CHEMICAL ENERGETICS

Total number of questions in Chemical Energetics are :

(i) In chapter Examples .......................... 11
(ii) Solved Examples .......................... 15
Total no. of questions .......................... 26
1. INTRODUCTION 4. TERMS USED IN THERMODYNAMICS

Chemical reactions involve the change in energy.

4.1 System
Some reactions like oxidation, hydration etc.
produce energy. Other like hydrolysis, ionisation, A specified part of the universe with real or
imaginary boundaries, on which studies of P, T
splitting of water into hydrogen and oxygen etc.
etc are to be made
use energy. These energy changes result due to
breaking of bonds in reactant molecules (consume 4.2 Surrounding
energy) and formation of bonds in product The rest part of the universe, adjacent to real or
molecule (release energy) during a chemical imaginary boundaries of the system .
reaction. Universe = System + Surrounding
4.3 Types of system
2. CHEMICAL ENERGETICS
(i) Homogenous systems : A system having
The branch of science which deal with the energy uniform nature throughout, made up of one
changes associated with chemical reactions is phase only
called chemical energetics. While the study of (ii) Heterogeneous system : A system not uniform
heat energy and its transformation is known as throughout, consists of more than one phase.
thermodynamics. 4.4 Another classification of system
(i) Open system : Those in which exchange of
3. ENERGY
mass and energy is possible with
surroundings
Basically energy is the capacity of do work. or
energy is the capacity of transfer heat It is Example - Boiling of water in beaker.
basically of two types - (ii) Closed system : Those in which only
exchange of energy (and not of mass) takes
(i) Kinetic Energy : It is the energy of motion
place with surrounding
and its magnitude depends upon mass of an
Example : Heating of liquid in a sealed tube.
object 'm' and its velocity u.
(iii) Isolated system : Those in which neither
1 exchange of mass nor exchange of energy
i.e.K.E. = mu2
2 takes place with surrounding
Example : Liquid in a sealed thermos flask.
(ii) Potential Energy : An object can also
possess energy by virtue of its position 4.5 Properties of a system
relative to other. This stored energy is known It is of two types
as potential energy. (i) Intensive properties : The properties of a
3.1 Units of Energy system which are independent of quantity of
matter present in the system.
(i) The SI units of energy is the Joule (J) :
Example : Temperature, Pressure, Density
Let one joule is defined as the kinetic energy etc.
associated with a mass of 2 kg object moving
(ii) Extensive properties : The properties of a
with a velocity of 1m/s system which depends upon the quantity of
then K.E. = 1 Joule . matter present in system.
(ii) Traditional unit of energy is calorie. Example : Mass, Volume, Energy etc.
One calorie is the amount of energy required 4.6 State functions
to raise the temperature of 1g water by 1ºC
The fundamental properties - Pressure, Volume,
from 14.5ºC to 15.5ºC is – Temperature, Energy, Enthalpy, Entropy etc.
1 calorie = 4.18 Joule which define the state of system are known as
state functions.
 Expansion work
5. THERMODYNAMIC PROCESS
= Pressure (P) × Change in Volume (V)
5.9 Units of Work
5.1 Isothermal Process
In C.G.S. = erg
(i) A process in which temperature of the system
does not change throughout the studies. M.K.S. = Joule or N × M
(ii) Means dT = 0 and thus dE = 0 5.10 Sign Conventions
(iii) It can be achieved by using thermostatic (i) Work done by the system is (– ve) Negative.
both. (ii) Work done on the system is (+ ve) positive.
5.2 Adiabatic Process Note :
(i) A process in which exchange of heat between (i) Work is not a state function because the
system and surrounding does not take place. amount of work performed depends upon the
(ii) Means q = 0 path followed.
(iii) It can be achieved by insulating the system (ii) Heat : It is a measure of quantity of energy
boundaries . transferred from one body to other
Heat absorbed by the system is positive 
5.3 Cyclic Process
H = + ve
(i) In which initial state of system is required
Heat evolved by the system is negative 
after a series of operation
H = – ve
(ii) For a cyclic process E = 0 and H = 0
5.4 Isochoric Process 6. INTERNAL ENERGY (E)
(i) A process in which volume of the system
remains constant throughout. The internal energy is comprised of many energy
terms such a translational, vibrational, rotational,
(ii) For an Isochoric process V = 0
potential, interaction energy etc.
5.5 Isobaric process Internal energy is a state function and thus
(i) A process in which pressure of the system depends upon the state of the system and not
remains constant upon how the system attains this state.
(ii) Means P = 0 Change in Internal Energy i.e. E
E = Efinal – Einitial
5.6 Reversible Process
A positive E results when E final > E initial
A reversible process is one in which all changes
indicating that the system has gained energy
occurring at any part of the process are exactly
from its surrounding.
reversed when change is carried out in opposite
direction. It involves a slow change during A negative E is obtained when Efinal < Einitial
operations and take place in either direction. indicating that the system has lost energy to its
surrounding.
5.7 Irreversible Process In a chemical reaction
An irreversible process is one in which direction E = Eproduct – Ereactant
of the change cannot be reversed by small change for Example :
in variables. It involves fast changes during
H2 + ½ O 2  H2O
operations and is unidirectional process.
i.e. E = EH2O – [EH2 + ½ EO2]
5.8 Nature of work and heat
6.1 Characteristics of internal Energy
Work : It is expressed as the product of two
factors i.e. (i) It is an extensive property and depends upon
the amount and physical state of substance.
W = Intensity factor x Capacity factor
(ii) Internal energy change during a cyclic
i.e. Mechanical work
process is zero.
= Force (F) × Displacement (d)
Electrical work
= Potential difference (E) ×Charge flown (Q)
6.2 Exothermic and Endothermic Reactions pressure, V is volume
Consider a Reaction - Reactant  Product According to F.L.O.T.
6.2.1 Exothermic Reactions q = E + W
A reaction that results in the evolution of heat is or q = E + PV
exothermic i.e. heat flows out of the system into or q = (E2 – E1) + P (V2 – V1)
its surrounding. or q = (E2 + PV2) – (E1 + PV1)
Means EProduct < EReactant i.e. E = – ve or q = H2 – H1 = H
Example - Combustion reactions In chemical reactions
6.2.2 Endothermic Reactions H = Hproduct – Hreactant

A reaction that result in the absorption of heat is H = E + PV

endothermic i.e. system absorb heat from its Thus the enthalpy change represents the heat
surrounding. change taking place during the process occuring
at constant temperature and constant pressure.
Means EProduct > EReactant i.e. E = + ve
Example - Melting of ice etc. 7.2 Relationship between H and E
H = E + PV
7. FIRST LAW OF THERMODYNAMICS or H = E + (PV)
(i) The first law of thermodynamics is also called at constant pressure :
the law of conservation of energy. H = E + PV
(ii) The law was first of all stated by Meyer and or H = E + (n) RT
Helmholtz. Where n = Change in number of
(iii) It states that the generation of any kind of gaseous moles.
energy is impossible without the expenditure 7.3 Enthalpies of Reactions
of an equivalent amount of another kind of
The enthalpy change for a chemical reaction is
energy.
given by
or Energy of the universe is conserved.
(i) H = Hproducts – Hreactant
or Energy can neither be created nor
Case I : When HP > HR.
destroyed although it may be changed from
one form to another. An equivalent amount of Heat i.e. qp = H =+ ve
is absorbed and the reaction is endothermic.
Let the system be supplied Q amount of heat
and E is the change in internal energy Case II : When HP < HR
associated with W work done then An equivalent amount of heat i.e. qp = H = -ve
Q = E – W is evolved. H = – ve
Exothermic reaction : E or H = – ve
7.1 Enthalpy (H) and Enthalpy Change (H)
Endothermic reaction : E or H = + ve
It expressed as the sum of the internal energy
and the pressure volume energy. 7.4 Characteristics of Enthalpy concept
i.e. H = E + PV (i) Enthalpy is an extensive property
but in other words, the heat changes of chemical (ii) The enthalpy change for a reaction is equal
reactions at constant pressure and constant in magnitude but opposite in sign to H for
temperature known as enthalpy. reverse reaction
Where H is enthalpy, E is internal energy, P is C+O2  CO2 ; H = – 94.3 Kcal
CO 2  C+ O2; H = + 94.3 Kcal
Examples
based on First Law of Thermodynamics 8. THERMOCHEMICAL EQUATIONS
Ex.1 A sample of gas is compressed by an average
It is an equation which represents chemical as
pressure of 0.50 atmosphere so as to
well as thermal changes taking place in a
decrease its volume from 400cm3 to 200cm3.
reaction.
During the process 8.00 J of heat flows out
to surroundings. Calculate the change in Example :
internal energy of the system. A Chemical equation
Sol. Here V = 200 – 400 = –200 cm 3 C +O2  CO2
A we know 1 Litre = 1000 cm 3 A thermochemical equation
 V = – 0.2 Litre. C(s) + O 2(g) CO2(g)   H = – 943 Kcal
External Pressure (P) = 0.50 then reactants products Energy change.
Work done = – PV = + 0.50 (0.2) 8.1 Heat of Reaction
= + 0.1 atm Litre It is defined as the change in heat enthalpy or
and 1 litre – atmosphere = 101.3 Joule change in internal energy or amount of heat
 W = + 10.13 Joule evolved or absorbed during the complete course
According to F.L.O.T. of reaction as represented by a balanced
thermochemical equation.
q = E – W
Example : C + O2  CO2 ; H = – 94.3 Kcal
then E = q + W
It signifies that 12g of carbon on reaction with
Given q = – 8.00 J
32g O2 gives 44g CO2 along with 94.3 Kcal of
 E = – 8 + 10.13 = 2.13 Joule heat evolution.

Ex.2 The heat of combustion of napthalene 8.2 Factors Influencing Heat of Reaction
(C10H8(s)) at constant volume was measured 1. Physical nature of reactants and products :
to be – 5133 kJ mol–1 at 298K. Calculate the The heat of reaction varies for a given reaction
value of enthalpy change (Given R = 8.314 with the change in physical nature of reactant
JK–1 mol –1). or products.
Sol. The combustion reaction of napthalene. Exmaple : C diam ond + O2    CO2 ;
C10H8(s) + 12O2(g)  10CO2(g) + 4H2O (l); H = – 94.3 Kcal
E = – 5133kJ Camorphous + O 2   CO2 ;
H = – 97.7 Kcal
n = 10 – 12 = – 2 mol.
2. Reaction carried out at constant pressure or
Now applying the relation.
constant volume :
H = E + (n) RT
At Constant
= – 5133 × 103 + (–2) (8. 314) (298) V.qv = E Change in Internal Energy
= – 5133000J – 4955.14J At Constant
= – 5137955. 14 Joule P.qp = H Change in Enthalpy
3. Temperature : Heat of reaction also depends
Ex.3 W hat is the true regarding complete on the temperature :
combustion of gaseous isobutane - In terms of Enthalpy
(A) H = E (B) H > E H2 – H1 = Cp (T2 – T1)
(C) H = E = O (D) H < E and In terms of Internal Energy
Sol. (D) E2 – E1 = Cv (T2 – T1)
C4H10(g) + 6.5O2 (g)  4CO 2(g) + 5H2O (l) When CP= CP of products – CP of reactants
n = [4 – 7.5] = –3.5 CV = CV of products – CV of reactants
H = E + ngRT
 H < E
8.3 Types of heat reactions HCl(aq)+ NH4OH(aq)  NH4Cl (aq) + H2O ;
H = – 12.3 K Cal
(a) Heat of formation or Enthalpy of formation
Examples
It is the change in enthalpy when one mole based on Thermochemical Equation
of a substance is formed directly from its
constituent element Ex.4 How much heat is produced when 4.50g
Example :C + O2  CO2 ; H = – 94.3 Kcal methane gas is burnt in a constant pressure
system.
C + 2S  CS2 ; H = 22.0 Kcal Sol. Given
Standard Heat Enthalpy : (Hf0) CH4 + 2O2  CO2 + 2H2O ; H = – 802
The heat enthalpy of a compound at 25ºC KJ
and one atmosphere pressure is known as  16g CH4 on burning produces heat = – 802KJ
standard heat enthalpy of that compound.  4.5 g CH4 on burning produces heat

Note : Assuming the enthalpy of a pure element in  802  4.5

= = 225.6 KJ .
its most stable state at 25ºC and 1 atm, is 16
equal to zero.
Ex.5 Hf0 for Al2O3 is –1670 KJ. Calculate the
(b) Heat of combustion enthalpy change for the reaction
It is defined as the change in heat enthalpy 4Al + 3O2  2Al 2O 3
when one mole of a substance is completely 3
burnt in oxygen. Sol. Given 2Al + O  Al2O 3  
2 2
Example :C + O2  CO 2 ; H = – 94.3 Kcal
H = – 1670KJ
(c) Heat of solution
Multiplying it by 2
It is defined as the change in heat enthalpy
then 4Al + 3O2  2Al 2O 3
when one mole of a substance is dissolved
in excess of water so that further dilution H = 2 × (–1670)
does not involve any heat change. = – 3340KJ
Ex. :KCl(s) + aq.  KCl (aq) H = 4.4 KCal
Ex.6 The specific heats of iodine vapours and solid
(d) Heat of Hydration
are 0.031 and 0.055 Cal/g respectively. If heat
It is defined as the change in heat enthalpy of sublimation of iodine is 24Cal/g at 200º,
when one mole of an anhydrous is completely What is its value at 250ºC.
hydrated by combining with specific moles of
Sol. I2 (solid)  I2 (vapour) ; H = 24 Cal/g at
water.
200ºC
Ex. : CuSO4(s) + 5H2O (l)  CuSO4 .5H2O
 H = –15.8 Kcal Cp = Cp of product – Cp of reactant
Cp = 0.031 – 0.055 = – 0.024 Cal/g
(e) Heat of Neutralisation
 H2 – H1 = Cp(T2 – T1)
It is defined as the change in heat enthalpy
when one gram equivalent of an acid is H2 – 24 = – 0.024 (523 – 473)
completely neutralised by 1gram equivalent  H2 = 22.8 Cal/g
of a base in dilute solutions.
HCl(aq)+ NaOH(aq)  NaCl(aq) + H2O ; Ex.7 Calculate the heat of neutralization by mixing
H = 13.7 Kcal. 200ml of 0.1M H2SO 4 and 200 ml of 0.2 M
HNO3(aq)+ NaOH(aq)  NaNO 3 + H2O ; KOH if heat generated by the mixing is
H= –13.7 Kcal. 2.3 KJ.
Thus it is clear that heat of formation is -13.7 Sol. Meq of H2SO 4 = 200 × 0.1 x 2 = 40
K cal meq or KOH = 200 × 0.2 = 40
but in case when 1gm equivalent each of  40 Meq of H2SO 4 and 40Meq of KOH on
weak acid and strong base or a strong acid mixing gives heat 2.3 KJ
and weak base or weak acid and weak base
 1000 Meq of H2SO 4 and 1000 Meq of KOH
are allowed to react, the apparent value of
heat of neutralization is lesser than on Mixing gives heat -
13.7 K Cal 2.3  1000
Example = KJ = 57.5 KJ
40
 10.2 Hess's Law of constant heat summation
9. ENERGETICS OF PHASE TRANSITION It state that the total heat change during the
9.1 Enthalpy of fusion complete course of a reaction is same whether
the reaction is made in one step or in several
It is defined as the change in heat enthalpy
steps.
(always increase i.e. H = + ve). When 1 mole
of a substance is completely converted from solid
state into liquid state at its freezing point.
H2O(s)  H2O () ; H = + 6.0 KJ
The reverse of fusion i.e. conversion of liquid to
solid is known as freezing and enthalpy change
shows an equivalent amount of decrease during H = q1 + q2 + q3 = Q2.
the process. Then According to Hess's Law Q1 = Q 2.
10.2.1 Significance of Hess's Law
9.2 Enthalpy of Vapourisation 1. Calculation of enthalpies of reactions :
It is defined as the change in heat enthalpy Example
(always decrease i.e. H = -ve) when 1 mole of
a substance is completely converted from liquid
state into vapour state at its boiling point.
H2O(l)  H2O (g)   H= + 40.6 KJ.
The reverse of vapourisation is known as
condensation. then H 2 = H + H1
 H = H2 – H1 ,
9.3 Heats of sublimation
= –393.5 – (–283)
It is defined as the change in heat enthalpy
(always increase i.e. H = +ve) When one mole = –110.5 KJ
of a solid is directly converted into its gaseous 2. Calculation of Bond Energies :
state at a temperature below its melting point. The energy required to break a bond in a
I2(s)  I2 (g) ; H = + 62.4 KJ gaseous molecule is referred to as bond
energy or bond dissociation Energy
9.4 Heats of Transition
[Enthalpy of reaction] =
It is defined as the change in heat enthalpy when [Sum of bond energies of reactants] – [Sum
one mole of a substance is completely converted of bond energies of products]
from one allotropic form to other as its transition
temperature. Examples
ExampleCdiamond  Cgraphite H = –1.9KJ based on Bond energy

Ex.8 Determine the enthalpy change for the

10. LAWS OF THERMOCHEMISTRY reaction
CH4(g) + Cl2(g)  CH3Cl(g) + HCl (g)
10.1 Lavoisier and Laplace law
Bond energies for C – H, C – Cl, Cl – Cl,
The enthalpy of decomposition of a compound of H – Cl are 412, 338, 242, 431 kJ/mol.
that compound is numerically equal to the respectively.
enthalpy of formation with opposite sign
Example
C(s)+O2(g)  CO2 (g) ; Sol.
H = – 94.3 Kcal
CO2(g)  C (s) + O 2 (g) ;
H = + 94.3 Kcal H = ( B.E)reactant – ( B.E)product
= 4(B.E.)C–H + 1(B.E.)Cl – Cl – 3(B.E.)C–H
 = [4(B.E.)C–H + 1(B.E.)Cl – Cl – {3(B.E.)C–H (i) Which need no initiation
+ 1 (B.E.)C – Cl + 1 (B.E.)H – Cl}] (1) Evaporation of water H2O (l)  H2O (g)
= 412 + 242 – 338 – 431 (2) Dissolution of sugar in water to form a
= –115 kJ/ mol solution. etc.
(ii) Which need initiation -
Ex.9 Calculate the enthalpy change (H) for the (1) Hydrogen react with oxygen gas to
following reaction produce water. It is initiated by passing
2C2H2 (g) + 5 O2(g)  4CO2 + 2H2O (g) an electric discharge.
Given average bond energies of various bonds 2H2(g) + O2(g)  
Electric
 2H2O(l)
disch arg e
i.e. C – H, C C , O = O, C = O, O – H as
414, 810, 499, 724 and 460 KJ/mole 12.1 Criterion of Spontaneity
respectively
(I) H as criterion of spontaneity -
Sol. 2 [H – C  C – H]+ 5 (O = O)  4 ( O = C
A process in which the enthalpy of the
= O) + 2(H – O – H)
system decreases (or an exothermic process)
The reaction involves the breaking of 4 C – H may tend to occur spontaneously, because
bonds, 2 C  C bonds, 5 O = O bonds and every system tends to change from higher
formation of 8 C = O bonds and 4 O – H energy level to lower energy level.
bonds.
Examples: C + O 2  CO2 H = – ve
H = [Total energy required to break bonds]
H2 + 1/2O2  H2O H = – ve
– [Energy given out in forming the bonds]
= [ 4HC – H + 2 H C  C + 5 HO = O] N2 + 3H2 2NH3 H = – ve
– [8 HC = O + 4 HO – H] the enthalpy change of process is not
enough, because the criteria of spontaneity
= (4 × 414 + 2 × 810 + 5 × 499)
on the basis of decrease in heat enthalpy
– (8 × 724 + 4 × 460)
fails in many of the examples.
= 5771 – 7632
Examples :
= – 1861 KJ
(i) Decomposition of Mercuric oxide

11. FUEL AND SOURCES OF ENERGY 2HgO (s)  2Hg (l) + O2 (g) ;
H = + ve
(1) Fossil Fuels : Coal, oil and natural gas which (ii) Formation of Water gas
are presently our major source of energy are
C(s)+H2O(steam)  CO(g)+H2 (g) ;
known as fossil fuels.
(2) Hydroelectric power H = + ve
(3) Geothermal Power (II) Randomness criterion for spontaneity :
(4) Nueclear Energy Spontaneity is the tendency of show maxi-
(5) Solar Energy mum disorder.
Process in which the disorder of the system
12. SPONTANEOUS PROCESS increase to occur spontaneously.
Spontaneity of some endothermic reactions
In our daily life, we come across many natural in terms of randomness.
processes which take place of their own in one Example :
direction but not in the other. For example, water
flows down the hill without the help of external (i) Dissolution of NH4NO 3 :-
agency but water cannot flow up the hill of its During dissolution, the ions which were tightly
own. held in crystal lattice are set free to move in
A process which has an urge or a natural all direction showing increase in randomness
tendency to occur either of its own or after proper
initiation under a given set of conditions is known
as spontaneous process.
Example
 (ii) Evaporation of water : (9) An increase in temperature increases entropy
During evaporation, the liquid molecules due to increase in motion which results in
having their motion restricted inside the liquid
more disorder.
level, move freely in open space to increase
disorder 13.2 Overall criterion of spontaneity
There are two driving forces that determine the
13. ENTROPY (S)
behav iour of molecular systems to show
Spontaneity is associated with an increase in spontaneity

randomness or disorder of the system. The (1) Achieve the lowest possible state of energy
(H = minimum)
randomness is impressed by a thermodynamic
(2) Acquire the state of minimum disorder.
quantity called entropy.
The overall tendency of a process to occur
13.1 Sailent Features of Entropy by itself is resultant of these two tendencies
(1) The change in entropy S is given by and is called driving force.
Gibbs gave a new state function (G). Known
S = Sfinal – Sinitial and it depends only on
as Gibb's free energy by incorporating both
the initial and final states of the system and H and S values in it.
not on the particular path way by which the
i.e. G = H – TS
system changes
or the change in free energy. at constant
(2) When S = +ve (Positive) temperature
- Increase in Randomness G = H – T S
S = –ve (Negative) Conditions:

- Decrease in Randomness (1) If G is negative, the reaction is spontaneous

in forward direction .
(3) For any substance
(2) If G is zero, the reaction is at equilibrium.
Ssolid < Sliquid < Sgas (3) If G is positive, the reaction in the forward
(4) At absolute zero temperature i.e. zero kelvin, direction is non spontaneous.
the entropy of pure crystal is arbitrarily taken  H S     G Properties
as zero. of reaction
(5) Mathematically, the entropy change Always Reaction is
– + Negative spontaneous at all
qrev
i.e. S = temperature
T Always Reaction is
Where qrev = Heat supplied to a system at + – positive nonspontaneous
temperature T. at all temperature
Negative at Spontaneous at
(6) Unit of Entropy change J/K mol.
low low temp. & non
(7) Larger is the space available for motion of temperature spontaneous at
– –
molecules, more is entropy but positive at high temperature
high
Example -Expansion of gas, dissolution temperature
(8) An increase in the number of molecules also Positive at low Nonspontaneous
leads to an increase in entropy temperature at low temp. &
+ + but negative at spontaneous at
Example - Decomposition of NH4Cl to NH3 high high temperature
and HCl temperature
13.3 Standard free energy changes Ex.11 Calculate the standard free energy change
Gº = Hº - TSº for the reaction
Second law of Thermodynamics : N2 (g) + 3H2 (g)  2NH3 at 298K
It states that the entropy of the universe always Given Hº = – 92.4 KJ and Sº
increases in the course of every spontaneous
(Natural) Change. = –1983 JK–1
The energy of universe is conserved whereas Sol.     Gº = Hº – TSº
entropy of universe always increases in any = – 92. 4 – 298 × (–198.3) × 10-3
natural or spontaneous process.
= – 33.306 KJ.
Third law of thermodynamics :
It states that at absolute zero, the entropy of a
perfectly crystalline substance is taken as zero.
S° = Sº(product) – Sº(reactant)
Examples
based on On Entropy (E)
Ex.10 The gaseous endothermic reaction :
P + Q  3R
at 327ºC takes place spontaneously,
because-
(A) H < 0; S < 0 (B) H > 0; S > 0
(C) H < 0; S > 0 (D) H> 0; S < 0
Sol. (B)
G = H – TS
For an endothermic reaction H = + ve
[less molecules  more molecules],
S = + ve
 TS > H, and G = – ve
Hence, the reaction occurs spontaneously.
 SOLVED EXAMPLES
Ex.1 A system does 100J work on surroundings Ex.4 A cooking gas cylinder is assumed to contain
by absorbing 150J of heat. Calculate the 112kg isobutane. The combustion of
change in internal energy- isobutane is given by-
(A) 100 J (B) 50 J
(C) 25 J (D) 150 J  13 
C4H10 (g) +  2  O2 (g)  4CO 2 (g) +
(Ans. B)
Sol. W = –100J , q = 150J 5H2O() ;  H = – 2658 KJ
 q = E – W If a family needs 15000 KJ of energy per day
150 = E – (–100) for cooking, how long would the cylinder last?
= 150 – 100 (A) 22 days (B) 28 days
E = 50 J (C) 32 days (D) 34 days
(Ans. D)
Ex.2 A gas absorbs 200J of heat and expands Sol.  58 g isobutane provides energy
against the external pressure of 1.5 atm from = 2658 KJ
a volume of 0.5 litre to 1.0 litre, Calculate the  11.2 × 103 g isobutane provides energy
change in internal energy-
(A) 124 J (B) 224 J . x 10 3
2658 x 112
= KJ = 513268.9 KJ
(C) 114 J (D) 154 J 58
(Ans. 2)
The daily requirement of energy = 15000KJ
Sol. W = –PV
= –1.5 (1– 0.5) 513268.9
 cylinder will last = = 34 days
= –0.75 atm-litre = – 0.75 × 101 Joule 15000
q = 200 J
Ex.5 Calculate the entropy change in melting 1
 q = E–W
mole of ice at 273K, Hfo = 6.025 KJ/mole-
200 = E–(–0.75 × 101)
(A) 11.2 JK–1 mol –1 (B) 22.1 JK–1 mol –1
E = 124.25 Joule
(C) 15.1 JK–1 mol –1 (D) 5.1 JK–1 mol –1
Ex.3 Heat of reaction for (Ans. B)
C6H12O6 (s) + 6O2 (g)   6CO2 (g) Hf 6025
Sol. S f = = = 22.1 JK–1 mol –1
+ 6H2O (l) T 273
at constant pressure is –651 Kcal at 17ºC.
Calculate the heat of reaction at constant Ex.6 Determine the standard free energy change
volume at 17ºC- for the following reaction at 298 K
(A) – 554.5 Kcal (B) – 654.5 Kcal N2 (g) + 3H2(g)  2NH3(g)
(C) – 354.5 Kcal (D) – 154.5 Kcal Given Gºf for N2(g) , H2(g) and NH3(g) are
(Ans. B) 0, 0 and -16.66 KJ mol–1
Sol. H = E + N RT (A) – 11.22 KJ (B) – 22.22 KJ
Given (C) – 33.32 KJ (D) – 44.44 KJ
H = – 651 x 103 cal. , R = 2 cal, (Ans. C)
T = 290 K and   n = 6 + 6 – 6 = 6
 E = – 651 × 103 – 6 × 2 × 290 Sol. Gº = 2 × Gº NH – Gº N – (Gº H × 3)
3 2 2
= – 654480 cal
= 2 × (–16.66) – 0 – 0
= – 654.5 Kcal
= – 33.32 KJ
Ex.7 For a gaseous reaction What would be the heat of reaction at
2A2(g) + 5B2(g)  2A2B5(g) constant volume ?
at 27ºC the heat change at constant pressure Sol. We have,
is found to be –50160J. Calculate the value H = E + ngRT
of internal energy change (E). Given that R Here, ng = 6 – 7.5 = – 1.5
= 8.314 J/K mol. Thus, E = H – ngRT
(A) –34689 J (B) –37689 J = – 780980 – (–1.5) × 2 × 298
(C) –27689 J (D) –38689 J = – 78090 calories.
(Ans. B)
Sol. 2A2(g) + 5B2(g)  2A2B5 (g); H Ex.11 From the following data of H of the following
= –50160 J reacts as,
n = 2– (5 + 2) = – 5 mol. C (s) + ½ O2 (g)  CO (g) ; H = –110 kJ
H = E + (n) RT and C (s) + H2O (g)  CO (g) + H2 (g) ;
– 50160 = E + (n) RT H = 132 kJ.
E = – 50160 – (–5) (8.314) (300) calculate the mole composition of the mixture
= – 50160 + 12471 = –37689 J of oxygen and steam on being passed over
coke at 1273K, keeping the reaction
Ex.8 Calculate the standard enthalpy change for a temperature constant.
reaction CO2(g) + H2(g)  CO(g) + H2O (g) Sol. From the question we see that the first
given that Hf0 for CO2(g), CO(g) and H2O(g) reaction is exothermic and the second one
as -393.5, -110.5 and -241.8 KJ/mol is endothermic. Thus, if a mixture of oxygen
respectively. and steam (H2O) is passed over coke and at
(A) –31.2 KJ (B) –21.2 KJ the same time, temperature does not change,
(C) –11.2 KJ (D) –41.2KJ the composition should be such that H of
(Ans. D) both the reactions are numerically equal.
Sol. In the first reaction, consumption of ½ mole
of O2 evolves 110 kJ of energy while in the
Hº= Hfº(products) –  Hfº(Reactants)
second reaction, for 1 mole of steam (H2O),
0 0 0 0
= [ Hf (H2O)  Hf (CO) ]  [ Hf (CO2 )  Hf (H2 ) ] 132 kJ of energy is obsorbed.
0.5
Hº = [–241.8 – 110.5] – [–393.5 + 0]  Mole of O2 needed to evolve 132 kJ =
110
= – 352.3 + 393.5 = + 41.2 KJ
× 132 = 0.6
Ex.9 Calculate the work performed when 2 moles  Mole ratio of O2 and steam (H2O) = 0.6 : 1
of hydrogen expand isothermally and
reversibly at 25ºC from 15 to 50 litres. Ex.12 200 ml of KOH and 200 ml of HNO3 of same
molarity are mixed together and liberated
Sol. We have,
3.426 kJ of heat. Determine the molarity of
V2 each solution.
W = – 2.303 nRT log Sol. Let the molarity of KOH and HNO3 solution
V1
is x.
50  200 ml of x mole KOH solution
= 2.303 × 2 × 2 × 298 × log
15
= –1436 calories. 200
= × x mole OH¯ ions
1000
Ex.10 At 25ºC for the combustion of 1 mole of liquid = 0.2 x mole OH¯ ions
benzene the heat of reaction at constant Similarly,
pressure is given by,
200 ml of x mole HNO3 solution
15
C6H6 () + O (g)  6CO 2 (g)+ 3H2O (l)
2 2
; H = –780980 cal.
 200 According to Hess’s law
= × x mole H+ ions H1 = H + H2
1000
= 0.2 x mole H+ ions H = H1 – H2
H+ (aq) + OH¯ (aq)  H2O () = – 66.5 – 11.7 = – 78.2 KJ
0.2 0.2 x 0.2 x
Ex.15 Calculate the entropy change (S) per mole
Heat evolved during formation of 1 mole for the following reactions:
H2O = 57.1 kJ
(a) Combusiton of hydrogen in a fuel cell at 298 K
 Heat evolved during formation of 0.2 x mole
H2(g) + ½ O2(g)  H2O (g)
= 57.1 x 0.2 X x kJ
Heat evolved is = 3.426 kJ. H = – 241.6 kJ, G = – 228.4 kJ
 57.1 × 0.2 × x = 3.426 kJ (b) Vaporisation of methanol at its normal boiling
point.
3.426 CH3OH (l)  CH3OH (g)
or x = 57.1  0.2 = 0.3 mole.
Hvap = 23.9 kJ , boiling point = 338 K
(c) Fusion of ice at its normal melting point,
Ex.13 Calculate the heat change in the reaction
Ice  Water
4NH3 (g) + 3O2 (g)  2N2(g) + 6H2O ()
Hfusion = 6.025 kJ, melting point = 0ºC
at 298 K given that the heats of formation at 298
K for NH3 (g) and H2O (l) are – 46.0 and Sol.(a) According to the reaction .
– 286.0 KJ mol–1 respectively. H  G
G = H - TS of S =
T
Sol. Hº for the reaction Given that G = - 228.4 kJ, H
4NH3(g) + 3O2(g)  6H2O (l) + 2N2(g) = – 241.6 kJ and T = 298 K
Hº= Hºf (products) - Hºf (reactants)
Substituting the values, we get
= {6Hºf [H2O (l)] + Hºf [N2(g)}
– {4H [NH3(g)] + 3Hf [O2(g)]} (241.6kJ)  (228.4kJ)
S =
Hºf [H2O (l)] = – 286.0 kJ mol–1 298 K
Hºf [NH2 (g)] = 0 and Hºf [N2 (g)] = – 0.0443 kJ K–1 or = – 44.3 JK–1
= 0 (by convention) (b) Vaporisation represents a state of equilibrium
Hº = {6(-286) + 2 (0)} – {4(–46.0) + 3 (0)] between the liquid and the vapour state of
= – 1716 + 184 = – 1532 kJ the substance. At this state G = 0 so that
H
Ex.14 The heats of solution of anhydrous CuSO4 H TS or S =
and hydrated CuSO4 5H2O are – 66.5 and T
11.7 kJ mol–1 respectively. Calculate the heat Here H = 23.9 kJ . T = 338 K
of hydration of CuSO4 to CuSO45H2O.
23 .9kJ
 S = = 0.070 kJ K-1 = 70 JK-1
Sol. The required equation is : 338K
CuSO4(s) + 5H2O (l)  CuSO4.5H2O(s) (c) Fusion represent a state of equilibrium
H = ? between ice and water. At this state.
given that G = 0 so that
CuSO4(s) + (aq.)  CuSO4. (aq) H
H1 = – 66.5 kJ H = TS or S =
T
CuSO4 . 5H2O(s) + aq.  CuSO4.(aq) Here H = 6.025 kJ and T = 273 K
H2 = + 11.7 kJ
6.025kJ
The process of hydration may be expresed S = = 0.0220 kJ K–1 = 22 JK–1
as 273K
H1
CuSO4 (s)  CuSO4(aq)

H H 2

CuSO4. 5H2O