COLLEGE OF ENGINEERING

CENTRAL PHILIPPINE UNIVERSITY

ILOILO CITY, PHILIPPINES
Tel. Nos. (033) 3291971 (to 79) Local 1085
Fax No. (033) 3203004
Email: [email protected]

MODULE 3
SECOND LAW OF THERMODYNAMICS
 The Second law of Thermodynamics states that ∆S of the system and the surroundings
considered together, resulting from any process is positive and approaches zero for any process
that approaches reversibility.

If ∆ST = 0 (the process is reversible)

If ∆ST > 0 (the process is irreversible)

If ∆ST < 0 (the process is not possible)

The Second law of Thermodynamics is based on Planck’s and Rudolf Clausius statements.

➢ Planck’s Statement
It is impossible to construct an engine which will work in a complete cycle and
produce no other effect except work.
➢ Rudolf Clausius Statement
It is impossible for heat to transfer from a cold body to a hot body.

Properties of Entropy

1. It is an extensive factor of heat energy for a reversible process.

𝑄 ∆𝐻 𝑓𝑢𝑠𝑖𝑜𝑛 ∆𝐻𝑣𝑎𝑝
∆S = ;
𝑇
∆S fusion =
𝑇
; ∆S vaporization =
𝑇

2. It is a point function.
A point function is independent of the path taken of the reactants to form
products. It depends only on the initial and final states of the system.
𝑇 𝑉
For a reversible process: ∆𝑆 = 𝐶𝑣𝑙𝑛 𝑇2 + 𝑅𝑙𝑛 𝑉2
1 1

𝑇2 𝑃2
∆𝑆 = 𝐶𝑝𝑙𝑛 − 𝑅𝑙𝑛
𝑇1 𝑃1
𝑉2 𝑃2
∆𝑆 = 𝐶𝑝𝑙𝑛 + 𝐶𝑣𝑙𝑛
𝑉1 𝑃1
3. It may be used as thermodynamic coordinate.
 4. Its value changes whenever heat flows. If Q = (―), then ∆S = (―), thus if Q = (+), ∆S = (+)
5. ∆Ssystem of several bodies is obtained by adding the entropies of the constituent bodies
6. ∆S for the system and the surroundings considered together
Let Q1 = heat absorbed
Q2 = heat rejected
𝑄2 𝑄1 𝑄1 𝑄2
− = ; + = 0; ∆𝑆𝑇 = ∆𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + ∆𝑆𝑠𝑢𝑟𝑟 ≥ 0
𝑇2 𝑇1 𝑇1 𝑇2

7. For a mixing process, assuming no heat loss to the surroundings

Heat loss hot body = Heat gained cold body

-Q2 = Q1
-mhot Cphot ∆Thot = mcold Cpcold ∆Tcold

If Tf = temperature after mixing

T2 = initial temperature of hot body
T1 = initial temperature of cold body

Then ∆Thot = (T2 – Tf), and ∆Tcold = (Tf – T1)

• Hot body loses entropy (Tf < T2)

𝑇𝑓 𝑑𝑄 𝑇𝑓 𝑑𝑇 𝑇𝑓
∆Shot body = ∫𝑇2 = ∫𝑇2 𝑚𝐶𝑝 = 𝑚𝐶𝑝𝑙𝑛
𝑇 𝑇 𝑇2

• Cold body gains entropy (Tf >T1)

𝑇𝑓 𝑑𝑄 𝑇𝑓 𝑑𝑇 𝑇𝑓
∆Scold body = ∫𝑇1 = ∫𝑇1 𝑚𝐶𝑝 = 𝑚𝐶𝑝𝑙𝑛
𝑇 𝑇 𝑇1

Sample Problem 1.
 Calculate the change in entropy of 1 kg of solid ice at 1 atm and 0oC into vapor at 150 oC
and 0.25 atm.
Data: ∆H fusion @ 0oC = 143.4 Btu/lbm
∆H vaporization @ 100oC = 970 Btu/lbm
Cp liquid water = 1Btu/lbm-oF
Cp gaseous water= 4.7 Btu/lbm-oF
Given:
1 kg. of 1 kg. of
solid ice
fusion liq. H O P = k 1 atm vap 1 atm T=k 0.25 atm P=k 0.25 atm
2

1 atm → 1 atm → 100°C → 100°C → 100°C → 150°C

0°C ∆𝑆1 0°C ∆𝑆2 ∆𝑆3 ∆𝑆4 ∆𝑆5

𝐵𝑡𝑢 𝐵𝑡𝑢
𝐶𝑝𝑙𝑖𝑞 𝐻2𝑂 = 1 ∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛 @ 0℃ = 143.4
𝑙𝑏𝑚℉ 𝑙𝑏𝑚
𝐵𝑡𝑢 𝐵𝑡𝑢
𝐶𝑝𝑔𝑎𝑠 𝐻2 𝑂 = 4.7 ∆𝐻𝑣𝑎𝑝 @ 100℃ = 970
𝑙𝑏𝑚℉ 𝑙𝑏𝑚

Required: ∆ST
Solution:
Step 1:

1 kg. of solid ice fusion 1 kg. of liq. H2O

1 atm → 1 atm
0°C ∆𝑆1 0°C

𝐵𝑡𝑢
∆𝐻𝑓𝑢𝑠𝑖𝑜𝑛 143.4 1𝐾 2.2 𝑙𝑏𝑚 𝐵𝑡𝑢
𝑙𝑏𝑚
∆S1 = = (1.8℉) (1𝑘𝑔 ∗ ) = 0.642
𝑇 273𝐾 1 𝑘𝑔 ℉

Step 2

1 kg. of liq. H2O P=k 1 atm

1 atm → 100°C
0°C ∆𝑆2
 𝐵𝑡𝑢 373 2.2 𝑙𝑏𝑚 𝐵𝑡𝑢
∆S2 =1 ln (1𝑘𝑔 x ) = 0.68663
𝑙𝑏𝑚℉ 273 1𝑘𝑔 ℉

Step 3:

1 atm vap 1 atm

100°C → 100°C
∆𝑆3

𝐵𝑡𝑢
∆𝐻𝑣 970 1𝐾 2.2𝑙𝑏𝑚 𝐵𝑡𝑢
𝑙𝑏𝑚
∆S3 = = (1.8℉) (1𝑘𝑔 ∗ ) = 3.1784
𝑇 373𝐾 1𝑘𝑔 ℉

Step 4:

1 atm T=k 0.25 atm

100°C → 100°C
∆𝑆4

𝐵𝑡𝑢 1 𝑙𝑏𝑚𝑜𝑙𝑒 0.25 2.2 𝑙𝑏𝑚 𝐵𝑡𝑢

∆S4 = −1.986 ( ) 𝑙𝑛 ( ) = 0.3365
𝑙𝑏 𝑚𝑜𝑙𝑒℉ 18 𝑙𝑏𝑚 1 1𝑘𝑔 ℉

Step 5:

0.25 atm P=k 0.25 atm

100°C → 150°C
∆𝑆5

𝐵𝑡𝑢 150+273 2.2 𝑙𝑏𝑚

∆S5 = 4.1 (ln )( ) = 1.3
𝑙𝑏𝑚 ℉ 373 1 𝑘𝑔

∆𝑆𝑇 = ∆𝑆1 + ∆𝑆2 + ∆𝑆3 + ∆𝑆4 + ∆𝑆5

∆𝑆𝑇 = 0.642 + 0.68663 + 3.1784 + 0.3365 + 1.3
𝐵𝑡𝑢
∆ST = 6.14
℉
Sample Problem 2.
A lump of copper having a mass of 10 lbm at a temperature of 1000℉ is dropped into a
well – insulated bucket containing 100 lbm of water at a temperature of 70 oF. Calculate ∆Scopper,
∆S water and ∆ST.
𝐵𝑡𝑢 𝐵𝑡𝑢
Data: CpCu = 0.095𝑙𝑏𝑚 ℉ ; Cpwater = 1𝑙𝑏𝑚 ℉

Solution:

-Q2 = Q1
−𝑚𝐶𝑢 𝐶𝑝𝐶𝑢 ∆𝑇ℎ𝑜𝑡 = 𝑚𝑤𝑎𝑡𝑒𝑟 𝐶𝑝𝑤𝑎𝑡𝑒𝑟 ∆𝑇𝑐𝑜𝑙𝑑 → (1)
If Tf = temperature after mixing
T2 = initial temperature of copper = 1000℉
T1 = initial temperature of cold body = 70oF

Then ∆Tcopper = Tf - 1000, and ∆Twater = Tf – 70

Substitute in (1):
𝐵𝑡𝑢 𝐵𝑡𝑢
-10 lbm (0.095 )( Tf – 1000) = 100 lbm (1 )( Tf – 70)
𝑙𝑏𝑚 ℉ 𝑙𝑏𝑚 ℉

Tf = 78.75℉

Copper loses entropy (Tf < T2): Tf = 78.75 + 460 = 538

𝑇𝑓 𝑑𝑄 𝑇𝑓 𝑑𝑇 𝑇𝑓
∆Scopper = ∫𝑇2 = ∫𝑇2 𝑚𝐶𝑝 = 𝑚𝐶𝑝𝑙𝑛
𝑇 𝑇 𝑇2
78.75+460
∆Scopper = 10(0.95) ln[ ]
1000+460
𝐵𝑡𝑢
∆Scopper = - 0.95
𝑅
Water gains entropy (Tf >T1)
𝑇𝑓 𝑑𝑄 𝑇𝑓 𝑑𝑇 𝑇𝑓
∆Scold body = ∫𝑇1 = ∫𝑇1 𝑚𝐶𝑝 = 𝑚𝐶𝑝𝑙𝑛
𝑇 𝑇 𝑇1
538.75
∆SH2O = 100(1) ln [ ]
530
 𝐵𝑡𝑢
∆SH2O = 1.64
𝑅
𝐵𝑡𝑢
∆ST = -0.95 + 1.64 = 0.69
𝑅

Sample Problems:
1
(318) A quantity of ideal gas in an isolated system is expanded isothermally and

reversibly at 400K from a volume V1 to V2. During the expansion the gas absorbs 200cal of heat
from the reservoir in contact with it. Find (a) the entropy changes of the gas, (b) the entropy
changes of the reservoir, and (c) the entropy changes of the whole system.

Solution:
𝑞𝑟 200 𝑐𝑎𝑙
a. ∆Ss= = = 0.5 𝑒𝑢
𝑇 400 𝐾
𝑞𝑟 200 𝑐𝑎𝑙
b. ∆Sr= - =− = -0.5 eu
𝑇 400 𝐾

c. ∆ST= 0
12 7
(319) Assuming Cp for N2(g) to be 2 𝑅 cal mole-1 degree-1, find the change in entropy

undergone by 10 g of the gas on being cooled from 100 to 0oC at (a) constant pressure, and (b)
constant volume.

Solution:
a. @ P=k
𝑇 7 273
∆S = nCp ln 𝑇2 = 0.357 x 2 𝑥 1.987 𝑥 ln 373
1

∆S = -0.776 eu
b. @V=k
𝑇 5 273
∆S = nCv ln 𝑇2 = 0.357 x 2 𝑥 1.987 𝑥 ln 373
1

∆S = -0.556 eu
 16
(319) Using the equation for Cp as a function of T for CH4 (g), calculate the entropy

change which results from heating 2 moles of the gas from 300 to 600 K at constant
pressure.
Cp = 3.422 + 17.845x10-3 T – 41.65x10-7 T2

Solution:
T1= 300K; T2= 600K @ P=k

𝑇 𝑛𝐶𝑝𝑑𝑇
∆S = ∫𝑇 2
1 𝑇
600 3.422 + 17.845x10−3 T – 41.65x10−7 𝑇 2
∆S = 2 ∫300 𝑑𝑇
𝑇
600
= 2 [3.422 ln + 17.845x10−3 (600 − 300) − 20.825𝑥10−7 (6002 − 3002 )]
300

= 2 [2.365 + 5353.5 x10−3 − 561x10−3 ]

∆S = 2 (7.1575) = 14.32 eu

25
(319) Three moles of N2(g), originally at 1 atm pressure, are mixed isothermally with 5

moles of H2(g) , also at 1 atm pressure, to yield a mixture whose total pressure is 1 atm.
Assuming the gases to ideal, calculate (a) the total entropy of mixing, and (b) the entropy of
mixing per mole of gas.

Solution:
Pt= 1 atm
For N2(g), n1= 3 moles
3 3
P10 = 1 atm; P1= 8 𝑥 1 = atm
8

For H2(g), n2= 5 moles

5 5
P20 = 1 atm; P2= 𝑥 1 = atm
8 8
 𝑃1 𝑃1𝑜 1
∆S1= - n1Rln 𝑜 = +n1Rln = 3 (1.987) ln [ 3 ]
𝑃1 𝑃1
8

∆S1= 5.85 eu
𝑃2 𝑃2𝑜 1
∆S2= - n2Rln = +n2Rln = 5 (1.987) ln [ 5 ]
𝑃2𝑜 𝑃2
8

∆S2= 4.65 eu

∆ST= ∆S1+∆S2 = 10.5 eu

Assignments
14
(319) Assuming that for CH4 (g), Cp - Cv= R, find the entropy change resulting from

heating 2 moles of the gas from 300 to 600 K at constant volume.

For CH4 (g): Cp = 3.422 + 17.845x10-3 T – 41.65x10-7 T2

Solution:
Cv = Cp- R= 3.422 – 1.987 + 17.845x10-3 T – 41.65x10-7 T2
Cv = 1.435 + 17.845 x10-3 T - 41.65x10-7 T2
n= 2 moles; T1= 300 K; T2= 600k @ V=k

𝑇 𝑛𝐶𝑣𝑑𝑇 600 1.435 + 17.845x10−3 T – 41.65x10−7 𝑇 2

∆S = ∫𝑇 2 = = 2 ∫300 𝑑𝑇
1 𝑇 𝑇
600
= 2 [1.435 ln 300 + 17.845x10−3 (300) − 20.825𝑥10−7 (27x104 )]

= 2 [0.995 + 5.3535−0.561]
∆S = 2 (5.7875) = 11.58 eu

3
(318) Suppose the gas in problem 1 expands freely from V1 to V2 at 400K. what will be

the entropy changes for (a) the gas, (b) the reservoir, and (c) the entire system?
Problem 1: A quantity of ideal gas in an isolated system is expanded isothermally and
reversibly at 400K from a volume V1 to V2. During the expansion the gas absorbs 200 cal
of heat from the reservoir in contact with it.

Solution:
𝑉
∆E = q – W = q - ∫𝑉 2 𝑃𝑑𝑉
1

For free expansion: P=0; W=0

q= ∆E + W = 0; T= const.; ∆E= 0
200
a. ∆Ss= = 0.5 eu
400

b. ∆Sr= 0
c. ∆ST= 0.5 eu

26
(319) Repeat problem 25 0n the basis that the total pressure of the mixture is 10 atm.

Problem 25: Three moles of N2(g), originally at 1 atm pressure, are mixed isothermally
with 5 moles of H2(g) , also at 1 atm pressure, to yield a mixture whose total pressure is 1
atm. Assuming the gases to ideal, calculate (a) the total entropy of mixing, and (b) the
entropy of mixing per mole of gas.

Solution:
Pt= 10 atm
For N2(g), n1= 3 moles
3 30
P10 = 1 atm; P1= x10= atm
8 8

For H2(g), n2= 5 moles

5 50
P20 = 1 atm; P2= 8 x10= atm
8

𝑃1 𝑃1𝑜 1
∆S1= - n1Rln 𝑜 = +n1Rln = 3 (1.987) ln [ 30 ]
𝑃1 𝑃1
8

∆S1= -7.58 eu
 𝑃2 𝑃2𝑜 1
∆S2= - n2Rln 𝑜 = +n2Rln = 5 (1.987) ln [ 50 ]
𝑃2 𝑃2
8

∆S2= -18.1 eu
∆ST= ∆S1+∆S2 = -26 eu

14
(319) Assuming that nitrogen is an ideal gas, calculate ∆S for the compression of 200 g

of the gas from a pressure of 1 to 5 atm at 25oC.

Solution: wt. of N2= 200g

𝑛𝑁2 = 200⁄28 = 7.15 𝑚𝑜𝑙𝑒𝑠

P1= 1 atm; P2= 5 atm
T= 25oC = const.

𝑃2
∆S = -nRln = -7.15 x 1.978 x ln (5)
𝑃1

∆S = 22.8 eu

28
(320) One mole of an ideal gas, originally at a volume 8.21 liters at 1000K, is allowed to
3
expand adiabatically until the final volume is 16.42 liters. For gas Cv= 2 𝑅 cal mole-1 degree-1.

Calculate values of ∆S for the process when

a. The expansion takes place reversibly
b. The expansion takes place against a constant pressure of 3 atm
c. The change in volume involves a free expansion
Solution:
n= 1 mole
V1= 8.21 li; V2 = 16.42 li
T1= 1000K
3
Cv = 2 𝑅
a. For adiabatic reversible expansion:
𝑉2 𝑇 𝐶𝑣/𝑅 1000 3/2 16.42
= ( 1) =( ) = =2
𝑉1 𝑇 2 𝑇2 8.21

1000
= 20.667 = 1.583
𝑇2
1000
𝑇2 = = 630K
1.583

𝑇 𝑉
∆S = nCvln 𝑇2 + nRln 𝑉2
1 1

630 16.42
∆S = (1x 2.98 x ln 1000) + (1.987x ln )
8.21

∆S = 0

b. For adiabatic expansion: q=0; ∆E= -W

𝑃 = 3 𝑎𝑡𝑚
𝑇 2
∫𝑇1 𝑛𝐶𝑣𝑑𝑇 = −𝑃(𝑉2 − 𝑉1 )
3 𝑙𝑖−𝑎𝑡𝑚
1 mole x (0.08205 ) 𝑥 (𝑇2 − 1000𝐾) = −3𝑎𝑡𝑚 (16.42 − 8.21)𝑙𝑖
2 𝑚𝑜𝑙 𝐾

𝑇2 = 800 𝐾

3 800 16.42
∆S = (1𝑥 𝑥 1.987𝑥 𝑙𝑛 1000) + [1.987 x ln ( 8.21 )
2

∆S = -0.665 + 1.375 = 0.71 eu

c. q=0; P=0; W=0; ∆E=0 = nCv∆T

𝑉 16.42
∆S = nRln𝑉2 = 1.987x ln ( 8.21 )
1

∆S = 1.375 eu