Fundamentals of Analytical Chemistry: 8th ed.

Chapter 20

Chapter 20

2 2 
20-1 (a) 2Mn2  5S2 O8  8H 2 O  10SO 4  2MnO4  16H 

(b) NaBiO 3 ( s)  2Ce3  4H   BiO   2Ce 4  2H 2O  Na 

2
(c) H 2 O2  U 4  UO2  2H 


(d) V(OH) 4  Ag( s)  Cl   2H   VO 2  AgCl ( s)  3H 2 O


(e) 2MnO4  5H 2 O2  6H   5O2  2Mn2  8H 2 O


(f) ClO 3  6I   6H   3I 2  Cl   3H 2 O

2
20-2 (a) 2Fe3  SO 2 ( g )  2H 2 O  2Fe2  SO 4  4H 

(b) 2H 2 MoO4  3Zn( s)  12H   3Zn2  2MoO3  8H 2O

 
(c) 2MnO4  5HNO2  H   2Mn2  5NO3  3H 2 O


(d) BrO3  5Br   C6 H 5 NH 2  3H   Br3C6 H 5 NH 2  3Br   3H 2 O

2 2
(e) 2HAsO3  O2 ( g )  2HAsO4

(f) 2I   2HNO2  2H   I 2  2NO  2H 2O

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 

The excess HCl increases the tendency of this reaction to occur by the common ion

effect.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

20-4 Amalgamation of the zinc prevents loss of reagent by reaction of the zinc with hydronium

ions.

2
20-5 UO2  2Ag( s)  4H   2Cl  

U 4  2AgCl ( s)  H 2 O

20-6 2TiO2  Zn( s)  4H  


2Ti3  Zn2  2H 2 O

20-7 Standard solutions of reductants find somewhat limited use because of their susceptibility

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 2MnO4  3Mn2  2H 2 O  5MnO2 ( s)  4H 

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.


20-13 4MnO4  2H 2 O  4MnO2 ( s) 3O 2 ( g )  4OH 
brown
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

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   O2 ( g )  4H   2I 3  2H 2 O

2 
20-17 S2 O3  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.


IO3  5I   6H   3I 2  3H 2 O

20-19


BrO 3  6I   6H   Br   3I 2  3H 2 O
excess
2 2
I 2  2S2 O 3  2I   S 4 O 6

20-20

2
Cr2 O 7  6I   14H   2Cr 3  3I 2  7H 2 O
excess
2 2
I 2  2S2 O 3  2I   S 4 O 6

20-21 2I 2  N 2 H 4  N 2 ( g )  4H   4I 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

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

1000 mmol Fe2

0.2256 g sample   4.03961 mmol Fe2
55.847 g

4.03961 mmol Fe2 1 mmol Ce 4

(a)  2
 0.1142 M Ce 4
35.37 mL mmol Fe

2
4.03961 mmol Fe2 1 mmol Cr2 O 7 2
(b)   0.01904 M Cr2 O7
35.37 mL 6 mmol Fe2


4.03961 mmol Fe2 1 mmol MnO4 
(c)  2
 0.02284 M MnO4
35.37 mL 5 mmol Fe


4.03961 mmol Fe2 1 mmol V(OH) 4 
(d)  2
 0.1142 M V(OH) 4
35.37 mL mmol Fe


4.03961 mmol Fe2 1 mmol IO3 
(e)  2
 0.02855 M IO3
35.37 mL 4 mmol Fe

20-24

0.02500 mmol K 2 Cr2 O7 294.185 g K 2 Cr2 O 7

 500.0 mL   3.677 g K 2 Cr2 O7
mL 1000 mmol

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

20-25

0.02500 mmol KBrO3 1000 mL 167.001 g KBrO3

 2.000 L    8.350 g KBrO3
mL L 1000 mmol

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

Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

20-26

0.0500 mmol KMnO4 1000 mL 158.034 g KMnO4

 2.0 L    15.80 g KMnO4
mL L 1000 mmol

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

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 mmol I 3 L 1000 mmol

Dissolve between 25 and 26 g I2 in a concentrated solution of KI and dilute to 2.0 L.


20-28 2MnO4  5H 2 C2 O4  6H   2Mn2  10CO2 ( g )  8H 2 O

0.1756 g Na 2 C 2 O 4 1000 mmol Na 2 C2 O 4 2 mmol KMnO4

   0.01636 M KMnO4
32.04 mL KMnO4 133.999 g 5 mmol Na 2 C 2 O 4

20-29 Ce 4  Fe2  Ce3  Fe3

0.1809 g Fe 1000 mmol Fe 1 mmol Fe2 1 mmol Ce 4

4
   2
 0.1034 M Ce 4
31.33 mL Ce 55.847 g mmol Fe mmol Fe

20-30

2
Cr2 O 7  6I   14 H   2Cr 3  3I 2  7H 2 O
2 2
I 2  2S2 O 3  2I   S 4 O 6

1 mmol Cr2O72-  3 mmol I2  6 mmol S2O32-

2
0.1259 g K 2 Cr2 O7 1000 mmol K 2 Cr2 O7 6 mmol S2 O3
   0.06223 M Na 2S2 O3
41.26 mL Na 2S2 O3 294.185 g mmol K 2 Cr2 O7
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

20-31


BrO 3  6I   6H   Br   3I 2  3H 2 O
2 2
I 2  2S2 O 3  2I   S 4 O 6

1 mmol BrO3-  3 mmol I2  6 mmol S2O32-

2
0.1017 g KBrO3 1000 mmol KBrO3 6 mmol S2 O3
   0.09192 M Na 2S2 O 3
39.75 mL Na 2S2 O3 167.001 g mmol KBrO3

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 
 100%
0.978 g sample
 22.37% Sb 2S3

20-33

MnO2  2I   4H   Mn2  I 2  2 H 2 O
2 2
I 2  2S2 O 3  2I   S 4 O 6

1 mmol MnO2  1 mmol I2  2 mmol S2O32-

 0.07220 mmol Na 2S2 O 3 1 mmol MnO2 86.937 g MnO2 

  32.30 mL Na 2S 2 O 3   
 mL 2 mmol Na 2S2 O 3 1000 mmol 
 100%
0.1344 g sample
 75.42% MnO2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

 2
20-34 3CS( NH 2 ) 2  4BrO3  3H 2 O  3CO( NH 2 ) 2  3SO 4  4Br   6H 

4 mmol BrO3-  3 mmol CS(NH2)2

 0.00833 mmol KBrO3 3 mmol CS( NH 2 ) 2 76.122 g CS( NH 2 ) 2 

  14.1 mL KBrO3   
 mL 4 mmol KBrO3 1000 mmol   100%
0.0715 g sample
 9.38% CS( NH 2 ) 2


20-35 MnO4  5Fe2  8H   Mn2  5Fe3  4H 2 O

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

0.02086 KMnO4
mmol KMnO4   39.21 mL KMnO4  0.8179 mmol KMnO4
mL

(a)

 5 mmol Fe2 1 mmol Fe 55.847 g Fe 

 0.8179 mmoL KMnO4    
 mmol KMnO4 mmol Fe2 1000 mmol 
 100%
0.7120 g sample
 32.08% Fe

(b)

 5 mmol Fe2 O 3 159.692 g Fe2 O 3 

 0.8179 mmoL KMnO4   
 2 mmol KMnO4 1000 mmol 
 100%  45.86% Fe2 O 3
0.7120 g sample

2
20-36 3Sn 3  Cr2 O7  14H  

3Sn 4  2Cr 3  7H 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 
 100%  53.66% SnO 2
0.4352 g sample

20-37

2 H 2 NOH  4 Fe3 

N 2 O( g)  4 Fe2  4 H   H 2 O
2
Cr2 O 7  6Fe2  14 H  

2Cr 3  6Fe3  7 H 2 O

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

Zn2  H 2 C 2 O 4  ZnC2 O 4 ( s )  2 H 

2MnO4  5H 2 C 2 O 4  6H   2Mn2  10CO 2 ( g )  8H 2 O
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

2 mmol MnO4-  5 mmol Na2C2O4  5 mmol ZnO

 0.01508 mmol KMnO4 5 mmol ZnO 81.139 g ZnO 

  37.81 mL KMnO4   
 mL 2 mmol KMnO4 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  6Fe2  6H   Cl   3H 2 O  6Fe3

0.08930 mmol Fe2

mmol Fe2   50.00 mL Fe2  4.4650 mmol Fe2
mL
2 4 0.083610 mmol Ce 4
mmol Fe titrated by Ce   14.93 mL Ce 4 
mL
2
1 mmol Fe
 1.2483 mmol Fe2
mmol Ce 4
mmol Fe2 reacted with KClO3  4.4650  1.2483  3.2167 mmol Fe2

 1 mmol KClO3 122.549 g KClO3 

 3.2167 mmoL Fe2   
 6 mmol Fe2 1000 mmol 
 100%  51.37% KClO3
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
2 2
I 2  2S2 O 3  2I   S 4 O 6

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

0.02095 mmol I 2
mmol I 2   15.00 mL I 2  0.314250 mmol I 2
mL
2 0.03465 mmol Na 2S 2 O 3
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 reacted with Pb(C 2 H 5 ) 4  0.314250  0.10551  0.20874 mmol I 2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

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

0.20874 mmol I 2  
mmol I 2 mmol 2.70  103 mg Pb(C 2 H 5 ) 4

L L sample
25.00 mL sample 
1000 mL

20-41 H 3AsO3  I 2  H 2 O  H 3AsO4  2I   2H 

1 mmol I2  1 mmol H3AsO3  ½ mmol As2O3

 0.01985 mmol I 2 1 mmol As2 O 3 197.841 g As2 O 3 

  24.56 mL I 2   
 mL 2 mmol I 2 1000 mmol 
 100%
7.41 g sample
 0.651% As2 O 3

2 2
20-42 Cr2 O7  3U 4  2H   3UO2  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
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

20-43 2C2 H 5SH  I 2  C2 H 5SSC 2 H 5  2I   2H 

0.01293 mmol I 2
mmol I 2   50.0 mL I 2  0.6465 mmol I 2
mL
2
mmol I 2 titrated by S 2 O 3 
0.01425 mmol Na 2S 2 O 3 1 mmol I 2
 15.72 mL Na 2S2 O 3   0.1120 mmol I 2
mL 2 mmol Na 2S2 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

20-44

2
3TeO 2  Cr2 O 7  8H   3H 2 TeO 4  2Cr 3  H 2 O
2
Cr2 O 7  6Fe2  14 H   2Cr 3  6Fe3  7H 2 O

0.03114 mmol K 2 Cr2 O 7

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 Fe2 
0.1135 mmol Fe2 1 mmol K 2 Cr2 O 7
 10.05 mL Fe2   0.1901 mmol K 2 Cr2 O 7
mL 6 mmol Fe2
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 
 100%  13.16% TeO 2
4.971 g sample

20-45

2I   Br2  I 2  2 Br 

IO 3  5I   6H   3I 2  3H 2 O
2 2
I 2  2S 2 O 3  2I   S 4 O 6

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

Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

 0.05982 mmol Na 2S2 O 3 1 mmol KI 166.00 g KI 

  19.96 mL Na 2S 2 O 3   
 mL 6 mmol Na 2S2 O 3 1000 mmol 
 100%
1.309 g sample
 2.524% KI


20-46 MnO4  5Fe2  8H  

Mn2  5Fe3  4H 2 O

0.01920 mmol KM nO4 5 mmol Fe 500.0 mL

mmol Fe   13.72 mL KM nO4  
mL mmol KM nO4 50.00 mL
 13.1712 mmol Fe
0.01920 mmol KM nO4 5 mmol Fe 500.0 mL
mmol Fe and Cr   36.43 mL KM nO4  
mL mmol KM nO4 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

20-47 In the Walden reductor,


V(OH) 4  2H   e  

VO 2  3H 2 O

In the Jones reductor,


V(OH) 4  4H   3e  

V 2  4 H 2 O

In the first titration,

Ce 4  Fe2  Fe3  Ce 3

Ce 4  VO 2  3H 2 O  V(OH) 4  Ce 3  2H 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

0.1000 mmol Ce 4
mmol Fe and V  mmol Ce 4  17.74 mL Ce 4  1.7740 mmol Fe and V
mL

In the second titration,

Ce 4  Fe2  Fe3  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

4.4670  1.7740  2.6930  2  mmol V

2.6930
mmol V   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 Fe2 O 3   0.21375 mmol Fe2 O 3
2

0.67325 mmol V2 O5   181.88 g V2 O5

1000 mmol
 100%  47.85% V2 O 5
50.00 mL
2.559 g sample 
500.0 mL

0.21375 mmol Fe2 O 3   159.69 g Fe2 O 3

1000 mmol
 100%  13.34% Fe2 O 3
50.00 mL
2.559 g sample 
500.0 mL

20-48

2
2Tl  CrO 4  Tl2 CrO 4 (s)
2
2Tl2 CrO 4 (s)  2 H   4Tl  Cr2 O 7  H 2O
2
Cr2 O 7  6Fe2  14 H   2Cr 3  6Fe3  7 H 2 O
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

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

0.1044 mmol Fe2 4 mmol Tl 204.38 g Tl

 39.52 mL Fe2    0.5622 g Tl
mL 6 mmol Fe2 1000 mmol

20-49

2
SO 2 ( g )  2OH   SO 3  H 2O
   2
IO3  2H 2SO 3  2Cl  ICl 2  SO 4  2H 

1 mmol IO3-  2 mmol H2SO3  2 mmol SO2

2.50 L
In  64.00 min  160 L of sample, there are
min
0.003125 mmol KIO3 2 mmol SO 2 64.065 g SO 2
 4.98 mL KIO3    1.99402  10 3 g SO 2
mL mmol KIO3 1000 mmol
 
 1.99402  10 3 g SO 
 2
  10 6 ppm  10.4 ppm SO 2
 160 L  1.20 g 
 
 L 

20-50

I 2 O5 ( s )  5CO( g )  5CO 2 ( g )  I 2 ( g )
2 2
I 2  2S2 O 3  2I   S 4 O 6

1 mmol I2  5 mmol CO  2 mmol S2O32-

2
0.00221 mmol S 2 O 3 2 5 mmol CO 28.01 g CO
 7.76 mL S2 O 3  2
  1.2009  10 3 g CO
mL 2 mmol S2 O 3 1000 mmol
 
 1.2009  10 3 g CO 
   106 ppm  40.5 ppm CO
 24.7 L  1 .2 g 
 
 L 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

20-51

S2  I 2  S( s )  2I 
2 2
I 2  2S2 O 3  2I   S 4 O 6

1 mmol I2  1 mmol H2S  2 mmol S2O32-

0.01070 mmol I 2
mmol I 2 added   10.00 mL I 2  0.1070 mmol I 2
mL
2
0.01344 mmol S2 O 3 2 1 mmol I 2
mmol I 2 in excess   12.85 mL S 2 O 3  2
mL 2 mmol S 2 O 3
 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 
 106 ppm  19.5 ppm H 2S
 1.2 g 
 30.00 L  
 L 

20-52 (a)

2 3
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 2
I 2  2S 2 O 3  2I   S4 O 6

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

2
0.0352 mmol S 2 O 3 2 1 mmol AgI 234.77 mg AgI
 13.7 mL S 2 O 3  2

mL 6 mmol S 2 O 3 mmol
4.00 cm 2
4.72 mg AgI

cm 2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

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   4I  

4 Mn2  2I 2  6H 2 O

2
0.00942 mmol S 2 O 3 2 1 mmol O 2 32.0 mg O 2
 13.67 mL S2 O 3  2
  1.03 mg O 2
mL 4 mmol S 2 O 3 mmol
1.03 mg O 2 0.0423 mg O 2

 150 mL  mL sample
 25 mL sample  
 154 mL 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

A B C D E F G H
1 20-54 (a) Titration of 25.00 mL of 0.025 M SnCl2 with 0.050 M FeCl3
 Sn
2+ 3+ 4+ 2+
2 Reaction: Sn + 2Fe + 2Fe
3 For Fe3+/Fe2+, Eo 0.771
4 For Sn4+/Sn2+, Eo 0.154 Equivalence point will be at 25.00 x 0.025 x 2/0.050=25.00 mL
5 Initial concentration Sn2+ 0.025
6 Concentration Fe3+ 0.05
7 Volume SnCl2 solution 25.00
8 Equivalence point volume 25.00
9 Percentages Vol. Fe3+, mL [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 0.360
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$8 G22=($B$3+2*$B$4)/3
29 C10=($B$6*B10/2)/($B$7+B10) E23=($B$6*B23-$B$5*$B$7*2)/($B$7+B23)
30 D10=($B$5*$B$7-$B$6*B10.2)/($B$7+B10) F23=($B$5*$B$7*2)/($B$7+B23)
31 G10=$B$4-(0.0592/2)*LOG10(D10/C10) G23=$B$3-0.0592*LOG10(F23/E23)
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Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

A B C D E F G H
-
1 20-54 (b) Titration of 25.00 mL of 0.08467 M Na2S2O3 with 0.10235 M I2 (I3 )
Reaction: 2S2O3 + I3  S4O6
2- - 2- -
2 + 3I
3 For S2O32-/S4O62-, Eo 0.08
Equivalence point will be at 25.00 x 0.08467 / 2 / 0.10235=10.34
4 For I3-/I-, Eo 0.536 mL
5 Initial concentration S2O32- 0.08467
6 Concentration I3- 0.10235
7 Volume Na2S2O3 solution 25.00
8 Equivalence point volume 10.34
9 Percentages Vol. I3-, mL [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 0.384
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 Spreadsheet Documentation
28 B10=(A10/11)*$B$8 G22=($B$3+2*$B$4)/3
29 C10=($B$6*B10/2)/($B$7+B10) E23=($B$6*B23-$B$5*$B$7*2)/($B$7+B23)
30 D10=($B$5*$B$7-$B$6*B10*2)/($B$7+B10) F23=($B$5*$B$7*2)/($B$7+B23)
31 G10=$B$3-(0.0592/2)*LOG10(D10^2/C10) G23=$B$3-0.0592*LOG10(F23/E23)
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Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

A B C D E F G H
1 20-54 (c) Titration of 0.1250 g Na2S2O3 with 0.01035 M KMnO4
Reaction: 2MnO4 + 5H2C2O4 +6H  2Mn + 2CO2 +8H2O
- + 2+
2
3 For oxalate acid, Eo -0.49
4 For MnO4-, Eo 1.51 There are 0.1250 g X 1000 mg/g/133.999 = 0.93284 mmol oxalate
5 Initial mmol oxalate 0.93284 acid initially present. Every 5 mmol of oxalate requires 2 mmol
6 Concentration MnO4- 0.01035 MnO4-. Equivalence point will be at (0.93284 mmol X 2 / 5) / 0.01035
7 Initial volume solution 25.00 mmol/mL=36.05 mL KMnO4
8 Equivalence point volume 36.05
9 Percentages Vol. MnO4-, mL 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 Spreadsheet Documentation
28 B10=(A10/11)*$B$8 F22=$B$5*(2/5)/($B$8+B22)
29 D10=($B$5-$B$6*B10*5/2)/($B$7+B10) E23=($B$6*B23-$B$5*2/5)/($B$7+B23)
30 H10=$B$3-(0.0592/2)*LOG10(D10/(C10^2*G10^2)) H23=$B$4-(0.0592/5)*LOG10(F23/(E23*G23^8))
31 H22=((2*$B$3+5*$B$4)/7)-(0.0592/7)*LOG10(1/(C22*2*G22^10))
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Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

A B C D E F G H
2+
1 20-54 (d) Titration of 20.00 mL 0.1034 M Fe with 0.01500 M K2Cr2O7
Reaction: 6Fe + Cr2O7 +14H  6Fe + 2Cr +7H2O
2+ 2- + 3+ 3+
2
3 For dichromate, Eo 1.33
4 For Fe3+/Fe2+, Eo 0.771 There are 20.00 mL X 0.1034mmol/mL = 2.068 mmol Fe2+
5 Initial Fe2+ concentration 0.1034 initial present. Every mmol of dichromate requires 6 mmol Fe2+.
6 Concentration Cr2O72- 0.015 Equivalence point will be at (20.00 mL / 0.93284 mmol / 6) / 0.01500
7 Initial volume solution 20.00 mmol/mL=22.98 mL
8 Equivalence point volume 22.98
9 Percentages Vol. Cr2O72-, mL [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))
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Fundamentals of Analytical Chemistry: 8th ed. Chapter 20

A B C D E F G
-
1 20-54 (e) Titration of 35.00 mL 0.0578 M IO3 with 0.05362 M Na2S2O3
Reactions: IO3 + 5I + 6H  3I2 + 3H2O; I2 + 2S2O3  2I + S4O6
- - + 2- - 2-
2
3 For thiosulfate, Eo 0.08
o -
4 For I2/I-, E 0.615 There are 35.00 mL X 0.0578 mmol/mL = 2.023 mmol IO3
- 2-
5 Initial IO3- concentration 0.0578 initially present. Every mmol of IO3 requires 6 mmol S2O3 .
6 Concentration S2O32- 0.05362 Equivalence point will be at ( 2.023 mmol * 6) /
7 Initial volume solution 35.00 0.05362 mmol/mL=226.37 mL
8 Equivalence point volume 226.37
9 Percentages Vol. S2O32-, mL [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 0.35
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
27 Spreadsheet Documentation
28 B10=(A10/100)*$B$8 E23=(($B$6*B23)-($B$5*$B$7*6)/($B$7+B23)
29 C10=($B$6*B10)/($B$7+B10) F23=(($B$5*$B$7*3)/($B$7+B23)
30 D10=(($B$5*$B$7*3)-($B$6*B10/2))/($B$7+B10) H22=($B$3+$B$4)/2
31 H10=$B$4-(0.0592/2)*LOG10(D10^2/C10) H23=$B$3-(0.0592/2)*LOG10(E23^2/F23)
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