Chapter 1 - Assignments

1.9. Find the volume of CO2 gas produced from 100 g of CaCO3 if the CO2 is at a pressure of 746 torr and
a temperature of 301 K. Assume the gas to be ideal.

1.10. According to Dalton’s law of partial pressures, the pressure of a mixture of ideal gases is the sum
of the partial pressures of the gases. The partial pressure of a gas is defined to be the pressure that
would be exerted if that gas were alone in the volume occupied by the gas mixture.

a. A sample of oxygen gas is collected over water at 25◦C at a total pressure of 748.5 torr, with a partial
pressure of water vapor equal to 23.8 torr. If the volume of the collected gas is equal to 454 mL, find the
mass of the oxygen. Assume the gas to be ideal.

b. If the oxygen were produced by the decomposition of KClO3, find the mass of KClO3.

1.11. The relative humidity is defined as the ratio of the partial pressure of water vapor to the pressure
of water vapor at equilibrium with the liquid at the same temperature. The equilibrium pressure of
water vapor at 25◦ C is 23.756 torr. If the relative humidity is 49%, estimate the amount of water vapor
in moles contained in a room that is 8.0 m by 8.0 m and 3.0 m in height. Calculate the mass of the water.

1.17.

a. Find the fractional change in the volume of a sample of liquid water if its temperature is changed from
20◦C to 30◦C and its pressure is changed from 1 bar to 26 bar.

b. Estimate the percent change in volume of a sample of benzene if it is heated from 0◦C to 45◦C at 1
atm.

c. Estimate the percent change in volume of a sample of benzene if it is pressurized at 55◦C from 1 atm
to 50 atm

1.18.

a. Estimate the percent change in the volume of a sample of carbon tetrachloride if it is pressurized from
1 atm to 10 atm at 25◦C.

b. Estimate the percent change in the volume of a sample of carbon tetrachloride if its temperature is
changed from 20◦Cto 40◦C. Find the change in volume of 100 cm3 of liquid carbontetrachloride if its
temperature is changed from 20◦C to 25◦C and its pressure is changed from 1 atm to10 atm.

1.23. Assuming that the coefficient of thermal expansion of gasoline s roughly equal to that of benzene,
estimate the fraction of your gasoline expense that could be saved by purchasing gasoline in the
morning instead of in the afternoon, assuming a temperature difference of 5◦C.

1.25. The coefficient of thermal expansion of ethanol equals 1.12×10−3K−1 at 20◦C and 1 atm. The density
at20◦C is equal to 0.7893 g cm−3
a. Find the volume of 1 mol of ethanol at 10◦C and 1 atm.

b. Find the volume of 1mol of ethanol at 30◦C and 1 atm.

1.33 *

a. By differentiation, find an expression for the coefficient of thermal expansion of a gas obeying the van
der Waals equation of state.

b. Find the value of the coefficient of thermal expansion of nitrogen gas at 298.15 K and Vm=24.4 L mol−1.

1.36.* Write an expression for the isothermal compressibility of a nonideal gas obeying the Redlich–
Kwong equation of state.

1.37. The experimental value of the compression factor Z=PVm/RT for hydrogen gas at T=273.15 K and
Vm= 0.1497 L/mol−1 is 1.1336. Find the values of Z predicted by the van der Waals, Dieterici, and
Redlich–Kwong equations of state for these conditions. Calculate the percent error for each.

1.38. The parameters for the van der Waals equation of state for a mixture of gases can be
approximated by use of the mixing rules:

Where x1 and x2 are the mole fractions of the two substances and where a1,b1,a2, and b2 are the van der
Waals parameters of the two substances. The quantities a12 and b12 are defined by

a. Using these mixing rules and the van der Waals equation of state, find the pressure of a mixture of
0.79 mol of N2 and 0.21 mol of O2 at 298.15 K and at a mean molar volume (defined as V/ntotal) of
0.00350 m3mol−1. Compare your answer with the pressure of an ideal gas under the same conditions.

b. Using the van der Waals equation of state, find the pressure of pure N2 at 298.15 K and at a molar
volume of 0.00350 m3 mol−1.

c. Using the van der Waals equation of state, find the pressure of pure O2 at 298.15 K and at a molar
volume of 0.00350 m3mol−1.
1.43. The critical temperature of xenon is 289.73 K, and its critical pressure is 5.840 MPa (5.840×10 6 Pa).

a. Find the values of the van der Waals constants a and b for xenon.

b. Find the value of the compression factor,Z, for xenon at a reduced temperature of 1.35 and a reduced
pressure of 1.75.

1.48. j. Assume that the van der Waals equation of state can be used for a liquid. Calculate the molar
volume of liquid water at 100◦C and 1 atm by the van der Waals equation of state. (Get a numerical
approximation to the solution of the cubic equation by a numerical method.) Compare your answer with
the correct value, 18.798 cm3mol−1.
Chapter 2 - Assignments
2.1. Calculate the work done on the surroundings if 1 mol of neon (assumed ideal) is heated
from 0◦C to 250◦C at a constant pressure of 1 atm.

2.2. Calculate the work done on the surroundings if 100 g of water freezes at 0 ◦C and a
constant pressure of 1 atm. The density of ice is 0.916 g cm-3 and that of liquid water is 1 g
cm−3.

2.3. Calculate the work done on 100.0 g of benzene if it is pressurized reversibly from 1.00 atm
to 50 atm at a constant temperature of 293.15 K.

2.4. Calculate the work done on the surroundings if 1 kg of water is heated from 25 ◦C to 100◦C
at a constant pressure of 1 atm.

2.7.*

a. Obtain a formula for the work done in reversibly and isothermally compressing 1 mol of a van
der Waals gas from a volume V1 to a volume V2.

b. Using the formula from part a, find the work done in reversibly compressing 1 mol of carbon
dioxide from 10 L to 5 L at 298.15 K. Compare with the result obtained by assuming that the gas
is ideal.

c. Using the formula from part a, calculate the work done on the surroundings if 1 mol of carbon
dioxide expands isothermally but irreversibly from 5 L to 10 L at an external pressure of 1 atm.
Compare with the result obtained by assuming that the gas is ideal.

2.10. Calculate the amount of heat required to bring 1 mol of water from solid at 0◦C to gas at
100◦ C at a constant pressure of 1 atm. Calculate w for the process.

2.12. The normal boiling temperature of ethanol is 78.5◦C, and its molar enthalpy change of
vaporization at this temperature is 40.3 kJ mol−1. Find q and w if 3 mol of ethanol are vaporized
at 78.5◦C and a constant pressure of 1 atm.

2.13.

a. If a sample of 2 mol of helium gas is isothermally and reversibly expanded at 298.15 K from a
pressure of 2.5 atm to a pressure of 1 atm, find w and q.

b. If the sample of helium from part a is isothermally and irreversibly expanded from the same
initial state to the same final state with Pext =1 atm, find w and q.

2.14. Calculate q and w if 2 mol of helium is heated reversibly from a volume of 20 L and a
temperature of 300 K to a volume of 40 L and a temperature of 600 K. The heating is done in
such a way that the temperature remains proportional to the volume.
2.15. The normal boiling temperature of ethanol is 78.5◦C, and its molar enthalpy change of
vaporization at this temperature is 40.3 kJ mol−1. Find q and w if 3 mol of ethanol are reversibly
vaporized at 78.5◦C and a constant pressure of 1 atm. Neglect the volume of the liquid
compared with that of the vapor.

2.18.

a. Calculate q,w, and ∆U if 2 mol of neon (assumed ideal) is heated at a constant pressure of 1
atm from a temperature of 0◦C to a temperature of 250◦C.

b. Calculate q,w, and ∆U if the same sample of neon is heated at a constant volume from the
same initial state to 250◦C and is then expanded isothermally to the same final volume as in part
a.

2.19. Calculate q,w, and ∆U for melting 100 g of ice at 0◦C and a constant pressure of 1 atm.
The density of ice is 0.916 g mL−1.

2.20.Calculate q,w, and ∆U for vaporizing 2 mol of liquid water at 100 ◦C to steam at 100◦C at a
constant pressure of 1 atm.

2.21.* Consider the following three processes: (1) A sample of 2 mol of helium gas is
isothermally and reversibly expanded from a volume of 10 L and a temperature of 400 K to a
volume of 40 L. (2) The same sample is reversibly cooled at a constant volume of 10 L from 400
K to a temperature of 300 K, then expanded reversibly and isothermally to a volume of 40 L,
and then heated reversibly from 300 K to 400 K at a constant volume of 40 L. (3) The same
sample is expanded irreversibly and isothermally at a temperature of 400 K from a volume of 10
L to a volume of 40 L with a constant external pressure of 1 atm. Calculate ∆U,q, and w for each
process.

2.22. 1 kg of water is pressurized isothermally at 298.15 K from a pressure of 1 atm to a

pressure of 10 atm. Calculate w for this process. State any assumptions.

2.24. A sample of 3 mol of argon is heated from 25 ◦C to 100◦C, beginning at a pressure of 1

atm (101,325 Pa).

a. Find q,w, and ∆U if the heating is done at constant volume.

b. Find q,w, and ∆U if the heating is done at constant pressure.

2.25. Find the final pressure if 2 mol of nitrogen is expanded adiabatically and reversibly from a
volume of 20 L to a volume of 40 L, beginning at a pressure of 2.5 atm. Assume nitrogen to be
ideal with CV, m = 5R/2.

2.26. A sample of 1 mol of neon gas is expanded from a volume of 5 L and a temperature of
400 K to a volume of 8 L.

a. Find the final temperature if the expansion is adiabatic and reversible. Assume that the gas is
ideal and that CV=3nR/2=constant.
b. Find ∆U,q, and w for the expansion of part a.

c. Find ∆U, q, w, and the final temperature if the expansion is adiabatic but at a constant
external pressure of 1 atm, starting from the same state as in part a and ending at the same
volume as in part a.

d.Find ∆U, q, and w if the expansion is reversible and isothermal, starting at the same state as
in part a and ending at the same volume as in part a. State any assumptions and
approximations.

2.27. Find the final temperature and the final volume if 2 mol of nitrogen is expanded
adiabatically and reversibly from STP to a pressure of 0.6 atm. Assume nitrogen to be ideal with
CV, m=5R/2.

2.28. 1 mol of carbon dioxide is expanded adiabatically and reversibly from 298.15 K and a
molar volume of 5 L mol−1 to a volume of 20 L mol −1.

a. Find the final temperature, assuming the gas to be ideal withCV, m=5R/2 = constant.

b. Find the final temperature, assuming the gas to be described by the van der Waals equation
with CV, m=5R/2 = constant.

2.29. A sample of 20 g of acetylene, C2H2, is expanded reversibly and adiabatically from a

temperature of 500 K and a volume of 25 L to a volume of 50 L. Use the value of CV, m obtained
from the value in Table A.8 for 500 K with the assumption that acetylene is an ideal gas.

a. Find the percent difference between this value of CV, m that you obtain and 5R/2.

b. Find the final temperature.

c. Find the values of ∆U, q, and w for the process.

2.30.

a. A sample of 2 mol of argon gas is adiabatically and reversibly expanded from a temperature
of 453.15K and a volume of 15.0 L to a final temperature of 400.0 K. Find the final volume, ∆U,
w, and q for the process. Assume argon to be ideal and assume that CV, m= 3/2R.

b. Consider an irreversible adiabatic expansion with the same initial state and the same final
volume, carried out with P(transferred)=1 atm. Find the final temperature, ∆U, w, and q for this
process.

2.31.

a. Find the final temperature, ∆U, q, and w for the reversible adiabatic expansion of O2 gas from
373.15 K and a molar volume of 10 L to a molar volume of 20 L. Assume the gas to be ideal
with CV, m= 5R/2.

b. Repeat the calculation of part a for argon instead of oxygen. Assume that CV, m=3R/2.
c. Explain in physical terms why your answers for parts a and b are as they are.

2.32.

a. 2 mol of O2 gas is compressed isothermally and reversibly from a pressure of 1 atm and a
temperature of 100 ◦ C to a pressure of 3 atm. Find ∆U,q,w, and ∆H for this process. State any
assumptions or approximations. Assume that the gas is ideal.

b. The same sample is compressed adiabatically and reversibly from a pressure of 1 atm and a
temperature of 100.0◦ C to a pressure of 3 atm. Find ∆U,q, and w for this process. State any
assumptions or approximations. Assume that CV, m=5RT /2 and that the gas is ideal.

2.35. A sample of 1 mol of water vapor originally at 500 K and a volume of 10 L is expanded
reversibly and adiabatically to a volume of 20.0 L. Assume that the water vapor obeys the van
der Waals equation of state and that its heat capacity at constant volume is described by Eq.
(2.4-25) withα=22.2JK−1 mol−1 and β=10.3×10 −3 JK−2 mol−1.

a. Find the final temperature.

b. Find the value of w and ∆U.

c. Compare your values with those obtained if water vapor is assumed to be an ideal gas and its
heatcapacity at constant pressure is constant and equal to its value at 500 K.

2.36.

a. A sample of 2 mol of H2 gas is reversibly and isothermally expanded from a volume of 20 L

to a volume of 50 L at a temperature of 300 K. Find q,w, and ∆U for this process.

b.The same sample of H2 gas is reversibly and adiabatically (without any transfer of heat)
expanded from a volume of 20 L and a temperature of 300 K to a final volume of 50 L. Find the
final temperature. Find q,w, and ∆U for this process.

2.37. A sample of 2 mol of N2 gas is expanded from an initial pressure of 1 atm and an initial
temperature of 450 K to a pressure of 0.4 atm.

a. Find the final temperature if the expansion is adiabatic and reversible. Assume thatCV=
5nR/2, so that γ=7/5=1.400.

b. Find ∆U,q, and w for the expansion of part a.

c. Find ∆U,q,w, and the final temperature if the expansion is adiabatic but at a constant external
pressure of 0.400 atm, starting from the same state as in part a and ending at the same volume
as in part a.

d. Find ∆U,q, and w if the expansion is reversible and isothermal, ending at the same pressure
as in part a.

2.40.
a. The Joule–Thomson coefficient of nitrogen gas at 50 atm and 0◦C equals .044 K atm −1.
Estimate the final temperature if nitrogen gas is expanded through a porous plug from a
pressure of 60.0 atm to a pressure of 1.00 atm at 0◦C.

b. Estimate the value of (∂Hm/∂P)T for nitrogen gas at 50 atm and 0◦C. State any assumptions.

2.41. A sample of 3.00 mol of argon is heated from 25.00◦C to 100.00◦C, beginning at a
pressure of 1 atm (101,325 Pa).

a. Find q,w,∆U, and ∆H if the heating is done at constant volume.

b. Find q,w,∆U, and ∆H if the heating is done at constant pressure.

2.42

a. Calculate ∆H and ∆U for heating 1 mol of argon from 100 K to 300 K at a constant pressure
of 1.00 atm. State any assumptions.

b. Calculate ∆H and ∆U for heating 1 mol of argon from 100 K to 300 K at a constant volume of
30.6 L.

c. Explain the differences between the results of parts a and b.

2.43

a. Find q, w, ∆U, and ∆H for heating 1 mol of neon gas from 273.15 K to 373.15 K at a constant
pressure of 1 atm. State any approximations and assumptions.

b. Find q,w,∆U, and ∆H for heating 1 mol of neon gas from 273.15 K to 373.15 K at a constant
volume of 22.4 L. State any approximations and assumptions.

2.44. Supercooled steam is condensed irreversibly but at a constant pressure of 1 atm and a
constant temperature of 96.5 ◦C. Find the molar enthalpy change. State any assumptions and
approximations.

2.45. The enthalpy change of fusion of mercury is 2331 J mol−1. Find ∆H for converting 100.0
g of solid mercury at−75.0◦C to liquid mercury at 25.0◦C at a constant pressure of 1.000 atm.
Assume that the heat capacities are constant and equal to their values in Table A.6 of the
appendix.

2.46. Find ∆H if 100.0 g of supercooled liquid mercury at −50.0 ◦ C freezes irreversibly at

constant temperature and a constant pressure of 1.000 atm. The enthalpy change of fusion at
the normal melting temperature is 2331 J mol −1 Assume that the heat capacities are constant
and equal to their values in Table A.6 of the appendix.

2.47. Find the value of q and the value of ∆H if 2 mol of solid water (ice) at−10◦C is turned into
liquid water at 80◦C, with the process at a constant pressure of 1 atm. Assume that the heat
capacities are constant and equal to their values in Table A.6 of the appendix.
 Others

1. Is it true that it takes more energy to vaporize 1 kg of saturated liquid water at 100°C than it
would at 120°C?
2. Which process requires more energy: completely vaporizing 1 kg of saturated liquid water at 1
atm pressure or completely vaporizing 1 kg of saturated liquid water at 8 atm pressure?
3. Complete this table for H2O:
4. Complete this table for refrigerant-134a:
Chapter 3 - Assignments