Chem 213

Chemical Analysis
Final
June 9, 2003
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_100%
KEY
Name:___________________________________________
(please print)
1. Use activites (i.e., consult Kielland’s Table of Activity Coefficients on page 3 of
this exam) to calculate the molar solubility of Zn(OH)2 (Ksp = 3.0•10-16) in

a. 0.0167 M K2SO4 (5 points)

Zn(OH)2(s) ↔ Zn2+(aq) + 2OH-(aq)

µ = ½ [0.0334(1)2 + 0.0167(1)2] = 0.050

In the table, we find at µ = 0.050

γZn2+ = 0.48 and γOH- = 0.81

Ksp = aZn2+•aOH-2 = 3.0 •10-16 = γZn2+[Zn2+]γOH-2[OH-]2

[Zn2+] [OH-]2 = 3.00•10-16/(γZn2+γOH-2) = 3.00•10-16/0.48(0.81)2 = 9.53•10-16
Ksp = 9.53•10-16

Solubility = S = [Zn2+] = 1/2[OH-]

S(2S)2 = 9.53•10-16
S = 6.2•10-6 M

b. the solution that results when you mix 20.0 mL of 0.100 M KOH with 80
mL of 0.0250 M ZnCl2. (5 points)

Initial amounts:
20.0•0.100 = 2.00 mmol of K+ = 2.00 mmol of OH-
80.0•0.0250 = 2.00 mmol of Zn2+
80.0•0.0250•2 = 4.00 mmol of Cl-

cK+ = 2.00/100 = 0.0200 M

cOH- = 0 (it all reacted with Zn2+)
cZn2+ = (2.00 – 1.00)/100 = 0.0100 (left over Zn2+ after reaction with OH-)
cCl- = 4.00/100 = 0.0400

µ = ½ [0.0200(1)2 + 0.0100(2)2 + 0.0400(1)2] = 0.0500

γZn2+ = 0.48 and γOH- = 0.81
Ksp = aZn2+•aOH-2 = 3.0 •10-16 = γZn2+[Zn2+]γOH-2[OH-]2
[Zn2+] [OH-]2 = 3.00•10-16/(γZn2+γOH-2) = 3.00•10-16/0.48(0.81)2 = 9.53•10-16
Ksp’ = 9.53•10-16 = 0.0100[OH]2
[OH-] = (9.53•10-16/0.0100)1/2 = 3.09•10-7
S = [OH-]/2 = 1.5•10-7

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2. Use activities to calculate the electrode potential of a hydrogen electrode in
which the electrolyte is 0.0100 M HCl and the activity of H2 is 1.00 atm. (10
points)

2H+ + 2e- ↔ H2(g)

E = E0 = 0.0592/2 log (pH2/a2H+) = 0.00 – 0.0592/2 log (1.00.[H+]2•γ2H+)

The ionic strength of the solution µ is given by

µ = ½ (0.0100•12 + 0.0100•12) = 0.0100

From the table above, γH+ = 0.913

E = 0.00 – 0.0592/2 log(1.00/(0.0100•0.913)2)

E = 0.00 – 0.121 = -0.121 V

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3. (20 Points) Use the following table in the problem below:
pH α4 pH α4 pH α4
0 1.3•10-23 5 3.5•10-7 10 0.35
-18 -5
1 1.9•10 6 2.2•10 11 0.85
-14 -4
2 3.7•10 7 4.8•10 12 0.98
3 2.5•10-11 8 5.4•10-3 13 1.00
-9 -2
4 3.6•10 9 5.2•10 14 1.00
Derive a titration curve for 50.00 mL of 0.0150 M Fe2+ with 0.0300 M EDTA in
a solution buffered to pH 7.0 (KFe(II)Y = 2.1•1014) Calculate pFe values after the
addition of:
For all parts: K’Fe(II)Y = 2.1•1014 x 4.8•10-4 = 1.01•1011

a. 0.00 mL EDTA solution

[Fe2+] = 0.0150 and pFe = 1.82

b. 10.00 mL EDTA solution

[Fe2+] = (50.00•0.0150 – 10.00•0.030)/60.00 = 7.50•10-3
pFe = -log7.50•10-3 = 2.12

c. 24.90 mL EDTA solution

[Fe2+] = (50.00•0.0150 – 24.90•0.030)/74.90 = 4.00•10-5
pFe = -log(4.00•10-5) = 4.40

d. 25.00 mL EDTA solution

Here, [Fe2+] = cT and
[FeY2-] = (50.00•0.0150)/75.00 – [Fe2+] ≈ 0.01
K’FeY = 1.01•1011 = 0.01/(cT•[Fe2+] = 0.01/[Fe2+]2
[Fe2+] = (0.01/1.01•1011)1/2 = 3.15•10-7
pFe = -log(3.15•10-7) = 6.50

e. 25.10 mL EDTA solution

cT = (25.10•0.030 – 50.00•0.0150)/75.10 = 3.995•10-5
[Fe2+] = (50.00•0.0150)/75.10 = 9.987•10-3
(9.987•10-3)/[Fe2+]•(3.995•10-5) = 1.01•1011
[Fe2+] = (9.987•10-3)/ (3.995•10-5)•1.01•1011 = 2.48•10-9
pFe = -log(2.48•10-9) = 8.61

f. and 30.00 mL EDTA solution

cT = (30.00•0.030 – 50.00•0.0150)/80.00 = 1.875•10-3
[Fe2+] = (50.00•0.0150)/80 = 9.375•10-3
(9.375•10-3)/[Fe2+]•(1.875•10-3) = 1.01•1011
[Fe2+] = (9.375•10-3)/ (1.875•10-3)•1.01•1011 = 4.96•10-11
pFe = -log(4.96•10-11) = 10.30

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4. A 20.0 mL solution of 0.005 M Sn2+ in 1 M HCl was titrated with 0.02 M Ce4+ to
give Sn4+ and Ce3+. Calculate the potential after the following volumes of Ce4+
solution have been added, using the half-cell potentials: EºSn = 0.139 V, EºCe
= 1.47 V.
a. At 0.100 mL (3 points)

E = 0.139 – (0.0592/2)•log([Sn2+]/[Sn4+])

= 0.139 – (0.0592/2)•log(9.90/0.100) = 0.080 V

b. at 10.00 mL (4 points)

2E = 2(0.139) – 0.0592•log([Sn2+]/[Sn4+])
E = 1.47 – 0.0592•log([Ce3+]/[Ce4+])
3E = 1.748 – 0.0592•log([Sn2+][Ce3+]/[Sn4+][Ce4+])
At the equivalence point, [Sn4+] = ½[Ce3+] and [Sn2+] = ½[Ce4+] which
makes the log term 0. Therefore, 3E = 1.748, and E = 0.583 V

c. at 10.10 mL (3 points)

E = 1.47 – 0.0592•log([Ce3+]/[Ce4+])

= 1.47 – 0.0592•log(10.0/0.10) = 1.35 V

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5. How would you prepare exactly 1.00 L of a buffer with a pH of 9.60 from 0.300
M Na2CO3 and 0.200 M HCl? The acid dissociation constants of H2CO3 are:
Ka1 = 4.45•10-7; Ka2 = 4.69•10-11. (10 points)

pH = 9.60 [H3O+] = antilog (-9.60) = 2.512•10-10

[H3O+][CO32-]/[HCO3-] = 4.69•10-11

[CO32-]/[HCO3-] = 4.69•10-11/2.512•10-10 = 0.1867

Let VHCl and VNa2CO3 be the volume in milliliters of the two reagents. Then:

VHCl + VNa2CO3 = 1000 mL

[CO32-] ≈ c(Na2CO3) = (VNa2CO3 • 0.300 – VHCl • 0.200)/1000

[HCO3-] ≈ c(HCO3-) = VHCl • 0.200/1000

Substituting these relationships into the ratio [CO32-]/[HCO3-] gives

0.300VNa CO - 0.200 VHCl

2 3
= 0.1867
0.200 VHCl

0.300 VNa2CO3 – 0.200 VHCl = 0.03734 VHCl

0.300(1.000 – VHCl) = 0.23734 VHCl

VHCl = 300/0.5373 = 558 mL

VNa2CO3 = 1000 – 558 = 442 mL

Thus mix 442 mL of 0.300 M Na2CO3 with 558 ml of 0.200 M HCl.

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6. The solubility-product constant for Ag2SO3 is 1.5•10-14. Calculate E0 for the
process
Ag2SO3(s) + 2e- ↔ 2Ag(s) + SO32-(aq)

For the process Ag+ + e- ↔ Ag(s), E0 = 0.799 V. (10 points)

2Ag+ + 2e- ↔ 2Ag(s) E0 = 0.799 V

[Ag+]2[SO32-] = 1.5•10-14 = Ksp

E = 0.799 – 0.0592.2 log(1/[Ag+]2 = 0.799 – 0.0592/2 log ([SO32-]/Ksp)

When [SO32-] = 1.00, E = E0 for Ag2SO3(s) + 2e- ↔ 2Ag(s) + SO32-(aq)

Thus,

E0 = 0.799 – 0.0296 log(1.00/Ksp) = 0.799 – 0.0296 log(1/1.5•10-14)

E0 = 0.799 – 0.409 = 0.390 V

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7. Calculate the pH of the solutions during the titration of 50.00 mL of 0.100 M
solution of Na2CO3 with a 0.2000 M solution of HCl. Calculate the pH after
the addition of 0.00, 12.50, 25.00, 26.00, 50.00, and 51.00 mL of HCl. Enter
your results in the table below. The acid dissociation constants of H2CO3 are:
Ka1 = 4.45•10-7; Ka2 = 4.69•10-11. (10 points)

mL HCl added 0.00 12.50 25.00 26.00 50.00 51.00

pH 11.66 10.33 8.34 7.73 3.83 2.70

0.00 mL CO32- + H2O ↔ HCO3- + OH- Kb1 = Kw/Ka2 = 2.132•10-4

Kb1 = [OH-][HCO3-]/[CO32-] Since both [OH-] and [HCO3-] are made in the same
dissociation and Kb1 << cbase
[OH-] = (0.100•2.132•10-4)1/2 = 4.618•10-3
pH = 14.00 – (-log4.618•10-3) = 11.66

12.50 mL We are in the buffer region of Na2CO3/NaHCO3

[HCO3-] ≈ cNaHCO3 = 12.50•0.200/62.50 = 4.000•10-2
[CO32-] ≈ cNa2CO3 = (50.0•0.100 – 12.50•0.200).62.5 = 4.00•10-2
[H3O+] = 4.000•10-2 x 4.69•10-11/4.00•10-2 = 4.69•10-11
pH = 10.33

25.00 mL We are the first equivalence point, thus [H3O+] = (Ka1•Ka2)1/2 applies.
[H3O+] = (4.45•10-7•4.69•10-11)1/2 = 4.568•10-9
pH = 8.34

26.00 mL We are in the second buffer region of H2CO3/NaHCO3.

No. mmol HCl added = 26.00•0.200 = 5.200
No. mmol HCl consumed to form HCO3- = 50.00•0.100 = 5.000
No. mmol H2CO3 formed = 0.200
No. mmol HCO3- remaining = 50.00•0.100 – 0.2000 = 4.800
cH2CO3 = 0.200.76.00 = 2.632•10-3 ≈ [H2CO3]
cNaHCO3 = 4.800/76.00 = 6.316•10-2 ≈ [HCO3-]
[H3O+] = 4.45•10-7 x 2.632•10-3/6.316•10-2 = 1.854•10-8
pH = 7.73

50.00 mL. This is a solution that is 0.0500 M in H2CO3.

[H3O+] = = (Ka1•cH2CO3)1/2 = (4.45•10-7 x 0.0500)1/2 = 1.49•10-4

pH = 3.83

51.00 1.00 mL of 0.2000 M HCl is in exess.

cHCl = [H3O+] = 1.00•0.2000/101.0 = 1.980•10-3
pH = 2.70

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8. A 25.0-mL aliquot of a solution containing Tl(I) ion was treated with K2CrO4.
The Tl2CrO4 was filtered, washed free of excess precipitating agent, and
dissolved in dilute H2SO4. The Cr2O72- produced was titrated with 40.60 mL
of 0.1004 M Fe2+ solution. What was the mass of Tl in the sample? The
reaction are:

2Tl+ + CrO42- → Tl2CrO4(s)

2Tl2CrO4(s) + 2H+ → 4Tl+ + Cr2O72- + H2O
Cr2O72- + 6Fe2+ + 14H+ → 6Fe3+ + 2Cr3+ + 7H2O
(10 points)

6 mmol Fe2+ = 1 mmol Cr2O72- = 4 mmol Tl+

(40.60 •0.1004) mmol Fe x (4 mmol Tl/6 mmol Fe) x 0.20438 g Tl/mmol Tl

= 0.5554 g Tl

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9. A 2.50-mL aliquot of a solution that contain 3.8 ppm iron(III) is treated with an
appropriate excess of KSCN and diluted to 50.0 mL. What is the absorbance
of the resulting solution at 580 nm in a 2.50-cm cell? (ε(FeSCN)2+ = 7.00•103
L•mol-1•cm-1) (10 points)

cFe = 3.38 mg Fe/L x 10-3 g Fe/ mg Fe x 1 mol Fe/55.58 g Fe x 2.50 mL/50 mL

= 3.026•10-6 M

A = 7.00•103 x 2.50 x 3.026•10-6 = 0.0530

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