Physical Chemistry I

Chapter 3. The Second law of Thermodynamics

Overview
3-1. The Concepts

3-2. Entropy
3-2-1. Definition of entropy
3-2-2. Carnot cycle
3-2-3. Clausius inequality

3-3. Entropy change

3-3-1. ∆S in phase transition
3-3-2. ∆S in ideal gas
3-3-3. Entropy change during heat transfer

Physical Chemistry
Overview
3-4. The Third law of thermodynamics
3-4-1. The Approach to Absolute entropy
3-4-2. The Third Law of Thermodynamics

3-5. Free Energy : concentrating on system

3-5-1. Definition of A, G
3-5-2. Physical meaning of ∆A, ∆G

3-6. Maxwell relations

3-7. Pressure and Temperature dependence of G

3-8. Chemical potential & fugacity

Physical Chemistry
3-1. The Concepts : Second Law of Thermodynamics

- Presenting direction of energy conversion (에너지 전환의 방향성을

제시) ~ Conservation of energy (First law of thermodynamics)
-The Principle of Kelvin : No process is possible in which the
absorption of heat from a reservoir and its complete conversion into
work.

Others : Thomson, Clausius…

- Spontaneous change ~ a dispersal of energy into
more disordered form
-The entropy of an isolated system increases in
the course of a spontaneous change :

Stot  0 (3.1)
where Stot = S sys + S surr

Physical Chemistry
3-1. The Concepts : Second Law of Thermodynamics

* Direction of energy changes in spontaneous natural process

(에너지흐름과 관련된 자연현상이 일어나는 방향)

ex) • Heat transfer from High T → Low T

• Mixture of gas (기체의 혼합)
• Ball bouncing on a floor

“ the direction of change

→ more disorderly dispersal of the total energy of
isolated system”

Physical Chemistry
3-2-1. Entropy
- In 1865, Clausius, Entropy ~ “turning of energy” in Greek.

State function
1st law U , H …

2nd law S , A …

- Degree of disorder(무질서도) ~ q
ex) S solid  Sliquid  Svapor
- Thermodynamic definition of entropy
dq f dqrev
dS = rev (3.2) S = 
T i T
B A
 dS =  A
dS + 
B
dS = 0 (3.3) S : state function

Physical Chemistry
3-2-1. Entropy

dS = 1
T
( )
dqrev

dqrev : inexact differential

1
T : integrating factor
dS : exact differential
dqsurr ,rev dqsurr
dS surr = =
Tsurr Tsurr
q
S surr = surr (∵ Tsurr = constant)
Tsurr

For any adiabatic process, S surr = 0

Physical Chemistry
3-2-2. Carnot cycle
Heat engine reversibly working at hot/cold
reservoirs (TH /TC ) has the maximum
Heat reservoir conversion efficiency ( ), which only
depends on temperatures
TH
↓ qH
w
Carnot engine

↓ qC
Heat reservoir

TC

Physical Chemistry
3-2-2. Carnot cycle
①Isothermal reversible expansion at TH : qH transferred into system
qH
S =
TH
②Adiabatic reversible expansion (isentropic) : q = 0
TH → TC S = 0

③Isothermal reversible compression at TC : qC transferred to surround

qC
S =
TC
④Adiabatic reversible compression : q = 0
TC → TH S = 0
qH qC qH T
 dS = +
TH TC
=0
qC
=− H
TC
(3.4)

Physical Chemistry
 3-2-2. Carnot cycle

* Efficiency of the engine, 

work performed w
= = (3.5)
Heat absorbed qH ∵ U = qH + qC + w
(1st Law)
For Carnot engine
TC
 rev =1− (3.6)
TH

* Thermodynamic temperature scale by Kelvin

T = (1 −  )TH (3.7)
- independent of any thermodynamic substance
- at T → 0 ,  →1
Physical Chemistry
3-2-3. Clausius inequality

dStot  0 for any spontaneous change

Considering a system in thermal & mechanical contact with

surrounding at the same temperature

dS + dS sur  0
− dq
 dS sur =
T
dq
→ dS  (3.8) : Clausius Inequality
T

Physical Chemistry
 3-2-3. Clausius inequality

* Heat transfer (dq) from hot source(TH ) to cold sink surrounding (TC)

dq dq
dStot = dS sys + dS sur =− +
TH TC
 1 1 
= dq  −  (3.9)
 C
T TH 

Since TH  TC , dStot  0 (비가역 과정)

If TH = TC (thermal equilibrium),

dStot = 0

Physical Chemistry
 3-3-1. Entropy Change - ∆S in phase transition

trs H
trs S = (3.10)
Ttrs
ex] solid → liquid
<latent heat>

 m H = H (liquid ) − H ( solid )

m H
 m S = S (liquid ) − S ( solid ) =
Tm
-Trouton’s rule : “ A wide range of liquids give approximately the
same  vap S ”

Physical Chemistry
 3-3-1. Entropy Change - ∆S in phase transition

-Trouton’s rule : “ A wide range of liquids give approximately the

same  vap S ”

Atkins, Physical Chemistry, Oxford University Press

Physical Chemistry
3-3-2. ∆S in ideal gas

For ideal gas,

 U 
  =0 & dU = CV dT
 V T
Thus
nRTdV
dq = dU + PdV = CV dT + PdV = CV dT +
V
dq CV dT nRdV
→ dS = = + (4.11)
T T V
2 CV 2 nRdV
→ S =  dT + 
1 T 1 V

Physical Chemistry
3-3-2. ∆S in ideal gas

If CV = constant,

T2 V
→ S = CV ln + nR ln 2 (3.12)
T1 V1

For temperature change For isothermal

at constant volume expansion

T2 V2
S = CV ln (3.13) S = nR ln (3.14)
T1 V1

At constant pressure,
CP
dS = dT
T

Physical Chemistry
 3-3-3. Entropy Change during heat transfer
- For heat transfer from Th to Tc

q q 1 1
Sirrev = − = q − 
Tc Th  Tc Th 
Th − Tc
=q 0
TcTh
Th  Tc

The entropy of the isolated system would have

increased during the irreversible process
Physical Chemistry
3-4-1. The Third law (Absolute entropy)
The Approach to Absolute entropy

- Evaluation of entropy S (T ) at constant pressure

dH = TdS + VdP

 H   S 
⇒   = T 
 T  P  T  P

⇒  S  C
  = P
 T  P T

CP ( S ) dT  fus H CP ( l ) dT  vap H CP ( g ) dT
S (T ) = S ( 0 ) +
Tf Tb T

0 T
+
Tf
+ 
Tf T
+
Tb
+ 
Tb T
(3.15)

Physical Chemistry
 3-4-2. The Third Law of Thermodynamics
- Nernst Heat Theorem : As T → 0 , S → 0
* German Physical Chemist in 1920 received Novel Prize

- Third Law of thermodynamics (열역학 제 3법칙) : Lewis [1923]

If the entropy of each element in some crystalline state be taken
as zero at the absolute zero of temperature, every substance has
a finite positive entropy ; but at the absolute zero of temperature
the entropy may become zero, and does so become in the case
of perfect crystalline substances

Physical Chemistry
3-4-2. The Third Law of Thermodynamics

* “The 3rd Law of thermodynamics”

“The entropy of all perfect crystalline substance is zero at T = 0

* ‘Nernst heat theorem’

The entropy change accompanying any physical or chemical
transformation approaches zero as T → 0 if all substance
are perfectly ordered

Physical Chemistry
3-5. Free Energy : concentrating on system
* Definition of A, G
- Helmholtz free energy

A = U − TS (3.16)
- Gibbs free energy

G = H − TS (3.17)
dq
Clausius inequality dStot = dS − 0
T
-for heat transfer at constant volume, dqV = dU

dU
dS − 0 (3.18) → dSU ,V  0 (3.19)
T
⇒ 2nd Law
Physical Chemistry
3-5-1. Definition of ∆A, ∆G
From (3.18) and constant temperature process

dU −TdS  0
→ dAT ,V  0 (3.20)
<Criterion of spontaneous change for constant T, V process>

- for heat transfer at constant pressure, dqP = dH

dH
dS − 0 (3.21)
T
→ dH −TdS  0
→ dGT , P  0 (3.22)
<Criterion of spontaneous change for constant T, P process>

Physical Chemistry
 3-5-2. Physical meaning of ∆A, ∆G

* A = U − TS at constant temperature

A = wmax (3.23) for isothermal change

* G = H − TS at constant T
G = we,max (3.24) at constant T, P

: maximum non-expansion work

we,max
Electrochemical work: fuel cell, solar cell, etc…
(연료전지 및 전기화학적 방법에 의해 전기적 일이 행해질 때)

Physical Chemistry
 3-6. Maxwell relations
* First and Second Laws combined
dU = dq + dw
= TdS − PdV (3.25)

Since  U   U 
dU =   dS +   dV
 S V  V  S

 U   U 
  =T ,   = −P (3.26)
 S V  V  S

U is exact function
 T   P 
  = −   (3.27)
 V  S  S V   2U    2U 
  =  
 S V   V S 

Physical Chemistry
3-6. Maxwell relations
* Enthalpy
dH = dU + d (PV )
= TdS − PdV + PdV + VdP = TdS + VdP (3.28)

Thus
 H   H 
  =T   =V (3.29)
 S  P ,
 P  S
Also

 T   V 
  =  (3.30)
 P S  S P

Physical Chemistry
3-6. Maxwell relations
* Helmholtz energy
dA = dU − d (TS )
= TdS − PdV − TdS − SdT = − SdT − PdV (3.31)

Thus
 A   A 
  = −S ,   = −P (3.32)
 T V  V T

Also
 S   P 
  =  (3.33)
 V T  T V

Physical Chemistry
3-6. Maxwell relations
* Gibbs free energy
dG = dH − d (TS )

= TdS + VdP − TdS − SdT = − SdT + VdP (3.34)

Thus
 G   G 
  = −S   =V (3.35)
 T  P ,  P T
Also
 S   V 
  = −  (3.36)
 P T  T P

Physical Chemistry
3-7. Pressure and Temperature dependence of G

dG = −SdT + VdP
 G   G 
  = −S   =V
 T  P  P T

* Pressure dependence
At constant temperature, dG = VdP
for incompressible fluid, G = V P (3.37)
nRT P
for ideal gas, G =  dG =  P
dP = nRT ln 2
P1
(3.38)

Physical Chemistry
3-7. Pressure and Temperature dependence of G

* Temperature dependence

At constant pressure , dG = −SdT

 G  G−H
  = − S =
 T P T

  (G / T )  1  G  G H
 T  =   − = − (3.39)
  P T  T  p T
2
T2
→ Gibbs-Helmholtz equation
Also
 (G / T )  H
 T  = − (3.40)
 P T2

Physical Chemistry
3-8. Chemical potential & fugacity
(⇒ fugacity( f ) & fugacity coeff.(  =
f
P )

* Chemical potential  ⇒ Equilibrium i = i 

 G 
i =   (3.41)

 i T , P ,n j
n

G (T , P, n j )

 G   G   G 
dG =   dT +   dP + i   dni (3.42)
 T  P  P T  ni T , P ,n j

 i dni

Physical Chemistry
3-8. Chemical potential & fugacity

* For pure substance

 G   nGm 
 =  =   = Gm (3.43)
 n T ,P  n T ,P

: molar Gibbs energy

* For ideal Gas at constant T

dG = nRTd ln P
 P 
→ G (P ) = G + nRT ln  

(3.44)
P 
( P  : standard pressure of 1bar)

 P 
 =   + RT ln   
(3.45)
P 

Physical Chemistry
 3-8. Chemical potential & fugacity
* Fugacity f
: effective pressure : escaping tendency For real gas

  f 
 =  + RT ln    (3.46)
P 

For ideal gas, dG = RTd ln P

For real gas, dG = RTd ln f
f
* Fugacity coefficient  = (3.47)
P
for ideal gas,  =1

Physical Chemistry
 3-8. Chemical potential & fugacity
from (3.46),
 f 
 =   + RT ln  
P 
P
=   + RT ln 
P
P
=   + RT ln 
+ RT ln  (3.48)
P
P
(   + RT ln  :ideal gas Gm,
id
RT ln  :due to intermolecular force)
P

As P→0 ,  →1 ⇒  −  id = RT ln 

  −  id 
 = exp  
 RT 

Physical Chemistry
3-8. Chemical potential & fugacity

* Evaluation of 
P Z −1 
( )
P
ln  = 
0

 P 
 dP = 0
Vm − Vmid dP (3.49)

Z  1,   1 → f  P
Z =1  =1 → f = P
,
Z  1,   1 → f  P

Physical Chemistry
 3-8. Chemical potential & fugacity
<Derivation>
dG = VdP at constant T
G (P ) = G (P') +  VdP
P

P'

P
 =  '+  Vm dP when f ' = P' ,
P'

 f 
 (V )
P
RT ln   = m − Vmid dP
f P P 0
 −   = RT ln( ) =
f P
Vm dP
P ( Z − 1)
P P → RT ln  =  RT dP
−)  id −  id = RT ln( ) =
P  P
Vmid dP 0 P
P ( Z − 1)
→ ln  =  dP
 f P'  0 P
 (V ) dP
P
RT ln    = m − Vm id

 f' P 0

Physical Chemistry