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Journal of Analytical Chemistry, Vol. 57, No. 3, 2002, pp. 255–260. Translated from Zhurnal Analiticheskoi Khimii, Vol.

57, No. 3, 2002, pp. 304–309.


Original Russian Text Copyright © 2002 by Skvortsova, Kiryushov.

ARTICLES

Determination of Trace Sulfate Ions by Stripping Voltammetry


at a Renewed Silver Electrode
L. I. Skvortsova and V. N. Kiryushov
Institute of Solid-State Chemistry and Mechanochemistry, Siberian Division, Russian Academy of Sciences,
ul. Kutateladze 18, Novosibirsk, 630128 Russia
Received May 25, 2001

Abstract—The determination of trace sulfate ions by the known methods is considered. The most sensitive
methods are based on the reduction of sulfate ions to hydrogen sulfide followed by the detection of H2S in
absorbing alkaline solutions. The properties of reducing mixtures of different compositions were tested exper-
imentally. Working conditions were selected for the reduction of sulfate ions and the determination of sulfide
ions by stripping voltammetry at a silver electrode renewed on line by cutting off a thin layer. The detection
limit for sulfate ions was 10–5% in a 0.1-g sample.

Sulfate ions can be determined by almost all meth- with barium(II) solutions and procedures of ampero-
ods known in analytical chemistry. The most compre- metric titration of sulfate ions with lead(II) solutions
hensive list of these methods was presented in mono- are known. The use of these procedures is restricted
graphs [1, 2]. Trace amounts of sulfate ions can be because of the low solubility of BaSO4 and PbSO4; they
determined by colorimetry [3–7] and kinetic [8, 9], provide the determination of more than 10–2% sulfate
electrochemical [10–16], or special [17] methods. 2–
Much attention in the literature is given to the reduction ions in a sample. Similar amounts of SO 4 are deter-
of sulfate ions to hydrogen sulfide followed by its mined by indirect voltammetric methods based on the
detection by photometry or polarography [18–38]. 2– –
detection of signals of electroactive CrO 4 , IO 3 , or
Sensitive colorimetric methods are based on a chloranilate anions on their displacement from poorly
decrease in the color intensity of barium complexes of soluble compounds by sulfate ions [1, 2, 10–15].
organic reagents due to the formation of BaSO4 in the
presence of sulfate ions. The preconcentration of sul- The indirect electrochemical method based on the
2–
fate ions on ion exchangers and the evaporation of the SO 4 catalyzed electroreduction of Mo(VI) to Mo(V)
eluate allowed a detection limit of 5 × 10–4% to be and the detection of the oxidation peak of a molybde-
achieved for sulfate ions [3]. The difficulties encoun- num sulfate complex deposited on the electrode surface
tered in the determination of sulfate ions are associated at a selected potential [16] provides the determination
not only with a long time of analysis but also with the of more than 5 × 10–5–10–3 M SO 4 ions.
2–
use of specific dyes (Orthanilic K [3] or Methylthymol
Blue [4]). Dimethylsulfonazo III, Nitchromazo, and The authors of [17] proposed to determine sulfate
Beryllon II were also tested as dyes [7]. For different ions in reagents of high-purity grade by turbidimetry
reasons, they did not find wide application. The colo- after their preconcentration by low-temperature
rimetric procedure based on the reaction between sul- directed crystallization. They succeeded in lowering
fate ions and [Fe(CNS)6]3– exhibited insufficient sensi- the detection limit for sulfate ions to 1 × 10–5%. How-
tivity [6]. ever, the analysis was time-consuming and labor-inten-
The determination of 5 × 10–3% sulfate ions was sive.
based on their ability to catalyze the formation of col- Methods for the reduction of sulfate ions to S2– fol-
ored compounds in the reaction between zirconium(IV) lowed by the determination of hydrogen sulfide
and Methylthymol Blue [8] or Xylenol Orange [9]. In absorbed by an alkali attract attention because of their
the former case, the reaction proceeded most com- indifference to the composition of a test sample, selec-
pletely within 60–80 min, and the color intensity of the 2–
compound formed by zirconium and Xylenol Orange in tivity, and low detection limits for SO 4 (10–4%) [18–
the presence of sulfate ions continuously increased 38]. The high sensitivity of the methods is due to the
with time. low detection limit for sulfide sulfur in photometry,
Electrochemical methods used for the determination polarography, or voltammetry.
of sulfate ions [1, 2] are, as a rule, indirect. Procedures The goal of this work was to select a simple, rapid,
for the potentiometric determination of sulfate ions and reliable procedure for the determination of down to

1061-9348/02/5703-0255$27.00 © 2002 åAIK “Nauka /Interperiodica”


256 SKVORTSOVA, KIRYUSHOV

Ar flow was absorbed by an alkaline solution in an absorb-


ing test tube 6. The proposed procedure does not
require a reflux condenser and absorbing vessels with a
1 washing solution that are conventionally used in many
procedures [28–32] for removing vapors of the reduc-
ing mixture.
2
The concentration of sulfide ions was determined by
stripping voltammetry using a PA-2 or PU-1 polaro-
graphs equipped with an x–y recorder. A silver wire
6 0.5 mm in diameter (the working area of the electrode
3
end was 2 × 10–3 Òm2) whose side surface was isolated
with a cured epoxy resin served as the working elec-
trode. The stages of the accumulation of a sulfide film
and of sweeping the polarization potential were carried
4 out in a three-electrode cell containing a saturated
calomel reference electrode and a graphite auxiliary
5
electrode. All electrodes, including a changeable silver
working electrode, were installed in the body of a trans-
ducer, which was equipped with a mechanism for mov-
ing the electrode in the vertical direction and with a
Fig. 1. Schematic diagram of a device for the reduction of knife rotating in the horizontal plane for renewing the
2–
sulfate ions: 1, vessel for the reduction of SO 4 ions;
frontal surface of the working electrode. During the
renewal of the electrode end, a thin layer of its surface
2, thermometer; 3, heating beaker; 4, stand for the beaker;
5, electric hot plate; and 6, test tube with KOH solution.
(0.5 µm) was cut off with a hexanite knife [39] directly
in the test solution, each time before applying the accu-
mulation potential. The test solution was stirred with an
10–4% sulfate ions in lithium hydroxide and chloride air or an argon flow during the electrodeposition.
reagents. Cathodic stripping voltammograms of the deposit were
recorded at a potential sweep rate of 0.1 V/s.
Supporting KOH and NaOH solutions were pre-
EXPERIMENTAL pared from chemically pure reagents. Standard Na2S
Sulfate ions were reduced in a device schematically solutions were prepared by dissolving Na2S · 9H2O
depicted in Fig. 1. The device 1 for the reduction of sul- crystal hydrate in a deoxygenated 1 M KOH solution.
fate ions consisted of a glass vessel made as test tubes The concentration of sulfide ions was determined by
with branch tubes to feed an inert gas and to remove titration with a 0.04 N K3Fe(CN)6 solution [42].
hydrogen sulfide. It is not advisable to use rubber tubes
and stoppers in vessels for the reduction of sulfate ions,
because sulfur may be leached out of them. During the RESULTS AND DISCUSSION
experiment, vessel 1 was fitted into a pocket of a heat- To determine less than 0.01% sulfate ions, we used
ing metal beaker 3, which was placed on a metal 2–
the known methods of the displacement of CrO 4 and
stand 4 (in our case, the stand was made of duralumin)

and put on an electric hot plate 5. Temperature was IO 3 anions [1, 2, 10–15] followed by the electrochem-
measured with a thermometer 2 or a thermocouple. The ical determination of the displaced ions. The experi-
massive stand maintained the temperature in the reduc- ments failed. We also tested a method of the catalytic
tion vessel constant to within ±2°C. Because of a large formation of a molybdenosulfate complex [16] on a
contact area of the vessel with the heating beaker, the renewed graphite electrode and found that catalytic
heat-up of the reducing mixture could be accelerated. peaks degenerated in the presence of large amounts of
The deep pocket of the metal beaker provided a uni- chloride anions. The kinetic method based on the for-
form heat-up of 5 cm3 of a solution in the vessel. Simi- mation of zirconium colored complex of Xylenol
lar heating principle was used earlier [21]. It is more Orange [9] turned out to be difficult to accomplish
often recommended to heat a vessel with a mixture on under the conditions of routine analyses.
an open hot plate or in the flame of a gas burner. Taking into account the advantages and disadvan-
Because of this, the reduction temperature is difficult to tages of the above-mentioned methods for determining
maintain in a narrow range, so that the temperature trace amounts of sulfate ions in reagents, we dwelt on
must be continuously controlled during the reduction. the universal method of reducing sulfate ions to sulfide
Hydrogen sulfide was separated with an inert gas ions, which were then detected by stripping voltamme-
(argon), which was passed through the vessel at a rate try at a renewed silver electrode. To select the optimum
of 2–3 bubbles per second. H2S transferred with a gas determination conditions, we analyzed all the available

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 57 No. 3 2002


DETERMINATION OF TRACE SULFATE IONS BY STRIPPING VOLTAMMETRY 257

published data on this problem [18–38]. The optimum HI (100mL) + NaH2PO2 · H2O (2.5 g) + CH3COOH
conditions included the following parameters: the com- (25 mL). A reducing mixture of this composition was
position of the reducing mixture, the design of a glass tested in this work and demonstrated satisfactory prop-
vessel for the reduction of sulfate ions, the way of heat- erties for practical use. Hydroiodic acid for preparing
ing the system, a carrier gas for hydrogen sulfide, and the reducing mixture should be taken from a fresh
conditions for the determination of sulfide ions by strip- reagent, because free iodine is accumulated in it during
ping voltammetry. storage. However, the practice demonstrates that this
Selection of a reducing mixture. Sulfate ions are does not assure the absence of I2 from hydroiodic acid.
reduced to hydrogen sulfide either with mixtures of To purify the reducing mixture of I2, we extracted it two
phosphoric acid and some metal salts or with mixtures or three times with tributyl phosphate in chloroform
of hydroiodic acid and substances that reduce I2 liber- until the color became slightly yellow [45]. Boiling the
ated in the reaction [18–38]. reducing mixture for 30–40 min completely purified it
In the former mixtures, Ti(III) salts were most often of sulfate ions present in the reagents. This was con-
used as reducing agents [18–20] and it was proposed to firmed by the absence of the peak from the voltammo-
use Cr(II), Mo(IV), W(V), V(II), and Ti(II) salts as gram obtained in a blank experiment. The purified mix-
well. Sulfate ions in phosphoric acid-based mixtures ture could be used for a long time if stored in a dark
are reduced at 285–290°C [18, 19]. Simultaneously closed container in a refrigerator. A 5-mL aliquot of the
with the reduction of sulfate ions, phosphoric acid is reducing mixture is sufficient for analyzing five to
dehydrated to pyrophosphoric acid (the temperature of seven dry samples of 0.1 g and smaller.
the H3PO4-to-H4P2O7 transition was 215°C [44]). The temperature of the reduction of sulfate ions with
Because of the accumulation of pyrophosphoric acid, this mixture in the vessel (Fig. 1) was determined in
the reduction temperature of sulfate ions rose to 700– experiments with accurate aliquot portions (0.1 mL) of
800°C [18]. Thus, the main drawback of phosphoric 2–
a K2SO4 solution containing 10 mg/L SO 4 . As in [22,
acid-based mixtures of any composition was the loss of 24], the added sulfate ion was completely reduced to
their reducibility. During uncontrolled heating [20], the S2– at 115–120°C within 15 min.
mixture lost its reducibility just at a stage of boiling for
removing free reagents from sulfate ion-containing Selection of a carrier gas for hydrogen sulfide
compounds. We failed to obtain satisfactory results in and an absorbing solution. Carbon dioxide recom-
experiments performed with a (Ti(III) + H3PO4) mix- mended in some works [18–30] to isolate H2S some-
ture, because it solidified during previous boiling for 30 what complicated the analysis compared to argon
min and became unfit for the further use. because of the necessity of cooling the absorbing bottle
warmed up in the exothermic reaction of CO2 with an
The proposed modification of phosphoric acid-
based mixtures [21] by adding KI and metallic iron absorbing alkaline solution. In addition, the concentra-
serving as reducing agents for sulfate ions and the I2 tion of the absorbing alkali should be sufficiently high
(5 M) to neutralize the absorbed CO2 . Argon as a carrier
formed, respectively, implied that the mixture is used
once in a small (0.5 mL) volume without preliminary gas was free from these drawbacks. The absorbing
heating. Although the use of this mixture prevented the solution did not heat, and the concentration of alkali
accumulation of pyrophosphoric acid, the sensitivity of might be no higher than 1–2 M. In our experiments,
the method was low and the detection limit for sulfate carrier gas was not additionally purified, because it con-
tained no oxidants of sulfide ions. This was confirmed
ions was about 10–2%. by the stability of the sulfide ion concentration in the
Hydroiodic acid mixtures [22–38] reduce sulfate solution through which argon was purged.
ions at 115–120°C [22–24] within 5–15 min [25–28]. A 5 M NaOH solution was usually recommended as
2–
The analytical range of SO 4 concentrations varied an absorbing solution for H2S [22–38]. The experi-
from 5 × 10–4 to 10–2% [29–31]. For many years, the ments showed that reagents (KOH or NaOH) should be
composition of iodide mixtures was improved by of the highest degrees of purity, better of high-purity
selecting both components for creating an acid medium grade, because the reaction between heavy metal impu-
and reducing agents for I2 formed on the reduction of rities and sulfide ions shifted the starting point of the
sulfate ions. calibration curve along the x axis.
The acidity of the medium was created with hydro-
chloric [20, 21, 24, 25, 28–30], formic [22, 31], or ace- VOLTAMMETRIC DETERMINATION
tic [32, 33] acids. The iodine formed was reduced with OF SULFIDE IONS IN ABSORBING SOLUTIONS
red phosphorus [22, 31] or hypophosphorous acid
(H3PO2) [18–21, 24–31]. The systematic studies of It was proposed to determine sulfide ions in absorb-
mixtures of different compositions [32] showed that a ing solutions containing from 6 × 10–7 to 10–5 M S2– by
mixture of the following composition provided better stripping voltammetry at a mercury or silver working
2–
electrodes without unneeded additional preconcentra-
reproduced results in the determination of SO 4 ions: tion. The detection limits for S2– were 5 × 10–8 M [20]

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 57 No. 3 2002


258 SKVORTSOVA, KIRYUSHOV

I, µÄ I, µÄ
2.8 1
3.2
1
2.3
2
2.8
1.8
~
~ ~
~ ~
2 ~
0.5
2.4

0
2.0 0.7 0.5 0.3 0.1 +0.1
0 1 2 3 4 –E, V
KOH, M
Fig. 2. Current peak of a 4 × 10–6 M solution of sulfide ions
as a function of KOH concentration in the supporting elec- Fig. 3. Current peaks of (1) 5 × 10–6 M and (2) 1.2 × 10–6
trolyte stirred with (1) argon and (2) air at an accumulation M solutions of sulfide ions as functions of the accumulation
time of 2 min. potential of the deposit at an accumulation time of 3 min.

and 10–8 M [40] at a mercury and a silver electrode, Thus, the working conditions for determining sul-
respectively. We used silver electrodes renewed by cut- fide ions in alkaline solutions by stripping voltammetry
ting off a thin surface layer immediately in a test solu- at a silver electrode are as follows:
tion. The usefulness of the renewal of the surface of sil- (1) alkali concentration in the supporting electro-
ver electrodes in determining sulfide ion was discussed lyte, 0.2–2 M;
in [45]. (2) electroaccumulation potential of a silver sulfide
The application of a polarization potential to the sil- deposit, –0.2 to –0.5V;
ver electrode placed in the alkaline solution of sulfide (3) gas flow rate for stirring the solution during
ions stabilized the oxidation of silver (Ag – e– accumulation, 0.1 L/min.
Ag+), which also occurred without applying the poten- The time of Ag2S accumulation was selected as a
tial [41]. An Ag2S film formed at the electrode surface function of the concentration of sulfide ions in solution.
contained sulfide ions in the amount proportional to its The detection limit for sulfide ions equal to 10–9 M can
bulky concentration. The cathodic peak of the silver(I) be attained at an electrode of 0.5 mm in diameter at an
reduction from Ag2S to elemental silver served as the accumulation time of 20 min. This detection limit for
analytical signal. The accumulation of the Ag2S deposit sulfide ions corresponded to 2 × 10–7% sulfate ions in a
during the application of the polarization potential sig- 0.1-g sample of the reagent.
nificantly improved the precision of the results of anal- The mechanical renewal of the surface of a silver
yses [45]. electrode before each measurement essentially
improved the reproducibility of the peak height com-
When selecting the working conditions, we opti- pared to that attained with an unrenewed electrode. The
mized the concentration of an alkali in the supporting relative standard deviation (RSD) in the determination
electrolyte, the accumulation potential for Ag2S, and of 3 × 10–6 M sulfide ions accumulated for 3 min at a
the gas flow rate for stirring the solution during accu- renewed silver electrode was 2% (n = 20, P = 0.95)
mulation. The dependence of the cathodic current peak [45]. 500-fold amounts of thiocyanate, iodide, bromide,
(Ip) on the parameters under study served as the optimi- chloride, nitrate, and nitrite ions did not interfere with
zation criterion in all experiments. the determination of sulfide ions. These anions inter-
fered with the determination of sulfide ions at a solid
Figure 2 shows that Ip measured in 0.5–2.5 M KOH electrode without its mechanical renewal [41, 43].
solutions stirred with argon was virtually equal to that Determination of sulfate ions. A sample (~0.1 g)
measured in 0.5–2.0 M KOH solutions stirred with air was placed in a vessel containing 5 mL of the reducing
during the accumulation of a deposit. It follows from mixture and heated at 125°C in the flow of Ar admitted
Fig. 3 that the accumulation potentials found for differ- at a rate of 2–3 bubble/min for 15 min. The liberated
ent concentrations of sulfide ions falls in the range hydrogen sulfide was trapped in a test tube filled with
between –0.2 and –0.5 V, where the value of the peak 15 mL of 2 M KOH. The alkaline solution was trans-
current was independent of the accumulation potential. ferred to a 25-mL volumetric flask and diluted to the
The peak current also remained constant when the solu- mark with boiled distilled water. Thus prepared solu-
tion was stirred either with argon or with air passed at a tion was placed in an electrochemical cell, the surface
rate higher than 0.1 L/min during the accumulation of a of a silver electrode was renewed mechanically by cut-
deposit. ting off a layer, sulfide ions were electrodeposited at

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 57 No. 3 2002


DETERMINATION OF TRACE SULFATE IONS BY STRIPPING VOLTAMMETRY 259

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JOURNAL OF ANALYTICAL CHEMISTRY Vol. 57 No. 3 2002

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