Physical Chemistry II

Chapter 4 Physical Transformation of Pure

Substance
Exercise
4.1(a) How many phases are present at each of the points marked in Fig. 4.23a

4.1(b) How many phases are present at each of the points marked in Fig. 4.23b?

4.2(a) The difference in chemical potential between two regions of a system is +7.1 kJ mol1. By how much
does the Gibbs energy change when 0.10 mmol of a substance is transferred from one region to the other?

4.2(b) The difference in chemical potential between two regions of a system is 8.3 kJ mol1. By how much
does the Gibbs energy change when 0.15 mmol of a substance is transferred from one region to the other?

4.4(a) What is the maximum number of phases that can be in mutual equilibrium in a two-component
system?

4.4(b) What is the maximum number of phases that can be in mutual equilibrium in a four-component
system?

4.5(a) Water is heated from 25C to 100C. By how much does its chemical potential change?

4.5(b) Iron is heated from 100C to 1000C. By how much does its chemical potential change? Take
for the entire range (its average value).

4.6(a) By how much does the chemical potential of copper change when the pressure exerted on a sample is
increased from 100 kPa to 10 MPa?

4.6(b) By how much does the chemical potential of benzene change when the pressure exerted on a sample
is increased from 100 kPa to 10 MPa?

4.7(a) Pressure was exerted with a piston on water at 20C. The vapour pressure of water under 1.0 bar is
2.34 kPa. What is its vapour pressure when the pressure on the liquid is 20 MPa?

4.7(b) Pressure was exerted with a piston on molten naphthalene at 95C. The vapour pressure of
naphthalene under 1.0 bar is 2.0 kPa and its density is 0.962 g cm3. What is its vapour pressure when the
pressure on the liquid is 15 MPa?

4.8(a) The molar volume of a certain solid is 161.0 cm3 mol1 at 1.00 atm and 350.75 K, its melting
temperature. The molar volume of the liquid at this temperature and pressure is 163.3 cm 3 mol1. At 100
atm the melting temperature changes to 351.26 K. Calculate the enthalpy and entropy of fusion of the solid.

4.8(b) The molar volume of a certain solid is 142.0 cm3 mol1 at 1.00 atm and 427.15 K, its melting
temperature. The molar volume of the liquid at this temperature and pressure is 152.6 cm 3 mol1. At 1.2 MPa
the melting temperature changes to 429.26 K. Calculate the enthalpy and entropy of fusion of the solid.

4.9(a) The vapour pressure of dichloromethane at 24.1C is 53.3 kPa and its enthalpy of vaporization is
28.7 kJ mol1. Estimate the temperature at which its vapour pressure is 70.0 kPa.

4.9(b) The vapour pressure of a substance at 20.0C is 58.0 kPa and its enthalpy of vaporization is 32.7 kJ
mol1. Estimate the temperature at which its vapour pressure is 66.0 kPa.

4.12(a) When benzene freezes at 5.5C its density changes from 0.879 g cm3 to 0.891 g cm3. Its enthalpy
of fusion is 10.59 kJ mol1. Estimate the freezing point of benzene at 1000 atm.

4.12(b) When a certain liquid of molar mass 46.1 g mol1 freezes at 3.65C its density changes from 0.789
g cm3 to 0.801 g cm3. Its enthalpy of fusion is 8.68 kJ mol1. Estimate the freezing point of the liquid at
100 MPa.

4.15(a) Naphthalene, C10 H8, melts at 80.2C. If the vapour pressure of the liquid is 1.3 kPa at 85.8C and
5.3 kPa at 119.3C, use the ClausiusClapeyron equation to calculate (a) the enthalpy of vaporization, (b)
the normal boiling point, and (c) the enthalpy of vaporization at the boiling point.

4.15(b) The normal boiling point of hexane is 69.0C. Estimate (a) its enthalpy of vaporization and (b) its
vapour pressure at 25C and 60C.

4.16(a) Calculate the melting point of ice under a pressure of 50 bar. Assume that the density of ice under
these conditions is approximately 0.92 g cm3 and that of liquid water is 1.00 g cm3.

4.16(b) Calculate the melting point of ice under a pressure of 10 MPa. Assume that the density of ice under
these conditions is approximately 0.915 g cm3 and that of liquid water is 0.998 g cm3.