Thermodynamics:

The Second Law

Focus 3
 First Law of Thermodynamics
Energy can change from one form to another, but
total amount of energy remains constant
U  q  w;
w    pext dV ; q   C path dT
path path

For a cyclic process:  dU  0  q  w

Equivalence of heat & work: Heat can be

converted to useful work in a cycle process
(engine).
 Natural Processes and the First Law
Consider an uniform Temperature metal rod transform
to hot & cold ends

Consider the Collapse

of ideal gas in a rigid
adiabatic container into
half of its volume

* Natural (spontaneous) processes are unidirectional.

* First Law does not have an explanation !
 Direction of Natural Process

Matter has natural tendency Energy has a natural

to become disorder tendency to disperse

Matter as well as Energy tends to become

disordered (Direction of spontaneous process)
 Entropy
The measure of disorderly disposal (of matter &
energy) in thermodynamics is called Entropy (S).

qrev
S 
T

• The entropy is a state function

• The entropy is a measure of current state of
disorder of the system
 Entropy Change in Isolated System
For Reversible Processes: q q
sys sur
q
Isothermal:  S  sys  S
sys T sur
 S  S  S 0
tot sys sur

Adiabatic: q 0  S
sys
 0  S
sur
; S  0
tot
For Re versible Pr ocess : S  0
tot

S  0  = For Reversible Processes

> For Irreversible Processes
tot
 Entropy & 2nd Law of Thermodynamics
The entropy of an isolated system tends to
increase (Second law of thermodynamics)

1.Follows from observation of a directionality to

natural or spontaneous processes

2.Puts restrictions on useful conversion of q to w

3.Provides a set of principles for

- determining direction of spontaneous change
- determining equilibrium state of a system
 Experience Shows…
All naturally occurring processes always tend to
change spontaneously in a direction which leads to
equilibrium.

Work can be completely

transformed into heat
but heat cannot be
completely converted
into work, without
leaving permanent
change in the system or
surrounding!
Heat engines
For the process to be
spontaneous, change in
entropy should be positive.

The decrease in entropy

of the hot source must
be offset by the increase
in entropy of cold sink.

Efficiency of 𝑻𝑪
Engine: 𝜼=𝟏−
𝑻𝒉
 Calculation of Entropy changes

Infinitimal Change:
dqrev
dS 
T
Total Entropy Change:

2 dqrev
S  S2  S1  
1 T
 Entropy changes for typical processes
Variation with volume (perfect gas):
q  w  nRT ln(V f Vi )
rev
q
S  rev  nR ln(V V )
T f i
Variation with Temperature:
2 Tf
S   dS  
CdT (dS  dqrev T  C dT T )
T
1 T
i

For constant C:
T T
f dT
S  C   C ln f
T T
T i
i
Entropy change accompanying phase transition
At the transition
temperature, any
transfer of
energy as heat
between the
system and its
surroundings is
reversible
Solid Liquid Gas

because the two q = ΔtrsH (constant P)

phases in the
 trs H
system are in  trs S 
equilibrium. Ttrs
 Entropy change accompanying phase transitions
 fus H
Tf
C dT
S  
0
T

Tf
Tb
C dT  vap H
 
Tf
T Tb
T
C dT

Tb
T

Entropy change at very low Temperature:

Close to T = 0, Debye T 3 law is obeyed, i.e. Cv,m = aT 3
T T 3 T
CV ,m dT aT dT 1 3 1
S     a  T dT  aT  CV ,m (T )
2

0
T 0
T 0
3 3
 T
Absolute entropies
f CdT
S   ; For Ti = 0 and Tf = T, ΔS = S(T) – S(0)
T
T
i
Entropy at any
temperature S (T) is
equal to the area
under the graph on
C/T between T = 0
and temperature T

Absolute entropy can be obtained by knowing the

entropy at T= 0 K.
 Entropy at absolute zero
Transition from Rhombic to Monoclinic Sulfur occurs at
369K with ΔS = +1.09 J K-1 mol-1

Third Law of Thermodynamics: The entropies of all

perfectly crystalline substances are the same at T= 0 K and
for convenience it is set to ZERO.
The Statistical Entropy S k ln W
k: Boltzmann’s Constant, and W: weight / configuration of the sample,
W gives no. of ways the molecules in the sample can be
arranged corresponding to same total energy.

S = 0 when W = 1

At a given T, W is greater
when the energy levels
e.g. Arrangement of four molecules
are closely spaced than
in a system of three energy levels
when they are far apart.
with total energy of 4ε: Total 19
 Residual Entropy
For CO at 298 K: S (thermodynamics)= 192 J/(K-mol),
S(statistical) = 198 J/(K-mol)

Reason:
Thermo defn. is
incapable.

CO molecules are
disorder in solid
even at T = 0.

W  2 N  S  k ln 2 N  Nk ln 2  5.8 JK 1mol 1
 Focusing on the system
For Spontaneous Process : S  Ssys  Ssur  0
tot
For a constant T, P Process:
q q H
S  sur   sys   sys
sur T T T
 S  Ssys  Ssur
tot
H Gsys
 S  sys 
sys T T
(G TS  H )
sys sys sys

For Spontaneous Process :

S  0  G  0
tot sys
 Properties of Gibbs energy
For a const. T, P Process: G  H  TS

In general, Gibbs Free energy G = H – TS

G  H  TS  (U  PV )  TS
 dGT , P  dU  PdV  TdS
 ( PexdV  dw'dq)  PdV  TdS
 dw'

∆G is the maximum non-expansion work extracted

from the process at const. T & P.
The thermodynamics of phase transition
Phase I Phase II
Molar Gibbs energy:
Gm(1) Gm = G/n = μ Gm(2)

∆G = nGm(2) – nGm(1) = n [Gm(2) – Gm(1)]

So, ∆G < 0, IF Gm(2) < Gm(1)

i.e. Change from phase I to phase II is spontaneous if
the later has lower molar Gibbs energy than the
former.
A substance has a spontaneous tendency to change
Into the phase with the lowest molar Gibbs energy.
 Gibbs energy & pressure
For reversible changes: (Use G = H – TS, H = U + pV
dG = V dp – S dT and dU = dq + dW = TdS – pdV)
At const T: ∆Gm = Vm ∆p
• ∆Gm > 0 when ∆p > 0
• Gm is more for larger Vm
For solid & liquid
Vm is almost independent of p
and ΔGm = Gm(pf) - Gm(pi), so
Gas most stable

Gm(pf) = Gm(pi) + Vm (pf – pi)

For gases behaving ideal:

pf
G   Vm dp gives
m pi
Liquid most stable
Gm(pf) = Gm(pi) + RT ln(pf / pi)
 Gibbs energy & temperature
dGm = Vm dp – Sm dT
At constant p:
∆Gm = - Sm ∆T

• Sm > 0 =>
∆Gm < 0 when ∆T > 0

• Gm falls more steeply

with T for a gas than
for a condensed phase
Gibbs-Helmoltz Equation:
 The Thermodynamics of Reaction
For spontaneous change at constant T & P, ∆G < 0
A reaction mixture tends
to adjust its composition
until its Gibbs energy is a
minimum.

(a): Mostly reactants

(b): reactants + Products
(c): Mostly products

• How to use thermodynamic data to predict the

equilibrium composition ?
• How that composition depends on conditions?
 Criterion for Chemical Equilibrium
Consider the reaction: N 2 ( g )  3H 2 ( g )  2 NH 3 ( g )

Change in moles:  n  3n  2n

Change in G:   N2 n  H 2 3n   NH 3 2n
(μ: chemical potential)

G  ( N2  3 H 2  2 NH 3 )  n
G
Reaction Gibbs Energy: rG   2 NH 3   N 2  3 H 2
n
For a general reaction: aA  bB  cC  dD
G
rG   cC  d D  (a A  b B )
n
The criterion for chemical equilibrium at constant
P and T is ∆rG =0.
 The reaction Gibbs energy ∆rG

The criterion for chemical

equilibrium at constant P
and T is ∆rG =0.

The  of a substance depends on the composition of the mixture

in which it is present , and is high when its concentration is high.
Thus, ∆rG changes as the composition changes.
 Variation of ∆rG with composition
For ideal gases: Gm(pf) = Gm(pi) + RT ln(pf/pi); choose pi = 1 atm
Chemical potential (molar Gibbs energy of pure species)
 J   J  RT ln aJ aJ : activity of species J

For ideal solutes:

For the reaction, aJ = [J]/c°, c°=1 mol/L
aA  bB  cC  dD For ideal gases:
 r G  cC  d D  (a A  b B ) aJ = p/p°, p°=1 bar
For pure solids & liquids:
becomes aJ = 1.
 r G   r G   RT ln Q
At equilibrium:
where,  r G  0   r G    RT ln K
 r G   cC  d D  a A  b B where,
aCc aDd  aCc aDd 
Q a b K  Qequilibrium   a b 
a A aB
 a A aB equilibrium
 The Equilibrium Constant
At Equilibrium:
 r G  0   r G    RT ln K
where,
The standard reaction
a a 
c d
K  Qequilibrium   C
a

D
b
Gibbs energy
 a a equilibrium
A B

KC : K in terms of Molar concentration [J]:

aJ = [J]/c°, c°=1 mol/L
KP : K in terms of Pressure:
aJ = p/p°, p°=1 bar
∆𝑛
𝑐 0 𝑅𝑇
𝐾𝑝 = 𝐾𝐶 ×
𝑝0
 Thermodynamic criteria of spontaneity
K  1   r G   0 (exergonic ) / thermodynamically stable
 r G    RT ln K
K  1   r G   0 (endergonic) / thermodynamically unstable

 r G    r H   T r S 

The switch of non-spontaneity to spontaneity occurs  H

At T  r
when ∆rG° shift from positive to negative value, or 
when K swift from K < 1 to K > 1  S
r