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LECTURE NOTES
UNIT II
CHEMICAL THERMODYNAMICS
Unit syllabus: Terminology of thermodynamics - Second law: Entropy - entropy change for an
ideal gas, reversible and irreversible processes; entropy of phase transitions; Clausius
inequality. Free energy and work function: Helmholtz and Gibbs free energy functions
(problems); Criteria of spontaneity; Gibbs-Helmholtz equation (problems); Clausius-Clapeyron
equation; Maxwell relations – Van’t Hoff isotherm and isochore(problems).
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SESSION : Terminology of thermodynamics.
The term thermodynamics means flow of heat. In general it deals with the inter conversion of
various kinds of energy in physical and chemical systems.
Thermodynamics
1. Predicts the feasibility of a physical process or chemical reaction under given condition
of temperature and pressure.
2. Predicts whether a chemical reaction would occur spontaneously or not under a given set
of conditions
3. Helps to determine the extent to which a reaction would takes place.
Limitations of thermodynamics.
1. It predicts the extent to which a reaction can take place .however it does not say anything
about the rate.
2. It applies only to matter in bulk and not to individual atoms or molecules.
System and Surroundings: Any part of the universe which is selected for thermodynamic study
is called system and the rest of the Universe in its neighborhood is known as surroundings.
The system is separated from the surroundings by a real or imaginary boundary through which
exchange of energy or matter may take place.
Types of System
Homogeneous system: A system is said to be “homogeneous” if it consists of only one phase and
uniform thought. Ex. a solution of sugar in water.
Heterogeneous system: When a system consists of two or more phases and is not uniform
throughout it is called heterogeneous. Ex .Ice in water, chloroform in water.
Open system: A system which can exchange both energy and matter with the surroundings.
Ex. beaker of water.
Closed system: A system which can exchange energy but not matter with the surroundings. Ex
Water in as stoppered bottle.
Isolated System: In system in which neither matter nor energy can exchange with its
surroundings.
Properties of a system
The properties associated with a macroscopic system are called thermodynamic properties or
variables.
Extensive properties: These are thermodynamic properties which depend on the quantity of
matter specified in the system e.g. mass, volume energy etc.
Intensive properties: These are thermodynamic properties which depend on characteristics of
matter but independent of its amount e.g. pressure, temperature, viscosity, density m.p, bp etc.
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Thermodynamic process:
The method by which the state of a system is changed is called a “Process”. It can be effected
by changing any one of the state variables viz P,T,C etc.
Isothermal process: It is a process carried out at const temperature. Exchange of heat takes place
between system and surroundings dT = 0
Adiabatic process: It is a process in which no exchange of heat takes place .The temperature of
the system may increase or decrease during adiabatic process. dQ =0
Reversible process: It is a process which takes place infinitesimally slowly so that the system is
in thermodynamic equilibrium at any instant of the change. Since the process is carried out
extremely slowly the properties of the system remain virtually unchanged and the direction may
be reversed by small change in a variable like temperature, pressure etc. The driving force is
greater than the opposing force only by a infinitesimal quantity and hence the process would
require infinite time for its completion.
Internal Energy: U or E
The energy stored in a substance by virtue of its constituent atoms and molecules is called
Internal energy.
It is the sum of vibrational energy, rotational energy, electronic energy etc.
Internal Energy change (∆ )
It is the difference in the internal energies of initial and final states of the system.
∆ = +
But for the chemical reactions
∆ = −
∆ = −
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Enthalpy or Heat content of a system (H)
It is “the heat content of the system: or “The sum of internal energy and pressure-Volume change
work done) of s system , under a particular set of conditions”
Mathematically
= +
Unit: KJ mol-1
Enthalpy change : It is the difference in the enthalpy of initial and final stages of the system.
∆ = −
For the chemical reaction ∆ = −
We know that = +
Then ∆ = 2 + 2− ( 1+ 1) = ( 2 − 1 ) + ( 2 − 1)
∆ = ∆ + ∆
At constant volume ∆ = 0
∆ = ∆
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SESSION : Second law of thermodynamics – various statements.
Clausius statement : It states that heat cannot flow itself from a cold body to a hot body
spontaneously without the intervention of an external energy.
Kelvin statement: It is impossible to take heat from a hot body and convert it completely into
work by a cyclic process without transferring a part of heat to cold body.
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SESSION : Entropy concept - entropy change for an ideal gas.
The change in entropy ∆ of system is equal to the ratio of heat change to the temperature (T) of the
reversible cyclic process.
∆ =
Significance of entropy:
Measure of disorder of the system: All spontaneous process are accompanied by increase in entropy as
well as increases in the disorder .Increase in entropy implies increase in disorder.
Measure of probability: An irreversible process tend to proceed from less probable state to more probable
state. Since entropy increases in a spontaneous process, entropy may be defined as a function of
probability of thermodynamic state.
Entropy and unavailable energy: When heat is supplied to the system, some portion of heat is used to do
some work. This portion of heat is available energy. The remaining portion is called unavailable energy.
Hence entropy is defined as unavailable energy per unit temperature.
Entropy =
Temperature
= − -------------------------(1)
dS = -------------------------(2)
Using 1 and 2
= -------------------------(3)
But = and =
∴ = + -------------------------(4)
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At constant temperature (isothermal) process =0
∴ =0+ -------------------------(5)
∴ = = -------------------------(6)
ℎ
2
∫ = ∫
( 2 − 1) = ∆ = -------------------------(7)
For n mole
∆ = . ------------------------(8)
1 1 = 2 2 =
Equation 8 becomes
∆ = .
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SESSION : Entropy change for reversible and irreversible processes; entropy of phase transitions
∆ =
But the entropy of the surroundings decrease , because the surroundings loose the same of heat q i.e
∆ =
∆ =∆ +∆
∆ = +
∆ =0
Consider a system maintained at higher temperature T1 and its surrounding maintained at a lower
temperature T2.If q amount of heat passes irreversibly from the system to surroundings. then,
Decrease in entropy of the system , ∆ =
Increase in entropy of the surroundings. ∆ =
Net change in entropy is given by
∆ =∆ +∆
∆ = +
=q
∆ >0
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Entropy change accompanying change of phase.
When there is a change of state from solid to liquid or liquid to vapour or solid to vapour there is change
in entropy.
Solid to liquid:
Let us consider the process of melting of 1 mole of substance being carried out reversibvly .It would
absorb molar heat of fusion at te4mperature equal to its melting point.
∆H
∆ =
Where ∆ - molar heat of fusion - fusion temperature.
Liquid to vapour
One mole of a substance changes from liquid to vapour state reversibly at its boiling point Tb
Under constant pressure .If ∆ , molar heat of vaporization then the entropy change accompanying the
process
∆H
∆ =
9
SESSION : Clausius inequality. Free energy and work function –concepts.
.
∮ = - <0
Thus for any reversible or irreversible heat engines we obtain the Clausius inequality
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Free energy and work function –concepts.
In order to find out the spontaneity of a process ,we have to see the change in entropy of the system as
well as surroundings .It is difficult to find out entropy of the surrounding everytime. So new
thermodynamic functions are introduced , which can be determine more conveniently.
T- Absolute temperature
S- Entropy
∆ = ∆ − T∆S
By definition ∆ =
∆ = ∆ − (1)
∆ = -w (2)
∆ = − wrev
- ∆ =
Thus the decrease in function A gives the maximum work that can be obtained during an isothermal and
reversible change
W represents the total work i.e expansion, electrical work etc. so it is also called work function.
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Gibbs free energy:
It is defined as = −
G – available energy
H – total energy
TS – unavailable energy
∆ = ∆ − ∆
But ∆ = ∆ + ∆
∴∆ = ∆ + ∆
By definition ∆ = ∆ − ∆
∆ = ∆ − ∆ + ∆
∆ = ∆ + ∆
∆ = −
∆ = − + ∆ Or -∆ = − ∆
−∆ = −
−∆ =W useful
The decrease of free energy of a process at constant temperature and pressure is useful work obtainable
from the system.
The free energy change for a process at 25 oC in which the reactants are converted into products in their
standard states
Thus. ∆ = ∑ ( )−∑ ( )
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SESSION : Criteria of spontaneity – Gibbs-Helmholtz equation .
= = = -----------------(7)
Combining (4) and (7) we get
= + + −( + )−
= − -----------------(8)
At constant pressure dP = 0 and the above equation 8 becomes
= −
or
= -S -----------------(9)
= + -------------------------- (10)
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Let G1 initial free energy of a system at T and G1 and dG1 = initial free energy of the system at T + dT
where dT is infinitesimally small and pressure is constant.
1 =− 1 where S1 is the entropy of the system in the initial state.
Now suppose that the free energy of the system in final state is G2 at T. Let G2 + d G2 is the free energy
of the system at T + dT in the final state then.
2 =− 2 Where S2 is the entropy of the system in the final state.
Subtracting (11) from (12)
2 − 1 = −( 2 − 1)
( ∆ ) = −∆
At constant pressure
(∆ )
=-∆
We know∆ = ∆ − ∆
∆ ∆
− ∆ =
∆ ∆ (∆ )
=
(∆ )
∆ =∆ +
This is called Gibbs –Helmoltz equation in terms of free energy and enthalpy at constant pressure.
Another form of Gibbs – Helmholtz equation is obtained by the differentiation of the above equation with
respect to temperature, and given by
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(∆ )
- =∆ +
( )
- =∆ +
- =∆ − Or
∆ =− +
∆ =− −
- =∆ −
∆
= +
−∆ =
Substituting in A we get
( )
∆ = or ∆ =
The physical or chemical changes which proceed by themselves without the intervention of any external
agents are known as spontaneous process. All natural process are spontaneous. All spontaneous process
proceed in one direction and are thermodynamically irreversible.
Examples:
1. Heat flow from a hotter to a colder body till they attain thermal equilibrium.
2. Water flows by itself from a higher level to a lower level.
3. The expansion of gas into an evacuated space.
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The process which proceed in both directions are called spontaneous or reversible process.
Free energy and spontaneity
∆ = ∆ − ∆
The sign of ∆ depends on magnitude of ∆ ∆ .
For a spontaneous process.
> or >
I law states that
= +
∴ > +
Or
−( + )> 0
+ — <0
( + − )<0
( − )<0
dG <0
= −
Thus spontaneous process involve a decrease in decrease in free energy.
The free energy change (∆ ) is the criterion for predicting spontaneity or feasibility of a reaction.
∆ = ∆ − ∆
The sign of ∆ depends on the sign and numerical value of ∆ ∆
∆ ∆ ∆ = ∆ − ∆ Nature of process
16
SESSION : Clausius-Clapeyron equation
Consider a system consisting of only 1 mole of substance in two phases A and B. The free
energies of the substance in two phases A and B be GA and GB
Let the temperature and pressure of the system be T and P respectively.
The system is in equilibrium ,so there is no change in free energy
GA = GB
If the temperature of the system rised to T + dT and Presure becomes P + dP
GA + d GA = GB + d GB
G = H – TS
G= E + PV –TS
Diffentiating the above equation.
dG = dE + PdV + Vdp-TdS –SdT
dG = VdP-SdT
dGA = VAdP –SA dT ------------ (a)
dGB = VBdP –SB dT ------------(b)
Where VAand VB are the molar volume of phases A and B respectively.
SA and SB are molar entropies.
Since GA = GB
dGA = dGB
Substituting in equation (a) and (b)
VAdP –SA dT = VBdP –SB dT
= or
∆
= ∆ =
∆
=
∆
This is Clayperon equation.
The above equation was modified by Claussius and called Claussius –Clayperon equation.
Let us consider the following equilibrium
Solid ↔ vapour Vv ›› Vs
Liquid↔ vapour Vv ›› Vl
= ∆
∆
=
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PV = RT ; V= RT /P
∆
= 2
P
∆
= 2
∆
=
.
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SESSION : Maxwell relations – statement, explanation & derivation
MAXWELL RELATIONSHIP
dE = q − PdV
G = H − TS
H = E + PV
A = E − TS
Using the above fundamental equations any thermodynamic relationships can be derived.
Note: E,S,H,A,G,T,P,V are all state functions .
= −
dE = TdS − Pdv
(dE) = TdS
Differentiating with respect to V at constant S
∂2 E ∂T
= −−−−−( )
∂S ∂V ∂V
(dE) = −PdV
Differentiating with respect to S at constant V
∂2 E ∂P
=− −−−−−( )
∂V ∂S ∂S
∂H
=T
∂S
Differentiating with respect to P at constant S
∂2 H ∂T
= − − − − − (3)
∂S ∂P ∂P
∂H
=V
∂P
Differentiating with respect to S at constant P
∂2 H ∂V
= − − − − − (4)
∂P ∂S ∂S
Since H is a state function and dH is an exact differential then from equation 3 and 4
= −
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G = E + PV − TS
dG = TdS − PdV + PdV + VdP − TdS − SdT
dG = VdP − SdT
∂G
= −S
∂T
Differentiating with respect to P at constant T
∂2 G ∂S
=− − − − − − (5)
∂T ∂P ∂P
∂G
=V
∂P
Differentiating with respect to T at constant P
∂2 G ∂V
= − − − − − (6)
∂P ∂T ∂T
− =
= −
dA = −PdV − SdT
∂A
= −S
∂T
Differentiating with respect toV at constant T
∂2 A ∂S
=− − − − − − (7)
∂T ∂V ∂V
∂A
= −P
∂V
Differentiating with respect toT at constant V
∂2 A ∂P
=− − − − − − (8)
∂V ∂T ∂T
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= −
=−
= +
=
= − =−
= −
=
It gives the quantitative relationship between the free energy ∆ G and equilibrium constant K
Or dG = dE +PdV +VdP-TdS-SdT
dG = VdP-SdT
( ) = ---------(1)
Where dG is the free energy change for 1 mole of any gas at constant temperature.
∫ = ∫
Let the free energies of A,B, C and D at their respective pressure PA ,PB ,PC and PD are GA ,GB,GC and
GD respectively .
Then the free energy change for the above reaction is given by
∆G = G Products – G reactants.
∆G = (cGC + dGD ) –(aGA + bGB)
From (2)
aGA = aG0 A+ RT ln PA
bGB = bG0 B+ RT ln Pb
cGA = CG0 C+ RT ln PC
dGA = dG D+ RT ln PD
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= ( CG0 C+ RT ln PC + dG D+ RT ln PD ) –( aG0 A+ RT ln PA + bG0 B+ RT ln Pb )
( ) ( )
∆ = ∆ + ln
( ) ( )
( ) ( )
0= ∆ + ln
( ) ( )
( ) ( )
∆ = − ln
( ) ( )
∆ = −
( )( )
∆ = − +
( ) ( )
The effect of variation of equilibrium constant with temperature is given Vant’t Hoff Isochore
∆G 0 = - RT ln Keq
∆ ∆
= − +
1
∆ ∆
= − +
2
∆ 0
− = −
∆ 0
ln = −
∆ −
=
.
Problem 1.Calculate the change in entropy accompanying the isothermal expansion of 4 moles of
an ideal gas at 300K until its volume has increased three times.
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∆S = 2.3030 nR log (V2/V1) JK -1
= 36.54 JK-1
Problem 2: Calculate the entropy change when 100 g of ice converted into water at 0oC. Latent
heat of fusion of ice is 80Cal/g.
∆
∆ =
Problem 3: Gibbs free energy of a raction at 300K and 310 K are -29 k Cal and 29.5 k.cal
respectively.Determine its ∆H and ∆S at 300 K
(∆ )
∆ =∆ +
(∆ ) = ∆ −∆ = - 29.5-(-29) = -0.5
=T2-T1 = 10 K
∆H = - 14kcal
(∆ )
∆ =−
∆ −
=
.
∆H= 12.490 kJ
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1. What are the differences between reversible process and irreversible process?
2. What are intensive and extensive properties?
3. What is meant by state function?
4. What is internal energy? Mention its unit.
5. What is enthalpy? How is it related with internal energy?
6. Write the mathematical form of I law of thermodynamics.
7. State II law of thermodynamics.
8. Define entropy.
9. Write the mathematical expression and unit for entropy.
10. Define work function.
11. Define standard free energy.
12. What is the significance of decrease in free energy?
13. What is meant by spontaneous process.?
14. Mention any two applications of Gibb’s Helmholtz equation.
15. Write any two Maxwell’s relationships.
16. What is significance of Maxwell’s relationship?
17. Write the integral form of Claussius –Clapeyron equation.
18. Mention any two applications of Claussius –Clapeyron equation.
19. Write the significance of Van’t Hoff equation.
20. What is Claussius inequality?
Review Questions:(Section B)
1. Compare the the reversible process with the irreversible process.(May 2014)
2. Derive an expression for entropy change of an ideal gas at constant temperature .(Nov2002)
3. Explain Clausius inequality.
4. Explain the significance of free energy.(May 2014,May 2015)
5. Derive Gibb’s Helmoltz equation and discuss its application. .(May 2005,Jan 2005 ,Jan 2014 ,May 2014, Dec
2014,May 2015)
6. Discuss the criteria for chemical reaction to be spontaneous .(Nov 2002, Jan 2014)
7. What is meant by VantHoff reaction isotherm? Derive the expression for a reaction isotherm of
general reaction aA +bB →cC + dD. (Jan 2014,Dec 2014,May 2015) .
8. Derive the Claussius- Claperon equation. Discuss its applications.(Dec 2012,Dec 2014)
9. Derive all the four Maxwell’s relations. (May 2014,May 2015)
10. By combing Van’t Hoff isotherm and Gibb’s Helmholtz equation. Illustrate the effect of
temperature on equilibrium Constant.(May 2005)
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