3.

From 298 K up to its melting temperature of 1048 K, the constant pressure molar heat capacity of RbF
is given as Cp = 7.97 + 9.2 x 10 -3 T + 1.21 x 105 T-2 calories/degree and from the melting temperature to
1200 K, the constant-pressure molar heat capacity of liquid RbF is given as Cp = -11.30 + 0.833 x 10-3 T +
350.7 x 105 T-2 calories/degree. At its melting temperature the molar heat of fusion of RbF is 6300 calories.
Calculate the increase in the entropy of 1 mole of RbF when it is heated from 300 to 1200 K.

∆S1 : Heating solid RbF from 300 K to 1048 K.

∆S2 : Melting RbF at 1048 K.

∆S3 : Heating liquid RbF from 1048 K to 1200 K.

Tm Tm NC 1048
δq p(s)
∆S1 = ∫ =∫ dT = ∫ (7.97T −1 + 9.2 ∗ 10−3 + 1.21 ∗ 105 T −3 ) dT
Ti T Ti T 300

1048
−3
1.21 ∗ 105 −2
= [7.97 ln T + 9.2 ∗ 10 T + T ]
−2 300

∆S1 = 17.468 J/K

qm 6300
∆S2 = = = 6.01145 J/K
T 1048

Tf Tf NC 1200
δq p(l) −11.3
∆S3 = ∫ =∫ dT = ∫ ( + 0.833 ∗ 10−3 + 350.7 ∗ 105 T −3 ) dT
Tm T Tm T 1048 T

1200
350.7 ∗ 105 −2
−3
= [−11.3 ln T + 0.833 ∗ 10 T + T ] = 2.3846 J/K
−2 1048

∆Stotal = ∆S1 + ∆S2 + ∆S3 = 17.468 + 6.01145 + 2.3846 = 25.864 J/K

5. At a pressure of 1 atm the equilibrium melting temperature of lead is 600 K, and, at this temperature,
the latent heat of melting of lead is 4810 J/mole.
(a) Calculate the entropy produced when 1 mole of super-cooled liquid lead spontaneously freezes at 590 K
and 1 atm pressure.
(b) Calculate the Gibbs free energy change of the spontaneous freezing process. The constant-pressure
molar heat capacity of liquid lead, as a function of temperature, at 1 atm pressure is given by
Cp(l) = 32.4 – 3.1 × 10-3T J/K
And the corresponding expression for solid lead is
Cp(s) = 23.6 + 9.75 × 10-3T J/K

The freezing process happened spontaneously (irreversibly), so to calculate ∆Sirr consider the following
reversible steps:

1. Heating supercooled liquid lead from 590 K to 600 K.

2. Solidifying the liquid lead at 600 K.
3. Cooling solid lead from 600 K to 590 K.

600 δq 600 NCp(Pb(l)) 600

∆S1 = ∫590 = ∫590 dT = ∫590 (32.4T −1 − 3.1 ∗ 10−3 ) dT
T T

= [32.4 ln T − 3.1 ∗ 10−3 T]600

590 = 0.514 J/K

−qm −4810
∆S2 = = = − 8.017 J/K
T 600

590 590 NC 590

δq p(Pb(s))
∆S3 = ∫ =∫ dT = ∫ (23.56T −1 + 9.75 ∗ 10−3 ) dT
600 T 600 T 600

= [23.56 ln T + 9.75 ∗ 10−3 T]590

600 = −0.494 J/K

∆S = ∆S1 + ∆S2 + ∆S3 = 0.514 − 8.017 − 0.494 = − 7.997 J/K

Similarily …

600
∆H1 = ∫ (32.4 − 3.1 ∗ 10−3 𝑇) 𝑑𝑇 = 305.5
590

∆H2 = −4810

590
∆H3 = ∫ (23.56 + 9.75 ∗ 10−3 𝑇) 𝑑𝑇 = −294
600

∆H = 305.5 − 4810 − 294 = −4799 J

∆𝑆Heat reservoir = 4799/590 = 8.134 J/K

∆𝑆irr = −7.997 + 8.134 = 0.137 𝐽/𝐾

7. Derive Stirling’s approximation, ln N! = NlnN – N, when N is very large

𝑁
ln N! = ln 1 + ln 2 + ⋯ + ln N ≈ ∫ ln x dx = N ln N − N + 1 ≈ N ln N − N
1

8. 10 liters of a monoatomic ideal gas at 25 C and 10 atm pressure are

expanded to a final pressure of 1 atm. The molar heat capacity of the
gas at constant volume is 3/2R and is independent of temperature.
Calculate the work done, the heat absorbed, and the change in U and
in H for the gas if the process is carried out (a) isothermally and
reversibly, and (b) adiabatically and reversibly. Also, for adiabatic
expansion (c) compare the change in U for two paths (i) An
isothermal process followed by a constant-volume process and (ii) A
constant-volume process followed by a constant-pressure process.
n = P𝐴 𝑉𝐴 𝑅𝑇𝐴 = 10 ∗ 10 ∗ 0.08206 ∗ 298 = 4.09
a) Vb = PA VA PB = 10 ∗ 10 ∗ 1 = 100 L
𝐵 𝐵
𝑑𝑉
q = w = ∫ 𝑃𝑑𝑉 = 𝑛𝑅𝑇 ∫ = 4.09 ∗ 8.3144 ∗ 298 ∗ (ln 100 − ln 10) = 23.3 kJ
𝐴 𝐴 𝑉
the system performs 23.3 kJ of work and absorbs 23.3 kJ of heat from the constant-temperature surroundings.
Since for an ideal gas, H is a function only of T, ∆H (a to b) = 0.
∆𝐻(𝐴−𝐵) = ∆U(𝐴−𝐵) + (𝑃𝐵 𝑉𝐵 − 𝑃𝐴 𝑉𝐴 ) = (𝑃𝐵 𝑉𝐵 − 𝑃𝐴 𝑉𝐴 ) = 𝑛𝑅𝑇𝐵 − 𝑛𝑅𝑇𝐴 = 𝑛𝑅(𝑇𝐵 − 𝑇𝐴 ) = 0

b) 𝑃𝐴 𝑉𝐴 𝛾 = 𝑃𝐶 𝑉𝐶 𝛾
3
5 5
10 ∗ 103
𝑉𝐶 = ( ) = 39.8 𝐿
1

𝑃𝐶 𝑉𝐶 1 ∗ 39.8
𝑇𝐶 = = = 119 𝐾
𝑛𝑅 4.09 ∗ 0.08206
As the process is adiabatic, q = 0 and hence,
𝐶
∆𝑈(𝐴−𝐶) = −w = ∫ 𝑛 ∗ 𝐶𝑣 ∗ (𝑇𝐶 − 𝑇𝐴 ) = 4.09 ∗ 1.5 ∗ 8.3144 ∗ (119 − 298) = −9.13 𝑘𝐽 (𝐶𝑣 = 1.5 ∗ 𝑅)
𝐴

The w done by the system as a result of the process = the decrease in the internal energy of the system = 9.13 kJ

i) An isothermal process followed by a constant-volume process (a – e – c)

∆𝑈 ′ (𝐴−𝐸) = 0, as this is an isothermal change of state ∆𝑈 ′ (𝐸−𝐶) = 𝑞 ∗ 𝑣(∆V = 0, and hence, w = 0) =
𝐶
∫𝐸 𝑛 ∗ 𝑐 ∗ 𝑣 ∗ 𝑑𝑇 and as the state e lies on the 298 K isotherm, then…

∆𝑈 ′ (𝐸−𝐶) = 4.09 ∗ 1.5 ∗ 8.3144 ∗ (119 − 298) 𝐽 = −9.13 𝑘𝐽

∆𝑈 ′ (𝐴−𝐶) = ∆𝑈 ′ (𝐴−𝐸) + ∆𝑈 ′ (𝐸−𝐶) = −9.13 𝑘𝐽

ii) A constant-volume process followed by a constant-pressure process (a – f – c)

𝐹
∆𝑈 ′ (𝐴−𝐹) = q ∗ v(𝑉𝐴 = 𝑉𝐹 , and hencce, w = 0) = ∫ 𝑛 ∗ 𝑐 ∗ 𝑣 ∗ 𝑑𝑇
𝐴

𝑇𝐹 = 𝑃𝐹 ∗ 𝑉𝐹 ∗ 𝑛 ∗ 𝑅 = 1 ∗ 10 ∗ 4.09 ∗ 0.08206 = 30 𝐾

∆𝑈 ′ (𝐴−𝐹) = 4.09 ∗ 1.5 ∗ 8.3144 ∗ (30 − 298) = −13.67 kJ

𝐶
∆𝑈 ′ (𝐹−𝐶) = q ∗ p − w = ∫ 𝑛 ∗ 𝐶𝑝 ∗ 𝑑𝑇 − 𝑃𝐹 (𝑉𝐶 − 𝑉𝐹 ) (𝐶𝑝 = 2.5 ∗ R, since 𝐶𝑣 = 1.5 ∗ R and 𝐶𝑝 − 𝐶𝑣 = R)
𝐹

= [4.09 ∗ 2.5 ∗ 8.3144 ∗ (199 − 30)] − [1 ∗ (39.8 − 10) ∗ 101.3] = 7.57 − 3.02 𝑘𝐽

∆𝑈 ′ (𝐴−𝐹) = ∆𝑈 ′ (𝐴−𝐹) + ∆𝑈 ′ (𝐹−𝐶) = −13.67 + 7.57 − 3.02 = −9.12 kJ

9. For S, a monoclinic form is stable above 368.5 K and an orthorhombic form is stable below 368.5 K. The
following cycle is used for the experimental verification of the Third Law of Thermodynamics, which says
that the entropy at zero Kelvin is zero. The related experimentally measured heat capacities are on the
right. Using these, explain how the Third Law of Thermodynamics can be verified.

αβ

∆𝑆4 = ∆𝑆1 + ∆𝑆2 + ∆𝑆3

∆𝑆2 = −(∆𝑆1 + ∆𝑆3 )

1.09 J/K ≈ −(36.86 − 37.8) = 0.94 J/K

Since the difference between the experimental and the 3rd law entropy changes is less than the experimental error,
the equality is taken as being an experimental verification of the 3 rd law.

10. I have a machine stirring in a bucket with liquid. The bucket is under constant pressure and is insulated
from the environment (an adiabatic bucket). The bucket is defined as the physical bucket + the liquid in it.
Choose the correct answer.

(a) Does the enthalpy of the bucket during this process increase, decrease or stay the same?
(b) Does the entropy of the bucket during this process increase, decrease or stay the same?
(c) Does the enthalpy of the surroundings during this process increase, decrease or stay the same?
(d) Does the entropy of the surroundings during this process increase, decrease or stay the same?

14. The initial state of one mole of a monatomic ideal gas is P = 20 atm and T = 300 K. Calculate the
change in the entropy of the gas for (a) an isothermal decrease in the pressure to 10 atm, (b) a reversible
adiabatic expansion to a pressure of 10 atm.
0.08206 ∗ 300
𝑃1 = 20 𝑎𝑡𝑚 𝑇1 = 300 𝐾 𝑉1 = = 1.231 𝑙
20
𝑃1 𝑉1
a) 𝑃2 = 10 𝑇2 = 300 𝐾 𝑉2 = = 2.462 𝑙
𝑃2

𝑉2
∆S = R ∗ ln = 8.3144 ∗ 𝑙𝑛 2 = 5.76 J/K
𝑉1
b) q = 0, reversible. Hence, ∆S = 0

21. Air at 1 bar and 298 K is compressed to 5 bar and 298 K by two different reversible processes:
(1) Cooling at constant pressure followed by heating at constant volume.
(2) Heating at constant volume followed by cooling at constant pressure.
Calculate the heat and work requirements and the change in internal energy and enthalpy of the air for
each path. Assume that air is an ideal gas, regardless of the changes it undergoes and that Cp = Cv + R.
At 298 K and 1 bar the molar volume of air is 0.02479 m3/mol.
𝑉1 𝑃1 1
𝑉2 = = 0.02479 ( ) = 0.004958 𝑚3
𝑃2 5
𝑇1 𝑉2 0.004958
𝑎) T ′ = = 298.15 ( ) = 59.63 𝐾
𝑉1 0.02479
𝑄 = ∆𝐻 = 𝐶𝑃 ∆𝑇 = 29.1(59.63 − 298.15) = −6941 𝐽
𝑄 = ∆𝐻 − ∆(𝑃𝑉) = ∆𝐻 − 𝑃∆𝑉 = −6941 − (1 ∗ 105 )(0.004958 − 0.02479) = −4958 J
∆𝑈 = 𝑄 = 𝐶𝑉 ∆𝑇 = 20.78(298.15 − 59.63) = −4958 𝐽
𝑄 = −6941 + 4958 = −1938 𝐽
∆𝑈 = −4958 + 4958 = 0 𝐽
0 = −1983 + W W = 1983 J

∆𝐻 = ∆𝑈 + ∆(𝑃𝑉)
𝑇1 = 𝑇2
𝑃1 𝑉1 = 𝑃2 𝑉2 Hence, ∆(𝑃𝑉) = 0 and ∆𝐻 = ∆𝑈 = 0

𝑇1 𝑃2 5
𝑏) T ′ = = 298.15 ( ) = 1490.75 𝐾
𝑃1 1
𝑄 = ∆𝑈 = 𝐶𝑉 ∆𝑇 = 20.78(1490.75 − 298.15) = 24788 J
𝑄 = ∆𝐻 = 𝐶𝑃 ∆𝑇 = 29.1(298.15 − 1490.75) = −34703 J
∆U = ∆H − ∆(PV) = ∆H − P∆V = −34703 − 5 ∗ 105 (0.004958 − 0.02479) = −24788 J
Q = 24788 − 34703 = −9915 J
ΔU = 24788 − 24788 = 0 J
W = ΔU − Q = 0 − (−9915) = 9915 J
∆𝐻 = ∆𝑈 = 0

22. The following heat engines produce power of 95,000 kW. Determine in each case the rates at which heat
is absorbed from the hot reservoir and discarded to the cold reservoir.
1. A Carnot engine operatures between heat reservoirs at 750 K and 300 K.
2. A practical engine operatures between the same heat reservoirs but with a thermal efficiency η = 0.35.

1. 𝑇𝐻 = 750 𝐾 𝑇𝐶 = 300 𝐾 𝑊𝑜𝑟𝑘 = −95000 𝑘𝑊

𝑇𝐶
η= 1− = 0.6
𝑇𝐻
|work| |𝑤𝑜𝑟𝑘| 95000
η= hence, 𝑄𝐻 = = = 1.583 ∗ 105 𝑘𝑊
|𝑄𝐻 | η 0.6
𝑄𝐶 = |𝑄𝐻 | − |𝑤𝑜𝑟𝑘| ℎ𝑒𝑛𝑐𝑒, 𝑄𝐶 = 6.333 ∗ 104 𝑘𝑊

2. η = 0.35
 |𝑤𝑜𝑟𝑘|
𝑄𝐻 = = 2.714 ∗ 105 𝑘𝑊
η
𝑄𝐶 = |𝑄𝐻 | − |𝑤𝑜𝑟𝑘| = 1.764 ∗ 105 𝑘𝑊

33. One mole of a monatomic ideal gas is subjected to the following sequence of steps:
a. Starting at 300 K and 10 atm, the gas expands freely into a vacuum to triple its volume
b. The gas is next heated reversibly to 400 K at constant volume
c. The gas is reversibly expanded at constant temperature until its volume is again tripled
d. The gas is finally reversibly cooled to 300 K at constant pressure
Calculate the values of q and w and the changes in U, H, and S.
0.08206 ∗ 300
𝑇1 = 300 K 𝑃1 = 10 𝑎𝑡𝑚 𝑉1 = = 2.462 l
10
𝑃1
a) 1 to 2 𝑇2 = 300, 𝑉2 = 3𝑉1 = 7.386 𝑙, 𝑃3 = = 3.33 𝑎𝑡𝑚
3
𝑉2
𝑞 = 𝑤 = ∆𝑈 = ∆𝐻 = 0, ∆S = R ∗ ln = 8.3144 ∗ ln 3 = 9.134 𝐽/𝐾
𝑉1
𝑇3 𝑃2 4
b) 2 to 3 𝑇3 = 400, 𝑉3 = 7.386 𝑙, 𝑃3 = = ∗ 3.33 = 4.44 𝑎𝑡𝑚
𝑇2 3

∆𝑉 = 0, 𝑊 = 0, 𝑞 = ∆𝑈 = 𝐶𝑉 (𝑇3 − 𝑇2 ) = 1.5 ∗ 8.3144 ∗ 100 = 1247 𝐽

5
∆𝐻 = 𝐶𝑃 (𝑇3 − 𝑇2 ) =∗ 1247 = 2078 𝐽
3
𝑇3 400
∆𝑆 = 𝐶𝑃 ln = 1.5 ∗ 8.3144 ∗ ln = 3.588 𝐽/𝐾
𝑇2 300
𝑃3
c) 3 to 4 𝑇4 = 400, 𝑉4 = 3 ∗ 𝑉3 = 22.158 𝑙, 𝑃4 = = 1.481 𝑎𝑡𝑚
3

𝑉4
∆𝑈 = ∆𝐻 = 0, 𝑞 = 𝑤 = R ∗ 𝑇4 ∗ ln = 8.3144 ∗ 40 ∗ ln 3 = 3654 𝐽
𝑉3
𝑞 3654
∆𝑆 = = = 9.134 𝐽/𝐾
𝑇 400
0.08206∗300
d) 4 to 5 𝑇5 = 300, 𝑉5 = = 16.623 𝑙, 𝑃5 = 1.481 𝑎𝑡𝑚
1.481

∆𝑈 = 𝐶𝑉 (𝑇5 − 𝑇4 ) = 1.5 ∗ 8.3144(300 − 400) = −1247 𝐽

∆𝐻 = 𝑞𝑝 = 2.5 ∗ 8.3144 ∗ (300 − 400)) = −2078 𝐽
𝑤 = 𝑞 − ∆𝑈 = −2078 + 1247 = −831 J
𝑇5 300
∆𝑆 = 𝐶𝑃 ln = 2.5 ∗ 8.3144 ∗ ln = −5.980 𝐽/𝐾
𝑇4 400
del_U del_H w q del_S
1-2 0 0 0 0 9.134
2-3 1247 2078 0 1247 3.588
3-4 0 0 3654 3654 9.134
4-5 -1247 --2075 -831 -2078 -5.98
sum 0 0 2823 2823 15.88
35. A rigid container is divided into two compartments of equal volume by a partition. One compartment
contains 2 mole of ideal gas A at 2 atm, and the other contains 1 mole of ideal gas B at 1 atm. What would
have been the increase in entropy when the partition was removed?
∆SA = 2R ∗ ln 2, ∆SB = R ∗ ln 2, ∆Stotal = 3R ∗ ln 2 = R ∗ ln 8

37. Assuming that a silver-gold alloy is a random mixture of gold and silver atoms, calculate the increase
in entropy when 10g of gold are mixed with 20g of silver to form a homogeneous alloy. The gram atomic
weights of Au and Ag are, respectively, 198 and 107.9.

10
NAu = = 0.0508 moles
197

20
NAg = = 0.1854 moles .
107.9

NT = NAu + NAg = 0.0508 + 0.1825 = 0.2362 moles .

n! 0.2362!
Ω= = = undefined .
n1! ∗ n2! 0.0508! ∗ 0.1825!
∵ ln Ω = (n ∗ ln n – n)– ∑(ni ∗ ln ni − ni)

= ( 0.2362 ln 0.2362 – 0.2362 ) – (0.1854 ln 0.1854 – 0.1854 )

∴ ln Ω = 0.13016

∴ Ω = 1.139

∴ S = R ∗ ln Ω = 1.987 ∗ 0.13016 S = .2644