Beruflich Dokumente
Kultur Dokumente
1.
2.
[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 ]
= 0.330 V
= +0.08 V
= 0.25 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
= 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.
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
b)
O2 + 4H + + 2e 2H 2O E = .815 V at pH 7
E = .402 .815 = .413 V
6.
a)
= 1.215 V
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
= 0.324 V
= 0.551 V
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)
b)
c)
G = eF = 84.5 kJ mol1
d)
10.
a)
b)
c)
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 )
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)
b)
12.
G
14.8 kJ mol1
77.2 kJ mol1
a)
AA + 2H + + 2e -HB ; E = 0.346 V
O2 + 4H + + 4e 2H 2O;
E = +0.815 V
K = 1.78 10 39
13.
b)
a)
O2 + 4H + 4e 2H2O
= +0.815 V
Reversing the first reaction, dividing the second by 2
O2 + CH3CH2OH CH3CHO + H2O
= +1.008 V
b)
c)
d)
14.
e)
a)
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
c)
NADP + + H + + 2e NADPH;
E = 0.350V
2H + + 2e H 2 (g);
E = 0.414 V
E = 0.064 V
a)
b)
RT [MB( red )]
E = E
ln
e F ([MB( ox )][H + ]2
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 =
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)
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)
d)
= 0
e)
= 0
f)
G = G + RT ln Q so
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
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.
23.
24.
So a negative voltage of 0.972 V on the anode will be necessary to keep the zinc from
dissolving.