Chemistry 2300: Problem Set 6 Professor: C. E. Loader

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Chemistry 2300

Problem Set 6 Answers Professor: C. E. Loader


1. For the cell at 25 ºC:
Zn(s) | Zn2+ (4.0 x 10–3 mol L–1, aq) || Cd2+ (0.20 mol L–1, aq) | Cd(s)
(a) Write the cell reaction.
(b) Calculate the cell voltage.
(c) Calculate the equilibrium constant for the cell reaction
ANS:

(a) banode: Zn(s) Zn2+ + 2 e– Eoo = +0.763 v

cathode: Cd2+ + 2 e– Cd(s) Er o= – 0.403 v

cell reaction: Zn(s) + Cd2+(aq) Zn2+(aq) + Cd(s) Eo = + 0.360 V

RT [Zn 2+ ] 4.0 x 10 −3 mol L −1


(b) E = Eo – mF ln Q, Q = [Cd 2+ ]
= 0.20 mol L−1
RT
E = Eo – 2F ln Q
8.314 JK −1 mol −1 x 298.15 K
E = 0.360 – ln (2.0 x 10–2)
2 x 96500 C mol −1
E = (0.360 + .050) v = 0.410 volts
(c) at equilibrium, E = 0, Q = K
RT
Eo = + mF ln K = 0.360 v
ln K = 28.03, K = 1.49 x 1012
2. Explain why the Eo of the half cell reaction:
Cu(s) → Cu2+ + 2 e–,
does not equal the sum of the Eo's for
Cu(s) → Cu2+ + e– and Cu2+ → Cu+ + e–.
ANS:
Comparing the two paths
Path a. Cu Cu2+ + 2 e– Eo = –0.340 v

Path b. Cu Cu+ + e– E o1 = –0.518 v

Cu+ Cu2+ + e– E o2 = –0.153 v


If ∆G is independent of path, then clearly the Eo's are not additive since path a. involves 2
o

electrons while path b. involves 1 electron. The ∆Go's, however, are the same for the two paths
(within experimental error)

Path a. ∆Go = –nFEo = –(2)(96500 C mol–1)(–0.340 V) = 65.6 kJ mol–1

Path b. ∆Go = –nF(E o1 + E o2 ) = –(1)(96500 C mol–1)(–0.671 V) = 64.8 kJ mol–1

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Chemistry 2300

The difference reflects the Eo uncertainty in tables.


3. If the cell:
Zn(s) | ZnSO4(aq, 1.00 mol L–1) || CuSO4(aq, 0.500 mol L–1) | Cu(s)
were allowed to completely discharge at 25 ºC, what would be the final concentrations of ZnSO4
and CuSO4?
ANS:

(a) anode: Zn(s) Zn2+ + 2 e– Eo = +0.763 v

cathode: Cu2+ + 2 e– Cu(s) Eo = –0.340 v

cell reaction: Zn(s) + Cu2+(aq) Zn2+ + Cu(s) Eo = 1.003 v


RT [Zn 2+ ]
∴ E = O = Eo – mF ln [Cu 2+ ]
at equilibrium
o
or K =
[Zn 2+ ]
[Cu 2+ ]
= exp( ERTmF ) = 8.23 x 10 33

Let the starting (initial) concentrations be c Zn 2+ , c Cu 2+ and let x = concentration which has reacted.
Then from stoichiometry of cell reaction
[Cu2+] = c Cu 2+ – x
[Zn2+] = c Zn 2+ + x

c Zn 2+ + x [Zn 2+ ]
∴ c Cu 2+ − x = 8.23 x 1033 = [Cu 2+ ]
Solving for x; see that since K is so large (so [Cu 2+ ] must be very small) that x { 0.500 so that
[Zn2+] = c Zn 2+ + 0.500, then solve for [Cu2+]
1.50 mol L −1
[Cu2+] = K = 1.82 x 10–34 mol L–1
2+ –1
[Zn ] = 1.50 mol L
The reaction will appear to go to completion.
4. From the cell
Ag(s)|AgCl(s)|Cl–(aq)||Ag+(aq)| Ag(s)
and appropriate Eo data, calculate the solubility product of AgCl(s) at 25 ºC.
ANS:
Ag(s) + Cl–(aq) AgCl(s) + e– Eo = –0.2224 v
+ –
Ag (aq) + e Ag(s) Eo = 0.7790 v
__________________________________________________
Ag+(aq) + Cl–(aq) AgCl(s) E ocell = 0.5766 v

RT aAgCl(s) RT 1
Eo = mF ln [Ag + ][Cl− ]
= mF ln + –
K sp (since E = 0 at equilibrium, [Ag ], Cl ] are equilibrium
concentrations)

where since aAgCl(s) ≡ 1, Ksp = [Ag+][Cl –]

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Chemistry 2300

mFE o −(1)(96500 Cl mol−1 ) (.5766 v)


ln Ksp = − = = –22.
RT 8.314 J K −1 mol−1 x 298.15 K
∴ Ksp = 1.78 x 10–10 (mol L–1)2
5. Given that the cell below has a voltage of –0.0403 volts at 25 ºC, calculate the unknown [Cl–].
Pt | Cl2 (g, 1.00 atm) | Cl– (aq, c = 0.010 mol L–1) || Cl – (x mol L–1)|Cl2 (1.30 atm|Pt)
ANS:
anode: 2 Cl – (0.010) Cl2 (g, 1 atm) + 2 e–

cathode: Cl2 (1.30 atm) + 2 e– 2 Cl – (a)


__________________________________________________________
2 Cl – (.010) + Cl2 (1.30 atm) Cl2 (1 atm) + 2 Cl – (x) E ocell =0
RT
E = Eo – mF ln Q

mFE −(2)(96500 C mol−1 ) (−0.0403 v)


∴ ln Q = − RT = = + 3.138
8.314 J K −1 mol −1 298.15 K

∴ Q = 23.05

(1 atm) x2
ButQ = 23.05 = (1.3 atm) (.010 mol L −1 ) 2

∴ x = 5.47 x 10–2 mol L–1

6. The following reduction potentials (25 ºC) are available for iodine containing species present in
iodine titrations:
I2(s) + 2 e- › 2 I-(aq) E° = +0.536 V
I2(aq) + 2 e- › 2 I-(aq) E° = +0.620 V

I − (aq) + 2 e- › 3 I (aq)
-
E° = +0.536 V
3

(a) Calculate the equilibrium constant for the reactions

(i) I2(s) + I-(aq) › I − (aq)


3
ANS:
I2(s) + 2 e- › 2 I-(aq); E° = +0.536 V
3 I-(aq) › I − (aq) + 2 e-; E° = -0.536 V
3
_______________________________________
I2(s) + I-(aq) › I − (aq); E cell ° = +0.000 V
3
so K = 0

(ii) I2(aq) + I-(aq) › I − (aq)


3

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Chemistry 2300

ANS:
I2(aq) + 2 e- › 2 I-(aq); E° = +0.620 V
-
3 I (aq) › I −3 (aq) + 2 e-; E° = -0.536 V
_______________________________________
I2(aq) + I-(aq) › I −3 (aq); E cell ° = +0.084 V
o
E cell = RT
mF lnK
∴ 0.084 = 8.314 x 298
2 x 96485 lnK
∴ K = 6.9 x 102
(b) Calculate the solubility in g L-1 of I2(s) in water
ANS:
I2(s) + 2 e- › 2 I-(aq); E° = +0.536 V
2 I-(aq) › I2(aq) + 2 e-; E° = -0.620 V
_________________________________________________

I2(s) › I2(aq); E cell ° = -0.084 V


o
E cell = RT
mF lnK

∴ -0.084 = 8.314 x 298


2 x 96485 lnK
[I2 (aq)]
∴ K = 1.4 x 10-3 = [I2 (aq)]o
so [I 2 (aq)] = 1.4 x 10-3 mol L-1
or, in g/L = 1.4 x 10-3 mol L-1 x 253.8 g mol-1 = 0.355 g/L
Note how insoluble iodine is - barely enough to colour the water.
7. Determine the EMF at 298 K for

Cd(s)|Cd2+(0.020 mol L-1),KCN (0.090 mol L-1)||KCl(0.015 mol L-1)|AgCl(s)|Ag(s)

Given Cd2+ + 4 CN– › Cd(CN)42– KASS = 1.3 x 1017

This question involves a complex ion equilibrium. When the solutions in the
left-hand electrode are mixed complexation of the cadmium ion will take place
according to the above equation.
Half Cell reactions
Cd(s) t Cd2+(aq) + 2 e- Eo = 0.403 V
2 e- + 2 AgCl(s) t 2 Ag(s) + 2 Cl-(aq) Eo= 0.403 V

Cd(s) + 2 AgCl(s) t Cd2+(aq) + 2 Ag(s) + 2 Cl-(aq) Eocell = 0.625 V


Sine the solutions are fairly dilute we will assume that the activities are
approximately equal to the molar concentrations. The complexation of the
cadmium ion with the cyanide ion will lower the concentration of free cadmium ion
in the solution and therefore affect the Eo (the equilibria are connected through the

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Chemistry 2300

casdmium ion concentration). Since KASS is so large it is reasonable to assume


complete reaction so the concentration after mixing are
Cd2+(aq, very << 0.20 mol L-1) + 4 CN-(aq, 0.90 - (4 x 0.20 mol L-1) t Cd(CN)42-(aq, 0.20 mol L-1)
[Cd(CN)2− 4 (aq)]
KASS = [Cd 2+ (aq)][CN − (aq)]4 = 1.3 x 1017
and [Cd 2+ (aq)] = (1.3[Cd(CN) (aq)] (0.020)
2−

x 10 )[CN(aq)] =
17
4
4 (1.3 x 10 17 ) x (0.010)4 = 1.54 x 10 −11 mol −1
so the assumption is valid.
Now, Ecell = Eocell - RT
mF ln[Cd 2+ (aq)][Cl − (aq)] 2 =0.625 V- 8.314 x 298.15
2 x 96485 ln[(1.54 x 10 −11 ) x (0.015) 2 ]V

and Ecell = 1.053 V :Ans


7. (a) Determine the EMF of the cell
Sn(s)|SnSO4(aq, 0.010 M)||Na2SO4(aq, 0.030 M)|PbSO4(s)|Pb(s)
Sn(s) t Sn2+(aq) + 2 e- Eo = 0.140 V
2 e- + PbSO4(s) t Pb(s) + SO42-(aq) Eo = -0.361 V
Sn(s) + PbSO4(s) t Pb(s) + SO42-(aq) + Sn2+(aq) Eo = -0.221 V
The concentration of the solutions in the cell are not standard but can be assumed
to be close to the molality and the activity of the solutions. Using the Nernst
equation
Ecell = Eocell - RT
mF ln Q = −0.221 − 8.314 x 298.15
2 x 96485 ln(0.010 x 0.030) = −0.117 V :Ans

(b) When this cell is discharged what is [Sn2+]?


When the cell is discharged the voltage drops to 0 and Ecell = 0 and the cell is at
equilibrium so Q = Keq.
0 = Eocell - RT
mF ln K eq = −0.221 − 8.314 x 298.15
2 x 96485 ln K eq = −0.117 V
so Keq = 3.37 x 10-8 and the reaction is spontaneous in the reverse direction. Since
the equilibrium constant is so small hardly any Sn2+ ion is present at equilibrium
and in this cell will be used up and therefore also using up and equivalent amount
of sulfate ion
Keq = 3.37 x 10-8 = [Sn2+(aq)][SO42-(aq)] = [Sn2+(aq)](0.030 - 0.010)
3.37x10 −8
so [Sn2+(aq)] = 0.030−0.010 mol L −1 ) = 1.69 x 10-6 mol L-1 :Ans
Note: [Sn2+(aq)] is << 0.010 mol L-1 and the assumption is valid.
8. The EMF of the cell
Pt|Hg(l)|Hg2+(aq), KCN(aq)||Fe3+(aq), Fe2+(aq)|Pt is E = 0.962 V

when [KCN(aq)] = 0.025 mol·L–1,

[Hg2+(aq)] = 3.4 x 10–3 mol·L–1;

[Fe3+(aq)] = 0.020 mol·L–1; [Fe2+(aq)] = 0.060 mol·L–1.

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Chemistry 2300

Calculate KASS for


Hg2+(aq) + 4 CN–(aq) › Hg(CN)42–(aq).910

Cell reaction
Hg(l) t Hg2+(aq) + 2 e- Eo = -0.852 V
2 Fe3+(aq) + 2 e-t 2 Fe2+(aq) Eo = +0.771 V
2 Fe3+(aq) + Hg(l) t 2 Fe2+(aq) + Hg2+(aq) Eocell = -0.081 V

This reaction involves the formation of a complex ion Hg(CN)42–(aq) and it is the
equilibrium associated with this that controls the Hg2+(aq) ion concentration. KASS is
[Hg(CN) 2– ]
the association constant for the equilibrium so KASS = [Hg 2+ (aq)][CN4–(aq)]4 and the true
[Hg2+(aq)] in the cell will not be that stated (as the solutions were made) but the
value dictated by this equilibrium and can be calculated from the cell potential.

So the real concentrations in the left-hand cell are:


[Fe2+ (aq)]2 [Hg2+ (aq)]
Ecell = Eocell - RT
mF ln Q = −0.081 − 8.314 x 298.15
2 x 96485 ln [Fe 3+ (aq)]2
(0.060) 2 [Hg2+ (aq)]
+0.962 V = −0.081 − 8.314 x 298.15
2 x 96485 ln (0.020) 2 V
solving gives [Hg2+(aq)] = 6.07 x 10-37 mol L-1. Clearly the Hg2+(aq) reacts almost
completely and the concentrations are as shown.
Hg2+(aq, 5.99 x 10-37 mol L-1) + 4 CN–(aq, 0.025 - (4 x 0.0034) mol L-1) › Hg(CN)42–(aq, 0.0034 -
5.99 x 10-37 mol L-1)
Hg2+(aq, 5.99 x 10-37 mol L-1) + 4 CN–(aq, 0.0114 mol L-1) › Hg(CN)42–(aq, 0.0034 mol L-1)
[Hg(CN) 2–
4 ] (0.0034)
KASS = [Hg (aq)][CN – (aq)]4
2+ = (6.07 x 10 −37 )(0.0114) 4
= 3.4 x 1041 :Ans
10. The cell
Ag(s)|AgCl(s)|Cl–(aq, 0.050 mol·L–1)||(Ag+, 0.100 mol·L–1)|Ag(s)
has ECELL = 0.441 V at 25 ºC.
When 0.500 mol·L–1 NH3 is added to the 0.100 mol·L–1 Ag+, ECELL falls to 0.0775 V.
(ie. One litre of solution contains 0.500 mol NH3 and 0.100 mol of Ag+).
(a) Calculate Ksp for AgCl(s).
Taking the initial cell the cell reaction is
Ag(s) + Cl-(aq) t AgCl(s) + e-
e- + Ag+(aq) t Ag(s)
Ag+(aq) + Cl-(aq) t AgCl(s) measured Ecell = +0.441 V
The cell is effectively a concentration cell with the silver ion concentration on the
LHS dictated by the solubility product for AgCl(s). So the above can be rewritten
as

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Chemistry 2300

LHS Ag(s) t Ag+(aq, 0.050 mol L-1) + e-


RHS e- + Ag+(aq, 0.100 mol L-1) t Ag(s)
Ag+(aq, 0.100 mol L-1) t Ag+(aq, LHS mol L-1) measured Ecell = +0.441
and the solubility product expression is
K sp
AgCl(s) t Ag+(aq) + Cl-(aq); Ksp = [Ag+(aq)][Cl-(aq)] so [Ag+(aq)] = [Cl− (aq)]
8.314 x 298.15 K ks
so 0.441 = 0 V - 1 x 96485 ln 0.050 x 0.100

Ksp = 1.8 x 10-10 :Ans


Alternatively,
For the cell
− (aq)] )
RT 1
Ecell = Eocell - mF ln( [Ag + (aq)][Cl
8.314 x 298.15 1
0.441 = Eocell - 1 x 96485 ln 0.050 x 0.100 giving Eocell = 0.577 V
RT 8.314 x 298.15
Eo = mF ln K cell reaction so 0.577 = 1 x 96485 ln K cell reaction
K cell reaction = 5.675 x 109 but K cell reaction = 1
[Ag + (aq)][Cl− (aq)] = 1
K sp ]

so Ksp =1.8 x 10-10 :Ans


(b) Calculate KSTAB for the reaction
Ag+(aq) + 2 NH3(aq) → Ag(NH3)2+
The concentration of Ag+(aq) after the ammonia has been added can be
calculated as before
K sp
8.314 x 298.15 0.050
0.0775 = 0 V - 1 x 96485 ln [Ag + (aq)] RHS

+
giving [Ag (aq)] RHS =7.35 x 10 mol L-1 -8

The silver ion reacts almost completely with the ammonia so we can get the other
concentrations:
Ag+(aq) + 2 NH3(aq) → Ag(NH3)2+
7.35 x 10-8 mol L-1 0.500 - (2 x 0.100) = 0.300 mol L-1 0.100 mol L-1
[Ag(NH 3 ) +2 (aq)]
Kstab = [Ag + (aq)][NH 3 ]2 = 0.100
(7.35 x 10 −8 ) x (0.300) 2 = 1.5 x 107 :Ans
(c) Calculate the solubility of AgCl(s) in 0.070 mol·L–1 NH3.
The solubility is governed by the solubility product and the stability constant. The
silver ion concentration is common to both.
Ag+(aq) + 2 NH3(aq) → Ag(NH3)2+(aq); Kstab = 1.57 x 107
AgCl(s) t Ag+(aq) + Cl-(aq); Ksp = 1.75 x 10-10
adding gives

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Chemistry 2300

AgCl(s) + 2 NH3(aq) → Ag(NH3)2+(aq) + Cl-(aq); Koverall = (1.57 x 107) x (1.75 x 10-10)


= 2.75 x 10-3
Now if x mol L-1 of AgCl dissolves we have [NH3(aq)] = (0.070 -2x); [Ag(NH3)2+(aq)]
= x; [Cl-(aq)] = x.
[Ag(NH 3 ) +2 (aq)][Cl− (aq)] x2
Now, Koverall = [NH 3 (aq)]2 = (0.070 − 2x) 2 = 2.75 x 10 −3
taking the square root of both sides x
(0.070 − 2x) = 0.0524 (only the +ve answer is
meaningful).
This gives x = 3.29 x 10-3 mol L-1
Solubility of AgCl in 0.070 mol L-1 ammonia solution = 3.3 x 10-3 mol L-1 : Ans

Or, if x mol L-1 of AgCl dissolves the answer to (b) shows that most of the silver ion
in solution will be in the form of the complex ion (Kstab = 1.51 x 107) so that the
[Cl-(aq)] concentration is equal to x and [Ag(NH3)2+(aq)] = x - [Ag+(aq)] or
K sp 1.75x10 −10
approximately x since Kstab is large. So the remaining [Ag+(aq)] = [Cl− (aq)] = x
[Ag(NH 3 ) +2 (aq)] x2
Now Kstab = [Ag + (aq)][NH 3 (aq)]2 = 1.75 x 10−10 (0.070−2x) 2 = 1.51 x 107
This gives x = 3.29 x 10-3 mol L-1 as above.

(d) Calculate the solubility of AgCl(s) in a solution that is 0.070 mol·L–1 in NH3 and 0.070 mol·L–1 in
KCl.
Using the same overall equilibrium as in part (c), the only change is that [Cl-(aq)]
= (0.070 + x).
x(0.070 + x)
1.75 x 10−10 (0.070−2x) 2 = 1.51 x 107 . If we first assume that x<<0.0.70 then
x(0.070)
1.75 x 10−10 (0.070) 2 = 1.51 x 107 then x = 1.8 x 10-4 mol L-1: Ans
The approximation is OK.

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