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Solutions to exercises
Discussion questions
E10.1(b) The Debye–Hückel theory is a theory of the activity coefficients of ions in solution. It is the coulombic
(electrostatic) interaction of the ions in solution with each other and also the interaction of the ions
with the solvent that is responsible for the deviation of their activity coefficients from the ideal value
of 1. The electrostatic ion–ion interaction is the stronger of the two and is fundamentally responsible
for the deviation. Because of this interaction there is a build up of charge of opposite sign around any
given ion in the overall electrically neutral solution. The energy, and hence, the chemical potential
of any given ion is lowered as a result of the existence of this ionic atmosphere. The lowering of the
chemical potential below its ideal value is identified with a non-zero value of RT ln γ± . This non-zero
value implies that γ± will have a value different from unity which is its ideal value. The role of the
solvent is more indirect. The solvent determines the dielectric constant, , of the solution. Looking
at the details of the theory as outlined in Justification 10.2 we see that enters into a number of the
basic equations, in particular, Coulomb’s law, Poisson’s equation, and the equation for the Debye
length. The larger the dielectric constant, the smaller (in magnitude) is ln γ± .
E10.2(b) The potential difference between the electrodes in a working electrochemical cell is called the cell
potential. The cell potential is not a constant and changes with time as the cell reaction proceeds.
Thus the cell potential is a potential difference measured under non-equilibrium conditions as electric
current is drawn from the cell. Electromotive force is the zero-current cell potential and corresponds
to the potential difference of the cell when the cell (not the cell reaction) is at equilibrium.
E10.3(b) The pH of an aqueous solution can in principle be measured with any electrode having an emf that is
sensitive to H+ (aq) concentration (activity). In principle, the hydrogen gas electrode is the simplest
and most fundamental. A cell is constructed with the hydrogen electrode being the right-hand electrode
and any reference electrode with known potential as the left-hand electrode. A common choice is
the saturated calomel electrode. The pH can then be obtained from eqn 10.43 by measuring the emf
(zero-current potential difference), E, of the cell. The hydrogen gas electrode is not convenient to
use, so in practice glass electrodes are used because of ease of handling.
Numerical exercises
E10.4(b) NaCl(aq) + AgNO3 (aq) → AgCl(s) + NaNO3 (aq)
NaCl, AgNO3 and NaNO3 are strong electrolytes; therefore the net ionic equation is
Ag+ (aq) + Cl− (aq) → AgCl(s)
r H −
−
= f H −
−
(AgCl, s) − f H −
−
(Ag+ , aq) − f H −
−
(Cl− , aq)
= (−127.07 kJ mol−1 ) − (105.58 kJ mol−1 ) − (−167.16 kJ mol−1 )
= −65.49 kJ mol−1
E10.5(b) PbS(s)
Pb2+ (aq) + S2− (aq)
ν
KS = aJ J
J
Since the solubility is expected to be low, we may (initially) ignore activity coefficients. Hence
b(Pb2+ ) b(S2− )
KS = × b(Pb2+ ) = b(S2− ) = S
b−
− b−
−
148 INSTRUCTOR’S MANUAL
S2
KS =
(b −
− )2
S = (KS )1/2 b −
−
−r G−
−
Use ln KS = to obtain KS
RT
r G −
−
= f G−
− 2−
(S , aq) + f G−
−
(Pb2+ , aq) − r G−
−
(PbS, s)
= (+85.8 kJ mol−1 ) + (−24.43 kJ mol−1 ) − (−98.7 kJ mol−1 )
= 160.07 kJ mol−1
−160.07 × 103 J mol−1
ln KS = = −64.61
(8.314 J K−1 mol−1 ) × (298 K)
KS = e−64.61 = 8.7 × 10−29
S2
KS = S = (KS )1/2 b −
−
= (8.735 × 10−29 )1/2 = 9.3 × 10−15 mol kg−1
b−
− 2
We have hyd G−
−
(Cl− ) = −379 kJ mol−1 [Exercise 10.6a]
So hyd G−
−
(NO− −1
3 ) = (0.958) × (−379 kJ mol ) = −363 kJ mol
−1
E10.7(b) I = 21 (bi /b −
− 2
)zi [10.18]
i
and for an Mp Xq salt, b+ /b −
−
= pb/b −
−
, b− /b −
−
= qb/b −
−
, so
2
I = 21 (pz+ 2
+ qz− )b/b −
−
b b
(b) I (Ba(NO3 )2 ) = 21 (22 + 2 × 12 ) −
−
=3 − = 0.890
b b−
0.890 −
b= b
−
= 0.2967 mol kg−1
3
E10.12(b) Since the solutions are dilute, use the Debye–Hückel limiting law
= 0.125
B = 1.3
E10.15(b) PbI2 (s)
PbI2 (aq) KS = 1.4 × 10−8
r G −
−
= −RT ln KS = −(8.314 J K−1 mol−1 ) × (298.15 K) × ln(1.4 × 10−8 )
= 44.83 kJ mol−1
r G −
−
= f G−
−
(PbI2 , aq) − f G−
−
(PbI2 , s)
f G−
−
(PbI2 , aq) = r G−
−
+ f G −
−
(PbI2 , s)
= 44.83 kJ mol−1 − 173.64 kJ mol−1
= −128.8 kJ mol−1
E10.16(b) The Nernst equation may be applied to half-cell potentials as well as to overall cell potentials.
RT a(H+ )
E(H+ /H2 ) = ln
F (fH2 /p −
− )1/2
RT a2 (H+ ) RT γ± b2
E = E2 − E1 = ln +
[fH2 is constant] = ln
F a1 (H ) F γ± b 1
(0.830) × (5.0 × 10−2 )
= (25.7 mV) × ln = +56.3 mV
(0.929) × (5.0 × 10−3 )
E10.17(b) Identify electrodes using species with the desired oxidation states.
E10.18(b) The cell notation specifies the right and left electrodes. Note that for proper cancellation we must
equalize the number of electrons in half-reactions being combined.
(a) R: Ag2 CrO4 (s) + 2e− → 2Ag(s) + CrO2− 4 (aq) +0.45 V
L: Cl2 (g) + 2e− → 2Cl− (aq) +1.36 V
Overall (R − L): Ag2 CrO4 (s) + 2Cl− (aq) → 2Ag(s) + CrO2−
4 (aq) + Cl2 (g) −0.91 V
(b) R: Sn4+ (aq) + 2e− → Sn2+ (aq) +0.15 V
L: 2Fe3+ (aq) + 2e− → 2Fe2+ (aq) +0.77 V
Overall (R − L): Sn4+ (aq) + 2Fe2+ (aq) → Sn2+ (aq) + 2Fe3+ (aq) −0.62 V
(c) R: MnO2 (s) + 4H+ (aq) + 2e− → Mn2+ (aq) + 2H2 O(l) +1.23 V
L: Cu2+ (aq) + 2e− → Cu(s) +0.34 V
Overall (R − L): Cu(s) + MnO2 (s) + 4H+ (aq) → Cu2+ (aq) + Mn2+ (aq)
+ 2H2 O(l) +0.89 V
EQUILIBRIUM ELECTROCHEMISTRY 151
Na(s)|NaOH(aq)|H2 (g)|Pt
r G−
−
= −νF E −
−
[10.32]
−
(a) R: S2 O2− 2−
8 (aq) + 2e → 2SO4 (aq) +2.05 V
+ 1.51 V
L: I2 (s) + 2e− → 2I− (aq) +0.54 V
r G −
−
= (−2) × (96.485 kC mol−1 ) × (1.51 V) = −291 kJ mol−1
152 INSTRUCTOR’S MANUAL
(b) Zn2+ (aq) + 2e− → Zn(s) −0.76 V
E−
−
= −0.63 V
Pb2+ (aq) + 2e− → Pb(s) −0.13 V
r G−
−
= (−2) × (96.485 kC mol−1 ) × (−0.63 V) = +122 kJ mol−1
E10.23(b) (a) A new half-cell may be obtained by the process (3) = (1) − (2), that is
(3) 2H2 O(l) + Ag(s) + e− → H2 (g) + 2OH− (aq) + Ag+ (aq)
But, E3−
−
= E1−
−
− E2−
−
, for the reason that the reduction potentials are intensive, as opposed to
extensive, quantities. Only extensive quantities are additive. However, the r G− −
values of the
half-reactions are extensive properties, and thus
r G3−
−
= r G1−
−
− r G2−
−
−ν3 F E3−
−
= −ν1 F E1−
−
− (−ν2 F E2−
−
)
ν1 E1−
−
− ν2 E2−
−
(2) × (−0.828 V) − (1) × (0.799 V)
E3−
−
= = = −2.455 V
ν3 1
(b) The complete cell reactions is obtained in the usual manner. We take (2) × (2) − (1) to obtain
2Ag+ (aq) + H2 (g) + 2OH− (aq) → 2Ag(s) + 2H2 O(l)
E−
−
(cell) = ER−
−
− EL−
−
= E2−
−
− E1−
−
= (0.799 V) − (−0.828 V) = +1.627 V
RT 2RT
Hence, E = E −
−
− ln(γ±4 b4 ) = E −
−
− ln(γ± b)
2F F
= +300.3 kJ mol−1
−
∂r G−
r G −
− − H−
−
= −r S −
−
[r G−
−
r
= = r H − T r S]
∂T p T
(239 − 300.3) kJ mol−1
= = −0.206 kJ mol−1 K −1
298.15 K
Therefore, r G−
−
(308 K) ≈ (239) + (10 K) × (−0.206 K −1 ) kJ mol−1 ≈ +237 kJ mol−1
νF E −
−
E10.26(b) In each case ln K = [10.36]
RT
(a) Sn(s) + CuSO4 (aq)
Cu(s) + SnSO4 (aq)
R: Cu (aq) + 2e− → Cu(s) +0.34 V
2+
+ 0.48 V
L: Sn2+ (aq) + 2e− → Sn(s) −0.14 V
(2) × (0.48 V)
ln K = = +37.4, K = 1.7 × 1016
25.693 mV
−0.36 V
ln K = = −14.0, K = 8.2 × 10−7
25.693 mV
We see that (3) = (1) + (2); therefore (see the solution to Exercise 10.23(b))
ν1 E1−
−
+ ν2 E2−
−
(1) × (1.81 V) + (2) × (−0.28 V)
E3 = = = 0.42 V
ν3 3
154 INSTRUCTOR’S MANUAL
Then,
R: Co3+ (aq) + 3e− → Co(s) ER−
−
= 0.42 V
L: 3AgCl(s) + 3e− → 3Ag(s) + 3Cl− (aq) EL−
−
= 0.22 V
R − L: Co3+ (aq) + 3Cl− (aq) + 3Ag(s) → 3AgCl(s) + Co(s)
E−
−
= ER−
−
− EL−
−
= (0.42 V) − (0.22 V) = +0.20 V
E10.28(b) First assume all activity coefficients are 1 and calculate KS◦ , the ideal solubility product constant.
(1) AgI(s)
Ag+ (aq) + I− (aq)
S(AgI) = b(Ag+ ) = b(I− ) because all stoichiometric coefficients are 1.
b(Ag+ )b(I− ) S2
Thus KS◦ = = = (1.2 × 10−8 )2 = 1.44 × 10−16
b−
−2 b−
−2
= 1.13 × 10−97
RT 2RT RT
E = E−
−
− ln a(H+ )4 = E −
−
− ln a(H+ ) = E −
−
+ 2 × (2.303) × × pH
2F F F
F E + 0.15 V 1.15 V
pH = × (E − E −
−
)= = = 9.72
2 × (2.303RT ) 0.1183 V 0.1183 V
(b) KS = K −1 = e−224 ≈ 10−98 , since the cell reaction is the reverse of the solubility equilibrium.
2 3
b b
(a) KS ≈ 10−98 = − (Bi 3+
) × (S 2−
) = (2S)2 × (3S)3 = 108S 5
b− b−
−
1/5
10−98
S= ≈ 10−20 mol L−1
108
Solutions to problems
Solutions to numerical problems
P10.1 We require two half-cell reactions, which upon subtracting one (left) from the other (right), yields the
given overall reaction (Section 10.4). The half-reaction at the right electrode corresponds to reduction,
that at the left electrode to oxidation, though all half-reactions are listed in Table 10.7 as reduction
reactions.
E−
−
RT KS (PbSO4 )
E = (0.98 V) − ln
2F KS (Hg2 SO4 )
25.693 × 10−3 V 1.6 × 10−8
= (0.98 V) − × ln
2 6.6 × 10−7
[Table 10.6, 4th Edition, or CRC Handbook]
= (0.98 V) + (0.05 V) = +1.03 V
d ln Kw r H −
−
= [9.26]
dT RT 2
d
Hence, r H −
−
= −(2.303)RT 2 (pKw )
dT
d pKw pKw
then with ≈
dT T
13.79 − 14.23
r H −
−
≈ −(2.303) × (8.314 J K −1 mol−1 ) × (298.15 K)2 ×
10 K
= +74.9 kJ mol−1
r G −
−
= −RT ln Kw = 2.303RT × pKw = +80.0 kJ mol−1
r H −
− − G−
−
r S −
−
= −17.1 J K−1 mol−1
r
=
T
See the original reference for a careful analysis of the precise data.
P10.7 The cells described in the problem are back-to-back pairs of cells each of the type
Ag(s)|AgX(s)|MX(b1 )|Mx Hg(s)
Hg
R: M+ (b1 ) + e− −→ Mx Hg(s) (Reduction of M+ and formation of amalgam)
L: AgX(s) + e− → Ag(s) + X− (b1 )
Hg
R − L: Ag(s) + M+ (b1 ) + X− (b1 ) −→ Mx Hg(s) + AgX(s) ν=1
a(Mx Hg)
Q=
a(M+ )a(X− )
RT
E = E−
−
− ln Q
F
For a pair of such cells back to back,
Ag(s)|AgX(s)|MX(b1 )|Mx Hg(s)|MX(b2 )|AgX(s)|Ag(s)
RT RT
ER = E −
−
− ln QR EL = E −
−
− ln QL
F F
−RT QL RT (a(M+ )a(X− ))L
E= ln = ln
F QR F (a(M+ )a(X− ))R
(Note that the unknown quantity a(Mx Hg) drops out of the expression for E.)
γ+ b+ γ− b− b 2
a(M+ )a(X− ) = = γ±
2
(b+ = b− )
b−
− b−
− b−
−
A more precise procedure is described in the original references for the temperature dependence of
E−
−
(Ag, AgCl, Cl− ), see Problem 10.10.
P10.10 The method of the solution is first to determine r G−
−
, r H −
−
, and r S −
−
for the cell reaction
1
2 H2 (g) + AgCl(s) → Ag(s) + HCl(aq)
and then, from the values of these quantities and the known values of f G−
−
, f H −
−
, and S −
−
for
− −
− −
− −
− −
all the species other than Cl (aq), to calculate f G , f H , and S for Cl (aq).
r G−
−
= −νF E −
−
At 298.15 K(25.00◦ C)
E−
−
/V = (0.23659) − (4.8564 × 10−4 ) × (25.00) − (3.4205 × 10−6 ) × (25.00)2
+ (5.869 × 10−9 ) × (25.00)3 = +0.22240 V
Therefore, G−
−
= −(96.485 kC mol−1 ) × (0.22240 V) = −21.46 kJ mol−1
− − − − − ◦C
∂r G−
∂E ∂E
r S −
−
=− = × νF = νF [dθ/◦ C = dT /K] (a)
∂T p ∂T p ∂θ p K
−−
∂E
∂θ p
= (−4.8564 × 10−4 /◦ C) − (2) × (3.4205 × 10−6 θ/(◦ C)2 )
V
+ (3) × (5.869 × 10−9 θ 2 /(◦ C)3 )
∂E −−
∂θ p
= (−4.8564 × 10−4 ) − (6.8410 × 10−6 (θ/◦ C)) + (1.7607 × 10−8 (θ/◦ C)2 )
V/◦ C
Therefore, at 25.00◦ C,
− −
∂E
= −6.4566 × 10−4 V/◦ C
∂θ p
and
−
∂E −
= (−6.4566 × 10−4 V/◦ C) × (◦ C/K) = −6.4566 × 10−4 V K−1
∂T p
EQUILIBRIUM ELECTROCHEMISTRY 159
and r H −
−
= r G −
−
+ T r S −
−
= −131.25 kJ mol−1
Similarly, f H −
−
(Cl− ) = r H −
−
+ f H −
−
(AgCl) = (−40.03) − (127.07 kJ mol−1 )
= −167.10 kJ mol−1
For the entropy of Cl− in solution we use
r S −
−
= S−
−
(Ag) + S −
− +
(H ) + S −
−
(Cl− ) − 21 S −
−
(H2 ) − S −
−
(AgCl)
with S −
− +
(H ) = 0. Then,
S−
−
(Cl− ) = r S −
−
− S−
−
(Ag) + 21 S −
− (H ) + S −
2
− (AgCl)
= (−62.30) − (42.55) + 21 × (130.68) + (96.2) = +56.7 J K−1 mol−1
∂G
P10.12 (a) From = V [5.10]
∂p T
∂r G
we obtain = r V
∂p T
Substituting r G = −νF E [10.32] yields
∂E r V
=−
∂p T ,n νF
(b) The plot (Fig. 10.1) of E against p appears to fit a straight line very closely. A linear regression
analysis yields
Slope = 2.840 × 10−3 mV atm−1 , standard deviation = 3 × 10−6 mV atm−1
Intercept = 8.5583 mV, standard deviation = 2.8 × 10−3 mV
R = 0.999 997 01 (an extremely good fit)
From r V
∂E (−2.666 × 10−6 m3 mol−1 )
=−
∂p T ,n 1 × 9.6485 × 104 C mol−1
Pa m3 m3 V
Since J = V C = Pa m3 , C = or =
V C Pa
160 INSTRUCTOR’S MANUAL
13
12
11
10
8
0 500 1000 1500
Figure 10.1
Therefore
∂E 2.666 × 10−6 V 1.01325 × 105 Pa
= × = 2.80 × 10−6 V atm−1
∂p T ,n 9.6485 × 104 Pa atm
E = a + bp + cp 2
yields
a = 8.5592 mV, standard deviation = 0.0039 mV
b = 2.835 × 10−3 mV atm−1 , standard deviation = 0.012 × 10−3 mV atm−1
c = 3.02 × 10−9 mV atm−2 , standard deviation = 7.89 × 10−9 mV atm−1
R = 0.999 997 11
This regression coefficient is only marginally better than that for the linear fit, but the uncertainty
in the quadratic term is > 200 per cent.
∂E
= b + 2cp
∂p T
∂E
The slope changes from = b = 2.835 × 10−3 mV atm−1
∂p min
∂E
to = b + 2c(1500 atm) = 2.836 × 10−3 mV atm−1
∂p max
∂E
We conclude that the linear fit and constancy of are very good.
∂p
EQUILIBRIUM ELECTROCHEMISTRY 161
(d) We can obtain an order of magnitude value for the isothermal compressibility from the value of c.
∂ 2E 1 ∂r V
= − = 2c
∂p 2 νF ∂p T
1 ∂r V 2νcF
(κT )cell = − =
V ∂p T V
2(1) × (3.02 × 10−12 V atm−2 ) × (9.6485 × 104 C mol−1 ) × 82.058 cm3 atm
8.3145 J
(κT )cell =
1 cm3 18.016 g
0.996 g × 1 mol
= 0.75 eV
−
− −
−
r S =S (Uup, s) + S −
− +
(H , aq) − 21 S −
−
(H2 , g) − S −
−
(Uup+ , aq)
= (0.69) + (0) − 21 × (1.354) − (1.34) meV K −1 = −1.33 meV K−1
Figure 10.2
r G−
−
= r H −
−
− T r S −
−
= (0.75 eV) + (298.15 K) × (1.33 meV K −1 ) = +1.15 eV
b(M+ ) = S, b(X− ) = S + C
Ks = S(S + C), or S 2 + CS − Ks = 0
1 2 1/2 1 1 4Ks 1/2 1
which solves to S = 2 (C + 4Ks ) − 2C or S = 2C 1+ 2 − 2C
C
If 4Ks C 2 ,
2Ks Ks
S ≈ 2 C 1 + 2 − 21 C (1 + x)1/2 ≈ 1 + 21 x + · · · ≈
1
C C
Ks = S (S + C) × e−4.606AC
1/2
Ks
We solve S 2 + S C − =0
γ±2
1/2
1 2 4Ks 1 Ks
to get S = C + 2 − C≈ [as in Problem 10.21]
2 γ± 2 Cγ±2
Ks e−4.606AC
1/2
C
P10.25 The half-reactions involved are:
−
−
R: cyt ox + e− → cytred Ecyt
− −
−
L: Dox + e → Dred ED
The overall cell reaction is:
−
− −
−
R − L = cyt ox + Dred
cytred + Dox E−
−−
= Ecyt − ED
(a) The Nernst equation for the cell reaction is
RT [cyt red ][Dox ]
E=E− ln
F [cyt ox ][Dred ]
at equilibrium, E = 0; therefore
[cytred ]eq [Dox ]eq F −
− −
−
ln = Ecyt − ED
[cyt ox ]eq [Dred ]eq RT
[Dox ]eq [cyt]ox F − − −
−
ln = ln + Ecyt − ED
[Dred ]eq [cyt]red RT
[Dox ]eq [cyt]ox
Therefore a plot of ln against ln is linear with a slope of one and an
[Dred ]eq [cyt]red
F
−
− −
−
intercept of Ecyt − ED
RT
164 INSTRUCTOR’S MANUAL
–1
y = –1.2124 + 1.0116x R = 0.99427
–2
ln([Dox]eq / [Dred]eq)
–3
–4
–5
–6
–5 –4 –3 –2 –1 0 1
ln([cytox]eq / [cytred]eq) Figure 10.3
Solutions to application
P10.27 (a) molalityH2 SO4 = b(d) = a(d − d25 ) + c(d − d25 )2
where d is density in g cm−3 at 25 ◦ C, a = 14.523 mol kg−1 (g cm−3 )−1 ,
c = 25.031 mol kg−1 (g cm−3 )−2 , and d25 = 0.99707 g cm−3 .
For 1 kg solvent (mH2 O = 1 kg):
mH2 SO4 b × 100
mass %H2 SO4 = 100 = mH✘
mH2 SO4 + mH2 O b + mH ✘ 2O
m✘
2 SO4✘H2 O
100 × b(d)
mass %H2 SO4 (d) = where mH2 SO4 = 0.09807 kg mol−1
b(d) + mH 1SO
2 4
an equation for the solution molarity is deduced with a unit analysis.
mass %H2 SO4 (d) 10✚
✚
3 cm 3 kg
molarityH2 SO4 (d) = b(d) × 1 − d×
100 L 10✚
✚
3g
EQUILIBRIUM ELECTROCHEMISTRY 165
0
1 1.1 1.2 1.3 1.4
Density/(g / mL) Figure 10.4(a)
40
Mass Percentage
Sulfuric Acid
30
20
10
0
1 1.1 1.2 1.3 1.4
Density/(g / mL) Figure 10.4(b)
5
4
3
2
1
0
1 1.1 1.2 1.3 1.4
Density/(g / mL) Figure 10.4(c)
(b) cell: Pb(s) | PbSO4 (s) | H2 SO4 (aq) | PbO2 (s) | PbSO4 (s) | Pb(s)
cathode: PbO2 (s) + 3H+ (aq) + HSO− −
4 (aq) + 2e → PbSO4 (s) + 2H2 O(l)
−
−
Ecathode = 1.6913 V
anode: PbSO4 (s) + H+ (aq) + 2e− → Pb(s) + HSO− 4
−
−
Eanode = −0.3588 V
net: PbO2 (s) + Pb(s) + 2H+ (aq) + 2HSO− 4 (aq) → 2PbSO4 (s) + 2H2 O(l)
−
−
E−
−
= Ecathode ◦
− Eanode = 2.0501V (eqn 10.38)
r G−
−
= −νF E −
−
= −(2)(9.64853 × 104 C mol−1 )(2.0501 V)
f H −
−
values of Table 2.6 and the CRC Handbook of Chemistry and Physics are used in the
−
−
r H calculation.
r H −
−
= 2f H −
−
(PbSO4 ) + 2f H −
−
(H2 O(l)) − f H −
−
(PbO2 ) − f H −
−
(Pb)
−2f H −
− +
(H ) − 2f H −
−
(HSO−
4)
= 2(−919.94 kJ mol−1 ) + 2(−285.83 kJ mol−1 ) − (−277.4 kJ mol−1 )
−2(−887.34 kJ mol−1 )
r H −
−
= −359.5 kJ mol−1
r H −
− − G−
− −359.5 kJ mol−1 − (−395.6 kJ mol−1 )
r S −
− r
= =
T 298.15 K
= 121 J K−1 mol−1 (eqn 4.39)
r S −
−
E−
−
(15◦ C) = E −
−
(25◦ C) + E −
−
= E−
−
(25◦ C) + T (eqn 10.45)
νF
✟✘ ✘−1✘
K−1
(121 J ✟ mol )
= 2.0501 V + ✘ ✘
−1 (10 K)
✘
2(96485 C mol )
= 2.0501V + 0.006V = 2.0507V
The temperature difference makes a negligibly small difference in the cell potential.
When Q = 6.0 × 10−5 ,
RT
E = E−
−
− ln Q (eqn 10.34)
νF
✟✘ ✘−1✘
K −1
(8.31451 J ✟ mol )(298.15 K)
= 2.0501 V − ✘
✘−1 ln(6.0 × 10−5 )
2(96485 C ✘mol )
= 2.1750 V
(c) The general form of the reduction half-reaction is: ox + νe− + νH H+ + aA → red + xX using
eqn 10.34,
x
ared aX
−
− RT −
− RT
E =E − ln Q = E − ln νH a
νF νF aox aH + aA
RT 1
= E−
−
− ln νH
νF aH+
(all species other than acids are at unit activity in a Pourboix diagram)
νH RT νH RT ln(10)
= E−
−
+ ln aH+ = E −
−
+ log aH+
νF νF
−
− νH RT ln(10)
=E − pH (eqn 9.29)
ν F
ν
E = E−
− H
− (0.05916V) pH
ν
EQUILIBRIUM ELECTROCHEMISTRY 167
Since νH = O, E = E −
−
= −0.3588 V at all pH values in the Pourboix diagram.