CHAPTER

6 CHEMICAL
THERMODYNAMICS

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Chapter Objectives

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Fundamentals of thermodynamics: System and surroundings, Extenisive and intensive properties, and thermodynamic
Statefunctions.

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First law of thermodynamics : Concept of work, heat, internal energy and enthalpy, Heat capacity, Molar heut caacty
Hess's lavw of constant heat summation, Enthalpies of bond dissociation, combustion, formation, neutralization, solutio
hnydration, fusion, vnporisation and sublimation, Carnot engine.
Second law of thermodynamics: Entropy, Spontaneity of processes, AS for universe, AG of the system as criteria for
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spontaneity, Gbb's Helmholtz equation, AG (standard Gib's energy change) ad equilibrium constant
Third law ofthermodynamics:Briefintroduction.
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STUDY MATERIAL
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I.ConceptClarified:
Thermodynamics
between heat energy (Thermos) and
The branch of science that deals with the study of quantitative relationship
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or chemical transformation
is called thermodynamics.
other forms of energy, i.e., work (dynamics) during a physical
are first,
which is derived from experiments. These
The study of thermodynamics is based on three generalisations
second and third laws of thermodynamics that help us to determine the following
between heat and other forms of energy.
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(i) Derivation of quantitative ship

relation
conditions.
chemical reaction takes place under the given set of
(ii) An idea to predict whether
a

reaction before the equilibrium is attained.

(ii) Predict the extent of
distribution law etc.
such as law of mass action,
(iv) To deduce various laws
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(v) Predict the spontaneity of process.

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of various types of engines.

(vi) Determine the efficiency
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Limitations of Thermodynamics to individual atoms

and not to microscopic systems, i.e.,
systems (i.e., bulk)
G) It is applicable only to macroscopic
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or molecules.
will proceed.
indication of how fast the reaction
i) It does not give any value for the work obtainable from a chemical or physical
ii) Thermodynamic methods provide only a limiting
transformation. mechanism of the process.
remains silent about the
state of a system but
It deals only with initial and final
iv)
Thermodynamical Equilibrium equilibrium when it shows
no further tendency to

obtaineda state thermodynamical

of
A system is said to have
time.
change its property with is same throughout process.the
When the temperature or its boundaries.
Thermal equilibrium: the
It involves no
flow matter with systemwith
of
Mechanical equilibrium: remains constant changing time. Formere details,|
If the chemical composition
Chemical equilibrium: scan the code

Fundamentals of Thermodynamics which are as follows.

terms are used in thermodynamics
Some important observation.
ofspace that isunder
S y s t e m : t is any region universe outside the system.

Surroundings The
remaining part of the
 Formoredetaik
Boundary:
The actual or imaginary wall of layer that separates the system from the surroundings. scan the code

There are various types of boundaries:

(a) A rigid boundary: Its boundary and shape are fixed. D
the passage of matter.
(b) An impermeable boundary: Such boundary does not permit
the of matter and energy.
(c) Permeableboundary: Its permits passage
(d) An adiabatic boundary: It does not permit the passage of matter or energy.

Example:A
(e) A diathermalthermos bottle. boundary: A boundary that allows heat to flow through it is called diathermal
or diathermic
whereas a boundary which does not allow heat to flow through it is called adiabatic. It means that a diathermal
wall is impermeable but not adiabatic.
Surroundings Universe.
Universe :System
=
+

Types of Systems:
(i) Open system: It can exchange matter as well as energy with surroundings.
(ii) Closed system :Only energy is exchanged with the surroundings but not matter.

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(ii) Isolated system: Neither matter nor energy is exchanged with surroundings.
Energy, matter
Energy, matter Energy

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Isolated
Open Closed

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system
system system

.Homogeneous system: Uniform throughout one phase.

Heterogeneous systems: Non-uniform, two or more phases.
Thermodynamic Properties: ita
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i) Intensive properties: Properties that are independent of the quantity of matter present in the system, or sizeof
the system.
Examples: Pressure, temperature, density, concentration terms, pH, specific heat, molar heat capacity, molar
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entropy, molar enthalpy, molar internal energy, boiling point, melting point, etc.
(i) Extensive properties: Properties whose magnitude depends upon the quantity of matter present in thesystem
or the size of the system. Extensive properties are additive.
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Examples: Mass, volume, number of moles, internal energy, entropy, Gibb's free energy and heat capacity
Two important aspects regarding intensive and extensive properties :
(i) The ratio of two extensive properties to always an intensive property.
Mass
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Example:Density Volume
Mass and volume are extensive properties of a system but density is intensive property .
(i) Extensive property can be converted to intensive property by specifying a system with the quantity of mater
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Examples: (a) Molar entropy orentropy per mole

(b) Molar internal energy or internal energy per mole or internal energy per gram.
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Thermodynamic Processes
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When the system changes from one state into another final state.

Thermodynamic processes

(ii) Isobaric process (iv) Isochoric process

i) Isothermal process (ii) Adiabatic process

No exchange of heat between Pressure remains constant Volume of the system

Temperature remains constant
remains constant
throughout the process, i.e., system and surroundings
ie., dQ = 0
throughout thechange
i.e., dP = 0 during the change
heat can flow from the system
System is thermally isolated. ie., dV =0
to the surroundings and vice
versa, change in temperature
dT = 0
 Isobaric

hermal
Adiabatic
Volume

Graphical representation of four thermodynamic processes

it can be reversea
A
() Reversible process: process which infinitesimally slowly in such a way so that
is carried out

by applyirng the reversible condition and at any time the system and surroundings are in equilibrium.

systemPsurr t dP

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the successive steps of the direct
Irreversible process: A process which is carried out rapidly in such a way that

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(vi) and no equilibrium exists between system
and
process cannot be retraced without the help of external agency
surrounding.

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systemsurr t AP
State Functions or State Variables and are
value is upon the initial
and final states of the system
The thermodynamic properties whose dependent
independent of the path or route.
Examples: Internal energy (U), enthalpy (H), pressure (P), temperature (T),
(V), number of moles (n). ita
Gibb's free energy (G), entropy (S),
volume
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Path functions: The thermodynamic properties
whose value depends upon the path or process of transformation.
Examples: Work and heat.
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set of conditions is called

kinds of energies stored under a given
Internal energy (U): The total of all possible remains same.
the internal energy of that system
internal energy. When a system is in thermodynamic equilibrium,
volume (V) and temperature (T) of the system.
Internal energy depends on pressure (P),
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are called functions.

Therefore internal energy U fP T) f(PT) f" (V, T),f.f",f"
= =
=

Final state
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Path-I

Path-I
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U,
Initial state
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AU =U,-U,
of that system will be changed. If
in A,
final state B, internal energy
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from initial state A to II respectively, we can

When follow through Path I and Path
moves
a system -
-

and in B the internal energy U,

is
internal energy is U
measure the change in
internal energy as follows:
U Uj + W, [W,
=
= amount ofwork done in Path- I]
By the path-l; U-U = W
ii)
U-U W2
By the Path II,
-

work done in Path I]|

-

W a m o u n t of
=

we get W, W, i.e., it is not a path

function, it is a
=
state function.

Comparing the two equations,

forms of energy;
It is the of all microscopic
sum
tpotentialtyibrationalt Urotational
t
U= Uelectronic + nuclear+chemical
Characteristics of Internal Energy:
(i) It is an extensive property.
be measured
change of internal energy can
(i) It is a state function. not be determined but the
can
internal energy
(ii) The exact value of
accurately.
 Work, Energy and Heat
Work: Workisgenerally expressed as the force multiplied by the distance. If F is the force and is the displacen.
work done will be emen
W = Fx dl
Mechanical Work:
Mechanical work,W = Fxdl The general expression for the work done is written
Where F= force, dl =
displacement W=- Pext AV
tena
Force (F) Pext (V2-Vi)
-

Again, Pressure (P) =

=- Pext (V-V
Area(A)
F = PA
According to SI conversion, if work is done on
system, W is +ve and if work is done by system
Small work done by the gas
SW P x A x dl dl = difference of distance)
is-ve
Electrical work Potential difference x
Chargef
PaV A x dl dV
= =
(difference in volume) = VxQ= ExF
Integrating on both sides
Gravitational work Gravitational

h
=
force x
Height
W PdV = P(V, -V,)= PAV = mg x h

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Unit of work done : ] (S.I), ergs (C.G.S)
Energy: Energy is the capacity for doing work.

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Energy

Mechanical energy Electrical

energy
Chemical
energy ita Heat
energy
Light
energy
Mass
energy
Nuclear
energy
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Kinetic Potential
energy energy
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Heat (): This

type of energy is related with the molecular velocity
body to another through conduction, convection or radiation. proportionally, which can transform from one
Sign convention according to IUPAC:
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9Positive
Positive System Negative
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Negative
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Enthalpy (H) The pressure and volume of a

:
system are thermodynamic variables and product of PV is the
energy. The total heat content, i.e., enthalpy of the system is the sum of internal
H U + PV (At constant volume PV energy plus PV work done.
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0, actually in chemical laboratories, most

=

constant pressure.) processes occur at

Characteristics of enthalpy:
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(i) It is a state function.

(ii) It is an extensive property.
(ii) Its exact value can not be determined but enthalpy change can be determined
Consider a system; accurately.
Initial conditions Final conditions AH = AU +PAV
-(
Enthalpy
(

|H H2 For n moles, ideal gas equation is,

Pressure P PV = n,RT .. iv)
Volume PV= n,RT . (V)
Internalenergy U U P(V-V = (n1 - n^) RT
H = U + PV
.(i) PAV A n RT =
. (vi)
H U, + PV2
Subtracting () from (i) we get
.(ii) An, change in number of moles for
gases
H2-H = U2-U, + P(V2-Vi)
From equations (ii) & (vi) we get
AH AU+ An,RT
First Law of Thermodynamics | For more details,
The first law of thermodynamics is the law of conservation of energy. Some of the selected statements scan the code

are as follows:
() Energy can neither be created nor be destroyed but it can be converted from one form to another
ii) The total energy of the universe remains constant.
(ii) If some amount of energy is disappeared from a system, equal amount of energy come to the
system by means of else where.
Formoredetails,
(iv) It is very impossible to construct a perpetual motion that could produce work without applying| scan the coae
energy or applying small amount of energy to get greater work.

Mathematical formulation of the first law of thermodynamics: The internal energy of a system can
beincreased (i) by supplying heat to the system. (i) by
applying work on the system.

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+ + W

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U= Internal
energy Heat added Ut Work is done on Total internal
the system energy Ut q +W

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Suppose a gas is enclosed fitted with a weightless, frictionless piston having internal energy U. Now q amount of
heat is supplied to the system and the energy is raised to become U, +9.
Iffurther work 'w' is done on the system, the internal energy again increases and finally becomes U,+q+ W which

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is equal to U, then
U, = U, + q+ W
U-U= q+ W
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AU =q+ W
For a small change If work is done on surroundings, the above equation
dU 8q+8W| becomes
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dU ôq + PdV
q dU+8W
q =dU+ PdV
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Work done in isothermal reversible expansion of an ldeal gas:

The small amount of work done öw, when the gas Hence, we get from equation (i)
expands through a small volume dV, against the
W--
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external pressure, Pext is given by

W =- Pext dV

As it is a reversible expansion W=-nRT V

FextPint dP .1)
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W =-Pnt-dP) dV W= - nRT In
8W = - Pnt dV + dP x dV
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W =- Pint dV (As dP x dV is negligible)

.(ii) W=-2.303 nRTlog .
(iv)
From ideal gas equation, PV = nRT
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P= nRT P
V W=-2.303 PV log P . (v)
Total work done can be obtained when the volume
expands from V, to V2: Atconstarnt temperature P,V,= P2V21
Heat Capacity
The amount of heat required to increase the temperature of 1 g of substance by 1 K is called specific heat. The
heat input required to increase by 1K, the temperature of one mole of substance is called its molar heat capacity or
to increase temperature for one mole of substance, then
simply heat capacity. If Sq amount of heat required
is

C o
dT
But oq is path function and its value depends on the actual process followed.
To get precise values of heat capacity we can introduce certain restriction, for example, the restriction is heat capacity
at constant volume.
at constant pressure and heat capacity
Molar heat capacity at constant volume
From first law of
thermodynamics,
öq dU + 5W
oq-dU + Pdv Hence U )

SqdU Pdv
dT dT dT OH

dfd P.O C-C-T,T

(OU
dU
)
(oU
Molar heat capacity
H-U+ PV
at constant pressure, TPlTlT

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dH dU+ PdV + VdP

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dH Sq + VdP
For an-mole of ideal gas,|(OU
OV 0
dT T dT

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dH 9 V.0
C-C,- "|Tp
dT pdT
C-C P
Cp aT
Relation between C, & C
dH
.(i1) ita Cp-C, = Px =R
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As U = f(VT)
C-CR
Relation between T,P and V
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during Adiabatic Reversible Change

()Relation between pressure and volume:
According to 1t law of thermodynamics,
CPdVC,VdP
C,VP C, VP
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oq = dU + 6W
Dividing by C, VP]
For Adiabatic change ôq = 0
(i)
dU C, dT (ii)
ava-0o (vi)
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W = PdV
Integrating both sides,
From equation (i), (ü), (ii) and (iv) we get = constant
CdT + PdV = 0 TIav-par
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According to ideal gas equation, Inv+InP = constant

In PV = constant
PV RT
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PVT = constant ... (V)

Differentiating both sides we get,
This is the equation for adiabatic
Pdv+VdP =RdT change.
(ii) Relation between temperature and volume.
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d TPdV+Vdp PV = K
(vi) .(1)
R For 1 mole of ideal gas,
From equation (v) and (vi) we get, PV RT

C (PdV+VdP),pdv =0
R
PRT

From equation (i) and (ü) we get

CPdV+C,VdP +PRdV =0
PdV(Cy+ R) + C,VdP = 0 RT
V K
C PdV +C,VdP = 0
TV= constant
Calculation of Work Done in Adiabatic Expansion of ldeal Gas:
From 1 law of thermodynamics, From
oq = dU + öW
equation (i), (i), (ii) we get
For adiabatic change ôq = 0
i) W=-CdT ..
(iv)
.(ii) Integrating the above equations between tte
dU = C, dT . (ii) temperature T, to T2, we get
 RT P,V2 = RT
For isothermal process, PV, =

W--CdT RT ..11)
W=-C,T-T) . (v)

W- T-T)
C.(y-10T2
(y-1)
[Multiplying and dividing RT (ii)

(RT RT
c-1T-T) W-PPP
W=-
(-1)

c (T,-7,) -Rr1 ... (iv)

h
W=
(y-1) Now W,-Wrr

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. (V)
W- ) -RTInRT|1-
(y-1)
number of moles through infinitesimally

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For n occurs
Reversible process

W= nR(T-T) . (vi) slowly:

(y-1) .(vi)
n
(i) Isochoric process
From 1st law of thermodynamics,
A U = q. +W[W = PdV sin isochoric dV = 0]
ita P
From (v) and (vi) we get
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W,-WrRT
AU = 9

(i) Isobaric process

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W=-Pal(V-V,) -RT(P,-P
AH4
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(ii) Cyclicprocess: -RT(-B

Work done =Area enclosed in PV diagram

Case 1: For clockwise

P-P
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W=-ve
Case 2: For anti-clockwise RT
(P-P> positive quantity,
so

W = +ve V
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In irreversible work done W,-Wirr +ve,

W PV-V) W,Wirr Formore details,|

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scan the code

Constant Heat Summation:
Hess's Law of the matter
of reaction will be
same no
the same, the heat
Provided the other condition remaining
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in a number of steps.
or alternatively
whether the reaction takes place directly
AH = - 393.5 kJ

CO,(8)
C(s
AH =-110.5k]
+O8) CO(g)
(3)o For more details,|
scan the code

AH = AH +AH,
law: and can't be determined
Applications of Hess's are not stable, non-isolable
of intermediate compounds which
(i) Heat of formation Hess's law.
experimentally are
determined by applying from its element.
Benzene cannot be
synthesised directly
Example: 6C+3H,C,H,AH;
 By considering following reactions AH can be
calculated:
AHC,H
(a) C(s)+0,(s)CO,() AH=-393.1 kJ Equation 6i) x6 + Equation(i) x 3-Equation

b) H,+0,H,O) AH =-286.0 kJ
=
[-393. x 6+ (-286.0 x3) + 32661
= + 49.6 k

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(c) C.H,(0)+0,6Co,
2
+3H,O AH-3266.0kJ
(i) To determine heat of reaction: The reactions which are either very fast or occur simultaneously with o
reactions and cannot be studied experimentally, by applying Hess's law, heat of reaction of such reactions
ns can
be be evaluated.
(ii) Heat of transitions can be determined.
(iv) Lattice energy of ionic compounds can be calculated.
Enthalpy of Bond Dissociation:

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The amount of energy required to dissociate one mole of bonds between the atoms in a molecule in the gaseous sh,
is called enthalpy of bond dissociation.

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Hg)2H AH 435.4 kJ mol
The amount of energy released when a bond is formed between two atoms to form one mole of a compound
called bond enthalpy.

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2HH2 AH =-435.4 kJ mol
So, from the above two reactions it is evident that bond enthalpy is same as enthalpy of bond dissociation for
diatomic molecule.

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In case of polyatomic molecules the average value of enthalpy of bond dissociation is referred to as bond enthalpy

Examples: CH-H (8)> CH(8) + H(8) AH 425 kj mol

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HC-H(g)> CH,(8)+ H(8) AH = 470 kJ mol
HC-H (g)> CH(8) + H(g) AH = 416 kJ mol
C-H (8) C (8) + H(8) AH 335 kJ mol
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The variation in breaking of individual C - H bonds is high, that is why we consider the average of those four
dissociation enthalpies;
Bond dissociation enthalpy of C- H bond
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425+470+416+335
= 411.5 kJ
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Thus, bond enthalpy is defined as the average amount of energy needed to dissociate bond of a given type present
in one mole of the gaseous molecules.
Kirchoff's reaction (Variation of enthalpy of a reaction with temperature ): When asystem changesfns
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a given state to another state both the internal energy and the heat energy would change.
U-U AU
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Ha-H= AH
The suffixes 2 and 1 denote final and initial states.
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Equation () differentiating with respect to temperature at constant volume and equation (i) differentiating wiu

respect to temperature at constant pressure we get,

(DAU
OT - 7Cy-CyaCy .(

..(

Or, oaU-ACdT
and
aH= aC,dT
Integrating between the limit TK an OK we get;

AU AU + [AC,dT
 .(VI)
AH, =AH,+ JACpdT
Equations (v) and (vi) are called Kirchoff's equations.
in the
Lavoisier Laplace law: When a same reaction is reversed, heat of formation is equal to the heat absorption
of
reaction.

H,(8)+0,8s)->H,OU) AH =-285.8kJ mol

H,OU)H,(s)+0,(e) AH = + 285.8 kJ mol

Different Types of Enthalpies of Reactions

oxidized
(1) Enthalpy of combustion: The change in enthalpy when mole of substance is completely burnt
one
or

in oxygen. It is denoted by AHc. AHc is always negative as it is exothermic reaction.

(2) Enthalpy of formation: The change of enthalpy when one mole of the substance is formed from its element

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under given conditions. It is denoted by AH. It is negative for exothermic reaction and positive for endothermic

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reaction.

C(s)+0,(8)CO,(8) AH= -393.5 kJ

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AH = 90.15 kJ
N8)0)- 2NO
substance is formed from its
Standard enthalpy of formation: The change in enthalpy when one mole of a
constituent standard states (at 298 K and 1 atm pressure). It is denoted as AH.

i) If an element has two or more

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During determination of standard enthalpies, the following points are to be followed:
formation that
allotropes, during calculation of enthalpy of
be considered which is very stable at 298 Kand 1 atm pressure
allotrope is to
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i) Under standard conditions, the enthalpy of any element (stable allotrope) is taken as zero. [4 H, (graphite)
= 0 but A H (diamond +0)]
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by acid base is the change of enthalpy

neutralization: The enthalpy of neutralization of an a

one of
Enthalpy
(3) when gram equivalent of acid is neutralized by one gram equivalent base in a dilute solution.

The enthalpy of neutralization is maximum when a strong base is neutralized by a strong acid.
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HCI (4q) + NaOH (an) -> NaCl (aq) + H,O (0 AH=-57.1kJ

If the acid is strong, base is weak or acid is weak, base is strong. The evolved enthalpy is less than 57.1 kJ.
HCI (a9) + NH,OH(aq)-NH,Cl(a9) + H,O ()
am

AH =-(57.1-5.6)kJ
= - 51.5 kJ

CH,COOH (aq) + NaOH (aq) > CH, COONa (a9) + H2 O()

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AH=-(57.1-1.9)kJ
= - 55.2 k

combination of H* ions and OH ions, OH ions

A part of heat produced in the above two cases during the
le

are used up for complete dissociation

of weak base (NH,OH) or weak acid (CH,COOH), i.e., enthalpy of
ionisation.
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when mole of a substance is dissolved in large amount of

(4) Enthalpy of solution: It is the change enthalpy
in
water so that further dilution does not produce any more heat change.
KCI (9) +aq KCI(aq) AH = +18.6 kJ

in when one mole of the anhydrous salt combines with the

(5) Enthalpy of hydration: It is the change enthalpy
of water so as to get a hydrated salt.
specific number of moles
CuSO,()+ 5H,0 ()>CusO,.5 H,Os) AH=-78.2k]
mole of a solid is completely
change in enthalpy of the melting point when
one
(6) Enthalpy of fusion: It is the
converted into liquid state.
AH = +6kJ/mol
H,O)H,0) when mole of liquid is
is the change in enthalpy at its boiling point one a
(7) Enthalpy of vaporisation: It
into its vapour.
completely converted
HO)H,0g) AH +40.6 kJ/mol
the change in enthalpy when one mole of a solid is
completely converted into
(8) Enthalpy of sublimation: It is
its vapour at its sublimation temperature.
AH = +62.4 k/mol
11)1(8)
 (9) Enthalpy of phase transition: It is the change of enthalpy when one mole of one allotropic torm changes.

another allotropic form.

C(Graphite) » C(Diamond) AHrans 1.9 kJ moll
Limitations of First Law of Thermodynamics
() The first law cannot explain the feasibility of the process in the direction of change.
i ) The first law is unable to give any information about the extent to which the charge takes place. Al other form,
energy canbe converted into another form but heat energy cannot be completely converted into mechanicalene
nerg
Spontaneous process: The process which
(i) Process which occurs itself
can take place by itself or after proper initiation.

NH(g)+ HC(g) » NH,CI(S)

(ii) Salt dissolves in water.
(ii) Process which occurs after initiation.
Coal on ignition keeps on burning

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C(s)+0,(8) CO,8)

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Non-spontaneous process: The process which neither takes place itself nor by proper initiation.
Examples: )Flow of water upstream.

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ii) Flow of heat from cold to hot body.
Driving force for a spontaneous process: Overall tendency for a process to be spontaneous when it has

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i) tendency for minimum energy (E).
(i) tendency for maximum randomness.
The resultant of the two tendencies which gives overall tendency for a process to take place is known as drive
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force.
Some examples of spontaneous process are
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AH = +44 kJ mol
G)Evaporation of water: H,O0) >H,O(g)
Energy opposes but randomness favours.
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i) Dissolution of NH,Cl in water :

NH,CI(s) aq NH, (aq)+Cl (aq) AH +15.1 kJ mol"

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(Here R E)
(ii) Formation of H,O
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AH = -286.2 kJ mol
HC)+ O(g)->H,O0
(HereE> R)
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v) Formation of CO,
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AH = -393.5 kJ mol
C(s)+O8) >CO,(g)
(E, R both favours)
Carnot Engine
When one mole of an ideal gas is filled with a weightless frictionless piston, it is called Carnot engine

Cylinder
-

Source at Sink at
Temperature Temperature
T T
Insulating pad
Fig: Carnot Engine
 O
for the work
Source: big temperature bath and acts at
Tt is a a fixed temperature T,. Heat engine draws heat
expansion but temperature suffers no change.
Sink: It is a lower temperature bath. The heat is rejected by the engine to it, it also suffers no change in temperatu

It is kept at T,K.
isothermal and two are adiabatic.
There are four steps ina Carnot engine and all steps are reversible. In them two are
The four teps are:

(1) Isothermal reversible expansion.

(2) Adiabatic reversible expansion.
(3) Isothermal reversible compression.
(4) Adiabatic reversible compression.
The Carnot engine can be understood by considering the given P:V diagram.

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ng
PyT Step-l
PVT)
W,

Si
w Step-1I
Step-1vW

Step-I1I
(P,VT W (P,V,T)
ita
sh
Step 1
V= VV
ak

W = -RT2 x 2.303log Q2 = heat absorbed

..(i) V . (vii)

Step-2
-R

from equation (v) and (vii) we get

W=-C(T-T) (i)
N
Step-3 W= -2.303 RT, log+2.303 RT, log
V
am

W-RT x 2.303 log

V, = -2.303 (T,-T,)RT log V, . (ix)
=Q = heat released ii)

Step-4 Efficiency of engine:

gr

W,-CT2-T) Work done

(iv)
Efficiency of engine Heat absorbed
= - W2
le

Total work done (W) V

-2.303(T,-T)R log
= W + W+W+ W V
Te

-2.303 RT, log

= -2.303 RT, log -2.303RT, log (v) N
adiabatic
Step-2 and Step -4 are
T,V = T1 Vs

(vi) n-1-
Therefore n is
Case 1 T, is always greater than T1.
always less than 1.
Again Case-2 If T, = 0K
T,V = T2 V
n=1
.(Vii) However, 0K cannot be achieved. So efficiency of an
engine is always less than one.
we get
Comparing (vi) & (vi) equation
 or more detais,
Second Law of Thermodynamics scan the code
Second Law of Thermodynamics can be defined in a number of ways as follows
() All spontaneous processes (or naturally occurring processes) are thermodynamicallyirreversible.
(i) "Without the help of an external agency, a spontaneous process cannot be reversed". For example,
heat cannot by itself flow from a colder to hotter region.
(ii) "The complete conversion of heat into work is impossible without leaving some effect elsewhere". Formone detaia
can the code
iv) "All spontaneous processes are accompanied by a net increase of entropy".
(v)The entropy of the universe is continuously increasing"

EntroPy : Entropy is a thermodynamic state quantity which measures the disorderness or

randomness of a system (En - Energy, trope - change). It is denoted by 'S. For more details,
Entropy change : It is defined as integral of all terms involving heat exchanged (Eq) reversibly scan the code
divided by absolute temperature (T).

h
dS

ng
Calculating of change in entropy:
From Carnot theorem, we get,

Si
Efficiency (n) W_Q-Q-T-T For more details,
T scan the code

9,-Q1-
Q T
ita
sh
-
T 0
ak

Heat absorbed at T Heat released at T,

0
-R

T T
In reversible process heat released = - heat absorbed

Heat absorbed at T Heat released at T

am

2
Therefore, in any reversible process heat absorbed in different steps divided by state temperature, the summation
of these quantities will be zero. If T is small and absorbed heat is
öq amount the ratio of these two will be
quantities
gr

which is expressed mathematically 4=0. This ratioin reversible processis called entropy
EntropydS =
5=nC,InnRn PT
le

dS =du +(-oq) From 1" law of

Thermodynamics
Te

S, nC,InnRIn nRIn
dS = nC,dT+PdV
T A S , = (C, +R)nIn+ nRIn
dS=. C, dTnkl ay P
T VT
45nC,InnRIn
nCd nKav Entropy change for an isothermal process:
AU = 0
Integrating the above equation with appropriate
limits, we get
4S-nRin
|AS, nC, In+ nRIn The entropy of mixing of ideal gases is given as;
AS-n R in N, +n, R In N, +
 N, N are mole fractions of gases and n, n, are the number of moles of two gases.
Unit of Entropy: ]K*(s1)
Characteristics ofEntropy
)Entropy is a state function.
i) Entropy is an extensive property.
(ii) The exact value of entropy can be determined from third law of thermodynamics.
ASand Spontaneity:
i) For a spontaneous process
ASotal Agystem 4surroundings0
Here ASotal is also called
universe
i At equilibrium AS 0(for an isolated system.)
=

ii) AS < 0; direct process non-spontaneous and reverse process spontaneous.

Gibb's Free Energy

Heat energy cannot be converted completely into other energy or cannot be converted
completely For more details,

h
into work. By fraction of it which cannot be converted into useful work is termed as unavailable
energy. This unavailable energy affects the internal energy of the system. In every system internal the code
scan

ng
energy as well as PV work is always present. The summation of these two energies is enthalpy (H),
i.e., H = U+ PV. Some of its part of total energy is released as free energy which is denoted as G

and other part remains as unavailable energy. Unavailable energy is the product of temperature and

Si
entropy of the system, i.e., unavailable energy = TS
Total energy of system =Free energy +Unavailable energY
H G+ TS

ita
G H-Ts . (i)
Suppose a system passes from the initial to the final state at constant temperature then,
For initial state of the system equation (i) becomes
sh
G = H-TS (11)
and for final state G = H2- TS2 . (ii)
Change in free energy,
ak

G-G = (H-H)- T(S> -S1)

AG AH-TAS (iv)
Equation (iv) is known as Gibb's equation.
-R

Gibb's free energy change and spontaneity:

AH TAS Conditions AG
-ve +ve
am

-ve
any)
(favourable) (favourable) Spontaneous
-ve -ve -ve
AH> ITAS|
(favourable) (unfavourable) spontaneous
gr

-ve +ve -ve

ITAS|> AH|
(unfavourable) unfavourable) Spontaneous
Criteria for spontaneity for a process:
le

AH (EnthalPy) AS (Entropy) AG (Gibb's energy) Remarks

Te

AH <0 AS>0 AG<0 Spontaneous

AH 0 AS <0 AG>0
Non-spontaneous
AH: 0 AS>0 AG<0at high Spontaneous at high
temperature temperature
Non-spontaneous at low
AG> 0 at low temperature temperature

AH <0 AS <0 Spontaneous at low

AG <0 at low temperature temperature
Non-spontaneous at high
AG>0at high temperature
temperature
 Gibb's Helmholtz equation:
Gibb's free energy function G is defined
by the equation.
G H-TS
Differentiating equation(i) we get
dG dH- TdS- SdT
dG (dH +PdV) + -TdS -SdT [As H
VdP U
.
=
+ PV]
dG 8q+ VdP- 8q -SdT
dG= +VdP - SdT

OG
OTS
At two different
temperatures, if the free energy are G, Gz and entropy are S, S, then

OT
.V

h
and

ng
OT p -S
From (iv) and (v) we get

Si
(OAG

ita
AS
OT P .V
But AG AH- TAS
sh
OAG)
But AG AH-T|ar
This equation (vii) is known as Gibb's Helmholtz equation.
ak

Relation between standard free energy change (AG°) and equilibrium constant:
Consider a general reaction,
-R

A+B C+D
The free energy change and standard free energy change related with each other
by the following equation
AG AG°+RT In Q
am

Where, AG =
Gibb's energy change
AG = difference in standard Gibb's energies of formation of the products and reactants which are in
standard states.

CD
gr

Q = Reaction quotient =
.. ()
AB]
R =Universal gas constant
le

8.314 JK mol
At equilibrium AG=0 and Q=Kg
Te

0 AG°+ RT InKeq
AC°-2.303 RT log Keq ("
This equation (ii) is known as van't Hoff reaction isotherm. If AC° of the reaction is known, K can be calculated by
the above equation. The above equation (ii) can be written as
-AG"
Ke e RT .(IV

Keg10-4G/2.303RT
.. (V

Relation between free energy charge and electrical work done in a cell:
Electrical work done by a cell is the decrease of free energy of thecell
Electrical work done = Decrease in free energy

AG Electrical work done.

Electrical work done = Electrical energy produced
 =Quantity of electricity flowing x EMF
. ii)
As n
nFEel
number of moles of electrons get transferred, the quantity of electricity flowing = nrj

From equation (i) and (i) we get,

.. (iii)
-AG nFEell
Standard cell potential E is given as;
. (iv)
AG=- nF Em ..

Thus, knowing F G° can be calculated by using above equation.

Effect of Temperature : van't Hoff equation:

From van't Hoff equation we get;
AG =- RT In K (i)
AG
InK =

h
RT
Differentiating w.rt to T, we get

ng
nK1(a
OT RT

Si
oln K ((AH°) [by Gibb's Helmholtz equation]
OT

oln K
OT
AH
RT2
ita
.i)[ AH does not vary with pressure; AH°
=
AH]1
sh
This equation (i) is known as van't Hoff equation.
Integrating equation (i) we get
ak

AH
In K=- + Constant
RT

AH Cons
-R

InK=- tant (ii)

2.303 RT
when T T,;K =K,
and when T = T2;K = K2
am

Therefore, from equation (ii) we get;

K AH TT
2.303 R TT
gr

Third Law of Thermodynamics:

le

This is also known as Nernst heat theorem.

substance at the absolute zero
"The entropy of a pure and perfectly crystalline
Te

temperature is zero".
For a solid of entropy at 0 K is S, and at T K is S then,
S-5,-p4T

T I I |

According to third law Sy =

0 at OK T

- C, dn T=C, In T

2.303 C log T

from the shaded area. Crystals of CO, N,0,

Entropy 'S' can be calculated
zero entropy
even at absolute temperature. 100 200 300
NO and H,O do not have (K)