1

C-06:- THERMODYNAMICS

1. CHEMICAL ENERGETICS 4. THERMODYNAMIC PROCESSES

It is branch of chemistry which deals with the energy changes A. Isothermal process
in a chemical reaction. i. A process in which temperature of the system does not
2. SYSTEM AND SURROUNDINGS change throughout the studies is called isothermal process.
A. System ii. dT = 0 and thus dE = 0
It is the specific part of the universe in which energy changes iii. It can be achieved by using thermostatic bath.
are taking place. B. Adiabatic process
B. Surroundings i. A process in which exchange of heat between system and
It represents the rest of the universe which surrounds the surroundings does not take place.
system. Universe = system + surroundings. ii. Means q = 0.
C. Types of system iii. It can be achieved by insulting the boundaries of the
Systems are of three types: system.
i. Open system: A system is said to be open, if both mass and C. Cyclic process
energy can be exchanged with the surroundings. For example: i. A process in which system returns to the initial state after a
Boiling of water in beaker, tea in a cup. series of changes.
ii. Closed system : A system is said to be closed, if only ii. There is no change in energy in a cyclic process dE =0
exchange of energy takes place with the surroundings. For D. Reversible process
example : Heating of liquid in sealed tube, tea in a steel kettle. i. It is a process carried out infinitesimally slowly so that all
iii. Isolated system : A system is said to be isolated, if there changes ocurring in the direct process can be exactly reversed.
is neither exchange of mass nor of energy. For example : ii. The system and the surroundings remain in a state of
Liquid in a sealed thermos flask, tea in a thermos flask. equilibrium at any stage in the reversible process.
D. Homogeneous and heterogeneous systems E. Irreversible process
i. Homogeneous system: In homogeneous system, all the i. It is a process in which the change is brought about rapidly.
constituents present are in the same phase and the ii. System does not have chance to achieve equilibrium.
composition of the system is uniform throughout. For iii. The force which drives the reactants towards the products
example: A mixture of different gases. is greater than the opposing force which is to cay the reverse
ii. Heterogeneous system: In heterogeneous system process.
constituents are present in two or more phases and its F. Isobaric process
composition is not uniform. For example: Mixture of A process in which pressure of the system remains constants.
immiscible liquids. dP=0.
E. State function of state variables G. Isochoric process
A physical quantity is said to be a state function, if the change A process in which volume of the system remains constant
in its value during the process depends only upon initial state throughout. dV = 0.
and final state of the system and do not depend upon the path Check Your Grasp
by which this change has been brought. For example : 1. Which of the following is a close system?
Pleasure volume, enthalpy, internal energy etc. A. Jet engine
Red Alert B. Tea placed in steel kettle
3. INTENSIVE AND EXTENSIVE PROPERTIES C. Pressure cooker
A. Intensive Properties D. Rocket engine during propulsion
The properties which don not depend upon either the size of 2. The intensive property among these quantities is
the system or the quantity of matter present in it, are known as A. mass B. volume
intensive properties. For example: Pressure, temperature, C. enthalpy D. mass/volume
density, specific heat, surface tension, viscosity, refractive 3. Identify the extensive property among the following:
index, melting and boiling points etc. A. temperature B. pressure
B. Extensive properties C. viscosity D. enthalpy
The properties which depend upon the quantity of the matter
present in the system are known as extensive properties. For
example: Mass, volume, energy, enthalpy, work etc.
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4. An adiabatic expansion of an ideal gas always has
A. decrease in temperature
B. = 0
C. w = 0
D. = 0
5. During isothermal expansion of an ideal gas, its
A. internal energy increases
B. enthalpy decreases
C. internal energy remains unaffected
D. enthalpy reduces to zero
5. MODES OF EXCHANGE OF ENERGY BETWEEN
THE SYSTEM AND SURROUNDINGS
Energy is mainly exchanged as heat and work between the
system and the surroundings.
A. As heat energy
i. Heat absorbed by the system is positive; q=+ve
ii. Heat evolved by the system is negative; q= ve
iii. Heat is not a state function.
B. As work energy
i. Work is not a state function because the amount of work
done depends upon the path followed.
ii. Work done by the system is negative.
iii. Work done on the system is positive.
C. Nature of work
Work is expressed as the product of two factors
i.e., W=Intensity factor capacity factor
Mechanical work = force (F) displacement (d)
Electrical work = potential difference (E) charge flow (Q)
Expansion work = pressure (P) change in volume ()
D. Units of work and heat
Unit of heat
1 Joule = 0.2390 cal
1 litre - atm = 101.3 J = 1.013 109 erg = 24.206
Unit of both heat and work is joule (J), 1 Joule = 107 ergs
1 cal = 4.184 J, 1 calorie> 1 Joule > 1 erg.
E. Work done during various types of processes
i. Work done during expansion, w = PV
ii. Work done during contraction, w = PV
Red Alert
A. Work done in isothermal and reversible expansion of an
1
Ideal gas, w = 2.303 nRT. log
2
2 Also = + . For a reaction involving solids,
= 2.303 nRT log
1 liquids and gases, the value of is evaluated by the
B. Work done in irreversible process
wirr = (2 1 ); at constant volume wirr = 0.
C. Work done in irreversible process
R
wrev = (2 1 )
1
i. If 2 > 1, then Wrev is + ve, i.e. work is done on the system.
ii If 2 < 1 then, is ve, i.e. work is done by the system.
iii. is the poisson ratio =
Cp
Cv
= 1.66 monoatomic gas
= 1.40 diatomic gas
=1.33 polyatomic gas
D. Important results of adiabatic expansion
PV =constant;T(1 ) = constant
1 =constant. W = (2 1 ).
6. SOME THERMODYNAMIC QUANTITIES
A. Internal energy (E)
i. The energy stored within a substance is called its internal
energy. It is denoted by symbol E.
It is the sum of different types of energies.
= + + + + , =electronic energy;
= nuclear energy, =chemical bond energy
= potential energy, = kinetic energy
ii. = 2 1 , 2 =Iinternal energy of final state
1 = Internal energy of initial state, =
= Internal energy of products
= Internal energy of reactants
iii Internal energy is an extensive property and state function.
iv. For isothermal processes = 0; is negative if energy is
evolved ( < ); is positive if energy is absorbed.
( > )
v. is the heat energy exchanged between the system and
surrounding at constant temperature and volume ( )
vi. The magnitude of internal energy is determined by the state
of system i,e. E = 1 (, ) = 2 (, ) = 3 (, )
vii. For a cyclic process and = 0
B. Enthalpy
i. It is the sum of the internal energy and pressure volume work,
= +
ii. Enthalpy is a state function and extensive property.
iii. For adiabatic process = 0; is negative f energy is
evolved i,e. for exothermic reactions ( < ).
is positive if energy is absorbed i.e. for endothermic
reactions ( > ).
iv Change in enthalpy () is the heat energy exchanged
between the system and surrounding at constant temperature
and pressure ( ).
v. Relationship between heat of reaction at constant P and heat
of reaction at constant V is. = + .
Red Alert
vi. The change in enthalpy, = + .
difference in number of moles of gaseous reactants and
products.
TRICK
1. When = 0, then =
2. If > 0, then >
3. If < 0, then < .
vii. For reactions involving solids and liquids only,
=
viii Enthalpy change () is calculated using calorimeter (an
open vessel).
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ix. Enthalpies of formations of all the elements in their standard C. = D. =

state (at 298 K, 1 atm.) are zero. 12. is the heat absorbed at constant
x. Kirchoffs equation A. temperature (T) B. Pressure (P)
2 1
1. = (2 1 ) C. volume (V) D. T,P and V


13. Which of the following is not correct about enthalpy?
2. = (2 1 ) A. It is an extensive property

Where 1 ; 1 are heat of reactions at temperature 1 and B. It is not a state function
2 , 2 are heat of reactions at temperature 2 . C. Its absolute value cannot be determined
= () (). D. Enthalpy of a compound = Enthalpy of formation of that
= () (). and are molar compound
specific heats at constant pressure and constant volume 7. EXOTHERMIC AND ENDOTHERMIC REACTIONS
respectively. A. Exothermic Reactions
These are chemical reactions which proceed with evolution of
xi. The relationship between heat of reaction at constant
heat. In other words, heat is given out by the reacting
pressure and that at constant volume is = + .
substances and enthalpy of the product is lowered.
xii. Bomb calorimeter is used to measure the internal energy.
Or <
Red Alert
= = ve
xiii. Internal energy evolved by a substance
Hence is negative for exothermic reactions. Likewise
= is also negative in these reactions.

Where, B. Endothermic Reactions
= mass of the substance These are chemical reactions which proceed with absorption
= heat capacity of the calorimeter of heat by the reacting substances. The enthalpy of the
= rise in temperature products, therefore, becomes more than the enthalpy of
= molecular mass of the substance. reactants.
Check Your Gasp Or >
6. If a reaction involves only solids and liquids, which of the = = +ve
following is true Hence is + ve for endothermic reactions. Likewise is
A. < B. = positive for these reactions.
C. < D. = + . Red Alert
7. Heat exchanged in a chemical reaction at constant 8. HEAT CAPACITY OF A SYSTEM
temperature and pressure is called The amount of heat required to raise the temperature of the
A. entropy change unit mass of the substance (in the system) by one degree (K or
B. enthalpy change 0
C). Heat capacity = dQ/dt
C. internal energy change If m mass of substance absorbs q amount of heat to raise
D. free energy change temperature from 1 to 2 . then heat capacity (C) of a
8. Enthalpy of a reaction is expressed as
Substance is given as = =
(2 1 )
A. =
If mass of the substance involved is 1 g, the heat capacity is
B. = +

called specific heat capacity of the system.
C. =
Specific heat capacity =


D. = A. Molar heat capacity (C)

9. The enthalpy change of a reaction does not depend i. The amount of heat required to raise the temperature of one
A. The state of reactants and products mole of a substance (in the system) by 1K.

B. nature of reactants and products Molar heat capacity = atomic/molar mass

C. different intermediate reactions ii. Molar heat capacity = specific heat capacity molar mass
D. initial and final enthalpy change of a reaction of the substance.
10. Enthalpy change () of a system depends upon its iii. Unit of molar heat capacity CGS unit of molar heat
A. initial state capacity =cal K-1 mol-1. S.I. unit of molar heat capacity
B. final state = JK-1 mol-1
C. both initial and final state iv. Molar heat capacity is of two types
D. none of these 1. Molar heat capacity at constant volume ( )
11. The relation between enthalpy (H), pressure (P), volume
= ( )
(V) and internal energy is given by

A. = + B. = + 2. Molar heat capacity at constant pressure ( )

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v. Conditions of constant pressure and volume: The enthalpy

= ( )

of reaction () is expressed at constant pressure. In case,
3. Relationship between and , = volume is constant, then it is called change in internal energy
This is known as Meyers relationship. R = gas constant (). The two are related to each other as
(8.314 JK 1 mol1 ). = + .
Check You Grasp 10. DIFFERENT TYPES OF ENTHALPIES OF
14. An exothermic reaction is the one in which the reacting REACTIONS
substances A. Enthalpy of formation
A. have more energy than the products It is enthalpy change that accompanies the formation of one
B. have less energy than the products mole of a compound from its constituting elements at a given
C. have the same energy as the products temperature and pressure. For example:
D. are at a higher temperature than the products C() + 2H2 () CH4 () = 74.8 kJ/mol
15. For an endothermic reaction where represent the Standard enthalpy of reaction
enthalpy of the reaction in kJ/mol, the minimum value for = (Standard enthalpies of formation of products)
the energy of activation will be (Standard enthalpies of formation of reactants)
A. less than B. zero = 0 (products) 0 (reactants)
0
C. more than D. equal to
Red Alert
16. The heat required to raise the temperature of 1g of a Compounds with high heat of formation are less stable
body by 1K is called because energy rich state leads to instability.
A. specific heat B. thermal capacity
EXAMPLE
C. water equivalent D. none of these
EXAMPLE:1 The enthalpies of formation of and NO
17. Heat capacity is

are 28 and 90 kJ respectively. The enthalpy of the
A. B. reaction.

1
C. . D. none of these () + () () is equal to

9. THEMOCHEMICAL EQUATION A. 8 kJ B. 88 kJ
It is an equation which represents chemical as well as thermal. C. kJ D. 304 kJ
1
Changes taking place in a reaction. For example: () + SOLUTION: 2 + 2 2 ; = 28 kJ ..(i)
2
2 () 2 (); = 393.5 kcal. It signifies that 12 g of 1 1
N2 + 2 NO; = 90 kJ
2 2
carbon on reaction with 32.g of 2 gives 44 g 2 along with
By eq.[4 ()] [2 ()]; 2N2 O + O2 4NO; H =
393.5 kcal of heat evolution.
304 kJ
A. Factors influencing the enthalpy of reaction
B. Enthalpy of combustion
i. Physical state of reactants and products:
It is the enthalpy change that accompanies the combustion of
Since latent heat is involved in the change in the physical
1 mole of a substance in excess of air or oxygen.
state of reactants and products, therefore enthalpy of reaction
4 () + 22 () 2 () + 22 ();
change with change in the physical state. For example
1
= 890.3 kJ mol1
H2 () + O2 () H2 O(); = 286.0 kJ TRICK
2
1
H2 () + O2 () 2 (); = 242.0 kJ The heat of combustion depends upon number of atoms of
2
ii. Quantities of reactants : The change in enthalpy depends carbon and hydrogen. The greater the number of carbon and
upon the quantities of the reactants taking part in the reaction. hydrogen atoms the more will be the heat of combustion.
For example: Note
1 Calorific values
() + 2 () 2 (); = 289.0 kJ
2 The amount of heat produced when one gram of the substance
22 () + 2 () 22 (); = 572.0 kJ is completely burnt.
When the number of moles of reactants are doubled, the Red Alert
enthalpy change also becomes double. C. Enthalpy of hydrogenation
iii. Allotropic modifications of reactants: The enthalpy of It is the enthalpy change when one mole of an unsaturated
reactions are different for the different allotropic forms of a organic compound is fully hydrogenated.
particular substance. For example: 2 = 2 () + 2 () 3 3 ()
C(graphie) + O2 (g) CO2 (g)H = 393.5 kJ = 132.5 kJ mol1
C(diamond) + O2 () CO2 () = 393.4 kJ D. Enthalpy of neutralisation
iv. Conditions of temperature and pressure: A chemical It is the enthalpy change which takes place when one gram
reaction has different enthalpies at different temperature and equivalent of an acid and a base present in their their dilute
pressure. They are generally expressed under standard aqueous solution neutralise each other.
conditions of temperature (298 K) and pressure (1 atm).
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NaOH() + HC () NaC () + 2 (); SOLUTION: Given BaC2 () + BaC2 ();

= 57.1 kJ = 20.6 kJ. .(i)
The heat of neutralisation is due to formation of one mole of Ba2 . 22 () + BaC2 (); = +8.8 kJ ..(ii)
water. eq. (i) can be split in two steps as
+ + 2 ; = 57.1 kJ, mol1 BaC2 () + 22 () BaC2 . 22 (); = 1
(from acid) (from base). BaC2. 2H2 O(s) + aq BaC2 (); H = H2
i. The enthalpy of neutralisation of a strong acid by a strong 1 + 2 = 20.6
base is always constant ( = 57.1 kJ). Or 1 + 8.8 = 20.6
ii. Enthalpy of neutralisation of weak acid by weak base, strong 1 = 20.6 8.8 = 29.4 kJ
acid by weak base or weak acid by strong base is always less Red Alert
than 7.1 kJ. This is because some heat is used in the G. Bond Enthalpies
dissociation of weak acid or weak base. So, heat of i. Diatomic molecules : The amount of energy required to
neutralisation = 57.1 + enthalpy of dissociation of weak break one mole bonds of a particular type between two atoms
component. in gaseous state of a substance.
iii. Heat of neutralisation of HF is more than 57.1 kJ (68 kJ). For example:
This is due to very high heat of hydration of fluoride ions. H2 () 2(); 0 = 435.0 kJ mol1
EXAMPLE ii. Polyatomic molecules: The average of the bond
EXAMPLE:2 Enthalpy of neutralisation of HCl with NaOH dissociation energy of the bonds of the same type in a gaseous
is x. The heat evolved when 500 mL of 2N HCl are mixed substance. For example:
with 250 mL of 4N NaOH will be H O H (g) H(g) + O H (g); H = +497.8kJ
A. 500x B. 100x O H(g) H(g) + O(g); = +428.5kJ
C. x D. 10 x
SOLUTION: 250 mL o 4N NaOH = 500 mLof 2N NaOH. This 497.8+428.5
Bond energy of O H bond =
2
will completely neutralise 500 mL of 2N HCl. Heat evolved
= 463.15 kJ mol1
from 1000 mL of 1N HCl =x
H. Energetic of Phase changes
Heat evolved from 500 mL of 2N HCl=x
i. Enthalpy of fusion: It is the change in enthalpy when one
E. Enthalpy of solution
mole of a solid at its melting point changes to the liquid state.
It is enthalpy change when one mole of a substance is
H2 O(l) H2 O();
dissolved in such a large excess of the solvent at a given = +6.0 kJ mol1
Ice water
temperature that the further addition of the solvent does not ii. Enthalpy of vaporisation : It is the change in the enthalpy
produce any more heat energy change. when one mole of a liquid at its boiling point changes to the
NaC () + NaC () ; = +5.25 kJ mol1 gaseous state.
Red Alert H2 O () H2 O(); = +62.4 kJ mol1
i. The enthalpies of solution of the hydrated salts like sublimation = fusion + vaporisation
CuSO4 . 5H2 O or CaC2 6H2 O are positive.
Check Your Grasp
ii. The enthalpies of solution of salts which do not form hydrates
18. Which one of the following bonds has the highest average
like NaC, KC, NH4 C, etc are positive i.e. dissolution is
bond energy ( ) ?
endothermic.
A. S = O B. C = C
iii. The enthalpies of solution of the anhydrous salts like CuSO4 ,
C. C N D. N N
CaCl2 , MgSO4 etc. which form hydrates are negative i.e.
19. The heat of neutralisation is maximum when
dissolution is exothermic. A. sodium hydroxide is neutralised by acetic acid
F. Enthalpy of hydration B. ammonium hydroxide is neutralised by acetic acid
It is the enthalpy change when one mole of the anhydrous salt C. ammonium hydroxide is neutralised by hydrochloric acid.
changes to a hydrated salt by combining with specific number D. sodium hydroxide is neutralised by hydrochloric acid
of moles of water.
20. The neutralisation of a strong acid by a strong base
CuSO4 () + 5H2 O () CuSO4 . 5H2 O (); liberates an amount of energy per mole of +
= 78.2 kJ/mol A. depends upon which acid and base are involved
EXAMPLE B. depends upon the temperature at which the reaction takes
EXAMPLE:3 The enthalpy of dissolution of () and place
. () are . and 8.8 kJ respectively. C. depends upon which catalyst is used
The enthalpy of hydration for D. is always the same.
(s)+ . () is 21. The enthalpy of neutralisation of a weak acid by a strong
A. 29.4 kJ B. . kJ base is
C. . kJ D. 38.2 kJ A. 57.32 kJ B. 57.32 kJ
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C. equal to 57.32 kJ + enthalpy of ionisation of weak base B. Non spontaneous process

D. more than 57.32 kJ A process which can neither take place by itself nor by
11. FIRST LAW OF THERMODYNAMICS initiation is called a non-spontaneous process. The force
Energy cannot be created or destroyed, although one form of which is responsible for the spontaneity of a process is called
energy can be converted into the other form and vice versa. the driving force.
A. Mathematical representation of the first law of Driving forces for spontaneous processes
thermodynamics i. Tendency to acquire minimum energy
Suppose a system has internal energy 1 . If it absorbs heat ii. Tendency to acquire maximum randomness
energy () from the surrounding and (w) work is done on the 14. ENTROPY
system, then its final internal energy (2 ) becomes 2 = 1 + Entropy is a measure of randomness or disorder of the system.
+ , 2 1 = + , = + It is represented by S.

Change in internal energy = Heat energy added to the system = 2 1 = =

+ work done on the system. Entropy of a reaction decreases with increases in pressure.
B. Limitations of first law of thermodynamics Entropy is state function; Entropy is extensive property.
It provides no information concerning the spontaneity or Unit of entropy: SI unit of entropy : JK 1 mol1
feasibility of the process. A. Entropy changes during phase transformations
12. HESSS LAW OF CONSTANT HEAT SUMMATIONS i) Entropy of fusion : The entropy of fusion is the change in
The heat energy in a physical process of chemical reactions is entropy when one mole of a solid substance changes into
quite independent of the manner in which the change has been liquid form at the melting temperature.
carried.
fus = liquid solid =

= entropy of fusion
= entropy of the solid
liquid = entropy of the liquid
= melting temperature in kelvin
= enthalpy of fusion per mole
ii) Entropy of vaporisation : The entropy of vaporisation is
the change in entropy when one mole of liquid change into
Applications of Hesss law vapours at its boiling temperature.
A. To determine heat of transition i.e., conversion of one
= =

allotropic form into another.
B. To determine heat of intermediate steps in a reaction. = Enthalpy of vapoisation per mole
C. To calculate heat of a known/unknown reactions. = boiling temperature in kelvin
D. To calculate bond energies. iii) Entropy of sublimation : The entropy of sublimation is
i. For solving bond energy numericals, use, the entropy change when one mole of the solid changes into
= B. E B. E vapour at a particular temperature.

=Bond energy (reactants) bond energy (products) = =

or = (products) (). = Heat of sublimation at the temperature T.
ii. Average bond energy Entropy change of an ideal gas for 1 mol
Heat of dissociation of the substance 2 2
= = n + Rn
Number of covalent bond broken 1 1
TRICK 2 2
= Rn
1 1
iii. The order of average bond energies for different types of
At constant T (isothermal process)
bonds is single bond <double bond <triple bond. 2 2
iv. In case of allotropes, the enthalpy of formation of the most = Rn = Rn
1 1
stable allotrope is taken as zero e.g., the heat of formation of At constant volume (isochoric process)
graphite is zero but of diamond is not zero. Similarly, 2
= n
1
standard enthalpy of rhombic sulphur is zero.
At constant pressure (Isobaric process)
13. SPONTANEOUS AND NON SPONTANEOUS 2
PROCESSES = n
1
A. Spontaneous process Entropy change : The liquid is heated
A process which can either take place by itself no by initiation m = mass of liquid
= msn 2 [ ]
is called a non-spontaneous process. Spontaneous process is 1 s = specific heat
an irreversible process and may only be reversed by some Entropy and spontaneity
external agency. If Total > 0 reaction is spontaneous.
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Total > 0 reaction is non spontaneous B. Free energy change and predicting spontaneity of a
= 0 reaction mixture is at equilibrium reaction
EXAMPLE
EXAMPLE : 4 When one mole of an ideal gas is compressed Free energy change
to half of its initial volume and simultaneously heated to
= : This equation is called Gibbs-Helmholtz
twice its initial temperature the change in entropy () is
equation.
A. B.
i. is state function. ii. is an extensive property.
C. D. ( )
2 2
C. Criterion of spontaneity
SOLUTION = n + Rn =
1 1
If is ve, the process is spontaneous. If is +ve, the
1
= Cv n2 + Rn = Cv n2 Rn2 = (Cv R) n2 process is non-spontaneous. If is zero, the process is in
2
equilibrium.
B. Entropy changes in processes not involving any phase
TRICK
transformation
D. Effect of temperature on the spontaneity of a process
Entropy increases when number of molecules of products are
greater than the number of molecules of reactants. Sign of Sign of Value of Spontaneity
temperature
For example: 2SO3 (g) 2SO2 (g) + O2 (g) + Any Spontaneous
+ Any Non spontaneous
15. SECOND LAW OF THERMODYNAMICS
Low Spontaneous
A. The total entropy of the universe must tend to increase in a
High Non spontaneous
spontaneous process. Low Non spontaneous
+ +
+ + High Spontaneous
= + () > 0 (positive)
E. Physical significance of Gibbs energy change
B. Second law of thermodynamics
(Free energy change and useful work)
The entropy of universe always increases in the course of
= Wnon expansion Or =
every spontaneous (natural) process i.e. > 0.
Entropy change of the universe during a reversible isothermal The decrease in the free energy in a system of a process is the
process is zero. measure of maximum useful work done by the system. For
electrochemical cells, useful work is the electrical work
Red Alert
0 = 0 cell.
16. GIBBS FREE ENERGY AND FREE ENERGY
CHANGE Where = number of moles of electrons involved in the cell
= of the cell, = 1 faraday = 96500 C mol1
A. Gibbs free energy
F. Standard free energy change in terms of standard energy
It is the amount of energy available for doing useful work
of formation
under the conditions of constant temperature and pressure.
The Gibbs free energy is related to both enthalpy and entropy Standard free energy change is the change in free energy
as which takes place when the reactants in their standard states
are converted into the products, also in their standard states.
=
0 = 0 0
= Enthalpy of the system.
0 = standard change in enthalpy
= Entropy of the system
0 = standard change in entropy
= Temperature of the system on Kelvin scale
= standard temperature (298K)

0 = 0 (products) 0 (reactants)
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G. Relation between standard free energy change and B. fee energy change is less than zero ( < 0)
equilibrium constant
C. standard free energy change is less than zero ( 0 < 0)
=
D. standard free energy change is greater than zero
0
lnK = /
( 0 > 0)
0 /R
K=
26. A particular reaction has a negative value for the free
Where, energy change. Then at ordinary temperature

R = Gas constant A. it has a large ve value for the entropy change

T = Kelvin temperature B. it has a large + ve value for enthalpy change

K = Equilibrium constant C. it has small + ve value for enthalpy change

0 = Standard free energy change D. it has a + ve value for the entropy change and a ve value
for the enthalpy change
Red Alert
27. For a spontaneous chemical process, the free energy
0 log K K Comment change is
=0 log K=0 1 Amount of amount of
reactant = product A. positive B. negative
<0 log K >0 > 1 Equilibrium mixture is
mainly product and reaction C. zero D. any of the above
is spontaneous
>0 log K <0 < 1 Equilibrium mixture is 28. The occurrence of reaction is impossible if
mainly reactants and
reaction is non spontaneous A. is + ve ; is also + ve
Check Your Grasp
B. is ve ; is also ve
22. According to the second law of thermodynamics, a
process (reaction) is spontaneous, if during the process C. is ve ; is + ve

A. > 0 B. universe = 0 D. is + ve ; is ve

C. system > 0 D. universe = system 29. The free energy change for a reversible reaction at
equilibrium is
23. Considering entropy (S) as a thermodynamic parameter,
the criterion for the spontaneity of any process is A. zero B. small positive

A. system + surroundings > 0 C. small negative D. large positive

30. The burning silane is a spontaneous process because the

B. system surroundings > 0
value of is
C. system > 0 only
A. positive B. negative
D. surroundings > 0 only C. zero D. not significant

24. = was given by 17. THIRD LAW OF THERMODYNAMICS

A. Faraday B. Kirchoff This law was given by Nernst.

C. Einstein D. Gibbs-Helmholtz The entropy of an ideal of perfect crystalline solid may be

taken as zero at absolute zero temperature.
25. For the equilibrium (l) (g) at 1 atm and 298
K,

A. standard free energy change is equal to zero ( 0 = 0)

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A. Application of third law of thermodynamics Note

It helps in the calculation of absolute entropies of various
substances at room temperature or any other temperature.
= 0 ; = Entropy at T K; 0 = Entropy at 0K
According to third law of thermodynamics
0 = 0 therefore =
1. When a rubber band is stretched, entropy decreases because
the macro molecules get uncoiled and hence arranged in a
more ordered manner. i.e., randomness decreases.
2. When an egg is boiled, the entropy increases because
denaturation occurs resulting into a change of proteins from
helical form into random coiled form.

Efficiency of machine (): Fraction of heat absorbed by
= = = n = 2.303 log machine which is converted to useful work.

Where is the heat capacity of the substances at constant Q Q

= = =

pressure.
2 Heat absorbed from source at temperature 2 .
B. Entropy change () for a reaction is
1 Heat rejected to sink at temperature 1 .
= products reactants
EXAMPLE
= 2.303R log 2 /1 or = 2.303 R log 1 /2.
EXAMPLE:5 What percent is of for a heat engine
= n 2 /1 + Rln 2 /1
whose efficiency is 10%?
? EXCEPTIONS
A. 80% B. 90
C. Limitations of third law of thermodynamics
C. 10% D. 100%
i. Glassy solids even at 0 K has entropy greater than zero. 2 1 1
SOLUTION: = = 1
2 2
ii. Solid having mixture of isotopes do not have zero entropy
1
at 0 K. For example : entropy of solid chlorine is not zero at 0 Or = 1 = 1 0.1 = 0.9 = 90%
2
K.
Check Your Grasp
iii. Crystals of CO, N2 O, NO, H2 O etc. do not have perfect
order even at 0 K. Thus, their entropy is not equal to zero. 31. According to third law of thermodynamics, which one of
the following quantities for a perfectly crystalline solid is
Misconcepts
zero at absolute zero?
1. The concept is standard enthalpy of formation of graphite is
A. Entropy B. Free energy
zero while that of diamond is not zero but it is equal to 1.816
kJ mol1 . C. Internal energy D. Enthalpy

2. = + . In bomb calorimeter, = 0. Hence

should be equal to . But this is not true because
32. Formation of ice is a process in which entropy
= + holds good only at constant pressure.
A. decreases B. increases
= +
C. remain constant D. follows a wave pattern
= + +

At constant pressure, = 0

= +

At constant volume, = 0

= +
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