Thermodynamics

School of Chemical Science and Engineering

Yachay Tech University

BONILLA TAMBACO GISSELA PAOLA

UC-1: Introduction to Thermodynamics

1. Starting out on a trip into the mountains, you inflate the tires on your automobile to a recommended
pressure of 3.21x105 Pa on a day when the temperature is –5.00 °C. You drive to the beach, where the
temperature is 28.0 °C:
a. What is the final pressure in the tires, assuming constant volume?
b. Derive a formula for the final pressure, assuming more realistically that the volume of the tires increases

[ ]
with increasing pressure as Vf = Vi 1 + γ (Pf − Pi) where γ is an experimentally determined
constant.
2. Find the density of F2 gas at 20.0 °C and 188 torr.
3. Find the molar mass of a gas whose density is 1.80 g/L at 25.0 °C and 880 torr.

4. Consider the composite system, which is held at 298 K,

and assuming ideal gas behavior, calculate the total
pressure and the partial pressure of each component if the
barriers separating the compartments are removed. Assume
that the volume of the barriers is negligible.

5. A certain mixture of He and Ne in a 356-cm3 bulb weighs 0.1480 g and is at 20 °C and 748 torr. Find the
mass and mole fraction of He present.
6. Find the molar volume of an ideal gas at 20.0°C and 1.000 bar.
7. A certain mixture of N2 and O2 has a density of 1.185 g/L at 25°C and 101.3 kPa. Find the mole fraction of
O2 in the mixture.
8. A sample of 65 mg of an ideal gas at 0.800 bar pressure has its volume doubled and its absolute
temperature tripled. Find the final pressure.
9. For one mol of N2 gas at 0 °C, the following volumes are observed as a function of pressure:
P / kPa 101.325 303.975 506.625
V / cm3 22405 7461.4 4473.1
Calculate and plot PV/nT versus P for these three points and extrapolate to P 0 to evaluate R.
10. After 1.6 mol of NH3 gas is placed in a 1600-cm3 box at 25°C, the box is heated to 500 K. At this
temperature, the ammonia is partially decomposed to N2 and H2, and a pressure measurement gives 4.85
MPa. Find the number of moles of each component present at 500 K.
11. A 1.00-L bulb of methane at a pressure of 10.0 kPa is connected to a 3.00-L bulb of hydrogen at 20 kPa;
both bulbs are at the same temperature.
a. After the gases mix, what is the total pressure?.
b. What is the mole fraction of each component in the mixture?
12. A student decomposes KClO3 and collects 36.5 cm3 of O2 over water at 23 °C. The laboratory barometer
reads 751 torr. The vapor pressure of water at 23 °C is 21.1 torr. Find the volume the dry oxygen would
occupy at 0 °C and one atm.
13. Calculate the pressure exerted by at 300 K for molar volumes of 250 L mol-1 and 0.1 L mol-1 using the
ideal gas and the van der Waals equations of state. The values of parameters a and b for are 1.370 bar
dm6 mol-2 and 0.0387 dm3 mol-1, respectively. From the value for P calculated, Is the attractive or
repulsive interaction greater for at 300 K and Vm = 0.1 L mol-1 ?
14.A hypothetical gas obeys the equation of state PV = nRT(1 + aP), where "a" is a constant. For this gas:

a. Show that β = 1/T and κ = 1/P(1+ aP).

( ∂T )
∂P β
b. Verify that = .
V
κ
15.For liquid water at 25 °C, isothermal-compressibility data in the pressure range 1 to 401 bar are well fitted
by the equation: κ = a + bP + cP 2
where: a = 4.5259x10−5 bar −1 b = − 1.1706x10−8 bar −2 c = 2.3214x10−12 bar −3
The volume of one gram of water at 25 °C and 1 bar is 1.002961 cm3. Find the volume of one gram of
water at 25 °C and 401 bar. Compare the value with the experimental value 0.985846 cm3.
16.A liquid with thermal expansivity a is initially at temperature and volume T1 and V1. If the liquid is heated
from T1 to T2 at constant pressure, find an expression for V2 using the approximation that β is independent
of T.

17. For H2O at 17°C and 1 atm, β = 1.7x10-4 K-1 and κ = 4.7x10-5 atm-1. A closed, rigid container is completely
filled with liquid water at 14 °C and 1 atm. If the temperature is raised to 20 °C, estimate the pressure in
the container. Neglect the pressure and temperature dependences of β and κ.
18.Estimate the pressure increase needed to decrease isothermally by 1% the 1-atm volume of (a) a typical
solid with κ 5x10-6 atm-1. (b) a typical liquid with κ = 1x10-4 atm-1.

19. Estimate β, κ, and (∂P/∂T )V̄ at 25 °C and 1 atm for water, using the following data for the water density:

P = 1 atm P = 2 atm

T = 25 ºC T = 26 ºC T = 25 ºC

0.997044 g/cm3 0.996783 g/cm3 0.997092 g/cm3

UC-2: First Law of Thermodynamics
20. A person slowly lifts a 30.0-kg object to a height of 2.00 m above its initial position. Find the work done
on the object by the person, and the work done by the earth.
21.Calculate the work involved in expanding 20 L of an ideal gas to a final volume of 85 L against a constant
external pressure of 2.5 bar.
22.A bubble is expanded from a radius of 1.00 cm to a radius of 3.25 cm. The surface tension of water is
71.99 N m–1 . How much work is done in increasing the area of the bubble?
23.A current of 3.2 A is passed through a heating coil for 30 s. The electrical potential across the resistor is
14.5 V. Calculate the work done on the coil.
24.If the force to stretch a fiber a distance x is given by with, how much work is done to stretch the fiber 0.15
cm?
25.Find wrev for processes indicated in the figure if 3.00 atm, V1 = 500 cm3, P2 = 1.00 atm, and V2 = 2000
cm3. Find wrev for the reverse of process.

26.Calculate U when 1.00 mol of H2O goes from 25.0°C and 1.00 atm to 30 °C and 1.00 atm.
27.Calculate q, w, and U when 1.00 mol of water is heated from 0 °C to 100 °C at a fixed pressure of 1 atm.
Densities of water are 0.9998 g/cm3 at 0 °C and 0.9854 g/cm3 at 100 °C.
28.Find w for a non ideal gas is heated slowly and expands reversibly at a constant pressure of 275 torr from
a volume of 385 cm3 to 875 cm3.
29. When 45.0 g of a certain metal at 70 °C is added to 24.0 g of water (with cP = 1.00 cal/g-°C) at 10 °C in
an insulated container, the final temperature is 20 °C.
a. Find the specific heat capacity of the metal.
b. How much heat flowed from the metal to the water?
30. The potential energy stored in a spring is kx2, where k is the force constant of the spring and x is the
distance the spring is stretched from equilibrium. Suppose a spring with force constant 125 N/m is
stretched by 10.0 cm, placed in 112 g of water in an adiabatic container, and released. The mass of the
spring is 20 g, and its specific heat capacity is 0.30 cal/(g °C). The initial temperature of the water and the
spring is 18 °C. The water’s specific heat capacity is 1.00 cal/(g °C). Find the final temperature of the water.
20 °C.
a. Find the specific heat capacity of the metal.
b. How much heat flowed from the metal to the water?
31. Calculate the work done when 50 g of iron reacts with hydrochloric acid to produce FeCl2(aq) and
hydrogen in (a) a closed vessel of fixed volume, (b) an open beaker at 25 ºC.

32. What is the work done when a sample of 1.00 mol Ar, regarded here as a perfect gas, undergoes an
isothermal reversible expansion at 20.0 ºC from 10.0 dm3 to 30.0 dm3 ?

33. Estimate the molar volume of CO2 at 500 K and 100 atm by treating it as a van der Waals gas.

34. Can argon gas be treated as a perfect gas at 400 K and 3.0 atm?

35. Could 25 g of argon gas in a vessel of volume 1.5 dm3 exert a pressure of 2.0 bar at 30 ºC if it behaved as
a perfect gas? If not, what pressure would it exert?

36. The following data have been obtained for oxygen gas at 273.15 K. Calculate the best value of the gas
constant R from them and the best value of the molar mass of O2.
P (atm) 0.75 0.5 0.25
V̄ (dm3 mol-1) 29.9649 44.8090 89.6384

37. A certain sample of a gas has a volume of 20.00 dm3 at 0 ºC and 1 atm. A plot of the experimental data of
its volume against the Celsius temperature, θ, at constant p, gives a straight line of slope 0.0741 dm3 ºC−1.
From these data determine the absolute zero of temperature in degrees Celsius.

38. Recent communication with the inhabitants of Neptune have revealed that they have a Celsius-type
temperature scale, but based on the melting point (0 ºN) and boiling point (100 ºN) of their most common
substance, hydrogen. Further communications have revealed that the Neptunians know about perfect gas
behaviour and they find that in the limit of zero pressure, the value of pV is 28 dm3.atm at 0 ºN and 40
dm3 atm at 100 ºC. What is the value of the absolute zero of temperature on their temperature scale?

39. A vessel of volume 22.4 dm3 contains 1.5 mol H2 and 2.5 mol N2 at 273.15 K. Calculate:
a. The mole fractions of each component.
b. Their partial pressures.
c. Their total pressure.

40. Calculate the pressure exerted by 1 mol H2S behaving as a van der Waals gas when it is confined under
the following conditions (use the data in the table given above):
a. At 273.15 K in 22.414 dm3.
b. At 500 K in 150 cm3.
41. A gas at 350 K and 12 atm has a molar volume 12 per cent larger than that calculated from the perfect
gas law. Determine:
a. The compression factor under these conditions.
b. The molar volume of the gas.
c. Which are dominating in the sample, the attractive or the repulsive forces?

42. At 300 K and 20 atm, the compression factor of a gas is 0.86. Calculate:
a. The volume occupied by 8.2 mmol of the gas under these conditions.
b. An approximate value of the second virial coefficient B at 300 K.

43. Calculate the pressure exerted at 100 K by 0.104 mol O2(g) in a vessel of volume 0.225 dm3.

44. Calculate the volume occupied by one mol N2 using the van der Waals equation in the form of a virial
expansion at:
a. Its critical temperature.
b. Its Boyle temperature.
c. Its inversion temperature.
d. Assuming that the pressure is 10 atm throughout, at what temperature is the gas most perfect? Use the
following data: Tc = 126.3 K.

45.The second virial coefficient of methane can be approximated by the empirical equation B(T)=a +be−c/T2,
where a = − 0.1993 bar−1, b = 0.2002 bar−1, and c = 1131 K2 with 300 K < T < 600 K. What is the Boyle
temperature of methane?

46. Determine the energy supplied as heat for an current of 10.0 A from a 12 V supply is passed for 300 s.

47. Suppose a 55 W electric heater immersed in a gas in a constant- volume adiabatic container was on for
120 s and it was found that the temperature of the gas rose by 5 ºC. Determine the heat capacity of the
sample.

48. Water is heated to boiling under a pressure of 1.0 atm. When an electric current of 0.50 A from a 12 V
supply is passed for 300 s through a resistance in thermal contact with it, it is found that 0.798 g of water
is vaporized. What is the enthalpy change?

49. The change in molar internal energy when CaCO3(s) as calcite converts to another form, aragonite, is
+0.21 kJ mol−1. Calculate the difference between the molar enthalpy and internal energy changes when
the pressure is 1.0 bar given that the densities of the polymorphs are 2.71 g cm−3 (calcite) and 2.93 g cm−3
(aragonite).

50. What is the change in molar enthalpy of N2 when it is heated from 25 ºC to 100 ºC, assuming a -
temperature-dependence for the heat capacity?

51. A system containing 2.5 mol of an ideal gas, for which C̄V = 20.79 J . mol −1K −1, is taken through the
cycle in the following diagram in the direction indicated by the arrows. The curved path corresponds to
PV = nRT, where T1 = T3.
a. Calculate q, w, ∆U, and ∆H for each segment and for the cycle assuming that the heat capacity is
independent of temperature.
b. Calculate q, w, ∆U, and ∆H for each segment and for the cycle in which the direction of each
process is reversed.
52. An amount of 2.5 mol of an ideal gas with C̄V = 12.47 J . mol −1K −1 is expanded adiabatically against a
constant external pressure of one bar. The initial temperature and pressure of the gas are 325 K and 2.5
bar, respectively. The final pressure is 1.25 bar. Calculate the final temperature, q , w , ∆U, and ∆H.

53. Suppose 0.1 mol of a monoatomic ideal gas undergoes the reversible cyclic process shown in the figure,
where either P or V is held constant in each step.
a. Calculate q, w, ∆U, and ∆H for each step and for the complete cycle.
b. Verify that w for the reversible cyclic process equals minus the area enclosed by the lines
representing the cycle.


54. A cloud mass moving across the ocean at an altitude of 2000 m encounters a coastal mountain range. As
it rises to a height of 3500 m to pass over the mountains, it undergoes an adiabatic expansion. The
pressure at 2000 m and 3500 m is 0.802 atm and 0.602 atm, respectively. If the initial temperature of the
cloud mass is 288 K:

a. Assuming that C̄P = 28.86 J . mol −1K −1 and that air obeys the ideal gas law, what is the cloud
temperature as it passes over the mountains?
b. If you are on the mountain, should you expect rain or snow?

55. Evaluate the change in temperature when the pressure of carbon dioxide changes isenthalpically by −10
bar at 300 K and evaluate its molar isothermal Joule coefficient.
UC-3: Thermochemistry
56. The average bond enthalpy of the O—H bond in water is defined as one-half of the enthalpy change for
the reaction H2O(g)⟶ 2 H(g) + O(g) . The formation enthalpies (∆fH°) for H(g ) and O(g ) are 218.0 and
249.2 kJ mol-1, respectively, at 298.15 K, and for H2O(g ) is –241.8 kJ mol-1 at the same temperature.
a. Determine the average bond enthalpy of the O—H bond in water at 298.15 K.
b. Determine the average bond energy of the O—H bond in water at 298.15 K. Assume ideal gas
behavior.

57. Calculate the enthalpy of hydrogenation of benzene from its enthalpy of combustion and the enthalpy of
combustion of cyclohexane.

58. For CO(NH2)2 (s), ∆fH°298 = -333.51 kJ/mol. Find ∆fU°298 of CO(NH2)2 (s).

59. Determine the value of ΔfHº (Ag+,aq); the standard enthalpy of formation of AgBr(aq) is –17 kJ mol−1.

60. Evaluate the standard enthalpy of the reaction C(graphite) + H2O(g) → CO(g) + H2(g).

61. Estimate the standard enthalpy of formation of cyclohexane, C6H12(l), at 400 K.

62. Combustion of 2.016 g of solid glucose (C6H12O6) at 25 °C in an adiabatic bomb calorimeter with heat
capacity 9550 J/K gives a temperature rise of 3.282°C. Find ∆combU°298 of solid glucose.

63. Predict the heat output of the combustion of 1.0 dm3 of octane at 298 K. Its mass density is 0.703 g.cm−3.

64. 1.247 g of glucose is burned in an adiabatic bomb calorimeter whose heat capacity is 11.45 kJ/K, what
will be the temperature rise?

65. When 0.972 g of cyclohexane undergoes complete combustion in a bomb calorimeter, ∆T of the inner
water bath is 2.98 °C. For cyclohexane, ∆combU is –3913 kJ.mol-1. Taking into account that the amount of
the water in the inner bath is 1.812 L, and the CP of water is known to be 1 cal ºC-1.g-1 , What is the value
for ∆combU for the combustion of benzene if ∆T is 2.36 °C when 0.857 g of benzene undergoes complete
combustion in the same calorimeter?

66. In a constant pressure calorimeter, with a calorimeter constant of 342.5 J K-1, is determined the enthalpy
of solution for the reaction:

When 1.423 g of Na2SO4 is dissolved in 100.34 g of H2O(l), ∆T = 0.031 K. Calculate ∆Hºsolution for
Na2SO4. Compare your result with that calculated using the standard enthalpies of formation.

67. When a current of 10.0 A from a 12 V supply for 300 s, what is the energy supplied as heat?

68. Water is heated to boiling under a pressure of 1.0 bar. When an electric current of 0.50 A from a 12 V
supply is passed for 300 s through a resistance in thermal contact with it, it is found that 0.798 g of water
is vaporized. Calculate the molar internal energy and enthalpy changes at the boiling point.

69. When N2 is heated from 25°C to 100°C, what is the change in its molar enthalpy?

70. The standard enthalpy of formation of gaseous H2O at 298 K is -241.82 kJ mol-1. Estimate its value at 100
°C given the following values of the molar heat capacities at constant pressure: H2O(g): 33.58 J.K-1.mol-1;
H2(g): 28.84 J.K-1.mol-1; O2(g): 29.37 J.K-1.mol-1. Assume that the heat capacities are independent of
temperature.
71. Calculate the change in enthalpy when 124 g of liquid methanol initially at 1.00 bar and 298 K
undergoes a change of state to 2.50 bar and 425 K. The density of liquid methanol under these conditions
is 0.791 g.cm–3 , and CP,m for liquid methanol is 81.1 J K–1mol–1 .

72. Determine the average bond enthalpy and the average bond energy of the O—H bond in water at 298.15
K, taking into account that the average bond enthalpy of the O—H bond in water can be defined as one-
half of the enthalpy change for the reaction H2O → 2H(g) + 2O(g). The formation enthalpies (∆fHº) for
H(g) and O(g) are 218.0 and 249.2 kJ mol-1, respectively, at 298.15 K, and for H2O(g ) is –241.8 kJ mol-1 at
the same temperature. Assume ideal gas behavior.

73. From the data given below for ∆fHº(HCl,g) and heat capacities, valid over the temperature range
considered, calculate ∆rxHº1450 for the following reaction:

( K2 )
2
−3 T −7 T
C̄P(H2, g) = 29.064 − 0.8363 × 10 + 20.11 × 10 J . K −1m ol −1
K

( K )
T T2
C̄P(Cl2, g) = 31.695 + 10.143 × 10−3 − 40.373 × 10−7 2 J . K −1m ol −1
K

( K )
T T2
C̄P(HCl, g) = 28.165 + 1.809 × 10−3 + 15.464 × 10−7 2 J . K −1m ol −1
K
UC-4: Second and Third Laws of Thermodynamics
74. 1.00 mol of a monatomic ideal gas, used as the working substance of a Heat Engine, undergoes a
reversible cyclic process from an initial state of 10.0 atm and 600 K. lt expands isothermally to a pressure
of 1.00 atm (Step I), and then adiabatically to a temperature of 300 K (Step II). This expansion is followed
by an isothermal compression(Step III), and then an adiabatic compression (Step IV) back to the initial
state. Determine the values of q, w, ∆U, ∆H, for each stage of the cycle and for the cycle as a whole.

75. A heat pump is used to meet the heating requirements of a house and maintain it at 20 ºC. On a day
when the outdoor air temperature drops to -2 ºC, the house is estimated to lose heat at a rate of 80,000 kJ/
h. If the heat pump under these conditions has a COP of 2.5, determine:
a. The power consumed by the heat pump.
b. The rate at which heat is absorbed from the cold outdoor air.

76. The food compartment of a refrigerator is maintained at 4 °C by removing heat from it at a rate of 360 kJ/
min. If the required power input to the refrigerator is 2 kW, determine:
a. The coefficient of performance of the refrigerator.
b. The rate of heat rejection to the room that houses the refrigerator.

77. A 600-MW steam power plant, which is cooled by a nearby river, has a thermal efficiency of 40 percent.
Determine the rate of heat transfer to the river water. Will the actual heat transfer rate be higher or lower
than this value? Why?

78. Estimate the volume of cooling water used per minute by a 1000-MW power plant whose efficiency is
40%. Assume that the cooling water undergoes a 10 °C temperature rise (a typical value) when it cools the
steam.

79. Calculate the entropy change of a sample of ideal gas when it expands isothermally doubling its volume.

80. What is this change (∆S) when the pressure of the same (fixed) amount of a ideal gas is increased
isothermally from 1 bar to 3 bar.

81. Calculate the entropy change in the surroundings when 1.00 mol H2O(l) is formed from its elements
under standard conditions at 298 K.

82. Calculate the entropy change in the surroundings when 1.00 mol N2O4(g) is formed from 2.00 mol
NO2(g) under standard conditions at 298 K.

83. One mole of an ideal gas at 300. K is reversibly and isothermally compressed from a volume of 25.0 L to
a volume of 10.0 L. Because the water bath thermal reservoir in the surroundings is very large, T remains
essentially constant at 300 K during the process. Calculate ∆S, ∆Ssurroundings, and ∆STotal.

84. One mole of an ideal gas at 300. K is isothermally compressed by a constant external pressure equal to
the final pressure in previous exercise. At the end of the process, P = Pexternal. Because P ≠ Pexternal at all but
the final state, this process is irreversible. The initial volume is 25.0 L and the final volume is 10.0 L. The
temperature of the surroundings is 300. K. Calculate ∆S, ∆Ssurroundings, and ∆STotal.

85. What is the molar entropy of a system in which each molecule can be arranged in two different
orientations?

86. What is the molar entropy of a similar system to previous exercise in which each molecule can be
arranged in four different orientations?
87. In an engine running in accord with the Carnot cycle, 100 J of energy is withdrawn from the hot source at
500 K and some is used to do work, with the remainder deposited in the cold sink at 300 K. How much
work can be extracted from this engine?

88. How much work can be extracted when the temperature of the hot source is increased to 800 K?

89. Calculate the maximum work that can be done by a reversible heat engine operating between 500 K and
200 K if 1000. J is absorbed at 500. K.

90. A certain power station operates with superheated steam at 300 °C (TH = 573 K) and discharges the waste
heat into the environment at 20 °C (Tc = 293 K). What is the Carnot efficiency of this power station? At
what temperature of the hot source would the theoretical (Carnot) efficiency reach 80 per cent?

91. What is the change in entropy when 1.0 J of energy as heat transfers from a large block of iron at 30 ºC to
another large block at 20 ºC?

92. Calculate the change in entropy when a ideal gas expands isothermally to 10 times its initial volume (a)
reversibly, (b) irreversibly against zero pressure.

93. One mole of CO gas is transformed from an initial state characterized by Ti = 320 K and Vi = 80.0 L to a
final state characterized by Tf = 650 K and Vf = 120.0 L. Calculate ∆S for this process. Use the ideal gas
values for β and κ. For CO:
2 3
−1 −1 T −5 T −8 T
C̄V (J . mol K ) = 31.08 − 0.01452 + 3.1415 × 10 − 1.4973 × 10
K K2 K3
94. 3.00 mol of liquid mercury is transformed from an initial state characterized by Ti = 300 K and Pi = 1 bar
to a final state characterized by Tf = 600 K and Pf = 3 bar.
a. Calculate ∆S for this process considering the following information: β = 1.81x10–4 K–1, ρ = 13.54
g.cm–3, and C̄P(Hg, l) = 27.98 J.mol-1.K–1.
b. What is the ratio of the pressure-dependent term to the temperature-dependent term in ∆S? Explain
your result.

95. The heat capacity of O2 has been measured at 1 atm pressure over the
interval 12.97 K < T < 298.15 K. The data have been fit to the
following polynomial series in T/K, in order to have a unitless variable:
0 K < T < 12.97 K:
3
−1 −1 −3 T
C̄P(T )(J . m ol . K ) = 2.11 × 10
K3
12.97 K < T < 23.66 K:
T T2 T3
C̄P(T )(J . m ol −1 . K −1) = 5.666 + 0.6927 − 5.191 × 10−3 2 + 9.943 × 10−4 3
K K K
23.66 K < T < 43.76 K:
−1 −1 T T2 −4 T
3
C̄P(T )(J . m ol . K ) = 31.70 − 2.038 + −0.08384 2 − 6.685 × 10
K K K3
43.76 K < T < 54.39 K:
C̄P(T )(J . m ol −1 . K −1) = 46.094
54.39 K < T < 90.20 K:
−1 −1 T T2 T3
C̄P(T )(J . m ol . K ) = 81.268 − 1.1467 + 0.01516 2 − 6.407 3
K K K

The transition temperatures and the enthalpies for the transitions indicated are:
 Solid III solid II 23.66 K 93.8 J mol–1
Solid II solid I 43.76 K 743 J mol–1
Solid I liquid 54.39 K 445.0 J mol–1
Liquid gas 90.20 K 6815 J mol–1
a. Using these data, calculate for ∆S O2 at 298.15 K.
b. What are the three largest contributions to ∆S° ?

96. Calculate the standard reaction entropy for the combustion of methane to carbon dioxide and liquid
water at 298 K.

97. Calculate ∆combSº for the combustion of carbon monoxide at 475.0 K, taking into account the the
temperature dependence of constant pressure heat capacity for CO, CO2 , and O2 is given by:
2 3
−1 −1 −2 T −5 T −8 T
C̄P(CO, g)(J . mol . K ) = 31.08 − 1.452 × 10 + 3.1415 × 10 − 1.4973 × 10
K K2 K3
2 3
−1 −1 −2 T −5 T −8 T
C̄P(CO2, g)(J . mol . K ) = 18.86 + 7.937 × 10 − 6.7834 × 10 + 2.4426 × 10
K K2 K3
2
−1 −1 −2 T −5 T
C̄P(O2, g)(J . mol . K ) = 30.81 − 1.187 × 10 + 2.3968 × 10
K K2
98. Estimate (∂U/∂V)T for N2(g) and HCl(g) at 25°C and 1 atm using the van der Waals equation and their
respective coefficients. Why is (∂U/∂V)T larger for HCl(g) than for N2(g)?
99. For water:

T = 30 ºC ß = 3.04x10-4 K-1 , κ = 4.52x10-5 atm-1 , C̄p= 75.3 J.mol-1.K-1 , V̄ = 18.1 cm3.mol-1

T = 95 ºC ß = 7.232x10-4 K-1 , κ = 4.81x10-5 bar-1 , C̄p= 4.210 J.g-1.K-1 , ρ = 0.96189 g.cm3

Find C̄V of water at 30 °C and 95ºC (both at 1 atm).

100. For the construction of a fuel cell based on the oxidation of a hydrocarbon fuel, two choices for a fuel
are methane and octane. Taking into account the maximum work available through the combustion of
these two hydrocarbons (per mole and per gram) at 298 K and 1 bar pressure:
a. What is the best (or most convenient) fuel to be used?.
b. What is the maximum non-expansion work that can be produced by the fuel cell oxidation reactions?
101. How much energy is available for sustaining muscular and nervous activity from the combustion of 1.00
mol of glucose molecules under standard conditions at 37 ºC (blood temperature)? The standard entropy of
reaction is +182.4 J K−1 mol−1.
102. The value of ∆fGº for Fe(g ) is 370.7 kJ mol–1 at 298 K, and ∆fH° for Fe(g ) is 416.3 kJ mol–1 at the same
temperature. Assuming that ∆fHº is constant in the interval 250–400 K, calculate ∆fG° for Fe(g ) at 400. K.
103. Calculate the standard reaction Gibbs energy for the combustion of CH4(g) and CO(g) at 298 K.
1
104. Evaluate ΔfGº(Ag+,aq) from Ag(s) + Cl2(g) ⟶ Ag +(aq) + Cl −(aq) ΔrxGº = −54.12 kJ mol−1.
2
105. How does the entropy depend on the volume of a van der Waals gas?
 ( ∂V )
∂U
106. The relation is referred to the internal pressure denoted by πT , so the equation:
T

( ∂T )
∂p
πT = T −p is considered a thermodynamic equation state showing the pressure in terms of a
V
variety of thermodynamics properties of the system. Calculate πT for:
a. An ideal gas.
b. A vdW gas.
c. A gas that obeys the virial equation of state.

107. By how much does the molar Gibbs energy of liquid water change:
1. when the temperature reaches 303 K?

2. when the pressure is increased by 0.10 bar (ρH O(298 K) = 0.9970 g.cm−3).?
2

108. Calculate ∆S when 2.00 mol of water goes from 27°C and 1 atm to 37°C and 40 atm. Use data for CP,m,
ß, and Vmv neglecting the pressure and temperature variations.