Chemical

Thermodynamics

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Objectives

Terminologies in thermodynamics
Law of thermodynamics – I and II law
Need for the II law
Enthalpy
Entropy
Gibb’s free energy
Helmholtz free energy
Spontaneity and its criteria
Maxwell’s relation
Gibb’s-Helmholtz equation ((E&A) and (H&G))
Van’t Hoff equation
Terminologies
System:
A system may be defined as the specified portion of matter under
study which is separated from the rest of the universe by a boundary.
Ex: A substance kept in a beaker.

Surroundings:
The remaining part of the universe which should be in a position to
exchange energy and matter with the system is called as
surroundings.
Ex: All that is around the substance under study.
Types of system
Closed System :
A system which can exchange energy but not matter with its surroundings
is called as closed system.
Ex. substance kept in a closed vessel, but not insulated.

Open System:
A system, which can exchange energy as well as matter with its
surroundings is said to be an open system.
Ex: Water kept in an open beaker.

Isolated System:
A system which can exchange neither energy nor matter with its
surroundings is called an isolated system.
Ex: Hot water kept in a closed and insulated vessel.
Properties of system
Intensive Properties:
The properties which do not depend on the quantity of the
substance present in a system are called intensive properties.

Ex: temperature, pressure, density, viscosity, surface tension,

refractive index, freezing point etc.

Extensive Properties:
The properties which depend on the amount of the substance
present in a system are called extensive properties.

Ex: mass, volume, energy, internal energy, free energy, entropy,

etc.
Thermodynamic Processes
Isothermal process
Adiabatic process
Isobaric process
Isochoric process
Spontaneous and non-Spontaneous processes
Reversible process
Irreversible process
Exothermic and Endothermic processes
State function
Path function
Isothermal Process
A process is said to be isothermal if the temperature of
the system remains constant during each stage of the
process.
Ex: consider a chemical reaction taking place in a
vessel which is not insulated. The system is in thermal
equilibrium with the surroundings. If the process is
exothermic, the heat is given out from the system to
the surroundings at once (keeping temp constant). If
the process is endothermic, the required amount of
heat is absorbed instantaneously by the system from
the surroundings.
Adiabatic process
A process is said to be adiabatic if no heat enters or
leaves the system during the process.
Ex: consider a chemical reaction taking place in an
insulated vessel; no heat enters or leaves the system. If
the reaction is exothermic, the heat evolved increases
the temperature of the system. If the reaction is
endothermic, the heat absorbed decreases the
temperature of the system
Isobaric process
It is the process in which pressure is kept constant
throughout.
Ex: consider a reaction done in an open vessel which is
always at atmospheric pressure. In isobaric process
volume changes may occur.

Isochoric process
It is the process in which the volume is kept constant
during a reaction.
Ex: changes occurring in closed vessels.
Spontaneous and non-Spontaneous
processes
Spontaneous Processes:
A process which occurs by itself without the help of an
external force is called a spontaneous process. All
spontaneous processes are irreversible. e.g.,water
flowing down the hill(all natural processes are
spontaneous).
Non – spontaneous processes:
Any process which doesn’t proceed by itself is called as
a non- spontaneous process. e.g., water flowing up a
hill.
Reversible process
When a process is carried out infinitesimally slowly in
such a way that the driving force is infinitesimally greater
than the opposing force it is called as a reversible process.
If the opposing force becomes slightly greater than the
driving force, the process reverses itself.

Irreversible process
A process which cannot be reversed without spending
large amount of energy is an irreversible process. e.g.,
water flowing down the hill is an irreversible process. The
reverse of this process namely moving water up the hill can
be achieved only if we spend large amount of energy on it.
All irreversible processes are spontaneous in nature.
Exothermic and Endothermic processes
 Many processes are accompanied by energy changes.
These changes appear in the form of either evolution or
absorption of heat.

 Exothermic process is accompanied by evolution of

heat.

 Endothermic process is accompanied by absorption of

heat.
State Function
It is a thermodynamic property which depends on the state
of the system and it is independent of the path followed by
the system.
e.g., if the pressure and volume of the initial state of a system
is P1and V1 and in the final state P2 and V2 respectively, then
the differences,

Changes in pressure and volume viz., ΔP & ΔV

are state functions. Similarly ΔS, ΔG & ΔE are also state
functions.
Path function
Path function is also known as path variable.
Properties which depend on the path followed to bring
about the change are called as path functions.
e.g., heat, work, etc.
I Law of thermodynamics.
1. Energy can neither be created nor destroyed; but it can be
converted from one form to another form.

2. Energy of an isolated system remains constant.

3. It is impossible for any machine to produce work without

consuming energy. This law is a statement of the principle of
conservation of energy.
Mathematical expression of I Law of
Thermodynamics
Consider a system to which a heat energy ‘q’ is supplied. It
is used in two ways. One is to increase the internal energy
and the other is to do some useful work.

q = heat absorbed
w=work done by the system
Internal energy
A substance is associated with different types of
energies such as vibration energy (Ev), rotational
energy (Er), translation energy (Et), electronic energy
(Ee) and nuclear energy (En).

Internal energy is the sum of all these energies present

in a substance.

EInternal = Ev + Er + Et + Ee + En
Enthalpy
Enthalpy represents total energy stored in a system
i.e., the sum of internal energy and pressure volume
work of a system under a particular set of conditions.

It may be represented as, H=E+PV, change in enthalpy

of a system at constant P can be written as
ΔH = ΔE + PΔV
Relationship between ΔE & ΔV
By definition,
ΔH = ΔE + PΔV ------------ (1)
The ideal gas equation at constant pressure in two different states are
PV1 = n1RT------------ (2)
PV2 = n2RT----------- (3)
Subtracting eqn. (2) from eqn. (3)
P(V2-V1) = (n2-n1)RT
PΔV = ΔnRT
Substituting in eqn. (1),
ΔH = ΔE + ΔnRT--------- (4)
Where Δn = n2-n1
n1 = number of moles of gases reactant
n2 = number of moles of gases product
Limitations of the I law
1. I law is concerned only with the energy changes, but
not the direction in which energy changes take place

2. It does not tell about the feasibility of a reaction

3. It does not explain why the heat energy cannot be

completely converted into work.

The above statement leads to the need for the 2nd law
of thermodynamics.
Need for the second Law of
Thermodynamics
 The first law establishes the relationship between heat absorbed and the work
performed by a system. But it puts no restriction on the direction of the flow
of heat. (We know that heat can flow only from a hotter body to cooler body).

 According to first law the energy of an isolated system remains constant. But it
does not tell whether a process like a chemical reaction can spontaneously or
not.

 The first law tells us that heat can be converted to work. But it does not tell us
that heat energy cannot be completely turned in to work.

Thus there is a need for the second law to provide the above information.
Statement of II Law of Thermodynamics
In terms of inter-conversion of heat and work: Heat
cannot be completely converted into work without
producing changes elsewhere, either in the system or
surroundings.

In terms of flow of heat:

Heat never flows from a cooler to a hotter body on its own.

In terms of entropy:
The entropy of the universe is increasing continuously.
Gibbs free energy
In a system, a part of the total energy supplied is
converted into useful work and the rest is unavailable.
The part of energy which is converted into useful work
is called the available energy, which is called as the
Gibbs free energy.

Available energy = Total energy – Unavailable energy

Mathematical expression,
G = H - TS
Concept of entropy
Entropy is a measure of degree of disorder or
randomness in a given system. i.e., when a system goes
from a more orderly to less orderly state, the
randomness increases; hence entropy of the system
increases.

Ex: When a solid change into a liquid, there is an

increase in entropy since the arrangement of atoms
and molecules is less ordered in liquid.
Mathematical expression of entropy:
If any process is carried out between the limits of initial state 1 and final state 2, with
the absorption of heat qrev at constant temperature then the entropy change is shown
as,

ΔS = qrev/T
qrev/T is a state function which depends on the initial state (S 1) and final state (S2)

If qrev is positive, (heat is absorbed) S is also positive indicating an increase in entropy.

When heat is evolved, qrev is negative and S is also negative indicating the decrease in
entropy.

SI units of entropy and change in entropy is Joules/ Kelvin (JK -1 )

 Entropy change in reversible isothermal
expansion of an ideal gas.
Consider a certain mass of an ideal gas in a cylinder fitted with a frictionless and
weightless piston. The gas is allowed to expand isothermally and reversibly. As the
expansion is carried out isothermally, there will be no change of internal energy.
i.e. ΔE = 0
Hence from the I Law equation, = q-w i.e., q=w
In such a case the work done in expansion of one mole of a gas from volume V 1 to V2
at constant temperature ‘T’ is given by
w = PdV
qrev = PdV
For an ideal gas,
PV =nRT
Therefore, P = nRT/V
 Entropy change in reversible isothermal
expansion of an ideal gas.
Integrating within the limits V2 and V1

Change in entropy, S is given as

Criteria for Spontaneity
S.No ∆H Value ∆S Condition ∆G Value Result
Value
1. -ve +ve - -ve Spontaneous
2. -ve -ve ∆H›T∆S -ve Spontaneous
3. +ve +ve ∆H‹ T∆S -ve Spontaneous
4. +ve -ve - +ve Non- Spontaneous

5. 0 -ve - +ve Non- Spontaneous

6. 0 +ve - -ve Spontaneous

7. -ve 0 - -ve Spontaneous
Gibbs-Helmholtz equation
The Gibbs free energy is given by,
G = H – TS
We know that,
H = E + PV
i.e., G = E + PV - TS
On differentiation,
dG = dE + PdV + VdP –TdS – SdT ------- (1)
The first law equation for an infinitesimal change may be written as,
dE = dq – dw ----- (2)}
dq = dE + dw
If the work done is only due to expansion, then
dq = dE + PdV
The mathematical expression for II-law is,
dS = dq/T or dq = TdS
dq = TdS = dE + PdV
Or
dE = TdS – PdV ------------------(3)
 Gibbs-Helmholtz equation
Substituting this value in equation (1),
dG = TdS – PdV + PdV + VdP – TdS – SdT
dG = VdP – SdT --------------- (4)
at constant Pressure,
dG = -SdT-------------- (5)
Let us consider a closed system. Let us assume that in the initial state, at temperature T, the
free energy of the system is G1. In the same initial state, at temperature T + dT, the free energy
of the system is G1 + dG1

In the final state, at temperature T, the free energy of the system is G2. In the same final state
at the same temperature T + dT, the free energy is G2 + dG2

Therefore and can be written as,

dG1 = -S1dT
dG2 = -S2dT
d(G2-G1) = -(S2-S1)dT
The difference in free energies of state 1 and state 2 is
G2-G1 = ΔG
Therefore, dG2-dG1 - dΔG
Gibbs-Helmholtz equation
Since this equation is obtained by considering the change in free energy at
constant pressure, it can be written as,

According to Gibb’s, G = H – TS
For an isothermal process, ΔG = ΔH – TΔS

Comparing equations (7) and(8),

Application of Gibbs-Helmholtz equation
1) It is used to calculate the heat change H, for a
process or a reaction taking place at constant
pressure provided the values of free energy change at
two different temperatures are known
2) It is used to calculate H and S of a redox reaction
taking place in a Galvanic cell.
3) In a Galvanic cell electrical energy produced is equal
to the free energy decrease of the cell reaction.
Gibbs-Helmholtz equation for a galvanic
cell
Electrical energy produced =nFE
Where n is the no. of electrons, F is the Faraday, E is the emf
ΔG = - nFE --------- (1)
Substituting –nFE for We get

dividing the above equation by –nF

Gibbs-Helmholtz equation for a galvanic
cell

ΔG = ΔH – TΔS ----------------- (5)

Comparing equations (3) and (5)
Gibbs – Helmholtz equation using work
function ‘A’
We know that work function,
A = E – TS -------- (1)
On differentiation,
dA = dE – TdS – SdT -------- (2)
From I law we know that,
dE = TdS – PdV
Substituting the value of dE in equation(2)
dA = -PdV – SdT ---------- (3)
At constant volume, dV=0
dA = - SdT
For a given system at state1 and state2
dA1 = -S1dT --------- (4)
dA2 = -S2dT -------- (5)
Subtracting the equation (4) from (5)
d(A2-A1) = - (S2-S1)dT
dΔA = - ΔSdT
Gibbs – Helmholtz equation using work
function ‘A’
As the volume is constant,
-------- (6)
From equation of work function,
A = E –TS
ΔA = ΔE – TΔS
comparing the equation (6) and (7)

--------- (7)

------- (8)

Equation (8) is another form of Gibbs-Helmholtz equation.

Maxwell’s relations
A thermodynamic system is described by the state functions like P, V, T, S, E, H,
A and G. Using these functions, four important relations can be derived, which
are known as Maxwell’s relations.
We already know that,
H = E +PV
A = E – TS
G = H – TS
ΔE = q – W
From these equations we have,
dE = dq – dW = TdS – PdV --------------- (1)
Since, dS = dq/T, dW = -PdV,
dH = dE + PdV + VdP = TdS + VdP ------------- (2)
dA = dE – TdS – SdT = -PdV – SdT --------------- (3)
dG = dH – TdS – SdT = VdP – SdT -------------- (4)

The above four equations are called fundamental equation of Thermodynamics.

I – relation:
Consider the fundamental equation
dE = TdS – PdV ---------- (1)
If volume is kept constant, PdV = 0
dE = TdS

------- (2)

Differentiate equation (2) with respect to (V) at constant entropy,

--------- (3)

If entropy is kept constant, TdS = 0 dE = - PdV

-------------(4)

Differentiating equation (4) with respect to (S) at constant volume,

-------------- (5)

Comparing equations (3) and (5)

Equation – I, states that, the change of temperature with volume at constant entropy is negatively equal to the
change of pressure with entropy at constant volume. This is one form of Maxwell’s relation
II – relation:
Consider the fundamental equation
dH = TdS + VdP ------------- (1)
If pressure is kept constant, VdP = 0,
dH = TdS

------- (2)
Differentiate equation (2) with respect to (P) at constant entropy,

--------------- (3)

If entropy is kept constant, TdS = o

dH = VdP

---------- (4)

Differentiating equation (4) with respect to (S) at constant pressure

------------ (5)

Comparing equations (3) and (5)

This equation states that “the change of temperature with pressure at constant entropy is equal to the of change
III – relation:
Consider another fundamental equation,
dA = -PdV –SdT --------- (1)
If volume is kept constant, PdV = 0
dA = - SdT
----------- (2)

Differentiate equation (2) with respect to (V) at constant temperature,

---------------- (3)

If temperature is kept constant, SdT = 0

dA = - PdV

----------------- (4)

Differentiating equation (4) with respect to (T) at constant volume,

------------------- (5)

Comparing equations (3) and (5)

This is the third form of Maxwell’s relation which states that “the change of entropy with volume at constant
 IV – relation:
Consider another fundamental equation,
dG = VdP – SdT ------------- (1)
If pressure is kept constant, VdP = 0
dG = -SdT

---------- (2)
Differentiate equation (2) with respect to (P) at constant temperature,

----------- (3)
If temperature is kept constant, SdT = 0
dG = VdP

-------- (4)
Differentiating equation (4) with respect to (T) at constant pressure,

--------------- (5)
Comparing equations (3) and (5)

This is the fourth form of Maxwell’s relation which states that “the change of volume with temperature at
constant pressure is negatively equal to the change of entropy with pressure at constant temperature.
Van’t Hoff isotherm:
Let us consider the general reaction
aA + bB cC + dD ------------- (1)
We know,
G=H-TS
G=E+PV-TS ------------- (2)
On differentiation,
dG=dE+PdV+Vdp-TdS-SdT ------------ (3)
On combining I & II laws
dq = dE + PdV
dS = dq/T or dq = TdS
dq = TdS = dE + PdV
Or
dE = TdS – PdV -------------- (4)
Substituting the value of dE in equation (3)
dG=TdS-PdV+PdV+VdP-TdS-SdT
dG = VdP-SdT --------------- (5)
At constant temperature,
(dG)T=VdP ------------------------ (6)
Free energy change for one mole of gas at a constant temperature is given by,
 Van’t Hoff isotherm:
Since PV=RT
V = RT/P
i.e., dG=RT.dP/P, Since [PV=RT] ----------- (7)
On integration of equation (7)

G = Go+RTlnP

Where Go = integration constant and is known as standard free energy

i.e., Go=G when P=1atm
Let the free energy / mole of A,B,C and D at their respective partial pressures P A,PB,PC and PD are
GA,GB,GC and GD respectively.
GA = [GoA+RTlnPA ]
-------------- (8)
GB = [GoB+RTlnPB ]
GC = [GoC+RTlnPC ]
GD = [GoD+RTlnPD ]
Now the energy change for the reaction (1) is given by
ΔG = G products G reactants
ΔG = (GC+GD)-(GA+GB) ----------------- (9)
Substituting the value of (8) in (9)

i.e.
or
Van’t Hoff isotherm: ----------- (10)

For a reaction aA+bB cC+dD the equation becomes

Where ΔGº= the standard free energy of reaction (1)

We know at equilibrium, ΔG = 0

= -------- (11)
Since

i.e. ΔGº = - RTlnKeq

from equations (10) and (11) we get

or
------- (12)
Equation (12) is called van’t Hoff isotherm. This gives a quantitative relation for free energy change
accompanying a chemical reaction.
 Van’t Hoff isochore:
This is used to calculate the change in heat content or enthalpy (H) when the equilibrium
constants at two different temperatures are known. This is derived by combining Van’t Hoff
isotherm and Gibb’s Helmholtz equation.
The equation for the reaction isotherm when the reactants and the products are in gaseous state
and also in their standard states is represented as

Differentiating with respect to temperature at constant pressure

Multiplying the equation (2) by T

Substituting ΔGº for – RTlnKP

The Gibbs-Helmholtz equation for substances in their standard states may be shown as

Comparing the equations (4) and (5)

or
Van’t Hoff isochore – Integrated form
the enthalpy change, ΔH accompanying a chemical reaction does not vary
appreciably with change in partial pressures of the reactants and products.
ΔHº = ΔH

Integrating equation (8)