UNIVERSIDADE ESTADUAL PAULISTA JÚLIO DE MESQUITA FILHO

INSTITUTO DE QUÍMICA DE ARARAQUARA

DEPARTAMENTO DE ANALÍTICA, FÍSICO-QUÍMICA E INORGÂNICA

Cursos: Bacharelado em química (BQ) e química tecnológica (BQT).

Disciplina: Eletroanalítica.
Professores: Nelson Ramos Stradiotto e José Luiz da Silva.

LISTA 04: MÉTODOS ELETROGRAVIMÉTRICOS

1. A current of 0.50 amp is to be passed through a cell in which oxygen is deposited (p

= 1.00 atm) at a platinum anode having a surface area of 100 cm2; lead is to be plated
out at the cathode. The solution is 0.200 M in Pb2+ is buffered to a pH of 5.00. The
resistance of the cell is 0.80 ohm.
a) Calculate the theoretical potential (zero current potential) of the cell. (R.: -1.09
V)
b) Calculate the IR drop. (R.: 0.40 V)
c) Estimate the oxygen overvoltage (see Table 17·2). (R.: 0.77 V)
d) Estimate the total applied potential required to begin operation of the cell at
the specified conditions. (R.: -2.26 V)
e) If the solution volume were exactly 100 mL and the current were maintained
at 0.500 amp. how long would it take to reduce the Pb2+ concentration to
0.0100 M? (R.: 122 min)
f) What total applied potential would be required to operate the cell under the
specified conditions when the Pb2+ concentration is 0.0100 M? (R.: -2,30 V)

2. Electrodeposition has been proposed as a means for separation is feasible, indicate

the cation that is 0.080 F with respect to Zn2+ and 0.060 F with respect to Co2+.
a) Assuming for the moment that such a separation is feasible, indicate the cation
that will be deposited and the cation that will remain in solution.
b) Taking a residual concentration of l.0 × 10-6 M as a reasonable estimate of
quantitative separation, calculate the range (if such exists) with respect to a
saturated calomel electrode within which the potential of the cathode must he
maintained in order to achieve such a separation.
3. Halide ions can be deposited at a silver anode. the reaction being
𝐴𝑔 + 𝑋 − → 𝐴𝑔𝑋 + 𝑒 −
 UNIVERSIDADE ESTADUAL PAULISTA JÚLIO DE MESQUITA FILHO
INSTITUTO DE QUÍMICA DE ARARAQUARA
DEPARTAMENTO DE ANALÍTICA, FÍSICO-QUÍMICA E INORGÂNICA

a) Determine whether or not it is theocratically feasible to separate Cl- and Br-

ions from a solution that is 0.0500 M in each ion by controlling the silver
anode potential. Take l.0 × 10-6 M as the criterion of quantitative removal of
one ion.
b) Is a separation Cl- and I- theoretically feasible?
c) If a separation is feasible in either (a) or (b), that range of anode potentials (vs.
the saturated calomel electrode) should be employed?

4. What cathode potential (vs. the saturated calomel electrode) would be required to
reduce the total silver concentration of the following solutions to l.0 × 10-5 F.
a) Water containing AgNO3. (R.: 0.262 V)
b) A silver nitrate solution in which the equilibrium thiosulfate concentration is
l.0 × 10-3 M. (R.: -0.17 V)
𝐴𝑔+ + 2𝑆2 𝑂32− ⇌ 𝐴𝑔(𝑆2 𝑂3 )3− 2 𝐾𝑓 = 2.9 × 1013

c) A silver nitrate solution in which the equilibrium CN- concentration is 1.0 ×

10-2 M. (R.: -0.61 V)
𝐴𝑔+ + 2𝐶𝑁 − ⇌ 𝐴𝑔(𝐶𝑁)− 2 𝐾𝑓 = 1.3 × 1021

d) A silver nitrate solution in which the equilibrium NH3 concentration is 0.100

M. (R.: -0.042 V)
𝐴𝑔+ + 2𝑁𝐻3 ⇌ 𝐴𝑔(𝑁𝐻3 )∓ 2 𝐾𝑓 = 1.4 × 107

5. An internal-electrolysis cell such us that shown in Figure 20-10 contained 100.0 mL

of the 0.100 F Cu2+ and a copper electrode as the cathode compartment; a zinc
electrode immersed in 20.0 mL of l.0 × 10-3 F Zn2+ served as the anode. The cell
resistance was found to be 7.5 ohms.
a) What was the initial potential of this cell if no current was drawn? (R.: 1.159
V)
b) What would be the initial current if the electrodes were short-circuited with a
conductor? (R.: 0.155 amp)
c) What would be the cell potential when the Cu2+ concentration had been
reduced to l.0 × 10-5 M. (R.: 0.961 V)
d) What would be the theoretical current when the Cu2+ concentration was l.0 ×
10-5 F if the cell resistance did not change? Is it likely that the observed current
would be this large? Explain. (R.: 0.128 am;…)

REFERÊNCIA
SKOOG, D. A.; HOLLEN, F. J.; NIEMAN, T. A. Principles of instrumental analysis.
1st ed. New York: Holt, Rinehart and Winston, Inc.; 1971. Chapter 19: Conductometric
methods.
UNIVERSIDADE ESTADUAL PAULISTA JÚLIO DE MESQUITA FILHO
INSTITUTO DE QUÍMICA DE ARARAQUARA
DEPARTAMENTO DE ANALÍTICA, FÍSICO-QUÍMICA E INORGÂNICA