Chapter II

Second And Third Laws Of

Thermodynamics.

1
 Chemical Thermodynamics
• Chemical thermodynamics is used to predict whether
or not a reaction will occur when reactants are
brought together under a specific set of conditions.

• A reaction that does occur under the given set of

conditions is called a spontaneous reaction.

• A reaction that does not occur under specified

conditions is said to be non spontaneous

2
 Spontaneous Physical & Chemical Processes
• A waterfall runs downhill
• A lump of sugar dissolves in a cup of coffee
• At 1 atm, water freezes below 0 0C and ice melts above 0 0C
• Heat flows from a hotter object to a colder object
• A gas expands in an evacuated bulb
• Iron exposed to oxygen and water forms rust
spontaneous

Non spontaneous

3
18.2
 THE SECOND LAW OF THERMODYNAMICS:
THE HEAT FLOW STATEMENT

• Heat flows spontaneously from a substance at a

higher temperature to a substance at a lower
temperature & does not flow spontaneously in the
reverse direction

·˙· 2nd Law of thermodynamics state

Work and heat are not equivalent forms of energy.

That is mean: work can completely transferred into
heat but heat can’t be completely transformed into
work without additional changes in the universe.
5
• So, the most efficient method of getting a
transformation of heat to work can be done by
cyclic reversible process.

• heat can not be taken from reservoir and

converted into work by cyclic process without
delivering heat from the higher temperature to
a lower temperature at the same time.

6
 Heat Engine
A heat engine is a device that carries a
working substance through a cyclic process,

A heat engine typically uses energy provided

in the form of heat to do work and then
exhausts the heat which cannot be used to do
work.

7
 Heat engine performs work by
Heat Engine transferring heat from warm to cold
Reservoir.
a heat engine that takes some
"working substance" -- typically a
gas -- through a cyclic process.
Thermal energy Qh is absorbed
from a source at a hot temperature
Th. Net work W is done by the heat
engine on its surroundings.
Thermal energy Qc is given to a
Engine source at a cold temperature Tc.
containing surrounding
working fluid

9
 Heat Engine Examples
1. Carnot cycle
2. Refrigerator
3. Heat pump
4. Diesel engine

10
Heat Pumps and Refrigerators
A heat pump or a refrigerator is a device that absorbs
heat Qc from a cold temperature and releases heat Qh at
a hot temperature because work W is done to it from the
outside.

surrounding

11
 General statements of the second law
of thermodynamics

There are a number of equivalent physical

statements of the second law of thermodynamics.

1. Clausius principle: A process which involves no

change other than the transfer of heat from a
hotter body to a cooler body is irreversible;
or, it is impossible for heat to transfer
spontaneously from a colder to a hotter body
without causing other changes.

12
2. Thompson’s (or Kelvin’s) principle: A process in
which work is transformed into heat without any
other changes is irreversible; or, it is impossible to
convert all the heat taken from a body of uniform
temperature into work without causing other
changes.
3. Max Planck: It is impossible to devise an engine
operating in a cycle which does work by taking heat
from a single heat reservoir without producing any
other change.

13
 Carnot Engine (an Ideal Engine)
Carnot Cycles
• He is the first scientist shows the useful and valuable of
studying entropy.
• Thermodynamic can be used to show the production of
mechanical properties from thermal energy (of course
under a set of conditions)
• So, Carnot cycle proposed that :
All reversible heat engine operating between two different
temperatures (T1 & T2) have the same efficiency “ε”
W
Efficiency ( ) 
q
15
 Historical Development of the Second Law
The carnet's cycle
Carnot engine
Consider a heat engine operating
in an ideal, reversible cycle
called a Carnot cycle.

16
 Process 1-2:
A reversible isothermal expansion

The gas is allowed to expand

isothermally by receiving heat
( QH) from a hot reservoir.

T  0
E1  0
W1  nRTh ln(V2 / V1 )
q1  nRTh ln(V2 / V1 ) C
C

17
 Process 2-3:
A reversible adiabatic expansion
The cylinder now is insulated and
the gas is allowed to expand
adiabatically and thus doing work
on the surrounding.
The gas temperature decreases from
TH to TC. C

C
T  Tc  Th
q2  0
E2 W 2 nCV Tc  Th  C
W2  nCV Tc  Th 
W2   nCV Th  Tc 
18
 Process 3-4: A reversible isothermal
compression

The insulation is removed

and the gas is compressed
isothermally by rejecting C
heat (QC) to a cold reservoir.

T  0
E3  0
W3   nRTc ln V4 / V3 
q3  nRTc ln V4 / V3 
C
C

19
 Process 4-1: A reversible adiabatic
compression
• The cylinder is insulated
again and the gas is
compressed adiabatically to
state 1, raising its
temperature from Tc to Th C

T  Th  Tc C

q4  0 H

W4  nCV Th  Tc  C

E4 W 4 nCV Th  Tc 

20
E3  0
W3  nRTc ln V4 / V3 
q3  nRTc ln V4 / V3  21
22
 The efficiency of Carnot's engine
The efficiency )‫ )الكفاءة‬of a heat engine is the ratio of the work obtained to the
heat absorbed at the high temperature (the total heat divided by the heat absorbed
at the high temperature:
W W ( q  qc )
Efficiency    h - sign because W is(-) &  should be ( )
qh qh qh
nRTh ln(V2 / V1 )  nRTc ln(V4 / V3 )
Efficiency 
V 
nRTh ln 2 
 V1 
V2 V
  4
V1 V3
nRTh ln(V2 / V1 )  nRTc ln(V2 / V1 )
Efficiency 
V 
nRTh ln 2 
 V1 
qc
Efficiency  1 
qh
V 
nR ln 2 Th  Tc 
Efficiency   V1 
V 
nR ln 2 Th
 V1  23
 The efficiency of Carnot's engine
Efficiency 
Th  TC  TC
 (1  )
Th Th
TC
Efficiency %  (1  )  100
Th
qc TC
Efficiency  1   1
qh Th
qc TC
 
qh Th

• The efficiency depends only on the two temperatures & not

on the choice and amount of working substance.

• No other engine operating between the same two

temperatures can possibly have any higher efficiency.

24
 What’s Special about a Carnot Cycle?
• Heat is transferred to/from only two reservoirs at fixed
temperatures T1 & T2 - not at a variety of temperatures.

• Heat transfer is the most efficient possible because the

temperature of the working substance equals to the temperature
of the reservoirs. No heat is wasted in flowing from hot to cold.

• The cycle uses an adiabatic process to raise and lower the

temperature of the working substance. No heat is wasted in
heating up the working substance.

• Carnot cycles are reversible. Not all cycles are!

• The Carnot theorem states that the Carnot cycle is the most
efficient possible cycle. The Carnot cycle defines an upper limit
to the efficiency of a cycle. 25
Example #1
An ideal heat engine operates in a Carnot cycle between 235˚C &
115˚C. It absorbs 6.30x104 J per cycle at the higher temperature.
(a) What is the efficiency of the engine? (b) How much work per
cycle is this engine capable of performing?

(a ) 
Th  TC  (508  388) K
  0.236
Th 508 K
W

qH
(b) | W |  | q H | 0.236(6.30 x10 4 J )  1.49 x10 4 J

27
Example #2
In every cycle, a heat engine absorbs 1000 J from a hot
reservoir at 600K, does 400 J of work and expels 600 J into
a cold reservoir at 360K. Calculate the efficiency of the
engine.

W 400 J
   0 .4
qH 1000 J
q H  qC (1000  600) J 400 J
    0 .4
qH 1000 J 1000 J
TH  TC (600  360) K 240 K
    0 .4
TH 600 K 600 K
28
Example#3
A Carnot heat engine receives 500 kJ of heat per cycle from a
high-temperature heat reservoir at 652oC and rejects heat to a low-
temperature heat reservoir at 30oC. Determine
(a) The thermal efficiency of this Carnot engine.
(b) The amount of heat rejected to the low-temperature heat
reservoir.
qc Tc
Efficiency  1   1 Th = 652oC
qh Th
(30  273) K qh
Efficiency  1   0.672
(652  273) K HE
WOUT

qc Tc

qc

qh Th Tc = 30oC

qc (30  273) K
  0.328
qh (652  273) K
qc  500kJ (0.328)  164kJ
29
Example#4
During one cycle a Carnot engine extracts 890J from a 550K reservoir &
rejects 470J to a cooler reservoir.
A. How much work does the engine do during each cycle?
B. What is the efficiency of the engine?
C. What temperature is the cool reservoir?
a) For cyclic process,
W  -q  - (q h  q c )
W  - (890 - 470)  - 420J
b) The efficiency of the Carnot cycle
W 420 J
   0.472
qH 890 J
c) The temperature of the cool reservoir
TC
  1
TH
Tc  (1  Efficiency )Th  (1  0.472)550 K
Tc  290.4 K 30
 Carnot's engine and the new state function (entropy)

T  0, E1  0 T  0, E3  0
W1  nRTh ln( V2 / V1 ) W3  nRTc ln V4 / V3 
q1  nRTh ln( V2 / V1 )
q3  nRTc ln V4 / V3 
q1  V2 
 nR ln   q3 V 
Th  V1   nR ln 4 
Tc  V3 
q1 q3  V2   V4  V  V 
  nR ln   nR ln
   since ln 2    ln 4 
Th Tc  V1   V3   V1   V3 
q1 q3
 0
Th Tc
31
 q1 q3
 0
Th Tc
qrev
 0
T

• This means that qrev/T is state function & dqrev/T is exact differentiation.
• qrev is the amount of heat absorbed by the system in reversible process.

qrev
 T 0
dqrev
called entropy (S)
T
dqrev
dS 
T
32
 Entropy “S”
1. It is a stat function
2. It is measure degree of disorder or randomness in the
system.
3. According to 2nd L.T.D. for reversible cyclic process
i.e W<q
.∙. q = w + change in energy (called entropy)
.∙. heat = work + ∆S
.∙. ∆S ≥ 0

∆Suniv = 0 for reversible process

∆Suniv > 0 for irreversible process 33

System in equilibrium with surrounding at constant T (reversible process)

dS univ  dS sys  dS surr

dqsys dqrev
dS sys  
T T
dqsurr
dS surr 
T
qrev  qsys   qsurr
dqrev dq surr dqrev dq rev
dS univ     0
T T T T
so
dSuniv  0  Suniv  0

34
•System and surrounding not in equilibrium (irreversible process)

dSuniv  dS sys  dS surr

dqsys  dqrev
dqsurr  dqirrev
dqrev dqirrev
dSuniv  
T T

qrev  qirrev
dSuniv  0

35
 Entropy Change (∆S) for Different
Thermodynamic Processes
1. Adiabatic reversible changes
Heat flow from the gas to the surroundings is zero
dq = 0
qrev
·.· ∆Ssys + ∆Ssurr = ∆Stotal S sys  0
T
qrev
S surr   0
T
Stotal  Suniv  S sys  S surr  0
qrev q rev
Stotal   0
T T
 Stotal  0
36
2.Isothermal reversible of ideal gas:
 S univ  S sys  S sur  0
 E  0  E  q  w
p nR
 q  -w  (  PV)  PV since, 
T V
qrev PdV dV
 dS sys    nR
T T V
Vf
dV
  dS sys  nR 
Vi
V
Vf Pi
S sys  nR ln OR, S sys  nR ln
Vi Pf
Vf Pi
S surr   nR ln OR, S surr   nR ln
Vi Pf
37
 Example#5
Calculate the increase in entropy of 1 mole of an ideal gas when it expands
isothermally from 100 L to 200 L.

Vf
S sys  nR ln
Vi
J 200L J
S sys  (1mole)(8.314 )ln  5.76
mol.K 100L K

38
Example#6
Half a mole of an ideal gas expands isothermally and reversibly
at 298.15 k from a volume of 10 L to a volume of 20 L.
a) What is the change in the entropy of the gas
b) How much work is done on the gas
c) What is 𝑞𝑠𝑢𝑟𝑟
d) What is the change in the entropy of the surroundings

39
 Vf
a ) S sys  nR ln
Vi
1 J 20L J
S sys  ( mole)(8.314 )ln  2.88
2 mol.K 10L K
Vf
b) Wrev  - nRT ln
Vi
1 J 20L
Wrev  - ( mole)(8.314 )(298.15K)ln  859 J
2 mol.K 10L
c) Since the gas is ideal & isotherma,
then there is no change in its internal energy
E  0 & q  -w  -(-859J)  859J  q system
so, qsurr  859 J
qrev  859 J
d ) S  S surr   2.88
T 298.15 K
40
 3. Reversible, isothermal, & Phase Changes at constant pressure
In case of Liquid and Solid
• Melting • Boiling
 T = Tm = constant  T = Tb = constant
 P = constant, dP=0  P = constant, dP=0
 qP = Hfus  qP = Hvap
q H fus q H vap
S   S  
T Tm T Tb
Hvap latent heat of vaporization
Hfus latent heat of fusion Tb boiling temperature
Tm melting temperature
P, T

H transf .
S transf . 
P, T vapor

Ttransf . P, T
liquid

Fig. (IV-4) A liquid and its vapor in equilibrium

at P and T . Reversible transfer of heat to the
system at equilibrium causes transformation of
liquid to vapor 41
Example 7
Calculate the entropy changes involved in the conversion of 5
mole of ice at 0oC to liquid at 1 atm; the enthalpy of fusion per
mole of ice is 6008 J/mole.

Solution

n = 5 mole, Hf,m = 6008 J/mol, Tf = 0 + 273 = 273 K

H fus
S f 
Tm
6008 J
S f   22
273 k .mole
J J
S f for 5 moles  5molex 22  110
k .mole k
42
 4.Isobaric reversible of ideal gas:
 dq P  dH  C p dT at constant P
Tf Tf Tf
dqrev dT dT
S     Cp  Cp 
Ti
T Ti
T Ti
T
Tf
 S  nC p ln
Ti
C P    T  T 2  T 3
Tf Tf

S   
  T  T  T
2 dT
 
   dT  dT  TdT  T dT 
3

T Ti  T
2

Ti 
Tf  2 2  3 3
S   ln   (T2  T1 )  (T2  T1 )  (T2  T1 )
Ti 2 3
43
Example 8
Evaluate the change in entropy when 3 moles of a gas are heated from
27oC to 100oC at a constant pressure of 1 atm. Where the molar heat
capacity of the gas at constant pressure is 23.7 J/(K. mol).
Solution
n = 3mole, T1 = 27 + 273 = 300K , T2 = 100 + 273 = 373 K Pconst. = 1atm,
Cp,m = 23.7 J/(K.mol)

T2
S  nC p ln
T1
J 373K
S  3moleX23.7 ln  15.49 J / K
K.mole 300 K

44
Example 9
A solid copper block weighing 10.0 kg was heated from 500 to 1000 K at 1 bar
pressure. Calculate the entropy change for the process, assuming that the heat
capacity is independent of temperature.
Cp,m (Cu) = 24.44 J/(K.mole)

10 x1000
n  157.36 mole, T1  500K, T2  1000K
63.55
Pconstant  1 bar, C p, m (Cu)  24.44J/(K.mole)
T2
S  nC p ln
T1
J 1000 K
S  157.36 mole x 24.44 ln
K.mole 500 K
S  2665.76 J / K  2.67 kJ / K
45
Example# 10
Oxygen is heated from 300 to 500 k at constant pressure of 1 bar.
What is the increase in molar entropy
Given: 𝐶𝑝 = 25.503 + 13.612 × 10−3𝑇 − 42.553 × 10−7𝑇 2
𝑇2 𝑇2
𝑑𝑇 𝛼
𝛥𝑆 = 𝐶𝑝 = + 𝛽 + 𝛾 𝑇 𝑑𝑇
𝑇 𝑇
𝑇1 𝑇1
𝑇2 𝛾 2
𝛥𝑆 = 𝛼ln + 𝛽 𝑇2 − 𝑇1 − 𝑇2 − 𝑇12
𝑇1 2
500
𝛥𝑆 = 25.503 ln + 13.612 × 10−3 500 − 300 - 42.553
300
× 10 500 − 3002
−7 2

𝐽
𝛥𝑆 = 15.07
𝑘.𝑚𝑜𝑙

46
5.Isochoric reversible of ideal gas:

 dq V  dE  CV dT at constant V
Tf Tf Tf
dqrev dT dT
S    T CV T  CV T T
Ti
T i i

Tf
 S  nCV ln
Ti

47
Example# 11
The heat capacity of one mole sample of a perfect gas was
found to vary with temperature according to the expression
Cp(J/(deg.mole) = 20.17+0.3665 T. Calculate ∆S in
(KJ/(deg.mole)) when the temperature is raised from 25˚C to
200˚C if the process is carried out:
a) at constant pressure. b) at constant volume.

Constant pressure
T2 nC
p
∆S = dT
T1 T
473
= 20.17T −1 + 0.3665 dT
298
473
= 20.17 ln T + 0.3665T 298
= 73.456 J/K
= 0.073456 KJ/K
48
Constant volume
Cp − Cv = R
Cv = Cp − R
Cv = 20.17 + 0.3665T − 8.314
= 11.856 + 0.3665T
T2
nCv
∆S = dT
T1 T
473
= 11.856T −1 + 0.3665 dT
298
473
= 11.856 ln T + 0.3665T 298
= 69.615 J/K
= 0.069615 KJ/K

49
6. Isothermal irreversible changes
• ∆Ssys + ∆Ssurr > 0 i.e in irreversible change the total entropy is

bigger than zero .∙. ∆Stotal > 0 i.e +ve

 S sys   S sur
 E  0  E  q  w
 q  -w  PV
qrev PdV dV
 dS sys    nR
T T V
Vf Pi
S sys  nR ln OR, S sys  nR ln
Vi Pf

50
Isothermal, irreversible, free expansion of ideal gas:
Vf Pi
S sys  nR ln OR, S sys  nR ln
Vi Pf
• ∆Ssurr differs in the two process:-
Free expansion
P  0 w   PdV  0
Isothermal
 E  0 q0
 S surr  0
Vf Pi
S total  nR ln OR, S total  nR ln
Vi Pf
51
Example# 12
Calculate the change in entropy for a process in which 2.0 mole
of an ideal gas undergoes a free expansion to three times its initial
volume.
Vf
S  nR ln
Vi
J
S  ( 2.0mole)(8.314 )(ln 3)
mole.K
J
S  18.26
K

52
Isothermal, irreversible, expansion of ideal gas against
constant external pressure (isobaric):
Vf Pi
S sys  nR ln OR, S sys  nR ln
Vi Pf
Isothermal E  0
 q surr   qsys  Wsys   P  dV   P (V2  V1 )
P (V2  V1 )
 S surr  
T
Vf P (V2  V1 )
S total  nR ln 
Vi T
Pi P (V2  V1 )
S total  nR ln 
Pf T
53
Example# 13
An ideal gas expands isothermally at 298.15 k from a volume and
pressure of 0.01m3 and 1.0 atm to 0.1m3 and 0.1 atm calculate the
change in the entropy of the system, surroundings, and universe.
a) If the expansion is reversible.
b) If the expansion is irreversible against 0.1 atm external
pressure.
c) If the expansion is irreversible and free expansion.

54
 P1V1 1atmX 10 L
a) n    0.409moles
RT1 L.atm
0.08205 X 298 K
K .mol
Vf
S sys  nR ln
Vi
J 0.1 J
S sys  (0.409mole)(8.314 )ln  7.83
mol.K 0.01 K
J
S surr   S sys  7.83
K
J J
S uni  S sys  S surr  7.83  7.83  0
K K

55
 Vf
b) S sys  nR ln
Vi
J 0.1 J
S sys  (0.409mole)(8.314 )ln  7.83
mol.K 0.01 K
P (V2  V1 )
S surr  
T
 5 Pa 
 0.100atmX 1.013 X 10 0.100  0.010 m
3

S surr   
atm  J
 3.06
298 K K
J J J
S total  7.83  3.06  4.77
K K K
Vf
c) S sys  nR ln
Vi
J 0.1 J
S sys  (0.409mole)(8.314 )ln  7.83
mol.K 0.01 K
S surr  0
J J
S total  7.83  0  7.83
K K
56
 2nd Law of Thermodynamics
• All natural processes are spontaneous & irreversible.

• The Second Law of Thermodynamics states that the

entropy of the entire universe, as a closed isolated
system, will always increase over time.

• The second law also states that the changes in the

entropy in the universe can never be negative.

57
• For any substance, the solid state is more ordered than
the liquid state and the liquid state is more ordered
than gas state S solid < S liquid << S gas

• Entropy increases as the molecular weight of the

molecule increases. C4H10 Higher entropy
CH4

• Entropy increases as Temperature increases

58
 Entropy of mixing ideal gases at constant
temperature and pressure
V1  V2 V1  V2
S1  n1 R ln S 2  n2 R ln
V1 V2
V1  V2 V V
S mix  S1  S 2  n1 R ln  n2 R ln 1 2
V1 V2
 V1 V2 
S mix   R n1 ln  n2 ln 
 V1  V2 V1  V2 
n1 RT
V1 P n1
   X1
V1  V2 n1 RT
 2
n RT n1  n2
P P
n2 RT
V2 P n2
   X2
V1  V2 n1 RT  n2 RT n1  n2
P P
Where X 1 and X 2 are the mole frication.
The entropy of mixing becomes,  S mix   Rn1 ln X 1  n2 ln X 2 
59
To obtain the standard form write the total number of moles
(n1 + n2 + n3 +……) as n. Multiply and divide the above
equation by n.
S mix   Rn1 ln X 1  n2 ln X 2 

S mix   Rn1 ln X 1  n2 ln X 2 
n
n
 n1 n2 
S mix   nR ln X 1  ln X 2 
n n 
S mix   nR X 1 ln X 1  X 2 ln X 2 
S mix   nR X 1 ln X 1  X 2 ln X 2  X 3 ln X 3 
ni
S mix   nR  X i ln X i since X i 
i nt

60
Example# 14
What is the entropy of mixing of 1mole of oxygen with 1 mole of
nitrogen at 25 °C, assuming that they are ideal gases.
𝛥𝑆𝑚𝑖𝑥 = −𝑛𝑡𝑜𝑡𝑎𝑙 𝑅 𝑋𝑖 ln𝑋𝑖
𝑛𝑂 2 𝑛 𝑁2
𝛥𝑆𝑚𝑖𝑥 = - 𝑛𝑂2 + 𝑛𝑁2 𝑅 𝑛 𝑂2 +𝑛𝑁2
ln𝑋𝑂2 + 𝑛 ln𝑋𝑁2
𝑁2 +𝑛𝑂2

𝑛𝑂2 + 𝑛𝑁2 = 1+ 1 = 2 mole

𝑛𝑂 2 1 𝑛𝑁2 1
𝑋𝑂2 = 𝑛 =2 𝑋𝑁2 = 𝑛 =2
𝑂2 +𝑛𝑁2 𝑁2 +𝑛𝑂2
1 1 1 1
𝛥𝑆𝑚𝑖𝑥 = −2mole × 8.314J/(mole. K) × 2
ln + ln
2 2 2
𝐽
𝛥𝑆𝑚𝑖𝑥 = 11.526 𝐾

61
 Example # 15
Calculate the molar entropy change for mixing 79% N2, 1% Ar and
20% O2?

S mix   nR  X i ln X i
i

S mix
molar entropy change (S m ,mix )    R  X i ln X i
n i

S m ,mix  8.314
J
0.79 x ln 0.79  0.01x ln 0.01  0.20 x ln 0.20
mol.K
J
S m ,mix  4.61
mol.K

62
 Combined First and Second Laws
Reversible
dE  dq  pdV
Process
dE  dq rev  pdV
but we know from the second law that

dqrev
dS   dqrev  TdS
T
dE  TdS  pdV

Recall that H  E  PV

By differentiation dH  dE  pdV  VdP

Then dH  TdS  VdP

63
 Maxwell Relations
Why Use Maxwell Relations?

 Certain variables in
thermodynamics are hard to
measure experimentally such as entropy
 Maxwell relations provide a way to exchange variables

64
 Deriving Maxwell Relations
To derive Maxwell relation, we can refer back to the original equations of
state and define each element included in these equations.
Using the combined equation
dE  TdS  PdV
We can define both T and P as below
E  f ( S , V )
 E   E 
dE    dS    dV
 S V  V  S
 E   E 
T   & P 
 S V  V  S

65
 Deriving Maxwell Relations
Using the combined equation

dH  TdS  VdP
We can define both T and V as below
H  f ( S , P )
 H   H 
dH    dS    dP
 S  P  P  S
 H   H 
T   & V  
 S  P  P  S

66
Deriving Maxwell Relations
Z  f (x, y)  M   N 
Maxwell Relations     
dZ  Mdx  Ndy  y  x  x  y
Maxwell Relations can be derived from basic equations of state as
given in the Table below
Basic equation Maxwell relation
 dT   dP 
dE  TdS  PdV     
 dV S  dS V

 dT    dV 
dH  TdS VdP    
 dP  S  dS P

67
 The relationships between S,E and H
a) The relationships between S and E
For a reversible process one could write
dE  TdS  PdV TdS  dE  PdV
dE P
 dS   dV
T T
E  f (T ,V )
 E   E 
dE    dV    dT
 V T  T V
1  E   E   P
dS    dV    dT   dV
T  V T  T V  T
68
 1  E   E   P
dS    dV    dT   dV
T  V T  T V  T
 dE 
CV   
 dT V
1  E   P
dS    dV  CV dT   dV
T  V T  T
1  E  dT P
dS    dV  CV  dV
T  V T T T
dT 1  E    E 
dS  CV     P  dV For an ideal gas    0
T T  V T   V T

69
 dT P P nR
dS  CV  dV from the ideal gas law 
T T T V
dT dV
dS  CV  nR
T V
dT dV
 dS  CV
T
 nR V
T2 V2
Sideal  CV ln  nR ln
T1 V1
Where Sideal  S(T2 ,V2 ) - S(T1 ,V1 )
Therefor, the entropy change Sideal in a system of an ideal
gas being heated or cooled from T1 to T2 & expanding or
compressed from V1 to V2 is given by
T2 V2
Sideal  CV ln  nR ln
T1 V1 70
b) The relationships betweenS and H
In a similar fashion since for a reversible process
dH  TdS  VdP
 TdS  dH  VdP divide by T

dS 
dH V
 dP 1 
T T
H  f (T , P)
 H   H 
dH    dP    dT
 P T  T  P
1  H   H   V
dS    dP    dT   dP
T  P T  T  P  T
 H 
Since    CP
 T  P
71
 1  H   H   V
dS    dP    dT   dP
T  P T  T  P  T
 H 
Since    CP
 T  P
1  H   V
dS    dP  C P dT   dP
T  P T  T
dT 1  H  
dS  C P     V  dP
T T  P T 
 H 
For an ideal gas   0
 P T
dT V
dS  C P  dP
T T
72
 V nR
From the ideal gas law 
T P
dT dP
dS  C P  nR
T P
dT dP
 dS  CP  T  nR  P
T2 P2
S ideal  C P ln  nR ln
T1 P1
Where Sideal  S(T2 , P2 ) - S(T1 , P1 )
Therefor, the entropy change Sideal in a system of an ideal
gas being heated or cooled from T1 to T2 & expanding or
copressed from P1 to P2 is given by
T2 P2
S ideal  C P ln  nR ln
T1 P1
73
 Third Law of Thermodynamics
• Consider the constant-pressure transformation of solid from the absolute
zero of temperature to some temperature T below its melting point:
Solid (0 K, P)  Solid (T, P)
• The entropy change given by T
dT
S  S T  S 0   C P
0k
T
T
dT
ST  S 0   C P
0k
T
• In 1913, Max plank says that as absolute zero is approached, the entropy
change ΔS for a chemical or physical transformation approaches zero. This is
known as third law of thermodynamics
• The third law state that The entropy of a pure, perfect crystalline element
or substance is zero at the absolute zero of temperature (0K).
T
dT
ST   C P
0k
T
74
 Entropy changes for chemical reactions
• For any chemical reaction the change of standard
entropy ∆S° can be evaluated by using the relation:

 
S 0   nS 0 products
  
nS 0
reac tan ts

75
Example#13

76
Entropy as a Function of Temperature
dE  TdS  PdV
divided by dT at constsnt V, dV  0
 E   S   V 
  T   P 
 T V  T V  T V
 E   S 
  T    CV
 T V  T V
 S  dT
CV  T   dS  CV
 T V T
dT
 dS  CV  T
T2 T2
S 2  S1  CV ln S 2  S1  CV ln
T1 T1
 dH  TdS  VdP
divide by dT at constant P, dP  0
 dH   dS   dP 
   T  V  
 dT  P  dT  P  dT  P
 dH   dS 
   T   CP
 dT P  dT  P
dT
At constant pressure  dS  C P
T
dT
By integration  dS  C P
T
T2
S (T2 )  S (T1 )  C P ln
T1
T2 T2
S (T2 )  S (T1 )  C P ln S 2  S1  C P ln
T1 T1
78
Example #16

79
Example #17
Calculate 𝛥𝑆 at 348 k for the reaction:
1
2
𝑁2 (𝑔) + 𝑂2(𝑔) → 𝑁𝑂2 (𝑔)
Given: at 298 k
° 𝐽 ° 𝐽
𝑆 (𝑁2 ) = 191.61 𝐾 𝑚𝑜𝑙𝑒
𝐶𝑝 (𝑁2 ) = 29.13𝐾 𝑚𝑜𝑙𝑒
𝐽 𝐽
𝑆 ° (𝑂2) = 161.06 𝐶𝑝° (𝑂2) = 29.36
𝐾 𝑚𝑜𝑙𝑒 𝐾 𝑚𝑜𝑙𝑒
° 𝐽 ° 𝐽
𝑆 (𝑁𝑂2)= 240.06 𝐾 𝑚𝑜𝑙𝑒 𝐶𝑝 (𝑁𝑂2)= 37.20𝐾 𝑚𝑜𝑙𝑒
348𝑘
°
°
△ 𝑐𝑝
𝛥𝑆348𝑘 = 𝛥𝑆298𝑘 + 𝑑𝑇
𝑇
298𝑘
Since △ 𝐶𝑝° independent of temperate
348𝑘
° 𝑑𝑇
𝛥𝑆348𝑘 = 𝛥𝑆298𝑘 + 𝛥𝐶𝑝°
298𝑘 𝑇
80
 °
348𝑘
𝛥𝑆348 = 𝛥𝑆298 + 𝛥𝐶𝑝° ln
298𝑘
°
1 °
𝛥𝑆298𝑘= 𝑆 (𝑁𝑂2 ) − 𝑆 (𝑁2 ) − 𝑆 ° (𝑂2
°
2
°
1 𝐽
𝛥𝑆298𝑘 = 240.06 − 191.61 − 161.06 = −16.805
2 𝐾 𝑚𝑜𝑙𝑒
1
𝛥𝐶𝑝° = 𝐶𝑝° 𝑁𝑂2 − 𝐶𝑝° 𝑁2 − 𝐶𝑝° (𝑂2)
2
1 𝐽
𝐶𝑝° = 37.2 - 29.13 – 29.36 = -6.725 𝐾 𝑚𝑜𝑙𝑒
2
348𝑘
𝛥𝑆348 = −16.805 - 6.725 ln
298𝑘
𝛥𝑆348 = -17.85 𝐾 𝑚𝑜𝑙𝑒
𝐽

81
 Importance

T
dT
ST   C P
0 T
dT H fus
Tm T
dT
ST   C P ( s )    CP (l )
0
T Tm Tm
T

dT H fus b dT H vap
Tm T T
dT
ST   C P ( s )    CP (l )    CP ( g )
0
T Tm Tm
T Tb Tb
T
82
Enthalpy of Phase Changes

consider changes in phase; that is, the

system changes from phase to phase for
example, a solid to a liquid.

This diagram shows the names of the phase

transitions between solids, liquids, and gases.
The arrow to the right of the diagram
demonstrates that these three phases have
different enthalpies: gas has the highest
enthalpy, liquid has an intermediate enthalpy,
and solid has the lowest enthalpy.

83
The heating of ice at -25oC to +125oC
at constant pressure (1atm) will
exhibit the following characteristics:
• Initially, the heat input is used to
increase the temperature of the ice,
but the ice does not change its
phase (remains a solid)
• As the temperature approaches
some critical point (i.e. the melting
temperature of ice), the kinetic
energy of the molecules of water is
sufficient to allow the molecules to
begin sliding past one another.
• As the ice begins to melt, additional input of heat energy does not raise the
temperature of the water, rather it is used to overcome the intermolecular
attraction during the phase change from solid to liquid
• Once the water is completely in a liquid phase, the amount of heat input
raises the temperature of the liquid water
Ehteram A. Noor- King AbdulAziz Univ ersity
84
• As the temperature approaches
another critical point (the
vaporization, or boiling, temperature
of water) the kinetic energy of the
molecules is sufficient to allow the
separation of molecules into the gas
phase
• As the liquid begins to boil,
additional input of heat energy does
not raise the temperature of the water,
rather it used to overcome the
intermolecular attractions during the
phase change from liquid to gas
• Once the water molecules is completely exist in the gas phase,
additional heat input raises the temperature of the water vapour.

85
Example #18

86
Example #19
Example
Calculate the change in molar entropy of aluminum that is heated from
600 to 700 °C. The melting point of aluminum is 660 °C, the heat fusion is
𝐽
393 and the heat capacities of the solid and liquid may be taken 31.8
𝑔
𝐽
and 34.4 respectively
𝐾 𝑚𝑜𝑙𝑒
𝐽 27𝑔 𝐽
𝛥𝐻𝑓𝑢𝑠 = 393 × = 1061 = 𝛥𝐻𝑚𝑒𝑙𝑡
𝑔 𝑚𝑜𝑙 𝑚𝑜𝑙
𝑇1 = 600 + 273 = 873𝑘
𝑇2 = 700 + 273 = 973𝑘 𝑇𝑓𝑢𝑠 = 660 + 273 = 933𝑘 = 𝑇𝑚𝑒𝑙𝑡
𝐽 𝐽
𝐶𝑝 𝑠 = 31.8 𝐶𝑝 (l) = 34.4
𝑘 𝑘
𝑇𝑓𝑢 𝑇2
𝑐𝑝 (𝑠 △ 𝐻𝑓𝑢𝑠 𝑐𝑝 (𝑙
𝛥𝑆 = 𝑑𝑇 + + 𝑑𝑇
𝑇 𝑇𝑓𝑢𝑠 𝑇
𝑇1 𝑇𝑓
𝑇𝑓𝑢𝑠 △ 𝐻𝑓𝑢𝑠 𝑇2
𝛥𝑆 = 𝐶𝑝 (𝑠)ln + + 𝐶𝑝 (𝑙)ln
𝑇1 𝑇𝑓𝑢𝑠 𝑇𝑓𝑢𝑠
𝐽 933 10611 𝐽 𝐽 973
𝛥𝑆 = 31.8 ln + + 34.4 ln
𝑘 873 933𝑘 𝑚𝑜𝑙 𝑘 933
𝐽
𝛥𝑆 = 14.92
𝐾 𝑚𝑜𝑙𝑒
87
 Debye approximation
Ordinarily, measurements of heat capacity of some solids are made down to
a low temperature, which frequently lies in the range from 10 K to 15 K. At
such low temperatures, the heat capacity of solids follows the Debye " T-
cubed" law accurately; that is
C P  CV CP  T
3

CP  a T 3 a  cons tan t
C P  CV  a T 3
T
dT
ST   C P
0
T

 
T T
dT
ST   aT 3  a  T 2 dT
0
T 0

aT 3
ST 
3
1
ST  CP
3
88
 General Remarks

 At High Temperature Limits Debye Specific Heat is

constant and equal to 3R.
Cv = 3R/mole

 At absolute zero Kelvin a specific heat tending to be zero

according to the third low of thermodynamic.

 At low Temperature Limits Debye Specific Heat is

Cv = aT3

89
Example #19

Calculate the change in entropy at very low temperatures (-260°C),

given that Cv = 5R.

CP - Cv  R
CP  Cv  R
C P  5R  R  6R
1
ST  C P
3
1
S  290 K  x6 R  2 R
3

91