Chemistry 2300: Problem Set 6 Professor: C. E. Loader
Chemistry 2300: Problem Set 6 Professor: C. E. Loader
Chemistry 2300: Problem Set 6 Professor: C. E. Loader
electrons while path b. involves 1 electron. The ∆Go's, however, are the same for the two paths
(within experimental error)
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)
∴ Q = 23.05
(1 atm) x2
ButQ = 23.05 = (1.3 atm) (.010 mol L −1 ) 2
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
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
_________________________________________________
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
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
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.
+
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
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.