EXERCISES 213

solubility of the protein to such an extent that the protein precipitates

from solution. Tis observation is called the salting-out efect and is
used widely by biochemists to isolate and purify proteins. Consider
the equilibrium PX
n
(s) 7 P
n+
(aq) + nX

(aq), where P
n+
is a
polycationic protein of charge +n and X

is its counter-ion. Use Le

Chateliers principle and the physical principles behind the Debye
Hckel theory to provide a molecular interpretation for the salting-in
and salting-out efects.
5.15 Te overall reaction for the active transport of Na
+
and K
+
ions
by the Na
+
/K
+
pump is
3 Na
+
(aq,inside) + 2 K
+
(aq,outside) + ATP
ADP + P
i
+ 3 Na
+
(aq,outside) + 2 K
+
(aq,inside)
At 310 K, D
r
G

for the hydrolysis of ATP is 31.3 kJ mol

1
. Given that
the [ATP]/[ADP] ratio is of the order of 100, is the hydrolysis of
1 mol ATP suf cient to provide the energy for the transport of Na
+

and K
+
according to the equation above? Take [P
i
] = 1.0 mol dm
3
.
5.16 Vision begins with the absorption of light by special cells in
the retina. Ultimately, the energy is used to close ligand-gated ion
channels, causing sizable changes in the transmembrane potential.
Te pulse of electric potential travels through the optical nerve
and into the optical cortex, where it is interpreted as a signal and
incorporated into the web of events we call visual perception (see
Chapter 13). Taking the resting potential as 30 mV, the temperature
as 310 K, permeabilities of the K
+
and Cl

ions as P
K
+ = 1.0 and P
Cl
= 0.45,
respectively, and the concentrations as [K
+
]
in
= 100 mmol dm
3
,
[Na
+
]
in
= 10 mmol dm
3
, [Cl

]
in
= 10 mmol dm
3
, [K
+
]
out
= 5 mmol dm
3
,
[Na
+
]
out
= 140 mmol dm
3
, and [Cl

]
out
= 100 mmol dm
3
, calculate the
relative permeability (Case study 5.1) of the Na
+
ion.
5.17 Is the conversion of pyruvate ion to lactate ion
CH
3
COCO
2

(aq) + NADH(aq) + H
+
(aq)
CH
3
CH
2
(OH)CO
2

(aq) + NAD
+
(aq)
a redox reaction?
5.18 Express the reaction in Exercise 5.17 as the diference of two
half-reactions.
5.19 Express the reaction in which ethanol is converted to
acetaldehyde (propanal) by NAD
+
in the presence of alcohol
dehydrogenase as the diference of two half-reactions and write
the corresponding reaction quotients for each half-reaction
and the overall reaction.
5.20 Express the oxidation of cysteine, HSCH
2
CH(NH
2
)COOH,
to cystine, HOOCCH(NH
2
)CH
2
SSCH
2
CH(NH
2
)COOH, as the
diference of two half-reactions, one of which is O
2
(g) + 4 H
+
(aq)
+ 4 e

2 H
2
O(l).
5.21 One of the steps in photosynthesis is the reduction of NADP
+
by
ferredoxin (fd) in the presence of ferredoxin:NADP oxidoreductase:
2 fd
red
(aq) + NADP
+
(aq) + 2 H
+
(aq) 2 fd
ox
(aq) + NADPH(aq).
Express this reaction as the diference of two half-reactions. How
many electrons are transferred in the reaction event?
5.22 From the biological standard half-cell potentials E

cell
(O
2
,H
+
,H
2
O)
= +0.82 V and E

cell
(NAD,H
+
,NADH) = 0.32 V, calculate the standard
potential arising from the reaction in which NADH is oxidized to
NAD
+
and the corresponding biological standard reaction Gibbs
energy.
5.23 Cytochrome c oxidase receives electrons from reduced
cytochrome c (cyt-c
red
) and transmits them to molecular oxygen,
with the formation of water. (a) Write a chemical equation for this
process, which occurs in an acidic environment. (b) Estimate the
values of E

cell
, D
r
G

, and K for the reaction at 25C.

5.24 A fuel cell develops an electric potential from the chemical
reaction between reagents supplied from an outside source. What is
the cell potential of a cell fuelled by (a) hydrogen and oxygen, each
at 1 bar and 298 K, and (b) the combustion of butane at 1.0 bar and
298 K?
5.25 Consider a hydrogen electrode in HBr(aq) at 25C operating
at 1.45 bar. Estimate the change in the electrode potential when the
solution is changed from 5.0 mmol dm
3
to 25.0 mmol dm
3
.
5.26 A hydrogen electrode can, in principle, be used to monitor
changes in the molar concentrations of weak acids in biologically
active solutions. Consider a hydrogen electrode in a solution of lactic
acid as part of an overall galvanic cell at 25C and 1 bar. Estimate the
change in the electrode potential when the concentration of lactic acid
in the solution is changed from 5.0 mmol dm
3
to 25.0 mmol dm
3
.
5.27 Write the cell reactions and electrode half-reactions for the
following cells:
(a) Pt(s) | H
2
(g, p
L
) | HCl(aq) | H
2
(g, p
R
) | Pt(s)
(b) Pt(s) | Cl
2
(g) | HCl(aq) | | HBr(aq) | Br
2
(l) | Pt(s)
(c) Pt(s) | NAD
+
(aq), H
+
(aq),NADH(aq) | | oxaloacetate
2
(aq),
H
+
(aq),malate
2
(aq) | Pt(s)
(d) Fe(s) | Fe
2+
(aq) | | Mn
2+
(aq), H
+
(aq) | MnO
2
(s) | Pt(s)
5.28 Write the Nernst equations for the cells in the preceding exercise.
5.29 Devise cells to study the following biochemically important
reactions. In each case state the value for n to use in the Nernst
equation.
(a) CH
3
CH
2
OH(aq) + NAD
+
(aq)
CH
3
CHO(aq) + NADH(aq) + H
+
(aq)
(b) ATP
4
(aq) + Mg
2+
(aq) MgATP
2
(aq)
(c) 2 cyt-c(red, aq) + CH
3
COCO
2

(aq) + 2 H
+
(aq)
2 cyt-c(ox, aq) + CH
3
CH(OH)CO
2

(aq)
5.30 Use the standard potentials of the electrodes to calculate the
standard potentials of the cells devised in Exercise 5.29.
5.31 Te permanganate ion is a common oxidizing agent. What is the
standard potential of the MnO
4

,H
+
/Mn
2+
couple at (a) pH = 6.00 and
(b) general pH?
5.32 State what you would expect to happen to the cell potential
when the following changes are made to the corresponding cells
in Exercise 5.27. Confrm your prediction by using the Nernst
equation in each case. (a) Te pressure of hydrogen in the lef-hand
compartment is increased. (b) Te concentration of HCl is increased.
(c) Acid is added to both compartments. (d) Acid is added to the
right-hand compartment.
5.33 State what you would expect to happen to the cell potential when
the following changes are made to the corresponding cells devised in
Exercise 5.29. Confrm your prediction by using the Nernst equation
in each case. (a) Te pH of the solution is raised. (b) A solution of
Epsom salts (magnesium sulfate) is added. (c) Sodium lactate is added
to the solution.
5.34 (a) Calculate the standard potential of the cell
Hg(l) | HgCl
2
(aq) | | TlNO
3
(aq) | Tl(s) at 25C. (b) Calculate
the cell potential when the molar concentration of the Hg
2+
ion
is 0.150 mol dm
3
and that of the Tl
+
ion is 0.93 mol dm
3
.