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 05: MÉTODOS COULOMÉTRICOS

1. Nickel and cobalt can be separated by deposition at a mercury cathode from an

aqueous pyridine solution. At -0.95 V (vs. the SCE) the nickel is deposited without
interference from the cobalt. By raising the cathode potential to -1.20 V, cobalt can
then be deposited quantitatively.
A sample of an are weighing 1.32 g was dissolved and treated in such a way as to
give Co2+ and Ni2+ ions. The sample was then electrolyzed with a mercury cathode
that was maintained at -0.95 V until current ceased. The volume of gas produced in a
hydrogen-oxygen coulometer, in series with the electrolysis cell, was 47.4 mL
(corrected for water vapor) at a temperature of 19.0 ºC and a barometric pressure of
748 mm of Hg. The electrolysis was then continued at -1.2 V, and 11.3 mL of gas
were collected.
Calculate the percent Co and Ni in the sample.
(R.: 5.76 percent Ni and 1.35 percent Co).

2. A chloride-iodide sample weighing 2.10 g was dissolved, made ammoniacal, and

introduced into a coulomciric cell equipped with a silver anode. By maintaining the
anode at -0.060 V (vs. the SCE), iodide was quantitatively precipitated as AgI without
interference from chloride. The volume of hydrogen and oxygen produced in a
coulometer in series with the cell was 38.1 mL (corrected for water vapor) at 23.5 ºC
and at a pressure of 755 mm of Hg.
Upon completion of the iodide analysis, the solution was acidified and the
potential of the anode was maintained at +0.25 V (vs. the SCE), whereupon
quantitative deposition of AgCl occurred. The volume of gas formed in the
coulometer during this process was 44.6 mL.
Calculate the percent BaCl2, and BaI2 in the sample.
(R.: 19.3 percent BaI2 and 12.0 percent BaCl2).
 UNIVERSIDADE ESTADUAL PAULISTA JÚLIO DE MESQUITA FILHO
INSTITUTO DE QUÍMICA DE ARARAQUARA
DEPARTAMENTO DE ANALÍTICA, FÍSICO-QUÍMICA E INORGÂNICA

3. The odorant concentration of household gas can be monitored by passage of a fraction

of the gas stream through a solution containing an excess of bromide ion:
electrogenerated bromine reacts rapidly with the mercaptan odorant
𝑅𝑆𝐻 + 𝐵𝑟2 → 𝑅𝑆𝑆𝑅 + 2𝐻 + + 2𝐵𝑟 − .
Continuous, analysis is made possible by means of an electrode system that
signals the need for additional Br2 to oxidize the mercaptan. Ordinarily, the current
required to keep the unreacted orant level at zero is automatically plotted as a function
of time. Suppose the following data were obtained from the smooth curve from the
recorder when a gas stream was being sampled at the rate of 10.0 liters/min.
Time (P. M.) Current (mamp)
2:32 1.65
2:33 1.55
2:34 1.50
2:35 1.50
2:36 1.53
2:37 1.58
2:38 1.65
2:39 1.70
2:40 1.73
2:41 1.74

a) Calculate the minimum concentration of odorant (as C2H5SH) in parts per

million during the during the 10-min interval. The gas density was 2.00 ×
10-3 g/mL. (R.: 2.90 ppm)
b) What was the average odorant concentration during the 10-min period?
(R.: 3.08 ppm)

4. The calcium-content of a water sample was determined by introducing an excess or a

solution of HgNHY2- into a 50.0-mL sample. The anion of EDTA was then generated
at a mercury cathode (see Table 21- 1). A constant current of 0.0180 amp was
employed to reach an end point after 3 min and 32 sec. Calculate the milligrams of
CaCO3 per milliliter of sample. (R.: 0.0396 mg CaCO3)
 UNIVERSIDADE ESTADUAL PAULISTA JÚLIO DE MESQUITA FILHO
INSTITUTO DE QUÍMICA DE ARARAQUARA
DEPARTAMENTO DE ANALÍTICA, FÍSICO-QUÍMICA E INORGÂNICA

5. The equivalent weight of an organic acid was obtained by dissolving O.0231 g of the
purified compound in an alcohol-water mixture and titrating with coulometrically
generated hydroxide ions. With a current of 0.0427 amp, 402 sec were required to
reach a phenolphthalein end point. Calculate the equivalent weight of the compound.

6. Ascorbic acid is oxidized to dehydroascorbic acid with Br2

A vitamin C tablet was dissolved in sufficient water to give exactly 250 mL of

solution. A 50.0-mL aliquot was then mixed with an equal volume of 0.100 F KBr.
Calculate the weight of ascorbic acid in the tablet if the bromine generated by a steady
current of 0.050 amp for a total or 7.53 min was required for the titration.
(R.: 103 mg)

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.