CY11003 – Week 2

Lectures 4-6
"Thermodynamics is a funny subject.

The first time you go through it, you don't understand it at all.

The second time you go through it, you think you understand it,
except for one or two small points.

The third time you go through it, you know you don't understand
it, but by then you are so used to it, it doesn't bother you any
more."

-Arnold Sommerfeld
German physicist

Revision of Basic Concepts

• Equilibrium state under different experimental conditions
• Equation of state
• Thermodynamic processes in a closed system
 reversible
 irreversible
• Work and heat – path dependence, application to ideal gases
• Change in State – First law of thermodynamics
• Internal energy, 𝑼 and enthalpy, 𝑯
• Measurement of variation in 𝑼 and 𝑯
 specific heat at constant volume, 𝑪𝑽
 specific heat at constant pressure, 𝑪𝒑
 internal pressure or Joule’s coefficient, 𝝁𝑱
 Joule Thomson coefficient, 𝝁𝑱𝑻

Swagata Dasgupta, Chemistry IIT Kharagpur 1

 Partial derivatives of p, Vm, and T with respect to each other
Vm = f(p,T); p = f(Vm,T); T = f(p,Vm)

 T   T 
dT    dp    dVm  p   Vm   T 
 p Vm  Vm  p        1
 Vm T  T  p  p Vm
 p   p 
dp    dT    dVm
 T Vm  Vm T
 2T  2T  1 
 V   V     for ideal gas 
dV m  m  dT   m  dp pVm Vmp  R
 T  p  p T 

1 𝜕𝑉 1 𝜕𝑉
𝛼 𝜅
𝑉 𝜕𝑇 𝑉 𝜕𝑝
How fast the (fraction of)
volume increases with
Expansion coefficient Isothermal compressibility temperature and decreases
with pressure
 p  Vm / T  p  (T , p )
    For ideal gas
 T Vm Vm / p T  (T , p ) 1/T and 1/p

Summary: Internal Energy

• Internal energy, 𝑼 of a system is the total of kinetic and

potential energies of all its constituent particles

• 𝒅𝑼 𝟎 for an isolated system at equilibrium

𝝏𝑼
• 𝒅𝑼 𝑪𝑽 𝒅𝑻 𝝅𝑻 𝐝𝐕 where 𝝅𝑻 𝝁𝑱 𝑪𝑽
𝝏𝑽 𝑻

• 1st law of thermodynamics: ∆𝑼 𝒒 𝒘; d𝑼 ð𝒒 ð𝒘

• For constant volume processes, 𝑸𝒗 ∆𝑼 𝒎 𝑪𝒗 ∆𝑻

𝝏𝑼
• For an ideal gas, 𝝅𝑻 𝟎 and 𝑼 𝑼 𝑻 (closed system).
𝝏𝑽 𝑻

Swagata Dasgupta, Chemistry IIT Kharagpur 2

 Estimating ∆𝑼 and ∆𝑯 during change in state
Change in internal energy 𝑼 𝑼 𝑻, 𝑽

 Constant volume process ∆𝑼 𝑸𝑽 𝑪𝑽 ∆𝑻

 Constant temperature process ∆𝑼 𝝁𝑱 𝑪𝑽 ∆𝑽

 With change in both 𝑻 and 𝑽 ∆𝑼 𝑪𝑽 ∆𝑻 𝝁𝑱 𝑪𝑽 ∆𝑽

Change in enthalpy 𝑯 𝑯 𝑻, 𝒑
∆𝑯 𝑸𝒑 𝑪𝒑 ∆𝑻
 Constant pressure process
∆𝑯 𝝁𝑱𝑻 𝑪𝒑 ∆𝒑
 Constant temperature process

 With change in both 𝑻 and 𝒑

∆𝑯 𝑪𝒑 ∆𝑻 𝝁𝑱𝑻 𝑪𝒑 ∆𝒑

Work done by Isothermal expansion of an ideal gas

Reversible isothermal change: 𝒑𝒆𝒙𝒕 𝒑 at every stage
𝟐 𝑽𝟐 𝑽𝟐
𝒏𝑹𝑻 𝒅𝑽 𝑽𝟐
𝒘𝒓𝒆𝒗 𝒑𝒅𝑽 𝒅𝑽 𝒏𝑹𝑻 𝒏𝑹𝑻 𝐥𝐧
𝟏 𝑽𝟏 𝑽 𝑽𝟏 𝑽 𝑽𝟏

At higher T, work done is more for

same expansion of volume.

Irreversible isothermal change:

Work against a constant pressure
𝒑𝒆𝒙𝒕 𝒑𝒇
𝟐 𝟐
𝒘𝒊𝒓𝒓𝒆𝒗 𝒑𝒆𝒙𝒕 𝒅𝑽 𝒑𝒇 𝒅𝑽 𝒑𝒇 𝑽𝟐 𝑽𝟏
𝟏 𝟏

Maximum work is done by the system during reversible expansion

𝒘𝒓𝒆𝒗 𝒘𝒊𝒓𝒓𝒆𝒗

Swagata Dasgupta, Chemistry IIT Kharagpur 3

 Work done by adiabatic expansion of an Ideal Gas
d𝑼 ð𝒒 ð𝒘, ð𝒒 𝟎 ⇒ ð𝒘 𝒅𝑼 𝒏 𝑪𝑽 𝒅𝑻
𝟐
𝒘 𝒑𝒆𝒙𝒕 𝒅𝑽 𝒏 𝑪𝑽 𝑻𝟐 𝑻𝟏
𝟏

Reversible adiabatic expansion

Obtain 𝑻𝟐 using any of the following
𝒑𝑽𝜸 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 or 𝐓𝑽𝜸 𝟏 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 or 𝑻𝜸 𝑷𝟏 𝜸 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
Irreversible adiabatic expansion against a constant pressure 𝒑𝒆𝒙𝒕 𝒑𝟐
Obtain 𝑻𝟐 as follows
𝒏𝑹𝑻𝟐 𝒏𝑹𝑻𝟏
𝒏 𝑪𝑽 𝑻𝟐 𝑻𝟏 𝒑𝒆𝒙𝒕 𝑽𝟐 𝑽𝟏 𝒑𝟐
𝒑𝟐 𝒑𝟏
𝑪𝑽 𝒑𝟐
𝑹 𝒑𝟏
∴ 𝑻𝟐 𝑻𝟏
𝑪𝑽
𝟏
𝑹

An adiabat depicts the variation of

pressure with volume when a gas expands
adiabatically and, in this case, reversibly.

As the volume and temperature of a system are

changed, the internal energy changes. An adiabatic
and a nonadiabatic path are shown as Path 1 and
Path 2, respectively:
They correspond to different values of q and w but
to the same value of ΔU.

Swagata Dasgupta, Chemistry IIT Kharagpur 4

 Variation of the internal energy of a system with volume and temperature

The variation of the internal energy with

temperature at one particular constant volume
is illustrated by the curve drawn parallel to the
temperature axis.

The slope of this curve at any point is the

partial derivative (∂U/∂T)V.

(∂U/∂V)T , denoted πT , plays a major role in thermodynamics because it is a measure of

the variation of the internal energy of a substance as its volume is changed at constant
temperature.

πT has the same dimensions as pressure but arises from the interactions between the
molecules within the sample, it is called the internal pressure:

Swagata Dasgupta, Chemistry IIT Kharagpur 5

 Variation of the internal energy of a system with volume and temperature

U  f (V , T );U  f (T , V );U  f ( P, V )
Of the three thermodynamic variables, only two are  U   U 
dU    dV   dT
independent. It is convenient to choose V and T as  V T  T V
the independent variables for U.

State and Path Functions Path 2 - Non-

adiabatic
State functions: e.g., U and H w≠0;q≠0
Path 1 -
• Value of a state function is independent of path Adiabatic
• Depends on on initial and final state, w≠0;q=0
e.g. U = Ufinal-Uinitial
• Overall Change U   final dU
initial

dU is an exact differential

• Path from initial to final state has a functional Upath1 = Upath2 = Uf -Ui
dependence
– For U work may be done, heat may flow or both
– Equations that describe how you get to final state q  initial,path
final
dq
are path functions
dq  dq  is an inexact differential
• Path functions are path specific

Swagata Dasgupta, Chemistry IIT Kharagpur 6

 Changes in 𝑼 and 𝑯
are measured in terms of
Thermodynamic Response Functions

Thermodynamic Response Functions

These are measurable quantities that can be obtained from
experiments involving variation of 𝒑, 𝑽, 𝑻of closed systems

Response function Definition

Specific heat at constant volume 𝝏𝑼
𝑪𝑽
𝝏𝑻 𝑽

Specific heat at constant pressure 𝝏𝑯

𝑪𝒑
𝝏𝑻 𝒑

Isobaric expansion coefficient 𝟏 𝝏𝑽

𝜶
𝑽 𝝏𝑻 𝒑

Joule coefficient 𝝏𝑻
𝝁𝑱
𝝏𝑽 𝑼

Joule Thomson coefficient 𝝏𝑻

𝝁𝑱𝑻
𝝏𝒑 𝑯

Swagata Dasgupta, Chemistry IIT Kharagpur 7

 Thermodynamic Response Functions for an Ideal Gas
Measurable quantities that can be obtained from
experiments involving variation of 𝒑, 𝑽, 𝑻 of closed systems

Response function Definition Ideal

Idealgas
gasbehaviour
behaviour
Specific heat at constant volume 𝝏𝑼
𝑪𝑽
𝝏𝑻 𝑽

Specific heat at constant pressure 𝝏𝑯

𝑪𝒑
𝝏𝑻 𝒑

Isobaric expansion coefficient 𝟏 𝝏𝑽

𝜶
𝑽 𝝏𝑻 𝒑

Joule coefficient 𝝏𝑻
𝝁𝑱
𝝏𝑽 𝑼

Joule Thomson coefficient 𝝏𝑻

𝝁𝑱𝑻
𝝏𝒑 𝑯

Limitations of the First Law of Thermodynamics

The first law assures us that the total energy of system plus
surroundings remains constant during the reaction. Energy can be
transferred/transformed, keeping the total energy fixed.

dUuniverse = dUsystem + dUsurrounding = 0

Does not say:

Whether energy will get transferred / transformed?

If yes, in which direction?
If yes, how long and how fast?

Swagata Dasgupta, Chemistry IIT Kharagpur 8

 First law of Thermodynamics
Information from the 1st law Limitation of the 1st law

• The concept of internal • Will the change in state take

energy and enthalpy place?

• Constant total energy of the • If yes, what will be the

system plus surroundings spontaneous direction of
during any change in state change?

• Transfer/transformation of • What will be the new

energy between system and equilibrium state? Under
surrounding, keeping the what condition will the
total energy fixed. change stop?

𝒅𝑼𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 𝒅𝑼𝒔𝒚𝒔𝒕𝒆𝒎 𝒅𝑼𝒔𝒖𝒓𝒓𝒐𝒖𝒏𝒅𝒊𝒏𝒈 𝟎

Limitations of the 1st law of Thermodynamics

Initial equilibrium state Final equilibrium state

Swagata Dasgupta, Chemistry IIT Kharagpur 9

 Second Law of Thermodynamics

• A spontaneous process occurs naturally and needs no

external source of work.

• A non-spontaneous process, although allowed by the 1st law,

requires an external source of work to drive it.

• The 2nd law of thermodynamics tells us

the direction of a spontaneous change in state

the new equilibrium state achieved at the end of the change

Converting Heat into Work

• From the 1st law, when ∆𝑼 𝟎 ∴ 𝒒 𝒘

• So heat supplied to a system can be completely converted to work

• Such possibility is tested by the construction of heat engines

1 cal = 4.184 J
Joule’s Mechanical Equivalent of Heat

Swagata Dasgupta, Chemistry IIT Kharagpur 10

 Heat Engine

An engine is a device (system) that converts energy to work.

A heat engine draws heat from a hot reservoir, converts some heat
to work, and releases some heat to a cold reservoir.

The engine itself is a system that undergoes a cyclical process

Experiments suggested:

(Clausius) An engine does not exist whose sole effect is to

transfer heat from a cold body to a hot body.

(Kelvin) An engine does not exist that operates in a cycle and

performs work by exchanging heat with only one reservoir.

Converting Heat into Work

An engine is a device (system) that
converts energy to work.
𝑸𝒉

A heat engine 𝒘
• draws heat from a hot reservoir,
• converts some heat to work, and
• releases some heat to a cold 𝑸𝒄
reservoir.

The engine itself is a system that

undergoes a cyclic process
Efficiency of the
A reservoir is a large body whose heat engine
temperature does not change when it 𝒘
absorbs or gives up heat 𝜼
𝑸𝒉

Swagata Dasgupta, Chemistry IIT Kharagpur 11

 For a cyclic process,
𝑸𝒉 ∆𝑼 𝟎 ⇒
𝒘 𝑸 𝑸𝒉 𝑸𝒄
𝒘

𝒘 𝑸𝒉 𝑸𝒄 𝑸𝒄
⇒ 𝜼 𝟏
𝑸𝒄 𝑸𝒄 𝑸𝒄 𝑸𝒉

∴𝜼 𝟏 as 𝑸𝒄 𝟎

Kelvin’s Statement of 2nd Law

The perfect
heat engine It is impossible for any system to
operate in a cycle that takes heat
𝜼 𝟏 from a hot reservoir and converts it
to work in the surroundings without
at the same time transferring some
heat to a colder reservoir

Carnot Engine
A reversible cycle using an ideal gas as the working substance

A→
B

D→A B→
𝑸𝒉 C

C→D

𝑸𝒄

Swagata Dasgupta, Chemistry IIT Kharagpur 12

 The Carnot Cycle

Carnot Cycle: Four steps

STEP 1 STEP 2 STEP 3 STEP 4
(A to B) (B to C) (C to D) (D to A)
ISOTHERMAL ADIABATIC ISOTHERMAL ADIABATIC
EXPANSION EXPANSION COMPRESSION COMPRESSION
w V
 nRTH ln B
VA

U 0

q V
nRTH ln B
VA

qrev
T

Swagata Dasgupta, Chemistry IIT Kharagpur 13

 Carnot Cycle: Four steps

ISOTHERMAL ADIABATIC ISOTHERMAL ADIABATIC

EXPANSION EXPANSION COMPRESSION COMPRESSION
1 (A to B) 2 (B to C) 3 (C to D) 4 (D to A) Total (A to A)

w -nRTh ln(VB/VA) CV (Tc-Th) -nRTc ln(VD/VC) CV (Th-Tc) -nR(Th-Tc) ln(VB/VA)

q nRTh ln(VB/VA) 0 nRTc ln(VD/VC) 0 nR(Th-Tc) ln(VB/VA)

U 0
0 CV (Tc-Th) 0 CV (Th-Tc)

0 nR ln(VD/VC) 0 0
(qrev/ T) nR ln(VB/VA)

Efficiency of Carnot cycle

work performed

heat absorbed from source
 wtot nR (Th  Tc ) ln(V B / V A )
 
q nRT h ln(V B / V A )
Th  Tc T
  1 c  1
Th Th
Tc q
  1  1 c
Th qh
All reversible engines have same efficiency regardless of their construction

The total change in q/T during a Carnot cycle:

𝑞 𝑞 Change in q/T around any closed path is 0.

0
𝑇 𝑇
Quantity q/T is a state function.

Swagata Dasgupta, Chemistry IIT Kharagpur 14

 Efficiency of Carnot Engine
For any cyclic engine, ∆𝑼 𝟎⇒ 𝒘 𝑸 𝑸𝒉 𝑸𝒄

𝒘 𝑸𝒉 𝑸𝒄 𝑸𝒄
Thus, by definition 𝜼 i.e. 𝜼 𝟏
𝑸𝒉 𝑸𝒉 𝑸𝒉

As the Carnot engine works reversibly and employs an ideal gas,

𝑽𝑩 𝑽𝑩
𝑸𝑯 𝒏𝑹𝑻𝒉 𝒍𝒏 and 𝒘 𝒏𝑹 𝑻𝒉 𝑻𝒄 𝒍𝒏
𝑽𝑨 𝑽𝑨

𝒘 𝑻𝒉 𝑻𝒄 𝑻𝒄
∴𝜼 i.e. 𝜼 𝟏
𝑸𝑯 𝑻𝒉 𝑻𝒉

𝑸𝒄 𝑻𝒄 𝑸𝒉 𝑸𝒄
Note: 𝟏 𝟏 ⇒ 𝟎
𝑸𝒉 𝑻𝒉 𝑻𝒉 𝑻𝒄
Isothermal, absorption of heat at 𝑻𝒉 Isothermal, release of heat at 𝑻𝒄

Entropy

ð𝒒𝒓𝒆𝒗 𝑸𝒉 𝑸𝒄
• Over one cycle of Carnot Engine, ∮ 𝟎
𝑻 𝑻𝒉 𝑻𝒄

• Since any reversible cycle can be approximated by a series of Carnot cycles,

ð𝒒𝒓𝒆𝒗
∮ 𝟎 along any reversible cyclic path
𝑻

• A state function called entropy, 𝑺 is identified such that

ð𝒒𝒓𝒆𝒗
 𝒅𝑺 is an exact differential
𝑻

𝒃 𝒃 ð𝒒𝒓𝒆𝒗
 ∆𝑺 𝑺𝒃 𝑺𝒂 𝒂
𝒅𝑺 𝒂 𝑻
is independent of the path

Swagata Dasgupta, Chemistry IIT Kharagpur 15

 Entropy Change in Non-isolated Systems

• ∆𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 ∆𝑺𝒔𝒚𝒔 ∆𝑺𝒔𝒖𝒓𝒓

• All natural processes are cyclic and

irreversible.
∴ ∆𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 𝟎

Consider an irreversible engine that At the end of the cycle, the working
system is restored to its initial state
• absorbs 𝑸𝒉 ∗ heat at 𝑻𝒉
• undergoes an irreversible isothermal ∆𝑺𝒔𝒚𝒔 𝟎
expansion at 𝑻𝒉
𝑸𝒉 ∗ 𝑸𝒄
• has the same steps as Carnot engine ∆𝑺𝒔𝒖𝒓𝒓 𝟎
otherwise 𝑻𝒉 𝑻𝒄
𝑸 𝒉 ∗ 𝑸𝒄
𝟎 ∴ ∆𝑺𝒖𝒏𝒊𝒗𝒆𝒓𝒔𝒆 𝟎
𝑻𝒉 𝑻𝒄

Key Questions about Entropy

• Can we estimate the change in entropy, ∆𝑺 for different

processes?

• Can entropy be used to predict the following?

 the direction of spontaneous change

 the condition of equilibrium

Swagata Dasgupta, Chemistry IIT Kharagpur 16

 In all the cases first law allows either
outcomes, but we observe only one
outcome spontaneously.

Spontaneity:

A spontaneous process occurs naturally and needs no external

source of work. A non-spontaneous process, although allowed by
first law of TD, requires an external source of work to drive it.

Who drives, a spontaneous process?

Swagata Dasgupta, Chemistry IIT Kharagpur 17

 Entropy
• The thermodynamic property of a system that is related to its
degree of randomness or disorder is called entropy (S).

• The entropy S and the entropy change ΔS = S2 - S1 are

state functions.

• The entropy S has a unique value, once the pressure p, the

temperature T and the composition n of the system are specified,
S=S(p,T,n).

• The entropy is an extensive property, i.e., increases with the

amount of matter in the system. Sm= S/n (molar entropy).

Thermodynamic definition of entropy

dSsyst = Change in entropy that occurs during a

chemical or physical process
surrounding
= dqrev / T (qrev is the heat supplied reversibly)
system
2
dq rev
 S system  1 T

For surroundings,
Large change in entropy
dSsurr = - dq/Tsurr
occurs when heat is
dissipated to
q
 S surr  surrounding at low
Tsurr temperature.

Swagata Dasgupta, Chemistry IIT Kharagpur 18

 How do you calculate entropy change?
For surrounding
surrounding system

dSsurr = - dq / Tsurr  S q
surr 
Tsurr

Calculate the actual q for the process from state 1 to state 2 and apply the above formula

For system
• Find out state 1 and state 2
• Construct reversible pathway(s) from state 1 and state 2
• Apply the formula
2
dq
 S   rev
1
T

Change in Entropy of the System for

Different Processes

Swagata Dasgupta, Chemistry IIT Kharagpur 19

 Simple test cases
ð𝒒𝒓𝒆𝒗 𝟐 ð𝒒𝒓𝒆𝒗
By definition𝒅𝑺 and ∆𝑺 𝟏 𝑻
𝑻

For any isothermal process

𝟐 𝟐
ð𝒒𝒓𝒆𝒗 𝟏 𝑸𝒓𝒆𝒗
∆𝑺 ð𝒒𝒓𝒆𝒗 ∴ ∆𝑺
𝟏 𝑻 𝑻 𝟏 𝑻

For an isothermal expansion of an ideal gas

𝑽𝟐
∆𝑼 𝟎 ⇒ 𝑸𝒓𝒆𝒗 𝒘𝒓𝒆𝒗 𝒏𝑹𝑻 𝒍𝒏
𝑽𝟏
𝑽𝟐
∆𝑺 𝒏𝑹 𝒍𝒏
𝑽𝟏

Simple test cases

ð𝒒𝒓𝒆𝒗 𝟐 ð𝒒𝒓𝒆𝒗
By definition 𝒅𝑺 and ∆𝑺 𝟏 𝑻
𝑻

For an isochoric reversible process

ð𝒘𝒓𝒆𝒗 𝟎 ⇒ 𝒅𝑼 ð𝒒𝑽 𝑪𝑽 𝒅𝑻

𝟐 𝟐
ð𝒒𝑽 𝒅𝑻
∆𝑺 𝑪𝑽
𝟏 𝑻 𝟏 𝑻

𝑻𝟐
∴ ∆𝑺 𝑪𝑽 𝒍𝒏
𝑻𝟏

Swagata Dasgupta, Chemistry IIT Kharagpur 20

 Estimation of change in entropy
Simple test cases
• For a reversible process involving changes in 𝑻 and 𝑽 of 1 mole of an ideal gas
ð𝒒𝒓𝒆𝒗 𝒅𝑼 𝒑
ð𝒒𝒓𝒆𝒗 𝒅𝑼 𝒑𝒅𝑽 ⇒ 𝒅𝑽
𝑻 𝑻 𝑻

𝑪𝑽 𝑹
𝒅𝑺 𝒅𝑻 𝒅𝑽
𝑻 𝑽
𝟐 𝑻𝟐 𝑽𝟐
𝒅𝑻 𝒅𝑽
𝒅𝑺 𝑺𝟐 𝑺𝟏 ∆𝑺 𝑪𝑽 𝑹
𝟏 𝑻𝟏 𝑻 𝑽𝟏 𝑽

𝑻𝟐 𝑽𝟐
∆𝑺 𝑪𝑽 𝒍𝒏 𝑹 𝒍𝒏
𝑻𝟏 𝑽𝟏

Estimation of change in entropy

Simple test cases

• For a reversible process 𝑻𝟏 𝑽𝟏 𝑵 → 𝑻𝟐 𝑽 𝟐 𝑵

𝑻𝟐 𝑽𝟐
∆𝑺 𝑪𝑽 𝒍𝒏 𝑹 𝒍𝒏
𝑻𝟏 𝑽𝟏

• For an irreversible process between the same two states

𝑻𝟐 𝑽𝟐
∆𝑺 𝑪𝑽 𝒍𝒏 𝑹 𝒍𝒏
𝑻𝟏 𝑽𝟏
This is because
entropy 𝑺 is a state function and
∆𝑺 is independent of the path connecting the two states

Swagata Dasgupta, Chemistry IIT Kharagpur 21

 Simple test cases
ð𝒒𝒓𝒆𝒗 𝟐 ð𝒒𝒓𝒆𝒗
By definition 𝒅𝑺 and ∆𝑺 𝟏 𝑻
𝑻

Reversible heating at constant pressure (no phase change)

𝑻𝟐
𝒅𝑻
ð𝒒𝒓𝒆𝒗 ð𝒒𝒑 𝑪𝒑 𝒅𝑻 ⇒ ∆𝑺 𝑪𝒑
𝑻𝟏 𝑻
𝑻𝟐
∴ ∆𝑺 𝑪𝒑 𝒍𝒏
𝑻𝟏
Reversible heating at constant pressure (with phase change)
𝑸𝒓𝒆𝒗 ∆𝑯
∆𝑺
𝑻 𝑻
Here, ∆𝑯 is the enthalpy of phase change (latent heat) at the
transition temperature 𝑻

Calculation of Entropy Changes (A few special cases) 2

dq rev
1. Cyclic Process Ssyst= 0 (S is a state function)
 S system   1
T
2. Reversible adiabatic process Ssyst= 0 (dqrev=0)
3. Reversible phase-change at constant p and T
2 dq 2
rev  1 q rev H
 S syst    dq rev  
T T T T
1 1
4. Constant p heating (reversibly) with no phase change:
T T
dq rev  dq p  C p dT 2 dq 2 dT T 
  T  C p ln  T2 
 S syst  rev  C
p
T
T
T  1 
1 1
5. Reversible isothermal process:
2 dq 2 q rev
rev  1
 S syst   T T  dq rev 
T
1 1
6. For ideal gas:
dq rev dU  wrev C dT  pdV dT dV
dS    V  CV  nR
T T T T V
T V T2 p1
 S  CV ln 2  nR ln 2  S  C p ln  nR ln
T1 V1 T1 p2

Swagata Dasgupta, Chemistry IIT Kharagpur 22

 Calculation of Entropy at any temperature
Heating at constant pressure/Volume


Cp T2
S p  dT  C p ln
T T1


CV T2
SV  dT  CV ln
T T1

Entropy at any temperature,

Tf Tb T
C p (s) Hfus C p (l) Hvap C p (g)
S(T)  S(0)   dT   dT   dT
0
T Tfus Tf
T Tvap Tb
T

Debye Extrapolation: At low T, Cp  T3

Trouton’s Rule
A wide range of liquids give approximately the same
standard entropy of vaporization ~ 85 J K-1 mol-1 .
Exception: water, it is 109 J/K/mol

Construction of Reversible Steps to Describe an Irreversible Process

Example 1:

Liquid Water at - Irreversible S  Ice at -10 0C, 1

10 0C, 1 atm S S1 S2 S3 atm

Reversible
Reversible
heating at
cooling at
constant
constant
pressure, S1
pressure, S3

Reversible phase
Liquid Water at 0 change at constant
0C, 1 atm Temperature and Ice at 0 0C, 1 atm
pressure, S2

Entropy is an extensive property. S S1 S2 S3

Swagata Dasgupta, Chemistry IIT Kharagpur 23

 q0
S  ?
w   pext  V p1,V1,T1 p2,V2,T2
U  w  S   S1   S 2

 T   U / CV
Reversible Reversible
heating at isothermal
constant expansion
volume V
 S 2  nR ln 2
 S1  CV ln
T2 V1
T1
p’,V1,T2
dT dV
dS  CV  nR
T V

Statistical View of Entropy

The equilibrium thermodynamic state of an isolated system is the most probable state.

S  k B ln W
kB is Boltzmann’s constant

W is number of different ways in which the energy of the system can be arranged
(number of microstates)

W = 21 X 20 X 19 = 7,980 W = 63 X 62 X 61 = 2,38,266

Swagata Dasgupta, Chemistry IIT Kharagpur 24

 Relevance of Entropy
in
Spontaneity and Equilibrium

Entropy and Clausius Inequality

• For any reversible engine, operating between two temperatures 𝑻𝒉
and 𝑻𝒄 ,

𝒘𝒓𝒆𝒗 𝑻𝒄
𝜼𝒓𝒆𝒗 𝟏
𝑸𝒉 𝑻𝒉

• For any arbitrary engine (NOT reversible) operating between the same
two temperatures 𝑻𝒉 and 𝑻𝒄 , with the same input of 𝑸𝒉

𝜼 𝜼𝒓𝒆𝒗 because 𝒘𝒊𝒓𝒓𝒆𝒗 𝒘𝒓𝒆𝒗

𝑸𝒄 𝑻𝒄 𝑸𝒉 𝑸𝒄 ð𝒒
∴𝟏 𝟏 ⇒ 𝟎⇒ 𝟎
𝑸𝒉 𝑻𝒉 𝑻𝒉 𝑻𝒄 𝑻

Swagata Dasgupta, Chemistry IIT Kharagpur 25

 Entropy and Clausius Inequality

ð𝒒
For any irreversible cycle ∮ 𝟎
𝑻

Irreversible Reversible
State 1 State 2 State 1
𝟐 𝟏
ð𝒒𝒊𝒓𝒓 ð𝒒𝒓𝒆𝒗
∴ 𝟎
𝟏 𝑻 𝟐 𝑻

𝟐 𝟐 𝟐
ð𝒒𝒊𝒓𝒓 ð𝒒𝒊𝒓𝒓
𝒅𝑺 𝟎 ⇒ ∆𝑺 𝑺𝟐 𝑺𝟏
𝟏 𝑻 𝟏 𝟏 𝑻

Entropy and Clausius Inequality

For an irreversible change in state from state 1 to state 2
𝟐 𝟐
ð𝒒𝒊𝒓𝒓 ð𝒒𝒊𝒓𝒓
𝒅𝑺 ⇒ 𝒅𝑺
𝟏 𝟏 𝑻 𝑻

Mathematical statement of 2nd law of thermodynamics

ð𝒒
𝒅𝑺
𝑻

ð𝒒 Irreversible and spontaneous change in state

𝒅𝑺
𝑻
ð𝒒 Reversible process
𝒅𝑺
𝑻
ð𝒒 Process associated with the change in state is
𝒅𝑺 NOT permitted
𝑻

Swagata Dasgupta, Chemistry IIT Kharagpur 26

 Application to transformations in real systems

• From Clausius inequality

ð𝒒𝒊𝒓𝒓𝒆𝒗
𝒅𝑺
𝑻

• In an isolated system, during an irreversible process,

ð𝒒𝒊𝒓𝒓𝒆𝒗 𝟎⇒ 𝒅𝑺 0

• For a real transformation in an isolated system, upon

withdrawal of an internal constraint, the system
spontaneously changes towards that direction that
increases the entropy.

Initial equilibrium state Final equilibrium state

𝑻 𝑽𝒊 𝑵 𝑻 𝑽𝒇 𝑵

Isothermal Isothermal
irreversible irreversible
compression expansion

What is ∆𝑺 as the system goes from 𝑻 𝑽𝒊 𝑵 to 𝑻 𝑽𝒇 𝑵 ?

∆𝑺 𝟎 if 𝑽𝒇 𝑽𝒊
𝑽𝒇
∆𝑺 𝑹 𝒍𝒏
𝑽𝒊 The ideal gas will spontaneously expand
under the given experimental condition

Swagata Dasgupta, Chemistry IIT Kharagpur 27

 Initial equilibrium state Final equilibrium state
𝑻 𝑽𝒊 𝑵 𝑻 𝑽𝒇 𝑵

Isothermal
irreversible
expansion

Under what condition does the gas stop expanding

any further so that a new equilibrium state is
reached? ∆𝑺 reaches a maximum when 𝑽 is 𝒇
𝑽𝒇 maximum
∆𝑺 𝑹 𝒍𝒏 ⇒ 𝑺𝒇𝒊𝒏𝒂𝒍 is maximum when 𝑽𝒇 𝑽𝟐
𝑽𝒊
The ideal gas will spontaneously
d till it fill th ti

Entropy Change in an Isolated System

• In the absence of any exchange of heat,
𝒅𝑺 0
• Upon withdrawal of an internal constraint, the system spontaneously
changes towards that direction that maximizes the entropy.
Final equilibrium state
Initial equilibrium state

𝑽𝒇𝒊𝒏𝒂𝒍
The change in entropy, ∆𝑺 𝒏𝑹 𝒍𝒏 is maximum when the
𝑽𝟏
final volume, 𝑽𝒇𝒊𝒏𝒂𝒍 is maximum

Therefore, the final equilibrium state is reached when 𝑽𝒇𝒊𝒏𝒂𝒍 𝑽𝟐

Swagata Dasgupta, Chemistry IIT Kharagpur 28

 Entropy Change in an Isolated System
• Any natural change within an isolated system
is accompanied by an increase in entropy

• The entropy continues to increase as long as

the changes occur within the system

• When entropy attains its maximum value, the

system reaches a new equilibrium state.

𝒅𝑺 𝟎 Irreversible and spontaneous change in state

𝒅𝑺 𝟎 No further change, a new equilibrium is reached

𝒅𝑺 𝟎 Process associated with the change in state is

NOT permitted

Entropy and Clausius Inequality

For an irreversible change in state from state 1 to state 2
𝟐 𝟐
ð𝒒𝒊𝒓𝒓 ð𝒒𝒊𝒓𝒓
𝒅𝑺 ⇒ 𝒅𝑺
𝟏 𝟏 𝑻 𝑻

Mathematical statement of 2nd law of thermodynamics

ð𝒒
𝒅𝑺
𝑻
ð𝒒 Irreversible and spontaneous change in state
𝒅𝑺
𝑻
ð𝒒 Reversible process
𝒅𝑺
𝑻
ð𝒒 Process associated with the change in state is
𝒅𝑺 NOT permitted
𝑻

Swagata Dasgupta, Chemistry IIT Kharagpur 29

 Construction of Reversible Steps to Describe an Irreversible Process:
Entropy of Mixing of ideal gases
p, T, V1, n1 p, T, V2, n2

Irreversible mixing
of gases S=?

p, T, V1 +V2, n1 + n2
p, T, V1, n1 p, T, V2, n2

Reversible,
isothermal
expansion

T, V1 +V2, n2
T, V1 +V2, n1
V1  V2 V1  V2
 S1  n1 R ln  S 2  n 2 R ln  S mix   S1   S 2
V1 V2

Construction of Reversible Steps to Describe an Irreversible Process

Entropy of Mixing of ideal gases
p, T, V1, n1 p, T, V2, n2

Irreversible mixing
of gases

Δ𝑆mix Δ𝑆 Δ𝑆
p, T, V1 +V2, n1 + n2
𝑉 𝑉 𝑉 𝑉
Δ𝑆 𝑛 𝑅 ln , Δ𝑆 𝑛 𝑅 ln
𝑉 𝑉

𝑛 𝑅𝑇
𝑉 𝑝 𝑛
𝑥
𝑉 𝑉 𝑛 𝑅𝑇 𝑛 𝑅𝑇 𝑛 𝑛
𝑝 𝑝
Find out x1 for which
Smix is maximum Δ𝑆mix 𝑛 𝑅 ln 𝑥 𝑛 𝑅 ln 𝑥
𝑛𝑅 𝑥 ln 𝑥 𝑥 ln 𝑥

Swagata Dasgupta, Chemistry IIT Kharagpur 30