c = ; Kp =
[ N 2 ] [O 2 ] p N2 . p O2
Relationshipbetween KP&KC
aA(g) + bB(g) ⇌ cC(g) + dD(g)
[C]c [D]d PcC ×Pd
D
K c = [A]a [B]b and Kp =
PaA ×Pb
B
n
From the ideal gas equation,PV = nRT, P = V RT
So, PA = [A]RT ; PB = [B]RT; PC = [C]RT ; PD = [D]RT
Substituting the values of PA, PB, PC and PD, we get,
[C]c (RT)c ×[D]d (RT)d [C]c [D]d (RT)(c+d)
K p = [A]a(RT)a OrK p = × (RT)(a+b)OrK p = K c (RT)Δn
×[B]b (RT) b [A]a [B]b
Where,Δn = (c + d) − (a + b)
i.e.,Δn=no of moles of gaseous products - no. of moles of gaseous reactants.
Case (i):If Δn = O; K c = K p , Ex:H2 (g) + I2 (g) ⇌ 2HI(g)
Case (ii):If Δnis positive;K p > K c Ex:PCl5 (g) ⇌ PCl3 (g) + Cl2 (g),Δn = 2 − 1 = 1 ∴ K p = K c (RT)
Case (iii):If Δnis negative; K p < K c
Ex: N2 (g) + 3H2 (g) ⇌ 2NH3 (g)
Δn = 2 − 4 = −2
K p = K c (RT)−2
Initial mole 1 2 0
Mole of AB = 2x = 2(0.93) = 𝟏. 𝟖𝟔
Problem 6. NH3 is heated at 15atm from 27°C to 247°C assuming volume constant.
The new pressure becomes 50atm at equilibrium of the reaction 2NH3 ⇌ N2 + 3NH2 .
Calculate % of mole of NH3 actually decomposed.
Solution 2NH3 ⇌ N2 + 3H2
Initial mole a 0 0
Mole at equilibrium (a − 2x) x 3x
Initial pressure of a mole of NH3 of NH3 = P atm at 347°C
15 P
300 = 620P = 31atm
At constant volume and at 347°C mole pressure
a ∝ 31(Before equilibrium)
a + 2x ∝ 50(After equilibrium)
𝑎+2𝑥 50 19
𝑎
= 31 x = 62 a
2x 2×19a
% of NH 3 decomposed = a
× 100 = 62×a
× 100 = 𝟔𝟏. 𝟑%
177 .3 135
=
2.303 8.314 1473 1338 10 − 3
177 .3 135 10 3
= = 0.6342
2.303 8.314 1473 1338
K11
p
= 4.307
K1p
p =4.307 K p = 4.307 0.0118atm = 0.0508atm
K 11 1
Problem 2. For the reaction N2(g)+3H2(g) 2NH3(g) at 773K, the equilibrium constant
Kp=1.40410-5Pa-2. Calculate the value of Kc for this equilibrium with concentration
units of mol/L and mol/m3. [R = 8.134J/k/mol]
Solution:N2(g) + 3H2(g) 2NH3(g)
n= - 2.0
Kp = 1.404 10-5Pa-2 = 1.404 10-5(N/m2)2
Kp = Kc.(RT)-2
−2 2
N 8.314
Kc = Kp. (RT)2 = 1.404 10-5 (773 K )2
m2 K.mol
=
1.404 10 − 5 m 4
(8.314 )2 N 2 m 2 (773 K )2
N2 K 2 .mol 2
5.798 10 −10 m 6 5.798 10 −8
= =
mol 2 mol 2 / m 6
= 5.79810-8C-2 where C = conc. in mol/m3
Problem 2. For the reaction: A(aq)+ B(aq)⇌C(aq)+D(aq) , the net rate of consumption
of B at 25C and at any time 't' is as given below,
𝑑[𝐵]
− = {410-4[A] [B] – 1.3310-5 [C] [D]} mol L-1 min-1.
𝑑𝑡
Predict whether the reaction will be spontaneous in the direction as written in
reaction mixture in which each A, B, C & D is having a concentration of 1mol L-1?
K1 4×10−4
Solution: K = = 1.33×10−5 = 30
K2
[C][D] 1×1
Q = [A][B]
= 1×1= 1 < K
Since Q < K, so the above reaction is spontaneous in the forward direction.
[HI]2
Kc =
[H2 ][I2 ]
Substituting the equilibrium concentrations ofH2 , I2 and HIin above equation, we get
2x 2
(V) 4x 2
Kc = a−x b−x
=
( V )( V ) (a − x)(b − x)
P 2 HI
Kp =
PH2 , PI2
Total no. of moles at equilibrium = (a – x) + ( b – x) + 2x = ( a + b)
a−x
PH2 = P × xH2 = P ×
a+b
P×(b−x)
Similarly, PI2 = (a+b)
Three main factors which can change the state of equilibrium in a reversible system
i.e., concentration, pressure and temperature.
Le Chatelier explained the effect of change in concentration, pressure and
temperature on any reversible system whether physical or chemical.
i.e., If pressure is increased, then process will move in that direction where number
of moles of gaseous species are fewer and vice versa.
• Change in temperature: In a reversible chemical reaction, if one reaction is
endothermic, other will be exothermic in nature.
• Addition of an inert gas: When inert gas addedto a system at equilibrium, inert
gas neither reacts with reactants nor with products.
Case I: Addition of inert gas at constant pressure process will move in that
direction where number of moles of gaseous species are greater.
Addition of inert gas will increase the total volume at equilibrium. Now
• When Δn = 0e.g.,2HI ⇌ H2 + I2
x2
For this equilibrium K c = K p = 4(1−x)2 ; where x is the degree of dissociation
The equation is independent of P and V terms and thus there is no effect of
addition of inert gas to this type of equilibrium.
• When Δn > 0;eg.,PCl5 ⇌ PCl3 + Cl2
Moles at t = 0 1 0 0
Moles at equilibrium (1–x) xx
x2
Kc =
V(1 − x)
Where x is the degree of dissociation
Since V increases and thus to keep 𝐾𝑐 constant, ‘x’ must increase i.e., degree
of dissociation of PCl5 increases or [PCl3 ] and [Cl2 ]increases at equilibrium and the
[PCl5 ]decreases at equilibrium
• At high pressure reaction will shift in forward direction to form more product
• When concentration of N2 and H2 is raised or concentration of NH3 is lowered,
thenequilibrium shifts in forward direction to from more amonmia.
• The reaction shifts in forward direction at low temperature.
But at very low temperature the rate of reaction becomes very low; thus moderate
temperature is favourable for this reaction.
Example 1. At what conditions will the following reaction go in the forward direction?
1. N2 (g) + 3H2 (g) ⇌ 2NH3 (g) + 23kcal.
2. 2SO2 (g) + O2 (g) ⇌ 2SO3 (g) + 45kcal
3. N2 (g) + O2 (g) ⇌ 2NO(g) − 43.2kcal
4. 2NO(g) + O2 (g) ⇌ 2NO2 (g) + 27.8kcal
5. C(s) + H2 O(g) ⇌ CO2 (g) + H2 (g) + Xkcal
6. PCl5 (g) ⇌ PCl3 (g) + Cl2 (g) − Xkcal
7. N2 O4 (g) ⇌ 2NO2 (g) − 14kcal
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NCERT SOLUTIONS
Introduction
‘The branch of chemistry dealing with these compounds, which are widely distributed in
nature and play an important role in our daily lives’, is called organic chemistry.
Soon afterwards the pioneering work of Herman Kolbe who synthesized acetic acid and of
Berthelot who synthesized methane showed conclusively that organic compounds are
essentially the compounds formed by carbon with itself and other elements and that they
can be synthesized in a laboratory as easily as inorganic compounds.
CH 3 − CHO ⎯[⎯→
O]
CH 3 − COOH
Acetic acid
Acetaldehyde
(First organic compound synthesized from its elements)
As per Lewis theory, Carbon can easily form tetra-bonds with other carbon atoms & other atoms. C-C,
C=C, C≡C exists in nature but not Carbon-Carbon tetrabonds.
Carbon can form single, double or triple bond (covalent). When a single bond is formed between carbon
atoms (or any atoms), energy is released. Changing the molecule's electron arrangement to make a
double bond releases more energy, but not as much as when the first bond was made. Making a triple
bond again releases energy, but again to a lesser degree. However, when a fourth bond is attempted,
the overcrowded electrons between the atoms resist the change so strongly that it releases little, if
any, energy. This arrangement is therefore unstable, so a quadruple bond will be essentially impossible.
• Hybridization in carbon compounds
Hybridization is defined as intermixing of degenerate orbitals (orbitals at nearly same
energy) to produce entirely equivalent number of new orbitals of same energy, identical
shapes and symmetrically disposed in planes. The orbitals formed are called hybrid
orbitals.
(iii) (iv) HC C − CH = CH 2
CH 3 − CH = CH − CH 2 − C N
sp3 sp
2
sp 2 sp3 sp sp sp sp sp 2 sp 2
(ii) Second Method (Electron pair method): The hybridized state of an atom of a molecule
or an ion or radical can be predicted by calculating number of orbitals or electron pairs
involved in hybridization (H) which is evaluated as follows.
H = (number of bonds formed with adjected atom/s + number of lone pairs of electrons
ep = bp + lp;
where, ep = electron pair present in hybrid orbitals,
bp = bond pair present in hybrid orbitals
Number of bp = Number of atoms attached to the central atom of the species (do not include electron pairs).
Pitfall - It may be noted that, the hybridized state of a heteroatom containing lone
pair electrons or carbanion or free radical bonded in conjugation with multiple bond/s is
sp2. For example, hybridized state of allylic or benzylic carbanions or free radicals or
atoms of aromatic ring is sp2.
Problem 1: How many sigma () and pi () bonds are present in each of the following
molecules? a) CH2 = C = CH2 b) CH3 – CH = CH – C C – CH3
Solution: Every single bond is a bond; every double bond contains one −bond and one
−bond while every triple bond consists of one − and two −bonds. Thus
a) C−C : 2, C−H : 4, C−C : 2 b) C−C : 5, C−H : 8, C−C : 3
Problem 2: Predict the shape of each of the following molecules.
a) HC CH b) CH3Cl c) H2C = O
Solution: sp hybridization can always be correlated to tetrahedral shape, sp2 to trigonal
3
sp 2 sp
(c) Electro negativities of hybrid & unhybrid orbitals in decreasing order is as follows
2 3
s sp sp sp p
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→
% s-character and electronegativity in decreasing order.
(iii) Bond length in hydrocarbons,% of s orbital character 1
1
C − C bond length C − H bond length
Bond type (C – H) Bond length Bond type (C – C) Bond length
sp − s (alkanes)
3
1.112Å sp − sp (alkanes)
3 3
1.54 Å
sp − s (alkenes)
2
1.103Å sp − sp (alkenes)
2 2
1.34Å
sp − s (alkynes) 1.08Å sp − sp (alkynes) 1.20Å
(iv) Bond strength in hydrocarbons: The shorter is the bond length, the greater is the
compression between atomic nuclei and hence greater is the strength of that bond.
Bond type(C – H) Bond energy (kcal/mole) Bond type (C – C) Bond energy (kcal/mole)
3 3 3
sp -s (in alkanes) 104 sp -sp (in alkanes) 80 – 90
sp2-s (in alkene) 106 sp2-sp2 (in alkenes) 122 – 164
H H H H
| | | |
H − C− C− H H − C = C− H H−C C −H
| |
H H
Ethane Ethene Ethyne
H H H H
| | | |
H − C− Cl or H − C− Cl H − C− O− H or H − C− O − H
| | | |
H H H H
Methyl chloride Methyl alcohol
chloromethane methanol
4) Bond-line structural formula: For further simplification only lines are used to represent
the structures of organic molecules. Here carbon and hydrogen atoms are not shown. The
lines denoting the carbon – carbon bonds are drawn in a zig – zag fashion. The only atoms
especially written are the hetero atoms (oxygen, nitrogen etc). They are neither carbon nor
hydrogen bonded to carbon. The termini describe methyl (CH3 − ) groups (unless denoted
otherwise by a functional group). The line junctions indicate carbon atoms bonded to
suitable number of hydrogens needed to satisfy the covalency of the carbon atoms: Thus
The bond-line representation is the quickest of all to write because it shows only the carbon
skeleton.
CH3
a) CH3CH2CH2CH(CH3)CH2CH2CH2CH3 ⎯⎯⎯
step 1
⎯→ CH2 CH CH2 CH3
Step 2
Cl
CH CH2
b) CH3CHClCH2CH2CH3 ⎯⎯⎯→
step1
CH3 CH2 CH3
step 2
Cl
OH
CH2 CH2
Cyclohexanol Cyclohexane carboxylic acid
CH3
CH2 CH CH 2 OH .
OH
Exp 1: Convert each of the following Lewis structures into complete structural formulae:
O H
a) H C O H b) H C N c) H C Cl
H
Solution: Use the dash to represent the shared electron pair.
H H
O O | |
a) || || b) H – C N: or H – C N c) H − C − Cl or H − C− Cl
H − C − O − H or H − C− O − H | |
H H
Exp2: Convert each of the complete structural formulae into condensed formulae.
H H H H H H H
a) | |
H − O − C− C− N− H
b) | | | | |
H − C− C C − C − C − C − C − H
| | | | | | | |
H H H H H H H H
H O H H H H H
c) H − C| − C|| − C| − H d) H − C| − C| − C| − C| − N = O
| | | | | |
H H H H H H O
Solution: Omitting some or all of the dashes and indicating the number of identical groups by
a subscript we get
a) HO(CH2)2NH2 b) CH3C C(CH2)3CH3 c) H3CCOCH3 d) CH3(CH2)3NO2
H C C C C H
H H H
H C H
Exp 4: Write the bond–line formula for H3C− CH−CH2− CH2− CH2− OH
|
CH3
Solution: First, outline the carbon skeleton, including the OH group as follows:
H3C CH2 CH2 C C
C
C C OH
CH CH2 OH
C
CH3
Thus, the bond–line formula is .
OH
.
Exp 5: For following condensed formulae write the corresponding bond-line formula.
a) (CH3)2CH(CH2)2CH2OH b) CH3(CH2)4CHICH2CHO
c) (CH3)2CHCH3CH(CH2)3NO2 d) (CN)2CHCH2COCl
Solution: In bond-line formula carbon and hydrogen atoms except those that are part of the
functional groups are not shown. We show only the carbon skeleton. The number of hydrogen
atoms necessary to fulfill the carbon atoms’ valences is assumed to be present, but we do not
write them in. Other atoms (e.g., Cl, O, N) are written in. Each intersection of two or more
lines and the end of a line represent a carbon atom unless some other atom is written in.
CH3
OH
I
b) CH3(CH2)4CHICH2CHO ⎯⎯⎯→
step1
CH2 CH2 CH CHO
CH3 CH2 CH2 CH2
step 2
. NO 2
c) (CH3)2CHCH3CH(CH2)3NO2 ⎯⎯⎯
step 2
⎯→
.
CH2 Cl
NC
CH C
d) (CN)2CHCH2COCl ⎯⎯⎯→ step1
CN O
step 2
Cl
NC
C
CN O
Exp 6: Draw all possible bond-line formulae for a cyclic compound, C5H10.
Solution: Start with the maximum number of carbon atoms in the ring and move towards the
ring of 3 carbon atoms. Explore all sorts of possibilities on this route:
H or H
H H H
H
The two carbon-hydrogen bonds represented by normal lines are in the plane of paper,
whereas the carbon-hydrogen bond represented with a solid wedge is aimed to be in front of
the plane of paper. The hydrogen bonded to carbon by dashed wedge is intended to be
behind the plane of paper. Note that the carbon atom is lying in the plane of paper.
Wedge and dashed-wedge formulae are an important tool for clearly showing three
dimensions.
The compounds with C and H are called hydrocarbons. Organic compounds are considered as
the derivatives of hydrocarbons obtained by replacing H-atoms by other atoms or groups.
Based on C - skeleton, organic compounds divided as below,
1. Acyclic compounds - The open chain organic compounds are called acyclic compounds.
The carbon chains may be linear or branched.
The open chain compounds are classified into two groups.
a. Saturated compounds: Open chain compounds in which carbon atoms of parent chain are
bonded with single bonds are called saturated acyclic compounds.
Example:
CH3CH2CH2CH3 O CH3
CH − CH − CH || |
n–Butane 3 3
H − C− H
| CH3 −C− OH
CH3 |
Formaldehyde CH3
Isobutane
tert-Butyl alcohol
b. Unsaturated compounds: The open chain organic compounds in which parent chain contains
one or more carbon-carbon double bonds or triple bonds are called unsaturated acyclic
compounds.
CH3 CH3
CH2 CH2 CH3CH CH2 CH3CH CHCH3 CH3C CHCH3 CH3 CH C CH
ethylene propene 2-butene 2-methyl-2-butene 2-methyl-1-butyne
H2 H2
C C
H2 C CH2 H2 C CH2
or or
H2 C CH2 H2 C CH2
C
cyclopentane H2 cyclohexane
Aromatic compounds: Benzene is the parent aromatic hydrocarbon. The organic compounds
containing one or more isolated or fused benzene rings and their functionalized derivatives
are called aromatic compounds or benzenoid compound.
CH3
OH CHO
O
azulene tropolone
ii. Aromatic heterocyclic compounds: The aromatic cyclic compounds containing one or
more hetero atoms in their molecules are called aromatic heterocyclic compounds.
O N N S
furan pyrrole pyridine thiophene
H
Hydrocarbon Containing
functional Homocyclic/ Heterocyclic
group Carbocyclic [Ring having at least one
[Ring having only hetero Atom][N, O, S]
Saturated C atoms]
Unsaturated
Ex :- Alkane
CnH2n+2
Alicyclic Aromatic
Alicyclic Aromatic
Ex :- CH2–CH2
Alkene Alkyne Alkenyne Containing O
CnH2n CnH2n–2 CnH2n–4 Alternate O
– and = Bond Oxirane
[C=C] [C C] [C=C–CC] Cyclo Cyclo Furan
CH2–CH2
Propane Butane Ex :-
Cl
CH2–CH2
O NH
Benzene Tetra hydrofuran Pyrrole
Cyclo Cyclo Chloro (THF)
Pentane Hexane benzene CH2–CH2
S
CH2–CH2
Thiophene
Nephthalene NH
Pyrrolidine
N
Anthracene Pyridine
Functional groups: is defined as “an atom or group of atoms present in a molecule which
decides the chemical properties of the organic compounds”.
Double and triple bonds are also considered as functional groups.
The organic compounds are further classified into different classes depending upon the
nature of functional group. Classification of organic compounds based on functional group is
summarized in the table.
Homologous Series
A series of structurally related organic compounds with same functional group can be
represented by a general formula and differ by -CH2 group is called homologous series.
The individual members of such series are called homologue and this phenomenon is known
as homology.
• Chemical properties of the members of a homologous series are similar though the first
homologue may vary considerably from the rest of the homologues.
a. Root word – is assigned to organic molecule based on the number of carbon atoms
present in the main parent chain
No. of C atoms Root word Molecular formula Molecular structure IUPAC name
1 Meth CH4 CH4 Methane
2 Eth C2H6 CH3CH3 Ethane
3 Prop C3H8 CH3CH2CH3 Propane
4 But C4H10 CH3(CH2)2CH3 Butane
5 Pent C5H12 CH3(CH2)3CH3 Pentane
6 Hex C6H14 CH3(CH2)4CH3 Hexane
7 Hept C7H16 CH3(CH2)5CH3 Heptane
8 Oct C8H18 CH3(CH2)6CH3 Octane
9 Non C9H20 CH3(CH2)7CH3 Nonane
10 dec C10H22 CH3(CH2)8CH3 Decane
11 Undec
12 dodec
b. Suffix – is based on the nature of bonds and functional group present in the molecules.
It is of 2 types,
• Primary suffix: A primary suffix is added next to the root word to indicate whether the
parent chain is saturated or unsaturated.
Note: A carbon-carbon double bond or triple bond must be included in parent chain even if it
contains less number of carbon atoms.
• Secondary suffix added next to the primary suffix to indicate the presence of a functional
group in organic compounds which determines the class of organic compounds.
Secondary suffix of a few functional groups are given.
Functional group Structure Secondary suffix Class of organic compounds
Aldehydic O
- al Aldehydes
C H
Carboxy O
-oic acid Carboxylic acids
C OH
Ester O
alkylalkanote Esters
C OR
Note - While adding the secondary suffix, the letter ‘e’ of the primary suffix (i.e., ane, ene
and yne) is dropped if the secondary suffix begins with a vowel (a, e, i, o or u). It is retained
if secondary suffix begins with a consonant.
c. Prefix (substituent)
All the groups which are not names in parent chain and functional groups are called as
substituents. Its name placed before the root word.
Exp – Alkyl group, halo atoms, nitro group
Substituents group Prefix
-CH3 Methyl
-C2H5 Ethyl
-NO2 Nitro
-Cl Chloro
-OR Alkoxy
–C–C– Epoxy
O
-NO Nitroso
Alkyl groups – derived from an alkane, by removing a hydrogen atom bonded to carbon.
These groups are named simply by dropping –ane from the name of the corresponding alkane
and replacing it by –yl. R is a general symbol, general formula for an alkyl group is CnH2n+1,
because it contains one less hydrogen atom than the parent alkane, CnH2n+2.
Isobutyl, CH3CHCH2
|
CH3 i-Bu–
Isobutane, CH3CHCH3
| CH3
CH3 |
tert–Butyl, CH3−C−
| t-Bu−
CH3
Both these alkyl groups contain the propane chain, but differ in the point of attachment of
the group to the rest of the molecule.
(2) There are four butyl groups, two derived from the straight–chain n-butane, and two
derived from the branched–chain isobutane. These are given the designations: n− (normal),
sec– (secondary), iso– and tert– (tertiary) as shown below:
−H
−H
CH3−CH 2CH 2CH 2 − from a terminal CH 3−CHCH 2−
from a terminal carbon |
n-Butyl group
carbon CH 3
Isobutyl group
CH3CHCH3
CH3CH2CH2CH3 |
n-Butane CH3
−H |
−H CH 3−C− CH 3
CH 3CH 2C HCH 3 from the central |
from the | carbon CH 3
non-terminal carbon sec− Butyl group tert-Butyl group
CH3 CH3
CH3 CH2 CH2 CH2 CH3 CH3 CH CH2 CH3 CH3 C CH3
n-pentane iso-pentane CH3
neo-pentane
Problem 1: Classify each of the following alkyl groups as primary, secondary or tertiary:
Butyl, Isopropyl, Isobutyl, sec-Butyl and tert-Butyl.
Solution: Primary alkyl group is RCH2 −
CH3CH2CH2CH2− CH3CHCH2−
Butyl |
CH3
Isobutyl
Secondary alkyl group is
CH3CH2
CH3
R CH − CH −
CH − CH3 H3C
R Isopropyl sec - Butyl
R
R C
Prefix n-(normal) is used for those alkanes in which all the carbon atoms form a
continuous chain with no branching.
CH 3 CH 2CH 2CH 3 ; CH 3 CH 2 CH 2 CH 2 CH 3
n − Butane n − Pentane
Prefix iso is used for those alkanes in which one methyl group is attached to the next-to-
end carbon atom (second last) of the continuous chain.
CH 3 − CHCH 3 CH 3 − CH − CH 2 CH 3 CH 3 − CHCH 2 CH 2 CH 3
| | |
CH 3 CH 3 CH 3
Isobutane Isopentane Isohexane
Prefix neo is used for those alkanes which have two methyl groups attached to the second
last carbon atom of the continuous chain.
CH 3 CH 3
| |
CH 3 − C − CH 3 CH 3 − C − CH 2 − CH 3
| |
CH 3 CH 3
Neopentane Neohexane
CH3 ( CH2 )3CHCH3CH2CH3 → CH3 − CH2 − CH2 − CH2 − CH − CH3 Substituted heptane
|
CH2
|
CH3
CH2CH3 CH2CH2CH2CH3
| |
CH3CH2CHCH3 ( CH2 )2 CHC2H5 ( CH2 )3 CH3 → H3C −CH− CH2 − CH2 − CH− CH2CH3
substituted decane
Note:
• If two different chains of equal length are possible, the chain with maximum number
of side chains or alkyl groups is selected.
• Number used to specify the position of the substituents is called locant.
1 2 3 4 5 5 CH 3 1
7 6 5 4 3 |
CH 3CH 2CH 2CH 2− CH−CH 3 CH34 CH 2 2
| | | 9 8 7 6 5 4 3 2 1
2CH 2 6 CH3 − CH − CH − CH3 1 2 3 4 5 6 7 8 9
1 2 3 CH3CHCH 2CH2CH2CHCH 2CH2CH3
|
5 4 3
1CH 3 7 CH3 CH2CH3
When the parent chain contains two or more substituents, the numbering is done from the
end where the sum of the locants is least.
CH3
6 5 4 3 2 1 (2 + 5 + 5 = 12, wrong)
CH3 C2 CH2 CH2 CH CH3
1 2 3 4 5 6
CH3 CH3 (2 + 2 + 5 = 9, correct)
Parent chain with one substituent: Prefix the name of the substituent to the root word
of parent chain and indicate its position. The name of the substituent is separated from its
locant by a hyphen (-). Name of the organic compound is written as one word.
1 2 3 4 1 2 3 4 5 6
1 2 3
CH3 CH CH3 CH3 CH CH2 CH3 CH3CH2 CH CH2CH2CH3
• Parent chain has 5 carbon atoms, and it has more number of substituents. The root word is
‘pent’.
• Primary suffix is ‘ane’
• Sum of locants is 9, the substituent which comes first in alphabetical order gets the lower
number.
• Prefixes to the rootword are bromo, ethyl and methyl. Hence, IUPAC name is
• “2-bromo-3-ethyl-4-methylpentane”
•
2,2,4-trimethylpentane 2-bromo-3-ethyl-4-methylhexane
1 2 3 4 5 6 1 2 3 4 5 6 7 8 9
CH3CHCH 2CH2CH2CH3 C H 3C H C H 2C H 2C H 2C H C H 2C H 2C H 3
| |
CH3
CH 3 CH 2CH 3
2−Methylhexane 6–Ethyl–2−methylnonane
CH3
1 2 3 4 5 6 7 1 2 3 4 5 6 7
CH3CH2CHCH2CH2CH2CH3 CH3 CH 2 C CH 2CH2CH2CH3
|
CH3 CH2
CH3
3−Methylheptane 3–Ethyl–3–methylheptane
1 2 3 4 5 6
C H 3C H −C H 2CHCH2C H 3
| |
4–Ethyl–2–methylhexane
CH 3 CH 2
|
CH 3
not
2–Methyl–4−ethylhexane because ethyl comes before methyl alphabetically
1 2 3 CH 3 CH3 CH3
C H 3− C H− C H − CH 3 2 |3 4
| | 1 5 1| 3 4| 5
2
CH 3 4 CH 2
C H 3C H C HCH−CH 3 C H3−C − CH2− C− C H 3
| | | |
| CH3 CH3
5
CH 3
CH 3 CH 3
8 10 7 5 3 1
2 3 4 5 6
1 7 9 4 2
6
8
1 CH CH 3
1 2 3 4 5 6 7 8 9 10
7 6 5 4 3 2 CH3CH2CH2 CH CH CH 2CH2CH2CH2CH3
8
H3C CH CH 2 CH 3
5–(1, 1-Dimethylethyl)−3−ethyl-6-methyloctane 5–sec–Butyl– 4−isopropyldecane
(“di” is being part of substituent name)
4 CH2
H3C C CH 3
3
CH2 CH 3
2 1
5–(2–Ethylbutyl)–3, 3–dimethyldecane
N.B. Longest chain selected has maximum number of side chains.
Naming of organic compounds containing a functional group
Prefix and suffix names of a few common functional groups and their decreasing order of
priority are given in the table.
− -ene Alkenes
C C
1. Write the correct IUPAC names of the following bond line formula:
Me
O
C
O
(i) (ii) (iii) (iv)
Cl H3CO
O OMe
Me Me OH Me Et
H OH Me Me Me
HO H Me Me
(v) Me (vi) (vi) H H (vii) Me COOH
O
Me
N CHO
O
(xiii) H H (xiv) O
Answers
(i) 2-Methylpropanoyl chloride (ii) Methyl propanoate
(iii) Methyl 2-ethylbutanoate (iv) 5-Ethyl-4, 6-dimethyloct-1-ene
(v) Butane-2,3-diol (vi) 5,6-Diethyl-3-methylundec-4-ene
(vii) 3-Methyl cyclopentam-1-ol (viii) 7-Ethyl-6-methylundec-6-cnoic acid
(ix) Ethyl propanoate (x) N-Ethyl-N-methyl propan-1-amine
(xi) Hex-3-yne (xii) 3-Ethyl-4-methylpentanal
(xiii) 2,3-Dimethyloxirane (xiv) Tetrahydrofuran
–CH–CCl3
(vii) (viii) C H –CH = CH – COOH
6 5
O
(ix) CH3–CH – C – CH – OCH2CH3 (x) CH2–CH–CH2
OCH3 CH3 OH OH OH
O CH3
(xii) –O–C–CH–CH3 (xiii) [(CH3)2CH]3COH
CH3
(xiv) (CH3)3COH (xv) CH3–CH2 – CH – C – CH2Cl
Br Br
NO2
(xvi) CH3CH2CH(CHO)CH2COOH (xvii)
H2N NO2
or
(i) Naming of monosubstituted benzene
It is derived by adding the name of the substituent with the word benzene.
Example:
methylbenzene bromobenzene nitrobenzene
Special names of some monosubstituted benzene compounds
Molecular formula Structural formula IUPAC name Special name
CH3
C6H5CH3 methylbenzene Toluene
NH2
C6H5NH2 benzenamine Aniline
OH
C6H5OH phenol Phenol
If the functional group is attached to the carbon chain connected to benzene ring, then
benzene ring is considered as substituent and is prefixed before the root word as phenyl.
Example: CH CH CHO CH CH Cl
2 2 2 2
3-phenylpropanal 2-phenylchloroethane
(ii) Naming of disubstituted benzene
(a) If the substituents are same: In such case, the relative position of the substituents
must be indicated by adding the symbols o − (1, 2) ; m − (1, 3) ; p − (1, 4).
X o-ortho : positions 2, 6
1 m-meta : positions 3, 5
6 2
p-para : positions 1, 4
5 3
4
In the trivial system of nomenclature, the terms ortho(o), meta(m) and para(p) are used as
prefixes to indicate the relative positions 1, 2-; 1, 3 and 1, 4-respectively.
Example: NO2
SO3 H
1,2-dichlorobenzene 1,3-dinitrobenzene 1,4-benzenedisulphonic acid
(or) o-dichlorobenzene (or) m-dinitrobenzene (p-benzenedisulphonic acid)
(b) If the two substituents are different, they are named in the alphabetical order.
I Cl
NO2
Br
1-bromo-4-iodobenzene 1-chloro-3-nitrobenzene
(or) p-bromoiodobenzene (or) m-chloronitrobenzene
(c) If there are more than two substituents: The numbering is done in such a way that it
satisfies the lowest sum rule.
Cl 1 COOH
3
CH3 2
1
2 Cl 4 3
Br NO2
1-bromo-3-chloro-2-methylbenzene 4-chloro-3-nitrobenzoic acid
3
7
6
5
Bicyclo [2, 2, 1] heptane
It's common name is norborane
2 2
CH 4
Bridge head
1 5
3
2
Biyclo [4.1.0] heptane Bicyclo [2.2.1] hept-2-ene Bicyclo [3.2.2] nonane
1 7 1 2
7
2 (6) CH2 CH CH2
6 3
(5) CH2
5 8 CH3 8CH
3
4
CH2 CH CH2
6 5 4
Bicyclo [2.2.2] octa-2,6-dione 8-Methylbicyclo [3.2.1] octane
Isomerism
The existence of two or more compounds with the same molecular formula but different
physical and chemical properties is known as isomerism and the molecules themselves called
as isomers.
The term was given by Berzelius. The difference
in properties of the two isomers is due to
difference in the arrangement of atoms within
their molecules.
For example,
(i) Butane (C4H10) has two isomers – normal butane and isobutene. One isomer has a straight
chain and the other has a branched chain.
CH3−CH2−CH2−CH3 CH3−CH−CH3
|
n−butane CH3
isobutane
(ii) cyclohexane and methylcyclopentane are nuclear isomers.
CH3
CH2 |
CH
CH2 CH2
CH2 CH2
CH2 CH2
CH2 CH2 CH2
cyclohexane methylcyclopentane
(iii) C5H12 has three chain isomers.
CH3
CH3CH2CH2CH2CH3 CH3CH2 − CH − CH3 CH3 − C − CH3
CH3 CH3
n−pentane Isopentane neopentane
n−butylamine tert.butylamine
n − Propylbenzene Isopropylbenzene
• Diethyl ether butyl alcohol both has the molecular formation C4 H6 O, but contains different
functional groups.
C2 H5 − O − C2 H 5 C4 H9 − OH
diethyl ether butyl alcohol
Thus, functional group in diethyl ether is ( −O − ) , while is butyl alcohol it is ( −OH ) .
• Acetone and propionaldehyde both with the molecular formula C3 H 6 O are functional isomers.
CH3 − CO − CH3 CH3 − CH 2 − CHO
acetone acetaldehyde
In acetone the functional group is ( −CO − ) , while in acetaldehyde it is ( −CHO )
• Sometimes a double bond containing compound may be isomeric with a triple bond containing
compound. This also is called as functional isomerism. Thus, butyne is isomeric with butadiene
(molecular formula C 4 H 6 ).
CH3 − CH 2C CH CH 2 = CH − CH = CH 2
1 – Butyne 1, 3 – Butadiene
• Unsaturated alcohols are isomeric with aldehydes. Thus,
CH 2 = CH − OH CH3CHO
Vinyl alcohol Acetaldehyde
• Unsaturated alcohols containing three or more carbon atoms are isomeric to aldehydes as well
as ketones:
CH 2 = CH − CH 2OH CH3CH 2CHO CH3COCH3
Allyl alcohol Propionaldehyde Acetone
• Aromatic alcohols may be isomeric with phenols
CH 2 OH CH 3
OH
CH3CH 2CH = CH 2 CH 3
Butene
Cyclobutane
Methycyclopropane
• Such isomers in which one is cyclic and other is open chain are called ring-chain isomers. Alkynes
and alkadienes are isomeric with cycloalkanes.
CH3CH 2C CH CH 2 = CH −−CH = CH 2
1 − Butyne 1,3 − Butadinene
Cyclobutene
CH3
CH 3
CH 3
CH3 CH3
H3 C CH3
CH3
CH3
1 – Chloronaphthalene 2 – Chloronaphthalene
Polyhalogen compounds containing just one benzene ring can also exhibit position isomerism. For example:
Br
Br
Br
Br Br
Br
1, 2 – Dibromobenzene 1, 3 – Dibromobenzene 1, 4 – Dibromobenzene
f) Alcohols containing three or more carbon atoms exhibit position isomerism due to the difference in the
position of functional group ( −OH). For example :
i) The molecular formula C3H8O represents two isomeric alcohols:
CH3CH2CH2OH CH3CHCH3
|
OH
Propan-1-ol Propan-2-ol
ii) Four monohydric alcohols differing in the position of – OH group can be derived from isopentane:
OH
CH3CH− CH2CH2− OH |
| CH3CH− CHCH3
CH3 |
CH3
3 – Methylbutan-1-ol 3 – Methylbutan-2-ol
OH
| HO − CH2− CHCH2CH3
CHCCH |
3 2CH3
| CH3
CH3
2 – Methylbutan-2-ol 2 – Methylbutan-1-ol
g) Primary amines (RNH2) containing three or more carbon atoms can exhibit position isomerism due to the
difference in the position of amino group on the same carbon skeleton. For example:
NH2
|
CH3CH2CH2NH2 CH3 − CH − CH3
1 – Aminopropane 2 – Aminopropane
(iv) Metamerism
Here two or more different compounds having the same molecular formula but different number and
arrangement of carbon atoms on either side of the functional group is called metamerism. Such
compounds are known as metamers.
Metamerism is never possible in compounds possessing the univalent functional group.
Metamerism is due to the difference in the nature of alkyl groups attached to the same polyvalent
functional group such as −C−, −Ö̤ −, −S̤̈ −, −N̈H−, −N̈ −and − C− O − .
|| |
O
||
O
c) Thioethers, R–S–R, exhibit metamerism due to the difference in the nature of the alkyl groups
attached to the sulphur atom. Thus, the molecular formula, C4H10S, represents the following
metamers:
CH3 − S − CH2CH2CH3 CH3 − CH2 − S − CH2 − CH3 CH3 − S − CH − CH3
|
CH3
(v) Tautomerism
Here a single compound exists in two readily interconvertible structures that differ in
position of hydrogen atom. Tautomer exhibits dynamic equilibrium with each other.
A very common form of tautomerism is that between a carbonyl compound containing an -
hydrogen and its enol form. This type of isomerism is also known as keto−enol isomerism.
R' R' O OH
H O
R − C − C − R'' R − C = C − R" O H
H CH3 C CH3 CH3 C CH2
H O O−H
keto form enol form
Keto form Enol form
The percentage of enol form increases in the order simple aldehydes and ketones <
−keto esters < −diketones < −diketones having phenyl group < phenols. This
increase in the enol content is due to the fact that the enol form of the above type of
compounds is increasingly stabilized by resonance and hydrogen bonding than the
corresponding keto form.
Propene Cyclopropane
ii) Six pairs of ring-chain isomers are possible for the molecular formula C4H8:
CH3CH2CH = CH2 and
Me
CH3CH2CH = CH2 and
CH3 − CH = CH2
| and
CH3
CH3 − CH = CH2 CH 3
| and
CH3
iii) The molecular formula C3H4 represents the two ring – chain isomers:
and
CH3 – C CH
Ring chain isomerism, can be included in functional isomerism, if not considered separately.
R :X-
1) Homolytic cleavage (Homolytic fission)
“In this type of fission bond breaks symmetrically and each fragment formed gets an odd
electron from the shared bond pair electrons”.
This cleavage results in the formation of
specie(s) with unshared electron called free
radicals. It is also known as free radical cleavage
or non-polar bond fission. The homolytic fission of a sigma () bond is shown as follows.
A – B ⎯⎯→ A• + B•
H Br H
+
+
..
Br
electrophile nucleophile
CH3 Br
+
CH3 + Br
..
electrophile nucleophile
Both electrophile and nucelophile contain even number of electrons, influenced by strong
electrical field as they possess positive or negative charge and they are diamagnetic.
• The factor which favors heterolysis is greater difference of electro
negativities between A and B.
• The energy required for heterolysis is always greater than that for
homolysis due to electrostatic forces of attraction between ions.
• Low temperature
• Polar nature of substrate and attacking reagent
• Presence of acid or base catalyst
Reaction intermediates
Highly reactive, short lived and energetic intermediate formed in multistep organic
reactions by the action of reagent on substrate and readily transformed into product(s)
is called reaction intermediate.
The important reaction intermediates are free radicals, carbocations, carbanions, carbenes,
benzyne and nitrenes.
(i) Carbocations or Carbonium ions
A reaction intermediate formed by heterolytic fission of a covalent bond which contains
one positively charged carbon with three bond pair electrons (sextext of electrons) is
called carbocation.
For example,
CH 3+ ,CH 3 CH 2+ ,(CH 3 CH 2 )2 CH + ,(CH 3 )3 C + et c.
+ –
C X C +X
Formation of carbocations:
(i) (CH3)3CCl ⎯⎯→ (CH3)3C+ + Cl− (Heterolytic fission)
+
(ii) CH3 – OH ⎯⎯→
H
CH3 – OH2+ (Protonation)
_
H 3C Br ⎯⎯⎯
FeBr3
⎯
→ CH 3+ + F eBr 4 (Abstraction of halide ion by Lewis acid)
+
H 3C N (Removal of N2 from diazonium cation)
⎯⎯→ CH 3+ + N 2
N
The carbocations are classified into different groups depending upon the nature of carbon
bearing the positive charge. Alkyl carbocations may be primary (1), secondary (2) or
tertiary (3) carbocations.
+ + + +
CH3 CH3 CH2 CH3 CH CH3 CH3 C CH3
methyl ethyl iso propyl CH3 tertiary butyl
carbocation carbocation carbocation carbocation
(1o ) (1o ) (2o ) (3o )
+
CH2
+ +
CH2 CH CH2 CH CH2
vinyl carbocation allyl carbocation beznyl carbocation
Structure of carbocation: The carbocations are electron deficient and contain six electrons
(three bond pair electrons). In strong electrical field, carbocations move towards cathode.
The carbocations have trigonal planar structure and the positively charged carbon in sp2
hybridized.
Rate of formation of carbocations:
More stable carbocation forms at faster rate as compared to less stable carbocation.
For example,
(i) R – CH2 – Cl ⎯⎯→ R – CH2+ + Cl−
(ii) R3C – Cl ⎯⎯→ R3C+ + Cl−
A tertiary carbocation is more stable, the transition state of tertiary carbocation is lower in
energy than transition state of primary carbocation. As a result, a tertiary carbocation will
form more rapidly than primary carbocation.
H
..
H shift +
+
(ii) Carbanions
A reaction intermediate formed by heterolytic fission of a covalent bond which results
negatively charged carbon with eight electrons in its valence shell is called carbanion.
The heterolytic cleavage of a covalent bond as indicated inC the
X following
C – +X reactions gives +
carbanions.
O H O H
–
– + OH –
C X C +X H C C H H C C + H2O
H H
H H
(ii) C2H5O− + CH3 − COOC2H5 ⎯⎯→CH2− − COOC2H5 + C2H5OH
Stability of carbanions:
➢ Alkyl group bonded to negatively charged carbon increases the intensity of negative
charge due to +I effect and destabilize the carbanion. The order of stability of alkyl
carbanions is:
.. .. .. >
..
CH3 > CH3 CH2 > CH3 CH CH3 CH3 C CH3
CH3
methyl
carbanion 1° 2° 3°
➢ The order of reactivity of carbanions is reverse that of its stability. Therefore, order
..
of reactivity of carbanions follows the sequence: 3o > 2o > 1o > CH3
➢ Higher the s character greater the stability of carbanion. Order of stability is
.. .. .. ..
HC C > > CH2 CH > CH3 CH2
Cl Cl
light
2 Cl
.
homolysis
chlorine radical
. light .
CH3 H + Cl CH3 + HCl
methane homolysis
reagent
methyl radical
methyl radical (1o ) ethyl radical (1o ) iso propyl radical (2o )
.
. . CH2
CH3 C CH3 CH2 CH CH2
CH3
tertiary butyl radical (3o ) allyl radical (1o ) benzyl radical (1o )
Structure of free radical: The free radicals are electron deficient since they contain seven
electrons on carbon atom. They are electrically neutral and paramagnetic. The structure of
alkyl radical is not known with certainty. For alkyl radicals two possible structures have been
proposed. The first is a planar sp2 hybridised radical similar to a carbocation. The second one
is a pyramidal sp3 hybridised radical similar to a carbanion.
• Resonance stabilised free radicals such as allyl radicals and benzyl radicals are planar sp2
hybridised.
• The bridge head free radicals are pyramidal (sp3-hybridised) because they cannot assume
planar geometry due to angle strain. Further, the free radicals in which carbon is bonded
to highly electronegative atoms are pyramidal.
.
. CF3
.
bridge head radical (sp3-hybridised) trifluoromethyl radical
(sp3-hybridised)
Stability of free radicals: The relative stability of alkyl free radicals is explained on the
basis of hyperconjugation and inductive effects. Greater the number of alkyl groups attached
to the carbon atom carrying unpaired electron, higher the delocalisation and hence more stable
is the alkyl radical. The order of stability of a few alkyl radicals is given below
. . . .
CH3 C CH3 CH3 CH CH3 CH3 CH2 CH3
CH3
t-butyl radical (3o) iso propyl radical (2o) ethyl radical (1o) methyl radical (1o)
The order of stability of free radicals on the basis of resonance inductive effect is as follows:
(C 6 H 5 )3 C• > (C 6 H 5 )2 CH• > C 6 H 5• > CH 2 = CH CH •2 > 3° > 2° >1° > CH •3
Like carbocations and carbanions, free radicals are highly reactive and short-lived
intermediates because of the strong tendency of the carbon atom carrying the unpaired
electron to acquire one more electron from an atom or a group to complete its octate. The
•
reactivity of alkyl radical is reverse the order of stability CH3 1 2 3
The allyl and benzyl radicals are stabilised by resonance. The stability of allyl and benzyl
radicals is comparable.
.
CH2 .
> CH2 CH CH2
The allyl or benzyl radicals are more stable than alkyl radicals.
(iv) Carbenes
They are neutral and highly reactive species generally obtained by successive elimination of an
electrophile and a nucleophile from the same carbon atom (-elimination). The carbon atom of
carbene has six electrons in valence shell, out of which two constitute unshared electrons and
two bond pair electrons. So they are divalent carbon species containing two unshared electrons
and electrically neutral.
Carbenes exist in two possible forms
(i) Singlet
(ii) Triplet
(i ) Sin glet (ii ) Tr iplet
H
C
H C H
H
sp 2 h ybr idized sp h ybridized
Two elect r on s a r e Two elect r on s a r e in
in sa m e or bit a l t wo differ en t or bit a ls
(spin pa ir ed ) (spin fr ee)
O
. . . . .
H C. H R C. H Cl C
. H R C C. H Cl C. Cl
carbene alkyl carbene chloro carbene acyl carbene dichloro carbene
Attacking Reagents
The organic reactions proceed by the attack of highly reactive reagents on the substrate molecule.
These reagents are called attacking reagents which may be electron deficient or electron rich. They
are classified into two groups.
Electrophiles
The electron deficient molecules or positively charged ions which are capable of accepting an
electron pair from substrate molecule are called electrophiles.
These species act as Lewis acids and attack the electron rich centre of the organic molecules.
C..
+
+ E C E
substrate electrophile
They are of following types,
(i) Positively charged: The species having a positive charge, e.g.
H+ ,CH3+ ,NO2+ ,H3O + ,NO + ,Br + ,CH3CO + etc .
(ii) Neutral: The molecules containing electron deficient atom (i.e. Lewis acids) e.g. :CH2, AlCl3,
BF3, ZnCl2, FeCl3, SO3, etc.
(ii) Ambident: Molecules with 2 electrons deficient centers,
e.g. , -unsaturated carbonyl compounds.
It may be noted that all the positively charged species do not act as electrophiles. The positively
charged species which can accept an electron pair can act as electrophiles. The positively charged ions
+ + + 2+
such as H3 O, N H4 , Na, C a , etc. do not act as electrophile as they cannot accept electron pair, since all
the ions have an octet configuration.
Nucleophiles
The molecules or negatively charge ions which are capable of donating an electron pair
to electron deficient centre of the substrate are called nucleophiles.
These species act as Lewis bases & attack on electron deficient centre of organic molecule.
..
C+ + Nu C Nu
substrate nucleophile
− − − − +
C C C C Y
+
C Y
− −− − +
+ I effect C3 C2 C1 Z
Electronegativity of Y or Z is less than carbon atom, so the Y or Z group releases electron and
gets a partial positive charge (i.e. +) and induces a partial negative charge (i.e. −) on C1. As we
move along the chain from C1 to C3, the partial negative charge decreases.
The examples of electron donating group are (CH3)3C, (CH3)2CH, CH3CH2, CH3 etc.
The order of electron releasing or releasing ability of substituent is given below.
O
.. .. o
C6 H5 O > C O > (CH3)3C > (CH3)2CH > CH3 CH2 > CH3 > D > H
phenate ion carboxylate ion 3oalkyl 2oalkyl 1oalkyl
+ I power in decreasing order with respect to the reference H
(ii) Reactivity of alkyl halide: + I effect of methyl group enhances – I effect of the halogen
atom by repelling the electron towards tertiary carbon atom.
CH 3 CH 3
H 3C C X H3C CH X CH 3 CH 2 X CH 3 X
CH 3
Tertiary > Secondary > Primary > Methyl
(iii) Relative strength of the acids:
(a) Any group or atom showing +I effect decreases the acid strength as it increases the
negative charge on the carboxylate ion which holds the hydrogen firmly. Alkyl groups have + I
effect. Thus, acidic nature is, HCOOH CH 3 COOH C2 H 5 COOH C3 H7 COOH C4 H 9 COOH
+I effect increases, so acid strength decreases
Formic acid, having no alkyl group, is the most acidic among these acids.
Hence benzoic acid is stronger acid than aliphatic carboxylic acids but exception is formic
acid. Thus, HCOOH > C6 H 5 COOH > RCOOH
Acid strength in decreasing order
As compared to water, phenol is more acidic (–I effect) but methyl alcohol is less acidic (+I
effect).
OH H − OH > CH 3 OH
Phenol Water Methyl alcohol
(viii) Stability of carbonium ion: +I effect tends to decrease the (+ve) charge and –I effect
tends to increases the +ve charge on carbocation.
(CH 3 )3 C (CH 3 )2 CH CH 3 CH 2 CH 3
(x). Dipole moment: Inductive effect produces dipole moment in a molecule. As this effect
increases (electronegativity difference increases) the dipole moment also increases.
CH3 − I CH3 − Br CH3 − Cl
1.648 D 1.79 D 1.83 D
The movement of electrons from one end to the other end of the chain through a conjugated
system of double bond is observed in resonance effect. It is a permanent effect.
Depending upon the direction of shift of electron pair in conjugate system, R−effect is
classified into two types.
a. Positive resonance effect (+R effect / +M effect): In this effect, of electron pair
( or lone pair) moves away from the substituent or towards the conjugate system.
The +R effect in aniline as shown below.
.. ..
Substituents exert only +R effect as follows, −𝐂𝐥, −𝐁𝐫, −𝐈, −𝐍𝐇𝟐 , −𝐍𝐑𝟐 , −𝐎𝐇, −𝐎𝐑, −𝐒𝐇, −𝐎𝐂𝐇𝟑 , −𝐒𝐑
..
The substituent which exerts +R effect are called electron releasing groups.
The resonance effect in which resonance structure violates the octate rule should not be
considered. For example, structure (II) cannot be considered as resonance structure since it
violates the octate rule because oxygen has 10 electrons in the valence shell.
.. + ..
CH2 CH ..OCH3 X CH2 CH ..OCH3
I II
b. Negative resonance effect (−R effect / −M effect): isthe shift of or lone pair
electrons is towards the substituent attached to the conjugate system. The electron
displacement depicted in nitrobenzene represents −R effect.
.. .. .. .. .. .. .. ..
O + O O + O +
O N O +
O N O +
O N O
N N
+ +
or
(Actual Structure)
(resonating structures) (Resonance hybrid)
Condition for showing resonance:
(i) Molecule should be planar, nearly planar or a part of it is planar
(ii) Molecule should possess conjugated system.
Note:
They are not resonating structures rather they are tautomers.
➢ Resonating Structure
• Hypothetical structure existing on paper.
• The energy difference b/w different resonating structure is very small.
• All R.S. contribute towards the formation of resonance hybrid (Their contribution
may be different).
• A single R.S. can't explain each & every property of that particular compound.
Sol. (i)
(ii)
➢ Fries Rule:
• Compounds with more benzenoid structures are more stable.
• As the Resonance energy is greater than those in which lesser no. of benzenoid
structures are present.
• R. E. is <
• If a double bond is participating in resonance then it will acquire a partial single
bond character as a result of which bond length increases & bond strength
decreases.
• If a single bond is involved in resonance then it will acquire partial double bond
character. As a result of which bond length decreases & bond strength increase.
(i)
(iii)
Note:
When lone pair, as well as a double bond, is present in some atom then only p bond will be
participating in resonance. Whereas lone pair remains sp2 hybridized orbital. When an atom
has two or more than two lone pairs then only one lone pair will participate in resonance and
the other one remains in sp 2 hybridized orbital.
H ( conjugation) hyperconjugation
bond orbital
H
C C
H C H
H
H
bond
Orbital diagram showing hyperconjugation in propene
Propene molecule may be regarded as the resonance hybrid of the following hyperconjugative
structures (I – IV).
+
H H H H
.. + .. ..
H C CH CH2 H C CH CH2 H C CH CH2 H C CH CH2
+
H H H H
(I) (II) (III) (IV)
Since there is no bond between carbon and hydrogen atoms in these structures (II –IV),
hyperconjugation is also called no bond resonance. It may be noted that although a free proton
(H+) has been shown in the above structures, it is still bound firmly to the - cloud and hence
is not free to move.
Hyperconjugation effect in carbocations, let us take an example of ethyl carbocation
+
(CH3 − CH 2 ) , in which the positively charged carbon atom has an empty p orbital. One of the C–
H bond orbital of methyl group align in the plane of empty p orbital and this bond pair
electrons delocalise into the empty p-orbital as shown in figure.
( conjugation) hyperconjugation
H
sp3 s
bond
H
+
C C
H H
H empty p-orbital
Orbital diagram showing hyperconjugation in ethylcarbocation
The overlap of completely filled C–H bond orbital with empty p-orbital of carbocation
causes dispersion of positive charge and stabilize the carbocation. The ethyl carbocation is
resonance hybrid of following contributing structures.
+
H H H H
+ +
H C CH2 H C CH2 H C CH2 H C CH2
+
H H H H
(I) (II) (III) (IV)
Due to hyperconjugation, there are nine different structures having negative charge at ortho
and para positions. Hence, + M effect of alkyl group attached to benzene ring follows the
order: 𝐦𝐞𝐭𝐡𝐲𝐥 > 𝐞𝐭𝐡𝐲𝐥 > 𝐢𝐬𝐨𝐩𝐫𝐨𝐩𝐲𝐥 > 𝐭𝐞𝐫𝐭 − 𝐛𝐮𝐭𝐲𝐥.
In the same way, the meta directing influence and deactivating effect of –CCl3 group in
benzotrichloride can be explained on the basis of hyperconjugation as follows,
Cl
Cl Cl Cl Cl Cl Cl
- - -
Cl Cl Cl Cl Cl
Due to low electron density at ortho and para positions, the meta position becomes point
of high electron density, hence electrophilic substitution takes place in meta position.
H H H H
Depending upon the direction of displacement, E effect is also of two types.
• −E effect: An attacking reagent is said to have −E effect when the direction of
electron pair transfer of multiple bond is away from the attacking reagent.
CH3 H
.. ..
C O + CN CH3 C O
H
CN
acetaldehyde; (-E effect)
The −E effect operates during nucleophilic addition reaction of aldehydes and ketones.
• +E effect: An attacking reagent is said to have +E effect when the direction of
electron pair transfer of a multiple bond is towards the attacking reagent.
+ +
CH3CH CH2 + H CH3CHCH3
Propene ; (+E effect) isopropyl carbocation
The +E effect is observed during electrophilic addition reaction of alkenes and alkynes
.. +
CH3 MgI CH3 + MgI
.. ..
HO + H CH2 CHO CH2 CHO + H2O
ethanal ethanal carbanion
.. ..
H2N + H C CH C CH + NH3
amide acetylide ion
Steric Hindrance or Steric Strain
When two atoms are closer to each other than the sum of their van der Waal’s radii
they repel each other due to spatial crowding. Steric hindrance or steric strain refers
to non-bonded repulsive interactions between atoms which arise when the atoms come
too close due to the shape of the molecule. The repulsion arises due to nuclear-nuclear
and electron-electron repulsive forces which start dominating the attractive forces.
Molecules with steric strain are relatively less stable than those having no strain or
less strain.
For example, in cis-but-2-ene steric hindrance is present because the two methyl
groups are quite close to each other wheras in trans-but-2-ene no steric hindrance is
there because the two methyl groups on the opposite sides.
Steric hindrance NoSteric hindrance
CH3 H
C=C C=C
H H H CH3
cis-But-2-ene trans-But-2-ene
(Sterically hindered (No Steric hindrance,
molecule, less stable) more stable)
Steric factors have great influence on orientation and reactivity of organic molecules
in various reactions.
O
h/CCl4
+ N Br + HBr
heat
Br
O
N-bromosuccinamide(NBS)
h
Br
+ Br2 + HBr
R + R
R .. + H3O
C O + R// Mg.X R/ C O . MgX R/ C OH
R/
R
C O + NaHSO3 R/ C OH
SO3Na (white solid)
Addition of sodium bisulphite R/
[Note: If these two groups or atoms are removed from adjacent carbon atoms, then it is known
as elimination reaction.]
R
R
⎯⎯⎯⎯
con c.
H SO
→ + H 2O
H OH 2 4 CH 2
The elimination reactions are two types, -elimination reactions and -elimination reactions
(i) -elimination reactions
This type of reaction involves loss of two atoms or groups from vicinal (adjacent) carbon
atoms resulting in the formation of a bond. Thus, it is the reverse of addition reactions.
The most familiar example of
-elimination reactions are dehydrohalogenation reactions of alkylhalides, dehalogenation of
dihaloalkanes, dehydration of alcohols, pyrolysis of esters, Hofmann elimination of
quaternary ammonium hydroxide.
Dehydrohalogenation
When alkylhalides are treated with alcoholic potassium hydroxide solution or sodamide the
corresponding alkenes are formed with the elimination of hydrogen halide.
alcohol
R CH CH R/ + KOH R CH CH R/ + KX + H2O
alkene
H X
-elimination
R H
C heat H + NaX + NH3
C + NaNH2 R C C
H X alkyne
-elimination
(i) Sodamide (NaNH2) is stronger dehydrohalogenating agent.
(ii) An example of 1,4-elimination (-elimination) is
Dehalogenation
The dehalogenation involves the removal of halogen molecule (X2) from vicinal dihalide by
heating with zinc dust in alcoholic medium.
ethanol
R CH CH R/ + Zn R CH CH R/ + ZnBr2
Br Br
-elimination
H OH
170o C
CH3 CH CH2 CH3 CH CH2 + H2O
H OH
100o C
CH3 CH CH2 CH3 CH CH2 + H2 O
OH H
(ii) -elimination: It involves loss of two atoms from same atom resulting in the formation of
reaction intermediates like carbine
H
H
H C H + alc.KOH C : + KCl + H2O
H
H
IV. Rearrangement reactions
The reactions which proceed by a rearrangement or reshuffling of atoms or groups in the
molecule to produce a structural isomer of the original substance are called rearrangement
reactions.
A B A B
X Y Y X
H H
OH O+ H
H+ +
–H2O Rearrangement –H+
CH3
+
OH
HN NH2
⎯⎯
→
OH
P h en yl h ydroxyla m in e p − a m in oph en ol
(i)
H3C N N
H3C C
(ii) O
O
acetyl nitrene methyl isocyanate
CH3
+ +
H3C CH H3C C
CH3
CH3
CH3
(iii) sec − ca rboca t ion t ert − ca rboca t ion
(1) Purification of organic compounds: A large number of methods are available for the
purification of substances. The choice of method, however, depends upon the nature of
substance (whether solid or liquid) and the type of impurities present in it. Following methods
are commonly used for this purpose,
(i) Filtration
The process of filtration is used to separate insoluble
solid component of a mixture from the soluble
components in a given solvent.
Exp- It is used to separate a mixture of Naphthalene
and Urea using a water as solvent. Urea dissolves in
water while Naphthalene remains insoluble. Upon
filtration, naphthalene remains on the filter paper
while urea is recovered from the filtrate by
evaporating water.
Filtration is very slow and takes along time. In
such cases, filtration is carried out under reduced
pressure using a Buchner funnel and water suction pump.
(ii) Sublimation is the process of direct conversion of a solid into the gaseous state on
heating without passing through the intervening liquid state and vice versa on cooling.
Heat
Solid Vapour
Cool
Only those substances whose vapour pressure becomes equal to the atmospheric pressure
much before their respective melting points are capable of undergoing sublimation.
There exists an equilibrium between the solid and its vapours.
Camphor, naphthalene, anthracene, iodine, benzoic acid, salicylic acid, NH4Cl, HgCl2, etc are
purified by sublimation.
This method can also be used for separating liquids having sufficient difference in their boiling
points. For example,
(i) benzene (boiling point 353 K) and aniline (boiling point 475 K)
(ii) chloroform (boiling point 334 K) and aniline (boiling point 457 K)
(iii) ether (boiling point 308 K) and toluene (boiling point 383 K)
Nitrobenzene prepared in the laboratory can also be purified by distillation.
• Fractional distillation: This method is used for the separation of two or more volatile
liquids from a liquid mixture which has boiling points close to each other. Liquids forming a
constant boiling mixture (azeotropic mixture) such as rectified spirit cannot be separated
by this method.
Glycerin is one such compound which decomposes at its boiling point. The pressure is reduced
by suction pump and the distillation is carried out at lower temperature as glycerine can be
distilled at 453 K (normal boiling point 563 K) under a pressure of 10-12 mm. Cane juice can
also be concentrated by this method. This technique can be used to separate glycerol from
spent lye in soap industry.
The compound to be purified is distilled with steam and impurities being nonvolatile remains in
mother liquor. For example, o- nitrophenol (volatile) and p-nitrophenol (non volatile) are
separated by this method.
(v) Chromatography
Chromatography is the technique of separating the components of mixture in which the
separation is achieved by the differential movement of individual components through a
stationary phase under the influence of a mobile phase.
Chromatography
Column chromatography
Paper Chrom.
High Performance Liquid Chrom. (HPLC)
Ascending Decending Radial
Thin Layer Chrom. (TLC)
Procedure The compound is intimately mixed with dry cupric oxide. The mixture is strongly
heated in a hard glass test tube fitted with a cork and a delivery tube. The liberated gases
are passed into lime water.
Passed into
lime water
Ca(OH) 2 Passed into
anhydrous
CuSO4
lime water
turns milky
Copper sulphate
turns blue
Excess of HCl
and FeCl 3
𝑭𝒆𝟒 [𝑭𝒆(𝑪𝑵)𝟔 ]𝟑
𝒇𝒆𝒓𝒓𝒊𝒇𝒆𝒓𝒓𝒐𝒄𝒚𝒂𝒏𝒊𝒅𝒆(𝑷𝒓𝒖𝒔𝒔𝒊𝒂𝒏 𝒃𝒍𝒖𝒆)
Note- If organic compound contains N and S, sodium thiocyanate is formed in sodium extract
which gives blood red colouration with FeCl3 due to the formation of ferric thiocyanate.
𝒇𝒖𝒔𝒆
[𝑪, 𝑵, 𝑺] + 𝑵𝒂 → 𝑵𝒂𝑪𝑵𝑺
𝒐𝒓𝒈𝒂𝒏𝒊𝒄𝒄𝒐𝒎𝒑𝒐𝒖𝒏𝒅
Note: Beilstein’s test: Beilstein’s test is used to detect the halogen in an organic compound.
A copper wire is heated in a Bunsen flame till no colour is imparted to the flame. The copper
wire is dipped in the given organic compound and exposed to the non-luminous zone of the
Bunsen flame. A bluish green coloured flame indicates the presence of halogen.
Phosphorus present in organic compound
Organic compound
With Na2O change to phosphate (Na
3PO4)
(sodium peroxide)
boiled with nitric acid
(HNO3) and added
ammonium molybdate
[(NH4)2MoO4]
Yellow ppt of
ammonium
phosphomolybdate
[(NH4)3PO4.12MoO3]
confirms the presence
of phosphorus in
organic compound
(3) Quantitative analysis The quantitative analysis deals with the determination of
percentage of various elements. The following methods are employed for the determination
of percentage composition of elements present in the organic compounds.
Estimation of carbon and hydrogen by Liebig’s combustion method
Principle: A known mass of organic compound is oxidized with cupric oxide in C02 free
atmosphere. C gets oxidized to C02, H to H2O. Water formed is absorbed in weighed anhydrous
CaCl2 U bulbs and carbon dioxide absorbed in weighed KOH bulbs. Increase in mass of CaCl2
and KOH bulbs are determined. Difference in mass corresponds to the mass of H2O and C02
respectively.
Knowing the increase in mass, the percentage of C and H in the organic compound can be
calculated.
𝒚 𝜟 𝒚
𝑪𝒙 𝑯𝒚 + ቀ𝒙 + ቁ 𝑶𝟐 → 𝒙𝑪𝑶𝟐 + 𝑯𝟐 𝑶
𝟒 𝟐
Calculations
• Let the mass of organic compound taken = m g
• Mass of water formed = m1 g
(increase in CaCl2 U-tube)
• Mass of carbon dioxide formed = m2 g
(increase in potash tubes)
(a) Percentage of Carbon
We know that 1 mole of carbondioxide (44 g) contains 1 gram atom of carbon (12g).
44 g of CO2 contain C = 12g
12
m2 g of CO2 contains C = × m2 g
44
12m2
Hence Percentage of carbon = × 100
44×m
(b) Percentage of Hydrogen
We know that one mole of water (18g) contains 2gram atom of hydrogen (2g)
H2O = 2H
18g of H2O contain H = 2g
2
m1 g of H2O contains H = × m1 g
18
2m1
Percentage of hydrogen = × 100
18×m
Calculations
Let the mass of organic compound = w g
Volume of standard acid taken = V cm3
Normality of acid = N1
Let vol. of standard alkali used for neutralisation of unused acid = V2 cm3
Normality of standard alkali = N2
𝑁
⏟ 1 𝑉1 =𝑁
⏟2 𝑉2
𝑎𝑙𝑘𝑎𝑙𝑖 𝑎𝑐𝑖𝑑
Let this volume of v cm3
Vol. of acid used for neutralisation of ammonia = (V – v) cm3 of N1 normality
Ammonia liberated = (V – v) cm3 of N1 solution
Now, 1000 cm3 of 1N NH3 solution contains nitrogen = 14 g
(V – v) cm3 of N1 NH3 solution contains
14(V − v)x N1
nitrogen = g
1000
Mass of nitrogen
Percentage of nitrogen = × 100
Mass of organic compound
Calculations
Let the mass of organic compound = wg
The volume of nitrogen collected = Vcm3
Atmospheric pressure from barometer) = P mm of Hg
0
Room temperature = t C
0
Aqueous tension at t C = a mm of Hg
Pressure of dry nitrogen = (P – a) mm of Hg
Let us first convert the volume of nitrogen to volume at S.T.P.
Experimental conditions S.T.P. conditions
P1 = (P – a)mmHg P2 = 760 mm
T1 = (273 + t)K T2 = 273
V1 = V cm3 V2 = ?
Principle: A known mass of an organic compound is heated with fuming nitric acid and a few
crystals of silver nitrate in a sealed tube called Carius tube. The Carbon, hydrogen or sulphur
present in the compound will be oxidised to CO2, H2O and H2SO4 respectively. Halogen is
precipitated to give silver halide.
[C H X] + [O] ⎯⎯⎯⎯⎯
fuming HNO3
→ CO 2 + H 2O + HX
heat
Organic compound
• This method does not give satisfactory results in the estimation of iodine as AgI is slightly
soluble in nitric acid and iodide may oxidise to iodine to some extent.
• The results of this method is not very accurate in case of polyhalogenated aromatic
compounds
• Estimation of fluorine can not be carried out as AgF is soluble in water.
Calculations:
Let the mass of organic compound be w g
Mass of silver halide formed = a g
Now, AgX = X
108 + X parts by weight of silver halide contains X parts by weight of halogen (X is its atomic mass)
(108 + X) g of silver halide give halogen = X
𝑋
a g of silver halide will give halogen = (108+𝑋) × ag
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THEORY
NCERT SOLUTIONS
HALOALKANES AND
HALOARENES
Introduction:
Compounds derived from hydrocarbons by the replacement of one or more hydrogen atoms
by the corresponding number of halogen atoms are termed as halogen derivatives.
They are the compounds which have the general formula ‘RX’ , where
‘R’ is an alkyl or substituted alkyl group & ‘X’ is the halogen (F, Cl, Br, I). Likewise, haloarenes
or aryl halides are the compounds containing halogen attached directly to an aromatic ring.
They have the general formula ‘ArX’ (where ‘Ar’ is phenyl or substituted phenyl).
R–X Ar – X
An alkyl halide An aryl halide
(Haloalkane) (Haloarene)
R = Alkyl or substituted alkyl Ar = Phenyl or substituted phenyl
X = F, Cl, Br, I X = F, Cl, Br, I
Halogen containing organic compounds occur in nature & some of these are medicinally useful.
For exp, the chlorine containing antibiotic chloromycetin or chloramphenicol, produced by soil
microorganism, is very effective for the treatment of typhoid fever.
Our body produces an iodine containing hormone called thyroxine, the deficiency of which
causes the disease goiter.
Some synthetic halogen containing compounds are very useful in health–care and medicine.
For example, chloroquine is used for the treatment of malaria fever.
Classification:
Halogen derivation of hydrocarbons broadly classified in to two types:
A. Aliphatic halogen compounds:
These are obtained by replacement of one or more hydrogen atoms of an aliphatic
hydrocarbon by an equal number of halogen atoms. Depending upon the nature of the
aliphatic hydrocarbon, whether alkane, alkene, alkyne aliphatic halogen compounds are of the
following three types:
a) Haloalkanes: are the halogen derivatives of alkanes. They derived from alkanes by the
replacement of one or more hydrogen atoms by the corresponding number of halogen
atoms (fluorine, chlorine, bromine, or iodine) are called as halo–alkanes.
These are named as fluro, chloro, bromo or iodo compounds according to the type of halogen
present in them.
CH3 Cl C2 H5 I C3 H7 Br
Ex:
Methyl chloride Ethyl Iodide Propyl Bromide
Depending on the number of halogen of atoms present in the halogen derivative, these are
termed as mono-, di-, tri-and tetra halogen derivatives.
• Monohalogen derivatives are formed by the replacement of one hydrogen atom by one
halogen atom
CH3 Cl CH3 CH2 Cl
Methyl chloride Ethyl chloride
Monohalogen derivatives or alkyl halides are classified as primary (1°), secondary (2°) or
tertiary (3°) depending upon whether the halogen atom is attached to primary, secondary
or tertiary carbon atoms.
i] Primary (𝟏°) alkyl halide: When the carbon atom containing halogen atom is linked to only
one carbon atom (i.e., primary carbon atom).
e.g. CH3 – CH2 – Cl, CH3 – CH2 – CH2 – CH2 – Cl, CH3 – CH – CH2 – Cl
Chloroethane Chlorobutane CH3 or
1-chloro-2-methyl propane
• Dihalogen derivatives: These are formed by the replacement of two hydrogen atoms by
two halogen atoms. The dihalogen derivatives are mainly three types.
a] Geminal or Gem-dihalides- Here both the halogen atoms are attached to the same
carbon atom. These are also called alkylidene halides
H Cl H H H
H–C–C–C–H H – C – C – Cl
H Cl H H Cl
(Isopropylidene chloride) (Ethylidene chloride)
(2,2-Dichloro propane) (1,1-Dichloro ethane)
b] Vicinal or vic-dihalides- Here both the halogen atoms are attached to adjacent carbon
atom. These are also called alkylene halides
Cl
Cl – CH2 – CH2 – Cl CH3 – CH – CH2 – Cl
(Ethylene chloride) (Propylene chloride)
(1,2-Dichloride ethane) (1,2-Dichloropropane)
c] 𝛂 − 𝛚 Halides (terminal dihalides)- Here both the halogen atoms are attached to
terminal carbon atoms. These are also called polymethylene halides.
Cl – CH2 – CH2 – CH2 – Cl
(1,3-Dichloropropane)
• Trihalogen derivatives- These are formed by the replacement of three hydrogen atoms
from three halogen atoms. These are also known as haloforms
Cl
Cl – C – H
Cl
1,1,1-trichloropropane(Chloroform)
• Tetrahalogen derivatives
These are formed by the replacement of four hydrogen atoms from four halogen atoms
CHCl3
Cl – C – H CCl4
CHCl3 Tetrachloromethane
1,1,2,2-tetrachloroethane
(b) Haloalkenes or Alkenyl halides are the halogen derivates of alkenes. The mono halogen
derivates of alkenes with formula is CnH2n–1X .
where X = F, Cl, Br or I and n = 2,3,4….., etc.
(c) Haloalkynes of Alkynyl halides are the halogen derivatives of alkynes. The monohalogen
derivatives of alkynes have the general formula CnH2n–3X,where X = F, Cl, Br or I and n = 2, 3,
4…., etc. For example,
(ii) Side chain halogen derivatives (aralkyl halide). Halogen derivatives of aromatic
hydrocarbons in which the halogen atom is linked to one of the carbon atoms of the
side chain carrying the aryl group are called aralkyl halides. For example,
Cl CH2 CH 2 Br
chlorobenzene (2-bromoethyl)benzene
H H R3
(Primary haloalkane) (Secondary haloalkane) (Tertiary haloalkane)
(ii) Allylic halides: In these halides, the halogen atom is attached to allylic carbon like
C = C – C* – X. i.e., carbon atom next to C=C.
Allylic halides may be primary secondary or tertiary.
CH2 = CH – CH2 – X X
(Allyl halide)
(3-Halo-1-propene)
(3-Halocyclohex-1-ene)
(iii) Benzylic halides: In these halides, the halogen atom is attached to a benzylic carbon
i.e.,the carbon atoms of the side chain carrying
,
the aryl group.
CH2X X R1
C–X
R2
(Benzyl halide) (1-Halo-1,2,3,4-tetra- (Dialkylbenzyle halide)
hydro naphthalene)
✓ NOTE :- Benzylic halides may be primary, secondary or tertiary.
(ii) Vinylic halides:In these halides, the halogen atom is attached to vinylic carbon
i.e., one of the carbon atoms of C= C.
CH2 = CH – X X
(Vinyl halide)
(1-Halocyclohex-1-ene)
Br
Monohalogenation does not depend upon the type of carbon atoms present in given alkanes,
but on type of replaceable H atoms in the given structures.
The relative amounts of the isomeric haloalkanes depends upon the nature of halogen and the
number type of hydrogens (1°, 2°, 3°) being substituted. The ease of substitution of various
H atoms generally follows the order 3° > 2° > 1°, but their relative rate of abstraction varies
with the nature of halogens.
The abstraction of H is in the order: Benzylic allylic > 3° > 2° > 1° > CH4> Vinylic = aryl
Chlorination of n–alkanes (C4 and above) gives a mixture of d– and l–optical isomers i.e., racemic
mixture (optically inactive)
Allylic substitution: When alkenes are heated with Cl2 or Br2 at high T, H atom of allylic
carbon is substituted with the halogen atom without breaking double bond and forms allyl
halide.
𝟓𝟎𝟎°𝐂 𝐂𝐥 − 𝐂𝐇𝟐 − 𝐂𝐇 = 𝐂𝐇𝟐
𝐂𝐇𝟑 − 𝐂𝐇 = 𝐂𝐇𝟐 + 𝐂𝐥𝟐 → + 𝐇𝐂𝐥
𝐚𝐥𝐥𝐲𝐥 𝐜𝐡𝐥𝐨𝐫𝐢𝐝𝐞
Allylic substitution can also be carried out by heating the alkene with NBS or SO2Cl2 at 200°C
in presence of light and traces of organic peroxides.
𝐇𝐈
𝐂𝐇𝟐 = 𝐂𝐇𝟐 → 𝐂𝐇𝟑 − 𝐂𝐇𝟐 𝐈
−
CH3−CH=CH2 ⎯⎯
⎯→ CH3−CH−CH3 ⎯⎯
HX
⎯→
X
CH3−CH−CH3
(2° carbocation)
X
Mechanism: The addition of HBr to alkenes in presence of peroxides occurs by a free radical
mechanism. It consists of the following three steps:
a. Initiation
b. Propagation: During the first step, a Br adds to the double bond in such a way to give the
more stable free radical. In the second step, the free radical thus produced abstracts a
H from HBr to complete the addition.
Exceptional behaviour of HBr: Peroxide effect is effective only in the case of HBr,
because HF and HCl are held by strong electrostatic force hence they cannot be broken
into free radicals.
H–I also give corresponding halogen free radicals. I° free radical being larger in size is less
reactive towards C= C bond but readily combines with another I° to give I2 molecule.
𝐙𝐧𝐂𝐥𝟐
𝐑 − 𝐎𝐇 + 𝐇𝐂𝐥(𝐠)𝐨𝐫𝐇𝐂𝐥(𝐜𝐨𝐧𝐜. ) → 𝐑𝐂𝐥 + 𝐇𝟐 𝐎
𝐙𝐧𝐂𝐥𝟐
𝐂𝐇𝟑 𝐂𝐇𝟐 𝐎𝐇 + 𝐇𝐂𝐥 → 𝐂𝐇𝟑 𝐂𝐇𝟐 𝐂𝐥 + 𝐇𝟐 𝐎
𝐞𝐭𝐡𝐲𝐥𝐜𝐡𝐥𝐨𝐫𝐢𝐝𝐞
The reactivity of halogen acids is in the order: HI > HBr > HCl.
The order of reactivity of alcohols for halogen acid is as: 3° > 2° > 1°.
Reason: This reaction is an example of a nucleophilic substitution reaction in which the
nucleophile i.e., halide ion attacks the protonated alcohol molecule with the expulsion of water–
a good leaving group.
H+ SN1 +X−
R −OH R−O−H R R−X + (Some rearranged
−H2O
product, if possible)
H
X− SN2
R − X + H2O
∵ the reaction of alcohol with HX proceeds via the formation of a carbocation, hence 𝐶𝑙 −
attacks the most stable carbocation.
The best method of preparation of haloalkanes from alcohols is using SOCl 2. In this method,
both the by-products (SO2 & HCl) are gaseous. They escape, leaving behind the product. Hence,
the product, does not need purification.
Corresponding bromides and iodides cannot be obtained by this method because thionyl bromide
is unstable while thionyl iodide does not exist.
This reaction gives the product with one carbon atom less than the fatty acid.
The yield of RX by this method is in the order: 1° > 2° > 3°.
5. By halide exchange method: This is a convenient method for the preparation of RI.
• The corresponding RBr or RCl are heated with a sol. of NaI in acetone or methanol. This is
called Finkelstein reaction.
𝑵𝒂𝑰
R−Cl → R−I + NaCl
𝑨𝒄𝒆𝒕𝒐𝒏𝒆
𝑵𝒂𝑰
R−Br → R−I + NaBr
𝑨𝒄𝒆𝒕𝒐𝒏𝒆
• Alkyl fluorides may also be obtained by treating an RCl or RBr with Hg2F2 or SbF3 or AgF.
This is called Swart’s reaction.
𝟐𝐂𝐇𝟑 𝐂𝐥 + 𝐇𝐠𝐅𝟐 → 𝟐𝐂𝐇𝟑 𝐅 + 𝐇𝐠𝐂𝐥𝟐
𝐂𝐇𝟑 𝐁𝐫 + 𝐀𝐠𝐅 → 𝐂𝐇𝟑 𝐅 + 𝐀𝐠𝐁𝐫
𝟑𝐂𝐇𝟑 𝐂𝐂𝐥𝟐 𝐂𝐇𝟑 + 𝟐𝐒𝐛𝐅𝟑 → 𝟑𝐂𝐇𝟑 𝐂𝐅𝟐 𝐂𝐇𝟑 + 𝟐𝐒𝐛𝐂𝐥𝟑
Physical Properties:
1. CH3F, CH3Cl, CH3Br and C2H5Cl are gases at room temperature, while CH3I is a liquid at room
temperature. Haloalkanes upto C18 are colourless liquids while higher members are
colourless solids.
2. RXs being polar in nature are water insoluble.
3. They burn on Cu wire with green edged flame (Beilstein test for halogens)
4. RBrs and RIs are heavier than water, RCls and RFs are lighter than water.
5. RIs become brown or violet in colour on exposure to light.
𝐥𝐢𝐠𝐡𝐭
𝟐𝐑𝐈 → 𝐑 − 𝐑 + 𝐈𝟐
The I2 thus liberated dissolves in RX to impart dark colour.
6. The B.Ps of RXs are in the order: RI > RBr > RCl > RF.
Greater the molecular mass, stronger the vanderwaal’s forces of attraction and hence higher
is the M.P and B.P. For a given halogen, the B.Ps of RXs increases with the increase of the size
of ‘R’ group.
In isomeric RXs, as branching increases, surface area is decreased and hence B.P is decreased.
This it is in the order: 1° > 2° > 3°.
7. Decreasing order of density among RXs is in the order: RI > RBr > RCl > RF.
High density is observed for CH3I. Thus, for RI, the decreasing order of density is as follows:
CH3I > CH3CH2I > CH3CH2CH2I >……
8. Stability of C–X bond decreases as the strength of C–X bond decreases. Bond strength
of C–X bond decreases as the size of halogen atom increases.
∴ bond strength of C–X bond is in the order: CH3–F > CH3–Cl > CH3–Br > CH3–I
9. Dipole moment of RXs decreases as E.N. of halogen atom decreases from Cl to Br to I.
fluorides have lower ′𝜇′than chlorides due to very small size of F which out weights the
effect of greater E.N. The actual order is: CH3Cl > CH3F > CH3Br > CH3I
Chemical Properties:
Nature of C–X Bond
The high reactivity of RXs can be explained in terms of the nature of C–X bond which is highly
polarized covalent bond due to large difference in E.N of C and halogen atoms.
- or −𝐶 𝛿+ − 𝑋 𝛿−
This polarity gives rise to 2 types of reactions namely nucleophilic substitution reactions and
elimination reactions.
Such reactions in which a stronger nucleophile displaces a weaker nucleophile are called
nucleophilic substitution reactions and the atom or group (halide ion in the present case) which
departs with its bonding pair of electrons is called the leaving group. Better the leaving group,
more facile is the nucleophilic substitution reaction.
Mechanism of nucleophilic substation reactions:
2 types of nucleophilic substitution reaction namely sN2 and sN1 .
1] Substitution nucleophilic bimolecular reactions 𝐬𝐍 𝟐
If the rate of the reaction depends on the concentration of alkyl halide as well as
nucleophile, then the reaction is known as 𝑠N2 reaction.
Rate ∝ [alkyl halide] [nucleophile]
sN2 Reactions are occurred in one step. During the reaction the nu attacks from the back
side (opposite side) of the halogen atom, the carbon-halogen band starts breaking and a
new carbon–nu bond starts forming. These two processes take place simultaneously in a single
step and a transition state is formed.
In the transition state, the carbon atom is simultaneously bonded to the incoming
nucleophile and the outgoing leaving group. This is unstable state, it ultimately decomposes
to form the product (CH3OH) and the leaving group (Cl– ion).
H H
HO C I H
-
H HO C I HO C I
H H
H H H
iodomethane transition state methanol
Since the nucleophile attacks from the back side, hence optical property is inversion of
configuration so 𝐬𝐍 𝟐 reaction also called as Walden inversion.
Note-Since nucleophile attacks from the back side hence most favorable substrate will be
primary alkyl halide because less no. of alkyl groups will hinder the approach of nucleophile to
the carbon atom C-X bond among the 𝟏° alkyl halide, the most favorable R – X is methyl halide
Thus, the overall order of reactivity of different alkyl halides towards 𝑠N2 reaction is:
Methyl halides > 𝟏°halides > 𝟐°halides > 𝟑°halides.
CH3 CH3
CH3 CH3
Carbocation
Step 2: The nucleophile can attack the planar carbocation from either side to give the
substituted product. This step is fast and hence does not affect the rate of the reaction
(b) Reaction rate & order Rate = k1[RL]; first order Rate = k1[RL] [:Nu−]; second order
(c) Molecularity Unimolecular Bimolecular
−
(d) TS of slow step + − Nu……C…… L− (with : Nu−)
R …… L ……HNu: +
HNu……C…. L− (with : HNu)
(e) Stereochemistry Inversion and retention (Partial racemization) Inversion of configuration (backside
attack)
(f) Reacting nucleophile Nucleophilic solvent; stable R+ may react with added Added nucleophile
nucleophile
(g) Structure of R 3° > 2° > 1° > Me Me > 1° > 2° > 3°
(h) Nature of Leaving group Weakest base is best leaving group, i.e. Weakest base is best leaving group,
I− > Br− > Cl− > F− i.e. I− > Br− > Cl− > F−
(i) Nature of nucleophile For HNu: (solvent), In protic solvents,
rate basicity of HNu: (i) Within a periodic table group, rate
polarizability of Nu
(ii) For same nucleophilic site, rate
basicity of Nu
In polar aprotic solvents, rate
basicity of Nu
(j) Solvent effect Rate H−bonding ability and dielectric constant Depends on charge type. Polar aprotic
solvents leave “freest” most reactive
Nu.
(k) Determining factor Stability of R+ Steric hindrance
(l) Rearrangement Observed Not observed, except for allylic
(m) Catalysis Lewis and Bronsted acids: No specific catalyst
Ag+, AlCl3 , ZnCl2 etc.
Explanation: The formation of cyanides or isocyanides from alkyl halides involves nucleophilic
substitution reaction.
• Alkali metal cyanides (KCN or NaCN) are predominantly ionic. Therefore, both carbon and
nitrogen atoms are free to donate electron pair. Since C–C bond is relatively stronger than
C–N bond, therefore, in this case attack mostly occurs through the carbon atom of the
cyanide group and alkyl cyanides are the major product.
• Silver cyanide is predominantly covalent. Consequently, only nitrogen electron pair is available
for bond formation, and the attack mostly occurs through the nitrogen atom of cyanide group
giving alkyl isocyanides as the major product.
6] Substitution by nitrite group:
Alkyl halides react with aq, ethanolic solution of 𝐾𝑁𝑂2,alkyl nitrite major product formed along
with a small amount of nitro alkane.
alochol
RX + K + O− − N = 0→ R − O − N = O + KX
Δ
alochol
Ex: C2 H5 Cl + K + O− − N = O→ C2 H5 − O − N = O + KCl
Δ
7] Substitution by nitro group:
Haloalkanes react with aqueous ethanolic solution of AgNO2 gives nitro alkane as the major
product with a small amount of alkyl nitrite
alochol
Ex: C2 H5 Br + AgNO2 → C2 H5 − NO2 + AgBr
Δ
Explanation: Nitrite ion (–O–N=O) like cyanide ion is an ambident nucleophile since it has two
sites (oxygen and nitrogen) through which it can attack an alkyl halide. Whereas attack through
nitrogen gives nitro compounds, attack through oxygen gives nitrites.
Alkali metals nitrites are ionic compounds and hence have a negative charge on one of the
oxygen atoms. Hence, it gives alkyl nitrites.
In contrast, silver nitrite is a covalent compound and hence does not have a negative charge
on the oxygen atom, therefore, lone pair of electrons on the nitrogen atom is more easily
available for bond formation or nucleophilic attack occurs through nitrogen and hence silver
nitrite predominantly gives nitro compounds
C2 H5 OH
C2 H5 NH2 + C2 H5 Br → (C2 H5 )2 NH + HBr
Δ
2° amine
C2 H5 OH
(C2 H5 )2 NH + C2 H5 Br → (C2 H5 )3 N + HBr
Δ
3° amine
C2 H5 OH
(C2 H5 )3 N + C2 H5 Br → (C2 H5 )4 N+ Br −
Δ
4° ammonoium salt
10] Substitution of chlorine or bromine by iodine:
Alkyl chlorides or bromides on treating with NaI or KI in acetone give alkyl iodides. This
reaction is called finkelstein reaction.
acetone
C2 H5 Br + NaI → C2 H5 I + NaBr.
H 3C CH CH CH 3
CH 3 But- 2-ene
alc. KOH (Major ) (80%)
H 3C
H 3C CH 2 CH CH 2
Br
But- 1-ene
(Minor) (20%)
but-1-ene
(minor)
but-2-ene(Major)
can exist as cis and trans isomers
• Alkyl halides reacts with lithim dialkyl cuprate (R2CuLi) to form unsymmetrical alkanes
(Corey –House Synthesis).
(Thioalcohol)
+ Na+C-≡ CH O
R – C ≡ CH + NaX R – C – O – R1 + AgX
(Higher Alkyne) (Ester)
Dihalogen compounds
General methods of preparation of gem-dihalides
1] From aldehydes and ketones:
Aldehydes and ketones on treating with PCl5 gives gem-dehalides.
𝐶𝐻3 𝐶𝐻𝑂 + 𝑃𝐶𝑙5 → 𝐶𝐻3 𝐶𝐻𝐶𝑙2 + 𝑃𝑂𝐶𝑙3
Ethylidene chloride
Trihalogen derivatives
Chloroform(𝐶𝐻𝐶𝑙3): It was discovered by Liebig and named chloroform by Dumas. Earlier it
was extensively used as anesthesia for surgery. But now it is rarely used as it causes liver
damage.
Preparation of chloroform- By distillation of ethyl alcohol and bleaching powder:
Chloroform is prepared by the distillation of ethyl alcohol with bleaching powder and water.
The yield is about 40% the available chlorine from bleaching powder serves as oxidising agent
and chlorinating agent.
The reaction takes place in 4 steps.
a] Hydrolysis of bleaching powder, 𝐶𝑎𝑂𝐶𝑙2 + 𝐻2 𝑂 → 𝐶𝑎(𝑂𝐻)2 + 𝐶𝑙2
b] Oxidizing of ethyl alcohol to acetaldehyde by Cl2 , 𝐶𝐻3 𝐶𝐻2 𝑂𝐻 + 𝐶𝑙2 → 𝐶𝐻3 𝐶𝐻𝑂 + 2𝐻𝐶𝑙
c] Chlorination of acetaldehyde to chloral, 𝐶𝐻3 𝐶𝐻0 + 3𝐶𝑙2 → 𝐶𝐶𝑙3 𝐶𝐻𝑂 + 3𝐻𝐶𝑙
d] Hydrolysis of chloral with Ca(OH)2, 2𝐶𝐶𝑙3 𝐶𝐻𝑂 + 𝐶𝑎(𝑂𝐻)2 → (𝐻𝐶𝑂𝑂)2 𝐶𝑎 + 2𝐶𝐻𝐶𝑙3
Physical properties:
1] It is a colorless sweet-smelling liquid
2] It is a heavier than water. (d= 1.485 g/cc)
3] It is less soluble in water but more soluble in organic solvents
4] It is a non-inflammable liquid. But vapors burn with green flame
Chemical properties:
1] Oxidation: When chloroform is exposed to sunlight and air it is slowly oxidized to phosgene
a colourless poisonous gas.
1 ℎ𝜈
𝐶𝐻𝐶𝑙3 + 𝑂2 → 𝐶𝑂𝐶𝑙2 + 𝐻𝐶𝑙
2
The oxidation of chloroform is prevented by
a] Strong chloroform in dark brown-colored bottles filled up to the brim.
b] Adding 1% ethyl alcohol- Ethyl alcohol prevents the oxidation chloroform and converts
phosgene into harm less ethyl carbonate.
COCl2 + 2C2 H5 OH → (C2 H5 O)2 CO + 2HCl
Carbylamine reaction (isocyanide test): This reaction is actually a test of primary amines.
Chloroform, when heated with primary amine in presence of alcoholic potassium hydroxide
forms a derivative called isocyanide (carbylamines) which has a very offensive smell.
Preparation of DDT:
Cl H Cl Cl Cl
Cl – C – CH O + H+ Cl – C – CH
Cl H Cl Cl Cl
DDT
Properties It is a white powder insoluble in water but soluble in oils.
Uses It is a powerful insecticide. However, it is highly stable & is not easily decomposed in the
environment. Therefore, its long-term effect could be potentially dangerous & its use
is banned in many countries
Preparation of freons :
CCl4 + HF ⎯SbCl
⎯⎯→ CCl3F + HCl
5
Haloarenes
Compounds in which halogen is directly attached to an aromatic ring are known as aryl halides
or haloarenes and are represented as Ar –X, where 𝐴𝑟 is phenyl, substituted phenyl or a group
derived from other aromatic system.
General methods of preparation:
1. By direct halogenation of aromatic hydrocarbons: This method is used for the
preparation of chloro and bromo derivatives. Halogens react with aromatic hydrocarbons in
presence of catalysts or halogen carriers such as iron, iodine or anhydrous ferric or
aluminium chloride (Lewis acid) at room temperature in absence of direct sunlight.
H
+ X2 Fe or FeX3 / dark + HX (X = Cl, Br)
H
+ I2 HIO3 or HNO3 + HX (X = Cl, Br)
Cl
AlCl3
+ Cl2 + HCl
Br
Fe or
Br 2 HBr
FeBr 3
(Bromobenzene)
CH 3 CH 3
CH 3
Cl
FeCl 3
Cl 2
dark
(o-chlorotoluene)
Cl
(p-chlorotoluene)
The function of the Lewis acid is to carry the halogens to the aromatic hydrocarbon.
If toluene is used instead of benzene, a mixture of o–and p–chlorotoluenes is obtained since –
CH3 group is o, p–directing.
CH 3
CH 2Cl
Cl 2 338 K HCl
Sunlight
1-chloro-1-phenylmethane
Cl 2 338 K HCl
Sunlight
1-chloro-1-phenylmethane
If Cl2 is passed for a longer time, the initially formed benzyl chloride reacts further to form
first benzal dichloride and then benzo trichloride.
CuCl/HCl Cl + N2
Sandmayer’s reaction
CuBr/HBr Br + N2
N+≡NC𝑙 −
273-277 K
HNO 2 HCl 2H2 O
The diazonium compound is treated with CuCl and HCl or CuBr and HBr to give the
corresponding haloarene. This reaction is known as Sandmeyer reaction.
-
N2 Cl Cl
CuCl
N2
-
N2 Cl Br
CuBr
N2 CuCl
• From silver salt or aromatic acids–Hunsdiecker reaction: Like alkyl bromides, aryl
bromides can also be prepared by refluxing the silver salt of aromatic acids with bromine
in boiling carbon tetrachloride.
C6H 5COOAg X 2 ⎯⎯⎯⎯⎯
CCl4 / Xylene
→ C6H 5 X CO 2 AgX
(Cl 2 or Br 2)
Chemical properties of haloarenes:- Aryl halides are less reactive than that of alkyl halides
towards nucleophilic substitution reactions.
This can be explained as follows:
(i) Resonance Effect: In haloarenes (e.g., chlorobenzene), the lone pairs of electrons on the
halogen atom are delocalized on the benzene ring as shown below:
+ + +
X X X X X
CANONICAL FORM
𝛿+ X
𝛿− 𝛿−
𝛿−
As a result, C–Cl acquires some double bond character. On the other hand, in case of alkyl
halides (say methyl chloride) carbon is attached to chlorine by a pure single bond.
Consequently, C–X bond in aryl halides is little stronger than in alkyl halides, and hence cannot
be easily broken.
(ii) Bond energies due to difference in hybridization:
In alkyl halides, the carbon holding halogen is 𝑠𝑝3 −hybridised. In aryl halides, carbon is
𝑆𝑃2 −hybridized; the carbon −halogen bond is shorter and stronger, and the molecule is more
stable.
(iii) Polarity (or Nature) of the carbon halogen bond: Another reason for the low reactivity
of aryl/vinyl halides over alkyl halides is their lesser polar character.
The sp2–hybrid carbon due to greater s–character is more electronegative than a sp3–hybrid
carbon. Therefore, the sp2–hybrid carbon of C–X bond in aryl halides or vinyl halides has less
tendency to release electrons to the halogen than a sp3–hybrid carbon in alkyl halides. As a
result, the C–X bond in aryl halides or vinyl halides is less polar than in alkyl halides. This is
supported by the observation that the dipole moment of chlorobenzenes just1.69D as
compared to the dipole moment of methyl chloride i.e., 1.86 D. Consequently, the halogen atom
present in aryl halides cannot be easily displaced by nucleophiles.
1] Substitution reactions: Nucleophilic substitution reactions of chlorobenzene given below
(a) Replacemet of –Cl by –OH: When chlorobenzene is heated at 350°C under high pressure
with caustic soda, phenol is formed (Dow process).
Cl ONa OH
(b) Replacement by methoxy group: Ether is formed when chlorobenzene is heated with
sodium methoxide at 200°C in presence of copper salts.
Cl OR
Cu salt (catalyst)
NaOR, High pressure, 573 K
Ether
(c) Replacement by amino group: When chlorobenzene is treated with aqueous ammonia at
200°C under a pressure of 60 atmospheres in presence of cuprous oxide or cuprous chloride,
aniline is formed.
475 K
2 Cl 2NH 3 Cu 2O 2 NH 2 2 CuCl H 2O
60 atm
(d) Replacement by –CN group: When chlorobenzene is treated with cuprous cyanide in
pyridine or DMF at 200°C, phenyl cyanide is formed.
DMF
Br CuCN CN CuBr
470 K
Phenyl cyanide
2] Reaction with sodium: Alkyl halides when heated with sodium in presence of dry either
gives diaryls. This reaction is called fitting reaction.
When a mixture of aryl halide and alkyl halide is heated with sodium in presence of dry ether
gives alkyl derivatives of benzene. This reaction is called Wurtz –fitting reaction.
Cl 2Na ether
CH 3Cl CH 3 2 NaCl
Toluene
3] Reaction with magnesium: Bromo–and iodoarenes from Grignard reagents when their
ethereal solution is treated with magnesium turnings. Chloroarenes from Grignard
reagents only if the reaction is carried out in dry tetrahydrofuran (THF) as solvent.
Br MgBr
ether
Mg
+ + +
X X X X X
CANONICAL FORMATS
Due to resonance, the electron density increases more at ortho & para positions than at meta
position. Therefore, electrophilic substitution reaction take place at ortho & para position.
(i) Halogenation
Cl Cl Cl
Cl
Fe or FeCl 3
Cl 2 or anh. AlCl
3
1,2-dichlor o benzene
Cl
1, 4-dichloro benzene
(ii) Nitration
Cl Cl Cl
NO 2
HNO 3 H 2SO4
(conc.) (conc.)
l-chloro 2 nitro benzene
NO 2
l -chloro
benzene
(iv) Sulphonation
Cl Cl Cl
SO3H
H 2SO4
(conc.)
2-chloro benzene
sulphonic acid SO3H
4-chloro benzene
sulphonic acid
(iv) Friedel–Crafts reaction
Cl Cl Cl
CH 3
anhy. AlCl 3
CH 3Cl
2-chlorotoluene
CH 3
4-chlorotoluene
Cl Cl Cl
COCH 3
anlcy AlCl 3
CH 3COCl
o-chloro acetophenone
COCH 3
(Minor)
p-chloro acetophenone
(Major)
(v) Reaction with chloral: When chlorobenzene is heated with chloral (trichloracetaldehyde)
in the presence of conc. H2SO4, a powerful insecticide, DDT (p, p'–
dichlorodiphenyltrichloroethane) is formed.
H Cl Cl
Conc. H 2SO4
CCl 3 CHO CCl 3 CH
H Cl - H 2O Cl
Similarly, an organic molecule is asymmetric if there is no plane (or centre) of symmetry for example.
COOH C COOH
C
H OH H OH
H H F
OH H Br H
H HO
Br
COOH COOH
Mirror
Mirror
COOH COOH
Cl | |
| Cl
| C C
C
C H OH HO H
H F F H CH3 CH3
Br Br
Chirality: - This term has been recently used to describe such molecules as have no elements of
symmetry, thus symmetrical molecules are also called chiral molecules and optical activity is attributed
to certain chiral centres in them. An asymmetrical carbon is a chiral center.
Chirality is lost when the two atoms bonded to an asymmetric carbon become similar thus lactic acid
is optically active but propionic acid is inactive.
• It is obvious that optical isomers or enantiomers due to the presence of an asymmetric carbon atom
in a compound differ only in the arrangement or configuration of groups in tetrahedral perspective
this may be illustrated by taking a few examples of compounds which exist as (+) and (-) enantiomers.
COOH Mirror COOH H Mirror H
| | | |
C C C C
H OH H CH3 C6H5
HO C6H5 CH3
CH3 CH3 Cl Cl
H * OH HO * H
CH2OH CH2OH
D- glyceraldehyde L- glyceraldehyde
(– OH is on R.H.S.) (– OH is on L.H.S.)
• All molecules which could be chemically relative to D-glyceraldehyde are assigned the D-
configuration and those related to L-glyceraldehyde are designated L-configuration as illustrated
below -
COOH COOH COOH COOH
H * OH HO * H H2N * H H 2N * H
(D-form) (L-form)
(L-form) (D-form)
CH2OH
CHO
CHO COOH C=O
H * OH H * OH
H * OH H * NH2 HO * H H * OH
HO * H HO * H
H * OH HO * H
CH2OH CH3 H * OH
CH2OH
(L-form) (D-form)
CH2OH
(D-form) (L-form)
Special Point:
The method of separating a racemic mixture into its enantiomeric constituents is called as Resolution.
There is no direct relation between D, L– configuration with d, l or (+), (–) configuration.
k3
k1
R + x ⎯⎯→ R + y ⎯⎯→ P
P active, then K3 K4
k2 inactive, then K1 = K2 k4
S + x ⎯⎯→ P S + y ⎯⎯→ P
(5) They have different biological properties i.e. (+) sugar play significant role in animal metabolism
while (–) sugar do not.
Meso compounds; These are the compounds containing the more than one asymmetric
carbon atom but due to the presence of plane of symmetry, do not show optical activity.
They are optically inactive compounds.
DIASTEROMERS: Such configurational isomers which are neither be mirror image nor be
superimpossible on each other, called as diastereoisomer.
e.g.
CH3 CH3
H OH H OH
HO H & H OH
CH3 CH3
CH3 CH3 CH3 H
C=C & C=C
H H H CH3
(cis) (trans)
Cis-trans isomer are geometrical isomer but they are not the mirror image thus, they are said to be
diastereomer
CHARACTERISTICS OF DIASTEREOMERS:
(1) They are generally optical active, however geometrical isomers are exception.
(2) They have different physical properties like MP, BP, density, solubilities & value of specific rotation.
(3) They are separated by fractional distillation, fractional crystallisation & chromatography etc.
(4) They exhibit similar
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