CHAPTER 13: SUPPLEMENTARY PROBLEMS 27

S13-1. Calculate
Y
4- for EDTA at pH 6.62.
S13-2. (a) Find the conditional formation constant for Ca(EDTA)
2-
at pH 10.00.
(b) Find the concentration of free Ca
2+
in 0.050 M Na
2
[Ca(EDTA)] at pH 10.00.
S13-3. A brainbuster! What is the quotient [MgY
2-
]/[NaY
3-
] in a solution prepared by mixing 0.100
M Na
2
EDTA with an equal volume of 0.100 M Mg(NO
3
)
2
? Assume that the pH is high
enough that there is a negligible amount of unbound EDTA. You can approach this problem
by realizing that nearly all Mg
2+
will be bound to EDTA and nearly all Na
+
will be free.
S13-4. Consider the titration of 100.0 mL of 0.050 0 M EDTA at pH 10.00 with 0.100 M
metal ion, M
n+
.
(a) What is the equivalence volume, V
e
, in milliliters?
(b) Calculate the concentration of total free EDTA at V =
1
2
V
e
.
(c) What fraction (
Y
4-) of free EDTA is in the form Y
4-
at pH 10.00?
(d) The formation constant (K
f
) is 10
8.00
. Calculate the value of the conditional formation
constant K
f
'
(=
Y
4-

K
f
) .
(e) Calculate the concentration of free metal ion at V = V
e
.
(f) What is the concentration of total free EDTA ion at V = 1.100 V
e
?
S13-5. Calculate pFe
2+
at each of the following points in the titration of 25.00 mL of 0.020 26 M
EDTA by 0.038 55 M Fe
2+
at pH 6.00: (a) 12.00 mL (b) V
e
(c) 14.00 mL
S13-6. Consider the titration of 50.0 mL of 0.011 1 M Y
3+
(Y = yttrium) with 0.022 2 M EDTA at pH
5.00. Calculate pY
3+
at the following volumes of added EDTA and sketch the titration curve:
(a) 0 mL (d) 24.0 mL (g) 25.1 mL
(b) 10.0 mL (e) 24.9 mL (h) 26.0 mL
(c) 20.0 mL (f) 25.0mL (i) 30.0 mL
S13-7. Calculate pCd
2+
at each of the following points in the titration of 10.00 mL of 0.001 00 M
Cd
2+
with 0.002 00 M EDTA at pH 12.00 in a solution whose NH
3
concentration is somehow
fixed at 0.200 M:
(a) 0 mL (b) 1.00 mL (c) 4.90 mL (d) 5.00 mL (e) 5.10 mL (f) 6.00 mL
S13-8. Allosteric interactions. The molecule drawn below contains two large rings with oxygen
atoms capable of binding metal atoms, one on each ring.
ADVANCED TOPICS IN CHEMICAL EQUILIBRIUM
Chapter 13: Supplementary Problems 28


O
O
O
O
O
O
O
O
O
O
O
O

Calling the molecule L, we can represent the metal-binding reactions as
L + M LM K
1
=
[LM]
[L][M]
(A)
LM + M LM
2
K
2
=
[LM
2
]
[LM][M]
(B)
If binding at one site influences binding at the other site, there is said to be an allosteric
interaction between the sites. If binding at one site makes binding at the other site more
favorable than it was in the absence of the first binding, there is said to be positive
cooperativity between the sites. If binding at one site makes biding at the second site less
favorable, there is negative cooperativity between the sites. If there is no interaction between
sites, binding is said to be noncooperative. This means that a metal at one site has no effect on
metal binding at the other site.
The binding of Hg(CF
3
)
2
to the molecule above in benzene solution was found to have
K
1
= 4.0 (0.1) K
2
[J. Rebek, Jr., T. Costello, L. Marshall, R. Wattley, R. C. Gadwood, and
K. Onan, J. Amer. Chem. Soc. 1985, 107, 7481]. Show that K
1
= 4K
2
corresponds to
noncooperative binding. Hint: If the two binding sites are represented as we can
represent the equilibria as follows:

where represents metal bound at one site. In noncooperative binding, the four populations
, , , and must be equal when the ligand is 50% saturated with
metal.
S13-9. EDTA at pH 5 was titrated with standard Pb
2+
using xylenol orange as indicator (Table 13-3).
Which is the principal species of the indicator at pH 5? What color was observed before the
equivalence point? after the equivalence point? What would be the color change if the
titration were conducted at pH 8 instead of pH 5?
Chapter 13: Supplementary Problems 29


S13-10. A 25.00-mL sample containing Fe
3+
was treated with 10.00 mL of 0.036 7 M EDTA to
complex all the Fe
3+
and leave excess EDTA in solution. The excess EDTA was then back-
titrated, requiring 2.37 mL of 0.046 1 M Mg
2+
. What was the concentration of Fe
3+
in the
original solution?
S13-11. Express the hardness of water containing 3.2 mM Ca
2+
+ 1.1 mM Mg
2+
in terms of mg
CaCO
3
/L. (FM CaCO
3
100.09)
S13-12. Cyanide can be determined indirectly by EDTA titration. A known excess of Ni
2+
is added to
the cyanide to form tetracyanonickelate:
4CN
-
+ Ni
2+
Ni(CN)
4
2-

When the excess Ni
2+
is titrated with standard EDTA, Ni(CN)
4
2-
does not react. In a cyanide
analysis 12.7 mL of cyanide solution was treated with 25.0 mL of standard solution containing
excess Ni
2+
to form tetracyanonickelate. The excess Ni
2+
required 10.1 mL of 0.013 0 M
EDTA for complete reaction. In a separate experiment, 39.3 mL of 0.013 0 M EDTA was
required to react with 30.0 mL of the standard Ni
2+
solution. Calculate the molarity of CN
-
in
the 12.7-mL sample of unknown.
S13-13. A mixture of Mn
2+
, Mg
2+
, and Zn
2+
was analyzed as follows: The 25.00-mL sample was
treated with 0.25 g of NH
3
OH
+
Cl
-
(hydroxylammonium chloride, a reducing agent that
maintains manganese in the +2 state), 10 mL of ammonia buffer (pH 10), and a few drops of
eriochrome black T indicator and then diluted to 100 mL. It was warmed to 40 C and titrated
with 39.98 mL of 0.045 00 M EDTA to the blue end point. Then 2.5 g of NaF was added to
displace Mg
2+
from its EDTA complex. The liberated EDTA required 10.26 mL of standard
0.020 65 M Mn
2+
for complete titration. After this second end point was reached, 5 mL of 15
wt % aqueous KCN was added to displace Zn
2+
from its EDTA complex. This time the
liberated EDTA required 15.47 mL of standard 0.020 65 M Mn
2+
. Calculate the number of
milligrams of each metal (Mn
2+
, Zn
2+
, and Mg
2+
) in the 25.00-mL sample of unknown.
S13-14. Here is a procedure for the consecutive determination of Bi
3+
, Ti
4+
and Al
3+
in a mixture that
might arise in the analysis of aluminum ore, clays or cements
[M. A. El-Hamied Hafez, Talanta 1992, 39, 1189].
(1) The solution is acidified to pH 1-2 with HNO
3
, at which only Bi
3+
has a large enough
conditional formation constant to be titrated. The indicator semixylenol orange is added
and the solution is titrated with standard EDTA until just reaching the end point color
change from red (MIn) to yellow (In). This gives the Bi
3+
content of the solution and
Chapter 13: Supplementary Problems 30


leaves Ti
4+
and Al
3+
uncomplexed.
(2) Then excess EDTA is added and the pH is raised to 5 with hexamine, which serves as a
buffer and an auxiliary complexing ligand.


N
N
N
N
Hexamine ((CH
2
)
6
N
4
)
(also called hexamethylenetetramine)
pK
a
for (CH
2
)
6
N
4
H
+
= 5.1

The solution is boiled to complete the reaction with EDTA, cooled and titrated with Zn
2+

until just reaching the end point color change from yellow (In) to red (MIn). Now the
solution contains Bi(EDTA)
-
, Ti(EDTA) and Al(EDTA)
-
, with no excess EDTA.
(3) Excess H
2
PO
4
-
is added and the solution is boiled to displace Ti
4+
from EDTA. Titration
with standard Zn
2+
until the end point color change is just reached gives the Ti
4+
content.
(4) Finally, excess F
-
is added and the solution is boiled to displace Al
3+
from EDTA.
Titration of the hot solution with standard Zn
2+
until the end point color change is just
reached gives the Al
3+
content.
In step 1, 25.00 mL of unknown required 16.43 mL of 0.010 44 M EDTA. Step 3 required
4.22 mL of 0.012 76 M Zn
2+
and step 4 consumed 25.92 mL of 0.012 76 M Zn
2+
. Find the
molarity of each cation in the original unknown. What color change is observed in steps (3)
and (4)?
S13-15. A Spectrophotometric Metal-Ligand Binding Problem Using Nonlinear Least-Squares
Curve Fitting
The spectrum on the next page shows changes that occur as metal M is titrated with ligand L.

M + L ML K =
[ML]
[M][L]

Curve 0 is the spectrum of M and curves 1 through 5 result from additions of L. The species
M and ML absorb in the region shown, but L has no absorbance. Both the initial solution and
the titrant solution contain 2.12 10
-4
M metal ion, so the total concentration of M plus ML
remains constant throughout the experiment:
K
Chapter 13: Supplementary Problems 31


5
0
1
2
3
4
5
0.2
0.4
0.6
0.8
5
0
0
0
500 550 600 650
Wavelength (nm)
A
b
s
o
r
b
a
n
c
e

Spectrophotometric titration of species P (curve 0) with ligand X (curves 1-5).
[From J. R. Long and R.S. Drago, J. Chem. Ed. 1982, 59, 1037.]

Mass balance for M: C
m
= [M] + [ML] = 2.12 10
-4
M
Mass balance for L: C
l
= [L] + [ML]
where C
l
is the total ligand concentration after each addition. Substituting [M] = C
m
[ML]
and [L] = C
l
[ML] into the equilibrium constant above, you can solve for [ML]:
[ML] =
1
2

(
(
\

|
.
|
|
C
m
+ C
l
+
1
K

\

|
.
|
|
C
m
+ C
l
+
1
K
2
4C
m
C
l

Now we want to express the absorbance changes as a function of K and various known
quantities. For a 1-cm-pathlength cell, you can show from Beer's law that the change of
absorbance (A) at a given wavelength can be written A = [ML],where is the change
in molar absorptivity between product and reactant ( =
ML

M
).
Substituting in the expression for [ML] above gives
A =

(
(
\

|
.
|
|
C
m
+ C
l
+
1
K

\

|
.
|
|
C
m
+ C
l
+
1
K
2
4C
m
C
l

The least-squares problem: The table below gives A as a function of C
l
.
Chapter 13: Supplementary Problems 32


Absorbance
Curve C
l
(M) at 525 nm A
0 0 0.859
1 0.515 10
-3
0.745 0.114
2 1.03 10
-3
0.676 0.183
3 2.06 10
-3
0.609 0.250
4 4.11 10
-3
0.544 0.315
5 9.23 10
-3
0.494 0.365
Your job is to use a nonlinear least squares curve fitting procedure to find the best values of
and K in the equation A = f(C
l
, , K) where C
l
is the independent variable (x), A is
the dependent variable (y), and the adjustable parameters are and K. In the notation of the
least squares program, C
l
is the variable x[i], is the constant C[1] and K is the constant C[2].
To do the curve fitting, you can use the procedure "Nonlinear Least Squares Curve Fitting
with Microsoft Excel Solver" described at the website for this book. To begin the least-squares
procedure, we need estimates of and K. For this purpose, let's pretend that curve 5
corresponds to complete conversion of M to ML. Therefore, A
ML
=
ML
[ML]
0.494

ML
[2.12 10
-4
M]
ML


2.33 10
3
M
-1.
cm
-1

From curve 0 we know
M
= A/[M] = 0.859/2.12 10
-4
= 4.05 10
3
M
-1.
cm
-1
.
Therefore, =
ML

M


1.72 10
3
M
-1.
cm
-1
.
To estimate K, suppose that the conversion of M to ML for curve 1 is in proportion to the
absorbance change:
[ML]
\

|
.
|
|
A
1
A
0
A
5
A
0
C
m
) 10 12 . 2 (
859 . 0 494 . 0
859 . 0 745 . 0
4

|
|
.
|

\
|

= 6.61 10
-4
M
From the mass balance for metal, we estimate [M] = C
m
[ML] 1.46 10
-4
M. The mass
balance for ligand gives [L] = C
l
[ML] 0.513 10
-3
6.61 10
-5
= 4.49 10
-4
M. Our
estimate of the equilibrium constant is therefore
K =
[ML]
[M][L]


) 10 49 . 4 )( 10 46 . 1 (
10 61 . 6
4 4
4

= 1.0 10
3

Happy hunting! The values produced by your least-squares program should be = 1 944
(25) M
-1.
cm
-1
and K = 829 (35). If you crave more, you can find spectrophotometric data
for the sequence M + L ML ML
2
given by N. K. Kildahl, J. Chem. Ed. 1992, 69, 591.
Try deriving equations to fit these data with your least squares program and find the formation
constants K
1
and K
2
.
Chapter 13: Supplementary Problems 33


S13-16. Aliquots of a single metal ion solution were titrated with EDTA and two different indicators.
Results of replicate measurements are shown below. Do the two indicators give equivalent
results at the 95% confidence level?
Pyrocatechol violet: 2.034, 2.048, 2.000, 2.055, 2.018, 2.022 mM
Xylenol orange 2.044, 2.053, 2.061, 2.030, 2.049 mM
S13-17. An EDTA titration was used to monitor periodically a metal ion concentration in an industrial
process stream. Long experience with the method showed that the mean value was 0.166 4 M
with a standard deviation of 0.002 8 M.
(a) What percentage of measurements is expected in the range 0.170 0 to 0.175 0 M?
(b) What percentage is expected to exceed 0.175 0 M?
(c) To monitor the process, you plan to withdraw a sample of the stream and conduct four
replicate analyses. Explain how you would set the warning and action lines if you were
drawing a control chart for this process
S13-18. (a) A method involving ultrafiltration has been proposed for removing metal cations from
industrial waste. In ultrafiltration, a solution containing large and small molecules is forced
under pressure to flow through a semipermeable membrane whose pores are large enough
for small molecules to pass, but not large enough for large molecules to pass. To sequester
metal ions, a water-soluble polymer containing many carboxyl (CO
2
H) groups is added to
the waste. The carboxyl groups can bind cations. When the liquid is concentrated by
ultrafiltration, small molecules and solvent pass through the membrane, but the polymer
containing undesirable cations is retained.
Draw a sketch of this process and explain how it can be used to concentrate metals from a
waste stream.
(b) The effect of pH on the ultrafiltration of two cations is shown on the next page. Explain
the shapes of these curves. Which metal has a higher formation constant for binding to the
polymer?
Chapter 13: Supplementary Problems 34


0
20
40
60
80
100
P
e
r
c
e
n
t
r
e
t
a
i
n
e
d
b
y
m
e
m
b
r
a
n
e
2 3 4 5 6
pH
Cd
2 +
Ni
2 +

Effect of pH on retention of metal ion during ultrafiltration of waste stream containing added metal-
binding polymer.
[Data from K. E. Geckeler and K. Volchek, "Removal of Hazardous Substances from Water using
Ultrafiltration in Conjunction with Soluble Polymers," Environ. Sci. Tech. 1996, 30, 725.]
35



S14-1. (a) Identify the oxidizing and reducing agents among the reactants below and write a balanced
half-reaction for each.
2S
2
O
4
2-
+ TeO
3
2-
+ 2OH
-
4SO
3
2-
+ Te(s) + H
2
O
Dithionite Tellurite Sulfite
(b) How many coulombs of charge are passed from reductant to oxidant when 1.00 g of Te is
deposited?
(c) If Te is created at a rate of 1.00 g/h, how much current is flowing?
S14-2. Draw a picture of each of the following cells, showing the location of each chemical species.
For each cell, write an oxidation for the left half-cell and a reduction for the right half-cell.
(a) Au(s) | Fe(CN)
6
4-
(aq) , Fe(CN)
6
3-
(aq) || Ag(CN)
2
-
(aq) , KCN(aq) | Ag(s)
(b) Pt(s) | Hg(l) | Hg
2
Cl
2
(s) | KCl(aq) || ZnCl
2
(aq) | Zn(s)
S14-3. Find the theoretical electrical storage capacity of cells that make use of the following chemical
reactions. Express your answer in ampere
.
hours per kilogram of reactants, where 1 A
.
h
provides 1 A for 1 h. Thus if consumption of 0.5 kg of reactants produces 3 A
.
h, the storage
capacity would be 3 A
.
h/0.5 kg = 6 A
.
h/kg. Which cell produces the most electricity per
kilogram, and which the least?
(a) Lead-acid battery: Pb + PbO
2
+ 2H
2
SO
4
2PbSO
4
+ 2H
2
O
(FM of reactants = 207.2 + 239.2 + 2 98.079 = 642.6.)
(b) Carbon-zinc dry cell: Zn + 2NH
4
Cl + 2MnO
2
ZnCl
2
(NH
3
)
2
+ 2MnO(OH)
(FM of reactants = 346.25.)
(c) Nickel-cadmium cell: 2Ni(OH)
2
+ Cd(OH)
2
NiO(OH) + Cd + 2H
2
O
(FM of reactants = 331.84.)
(d) Sulfur-aluminum battery: 2Al + 3S + 3KOH + 3H
2
O 2Al(OH)
3
+ 3KHS
(FM of reactants = 372.525.)
(e) Hydrogen-oxygen fuel cell: 2H
2
+ O
2
2H
2
O (FM of reactants = 36.031)
S14-4. Which will be the strongest reducing agent under standard conditions (all activities = 1): Se,
Sn
4+
, Cr
2+
, Mg
2+
, or Fe(CN)
6
4-
?
S14-5. Use Le Chtelier's principle and half-reactions from Appendix H to find which of the
following become stronger reducing agents when the solution becomes more basic. Which are
unchanged, and which become weaker?
Cl
2
Al H
2
S

MnO
4
2-
S
2
O
3
2-

Chlorine Aluminum Hydrogen sulfide Manganate Thiosulate
CHAPTER 14: SUPPLEMENTARY PROBLEMS
FUNDAMENTALS OF ELECTROCHEMISTRY
Chapter 14: Supplementary Problems 36


S14-6. Consider the cell
Pt(s) | H
2
(g, 0.100 bar) | H
+
(aq,pH = 2.54) || Cl
-
(aq, 0.200 M) | Hg
2
Cl
2
(s) | Hg(l) | Pt(s)
(a) Write a reduction reaction and Nernst equation for each half-cell
For the Hg
2
Cl
2
half-reaction, E = 0.268 V.
(b) Find E for the net cell reaction and state whether reduction will occur at the left- or right-
hand electrodes.
S14-7. Consider a circuit in which the left half-cell was prepared by dipping a Pt wire in a beaker
containing an equimolar mixture of Cr
2+
and Cr
3+
. The right half-cell contained a Tl rod
immersed in 1.00 M TlClO
4
.
(a) Use line notation to describe this cell. (b) Calculate the cell voltage.
(c) Write the spontaneous net cell reaction.
(d) When the two electrodes are connected by a salt bridge and a wire, which terminal
(Pt or Tl) will be the anode?
S14-8. Write a balanced chemical equation (in acid solution) for the reaction represented by the
question mark below. Calculate E for the reaction.

NO
3
-
NO
2
(g)
NO
2
HNO
0.955
0.773 1.108 ?

S14-9. Calculate E, G, and K for each of the following reactions.
(a) Cu(s) + Cu
2+
2Cu
+
(b) 2F
2
(g) + H
2
O F
2
O(g) + 2H
+
+ 2F
-

S14-10. A solution contains 0.010 0 M IO
3
-
, 0.010 0 M I
-
, 1.00 10
-4
M I
3
-
, and pH 6.00 buffer.
Consider the reactions
2IO
3
-
+ I
-
+ 12H
+
+ 10e
-
I
3
-
+ 6H
2
O E = 1.210 V
I
3
-
+ 2e
-
3I
-
E = 0.535 V
(a) Write a balanced net reaction that can occur in this solution.
(b) Calculate G and K for the reaction.
(c) Calculate E for the conditions given above.
(d) Calculate G for the conditions given above.
(e) At what pH would the concentrations of IO
3
-
, I
-
, and I
3
-
listed above be in equilibrium
at 298 K?
Chapter 14: Supplementary Problems 37


K
f

S14-11. From the half-reactions below, calculate the solubility product of Mg(OH)
2
.
Mg
2+
+ 2e
-
Mg(s) E = 2.360 V
Mg(OH)
2
(s) + 2e
-
Mg(s) + 2OH
-
E = 2.690 V
S14-12. The standard free energy of vaporization of Cl
2
(aq) is G = 6.9 kJ/mol at 298 K. Given that
E for the reaction Cl
2
(g) + 2e
-
2Cl
-
(aq) is 1.360 V, find E for the reaction
Cl
2
(aq) + 2e
-
2Cl
-
(aq).
S14-13. Consider the cell S.H.E. || Ag(S
2
O
3
)
2
3-
(aq,0.010 M) , S
2
O
3
2-
(aq,0.050 M) | Ag(s)
(a) Using the half-reaction Ag(S
2
O
3
)
2
3-
+ e
-
Ag(s) + 2S
2
O
3
2-
, calculate the cell voltage
(E, not E).
(b) Alternatively, the cell could have been described with the half-reaction Ag
+
+ e
-
Ag(s)
Using the cell voltage from part a, calculate [Ag
+
] in the right half-cell.
(c) Use the answer to part b to find the formation constant for the reaction

Ag
+
+ 2S
2
O
2
3-
Ag(S
2
O
3
)
2
3-

Thiosulfate
S14-14. The following cell has a voltage of 1.018 V. Find K
a
for formic acid, HCO
2
H.
Pt(s) | UO
2
2+
(0.050 M) , U
4+
(0.050 M), HCO
2
H(0.10 M), HCO
2
Na(0.30 M)
|| Fe
3+
(0.050 M), Fe
2+
(0.025 M) | Pt(s)
S14-15. For the following cell , the half-reactions can be written
Right half-cell: Pb
2+
(right) + 2e
-
Pb(s)
Left half-cell: Pb
2+
(left) + 2e
-
Pb(s)
(a) Given that K
sp
for Pb(HPO
4
)(s) is 2.0 10
-10
, find [HPO
4
2-
] in the left half-cell.
(b) If the measured cell voltage is 0.097 V, calculate K
sp
for PbF
2
(s).
Chapter 14: Supplementary Problems 38



S14-16. The monstrous cell below was set up. Then 50.0 mL of 0.044 4 M Na
2
EDTA was added to the
right-hand compartment and 50.0 mL of 0.070 0 M NaOH was added to the left-hand
compartment. The cell voltage leveled off at +0.418 V. Find the formation constant for CuY
2-

(where Y = EDTA).
Sb
Cu
V
-
+
Sb
2
O
3
100.0 mL of 0.015 2 M
nitrilotriacetic acid
(a neutral compound, of course)
100.0 mL of solution containing
1.37 mMCu(EDTA)
2-
and
23.8 mM Ca(NO
3
)
2
buffered to pH 9.76
Sb

S14-17. Evaluate E' for the half-reaction CO
2
(g) + 2H
+
+ 2e
-
CO(g) + H
2
O.
S14-18. Evaluate E' for the half-reaction CO
2
(g) + 2H
+
+ 2e
-
HCO
2
H(aq).
S14-19. The standard reduction potential of anthraquinone-2,6-disulfonate is 0.229 V.


Chapter 14: Supplementary Problems 39


O
3
S
SO
3
O
O
O
3
S
SO
3
OH
OH
-
Anthraquinone-2,6-disulfonate
+ 2H
+
+ 2e
-
-
-
Acidic
protons
-

The reduced product is a diprotic acid with pK
1
= 8.10 and pK
2
= 10.52. Calculate E'
(pH = 7) for anthraquinone-2,6-disulfonate.
S14-20. How do we know that mercury(I) is a dimer? Techniques including X-ray crystallography,
spectroscopy, and magnetic measurements demonstrate that mercury(I) is almost always
found as the dimer, Hg
2
2+
. Here is a student electrochemical measurement that allows you to
distinguish monomeric Hg
+
from Hg
2
2+
. [D. Bhattacharya and D. G. Peters, "Use of
Electrochemical Concentration Cells to Demonstrate the Dimeric Nature of Mercury(I) in
Aqueous Media," J. Chem. Ed. 1995, 72, 64.] A concentration cell is one in which the only
difference between the two half-cells is the concentration of a reacting species. The following
concentration cell was used for all measurements:
Hg | Hg(I)(C
L
) || Hg(I)(C
R
) | Hg
where Hg(I) is present at a concentration C
L
in the left half-cell and at a concentration C
R
in the right half-cell. Stock solution A was prepared from 2.8 g of mercury(I) nitrate
monohydrate, which is either HgNO
3
.
H
2
O (FM 280.61) if Hg(I) is monatomic, or
Hg
2
(NO
3
)
2
.
2H
2
O (FM 561.22) if Hg(I) is diatomic. The salt was dissolved in 100.0 mL of
0.16 M HNO
3
containing a few drops of liquid Hg to prevent oxidation of Hg(I). Solution B
was 1.6 M HNO
3
. Five concentration cells in the following table were set up and their
voltage was measured.
Voltage
Cell Left half-cell Right half-cell (mV)
1 solution A solution A 0
2 10.0 mL A + 17.4 mL B diluted to 100.0 mL solution A 29
3 10.0 mL of cell 2 solution + 17.4 mL B diluted to 100.0 mL solution A 62
4 10.0 mL of cell 3 solution + 17.4 mL B diluted to 100.0 mL solution A 90
5 10.0 mL of cell 4 solution + 17.4 mL B diluted to 100.0 mL solution A 119

Chapter 14: Supplementary Problems 40


(a) Write the two half-reactions for the concentration cell and write the Nernst equation for the
complete cell if Hg(I) is monatomic (i.e., Hg
+
).
(b) Write the two half-reactions for the concentration cell and write the Nernst equation for the
complete cell if Hg(I) is diatomic (i.e., Hg
2
2+
).
(c) Prepare a graph of E versus log(C
L
/C
R
) showing the lines predicted by your answers to (a)
and (b).
(d) Calculate the quotient C
L
/C
R
for cells 1-5. Does your answer depend on whether Hg(I) is
monatomic or diatomic?
(e) Plot the experimental points on the graph in (c). Is Hg(I) monatomic or diatomic?
(f) What is the purpose of solution B in the left half-cell?
(g) We cheated a little. If the starting material were Hg
2+
, we would have obtained the same
experimental results. Suggest any analytical experiments that could tell you the oxidation
number of Hg in the starting material.
CHAPTER 15: SUPPLEMENTARY PROBLEMS 41
ELECTRODES AND POTENTIOMETRY

S15-1. Convert the potentials listed below. The Ag | AgCl and calomel reference electrodes are
saturated with KCl.
(a) 0.222 vs S.H.E. = ? vs Ag | AgCl (d) 0.035 vs Ag | AgCl = ? vs S.C.E.
(b) 0.523 vs Ag | AgCl = ? vs S.H.E. (e) 0.035 vs calomel = ? vs Ag | AgCl
(c) 0.523 vs S.C.E. = ? vs Ag | AgCl
S15-2. What is the cell voltage when saturated calomel and Pt electrodes are dipped into a solution
containing 0.002 17 M Br
2
(aq) and 0.234 M Br
-
?
S15-3. A 50.0 mL solution of 0.100 M NaSCN was titrated with 0.200 M AgNO
3
in the cell:
S.C.E. || titration solution | Ag(s)
Find the cell voltage for these volumes of titrant: 0.1, 10.0, 25.0 and 30.0 mL.
S15-4. The right-hand compartment of the cell below was titrated with ligand while monitoring the
cell voltage:Ag(s) | Ag
+
(aq, 0.100 M, 25.0 mL) || Ag
+
(aq, 0.100 M, 75.0 mL) | Ag(s)
With 1.52 M ammonia titrant, the end point was observed at 9.8 mL, while 1.72 M
ethylenediamine (Section 13-1) gave an end point of 5.0 mL. In both cases, the measured cell
voltage was near 0.15 V at the end point. [H. Meyer, J. Chem. Ed. 1992, 69, 499; D. C.
Luehrs, J. Chem. Ed. 1995, 72, 668.]
(a) Write the half-reactions, net reaction and Nernst equation for the cell.
(b) Write the stoichiometry of the observed reactions with the titrants.
(c) From the observed voltage, find the concentration of uncomplexed Ag
+
at the end points.
S15-5. The titration solution in the cell below had a total volume of 50.0 mL and contained 0.100 M
Mg
2+
and 1.00 10
-5
M Zn(EDTA)
2-
at a pH of 10.00
S.C.E. || Zn(s) | titration solution
What will be the cell voltage when 10.0 mL of 0.100 M EDTA has been added?
(Hint: See Exercise 15-B.)
S15-6. Which side of the liquid junction 0.1 M HCl | 0.1 M LiBr will be negative?
S15-7. How many seconds will it take for (a) OH
-
and (b) F
-
to migrate a distance of 1.00 cm in a field
of 1.00 kV/m?
Chapter 15: Supplementary Problems 42


S15-8. (a) Write an expression analogous to Equation 15-8 to describe the response of a La
3+
-
selective electrode to La
3+
ion.
(b) If 1.00, by how many mV will the potential change when the electrode is removed
from 1.00 10
-4
M LaClO
4
and placed in 1.00 10
-3
M LaClO
4
?
(c) By how many millivolts will the potential of the electrode change if the electrode is
removed from 2.36 10
-4
M LaClO
4
and placed in 4.44 10
-3
M LaClO
4
?
(d) The electrode potential is +100 mV in 1.00 10
-4
M LaClO
4
and the selectivity coefficient
k
La
3+,
Fe
3+
is
1
1 200
. What will be the potential when 0.010 M Fe
3+
is added?
S15-9. A metal ion buffer was prepared from 0.050 M ML and 0.50 M L, where ML is a metal -ligand
complex and L is free ligand. M + L ML K
f
= 3.6 10
10
Calculate the concentration of free metal ion, M, in this buffer.
S15-10. A calcium ion-selective electrode obeys Equation 15-8, in which = 0.970 and n
Ca
2+ = 2. The
selectivity coefficients for several ions are listed.
Interfering ion, Y k
Ca
2+
,Y


Mg
2+
0.040
Ba
2+
0.021
Zn
2+
0.081


In 1.00 10
-3
M Ca
2+
, the reading was +300.0 mV. What would be the voltage if the solution
had the same calcium concentration plus [Mg
2+
] = 1.00 10
-3
M, [Ba
2+
] = 1.00 10
-3
M, and
[Zn
2+
] = 5.00 10
-4
M? (Use concentrations instead of activities to answer this question.) If
they are present at equal concentrations, which ion interferes the most with the Ca
2+
electrode?
S15-11. An ion-selective electrode used to measure the cation M
2+
obeys the equation
E = constant +
0.057 1
2
log {[M
2+
] + 0.020 0 [Fe
2+
]}
When the electrode was immersed in 100.0 mL of unknown containing M
2+
in 0.020 0 M
Fe(NO
3
)
2
, the reading was 194.6 mV (versus S.C.E.). When 1.00 mL of 0.030 7 M M
2+

(in 0.0.020 0 M Fe(NO
3
)
2
) was added to the unknown, the reading increased to 200.7 mV.
Find the concentration of M
2+
in the original unknown.
S15-12. A magnesium ion buffer was made by mixing 10.0 mL of 1.00 mM MgSO
4
, 10.0 mL of 1.30
mM EDTA, and 5.00 mL of buffer, pH 10.00. What is the concentration of free metal ion in
this solution? Answer the same question for MnSO
4
used instead of MgSO
4
.
Chapter 15: Supplementary Problems 43


S15-13. I can't take all this activity! A pH electrode was immersed in solutions containing 0.010 0 M
HClO
4
and variable concentrations of NaClO
4
. After correcting for variation of junction
potential with ionic strength (), the results below were obtained. Calculate the activity
coefficient of H
+
as a function of ionic strength and make a graph of your results. Include a
point for = 0 on your graph.
(M) pH (M) pH (M) pH
0.10 2.13 1.20 2.05 2.00 1.86
0.30 2.16 1.50 1.99 2.40 1.76
0.50 2.16 1.60 1.96 2.50 1.73
1.00 2.09 1.80 1.92 3.00 1.59
Data from L. Pezza, M. Molina, M. de Moraes, C. B. Melios, and J. O. Tognolli, Talanta 1996, 43, 1689.
S15-14. Standard addition. A perchlorate ion-selective electrode immersed in 50.0 mL of unknown
ClO
4
-
solution gave a potential of 358.7 mV versus S.C.E. When 1.00 mL of 0.050 M NaClO
4

was added, the potential changed to 346.1 mV. Assuming that the electrode has a Nernstian
response ( = 1.00), find the concentration of ClO
4
-
in the unknown.
S15-15. Cyanide ion was measured indirectly with a solid-state ion-selective electrode containing a
silver sulfide membrane. Assuming that the electrode response is Nernstian and that the ionic
strength of all solutions is constant, we can write the electrode response as E = constant +
0.059 16 log[Ag
+
]. To an unknown cyanide solution was added Ag(CN)
2
-
such that
[Ag(CN)
2
-
] = 1.0 10
-5
M in the final solution. This complex ion behaves as a silver ion
buffer in the presence of CN
-
:
Ag
+
+ 2CN
-
Ag(CN)
2
-
K =
2
=
[Ag(CN)
2
-
]
[Ag
+
][CN
-
]
2
= 10
19.85

(a) Suppose that the unknown contained 8.0 10
-6
M CN
-
and the potential was found to be
+206.3 mV. Then a standard addition of CN
-
was made to bring the CN
-
concentration to
12.0 10
-6
M. What will be the new potential?
(b) Now consider a real experiment in which 50.0 mL of unknown gave a potential of 134.8
mV before a standard addition of CN
-
was made. After adding 1.00 mL of 2.50 10
-4
M
KCN, the potential dropped to 118.6 mV. What was the concentration of CN
-
in the 50.0-
mL sample? For this part, we do not know the value of the constant in the equation for E.
That is, you cannot use the value of the constant derived from part (a) of this question.
Chapter 15: Supplementary Problems 44


S15-16. The following standard addition table assumes that an electrode has a Nernstian response to
analyte:
Standard addition table: 10 mL of standard added to 100 mL of sample.
(To obtain sample concentration, multiply standard concentration by Q.)
E mV Q E mV Q E mV Q E mV Q
0 1.00 8 0.199 16 0.095 2 24 0.055 6
1 0.696 9 0.178 17 0.088 4 25 0.052 3
2 0.529 10 0.160 18 0.082 2 26 0.049 4
3 0.423 11 0.145 19 0.076 7 27 0.046 6
4 0.351 12 0.133 20 0.071 6 28 0.044 0
5 0.297 13 0.121 21 0.067 1 29 0.041 6
6 0.257 14 0.112 22 0.062 9
7 0.225 15 0.103 0 23 0.059 1

As an example, suppose chloride ion is measured with an ion-selective electrode and a
reference electrode. The electrodes are placed in 100.0 mL of sample, and a reading of 228.0
mV is obtained. Then 10.0 mL of standard containing 100.0 ppm of Cl
-
is added, and a new
reading of 210.0 mV is observed. Because |E| = 18.0 mV, Q = 0.082 2 in the preceding table.
Therefore, the original concentration of Cl
-
was (0.082 2)(100 ppm) = 8.22 ppm.
(a) What molarity of Cl
-
is 8.22 ppm? Assume that the density of unknown is 1.00 g/mL.
(b) Use the original concentration of 8.22 ppm and the original potential of 228.0 mV to show
that the second potential should be 210.0 mV if the electrode response obeys the equation
E = constant 0.059 16 log[Cl
-
]
(c) How would you change the table to use it for Ca
2+
instead of Cl
-
?
S15-17. (a) Derive the value of 0.696 for the second value of Q in the standard addition table of the
previous problem.
(b) On the basis of your derivation, create a spreadsheet that computes Q as a function of E
and reproduce the table in the previous problem.
S15-18. Fourteen ion-selective electrodes were used to measure Ca
2+
in the same solution with the
following results:
25
[Ca
2+
] = 1.24, 1.13, 1.20, 1.20, 1.30, 1.12, 1.27, 1.19, 1.27, 1.22, 1.23,
1.23, 1.25, 1.24 mM [M. Umemoto, W. Tani, K. Kuwa, and Y. Ujihira, "Measuring Calcium in
Plasma," Anal. Chem. 1994, 66, 352A.]. Find the 95% confidence interval for the mean. If the
actual concentration is known to be 1.19 mM, are the results of the ion-selective electrode
within experimental error of the known value at the 95% confidence level?
Chapter 15: Supplementary Problems 45


S15-19. Calibration data for a F
-
electrode in pure KF solutions is given in the table. Convert each
concentration from 10
-1
to 10
-7
M into an activity and make a graph of E versus log A
F
-.
Decide which points lie on a straight line and find the least-squares slope of the line. Find the
value of in the equation E = constant (0.059 16) log(A
F
-).
[KF] (M) E (mV) [KF] (M) E (mV)
1.00 0.0 1.00 10
-4
217.4
1.00 10
-1
52.2 1.00 10
-5
276.1
1.00 10
-2
106.1 1.00 10
-6
323.0
1.00 10
-3
161.7 1.00 10
-7
340.0
S15-20. Cu
2+
buffers were prepared for the range pCu
2+
= 3 to 19 for calibration of a Cu
2+
ion-
selective electrode at a constant ionic strength of = 0.6 M [R. De Marco, "Response of
Copper(II) Ion-Selective Electrodes in Seawater," Anal. Chem. 1994, 66, 3202.]. Buffers were
prepared by mixing 0.001 00 M Cu(NO
3
)
2
, 0.015 0 M ethylenediamine (H
2
NCH
2
CH
2
NH
2
,
abbreviated en), and adjusting the pH to selected values with HNO
3
. The value of pH fixes the
value of pCu
2+
. The following equilibrium constants apply at = 0.6 M:
enH
2
2+
enH
+
+ H+ log K
1
= 7.347
enH
+
en + H
+
log K
2
= 10.046
Cu
2+
+ en Cu(en)
2+
log
1
= 10.688
Cu
2+
+ 2en Cu(en)
2
2+
log
2
= 19.890
(a) Write an equation for the fraction of free en (i.e., en not bound to Cu
2+
) in the form enH
+

at a given pH. (Once you've figured this out, it should be trivial to write equations for
the fractions in the forms en and enH
2
2+
, as well.)
(b) There are six unknown concentrations in this system: [enH
2
2+
], [enH
+
], [en], [Cu
2+
],
[Cu(en)
2+
], and [Cu(en)
2
2+
] (because the pH is known). Four of the six equations needed
to define the system are the preceding equilibrium equations. Write the other two
necessary equations.
CHAPTER 16: SUPPLEMENTARY PROBLEMS 46
REDOX TITRATIONS

S16-1. Consider the titration of 50.0 mL of 0.020 0 M In
+
by 0.050 0 M Cu
2+
using Pt and saturated
calomel electrodes to find the end point.
(a) Write a balanced titration reaction.
(b) Write two different half-reactions for the indicator electrode.
(c) Write two different Nernst equations for the net cell reaction.
(d) Calculate E at the following volumes of Cu
2+
: 1.00, 20.0, 39.0, 40.0, 41.0, and 80.0 mL.
Sketch the titration curve.
S16-2. Consider the titration of 50.0 mL of 0.025 0 M Fe
3+
by 0.050 0 M Cu
+
to give Fe
2+
and Cu
2+
,
using Pt and saturated Ag | AgCl electrodes to find the end point.
(a) Write a balanced titration reaction.
(b) Write two different half-reactions for the indicator electrode.
(c) Write two different Nernst equations for the net cell reaction.
(d) Calculate E at the following volumes of Cu
+
: 1.0, 12.5, 24.5, 25.0, 25.5, and 30.0 mL.
Sketch the titration curve.
S16-3. Vanadium(II) undergoes three stepwise oxidation reactions: V
2+
V
3+
VO
2+
VO
2
+

Calculate the potential (versus S.C.E.) at each of the following volumes when 10.0 mL of
0.010 0 M V
2+
is titrated with 0.010 0 M Ce
4+
in 1 M HClO
4
: 5.0, 15.0, 25.0, and 35.0 mL.
Sketch the titration curve.
S16-4. When 50.00 mL of unknown was passed through a Jones reductor, molybdate ion (MoO
4
2-
)
was converted to Mo
3+
. The filtrate required 22.11 mL of 0.012 34 M KMnO
4
to reach the
purple end point.
MnO
4
-
+ Mo
3+
Mn
2+
+ MoO
2
2+

A blank required 0.07 mL. Find the molarity of molybdate in the unknown.
S16-5. A 25.00-mL sample containing La
3+
was treated with sodium oxalate to precipitate
La
2
(C
2
O
4
)
3
, which was washed, dissolved in acid, and titrated with 12.34 mL of 0.004 321 M
KMnO
4
. Calculate the molarity of La
3+
in the unknown.
S16-6. An aqueous glycerol solution weighing 153.2 mg was treated with 50.0 mL of 0.089 9 M Ce
4+

in 4 M HClO
4
at 60C for 15 minutes to oxidize the glycerol to formic acid:

Chapter 16: Supplementary Problems 47



CH
2
CH CH
2
OH OH OH
HCO
2
H

Glycerol Formic acid
FM 92.095
The excess Ce
4+
required 10.05 mL of 0.043 7 M Fe
2+
to reach a ferroin end point. What is the
weight percent of glycerol in the unknown?
S16-7. A mixture of nitrobenzene and nitrosobenzene weighing 24.43 mg was titrated with Cr
2+
to
give aniline:

NO + NO
2
NH
2
Cr
2+

Nitrosobenzene Nitrobenzene Aniline
FM 107.112 FM 123.111
The titration required 21.57 mL of 0.050 00 M Cr
2+
to reach a potentiometric end point. Find
the weight percent of nitrosobenzene in the mixture.
S16-8. A solution containing Be and several other metals was treated with excess EDTA to mask the
other metals. Then excess acetoacetanilide was added at 50C at pH 7.5 to precipitate
beryllium ion:
O
O
Be
C
6
H
5
NH
O
O
NHC
6
H
5
NHC
6
H
5
O
O
Be
2+
+ 2
precipitate

The precipitate was dissolved in 6 M HCl and treated with 50.0 mL of solution containing
0.139 2 g of KBrO
3
(FM 167.00) plus 0.5 g of KBr. Bromine produced by these reagents
reacts with acetoacetanilide as follows:
O
O O O
Br NH
+ HBr + Br
2

NHC
6
H
5

After five minutes, the excess Br
2
was destroyed by adding 2 g of KI (FM 166.00). The I
2

released by the Br
2
required 19.18 mL of 0.050 00 M Na
2
S
2
O
3
. Calculate the number of
milligrams of Be in the original solution.
S16-9. As in Problem 16-30, a sample of Bi
2
Sr
2
(Ca
0.8
Y
0.2
)Cu
2
O
x
(FM 770.14 + 15.999 4 x) was
analyzed to find the oxidation states of Bi and Cu. In Experiment A, a sample of
Bi
2
Sr
2
(Ca
0.8
Y
0.2
)Cu
2
O
x
weighing 110.6 mg was dissolved in 50.0 mL of 1 M HCl containing
2.000 mM CuCl. After reaction with the superconductor, coulometry detected 0.052 2 mmol of
Chapter 16: Supplementary Problems 48


unreacted Cu
+
in the solution. In Experiment B, 143.9 mg of superconductor was dissolved in
50.0 mL of 1 M HCl containing 1.000 mM FeCl
2
.
4H
2
O. After reaction with the
superconductor, coulometry detected 0.021 3 mmol of unreacted Fe
2+
. Find the average
oxidation numbers of Bi and Cu in the superconductor, and the oxygen stoichiometry
coefficient, x.
S16-10. A sensitive titration of Bi
3+
is based on the following sequence [G.A. Parker, J. Chem. Ed.
1980, 57,721]:
1. Bi
3+
is precipitated by Cr(SCN)
6
3-
: Bi
3+
+ Cr(SCN)
6
3-
Bi[Cr(SCN)
6
](s) (a)
2. The precipitate is filtered, washed, and treated with bicarbonate to release Cr(SCN)
6
3-
:
Bi[Cr(SCN)
6
] + HCO
3
-
+ H
2
O (BiO)
2
CO
3
(s) + Cr(SCN)
6
3-
+ H
+
(b)
3. I
2
is added to the filtrate after removal of the (BiO)
2
CO
3
(s):
Cr(SCN)
6
3-
+ I
2
+ H
2
O SO
4
2-
+ ICN + I
-
+ H
+
+ Cr
3+
(c)
4. Upon acidification to pH 2.5, HCN is created:
ICN + I
-
+ H
+
I
2
+ HCN (d)
5. The I
2
in this mixture is removed by extraction with chloroform. Excess bromine water is
then added to the aqueous phase to convert iodide to iodate and HCN to BrCN:
Br
2
+ I
-
+ H
2
O IO
3
-
+ H
+
+ Br
-
(e)
Br
2
+ HCN BrCN + H
+
+ Br
-
(f)
6. Excess Br
2
is destroyed with formic acid:
Br
2
+ HCO
2
H Br
-
+ CO
2
+ H
+
(g)
7. Addition of excess I
-
produces I
2
:
IO
3
-
+ I
-
+ H
+
I
2
+ H
2
O (h)
BrCN + I
-
+ H
+
I
2
+ HCN + Br
-
(i)
8. Finally, the iodine is titrated with a standard solution of sodium thiosulfate.
Show that 228 mol of thiosulfate will be required for each mole of Bi
3+
that is analyzed.
S16-11. Analysis of Organic Compounds with Periodic Acid. Periodic acid is a powerful oxidizing
agent that exists under different conditions as paraperiodic acid (H
5
IO
6
), metaperiodic acid
(HIO
4
), and various deprotonated forms of the acids. Sodium metaperiodate (NaIO
4
) is
usually used to prepare a solution that is standardized by addition to excess KI in bicarbonate
solution at pH 8-9:
IO
4
-
+ 3I
-
+ H
2
O IO
3
-
+ I
3
-
+ 2OH
-
(A)
Chapter 16: Supplementary Problems 49


The I
3
-
released is titrated with thiosulfate to complete the standardization. (In acidic
solution, Reaction A goes further: H
5
IO
6
+ 11I
-
+ 7H
+
4I
3
-
+ 6H
2
O.)
Periodate is especially useful for the analysis of organic compounds (such as carbohydrates)
containing hydroxyl, carbonyl or amino groups adjacent to each other. In this oxidation,
known as the Malaprade reaction, the carbon-carbon bond between the two functional groups
is broken and the following changes occur:
1. A hydroxyl group is oxidized to an aldehyde or a ketone.
2. A carbonyl group is oxidized to a carboxylic acid.
3. An amine is converted to an aldehyde plus ammonia (or a substituted amine if the original
compound was a secondary amine).
When there are three or more adjacent functional groups, oxidation begins near one end of the
molecule.
The reactions are performed at room temperature for about one hour with a known excess of
periodate. At higher temperatures, further nonspecific oxidations occur. Solvents such as
methanol, ethanol, dioxane, or acetic acid may be added to the aqueous solution to increase the
solubility of the organic reactant. After the reaction is complete, the unreacted periodate is
analyzed by using Reaction A, followed by thiosulfate titration of the liberated I
3
-
.
Some examples of the Malaprade reactions follow:
(1)
OH OH
- -
O O
CH
3
CH CHCH
3
+ IO
4
CH
3
CH + HCCH
3
+ IO
3
+ H
2
O

2,3-Dihydroxybutane

(2)
CH
2
CH CH
2
+ IO
4
CH
2
+ HC CH
2
+ IO
3
+ H
2
O
O O
-
-
OH OH
OH OH

Glycerol


O
HC CH
2
+ IO
4
HCOH + CH
2
+ IO
3
O O
-
-
OH


(3)
+
- -
-
+
OH
-
O O
CH
2
CH CO
2
+ IO
4
CH
2
+ CH CO
2
+ NH
4
+ IO
3
NH
3

Serine
Finally, here is your problem. Write a balanced equation for the reaction of periodate (IO
4
-
)
with:
Chapter 16: Supplementary Problems 50


(a)

OH H
H HO
OH H
OH H
CH
2
OH
HC=O

(b)
NH
2
H
H HO
OH H
OH H
HC=O
CH
2
OH

(c)
OH
OH
O

Glucose 2-Amino-2-deoxyglucose Dihydroxyacetone
S16-12. An enzyme involved in the catalysis of redox reactions has an oxidized form and a reduced
form differing by two electrons. The oxidized form of this enzyme was mixed at pH 7 with the
oxidized form of a redox indicator whose two forms differ by one electron. The mixture was
protected by an inert atmosphere and partially reduced with sodium dithionite. The
equilibrium composition of the mixture was determined by spectroscopic analysis:
enzyme(oxidized) 4.2 10
-5
M indicator(oxidized) 3.9 10
-5
M
enzyme(reduced) 1.8 10
-5
M indicator(reduced) 5.5 10
-5
M
Given that E' = 0.187 V for the indicator, find E' for the enzyme.
S16-13. This problem uses Beer's law. Aqueous solutions of radioactive materials develop micromolar
concentrations of H
2
O
2
as a result of nuclear irradiation of H
2
O. The following procedure was
developed to measure aqueous H
2
O
2
with a detection limit near 0.3 M [N. V. Klassen,
D. Marchington, and H. C. E. McGowan, "H
2
O
2
Determination by the I
3
-
Method and by
KMnO
4
Titration," Anal. Chem. 1994, 66, 2921.]. To 500.0 mL of unknown H
2
O
2
solution
are carefully added 20 mL of 18 M H
2
SO
4
with stirring. After cooling to room temperature,
the solution is titrated with standard 0.02 m (molal) KMnO
4
until pink color persists. Titrant is
delivered from a dropper with a fine tip and the quantity of titrant is measured gravimetrically
by weighing the delivery bottle plus the dropper before and after the titration. Excess KMnO
4

in the titrated solution is measured spectrophotometrically at the end of the experiment. In one
experiment, 0.933 g of 0.020 46 m KMnO
4
(FM 158.03) was added to produce pink color and
the absorbance of the titrated solution at 525 nm was 0.018 in a 1.000-cm cuvet. The molar
absorptivity of KMnO
4
at the 525 nm is 2.45 10
3
M
-1
cm
-1
. Assuming that the final titration
volume was 500.9 mL, find the molarity of H
2
O
2
in the unknown. After you see how the
numbers work out in this example, suggest experimental modifications that will increase the
sensitivity (lower the detection limit) of the procedure.