CHAPTER 7

1.

= 5 8.8542 1012 Farad/m; A = 4 1010 m2 = 1.257 109 m2; D = 5 109 m.

C = A/D = 3.495 1012 Farad. Q = CV = 3.495 1013 C = 3.495 1013 C/96485.3 C/mol =
3.623 1017 mol unipositive ions = 2.181 107 unipositive ions.

2.

The two half-cell reactions

MnO2(s) + 4H+ (aq) + 2e Mn2+ (aq) + 2H2O (l) = +1.23V
O2 (g) + 4H+ (aq) + 4e 2H2O (l) = +1.229V
Reverse the first, double, and add to the second
O2 (g) + 2Mn2+ (aq) + 2H2O 2MnO2(s) + 4H+ (aq) (l) = 0.001V
Q=

[H + ]4
0.14
=
= 5 10 2
pO2 [Mn 2+ ]2 0.2 0.12

E = E

RT
8.3145 J mol1 K 1 298 K
lnQ = 0.001 V
ln(5 10 2 ) = 0.018 V
1
eF
4 96485.3 C mol

G = eF = 7.036 kJ mol1
At equilibrium, = 0, and therefore

RT
4 96485.3 C mol1 0.001 V
lnQ = E = 0.001 V, so lnQ =
= 0.158
eF
8.3145 J mol1 K 1 298 K
Q=

3.

4.

0.14
= 0.856 so [Mn 2+ ]2 = 0.000584, so [Mn 2+ ] = 0.0242 M
2+ 2
0.2 [Mn ]

Double and reverse the first reaction

2 MDHA + 2H+ + 2e 2 Asc
Add the second reaction
Asc DHA + H+ + 2e
Result
2 MDHA + H+ Asc + DHA
G = eF = 48.2 kJ mol1.

= 0.330 V
= +0.08 V
= 0.25 V

First evaluate the reduction potential for the first reaction at pH 7

NO3 + 3H+ + 2e HNO2 + H2O
= +0.934 V

RT
8.3145 J mol1 K 1 298 K 1
E = E
lnQ = 0.934V
ln
7
eF
2 96485.3 C mol1
10

= 0.313 V
3

Then calculate G: G = eF = 60.4 kJ mol1

Now calculate G for the second reaction HNO2 NO2 + H+
G = RT ln K = 8.3145 J mol1K1 298 K ln 10 3.398 = 19.4 kJ mol1

Convert to G: G = G + RT ln Q = 19.4 kJ mol1 + 8.3145 J mol1K1 298 K ln 107

Chapter 7 solutions manual to accompany 5th edition of Physical Chemistry

Tinoco, Sauer, Wang, Puglisi Harbison, Rovnyak

= 20.5 kJ mol1
Add the two reactions NO3 + 2H+ + 2e NO2 + H2O
G = 81.0 kJ mol1
And finally, convert back to volts: = G/eF = 81.0 kJ mol1/(2 96485.3 C mol1)
= 0.420 V.
5.

Full reaction Fe(CN)63 + Cyt red Fe ( CN )6 + Cyt ox

4

E =

RT
8.3145 J mol1 K 1 298 K 2.0
lnQ =
ln
= 0.038 V
eF
2 96485.3 C mol1
0.1

a)

At equilibrium
Subtract Fe(CN)63 + e Fe(CN)64
= +0.440 V

Leaves Cytred Cytox + e

= 0.402 V
Write it as a reduction: Cytox + e Cytred = 0.402 V

b)

O2 + 4H + + 2e 2H 2O E = .815 V at pH 7
E = .402 .815 = .413 V

G = e FE > 0 so not spontaneous

Thus Cytox is not a good enough oxidizing agent at pH 7.0 to cause the formation of O2
from H2O

6.

a)

For the reaction O2 + H+ + e HO2

G = eF = 117.2 kJ mol1

= 1.215 V

For the reaction HO2 H+ + O2 K = 104.9, G = RT ln K = 28.0 kJ mol1

G = G + RT ln [107] = 12.0 kJ mol1
Add the two reactions: O2 + e O2
G = 105.2 kJ mol1
Reconvert to volts: = G/eF = 105.2 kJ mol1/(96485.3 C mol1) = 1.091 V
b)

Add
To the reverse of
E = E

7.

O2 + e O2
Fe3+-Mb + e Fe2+-Mb
Fe2+-Mb + O2 Fe3+-Mb + O2

= 1.091 V
= +0.046 V
= 1.137 V

RT
8.3145 J mol1 K 1 298 K 1
lnQ = 1.137V
ln
= 1.237 V
eF
96485.3 C mol1
0.02

Reverse both reactions and add

1,3 diphosphoglycerate + NADH + H+ glyceraldehyde-3-phosphate + NAD+ + Pi
rG = 6.3 kJ mol1
3-phosphoglycerate + ATP 1,3 diphosphoglycerate +ADP:
rG = 18.8 kJ mol1
+
3-phosphoglycerate + ATP + NADH + H
glyceraldehyde-3-phosphate + NAD+ + ADP + Pi
rG = 12.5 kJ mol1
Subtract ATP hydrolysis: ATP + H2O ADP + Pi
rG = 31.3 kJ mol1
3-phosphoglycerate + NADH + H+
glyceraldehyde-3-phosphate + NAD+ + H2O
rG = 43.8 kJ mol1

Chapter 7 solutions manual to accompany 5th edition of Physical Chemistry

Tinoco, Sauer, Wang, Puglisi Harbison, Rovnyak
Convert to volts = rG/eF = 0.227 V
Add NAD+ reduction: NAD+ + H+ + 2e NADH
3-phosphoglycerate + 2H+ + 2e
glyceraldehyde-3-phosphate + H2O
8.

= 0.324 V
= 0.551 V

The concentration of lysozyme (cM) is 50 g L1/14300 g mol-1 = 3.50 mM. c = 0.1

r=
M.

cK, in
c

Z c
ZM cM
=
+ M M +1
2c
2c
2

18 3.50 103
18 3.50 103
=
+
+ 1 = 0.734
0.2
0.2

RT
8.3145 J mol1 K 1 298 K
From eqn 7.27 V =
ln r =
ln ( 0.734 ) = 0.008 V
F
96485.3 C mol1

cK, in = rc = 0.00734 M
9.

a)

Pyruvate + 2H + + 2e Lactate; E = 0.184 V

Cyt-c[Fe 3+ ] + e Cyt-c[Fe 2+ ]; E = +0.254 V
Pyruvate + 2H + + 2Cyt-c[Fe 2+ ] 2Cyt-c[Fe 3+ ] + Lactate; E = 0.438 V

b)

G = eF = RT ln K, so ln K = (eF/RT) = 34.1, so K = 1.56 1015

c)

G = eF = 84.5 kJ mol1

d)

10.

G = G + RT ln([lac][Cyt-c(Fe 3+ )]2 [pyr][Cyt-c (Fe 2+ )]2 )

= 84.5 kJ mol1 + (8.314 J mol1 K 1 )(298 K) ln[5(10)2 ] = 99.9 kJ mol1

a)

Cl2 (g) + 2Ag(s) + 2I 2AgI(s) + 2Cl

b)

G = eF = 2 96485 C mol1 1.5702 V = 303.0 kJ mol1

c)

G = G RT ln Q = 303.0 kJ mol1 ln[(103)2/(102)2] = 291.6 kJ mol1

d)

The half cell on the left is Ag(s) + I AgI(s) + e. This is not given in Table 7.1, but
that on the right is: Cl2(g) + e 2 Cl
= 1.358 V. The standard potential for
the full cell reaction is
RT
8.3145 J mol1 K 1 298 K (10 3 )2
E = E +
lnQ = 1.5702V +
ln 2 2 = 1.5110 V
eF
2 96485.3 C mol1
(10 )

Chapter 7 solutions manual to accompany 5th edition of Physical Chemistry

Tinoco, Sauer, Wang, Puglisi Harbison, Rovnyak
Subtracting the right hand half cell, we are left with:
2Ag(s) + 2I 2AgI(s) + 2e = 0.153 V
Dividing by two and making it a reduction: AgI(s) + e Ag(s) + I = 0.153 V
e)

11.

AgI(s) + e Ag(s) + I
0.153 V
Ag+(aq) + e Ag(s)
0.800 V
Reverse the second reaction, and add
AgI(s) Ag+(aq) + I(aq) :
ln K = G/RT = 37.1 so K = 7.8 1017

92.0 kJ mol1

f)

0
S 298
= (96,485)(2)(E / T ) = 183.3 J K 1 mol 1

a)

At pH 7 the proton activity is 1, so K = [Fd red ] ( p1/2

H 2 [Fd ox ]) = (1 3) / (2 3) = 1 / 2

b)

For the full reaction:

RT
8.3145 J mol1 K 1 298 K
E =
ln K =
ln ( 0.5 ) = 0.0180 V
eF
96485.3 C mol1
Adding the half reaction H+ + e H2: = 0.414 V
Fd ox + e Fd red ;

12.

G
14.8 kJ mol1
77.2 kJ mol1

a)

E = 0.0180 0.414 = 0.432 V

AA + 2H + + 2e -HB ; E = 0.346 V

O2 + 4H + + 4e 2H 2O;

E = +0.815 V

-HB + 12 O2 AA + H 2O; E = 1.161 V

G = 96.485(2)(1.161) = 224.0 kJ mol1
ln K = G RT = 90.4

K = 1.78 10 39

13.

b)

[AA ] [ -HB ] = K ( pO2 )1/2 = 7.95 10 38

a)

CH3CHO + 2e + 2H+ CH3CH2OH

= 0.193 V
+

O2 + 4H + 4e 2H2O
= +0.815 V
Reversing the first reaction, dividing the second by 2
O2 + CH3CH2OH CH3CHO + H2O
= +1.008 V

b)

G = G = 96485.3 C mol1 2 1.008 V = -194.6 kJ mol1

c)

ln K = G/RT = 78.5 so K = 1.20 1034

Chapter 7 solutions manual to accompany 5th edition of Physical Chemistry

Tinoco, Sauer, Wang, Puglisi Harbison, Rovnyak
E = E

d)

14.

e)

G = 96485.3 C mol1 2 0.984 V = 189.9 kJ mol1

a)

Mg(s) | Mg2+ || Mg2+, 0.1 M ATP| Mg(s)

RT a(Mg 2+
in ATP)
E=
ln
eF
a(Mg 2+ )
Equal concentrations of Mg2+ are placed in two compartments of an electrochemical
cell containing Mg electrodes. The EMF is a measure of the ratio of the activities of
Mg2+ in the presence and absence of the ATP.

b)

15.

RT
8.3145 J mol1 K 1 298 K
1
lnQ = 1.008 V
ln( 1
) = 0.984 V
1
eF
2 96485.3 C mol
4 2 0.1

a)

[ATP Mg 2+ ]
K=
[ATP][Mg 2+ ]
The voltage of the cell in part a) gives us the activity of Mg2+ in an ATP solution.
Assuming dilute solutions aI =[I]. By knowing a(Mg2+ in ATP) we can solve for the
equilibrium constant.
[Mg2+]EMF from EMF
[ATP Mg2+] = [Mg2+]total [Mg2+]EMF
[ATP] = [ATP]total [Mg2+]total + [Mg2+]EMF

P700 + + e P700;

A+e A ;

E = 0.490 V
E = 0.900 V

P700 + A P700 + + A ; E = 1.390 V

b)

G = FE = 96485 C mol1 1.390 V = 134.1 kJ mol1

c)

NADP + + H + + 2e NADPH;

E = 0.350V

2H + + 2e H 2 (g);

E = 0.414 V

NADP + + H 2 (g) NADPH + H + ;

E = 0.064 V

G = (96485.3)(2)(0.064) = 12.35 kJ mol1

16.

a)

b)

RT [MB( red )]
E = E
ln

e F ([MB( ox )][H + ]2

8.3145 J mol1 K 1 298 K 10 3

E = 0.400 V
ln
= 0.075 V
7 2
2 96485.3 C mol1
10

Chapter 7 solutions manual to accompany 5th edition of Physical Chemistry

Tinoco, Sauer, Wang, Puglisi Harbison, Rovnyak
O2 + 2 cysteine cystine + H 2O; E = 1.155 V

17.

eF
2 96485.3 C mol1
E =
1.1155 V = 89.95 so K = 1.17 10 39
RT
8.3145 J mol1 K 1 298 K
[cystine]
K=
1/2
[cysteine]2 pO
2

ln K =

[cystine] [cysteine]2 = (1.17 10 39 )(0.2)1 2 = 5.2 10 38

because reaction proceeds almost entirely to the right
[cystine]eq .005 M
[cysteine]eq = [(0.005) (5.2 10 38 )]1 2 = 3.10 10 21;
[cystine] [cysteine] = 1.61 1018

b)

ZFV
2 96485.3 C mol1 0.090 V
=
= 6.735
RT
8.3145 J mol1 K 1 310.15 K
K = [Mg2+]in/[Mg2+]out = 841 so [Mg2+]in = K[Mg2+]out = 1.85 M
ln K =

18.

19.

At equilibrium, G = 0

a)

transGm = RT ln (aout ain )

a = activity of NaCl (either inside or outside), but with the same standard state.
transGm is the free energy change to transport 1 mol NaCl.

0.20
= 3575 J. Not spontaneous.
0.05

b)

= RT ln

c)

transG = 3transGm = 10725 J

d)

= 0

e)

= 0

f)

G = G + RT ln Q so

( 40000 + 31300) J mol1 = 3.374 or Q = 0.0343

G G
=
RT
8.3145 J mol1 K 1 310.15 K
Q = [ADP][Pi]/[ATP] so [Pi] = ([ATP]/ [ADP])Q = 0.343 M
ln Q =

g)

31300 J mol1
5 [ADP][Pi ]
K = e
= exp
=
1.87

10
=

1 1
[ATP]
8.3145 J mol K 310.15 K
This requires [Pi] be 1.87 106 M, which is impossible.
G RT

Chapter 7 solutions manual to accompany 5th edition of Physical Chemistry

Tinoco, Sauer, Wang, Puglisi Harbison, Rovnyak

20.

21.

RT a(Ca 2+
8.3145 J mol1 K 1 310.15 K
0.1
in )
ln
=

ln
= 0.062 V
2+
1
ZF
0.001
a(Ca out)
2 96485.3 C mol

a)

V=

b)

Reversible electrical work is free energy change; molar free energy change is the
electrochemical potential difference aross the membrane. From Eq. 7.17
= ZFV + RT ln Q
= 2 96485.3 C mol1 0.1 V + 8.31447 J mol1 K1 310.15 K ln(0.1/0.001)
= 31.2 kJ mol1.

RT a(Li+in )
a(Liin + ) ZFV
96485.3 C mol1 0.04 V
so ln
V=
ln
=
=
= 1.497
ZF
a(Li+out)
a(Liout + ) RT
8.3145 J mol 1 K 1 310.15 K
a(Li+in )
= 4.467 so the internal lithium concentration is 4.467 150 mM = 670 mM.
a(Li+out)

22.

2 Cu2+ + Ascorbate 2 Cu+ + Dehydroascorbate + 2H+

= 0.159 V 0.08 V = 0.079 V
At equilibrium, = 0. So ln Q = E (nF/RT) = .079 [2 96485.3/(8.31447 298.15)]
= 6.149, so Q = 468.5
[Dehydroascorbate] [Cu+]2/([Cu2+]2 [Ascorbate]) = Q
Let x = [Dehydroascorbate]; [Ascorbate] = (0.01 - x); [Cu+] = 2x; [Cu2+] = (0.01 2x)
Q = 4x3/[(0.01 x) (0.01 2x)2]
Three solutions, the only physically possible one is
[Ascorbate] = 0.00521 M; [Dehydroascorbate] = 0.00479 M; [Cu+] = 0.00958 M;
[Cu2+] = 0.0000424 M

23.

= 1.189 V, so G = 2 96485.3 C mol1 1.189 V = 229.4 kJ mol1.

G = G + RT ln Q = 229.4 kJ mol1 + 8.3145 J mol1 K1 298 K ln(.0003)
= 249.6 kJ mol1

24.

cZn = 5 106 g L1 /65.39 g mol1 = 7.65 108 g/mol

RT
8.3145 J mol1 K 1 298 K 7.65 10 8
E = E
lnQ = 0.7618V
ln
= 0.972 V
eF
1
2 96485.3 C mol1

So a negative voltage of 0.972 V on the anode will be necessary to keep the zinc from
dissolving.