Answers to Exercises

Chapter 1
Exercise 1.1 The pressure exerted by a gas depends on both the mass and the average speed of the molecules.
At a given temperature, the heavier molecules have a lower average speed in just such a way that the
pressures of two gases are equal if (N/V) is the same!
Exercise 1.3 (a) 40.9 mol, (b) About 7 × 1016 mol, (c) 4.3 × 1019 mol, (d) 9100 years
Exercise 1.4 150 atm and 180 atm
Exercise 1.5 (a) 0.08%
Exercise 1.6 U(ideal) − U(vw) = 263 J = 4.2% of U(ideal)
Exercise 1.7 (a) 24.5 L, (b) 1.174 L, (c) The Avogadro volume using the VW equation is 1.178 L.
Exercise 1.8 2.5 × 10–10 m
Exercise 1.12 Gas Tc (K) pc (atm) Vmc (L)
CO2 303.4 72.9 0.128
H2 33.1 12.7 0.0798
CH4 189.7 45.5 0.128
Exercise 1.13 The Mathematica code is in Appendix 1.2, Code C.

Chapter 2
Exercise 2.2 Energy turned to heat = 23.05 kcal; change of T of 1.0 L of water = 23.0 K
Exercise 2.3 (a) 4.54 amp, (b) 11.6 min
Exercise 2.4 (a) See Box 2.2, (b) 2.02 kJ
Exercise 2.5 Sound velocity for argon = 320 m s−1 ; for nitrogen = 352 m s−1
Exercise 2.6 He: 𝛾 = 1.667, M = 4.00 × 10−3 kg, C = 972 m s−1 (965 m s−1 )
CO2 : 𝛾 = 1.304, M = 44.01 × 10 kg, C = 259 m/s (259 m/s)
−3

N2 : 𝛾 = 1.404, M = 28.01 × 10−3 kg, C = 337 m s−1 (334 m/s)

Exercise 2.8 Final T = 334 K
Exercise 2.9 Enthalpy change = 4.22 kJ
Exercise 2.10 (a) −542.2 kJ, (b) −4817.2 kJ, (c) −1030 kJ
Exercise 2.11 Note that these values are only estimates and are not very accurate. Combustion enthalpy of
C7 H16 = −3672 kJ mol−1 ; of C8 H18 = −4168 kJ mol−1 ; of C9 H20 = −4664 kJ mol−1 . Divide these values
by the molecular weight of the corresponding compound to obtain the enthalpy per gram.
Exercise 2.12 Combustion energy of 1.0 g of sucrose = 16.8 kJ. Energy needed to lift 100 kg wt through 1 m
is 980 J. With 16.8 kJ, the 100 kg mass can be lifted (16.8 kJ/0.98 kJ m−1 ) = 17.1 m!

Modern Thermodynamics: From Heat Engines to Dissipative Structures, Second Edition. Dilip Kondepudi and Ilya Prigogine.
© 2015 John Wiley & Sons, Ltd. Published 2015 by John Wiley & Sons, Ltd.
504 Answers to Exercises

Exercise 2.13 When 𝜉 = 0.25 mol, the amount of CH4 = 2.75 mol, O2 = 1.5 mol, CO2 = 0.25 mol, H2 O =
0.5 mol. The amount of heat released = 222 kJ. When all the 2.0 mol of O2 (which is the limiting reactant)
has reacted 𝜉 = 1.0 mol.
Exercise 2.14 Change in the mass of the Sun in 1 million years = 1.37 × 1023 kg (for comparison: mass of
the Earth 5.98 × 1024 kg. Present mass of the Sun = 1.99 × 1030 kg)
Exercise 2.15 2.72 × 1012 J

Chapter 3
Exercise 3.2 201 K
Exercise 3.3 242 J
Exercise 3.4 (a) Maximum efficiency = 0.952, (b) Maximum energy available = 97 J
Exercise 3.5 30 m
Exercise 3.6 1.6 J/K
Exercise 3.7 Change in entropy = 2.2 × 10−4 J/K. Rate of change = 9.6 × 10−4 J K−1 s−1
Exercise 3.8 Entropy = 13.1 J K−1
Exercise 3.9 Maximum power = 1.2 kW m−2 . Solar cells that cost about $540 m−2 produce power at a cost
of about $0.15 per kW h.

Chapter 4
Exercise 4.1 In a living cell, which is an open system, dS = di S + de S. The entropy de S due to the exchange
of matter and energy can be negative, but according to the Second Law di S > 0. Thus, though di S > 0,
since de S < 0, the total dS < 0; this does not violate the Second Law.
Exercise 4.2 Quantity Units
Entropy, S J K−1
Chemical potential, 𝜇 J mol−1
Affinity, A J mol−1
Exercise 4.3 S1 and S3 are not extensive.
Exercise 4.4 (c) S at any time t is given by
[ ( )] [ ( )]
V V
S(t) = (NA0 − 𝜉) S0A + CVA ln T + Rln + 2𝜉(t) S0B + CVB ln T + R ln
NA0 − 𝜉 2𝜉

Chapter 5
( )
Vf
Exercise 5.2 Ff − Fi = −NRT ln
( Vi )
ΔGf ΔGi 1 1
Exercise 5.8 = + ΔH −
Tf Ti Tf Ti
Exercise 5.9 For an ideal gas F = N(u0 + CV T) − TN[s0 + CV ln T + R ln(V∕N)]
c 2c
Exercise 5.10 S = 2 − a and H = b +
T T
Exercise 5.12 (b) h = 3.1 cm
Exercise 5.13 (b) 1.5 atm
 Answers to Exercises 505

Chapter 6
Exercise 6.1

(a) F(V, T, N) = N(u0 + CV T) − TN[s0 + CV ln T + R ln (V∕N)]

(b) G(p, T, N) = N(u0 + CV T + RT) − NT[s0 + CV ln T + R ln (RT)] + NRT ln p
(c) Thus 𝜇(T, n) = (u0 + CV T) − T[s0 + CV ln T − R] + RT ln (n),
where n = (N/V)
Exercise 6.2 van der Waals: a = 0.816 atm L2 mol−2 , b = 30.0 × 10−3 L mol−1 ,
Berthelot: a = 80.0 atm L2 K mol−2 , b = 30.0 × 10−3 L mol−1 ,
2
Dieterici: a = 2.00 atm L mol ,−2 b = 45.0 × 10−3 L mol−1 ,
Exercise 6.6 (a) U(ideal) = 8.54 kJ, U(ideal) − U(vw) = 0.728 kJ
Exercise 6.8
[ ]
Vm a 1
(a) Z = −
Vm − b RT Vm
( ) ( )
3.59 × 101.3 V − 0.0427 L
(b) Fvw − Fideal = − J − 8.314 J K−1 T ln
V V

Chapter 7
Exercise 7.1 BP of hexane at 0.5 atm = 48.3 ◦ C
Exercise 7.2 At an altitude of 2 miles water boils at about 87 ◦ C
Exercise 7.4 Number of phases = 4

Chapter 8
Exercise 8.2

(a) Mole fractions: NaOH: 0.07, H2 O: 0.93

(b) Molality = 4.17 mol kg−1
(c) Molarity = 4.0 M

Exercise 8.3

(a) PO2 = 0.21 atm, PN2 = 0.78 atm, etc.

(b) Concentration of O2 in lakes = 2.7 × 10−4 M

Exercise 8.4

(a) Concentration of N2 in blood = 5.1 × 10−4 M

(b) At a depth of 100 m N2 concentration in blood = 5.5 × 10−4 M

Exercise 8.5

(a) [N2 ] = 5.1 × 10−4 M

(b) [N2 ] = 5.5 × 10−3 M
506 Answers to Exercises

Exercise 8.6 Boiling point of sugar solution = 373.28 K

Boiling point of NaCl solution = 373.46 K
Exercise 8.7

(a) Tf = [273 − (0.032V)] K in which V is in mL per liter of water

(b) V = 312 mL perliter of water for a decrease of 10 ◦ C in freezing point
(c) Tb = 102.67 ◦ C

Exercise 8.8 Tb of nitrobenzene = 212.68 K

Exercise 8.9 X = 128.7 g/mol
Exercise 8.10

(a) Molecular weightt of hemoglobin is about 70 000

(b) 𝜋 = 31 atm

Exercise 8.11 Osmotic pressure of sea water = 27 atm

Exercise 8.12

(a) Pressure needed for reverse osmosis = 24 atm. Work = 2.4 kJ L−1
(b) Energy cost for 100 L is about $0.02
(c) Evaporation using sunlight

Exercise 8.13 1.66 × 108 N = 1.7 × 107 kg wt

Exercise 8.14 𝛾 Ca2+ = 0.317, 𝛾 Cl− = 0.750
Exercise 8.15 mAg+ = 1.33 × 10−5 m

Chapter 9
Exercise 9.1

(a) At about T = 33 000 the C H bond will break due to collisions.

(b) At about 5.6 × 1010 K, avg KE equals nucleon binding energy. So we may expect nuclear reactions
to take place at this temperature.

Exercise 9.2 At T = 300 K, k = 7.81 × 106 M−1 s−1 .

At T = 350 K, Rf = 4.38 × 10−2 M s−1 .
Exercise 9.3 Ea = 1.33 × 1013 s−1 , ΔH† = 125.6 kJ mol−1 and ΔS† = −2.89 J K−1 mol−1 .
Exercise 9.4

(a) Reaction velocity = −0.069 M/s

(b) [A]eq = [A]0 − 𝜉 eq , [B]eq = [B]0 + 2𝜉 eq
(c) [A]eq = 0.045 M, [B]eq = 0.007 M

Exercise 9.6 k = 3.83 × 10−12 s−1

Radioactive decay is unaffected by temperature.
Exercise 9.7 Chirping depends on a rate-limiting step that obeys the Arrhenius law.
Exercise 9.9 At 25 ◦ C, pH = 5.77 and at 35 ◦ C, pH = 5.75
 Answers to Exercises 507

Exercise 9.10

(a) K = 6.74
(b) K = 1.32 × 1090
(c) K = 4.53 × 10−31

Exercise 9.12

(a) K = 5.80 × 105 at T = 25 ◦ C

(b) K = 6.3 × 10−4 at T = 400 ◦ C and ΔGrxn = 41.24 kJ/mol

Exercise 9.13 K = 2.6, At equilibrium Ntrans = 1.8 mol; Ncis = 0.7 mol

Chapter 10
Exercise 10.1 Using the molar mass of N2 the pressure at 2.5 km is 0.73 atm
Boiling point of water = 91.1 ◦ C
Exercise 10.2 0.46 J K−1 s−1
Exercise 10.3

(a) K = 8.31 × 10148

(b) K = 1.12 × 1025
(c) K = 9.24 × 1018
(d) K = 5.36 × 10137

Exercise 10.4

(a) 0.70 V
(b) 0.79 V
(c) 0.78 V

min
k+
Exercise 10.5 = 33.2
mout
k+
Dn(0)gM −gMx∕RT
Exercise 10.7 JN = e
RT
Exercise 10.8 F(T) = eC−𝜇0 (T)∕RT
Exercise 10.9 Fraction of dipoles between 10◦ and 20◦ = 2.26 × 10−2

Chapter 11
∞ ( )4
8𝜋h kB x3 dx
Exercise 11.2 𝛽 =
∫ c3 h (ex − 1)
0
V
Exercise 11.4 2.8 K = 4.5 × 1028
V1010 K
Exercise 11.5 𝜆10000
max = 290 nm
508 Answers to Exercises

1 d𝜆
Exercise 11.6 u(𝜆, T)d𝜆 = 8𝜋hc ( ) 5
ehc∕𝜆kB T −1 𝜆
dS
Exercise 11.7 = 6.58 × 1014 J K−1 s−1
dt

Chapter 12
Exercise 12.1 −c 3.7 × 10−23 atm L K−1 = −c 3.7 × 10−21 J K−1

Chapter 13
No numerical answers

Chapter 14
No numerical answers

Chapter 15
No numerical answers

Chapter 16
Exercise 16.3 For this system, we see that the cross-diffusional current could be of the order of 2 ×
10−9 mol m−2 s−1

Chapter 17
No numerical answers

Chapter 18
Exercise 18.1
A x
(a) = ln L ≪ 1 in which xL and xD are mole fractions. This will be true when xL nearly equals xD ,
RT xD
i.e. when the two concentrations are nearly equal.
(b) For notational simplicity we use x = N2 O4 and y = NO2 .
A −4.71 kJ mol−1 p
= + ln 2x
RT RT py
A p
When T = 298 K, = −1.9 + ln 2x
RT py
( )
px −1.9
In the linear regime, near equilibrium (A/RT) ≪ 1 implies ln e ≪ 1 in which p is measured
p2y
in bars. At equilibrium, if px = 1.0 bar, py = 0.38 bar.
 Answers to Exercises 509

Chapter 19
No numerical answers

Chapter 20
Exercise 20.2 Rotational temperature for H2 is 88 K, for O2 it is 2.06 K