Exercises and problems 199

binary mixtures of nitroethane and liquid carbon dioxide the addition of P5E.3 Prove that a straight line from the apex A of a ternary phase diagram
arbitrary amounts of DEC will not cause phase separation. Find the range of to the opposite edge BC represents mixtures of constant ratio of B and C,
concentration for such binary mixtures. however much A is present.

TOPIC 5F Activities
Discussion questions
D5F.1 What are the contributions that account for the di erence between D5F.4 Why do the activity coe cients of ions in solution di er from 1? Why
activity and concentration? are they less than 1 in dilute solutions?
D5F.2 How is Raoult’s law modi ed so as to describe the vapour pressure of D5F.5 Describe the general features of the Debye–Hückel theory of electrolyte
real solutions? solutions.
D5F.3 Summarize the ways in which activities may be measured. D5F.6 Suggest an interpretation of the additional terms in extended versions of
the Debye–Hückel limiting law.

Exercises
E5F.1(a) e vapour pressure of water in a saturated solution of calcium nitrate E5F.4(a) Suppose it is found that for a hypothetical regular solution that
at 20 °C is 1.381 kPa. e vapour pressure of pure water at that temperature is ξ = 1.40, pA* = 15.0 kPa and p*B = 11.6 kPa. Draw plots similar to Fig. 5F.3.
2.3393 kPa. What is the activity of water in this solution? E5F.4(b) Suppose it is found that for a hypothetical regular solution that
E5F.1(b) e vapour pressure of a salt solution at 100 °C and 1.00 atm is ξ = −1.40, pA* = 15.0 kPa and p*B = 11.6 kPa. Draw plots similar to Fig. 5F.3.
90.00 kPa. What is the activity of water in the solution at this temperature? −1
E5F.5(a) Calculate the ionic strength of a solution that is 0.10 mol kg in
−1
E5F.2(a) Substances A and B are both volatile liquids with pA* = 300 Torr, KCl(aq) and 0.20 mol kg in CuSO4(aq).
−1
p*B = 250 Torr, and KB = 200 Torr (concentration expressed in mole fraction). E5F.5(b) Calculate the ionic strength of a solution that is 0.040 mol kg in
When xA = 0.900, pA = 250 Torr, and pB = 25 Torr. Calculate the activities of A K3[Fe(CN)6](aq), 0.030 mol kg−1 in KCl(aq), and 0.050 mol kg−1 in NaBr(aq).
and B. Use the mole fraction, Raoult’s law basis system for A and the Henry’s
E5F.6(a) Calculate the masses of (i) Ca(NO3)2 and, separately, (ii) NaCl to add
law basis system for B. Go on to calculate the activity coe cient of A.
to a 0.150 mol kg−1 solution of KNO3(aq) containing 500 g of solvent to raise its
E5F.2(b) Given that p*(H2O) = 0.023 08 atm and p(H2O) = 0.022 39 atm
ionic strength to 0.250.
in a solution in which 0.122 kg of a non-volatile solute (M = 241 g mol−1)
E5F.6(b) Calculate the masses of (i) KNO 3 and, separately, (ii) Ba(NO3)2 to add
is dissolved in 0.920 kg water at 293 K, calculate the activity and activity
to a 0.110 mol kg−1 solution of KNO3(aq) containing 500 g of solvent to raise its
coe cient of water in the solution.
ionic strength to 1.00.
E5F.3(a) By measuring the equilibrium between liquid and vapour phases of a
E5F.7(a) Estimate the mean ionic activity coe cient of CaCl2 in a solution that
propanone(P)/methanol(M) solution at 57.2 °C at 1.00 atm, it was found that
is 0.010 mol kg−1 CaCl2(aq) and 0.030 mol kg−1 NaF(aq) at 25 °C.
xP = 0.400 when yP = 0.516. Calculate the activities and activity coe cients
E5F.7(b) Estimate the mean ionic activity coe cient of NaCl in a solution that
of both components in this solution on the Raoult’s law basis. e vapour
is 0.020 mol kg−1 NaCl(aq) and 0.035 mol kg−1 Ca(NO3)2(aq) at 25 °C.
pressures of the pure components at this temperature are: pP* = 105 kPa and
p M* = 73.5 kPa. (xP is the mole fraction in the liquid and yP the mole fraction in E5F.8(a) e mean activity coe cients of HBr in three dilute aqueous solutions
the vapour.) at 25 °C are 0.930 (at 5.00 mmol kg−1), 0.907 (at 10.0 mmol kg−1), and 0.879 (at
E5F.3(b) By measuring the equilibrium between liquid and vapour phases of 20.0 mmol kg−1). Estimate the value of B in the Davies equation.
a solution at 30 °C at 1.00 atm, it was found that xA = 0.220 when yA = 0.314. E5F.8(b) e mean activity coe cients of KCl in three dilute aqueous solutions
Calculate the activities and activity coe cients of both components in at 25 °C are 0.927 (at 5.00 mmol kg−1), 0.902 (at 10.0 mmol kg−1), and 0.816 (at
this solution on the Raoult’s law basis. e vapour pressures of the pure 50.0 mmol kg−1). Estimate the value of B in the Davies equation.
components at this temperature are: pA* = 73.0 kPa and pB* = 92.1 kPa. (xA is
the mole fraction in the liquid and yA the mole fraction in the vapour.)

Problems
P5F.1‡ Francesconi, Lunelli, and Comelli studied the liquid–vapour equilibria P5F.2 Use mathematical so ware or a spreadsheet to plot pA/pA* against xA with
of trichloromethane and 1,2-epoxybutane at several temperatures (J. Chem. ξ = 2.5 by using eqn 5F.18 and then eqn 5F.19. Above what value of xA do the
Eng. Data 41, 310 (1996)). Among their data are the following measurements values of pA/pA* given by these equations di er by more than 10 per cent?
of the mole fractions of trichloromethane in the liquid phase (xT) and the P5F.3 e mean activity coe cients for aqueous solutions of NaCl at 25 °C are
vapour phase (yT) at 298.15 K as a function of total pressure. given below. Con rm that they support the Debye–Hückel limiting law and
that an improved t is obtained with the Davies equation.
p/kPa 23.40 21.75 20.25 18.75 18.15 20.25 22.50 26.30
xT 0 0.129 0.228 0.353 0.511 0.700 0.810 1 b/(mmol kg−1) 1.0 2.0 5.0 10.0 20.0
yT 0 0.065 0.145 0.285 0.535 0.805 0.915 1 γ± 0.9649 0.9519 0.9275 0.9024 0.8712
Compute the activity coe cients of both components on the basis of Raoult’s law.
200 5 Simple mixtures

P5F.4 Consider the plot of log γ± against I with B = 1.50 and C = 0 in the
1/2
Debye–Hückel limiting law lead to an error in the value of the activity
Davies equation as a representation of experimental data for a certain MX coe cient of less than 10 per cent of the value predicted by the
electrolyte. Over what range of ionic strengths does the application of the extended law?

FOCUS 5 Simple mixtures

Integrated activities
I5.1 e table below lists the vapour pressures of mixtures of iodoethane Plot the data on a temperature–composition diagram and determine the
(I) and ethyl ethanoate (E) at 50 °C. Find the activity coe cients of both extent to which it ts the predictions for an ideal solution by calculating the
components on (a) the Raoult’s law basis, (b) the Henry’s law basis with activity coe cients of O2 at each composition.
iodoethane as solute.
I5.5 For the calculation of the solubility c of a gas in a solvent, it is o en
convenient to use the expression c = Kp, where K is the Henry’s law
xI 0 0.0579 0.1095 0.1918 0.2353 0.3718
constant. Breathing air at high pressures, such as in scuba diving, results in
pI/kPa 0 3.73 7.03 11.7 14.05 20.72 an increased concentration of dissolved nitrogen. e Henry’s law constant
pE/kPa 37.38 35.48 33.64 30.85 29.44 25.05 for the solubility of nitrogen is 0.18 μg/(g H2O atm). What mass of nitrogen is
dissolved in 100 g of water saturated with air at 4.0 atm and 20 °C? Compare
your answer to that for 100 g of water saturated with air at 1.0 atm. (Air is
xI 0.5478 0.6349 0.8253 0.9093 1.0000
78.08 mol per cent N2.) If nitrogen is four times as soluble in fatty tissues as in
pI/kPa 28.44 31.88 39.58 43.00 47.12 water, what is the increase in nitrogen concentration in fatty tissue in going
pE/kPa 19.23 16.39 8.88 5.09 0 from 1 atm to 4 atm?
I5.6 Dialysis may be used to study the binding of small molecules to
I5.2 Plot the vapour pressure data for a mixture of benzene (B) and ethanoic macromolecules, such as an inhibitor to an enzyme, an antibiotic to DNA,
acid (E) given below and plot the vapour pressure/composition curve for the and any other instance of cooperation or inhibition by small molecules
mixture at 50 °C. en con rm that Raoult’s and Henry’s laws are obeyed in attaching to large ones. To see how this is possible, suppose inside the dialysis
the appropriate regions. Deduce the activities and activity coe cients of the bag the molar concentration of the macromolecule M is [M] and the total
components on the Raoult’s law basis and then, taking B as the solute, its activity concentration of small molecule A is [A]in. is total concentration is the
and activity coe cient on a Henry’s law basis. Finally, evaluate the excess Gibbs sum of the concentrations of free A and bound A, which we write [A]free
energy of the mixture over the composition range spanned by the data. and [A]bound, respectively. At equilibrium, μA,free = μA,out, which implies that
[A]free = [A]out, provided the activity coe cient of A is the same in both
xE 0.0160 0.0439 0.0835 0.1138 0.1714 solutions. erefore, by measuring the concentration of A in the solution
pE/kPa 0.484 0.967 1.535 1.89 2.45 outside the bag, the concentration of unbound A in the macromolecule
solution can be found and, from the di erence [A]in − [A]free = [A]in − [A]out,
pB/kPa 35.05 34.29 33.28 32.64 30.90 the concentration of bound A. Now explore the quantitative consequences of
the experimental arrangement just described. (a) e average number of A
xE 0.2973 0.3696 0.5834 0.6604 0.8437 0.9931 molecules bound to M molecules, ν, is
pE/kPa 3.31 3.83 4.84 5.36 6.76 7.29
[A]bound [A]in −[A]out
ν= =
pB/kPa 28.16 26.08 20.42 18.01 10.0 0.47 [M] [M]

I5.3‡ Chen and Lee studied the liquid–vapour equilibria of cyclohexanol with
e bound and unbound A molecules are in equilibrium, M + A MA.
several gases at elevated pressures (J.-T. Chen and M.-J. Lee, J. Chem. Eng. Recall from introductory chemistry that the equilibrium constant for binding,
Data 41, 339 (1996)). Among their data are the following measurements of K, may be written as
the mole fractions of cyclohexanol in the vapour phase (y) and the liquid [MA]c−−○
phase (x) at 393.15 K as a function of pressure. K=
[M]free[A]free
Now show that
p/bar 10.0 20.0 30.0 40.0 60.0 80.0
ycyc 0.0267 0.0149 0.0112 0.00947 0.00835 0.00921 ν c−−○
K=
(1 −ν )[A]out
xcyc 0.9741 0.9464 0.9204 0.892 0.836 0.773
(b) If there are N identical and independent binding sites on each
Determine the Henry’s law constant of CO2 in cyclohexanol, and compute the macromolecule, each macromolecule behaves like N separate smaller
activity coe cient of CO2. macromolecules, with the same value of K for each site. It follows that the
average number of A molecules per site is ν/N. Show that, in this case, the
I5.4‡ e following data have been obtained for the liquid–vapour equilibrium
Scatchard equation
compositions of mixtures of nitrogen and oxygen at 100 kPa.
ν c−−○
T/K 77.3 78 80 82 84 86 88 90.2 = KN − Kν
[A]out
100x(O2) 0 10 34 54 70 82 92 100 is obtained. (c) To apply the Scatchard equation, consider the binding
100y(O2) 0 2 11 22 35 52 73 100 of ethidium bromide (E−) to a short piece of DNA by a process called
intercalation, in which the aromatic ethidium cation ts between two adjacent
p*(O2)/Torr 154 171 225 294 377 479 601 760 DNA base pairs. An equilibrium dialysis experiment was used to study the
 Exercises and problems 231

E6B.7(b) What is the standard enthalpy of a reaction for which the equilibrium reaction of A2B(s), calculate (i) the equilibrium constant, (ii) the standard
constant is (i) doubled, (ii) halved when the temperature is increased by 15 K reaction Gibbs energy, (iii) the standard enthalpy, and (iv) the standard entropy
at 310 K? of dissociation, all at 422 °C. Assume that the vapour behaves as a perfect gas
⦵ ⦵
and that ΔrH and ΔrS are independent of temperature in the range given.
E6B.8(a) Estimate the temperature at which the equilibrium constant for the
E6B.9(b) Solid ammonium chloride dissociates according to NH4Cl(s) →
decomposition of CaCO3(s, calcite) to CO2(g) and CaO(s) becomes 1; assume
NH3(g) + HCl(g). e dissociation vapour pressure of NH4Cl at 427 °C is
pCO2 = 1 bar .
608 kPa but at 459 °C it has risen to 1115 kPa. Calculate (i) the equilibrium
E6B.8(b) Estimate the temperature at which the equilibrium constant for
constant, (ii) the standard reaction Gibbs energy, (iii) the standard enthalpy,
CuSO4 ⋅ 5 H2O(s) → CuSO4(s) + 5 H2O(g) becomes 1; assume pH2O = 1 bar .
(iv) the standard entropy of dissociation, all at 427 °C. Assume that the
⦵ ⦵
E6B.9(a) e dissociation vapour pressure of a salt A2B(s) A2(g) + B(g) at vapour behaves as a perfect gas and that ΔrH and ΔrS are independent of
367 °C is 208 kPa but at 477 °C it has risen to 547 kPa. For the dissociation temperature in the range given.

Problems
P6B.1 e equilibrium constant for the reaction N2(g) + 3 H2(g) 2 NH3(g) was then sealed. e mass of acid present in the sealed container was 0.0519 g.
is 2.13 × 106 at 288 K and 1.75 × 105 at 308 K. Calculate the standard reaction e experiment was repeated with the same container but at 471 K, and it was
enthalpy, assuming it to be constant over this temperature range. found that 0.0380 g of the acid was present. Calculate the equilibrium constant
for the dimerization of the acid in the vapour, and the standard enthalpy of
P6B.2 Consider the dissociation of methane, CH4(g), into the elements H2(g)
the dimerization reaction.
and C(s, graphite). (a) Given that ΔfH (CH4,g) = −74.85 kJ mol−1 and that ΔfS
⦵ ⦵

= −80.67 J K−1 mol−1 at 298 K, calculate the value of the equilibrium constant P6B.8 e dissociation of I2(g) can be monitored by measuring the total
⦵
at 298 K. (b) Assuming that ΔrH is independent of temperature, calculate K pressure, and three sets of results are as follows:
at 50 °C. (c) Calculate the degree of dissociation, α, of methane at 298 K and
T/K 973 1073 1173
a total pressure of 0.010 bar. (d) Without doing any numerical calculations,
explain how the degree of dissociation for this reaction will change as the 100p/atm 6.244 6.500 9.181
pressure and temperature are varied. 104nI2 2.4709 2.4555 2.4366
P6B.3 e equilibrium pressure of H2 over U(s) and UH3(s) between 450 K and where nI2 is the amount of I2 molecules introduced into a container of volume
715 K ts the expression ln(p/Pa) = A + B/T + C ln(T/K), with A = 69.32, B = 342.68 cm3. Calculate the equilibrium constants of the dissociation and the
−1.464 × 104 K, and C = −5.65. Find an expression for the standard enthalpy of standard enthalpy of dissociation assuming it to be constant over the range of
⦵
formation of UH3(s) and from it calculate ΔfC p. temperatures.
e 1980s saw reports of ΔfH (SiH 2) ranging from 243 to 289 kJ mol−1.
⦵
P6B.4 Use the following data on the reaction H2(g) + Cl2(g) 2 HCl(g) to P6B.9‡
determine the standard reaction enthalpy: If the standard enthalpy of formation is uncertain by this amount, by what
factor is the equilibrium constant for the formation of SiH2 from its elements
T/K 300 500 1000 uncertain at (a) 298 K, (b) 700 K?
K 4.0 × 1031 4.0 × 1018 5.1 × 108
P6B.10 Fuel cells show promise as power sources for automobiles. Hydrogen
P6B.5 e degree of dissociation, α, of CO2(g) into CO(g) and O2(g) at high and carbon monoxide have been investigated for use in fuel cells, so their
temperatures and 1 bar total pressure was found to vary with temperature as solubilities, s, in molten salts are of interest. eir solubilities in a molten
follows: NaNO3/KNO3 mixture were found to t the following expressions:
T/K 1395 1443 1498 768
log(sH2 /molcm −3 bar −1 ) = −5.39 −
α/10−4 1.44 2.50 4.71 T /K
980
⦵
Assume ΔrH to be constant over this temperature range, and calculate K, log(sCO /molcm −3 bar −1 ) = −5.98 −
T /K
⦵ ⦵ ⦵
ΔrG , ΔrH , and ΔrS at 1443 K. Make any justi able approximations. Calculate the standard molar enthalpies of solution of the two gases at 570 K.
P6B.6 e standard reaction enthalpy for the decomposition of CaCl2 ⋅ NH3(s) P6B.11 Find an expression for the standard reaction Gibbs energy at a
into CaCl2(s) and NH3(g) is nearly constant at +78 kJ mol−1 between 350 K temperature T′ in terms of its value at another temperature T and the
and 470 K. e equilibrium pressure of NH3 in the presence of CaCl2 ⋅ NH3 is coe cients a, b, and c in the expression for the molar heat capacity listed
⦵
1.71 kPa at 400 K. Find an expression for the temperature dependence of ΔrG in Table 2B.1 (Cp,m = a + bT + c/T 2). Evaluate the standard Gibbs energy of
in the same range. formation of H2O(l) at 372 K from its value at 298 K.
P6B.7 Ethanoic acid (acetic acid) was evaporated in container of volume P6B.12 Derive an expression for the temperature dependence of Kc for a
21.45 cm3 at 437 K and at an external pressure of 101.9 kPa, and the container general gas-phase reaction.

TOPIC 6C Electrochemical cells

Discussion questions
D6C.1 Explain why reactions that are not redox reactions may be used to D6C.4 Why is it necessary to measure the cell potential under zero-current
generate an electric current. conditions?
D6C.2 Distinguish between galvanic and electrolytic cells. D6C.5 Identify contributions to the cell potential when a current is being
drawn from the cell.
D6C.3 Explain the role of a salt bridge.
232 6 Chemical equilibrium

Exercises
You will need to draw on information from Topic 6D to complete the answers. (i) 2 Na(s) + 2 H2O(l) → 2 NaOH(aq) + H2(g)
E6C.1(a) Write the cell reaction and electrode half-reactions and calculate the (ii) H2(g) + I2(g) → 2 HI(aq)
standard potential of each of the following cells: (iii) H3O+(aq) + OH−(aq) → 2 H2O(l)

(i) Zn(s)|ZnSO4(aq)||AgNO3(aq)|Ag(s) E6C.3(a) Use the Debye–Hückel limiting law and the Nernst
equation to estimate the potential of the cell Ag(s)|AgBr(s)|KBr(aq,
(ii) Cd(s)|CdCl2(aq)||HNO3(aq)|H2(g)|Pt(s)
0.050 mol kg−1)||Cd(NO3)2(aq, 0.010 mol kg−1)|Cd(s) at 25 °C.
(iii) Pt(s)|K3[Fe(CN)6](aq),K4[Fe(CN)6](aq)||CrCl3(aq)|Cr(s) ⦵
E6C.3(b) Consider the cell Pt(s)|H2(g,p )|HCl(aq)|AgCl(s)|Ag(s), for which
the cell reaction is 2 AgCl(s) + H2(g) → 2 Ag(s) + 2 HCl(aq). At 25 °C and
E6C.1(b) Write the cell reaction and electrode half-reactions and calculate the a molality of HCl of 0.010 mol kg−1, Ecell = +0.4658 V. (i) Write the Nernst
standard potential of each the following cells: equation for the cell reaction. (ii) Calculate ΔrG for the cell reaction. (iii)
Assuming that the Debye–Hückel limiting law holds at this concentration,
(i) Pt(s)|Cl2(g)| HCl(aq)||K2CrO4(aq)|Ag2CrO4(s)|Ag(s)
calculate E (AgCl/Ag,Cl−).
⦵

(ii) Pt(s)|Fe3+(aq),Fe2+(aq)||Sn4+(aq),Sn2+(aq)|Pt(s)
E6C.4(a) e standard potential of a Daniell cell, with cell reaction Zn(s) +
(iii) Cu(s)|Cu2+(aq)||Mn2+(aq),H+(aq)|MnO2(s)|Pt(s)
Cu2+(aq) → Zn2+(aq) + Cu(s), is 1.10 V at 25 °C. Calculate the corresponding
standard reaction Gibbs energy.
E6C.2(a) Devise cells in which the following are the reactions and calculate the − +
E6C.4(b) e cell reaction for the ‘Bunsen cell’ is Zn(s) + 2 NO3 (aq) + 4 H (aq)
standard cell potential in each case: 2+
→ Zn (aq) + 2 H2O(l) + 2 NO2(g). e standard cell potential at 25 °C is
(i) Zn(s) + CuSO4(aq) → ZnSO4(aq) + Cu(s) −0.040 V. Calculate the electrical work that can be done by the cell.
(ii) 2 AgCl(s) + H2(g) → 2 HCl(aq) + 2 Ag(s) E6C.5(a) By how much does the cell potential change when Q is decreased by a
(iii) 2 H2(g) + O2(g) → 2 H2O(l) factor of 10 for a reaction in which ν = 2 at 298 K?
E6C.5(b) By how much does the cell potential change when Q is increased by a
E6C.2(b) Devise cells in which the following are the reactions and calculate the factor of 5 for a reaction in which ν = 3 at 298 K?
standard cell potential in each case:

Problems
You will need to draw on information from Topic 6D to complete the answers. P6C.4 State what is expected to happen to the cell potential when the speci ed
changes are made to the following cells. Con rm your prediction by using the
P6C.1 A fuel cell develops an electric potential di erence from the chemical
Nernst equation in each case.
reaction between reagents supplied from an outside source. What is the
standard potential of a cell fuelled by (a) hydrogen and oxygen, (b) the (a) e molar concentration of silver nitrate in the le -hand compartment
combustion of butane at 1.0 bar and 298 K? is increased in the cell Ag(s)|AgNO3(aq,mL)||AgNO 3(aq,mR)|Ag(s).
⦵
P6C.2 Calculate the value of ΔfG (H2O,l) at 298 K from the standard potential (b) e pressure of hydrogen in the le -hand compartment is increased in
⦵
of the cell Pt(s)|H2(g)|HCl(aq)|O2(g)|Pt(s), E cell = +1.23 V. the Pt(s)|H2(g,pL)|HCl(aq)|H2(g,pL)|Pt(s).
(c) e pH of the right-hand compartment is decreased in the cell
P6C.3 Although the hydrogen electrode may be conceptually the
Pt(s)|K3[Fe(CN)6](aq),K4[Fe(CN)6](aq)||Mn2+(aq),H+(aq)|MnO2(s)|Pt(s).
simplest electrode and is the basis for the choice of reference potential
in electrochemical systems, it is cumbersome to use. erefore, several (d) e concentration of HCl is increased in the cell Pt(s)|Cl2(g)|HCl(aq)||
substitutes for it have been devised. One of these alternatives is the HBr(aq)|Br2(l)|Pt(s).
quinhydrone electrode (quinhydrone, Q ⋅ QH2, is a complex of quinone, (e) Some iron(III) chloride is added to both compartments of the cell Pt(s)|
C6H4O2 = Q, and hydroquinone, C6H4O2H2 = QH2), where the concentrations Fe3+(aq),Fe2+(aq)||Sn4+(aq),Sn2+(aq)|Pt(s)
of Q ⋅ QH2 and QH2 are equal to each other. e electrode half-reaction
(f) Acid is added to both compartments of the cell Fe(s)|Fe2+(aq)||Mn2+(aq),
is Q(aq) + 2 H+(aq) + 2 e− → QH2(aq), E = +0.6994 V. If the cell
⦵

H+(aq)|MnO2(s)|Pt(s).
Hg(s)|Hg2Cl2(s)|HCl(aq)|Q ⋅ QH2|Au(s) is prepared, and the measured cell
potential is +0.190 V, what is the pH of the HCl solution?

TOPIC 6D Electrode potentials

Discussion questions
P6D.1 Describe a method for the determination of the standard potential of a P6D.2 Suggest reasons why a glass electrode can be used for the determination
redox couple. of the pH of an aqueous solution.

Exercises
E6D.1(a) Calculate the equilibrium constants of the following reactions at 25 °C (i) Sn(s) + Sn4+(aq) 2 Sn2+(aq)
from standard potential data: (ii) Sn(s) + 2 AgCl(s) SnCl2(aq) + 2 Ag(s)
 Exercises and problems 233

E6D.1(b) Calculate the equilibrium constants of the following reactions at standard Gibbs energy and enthalpy of the cell reaction at 25 °C. (ii) Estimate
⦵
25 °C from standard potential data: the value of ΔrG at 35 °C.
E6D.3(b) Calculate the standard potential of the cell Pt(s)|cystine(aq),
(i) Sn(s) + CuSO4(aq) Cu(s) + SnSO4(aq)
cysteine(aq)|| H+(aq)|O2(g)|Pt(s) and the standard Gibbs energy of the cell
(ii) Cu 2+(aq) + Cu(s) 2 Cu+(aq) reaction at 25 °C. Use E = −0.34 V for cystine(aq) + 2 H+(aq) + 2 e− →
⦵

E6D.2(a) e standard potential of the cell Ag(s)|AgI(s)|AgI(aq)|Ag(s) is +0.9509 V 2 cysteine(aq).

at 25 °C. Calculate the equilibrium constant for the dissolution of AgI(s). E6D.4(a) Can mercury produce zinc metal from aqueous zinc sulfate under
E6D.2(b) e standard potential of the cell Bi(s)|Bi2S3(s)|Bi2S3(aq)|Bi(s) is +0.96 V standard conditions?
at 25 °C. Calculate the equilibrium constant for the dissolution of Bi2S3(s). E6D.4(b) Can chlorine gas oxidize water to oxygen gas under standard
E6D.3(a) (i) Use the information in the Resource section to calculate the conditions in basic solution?
standard potential of the cell Ag(s)|AgNO3(aq)||Cu(NO3)2(aq)|Cu(s) and the

Problems
6D.1 Tabulated thermodynamic data can be used to predict the standard Write the Nernst equation for the cell, and (d) predict and calculate the
potential of a cell even if it cannot be measured directly. e standard Gibbs change in cell potential when the pH is changed to 7.0 at 298 K.
energy of the reaction K2CrO4(aq) + 2 Ag(s) + 2 FeCl3(aq) → Ag2CrO4(s) + ⦵
6D.4 e potential of the cell Pt(s)|H2(g,p )|HCl(aq,b)|Hg2Cl2(s)|Hg(l) has
2 FeCl2(aq) + 2 KCl(aq) is −62.5 kJ mol−1 at 298 K. (a) Calculate the standard
been measured with high precision with the following results at 25 °C:
potential of the corresponding galvanic cell and (b) the standard potential of
the Ag2CrO4/Ag,CrO2− 4 couple. b/(mmol kg−1) 1.6077 3.0769 5.0403 7.6938 10.9474
6D.2 A fuel cell is constructed in which both electrodes make use of the E/V 0.600 80 0.568 25 0.543 66 0.522 67 0.505 32
oxidation of methane. e le -hand electrode makes use of the complete Determine the standard cell potential and the mean activity coe cient of HCl
oxidation of methane to carbon dioxide and liquid water; the right-hand at these molalities. (Make a least-squares t of the data to the best straight line.)
electrode makes use of the partial oxidation of methane to carbon monoxide
and liquid water. (a) Which electrode is the cathode? (b) What is the cell 6D.5 For a hydrogen/oxygen fuel cell, with an overall four-electron cell
potential at 25 °C when all gases are at 1 bar? reaction 2 H2(g) + O2(g) → 2 H2O(l), the standard cell potential is +1.2335 V
at 293 K and +1.2251 V at 303 K. Calculate the standard reaction enthalpy and
6D.3 One ecologically important equilibrium is that between carbonate and entropy within this temperature range.
hydrogencarbonate (bicarbonate) ions in natural water. (a) e standard
Gibbs energies of formation of CO2− − −1 6D.6 e standard potential of the AgCl/Ag,Cl− couple ts the expression
3 (aq) and HCO3 (aq) are −527.81 kJ mol
and −586.77 kJ mol−1, respectively. What is the standard potential of the E /V = 0.236 59 − 4.8564 × 10−4(θ/°C) − 3.4205 × 10−6(θ/°C)2
⦵

HCO−3 /CO2− 3 ,H 2 couple? (b) Calculate the standard potential of a cell in which + 5.869 × 10−9(θ/°C)3
the cell reaction is Na2CO3(aq) + H2O(l) → NaHCO3(aq) + NaOH(aq). (c)
Calculate the standard Gibbs energy and enthalpy of formation of Cl−(aq) and
its standard entropy at 298 K.

FOCUS 6 Chemical equilibrium

Integrated activities
I6.1‡ orn et al. (J. Phys. Chem. 100, 14178 (1996)) carried out a study of mean ionic activity coe cient of ZnCl2 from the Debye–Hückel limiting law.
Cl2O(g) by photoelectron ionization. From their measurements, they report (f) Given that (∂Ecell/∂T)p = −4.52 × 10−4 V K−1, Calculate ∆rS and ∆rH.
ΔfH (Cl2O) = +77.2 kJ mol−1. ey combined this measurement with literature
⦵
⦵
I6.4 Careful measurements of the potential of the cell Pt|H2(g,p )|
data on the reaction Cl2O (g) + H2O(g) → 2 HOCl(g), for which K = 8.2 × 10−2 −1 −1
NaOH(aq,0.0100 mol kg ),NaCl(aq, 0.011 25 mol kg )|AgCl(s)|Ag(s) have
and ΔrS = +16.38 J K−1 mol−1, and with readily available thermodynamic data
⦵

⦵ been reported. Among the data is the following information:

on water vapour to report a value for ΔfH (HOCl). Calculate that value. All
quantities refer to 298 K. θ/°C 20.0 25.0 30.0
⦵ −1
I6.2 Given that ΔrG = −212.7 kJ mol for the reaction Zn(s) + Cu (aq)
2+
Ecell/V 1.04774 1.04864 1.04942
→ Zn2+(aq) + Cu(s) in the Daniell cell at 25 °C, and b(CuSO4) = 1.00 ×
Calculate pKw at these temperatures and the standard enthalpy and entropy
10−3 mol kg−1 and b(ZnSO4) = 3.00 × 10−3 mol kg−1, calculate (a) the ionic
of the autoprotolysis of water at 25.0 °C. Recall that Kw is the equilibrium
strengths of the solutions, (b) the mean ionic activity coe cients in the
constant for the autoprotolysis of liquid water.
compartments, (c) the reaction quotient, (d) the standard cell potential, and
(e) the cell potential. (Take γ+ = γ− = γ± in the respective compartments. Use I6.5 Measurements of the potential of cells of the type Ag(s)|AgX(s)|MX(b1)
the Debye–Hückel limiting law.) |MxHg|MX(b2)|AgX(s)|Ag(s), where MxHg denotes an amalgam and the
−1 electrolyte is LiCl in ethylene glycol, are given below for M = Li and X = Cl.
I6.3 Consider the cell, Zn(s)|ZnCl2(0.0050 mol kg )|Hg2Cl2(s)|Hg(l), for which
Estimate the activity coe cient at the concentration marked * and then use
the cell reaction is Hg2Cl2(s) + Zn(s) → 2 Hg(l) + 2 Cl−(aq) + Zn2+(aq). e cell
⦵ ⦵ this value to calculate activity coe cients from the measured cell potential
potential is +1.2272 V, E (Zn2+,Zn) = −0.7628 V, and E (Hg2Cl2,Hg) = +0.2676 V.
at the other concentrations. Base your answer on the Davies equation
(a) Write the Nernst equation for the cell. Determine (b) the standard cell ⦵
⦵ (eqn 5F.30b) with A = 1.461, B = 1.70, C = 0.20, and I = b/b . For b2 =
potential, (c) ΔrG, ΔrG , and K for the cell reaction, (d) the mean ionic activity −1
0.09141 mol kg :
and activity coe cient of ZnCl2 from the measured cell potential, and (e) the
234 6 Chemical equilibrium

b1/(mol kg−1) 0.0555 0.09141 0.1652 0.2171 1.040 1.350* of molar concentrations, calculate the e ciency of aerobic respiration under
these physiological conditions. (c) A typical diesel engine operates between Tc
E/V –0.0220 0.0000 0.0263 0.0379 0.1156 0.1336
= 873 K and Th = 1923 K with an e ciency that is approximately 75 per cent
I6.6‡ e table below summarizes the potential of the cell Pd(s)|H2(g, 1 bar)| of the theoretical limit of 1 − Tc/Th (see Topic 3A). Compare the e ciency
BH(aq, b), B(aq, b)|AgCl(s)|Ag(s). Each measurement is made at equimolar of a typical diesel engine with that of aerobic respiration under typical
concentrations of 2-aminopyridinium chloride (BH) and 2-aminopyridine physiological conditions (see part b). Why is biological energy conversion
⦵
(B). e data are for 25 °C and it is found that E = 0.222 51 V. Use the data more or less e cient than energy conversion in a diesel engine?
to determine pKa for the acid at 25 °C and the mean activity coe cient (γ±) I6.10 In anaerobic bacteria, the source of carbon may be a molecule other than
of BH as a function of molality (b) and ionic strength (I). Use the Davies glucose and the nal electron acceptor is some molecule other than O2. Could
equation (eqn 5F.30b) with A = 0.5091 and B and C are parameters that a bacterium evolve to use the ethanol/nitrate pair instead of the glucose/O2
depend upon the ions. pair as a source of metabolic energy?
b/(mol kg−1) 0.01 0.02 0.03 0.04 0.05 I6.11 e standard potentials of proteins are not commonly measured by
Ecell(25 °C)/V 0.74 452 0.72 853 0.71 928 0.71 314 0.70 809 the methods described in this chapter because proteins o en lose their
native structure and function when they react on the surfaces of electrodes.
b/(mol kg−1) 0.06 0.07 0.08 0.09 0.10 In an alternative method, the oxidized protein is allowed to react with
Ecell(25 °C)/V 0.70 380 0.70 059 0.69 790 0.69 571 0.69 338 an appropriate electron donor in solution. e standard potential of the
protein is then determined from the Nernst equation, the equilibrium
Hint: Use mathematical so ware or a spreadsheet. concentrations of all species in solution, and the known standard potential
I6.7 Read Impact 9 on the website of this text before attempting this problem. of the electron donor. is method can be illustrated with the protein
Here you will investigate the molecular basis for the observation that the cytochrome c. e one-electron reaction between cytochrome c, cyt, and
hydrolysis of adenosine triphosphate (ATP) to adenosine diphosphate (ADP) 2,6-dichloroindophenol, D, can be followed spectrophotometrically because
is exergonic at pH = 7.0 and 310 K. (a) It is thought that the exergonicity each of the four species in solution has a distinct absorption spectrum.
of ATP hydrolysis is due in part to the fact that the standard entropies of Write the reaction as cytox + Dred cyt red + Dox, where the subscripts ‘ox’
⦵
hydrolysis of polyphosphates are positive. Why would an increase in entropy and ‘red’ refer to oxidized and reduced states, respectively. (a) Consider E cyt
⦵
accompany the hydrolysis of a triphosphate group into a diphosphate and and E D to be the standard potentials of cytochrome c and D, respectively.
a phosphate group? (b) Under identical conditions, the Gibbs energies of Show that, at equilibrium, a plot of ln([D ox]eq/[D red]eq) versus ln([cytox]eq/
⦵ ⦵
hydrolysis of H 4ATP and MgATP2−, a complex between the Mg2+ ion and [cytred]eq) is linear with slope of 1 and y-intercept F(E cyt − E D)/RT, where
ATP4−, are less negative than the Gibbs energy of hydrolysis of ATP4−. is equilibrium activities are replaced by the numerical values of equilibrium
observation has been used to support the hypothesis that electrostatic molar concentrations. (b) e following data were obtained for the reaction
repulsion between adjacent phosphate groups is a factor that controls the between oxidized cytochrome c and reduced D in a pH 6.5 bu er at 298 K.
exergonicity of ATP hydrolysis. Provide a rationale for the hypothesis and e ratios [Dox]eq/[D red]eq and [cyt ox]eq/[cyt red]eq were adjusted by titrating a
discuss how the experimental evidence supports it. Do these electrostatic solution containing oxidized cytochrome c and reduced D with a solution
e ects contribute to the ∆rH or ∆rS terms that determine the exergonicity of of sodium ascorbate, which is a strong reductant. From the data and
the reaction? Hint: In the MgATP2− complex, the Mg2+ ion and ATP4− anion the standard potential of D of 0.237 V, determine the standard potential
form two bonds: one that involves a negatively charged oxygen belonging to cytochrome c at pH 6.5 and 298 K.
the terminal phosphate group of ATP4− and another that involves a negatively
charged oxygen belonging to the phosphate group adjacent to the terminal [Dox]eq/[Dred]eq 0.00279 0.00843 0.0257 0.0497 0.0748 0.238 0.534
phosphate group of ATP4−. [cytox]eq/[cytred]eq 0.0106 0.0230 0.0894 0.197 0.335 0.809 1.39

I6.8 Read Impact 9 on the website of this text before attempting this problem. I6.12‡ e dimerization of ClO in the Antarctic winter stratosphere is believed
To get a sense of the e ect of cellular conditions on the ability of adenosine to play an important part in that region’s severe seasonal depletion of ozone.
triphosphate (ATP) to drive biochemical processes, compare the standard e following equilibrium constants are based on measurements on the
Gibbs energy of hydrolysis of ATP to ADP (adenosine diphosphate) with the reaction 2 ClO(g) → (ClO)2(g).
reaction Gibbs energy in an environment at 37 °C in which pH = 7.0 and the
ATP, ADP, and Pi− concentrations are all 1.0 mmol dm−3. T/K 233 248 258 268 273 280
I6.9 Read Impact 9 on the website of this text before attempting this problem. K 4.13 × 108 5.00 × 107 1.45 × 107 5.37 × 106 3.20 × 106 9.62 × 105
Under biochemical standard conditions, aerobic respiration produces
approximately 38 molecules of ATP per molecule of glucose that is completely T/K 288 295 303
oxidized. (a) What is the percentage e ciency of aerobic respiration under K 4.28 × 105 1.67 × 105 6.02 × 104
biochemical standard conditions? (b) e following conditions are more ⦵ ⦵
(a) Derive the values of ΔrH and ΔrS for this reaction. (b) Compute the
likely to be observed in a living cell: pCO2 = 5.3 × 10−2 atm, pO2 = 0.132 atm,
standard enthalpy of formation and the standard molar entropy of (ClO)2
[glucose] = 5.6 pmol dm−3, [ATP] = [ADP] = [Pi] = 0.10 mmol dm−3, pH = 7.4,
given ΔfH (ClO,g) = +101.8 kJ mol−1 and S m(ClO,g) = 226.6 J K−1 mol−1.
⦵ ⦵

T = 310 K. Assuming that activities can be replaced by the numerical values