1

Instrumental Analysis

Electrogravimetry , Coulometry
and Amperometry
Tutorial 6
2
Calculate the initial voltage that should be applied to electrolyze
0.010 M [Zn(OH)
4
]
2
in 0.10 M NaOH, using Ni electrodes. Assume that
the current is 0.20 A, the cell resistance is 0.35 , and O
2
is
evolved at 0.20 bar. The overpotential for O
2
evolution at a Ni
surface at a current of 0.20 A is 0.519 V. The reactions are:

Cathode: [Zn(OH)
4
]
2-
+ 2e

Zn(s) + 4OH

E = 1.199 V
Anode: H
2
O 1/2O
2
+ 2H
+
+ 2e

E = 1.229 V
V 179 . 2
519 . 0 ) 35 . 0 )( 20 . 0 ( 450 . 0 140 . 1
ial overpotent IR
anode
E
cathode
E
applied
E
V 450 . 0
2
]
13
10 [ .
2 / 1
) 2 . 0 ( log
2
05916 . 0
229 . 1
2
] H [ .
2 / 1
O
P
1
log
2
05916 . 0
E
anode
E
V 140 . 1
] 01 . 0 [
4
] 1 . 0 [
log
2
05916 . 0
199 . 1
]
2
4
) OH ( Zn [
4
] OH [
log
2
05916 . 0
E
cathode
E
2
=
=
=
=

+ =
+
=
= =

Example 1:
Solution
1/2O
2
+ 2H
+
+ 2e

H
2
O
Written as reduction:
NaOH]= 0.1, pOH = 1
pH = 13, [H+] = 10
-13
3
Ions that react with Ag
+
can be determined electrogravimetrically
by deposition on a silver working anode:
Ag(s) + X AgX(s) + e
-
What will be the final mass of a silver anode used to electrolyze
75.00 mL of 0.0238 M KSCN if the initial mass of the anode is
12.463 g.

Solution
Example 2:
75.00 mL of 0.0238 M KSCN = 1.785 mmol of SCN
-
which gives
1.785 mmol of AgSCN, CONTAINING 0.1037 g of SCN
-
.

Mass of SCN
-
= 1.785 mmol SCN
-
x 10
-3
x 58.09 (g/mol SCN
-
)
= 0.1037 g SCN
-

Final mass of silver anode = 12.4638 + 0.1037 = 12.5675 g
4 4
Faradays law: The amount of chemical reaction at an
electrode (mass of copper deposited on the
cathode surface) is proportional to the
quantity of electricity passed in the circuit.
Faradaic current: The current passes in the circuit as a result
of actual electrolysis
(oxidation and reduction at electrode
surface).
Theoretical Basis for coulometric Titration
t . I q =
Coulombs Amperes seconds
F
t . I
e of Moles =

F n
t . I
reacted Moles =
If a reaction requires n electrons per mole of
reactant, the quantity reacting of chemical species
in time t is
Faradays
Law
) mass molar ( .
F n
t . I
Mass =
5
H
2
S(aq) can be analyzed by titration with coulometrically
generated I
2
.
+
+ + + I H ) s ( S I S H 2 2
2 2
FW
F n
t I
mass =
g 7525 10
2
34
96500
10 x 6 . 52 812
n
FW
F
It
S H of Mass
6
3
2
=

= =

To 50.0 mL of sample were added 4 g KI. Electrolysis required
812 s at 52.6 mA. Calculate the concentration of H
2
S (g/mL) in
the sample.

Solution:
Faraday's Law
The number of grams reduced at the cathode or oxidized at the
anode is given by:
Where I = current in amps
t = time in seconds
FW = formula weight
n = number of electrons transferred per 1 mole
of species

Concentration of H
2
S = 7525/50 = 150.5 g/mL
Example 3:
6
Example 4:
A 1.00-L electrolysis cell initially containing 0.0250 M Mn
2+
and
another metal ion, M
3+
, is fitted with Mn and Pt electrodes. The
reactions are:
Mn(s) Mn
2+
+ 2e
-

M
3+
+ 3e
-
M(s)
a) Is the Mn electrode the anode or the cathode?
b) A constant current of 2.60 A was passed through the cell for
18.0 min, causing 0.504 g of the metal M to plate out on the
Pt electrode. What is the atomic mass of M?
c) What will the concentration of Mn
2+
in the cell be at the end
of the experiment?
7
Solution
a) Sine Mn is oxidized, Mn metal is the anode

b) .

(Since 1 mol of M gives 3 e
-
)

Atomic mass of M = 0.504 g / 0.0097 mol = 52.0 g/mol

c) In the electrolysis 0.0291/2 = 0.01455 mol of Mn
2+
were
produced.
[Mn2+] = 0.0250 + 0.01455 = 0.0396 M
M of mol . e of mol .
mol / C
) s . )( s / C . (
0097 0 0291 0
96500
60 0 18 60 2
= =

8
Example 5:
Chlorine has been used for decades to disinfect drinking water. An
undesirable side effect of this treatment is the reaction of
chlorine with organic impurities to create organochlorine compounds,
some of which could be toxic. Monitoring total organic halide is now
required for many water providers. A standard procedure is to pass
water through activated charcoal that adsorbs organic compounds.
Then charcoal is combusted to liberate hydrogen halide:
Organic halide (RX) CO
2
+ H
2
O + HX
The HX is absorbed into aqueous solution and measured by automatic
coulometric titration with a silver anode:
Ag(s) Ag
+
+ e
-
(Ag+ generated anodically)
X
-
(aq) + Ag
+
AgX(s) (formed AgX is deposited on anode)

When 1.00 L of drinking water was analyzed, a current of 4.23 mA was
required for 387 s.
A blank prepared by oxidizing charcoal required 6 s at 4.23 mA.
Express TOX of the drinking water as mol halogen/L. If all halogen
is chlorine, express the TOX as g Cl/L
9
The corrected coulometric titration time is 387 6 = 381 s
Number of moles of e
-
= It/F = [(4.23 mA)(381 s)] / (96500 C/mol)
= 0.0167 mmol e
-
=

16.7 mol e
-
.

Because 1e
-
is equivalent to one x
-
, the concentration of
organohalide is 16.7 M.

If all halogen is Cl, this corresponds to 592 g Cl/L
(16.7 mol/L x 35.45 g/mol).
Solution
10
Amperometry is the electroanalytical technique in which:
the potential of the working electrode is adjusted at a fixed
value on the plateau of i-E curve and
the current is measured as a function of concentration.
Amperometry is a measure of limiting current at a fixed applied potential
as a function of concentration
Amperometric titrations
Amperometry can be used to estimate the equivalence point of
titrations, provided at least one of the participants or products
of the reaction involved is oxidized or reduced at a
microelectrode.
In this case, the current at fixed potential (at the plateau of
the i-E curve) is measured as a function of the titrant volume
added.
11
reactant reacts at electrode
X ne A +

A
C i
V
T
i
EP
C
A
0
Titrant reacts at electrode
X ne T +

T
C i
V
T
i
EP
C
T
0
Both reactant and titrant react
V
T
i EP
Predict the shape of the
amperometric titration
curve if the product is the
only electroactive species
?
12
Exercise 1
Suppose we wish to electrolyze I
-
to I
3
-
in a 0.10 M KI
solution containing 3.0x10
-5
M I
3
-

at pH 10.00 with P
H
2
fixed
at 1.00 bar.
3I
-
+ 2H
2
O I
3
-
+ H
2
(g) + 2OH
-

a) Find the cell potential if no current is flowing .
b) Suppose that electrolysis increases |I
3
-
| to 3.0x10
-4
M,
but other concentrations are unaffected. If the cell
resistance is 2.0 O, the current is 63 mA, the cathode
overpotential is 0.382 V and the anode overpotential is
0.025 V, what voltage is needed to drive the reaction?
Answer: a) 1.081 V
b) 1.644 V
Hint:
Cathode : 2H
2
O + 2e
-
H
2
(g ) + 2OH

E
o
= 0.828 V
Anode : I
3

+ 2e

3I

E
o
= 0.535 V
13
Try to solve Exercise 17-B and problems 17-1, 17-2, 17-4, 17-8 17-
11, 17-12, 17-13, 17-19 (Harris text book, p400-403)
reacted with the 8-hydroxyquinoline (HOC
9
H
6
N) that was released when the
indium(III) compound was dissolved:

HOC
9
H
6
N + 2Br
2
HOC
9
H
4
NBr
2
+ 2HBr
A heated buffer solution containing indium(III), In
3+
, was treated with an
excess of 8-hydroxyquinoline (HOC
9
H
6
N) to precipitate quantitatively an
insoluble indium(III) compound, according to the following reaction:

In
3+
+ 3HOC
9
H
6
N In(OC
9
H
6
N)
3
(s) + 3H
+

After the precipitate was separated and washed, it was dissolved in dilute
hydrochloric acid solution (which caused the above reaction to proceed in the
right-to-left direction). Then an excess of bromide ion (Br

) was added, and

the solution was transferred to an electrochemical cell equipped with a
platinum generator anode and a platinum auxiliary cathode. Elemental bromine
(Br
2
), which was electrogenerated by oxidation of bromide ion,

2Br

Br
2
+ 2e

An end point was reached after a titration time of 186.6 seconds at a
constant current of 125.3 mA. Calculate the mass of In
3+
in milligrams in
the original sample solution.
Faraday constant (F) = 96,500 coulombs/mol e
-
.
Atomic mass of In = 114.8)
(Answer: 2.318 mg of In
3+
)
Exercise 2