Tdanta, Vol. 31, No. 11, pp. 1018-1020, 1984 0039-9140/84$3.00+ 0.
00
Printed in Great Britain Pergamon Press Ltd
TITRIMETRIC MICRODETERMINATION OF SILVER,
LEAD AND CADMIUM WITH THIOGLYCOLLIC
ACID AND OF MERCURY(I1) WITH
2-MERCAPTOPROPANOIC ACID
K. K. TIWARI and R. M. VERMA*
Department of Post-Graduate Studies and Research in Chemistry, University of Jabalpur, Jabalpur
(M.P.), 482001, India
(Received 25 November 1983. Revised 21 April 1984. Accepted 15 May 1984)
Sunnnary-A simple and rapid titrimetric method is described for the microdetermination of Ag+, Cd2+
and Pb*+, based on their formation of mercaptides with a measured excess of 2-mercaptopropanoic acid,
and similar determination of Hg*+ with thioglycollic acid. Univalent and bivalent metal ions release one
and two thiol protons respectively, which along with the carboxyl protons of the thiol reagent are titrated
with standard alkali. The difference from the blank titration gives the increase in acidity which is a function
of the metal-ion concentration. The proposed procedure is applicable to samples containing
0.025-0.25mmole of these ions, the average deviation being in the range 0.2-0.5x.
Silver and mercury(H) have been extensively used as with detection of the end-point. Though thioglycollic
reagents in the determination of mercaptans.’ Or- acid also gives a precipitate with these three metals,
ganomercuric salts have generally been employed but the precipitate dissolves just before the equivalence
some authors have recommended the use of mercuric point during the titration, and does not impair the
chloride.*’ Though a number of titrimetric pro- phenolphthalein end-point. The dissolution of the
cedures are available for determining ionized mercu- precipitate can serve as a guide to the approach of the
ric salts,4 these fail when applied to weakly ionized end-point. In the blank titration only the carboxyl
Hg(I1) salts such as mercuric chloride. The latter is proton is titrated, whereas for the samples the pro-
usually determined by titration with potassium iodide tons released from the thiol group and the carboxyl
or by reduction to mercury(I) chloride, which can be protons of the reagent are titrated. The difference in
collected and weighed,’ or titrated with iodine4 or the volume of alkali used (AI’ ml, molarity W
potassium iodate.6 It was, therefore, thought worth- corresponds to the metal concentration in the test
while to study the reaction of mercuric chloride with solution:
certain mercaptans with a view to developing a rapid atomic weight
and convenient titrimetric procedure for its deter- mg of metal ion = MAV
ionic charge >
mination. Our earlier work’ on the determination of
certain mercaptans was based on their treatment with
an excess of mercuric chloride and titration of the
acid liberated. Under these conditions the molar EXPERIMENTAL
reacting ratio was 1: 1. If the mercaptan is in excess, Reagents
however, a I:2 reacting ratio was observed: All solutions were prepared with analytical-reagent grade
chemicals and conductivity water.
2-Mercaptopropanoic acid. Standardized with potassium
Hg*+ + 2RSH+(RS)*Hg + 2H+
iodate solution,* and diluted to give 0.025,0.020,0.0125 and
O.OlM solutions.
This reaction has now been utilized in a simple and Thioglycollic acid. Standardized by titration with iondine
accurate method for determining mercuric chloride. solution9 and diluted to give 0.05, 0.025, 0.0125 and O.OlM
A micro procedure has been evolved for determining solutions.
Sodium hydroxide. Standardized with oxalic or preferably
mercury(II), and also silver, cadmium and lead.
furoic acid solution; 0.05,0.025 and 0.0125M solutions were
2-Mercaptopropanoic acid is suitable for the mercury prepared by dilution.
determination, but gives an insoluble mercaptide Phenolphthalein. A 1% solution in 1: 1 v/v ethanol-water
with silver, cadmium and lead, and this interferes mixture.
Metal salt solutions. Silver nitrate and mercuric chloride
solutions were prepared by dissolving a known weight of the
salt and diluting to known volume with water. Solutions of
*Address for correspondence: Dr. R. M. Verma, 226, lead nitrate and cadmium sulphate were standardized bv
Napier Town, Jabalpur 482001, India. titration with EDTAb and then suitably diluted.
1018
SHORT COMMUNICATIONS
1019
Table 1. Determination of some metal salts with mercaotans
Relative
Amount of metal, mg Average standard
deviation, deviation,
Compound Taken Recovered* % %
Silver nitrate 26.97 27.02 0.2 0.2
13.49 13.54 0.4 0.3
6.74 6.11 0.5 0.3
Mercuric chloride 20.06 20.10 0.2 0.1
10.03 10.06 0.3 0.2
5.01 5.03 0.4 0.2
Cadmium sulphate 22.48 22.55 0.3 0.2
11.24 11.27 0.3 0.2
5.62 5.64 0.4 0.3
Lead nitrate 25.90 25.95 0.2 0.1
10.36 10.40 0.4 0.2
5.18 5.20 0.4 0.3
*Average of 6 determinations.
Procedure titration method is generally used. Most of these
Pipette 5 or 10 ml of metal salt solution containing titrimetric procedures are applicable only to ionized
0.025-0.25 mmole of the substance and add about 100% mercury salts and cannot be used for determining
excess of mercaptan solution (Zmercaptopropanoic acid for
mercuric chloride. Most of the redox methods involve
mercuric chloride and thioglycollic acid for silver, cadmium
and lead salts). With mercuric chloride a precipitate appears reduction of mercury(I1) to mercury(I), followed by
initially but eventually dissolves when all the reagent has oxidimetric titration of the latter, which is time-
been added and the mixture is shaken. With silver, cadmium consuming.
and lead salts, the dissolution of the mercaptide occurs just The most extensively used methods for the deter-
before the end-point.
Add 5-10 drops of phenolphthalein solution and titrate mination of silver are precipitation as silver chloride
with standard sodium hydroxide solution. Run a blank with or bromide, or the so-calledi Volhard titration,
the same volume of mercaptan solution as that added to the which is satisfactory only at macro levels. Several
sample. From the difference between the volumes of alkali organic reagents have been used for gravimetric
needed for the blank and sample calculate the amount of
determination of cadmium, and there are several
metal: 1 ml of 0.02M sodium hydroxide = 2.006 mg of
mercury, 2.158 mg of silver, 1.124 mg of cadmium or procedures in which cadmium is precipitated by
2.072 mg of lead. suitable reagents and the precipitate analysed ti-
trimetrically. In most cases cadmium has to be sepa-
RESULTS AND DISCUSSION
rated from interfering elements before a titrimetric
method is feasible. Only the EDTA complex is suit-
Silver nitrate, mercuric chloride, cadmium sulphate able for the direct titrimetric determination of cad-
and lead nitrate were used for testing the proposed mium, but there is extensive interference from other
method at three concentration levels between 0.005 elements. However, a combination of pH control and
and 0.025M. The results recorded in Table 1 are the masking reactions will eliminate most interferences.”
averages of six determinations. The recovery studies The gravimetric determination of lead is based on its
showed that the average deviation is between 0.2 and precipitation as sulphate, chromate, molybdate, io-
0.5% and the relative standard deviation between 0.1 date, salicylaldoximate etc. The chromate precipitate
and 0.3%. can be analysed iodometrically. The best titrimetric
Several gravimetric methods have been proposed method is with EDTA.
for the determination of mercury(I1) but the most The procedure proposed here is simple, rapid and
suitable weighing form is the sulphide.” However, it accurate. No unusual reagent or indicators are re-
is difficult to keep volatilization losses within reason- quired and the reaction conditions are not critical. It
able limits.4 Titrimetric methods for determining mer- has been observed that addition of lOO-300% excess
cury(I1) involve neutralization, precipitation or redox of mercaptan solution or letting the mixture stand for
reactions. The Volhard titration with thiocyanate, 2-30 min before the titration does not affect the
using iron(II1) as indicator,” has the disadvantage results. There will obviously be interference by the
that the reaction is not quite stoichiometric,i2 and presence of any metals which react with mercaptans.
halides interfere. The EDTA titration can be done
in presence of chloride and even small amounts Acknowledgemenr-The authors are thankful to University
Grants Commission, New Delhi, for financial assistance to
of bromide, with Eriochrome Black T as indicator, at
one of them (KKT).
pH > 10. Because the mercury cannot be kept ini-
tially in solution at such high pH values without the
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1020 SHORT COMMUNICATIONS
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