Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

Chapter 20

20-1

(a) 2 Mn 2+ + 5S 2 O 8

+ 8H 2 O 10SO 4 + 2 MnO 4 + 16H +

3+
+
+
4+
+
(b) NaBiO 3 ( s ) + 2Ce + 4 H BiO + 2Ce + 2 H 2 O + Na

(c) H 2 O 2 + U 4+ UO 2

2+

+ 2H +

(d) V(OH ) 4 + Ag( s ) + Cl + 2 H + VO 2+ + AgCl( s ) + 3H 2 O

(e) 2 MnO 4 + 5H 2 O 2 + 6 H + 5O 2 + 2 Mn 2+ + 8H 2 O

(f) ClO 3 + 6I + 6H + 3I 2 + Cl + 3H 2 O

20-2

(a) 2 Fe 3+ + SO 2 ( g ) + 2 H 2 O 2 Fe 2+ + SO 4

+ 4H +

(b) 2 H 2 MoO 4 + 3Zn( s ) + 12 H + 3Zn 2+ + 2 MoO 3+ + 8H 2 O

(c) 2 MnO 4 + 5HNO 2 + H + 2 Mn 2+ + 5NO 3 + 3H 2 O

(d) BrO 3 + 5Br + C 6 H 5 NH 2 + 3H + Br3C 6 H 5 NH 2 + 3Br + 3H 2 O

(e) 2 HAsO 3

+ O 2 ( g ) 2 HAsO 4

(f) 2I + 2 HNO 2 + 2 H + I 2 + 2 NO + 2 H 2 O
20-3

Only in the presence of Cl- ion is Ag a sufficiently good reducing agent to be very useful
for prereductions. In the presence of Cl-, the half-reaction occurring in the Walden
reductor is
Ag( s ) + Cl AgCl( s ) + e

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

The excess HCl increases the tendency of this reaction to occur by the common ion
effect.
20-4

Amalgamation of the zinc prevents loss of reagent by reaction of the zinc with hydronium
ions.
2+

+ 2 Ag( s ) + 4 H + + 2Cl

U 4+ + 2AgCl( s ) + H 2 O

20-5

UO 2

20-6

2TiO 2 + + Zn( s ) + 4 H +

20-7

Standard solutions of reductants find somewhat limited use because of their susceptibility

2Ti 3+ + Zn 2 + + 2 H 2 O

to air oxidation.
20-8

Standard KMnO4 solutions are seldom used to titrate solutions containing HCl because of
the tendency of MnO4- to oxidize Cl- to Cl2, thus causing overconsumption of MnO4-.

20-9

Cerium (IV) precipitates as a basic oxide in alkaline solution.

20-10 2 MnO 4 + 3Mn 2+ + 2 H 2 O 5MnO 2 ( s ) + 4 H +

20-11 Freshly prepared solutions of permanganate are inevitably contaminated with small
amounts of solid manganese dioxide, which catalyzes the further decompositions of
permanganate ion. By removing the dioxide at the outset, a much more stable standard
reagent is produced.
20-12 Standard permanganate and thiosulfate solutions are generally stored in the dark because
their decomposition reactions are catalyzed by light.

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

2 ( s ) + 3O 2 ( g ) + 4OH
20-13 4 MnO 4 + 2 H 2 O 4 MnO
brown

20-14 Solutions of K2Cr2O7 are used extensively for back-titrating solutions of Fe2+ when the
latter is being used as a standard reductant for the determination of oxidizing agents.
20-15 Iodine is not sufficiently soluble in water to produce a useful standard reagent. It is quite
soluble in solutions containing excess I- because of formation of triiodide.
20-16 The solution concentration of I3- becomes stronger because of air oxidation of the excess
I-. The reaction is

6I + O 2 ( g ) + 4 H + 2 I 3 + 2 H 2 O
20-17 S 2 O 3

+ H + HSO 3 + S( s )

20-18 When a measured volume of a standard solution of KIO3 is introduced into an acidic
solution containing an excess of iodide ion, a known amount of iodine is produced as a
consequence of a reaction.

IO 3 + 5I + 6H + 3I 2 + 3H 2 O
20-19

BrO 3 + 6I + 6 H + Br + 3I 2 + 3H 2 O
excess
2

I 2 + 2S 2 O 3 2I + S 4 O 6

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-20

Cr2 O 7

+ 6I + 14 H + 2Cr 3+ + 3I 2 + 7 H 2 O
excess

I 2 + 2S 2 O 3

2I + S 4 O 6

20-21 2I 2 + N 2 H 4 N 2 ( g ) + 4 H + + 4I
20-22 Starch is decomposed in the presence of high concentrations of iodine to give products
that do not behave satisfactorily as indicators. This reaction is prevented by delaying the
addition of the starch until the iodine concentration is very small.
20-23

0.2256 g sample

1000 mmol Fe 2 +
= 4.03961 mmol Fe 2 +
55.847 g

4.03961 mmol Fe 2+ 1 mmol Ce 4+

= 0.1142 M Ce 4+
(a)
35.37 mL
mmol Fe 2+

4.03961 mmol Fe 2+ 1 mmol Cr2 O 7

(b)
35.37 mL
6 mmol Fe 2+

= 0.01904 M Cr2 O 7

4.03961 mmol Fe 2+ 1 mmol MnO 4

= 0.02284 M MnO 4
(c)
2+
35.37 mL
5 mmol Fe

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20
+

(d)

4.03961 mmol Fe 2+ 1 mmol V(OH ) 4

+

= 0.1142 M V(OH ) 4
2+
35.37 mL
mmol Fe

4.03961 mmol Fe 2+ 1 mmol IO 3

= 0.02855 M IO 3
(e)
2+
35.37 mL
4 mmol Fe
20-24

0.02500 mmol K 2 Cr2 O 7

294.185 g K 2 Cr2 O 7
500.0 mL
= 3.677 g K 2 Cr2 O 7
mL
1000 mmol

Dissolve 3.677 g K2Cr2O7 in water and dilute to 500.0 mL.

20-25

0.02500 mmol KBrO 3

1000 mL 167.001 g KBrO 3
2.000 L

= 8.350 g KBrO 3
mL
L
1000 mmol

Dissolve 8.350 g KBrO3 in water and dilute to 2.000 L.

20-26

0.0500 mmol KMnO 4

1000 mL 158.034 g KMnO 4
2.0 L

= 15.80 g KMnO 4
mL
L
1000 mmol

Dissolve about 16 g KMnO4 in water and dilute to 2.0 L.

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-27

0.0500 mmol I 3 1 mmol I 2

1000 mL 253.809 g I 2

2
.
0
L

= 25.38 g I 2

mL
L
1000 mmol
mmol I 3
Dissolve between 25 and 26 g I2 in a concentrated solution of KI and dilute to 2.0 L.

20-28 2 MnO 4 + 5H 2 C 2 O 4 + 6H + 2 Mn 2+ + 10CO 2 ( g ) + 8H 2 O

0.1756 g Na 2 C 2 O 4 1000 mmol Na 2 C 2 O 4

2 mmol KMnO 4

= 0.01636 M KMnO 4
32.04 mL KMnO 4
133.999 g
5 mmol Na 2 C 2 O 4

20-29 Ce 4+ + Fe 2+ Ce 3+ + Fe 3+

0.1809 g Fe
1000 mmol Fe 1 mmol Fe 2+ 1 mmol Ce 4+

= 0.1034 M Ce 4+
4+
31.33 mL Ce
55.847 g
mmol Fe
mmol Fe 2+

20-30

Cr2 O 7 + 6I + 14 H + 2Cr 3+ + 3I 2 + 7 H 2 O
2

I 2 + 2S2 O 3 2I + S 4 O 6

1 mmol Cr2O72- 3 mmol I2 6 mmol S2O32-

0.1259 g K 2 Cr2 O 7 1000 mmol K 2 Cr2 O 7 6 mmol S 2 O 3

= 0.06223 M Na 2S 2 O 3
41.26 mL Na 2S 2 O 3
294.185 g
mmol K 2 Cr2 O 7

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-31

BrO 3 + 6I + 6H + Br + 3I 2 + 3H 2 O
2

I 2 + 2S 2 O 3 2I + S 4 O 6

1 mmol BrO3- 3 mmol I2 6 mmol S2O32-

0.1017 g KBrO 3
1000 mmol KBrO 3 6 mmol S 2 O 3

= 0.09192 M Na 2S 2 O 3
39.75 mL Na 2S 2 O 3
167.001 g
mmol KBrO 3
20-32 1 mmol I2 1 mmol Sb3+ 2 mmol Sb2S3
(a)

0.02870 mmol I 2
1 mmol Sb 3+ 121.760 g Sb 3+
44.87 mL I 2

mL
mmol I 2
1000 mmol
100% = 16.03% Sb 3+
0.978 g sample

(b)

0.02870 mmol I 2
1 mmol Sb 3+ 1 mmol Sb 2S3 339.71 g Sb 2S3

44.87 mL I 2

mL
mmol I 2
2 mmol Sb 3+
1000 mmol

0.978 g sample
= 22.37% Sb 2S3

100%

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-33

MnO 2 + 2I + 4 H + Mn 2+ + I 2 + 2 H 2 O
2

I 2 + 2S 2 O 3 2I + S4 O 6

1 mmol MnO2 1 mmol I2 2 mmol S2O32-

0.07220 mmol Na 2S 2 O 3
1 mmol MnO 2
86.937 g MnO 2

32.30 mL Na 2S 2 O 3

mL
2 mmol Na 2S 2 O 3
1000 mmol

0.1344 g sample
= 75.42% MnO 2

20-34 3CS( NH 2 ) 2 + 4 BrO 3 + 3H 2 O 3CO( NH 2 ) 2 + 3SO 4

100%

+ 4 Br + 6H +

4 mmol BrO3- 3 mmol CS(NH2)2

0.00833 mmol KBrO 3

3 mmol CS( NH 2 ) 2 76.122 g CS( NH 2 ) 2

14.1 mL KBrO 3

mL
4 mmol KBrO 3
1000 mmol

0.0715 g sample
= 9.38% CS( NH 2 ) 2

20-35 MnO 4 + 5Fe 2+ + 8H + Mn 2+ + 5Fe 3+ + 4 H 2 O

1 mmol MnO4- 5 mmol Fe2+ 5/2 mmol Fe2O3

mmol KMnO 4 =

0.02086 KMnO 4
39.21 mL KMnO 4 = 0.8179 mmol KMnO 4
mL

100%

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

(a)

5 mmol Fe 2+
1 mmol Fe 55.847 g Fe

0
.
8179
mmoL
KMnO

mmol KMnO 4 mmol Fe 2+ 1000 mmol

100%
0.7120 g sample
= 32.08% Fe

(b)

5 mmol Fe 2 O 3
159.692 g Fe 2 O 3
0.8179 mmoL KMnO 4

2 mmol KMnO 4
1000 mmol

100% = 45.86% Fe 2 O 3
0.7120 g sample

2
3+
+
20-36 3Sn + Cr2 O 7 + 14 H

3Sn 4 + + 2Cr 3+ + 7 H 2 O

1 mmol Cr2O72- 3 mmol Sn3+ 3 mmol SnO2

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

(a)

mmol Sn =
0.01735 mmol K 2 Cr2 O 7
3 mmol Sn 3+
1 mmol Sn
29.77 mL K 2 Cr2 O 7

= 1.54953 mmol Sn
mL
mmol K 2 Cr2 O 7 mmol Sn 3+

118.71 g Sn

1.54953 mmol Sn 1000 mmol

100% = 42.27% Sn
0.4352 g sample

(b)

mmol SnO 2 =
0.01735 mmol K 2 Cr2 O 7
3 mmol SnO 2
29.77 mL K 2 Cr2 O 7
= 1.54953 mmol SnO 2
mL
mmol K 2 Cr2 O 7

150.71 g SnO 2
1.54953 mmol SnO 2
1000 mmol

0.4352 g sample

100% = 53.66% SnO

2

20-37

2 H 2 NOH + 4 Fe 3+
Cr2 O 7

N 2 O( g ) + 4 Fe 2 + + 4 H + + H 2 O

+ 6 Fe 2 + +14 H +

2Cr 3+ + 6 Fe 3+ + 7 H 2 O

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

1 mmol Cr2O72- 6 mmol Fe3+ 3 mmol H2NOH

0.0325 mmol K 2 Cr2 O 7

3 mmol H 2 NOH

19.83 mL K 2 Cr2 O 7
mL
mmol K 2 Cr2 O 7

= 0.0387 M H 2 NOH
50.00 mL sample

20-38

Zn 2+ + H 2 C 2 O 4 ZnC 2 O 4 ( s ) + 2 H +

2 MnO 4 + 5H 2 C 2 O 4 + 6H + 2 Mn 2+ + 10CO 2 ( g ) + 8H 2 O
2 mmol MnO4- 5 mmol Na2C2O4 5 mmol ZnO

0.01508 mmol KMnO 4

5 mmol ZnO
81.139 g ZnO

37.81 mL KMnO 4

mL
2 mmol KMnO 4
1000 mmol

100%
0.9280 g sample
= 12.46% ZnO

20-39 (Note: In the first printing of the text, the answer in the back of the book was in error.)

ClO 3 + 6 Fe 2+ + 6H + Cl + 3H 2 O + 6Fe 3+

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

0.08930 mmol Fe 2+
50.00 mL Fe 2+ = 4.4650 mmol Fe 2+
mL
0.083610 mmol Ce 4+
mmol Fe 2+ titrated by Ce 4+ =
14.93 mL Ce 4+
mL
1 mmol Fe 2+
= 1.2483 mmol Fe 2+
4+
mmol Ce
mmol Fe 2+ =

mmol Fe 2+ reacted with KClO 3 = 4.4650 1.2483 = 3.2167 mmol Fe 2+

1 mmol KClO 3 122.549 g KClO 3

3.2167 mmoL Fe 2+

6 mmol Fe 2+
1000 mmol

100% = 51.37% KClO 3

0.1279 g sample

20-40

Pb(C 2 H 5 ) 4 + I 2 Pb(C 2 H 5 ) 3 I + C 2 H 5 I
I 2 + 2S 2 O 3

2I + S 4 O 6

1 mmol I2 2 mmol S2O32- 1 mmol Pb(C2H5)4

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

0.02095 mmol I 2
15.00 mL I 2 = 0.314250 mmol I 2
mL
0.03465 mmol Na 2S 2 O 3
2
mmol I 2 titrated by S 2 O 3 =
6.09 mL Na 2S 2 O 3
mL
1 mmol I 2
= 0.10551 mmol I 2
2 mmol Na 2S 2 O 3
mmol I 2 =

mmol I 2 reacted with Pb(C 2 H 5 ) 4 = 0.314250 0.10551 = 0.20874 mmol I 2

1 mmol Pb(C 2 H 5 ) 4 323.4 mg Pb(C 2 H 5 ) 4

mmol I 2
mmol
2.70 10 3 mg Pb(C 2 H 5 ) 4
=
L
L sample
25.00 mL sample
1000 mL

0.20874 mmol I 2

20-41 H 3 AsO 3 + I 2 + H 2 O H 3 AsO 4 + 2I + 2 H +

1 mmol I2 1 mmol H3AsO3 mmol As2O3

0.01985 mmol I 2
1 mmol As 2 O 3 197.841 g As 2 O 3

24.56 mL I 2

mL
2 mmol I 2
1000 mmol

100%
7.41 g sample
= 0.651% As 2 O 3

Fundamentals of Analytical Chemistry: 8th ed.

20-42 Cr2 O 7

Chapter 20

2+

+ 3U 4+ + 2 H + 3UO 2 + 2Cr 3+ + H 2 O

1 mmol Cr2O72- 3 mmol U4+ 1 mmol NaCl

0.100 mmol K 2 Cr2 O 7

1 mmol NaCl
58.442 g NaCl

19.9 mL K 2 Cr2 O 7

mL
mmol K 2 Cr2 O 7
1000 mmol

100%
25.0 mL
0.800 g sample
50.0 mL
= 29.1% NaCl

20-43 2C 2 H 5SH + I 2 C 2 H 5SSC2 H 5 + 2I + 2 H +

0.01293 mmol I 2
50.0 mL I 2 = 0.6465 mmol I 2
mL
2
mmol I 2 titrated by S 2 O 3 =
mmol I 2 =

0.01425 mmol Na 2S 2 O 3
1 mmol I 2
15.72 mL Na 2S 2 O 3
= 0.1120 mmol I 2
mL
2 mmol Na 2S 2 O 3
mmol I 2 reacted with C 2 H 5SH = 0.6465 0.1120 = 0.5345 mmol I 2

2 mmol C 2 H 5SH 62.14 g C 2 H 5SH

0.5345 mmoL I 2

mmol I 2
1000 mmol

100% = 4.33% C 2 H 5SH

1.534 g sample

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-44

3TeO 2 + Cr2 O 7 + 8H + 3H 2 TeO 4 + 2Cr 3+ + H 2 O

2

Cr2 O 7 + 6Fe 2+ + 14 H + 2Cr 3+ + 6Fe 3+ + 7 H 2 O

0.03114 mmol K 2 Cr2 O 7

50.00 mL K 2 Cr2 O 7 = 1.5570 mmol K 2 Cr2 O 7
mL
mmol K 2 Cr2 O 7 titrated by Fe 2+ =
mmol K 2 Cr2 O 7 =

1 mmol K 2 Cr2 O 7
0.1135 mmol Fe 2 +
10.05 mL Fe 2 +
= 0.1901 mmol K 2 Cr2 O 7
mL
6 mmol Fe 2+
mmol K 2 Cr2 O 7 reacted with TeO 2 = 1.5570 0.1901 = 1.3668 mmol K 2 Cr2 O 7

3 mmol TeO 2
159.6 g TeO 2
1.3668 mmoL K 2 Cr2 O 7

mmol K 2 Cr2 O 7
1000 mmol

4.971 g sample

20-45

2I + Br2 I 2 + 2 Br

IO 3 + 5I + 6H + 3I 2 + 3H 2 O
2

I 2 + 2S 2 O 3 2I + S 4 O 6

100% = 13.16% TeO

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

1 mmol KI 1 mmol IO3- 3 mmol I2 6 mmol S2O32-

0.05982 mmol Na 2S 2 O 3
1 mmol KI
166.00 g KI

19.96 mL Na 2S 2 O 3

mL
6 mmol Na 2S 2 O 3 1000 mmol

100%
1.309 g sample
= 2.524% KI

2+
+
20-46 MnO 4 + 5Fe + 8H

mmol Fe =

Mn 2+ + 5Fe 3+ + 4 H 2 O

0.01920 mmol KMnO 4

5 mmol Fe
500.0 mL
13.72 mL KMnO 4

mL
mmol KMnO 4 50.00 mL

= 13.1712 mmol Fe
0.01920 mmol KMnO 4
5 mmol Fe
500.0 mL
mmol Fe and Cr =
36.43 mL KMnO 4

mL
mmol KMnO 4 100.0 mL
= 17.4864 mmol Fe and Cr
mmol Cr = (17.4864 13.1712 ) = 4.3152 mmol Cr

(13.1712 mmol Fe ) 55.847 g Fe

1000 mmol
100% = 69.07% Fe
1.065 g sample
( 4.3152 mmol Cr ) 51.996 g Cr
1000 mmol
100% = 21.07% Cr
1.065 g sample

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-47 In the Walden reductor,

+

V(OH ) 4 + 2 H + + e

VO 2+ + 3H 2 O

In the Jones reductor,

+

V(OH ) 4 + 4 H + + 3e

V 2+ + 4 H 2O

In the first titration,

Ce 4+ + Fe 2+ Fe 3+ + Ce 3+
+

Ce 4+ + VO 2+ + 3H 2 O V(OH ) 4 + Ce 3+ + 2 H +

mmol Fe and V = mmol Ce 4 + =

0.1000 mmol Ce 4 +
17.74 mL Ce 4 + = 1.7740 mmol Fe and V
mL

In the second titration,

Ce 4+ + Fe 2+ Fe 3+ + Ce 3+
+

3Ce 4+ + V 2+ + 4 H 2 O V(OH ) 4 + 3Ce 3+ + 4 H +

mmol Fe and 3 V = mmol Ce 4 + =

0.1000 mmol Ce 4 +
44.67 mL Ce 4 + = 4.4670 mmol Fe and 3 V
mL

Subtracting the first equation from the second equation gives

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

4.4670 1.7740 = 2.6930 = 2 mmol V

2.6930
= 1.3465 mmol V
2
1.3465 mmol V
mmol V2 O 5 =
= 0.67325 mmol V2 O 5
2
mmol Fe = 1.7740 1.3465 = 0.4275 mmol Fe
0.4275 mmol Fe
mmol Fe 2 O 3 =
= 0.21375 mmol Fe 2 O 3
2
mmol V =

( 0.67325 mmol V2 O 5 ) 181.88 g V2 O 5

1000 mmol
50.00 mL
2.559 g sample
500.0 mL

100% = 47.85% V2 O 5

( 0.21375 mmol Fe 2 O 3 ) 159.69 g Fe 2 O 3

1000 mmol
50.00 mL
2.559 g sample
500.0 mL

100% = 13.34% Fe 2 O 3

20-48

2Tl + + CrO 4

Tl 2 CrO 4 (s)
2

2Tl 2 CrO 4 (s) + 2 H + 4Tl + + Cr2 O 7 + H 2 O

2

Cr2 O 7 + 6Fe 2+ + 14 H + 2Cr 3+ + 6Fe 3+ + 7 H 2 O

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

0.1044 mmol Fe 2+
4 mmol Tl +
204.38 g Tl +
39.52 mL Fe 2+

= 0.5622 g Tl +
mL
6 mmol Fe 2+
1000 mmol

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-49

SO 2 ( g ) + 2OH SO 3 + H 2 O

IO 3 + 2 H 2SO 3 + 2Cl ICl 2 + SO 4 + 2 H +

1 mmol IO3- 2 mmol H2SO3 2 mmol SO2

2.50 L
64.00 min = 160 L of sample, there are
min
0.003125 mmol KIO 3
2 mmol SO 2 64.065 g SO 2
4.98 mL KIO 3

= 1.99402 10 3 g SO 2
mL
mmol KIO 3
1000 mmol

In

1.99402 10 3 g SO
2

1
.
20
g
160 L

10 6 ppm = 10.4 ppm SO 2

20-50

I 2 O 5 ( s ) + 5CO( g ) 5CO 2 ( g ) + I 2 ( g )
I 2 + 2S 2 O 3

2I + S 4 O 6

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

1 mmol I2 5 mmol CO 2 mmol S2O32-

0.00221 mmol S 2 O 3
mL

7.76 mL S 2 O 3

5 mmol CO
28.01 g CO

= 1.2009 10 3 g CO
2
1000 mmol
2 mmol S 2 O 3

1.2009 10 3 g CO

10 6 ppm = 40.5 ppm CO

1
.
2
g
24.7 L

20-51

S 2 + I 2 S( s ) + 2I
I 2 + 2S 2 O 3

2I + S 4 O 6

1 mmol I2 1 mmol H2S 2 mmol S2O32-

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

0.01070 mmol I 2
10.00 mL I 2 = 0.1070 mmol I 2
mL
2
0.01344 mmol S 2 O 3
1 mmol I 2
2
mmol I 2 in excess =
12.85 mL S 2 O 3
2
mL
2 mmol S 2 O 3
mmol I 2 added =

= 0.08635 mmol I 2
mmol I 2 reacted = mmol H 2S = 0.1070 0.08635 = 0.02065 mmol H 2S

34.082 g H 2S

0.02065 mmol H 2S

1000 mmol

10 6 ppm = 19.5 ppm H 2S

1.2 g

30.00 L

20-52 (a)

AgI + 2S 2 O 3 Ag(S 2 O 3 ) 2 + I

3Br2 + I + 3H 2 O IO 3 + 6Br + 6H +

5I + IO 3 + 6H + 3I 2 + 3H 2 O
2

I 2 + 2S 2 O 3 2I + S 4 O 6

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

(b) 1 mmol IO3- 3 mmol I2 1 mmol AgI 6 mmol S2O32-

0.0352 mmol S 2 O 3
mL

13.7 mL S 2 O 3

1 mmol AgI
234.77 mg AgI

2
mmol
6 mmol S 2 O 3

4.00 cm 2
=

4.72 mg AgI
cm 2

20-53

O 2 + 4 Mn (OH ) 2 ( s ) + 2 H 2 O

4 Mn ( OH ) 3 ( s )

4 Mn ( OH ) 3 ( s ) +12 H + + 4 I

4 Mn 2 + + 2I 2 + 6 H 2 O

0.00942 mmol S 2 O 3
mL

13.67 mL S 2 O 3

1.03 mg O 2
0.0423 mg O 2
=
mL sample

150 mL
25 mL sample

154 mL

1 mmol O 2
32.0 mg O 2

= 1.03 mg O 2
2
mmol
4 mmol S 2 O 3

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-54 (a) Titration of 25.00 mL of 0.025 M SnCl2 with 0.050 M FeCl3

Reaction: Sn2+ + 2Fe3+ Sn4+ + 2Fe2+

For Fe3+/Fe2+, Eo

4+

2+

For Sn /Sn , E

Initial concentration Sn2+

Concentration Fe3+

Volume SnCl2 solution

Equivalence point volume

0.154Equivalence point will be at 25.00 x 0.025 x 2/0.050=25.00 mL

0.025
0.05
25.00
25.00
Vol. Fe3+, mL

Percentages

[Sn4+]

[Sn2+]

[Fe3+]

[Fe2+]

E, V

10

10

2.50

0.0023

0.0205

0.126

11

20

5.00

0.0042

0.0167

0.136

12

30

7.50

0.0058

0.0135

0.143

13

40

10.00

0.0071

0.0107

0.149

14

50

12.50

0.0083

0.0083

0.154

15

60

15.00

0.0094

0.0063

0.159

16

70

17.50

0.0103

0.0044

0.165

17

80

20.00

0.0111

0.0028

0.172

18

90

22.50

0.0118

0.0013

0.182

19

95

23.75

0.0122

0.000641

0.192

20

99

24.75

0.0124

0.000126

0.213

21

99.9

24.98

0.0125

0.000013

0.243

22

100

25.00

23

101

25.25

0.0002

0.0249

0.653

24

105

26.25

0.0012

0.0244

0.694

25

110

27.50

0.0024

0.0238

0.712

26

120

30.00

0.0045

0.0227

0.730

27

Spreadsheet Documentation

28

B10=(A10/11)*$B$8

29
30

C10=($B$6*B10/2)/($B$7+B10)
D10=($B$5*$B$7-$B$6*B10.2)/($B$7+B10)

31

G10=$B$4-(0.0592/2)*LOG10(D10/C10)

32
33
34
35
36
37
38
39
40
41
42
43
44
45

0.771

0.360

G22=($B$3+2*$B$4)/3
E23=($B$6*B23-$B$5*$B$7*2)/($B$7+B23)
F23=($B$5*$B$7*2)/($B$7+B23)
G23=$B$3-0.0592*LOG10(F23/E23)

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-54 (b) Titration of 25.00 mL of 0.08467 M Na2S2O3 with 0.10235 M I2 (I3-)

Reaction: 2S2O32- + I3- S4O62- + 3I-

For S2O32-/S4O62-, Eo

For I3-/I-, Eo

Initial concentration S2O32-

0.08467

Concentration I3-

0.10235

Volume Na2S2O3 solution

Equivalence point volume

0.08

Equivalence point will be at 25.00 x 0.08467 / 2 / 0.10235=10.34

0.536mL

25.00
10.34
Vol. I3-, mL

Percentages

[S4O62-]

[S2O32-]

[I3-]

[I-]

E, V

10

10

1.03

0.0041

0.0732

0.076

11

20

2.07

0.0078

0.0626

0.089

12

30

3.10

0.0113

0.0527

0.098

13

40

4.14

0.0145

0.0436

0.106

14

50

5.17

0.0175

0.0351

0.114

15

60

6.20

0.0203

0.0271

0.123

16

70

7.24

0.0230

0.0197

0.132

17

80

8.27

0.0254

0.0127

0.145

18

90

9.31

0.0278

0.0062

0.165

19

95

9.82

0.0289

0.0030

0.183

20

99

10.24

0.0297

0.000605

0.225

21

99.9

10.33

0.0299

0.000064

0.283

22

100

10.34

23

101

10.44

0.000296

0.0896

0.525

24

105

10.86

0.0014736

0.0885

0.546

25

110

11.37

0.0029074

0.0873

0.555

26

120

12.41

0.00565611

0.0849

0.565

27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45

Spreadsheet Documentation
B10=(A10/11)*$B$8
C10=($B$6*B10/2)/($B$7+B10)
D10=($B$5*$B$7-$B$6*B10*2)/($B$7+B10)
G10=$B$3-(0.0592/2)*LOG10(D10^2/C10)

0.384

G22=($B$3+2*$B$4)/3
E23=($B$6*B23-$B$5*$B$7*2)/($B$7+B23)
F23=($B$5*$B$7*2)/($B$7+B23)
G23=$B$3-0.0592*LOG10(F23/E23)

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-54 (c) Titration of 0.1250 g Na2S2O3 with 0.01035 M KMnO4

Reaction: 2MnO4- + 5H2C2O4 +6H+ 2Mn2+ + 2CO2 +8H2O

For oxalate acid, Eo

For MnO4-, Eo

Initial mmol oxalate

0.93284acid initially present. Every 5 mmol of oxalate requires 2 mmol

Concentration MnO4-

0.01035MnO4-. Equivalence point will be at (0.93284 mmol X 2 / 5) / 0.01035

Initial volume solution

Equivalence point volume

-0.49
1.51There are 0.1250 g X 1000 mg/g/133.999 = 0.93284 mmol oxalate

25.00mmol/mL=36.05 mL KMnO4
36.05
Vol. MnO4-, mL

Percentages

pCO2

[H2C2O4]

[MnO4-]

[Mn2+]

[H+]

E, V

10

10

3.61

1.00

0.0294

1.00

-0.44

11

20

7.21

1.00

0.0232

1.00

-0.44

12

30

10.82

1.00

0.0182

1.00

-0.44

13

40

14.42

1.00

0.0142

1.00

-0.44

14

50

18.03

1.00

0.0108

1.00

-0.43

15

60

21.63

1.00

0.0080

1.00

-0.43

16

70

25.24

1.00

0.0056

1.00

-0.42

17

80

28.84

1.00

0.0035

1.00

-0.42

18

90

32.45

1.00

0.0016

1.00

-0.41

19

95

34.25

1.00 0.000788

1.00

-0.40

20

99

35.69

1.00 0.000154

1.00

-0.38

21

99.9

36.01

1.00 0.000016

1.00

-0.35

22

100

36.05

1.00

0.0061

1.00

0.94

23

101

36.41

6.05E-05

0.0061

1.00

1.49

24

105

37.85

2.97E-04

0.0059

1.00

1.49

25

110

39.66

5.77E-04

0.0058

1.00

1.50

26

120

43.26

0.0011

0.0055

1.00

1.50

27
28

Spreadsheet Documentation
B10=(A10/11)*$B$8

F22=$B$5*(2/5)/($B$8+B22)
E23=($B$6*B23-$B$5*2/5)/($B$7+B23)
H23=$B$4-(0.0592/5)*LOG10(F23/(E23*G23^8))

30

D10=($B$5-$B$6*B10*5/2)/($B$7+B10)
H10=$B$3-(0.0592/2)*LOG10(D10/(C10^2*G10^2))

31

H22=((2*$B$3+5*$B$4)/7)-(0.0592/7)*LOG10(1/(C22*2*G22^10))

29

32
33
34
35
36
37
38
39
40
41
42
43
44
45

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-54 (d) Titration of 20.00 mL 0.1034 M Fe2+ with 0.01500 M K2Cr2O7

Reaction: 6Fe2+ + Cr2O72- +14H+ 6Fe3+ + 2Cr3+ +7H2O

For dichromate, Eo

For Fe3+/Fe2+, Eo

Initial Fe2+ concentration

1.33
0.771There are 20.00 mL X 0.1034mmol/mL = 2.068 mmol Fe2+
0.1034initial present. Every mmol of dichromate requires 6 mmol Fe2+.

2-

Concentration Cr2O7

Initial volume solution

Equivalence point volume

0.015Equivalence point will be at (20.00 mL / 0.93284 mmol / 6) / 0.01500

20.00mmol/mL=22.98 mL
22.98
Vol. Cr2O72-, mL

Percentages

[Fe3+]

[Fe2+]

[Cr2O72-]

[Cr3+]

[H+]

E, V

10

10

2.30

0.0093

0.0835

1.00

0.715

11

20

4.60

0.0168

0.0673

1.00

0.735

12

30

6.89

0.0231

0.0538

1.00

0.749

13

40

9.19

0.0283

0.0425

1.00

0.761

14

50

11.49

0.0328

0.0328

1.00

0.771

15

60

13.79

0.0367

0.0245

1.00

0.781

16

70

16.09

0.0401

0.0172

1.00

0.793

17

80

18.38

0.0431

0.0108

1.00

0.807

18

90

20.68

0.0458

0.0051

1.00

0.828

19

95

21.83

0.0470

0.0025

1.00

0.847

20

99

22.75

0.0479

0.00047911

1.00

0.889

21

99.9

22.96

0.0481

4.349E-05

1.00

0.951

22

100

22.98

0.0160

1.00

1.26

23

101

23.21

8.05E-05

0.0160

1.00

1.33

24

105

24.13

3.91E-04

0.0156

1.00

1.33

25

110

25.28

7.62E-04

0.0152

1.00

1.34

26

120

27.58

0.0014

0.0145

1.00

1.34

27

Spreadsheet Documentation

28

B10=(A10/11)*$B$8

F22=($B$5*$B$7/3)/($B$7+B22)

29

C10=($B$6*B10*6)/($B$7+B10)

H22=(($B$4+6*$B$3)/7)-(0.0592/7)*LOG10(2*F22/G22^14)

30

D10=($B$5*$B$7-$B$6*B10*6)/($B$7+B10)

E23=($B$6*B23-($B$5*$B$7/6)/($B$7+B23)

31

H10=$B$4-0.0592*LOG10(D10/C10)

H23=$B$3-(0.0592/6)*LOG10(F23^2/(E23*G23^14))

32
33
34
35
36
37
38
39
40
41
42
43
44
45

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

20-54 (e) Titration of 35.00 mL 0.0578 M IO3- with 0.05362 M Na2S2O3

Reactions: IO3- + 5I- + 6H+ 3I2 + 3H2O; I2 + 2S2O32- 2I- + S4O62-

For thiosulfate, Eo

4
5

For I2/I-, E

0.08
0.615There are 35.00 mL X 0.0578 mmol/mL = 2.023 mmol IO3-

0.0578initially present. Every mmol of IO3- requires 6 mmol S2O32-.

Initial IO3 concentration

0.05362Equivalence point will be at ( 2.023 mmol * 6) /

23

Concentration S2O

Initial volume solution

Equivalence point volume

35.000.05362 mmol/mL=226.37 mL
226.37
Vol. S2O32-, mL

Percentages

[I-]

[I2]

[S2O32-]

[S4O62-]

E, V

10

10

22.64

0.0211

0.0948

0.684

11

20

45.27

0.0302

0.0605

0.669

12

30

67.91

0.0354

0.0413

0.660

13

40

90.55

0.0387

0.0290

0.653

14

50

113.19

0.0410

0.0205

0.647

15

60

135.82

0.0426

0.0142

0.641

16

70

158.46

0.0439

0.0094

0.635

17

80

181.10

0.0449

0.0056

0.628

18

90

203.73

0.0458

0.0025

0.617

19

95

215.05

0.0461

0.0012

0.608

20

99

224.11

0.0464

2.34E-04

0.587

21

99.9

226.14

0.0464

2.33E-05

0.557

22

100

226.37

23

101

228.63

4.60E-04

0.0230

0.23

24

105

237.69

2.23E-03

0.0223

0.19

25

110

249.01

4.27E-03

0.0214

0.17

26

120

271.64

7.92E-03

0.0198

0.15

30

Spreadsheet Documentation
B10=(A10/100)*$B$8
C10=($B$6*B10)/($B$7+B10)
D10=(($B$5*$B$7*3)-($B$6*B10/2))/($B$7+B10)

31

H10=$B$4-(0.0592/2)*LOG10(D10^2/C10)

27
28
29

32
33
34
35
36
37
38
39
40
41
42
43
44
45

0.35

E23=(($B$6*B23)-($B$5*$B$7*6)/($B$7+B23)
F23=(($B$5*$B$7*3)/($B$7+B23)
H22=($B$3+$B$4)/2
H23=$B$3-(0.0592/2)*LOG10(E23^2/F23)

Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20