EXERCISES 85

We now transform the remaining partial derivative. With V On division by dT, this relation becomes
regarded as a function of p and T, when these two quantities change
the resulting change in V is A ∂V D A ∂V D A ∂p D
B E = −B E B E (2.58)
A ∂V D A ∂V D C ∂T F p C ∂p F T C ∂T F V
dV = B E dT + B E dp (2.56)
C ∂T F p C ∂p F T and therefore
If (as in eqn 2.56) we require the volume to be constant, dV = 0
A ∂p D (∂V/∂T)p α
implies that B E =− = (2.59)
C ∂T F V (∂V/∂p)T κT
A ∂V D A ∂V D
B E dT = − B E dp at constant volume (2.57)
C ∂T F p C ∂p F T Insertion of this relation into eqn 2.55 produces eqn 2.48.

Discussion questions
2.1 Provide mechanical and molecular definitions of work and heat. 2.4 Explain the significance of a physical observable being a state function and
compile a list of as many state functions as you can identify.
2.2 Consider the reversible expansion of a perfect gas. Provide a physical
interpretation for the fact that pV γ = constant for an adiabatic change, 2.5 Explain the significance of the Joule and Joule–Thomson experiments.
whereas pV = constant for an isothermal change. What would Joule observe in a more sensitive apparatus?
2.3 Explain the difference between the change in internal energy and the 2.6 Suggest (with explanation) how the internal energy of a van der Waals gas
change in enthalpy accompanying a chemical or physical process. should vary with volume at constant temperature.

Exercises
Assume all gases are perfect unless stated otherwise. Unless otherwise stated, 2.4(b) A sample consisting of 2.00 mol of perfect gas molecules, for which
thermodynamic data are for 298.15 K. CV,m = 52 R, initially at p1 = 111 kPa and T1 = 277 K, is heated reversibly to
356 K at constant volume. Calculate the final pressure, ∆U, q, and w.
2.1(a) Calculate the work needed for a 65 kg person to climb through 4.0 m
on the surface of (a) the Earth and (b) the Moon (g = 1.60 m s−2). 2.5(a) A sample of 4.50 g of methane occupies 12.7 dm3 at 310 K.
(a) Calculate the work done when the gas expands isothermally against
2.1(b) Calculate the work needed for a bird of mass 120 g to fly to a height of a constant external pressure of 200 Torr until its volume has increased by
50 m from the surface of the Earth. 3.3 dm3. (b) Calculate the work that would be done if the same expansion
2.2(a) A chemical reaction takes place in a container of cross-sectional
occurred reversibly.
area 100 cm2. As a result of the reaction, a piston is pushed out through 2.5(b) A sample of argon of mass 6.56 g occupies 18.5 dm3 at 305 K.
10 cm against an external pressure of 1.0 atm. Calculate the work done by (a) Calculate the work done when the gas expands isothermally against
the system. a constant external pressure of 7.7 kPa until its volume has increased by
2.5 dm3. (b) Calculate the work that would be done if the same expansion
2.2(b) A chemical reaction takes place in a container of cross-sectional
occurred reversibly.
area 50.0 cm2. As a result of the reaction, a piston is pushed out through
15 cm against an external pressure of 121 kPa. Calculate the work done 2.6(a) A sample of 1.00 mol H2O(g) is condensed isothermally and
by the system. reversibly to liquid water at 100°C. The standard enthalpy of vaporization
of water at 100°C is 40.656 kJ mol−1. Find w, q, ∆U, and ∆H for this
2.3(a) A sample consisting of 1.00 mol Ar is expanded isothermally at 0°C
process.
from 22.4 dm3 to 44.8 dm3 (a) reversibly, (b) against a constant external
pressure equal to the final pressure of the gas, and (c) freely (against zero 2.6(b) A sample of 2.00 mol CH3OH(g) is condensed isothermally and
external pressure). For the three processes calculate q, w, ∆U, and ∆H. reversibly to liquid at 64°C. The standard enthalpy of vaporization of
methanol at 64°C is 35.3 kJ mol−1. Find w, q, ∆U, and ∆H for this process.
2.3(b) A sample consisting of 2.00 mol He is expanded isothermally at 22°C
from 22.8 dm3 to 31.7 dm3 (a) reversibly, (b) against a constant external 2.7(a) A strip of magnesium of mass 15 g is placed in a beaker of dilute
pressure equal to the final pressure of the gas, and (c) freely (against zero hydrochloric acid. Calculate the work done by the system as a result of the
external pressure). For the three processes calculate q, w, ∆U, and ∆H. reaction. The atmospheric pressure is 1.0 atm and the temperature 25°C.
2.4(a) A sample consisting of 1.00 mol of perfect gas atoms, for which 2.7(b) A piece of zinc of mass 5.0 g is placed in a beaker of dilute hydrochloric
CV,m = 32 R, initially at p1 = 1.00 atm and T1 = 300 K, is heated reversibly to acid. Calculate the work done by the system as a result of the reaction.
400 K at constant volume. Calculate the final pressure, ∆U, q, and w. The atmospheric pressure is 1.1 atm and the temperature 23°C.
86 2 THE FIRST LAW

2.8(a) The constant-pressure heat capacity of a sample of a perfect gas was 2.16(a) A certain liquid has ∆ vap H 7 = 26.0 kJ mol−1. Calculate q, w, ∆H,
found to vary with temperature according to the expression Cp /(J K−1) = and ∆U when 0.50 mol is vaporized at 250 K and 750 Torr.
20.17 + 0.3665(T/K). Calculate q, w, ∆U, and ∆H when the temperature is
2.16(b) A certain liquid has ∆ vap H 7 = 32.0 kJ mol−1. Calculate q, w, ∆H,
raised from 25°C to 200°C (a) at constant pressure, (b) at constant volume.
and ∆U when 0.75 mol is vaporized at 260 K and 765 Torr.
2.8(b) The constant-pressure heat capacity of a sample of a perfect gas was
found to vary with temperature according to the expression Cp /(J K−1) = 2.17(a) Calculate the lattice enthalpy of SrI2 from the following data:
20.17 + 0.4001(T/K). Calculate q, w, ∆U, and ∆H when the temperature is ∆H/(kJ mol−1)
raised from 0°C to 100°C (a) at constant pressure, (b) at constant volume.
Sublimation of Sr(s) +164
2.9(a) Calculate the final temperature of a sample of argon of mass 12.0 g Ionization of Sr(g) to Sr 2+(g) +1626
that is expanded reversibly and adiabatically from 1.0 dm3 at 273.15 K to Sublimation of I2(s) +62
3.0 dm3.
Dissociation of I2(g) +151
2.9(b) Calculate the final temperature of a sample of carbon dioxide of mass Electron attachment to I(g) −304
16.0 g that is expanded reversibly and adiabatically from 500 cm3 at 298.15 K Formation of SrI2(s) from Sr(s) and I2(s) −558
to 2.00 dm3.
2.17(b) Calculate the lattice enthalpy of MgBr2 from the following data:
2.10(a) A sample of carbon dioxide of mass 2.45 g at 27.0°C is allowed to
3 3
expand reversibly and adiabatically from 500 cm to 3.00 dm . What is the ∆H/(kJ mol−1)
work done by the gas? Sublimation of Mg(s) +148
2.10(b) A sample of nitrogen of mass 3.12 g at 23.0°C is allowed to expand Ionization of Mg(g) to Mg2+(g) +2187
reversibly and adiabatically from 400 cm3 to 2.00 dm3. What is the work done Vaporization of Br2(l) +31
by the gas? Dissociation of Br2(g) +193
2.11(a) Calculate the final pressure of a sample of carbon dioxide that Electron attachment to Br(g) −331
expands reversibly and adiabatically from 57.4 kPa and 1.0 dm3 to a final Formation of MgBr2(s) from Mg(s) and Br2(l) −524
volume of 2.0 dm3. Take γ = 1.4.
2.18(a) The standard enthalpy of formation of ethylbenzene is −12.5 kJ mol−1.
2.11(b) Calculate the final pressure of a sample of water vapour that expands
Calculate its standard enthalpy of combustion.
reversibly and adiabatically from 87.3 Torr and 500 cm3 to a final volume of
3.0 dm3. Take γ = 1.3. 2.18(b) The standard enthalpy of formation of phenol is −165.0 kJ mol−1.
Calculate its standard enthalpy of combustion.
2.12(a) When 229 J of energy is supplied as heat to 3.0 mol Ar(g) at constant
pressure, the temperature of the sample increases by 2.55 K. Calculate the 2.19(a) The standard enthalpy of combustion of cyclopropane is −2091 kJ
molar heat capacities at constant volume and constant pressure of the gas. mol−1 at 25°C. From this information and enthalpy of formation data for
2.12(b) When 178 J of energy is supplied as heat to 1.9 mol of gas molecules CO2(g) and H2O(g), calculate the enthalpy of formation of cyclopropane.
at constant pressure, the temperature of the sample increases by 1.78 K. The enthalpy of formation of propene is +20.42 kJ mol−1. Calculate the
Calculate the molar heat capacities at constant volume and constant pressure enthalpy of isomerization of cyclopropane to propene.
of the gas.
2.19(b) From the following data, determine ∆ f H 7 for diborane, B2H6(g), at
2.13(a) When 3.0 mol O2 is heated at a constant pressure of 3.25 atm, its 298 K:
temperature increases from 260 K to 285 K. Given that the molar heat capacity
(1) B2H6(g) + 3 O2(g) → B2O3(s) + 3 H2O(g) ∆ r H 7 = −2036 kJ mol−1
of O2(g) at constant pressure is 29.4 J K−1 mol−1, calculate q, ∆H, and ∆U.
3
(2) 2 B(s) + O2(g) → B2O3(s)
2 ∆ r H 7 = −1274 kJ mol−1
2.13(b) When 2.0 mol CO2 is heated at a constant pressure of 1.25 atm, its 1
temperature increases from 250 K to 277 K. Given that the molar heat capacity (3) H2(g) + O2(g) → H2O(g)
2 ∆ r H 7 = −241.8 kJ mol−1
of CO2(g) at constant pressure is 37.11 J K−1 mol−1, calculate q, ∆H, and ∆U.
2.20(a) When 120 mg of naphthalene, C10H8(s), was burned in a bomb
2.14(a) A sample of 4.0 mol O2(g) is originally confined in 20 dm3 at 270 K calorimeter the temperature rose by 3.05 K. Calculate the calorimeter
and then undergoes adiabatic expansion against a constant pressure of constant. By how much will the temperature rise when 10 mg of phenol,
600 Torr until the volume has increased by a factor of 3.0. Calculate q, w, ∆T, C6H5OH(s), is burned in the calorimeter under the same conditions?
∆U, and ∆H. (The final pressure of the gas is not necessarily 600 Torr.)
2.20(b) When 2.25 mg of anthracene, C14H10(s), was burned in a bomb
2.14(b) A sample of 5.0 mol CO2(g) is originally confined in 15 dm3 at 280 K calorimeter the temperature rose by 1.35 K. Calculate the calorimeter constant.
and then undergoes adiabatic expansion against a constant pressure of By how much will the temperature rise when 135 mg of phenol, C6H5OH(s),
78.5 kPa until the volume has increased by a factor of 4.0. Calculate q, w, ∆T, is burned in the calorimeter under the same conditions? (∆c H 7(C14H10,s) =
∆U, and ∆H. (The final pressure of the gas is not necessarily 78.5 kPa.) −7061 kJ mol−1.)
2.15(a) A sample consisting of 1.0 mol of perfect gas molecules with 2.21(a) Calculate the standard enthalpy of solution of AgCl(s) in water from
CV = 20.8 J K−1 is initially at 3.25 atm and 310 K. It undergoes reversible the enthalpies of formation of the solid and the aqueous ions.
adiabatic expansion until its pressure reaches 2.50 atm. Calculate the final
volume and temperature and the work done. 2.21(b) Calculate the standard enthalpy of solution of AgBr(s) in water from
the enthalpies of formation of the solid and the aqueous ions.
2.15(b) A sample consisting of 1.5 mol of perfect gas molecules with
Cp,m = 20.8 J K−1 mol−1 is initially at 230 kPa and 315 K. It undergoes 2.22(a) The standard enthalpy of decomposition of the yellow complex
reversible adiabatic expansion until its pressure reaches 170 kPa. Calculate H3NSO2 into NH3 and SO2 is +40 kJ mol−1. Calculate the standard enthalpy
the final volume and temperature and the work done. of formation of H3NSO2.