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Spectrophotometric Reaction-
Rate Method for The
Determination of Sulfide
by Catalytic Action on the
Oxidation of Sodium Azide by
Iodine
a a
Ali A. Ensafi & M. Samimifar
a
College of Chemistry, Isfahan University of
Technology, Isfahan, Iran
Version of record first published: 22 Aug 2006.

To cite this article: Ali A. Ensafi & M. Samimifar (1994): Spectrophotometric

Reaction-Rate Method for The Determination of Sulfide by Catalytic Action on the
Oxidation of Sodium Azide by Iodine, Analytical Letters, 27:1, 153-167

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 ANALYTICAL LETTERS, 27(1), 153-167 (1994)

SPECTROPHOTOMETRIC REACTION-RATE METHOD FOR THE

DETERMINATION OF SULFIDE BY CATALYTIC ACTION
ON THE OXIDATION OF SODIUM AZIDE BY IODINE

Keywords: Catalytic, Azide, Iodine, Sulfide, Water, Steel.

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Ali A , Ensafi* and M. Samimifar

College of Chemistry, Isfahan University of
Technology, Isfahan, Iran

ABSTRACT
A catalytic kinetic method has been used for the
determination of ultra trace amounts of total dissolved
sulfide based on its catalytic effect on the reaction
between sodium azide and iodine in aqueous solution. Sulfide
over the range of 0.020-0.500 ug.rn1-l was determined
spectrophotometrically by measuring the decrease in
absorbance of iodine at 348 nm by the fixed-time method. The
decrease in absorbance during the first 0.5-3.0 min from
initiation of the reaction is related to the concentration
of sulfide. The detection limit is 0.010 ug.ml-l. The
relative standard deviation for the determination of 0 . 0 5 0
ug.rnl-l of sulfide was 2.2%. The proposed method was
successfully applied for the determination of sulfide in
synthetic samples , spring water and of sulfur in steel.

153

Copyright 8 1994 by Marcel Dekker, Inc.

 154 ENSAFI AND SAMlMlFAR

INTRODUCTION
Determination of sulfide in various natural and
manufactured materials is of importance, since the sulfide
ion has a wide variety of industrial and biological effects
even at low concentrations. A s critical quantities of
sulfide are generally small ( trace level 1 , sufficiently
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sensitive and selective methods must be used for its

determination.
Classical titrimetry uses iodine or potassium hexacyano-
ferrate(II1) as the titrantl. The Methylene Blue method’ is
most often used for spectrophotometric determination. Other
methods such as ~otentiometry~, chemi l u m i n e ~ c e n c e ~ - ~ ,
p ~ l a r o g r a p h y ~ . ~ ,gas chromatography9, conductometry9,
cou 1 ometry lO, 18, cata1yt i c met hods ‘-13 and amperometri c
methods14-16,17 also have been used for the determination of
sulfide, but many of these methods suffer from more or less
time consuming procedures, complicated and expensive
instrumentation, or the reagents used are toxic and/or
relatively unstable and/or not commercially available.
The catalytic-kinetic spectrophotornetric method15 is one
of the most attractive approaches for ultra trace
determination of some species. Its advantage is that only a
spectrophotometer is required as the main instrumentation.
Sulfide ion has been determined through its catalytic
effects on the sodium azide-iodine system by amperometric
method16-18 with rotating Pt-electrode and by coulometric
method” with Hg-electrode. But these methods need
complicated instrumentation with time consuming procedures.
 DETERMINATION OF SULFIDE 155

and have high limit of detection and small linear dynamic

ranges.
Recently, we reported a sensitive and selective method
for the determination of sulfide based on the reaction with
Brilliant Green2'. This paper describes a kinetic-spectro-
photometric method for the determination of sulfide based on
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its catalytic effect on the oxidation reaction of sodium

azide by iodine. This method which is simple and sensitive,
uses only readily available reagents and instrumentation.
Suitable methods were used for the elimination of species
that potentially interfere.

EXPERIMENTAL
Reagents
All reagents except for sodium sulfide were analytical
reagent grade. Doubly distilled water was used throughout.
Stock sulfide solution ( 1000 ug.ml-l ) was prepared by
dissolving 749.2 mg of sodium sulfide ( Na2S.9H20. Merck )

in 50 ml of 0.001 M NaOH solution, then diluting to 100 ml

in a 100 ml volumetric flask with water. Its sulfide content
was established by iodometric method. Working solutions were
prepared daily from this stock solution by appropriate
dilution with water.
Sodium azide solution ( 1.00 M ) was prepared by
dissolving 6.501 g of sodium azide ( NaN3, Merck 1 in
water and diluting to 100 ml with water in a 100-ml
volumetric flask.
 156 ENSAFI AND SAMIMIFAR

Iodine solution ( l3-, 0.010 M 1 was Prepared by

dissolving 0.2540 g of 12 ( Merck 1 in potassium iodide

solution ( 4.500 g KI/100 ml 1 in a 100-ml volumetric flask.

Sodium hydroxide or hydrochloric acid were used for pH

adjustment. Phosphate buffer solution was used for the PH of
6.0.
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Apparatus
A UV-240 spectrophotometer ( Shimadzu ) was used for
measurements of the absorption spectra. A model 35-spectro-
photometer ( Perkin-Elmer ) with 1.0 cm glass cuvettes was
used for the measurement of the absorbance at 348 nm. A
thermostat ( Gallenkamp Griffine. BJL-420-V 1 was used to

keep the reaction temperature at 25 OC. A stop-watch wus

used for recording the reaction time.

RECOMMENDED PROCEDURE
The catalyzed reaction was monitored spectrophoto-
metrically by measuring the change in absorbance at 348 run
with the fixed-time method at the first 0.5 - 3.0 min from

initiation of the reaction.

To a solution containing 0.20 - 5.00 ug of sulfide in a
10 ml volumetric flask, 1.0 ml of buffer solution
(phosphate, pH-6.0) and 2.0 ml of 1.00 M NaN3 solution were
added and the solution was diluted to ca. 7 ml with water.
The solution was shaken and kept in a thermostated water
bath at 2 5 OC for 10 min. Then 2 . 0 ml of 8.75 x M
iodine solution was added and the solution was diluted to
the mark with water. The stop-watch was turned on when the
 DETERMINATION OF SULFIDE 157

last drop of iodine solution had fallen. Immediately, an

appropriate quantity of the reacting solution was
transferred into the cell chamber at the appropriate
temperature. The change in absorbance at 348 run was recorded
against water after 0 . 5 - 3.0 min from initiation of the
reaction. A calibration graph was constructed as the change
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in absorbance vs. sulfide concentration at the fixed time of

3.0 min.

RESULTS AND DISCUSSION

It was found that some oxidants such as iodine could
oxidize sodium azide. The reaction proceeds very slowly at
low concentration of the reagents without sulfide. However,
this solution underwent rapid oxidation when sulfide was
added at the part per billion range. This oxidation process
was monitored by means of the decrease in absorbance of the
characteristic band of iodine( Fig. 1 1 .

Effects Of Variables On The Reaction Rate

The effect of variables such as reagents concentration,
ionic strength and temperature were studied to give the best
sensitivity.
The effect of PH on the rate of catalyzed and
uncatalyzed reaction was studied with 0.010 M sodium azide,
1.0 x M iodine. 0.200 u9.ml-l sulfide and temperature
of 25 OC (Fig. 2). It was found that the rate of catalyzed
reaction increased with increasing pH values up to about 6.0
whereas up to this range of pH, the increase in the rate of
the uncatalyzed reaction is very small. Solutions with pH
 158 ENSAFI A N D SAMIMIFAR

1 . 30
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1.00

0.50

C
300 400 500

wavelength (nm)

1. Variation of Azide-Iodine system with sulfide

concentration; Conditions: sodium azide. 0.05 M; Iodine,

1 x M: pH, 6.0; Temperature, 25 OC; sulfide, 0.100

ug.ml-1 and a. 0.0 sec: b. 75 sec; c. 150 sec: d. 225
sec: e. 300 sec, and f . 375 sec from initiation of the

react ion.
 DETERMINATION OF SULFIDE 159
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AA

3 4 5 6 7 8 9

P"

2 . Effect of PH on the rate of catalyzed(.) and uncatalyzed

( 0 )reaction.

higher than 9.0 were not tested due to the instability of

the reagents. From these results, a p H of 6.0 was selected
for the study,
The effect of sodium azide concentration on the rate of
catalyzed and uncatalyzed reaction was studied in the
concentration range of 0 - 0 . 2 4 M in the presence of 1.0 x
M iodine, 0.200 vs.ml-l sulfide, pH 6.0 and temperature
of 25 OC ( Fig. 3 1 . The results show that by increasing
 ENSAFI AND SAMIMIFAR
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0 35 I0 105 140 175 210

Nap x l o 3 M
3

3 . Effect of sodium azide concentration on the catalyzed(.)

and uncatalyzed(o) reaction.

azide concentration up to 0.20 M. the catalyzed reaction

rate was increased whereas, from 0.002 M azide, the
uncatalyzed reaction rate became independent of azide
concentration. Thus 0.20 M sodium azide was chosen as the
optimum azide concentration.
The effect of iodine concentration on the rate of
catalyzed and uncatalyzed reaction was studied in the
concentration range of ( 1.5-2.75 ) x M in the presence
of 0.20 M sodium azide, pH 6.0, 0 . 2 0 0 ug.rnl-l of sulfide and
 DETERMINATION OF SULFIDE 161

0.211

0.151
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AA

0.19(

0.03(
1.5 2 2.5 3 3.5

4. Effect of iodine concentration on the reaction rate.

temperature of 25 OC ( Fig. 4 1 . The results show that the

rate of catalyzed and uncatalyzed reaction both increased
with increasing iodine concentration, but the increase for
the rate of catalyzed reaction became larger at 1.75 x
M than that of the uncatalyzed reaction. From the results,
1.75 x M iodine concentration was selected as the
optimum iodine concentration.
The effect of reaction temperature was studied for the
catalyzed and uncatalyzed reaction in the range of 5 - 40 OC
 162 ENSAFI AND SAMIMIFAR

at the optimum concentration of the reagents and PH 6.0 with

0.200 ug.ml-l sulfide. The results show that from a

temperature of 10 OC to 40 OC, the rate of catalyzed
reaction decreases, while the rate of uncatalyzed reaction
is nearly constant. This effect may be due to the
instability of the sulfide content at higher temperatures.
Thus a temperature of 25 OC was selected as the working
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temperature in order for the study to be more easily

performed.
The rate of catalyzed and uncatalyzed reaction were
independent of the change in ionic strength up to 1.0 M (3.0
M NaN03 solution was used for adjustment of ionic strength).

Calibration Graph, Precision and Detection Limit

The calibration graph was obtained by applying the fixed

time method under the optimum conditions. The effect of
measuring time on the correlation coefficient and
sensitivity for the calibration graph was studied. From the
results, 3.0 min from initiation of the reaction was chosen
as the optimum measuring time. The decrease in absorbance is
directly proportional to the sulfide concentration in the
range of 0.020 - 0.500 ug.ml-l, with the regression equation
of AA = -3.034 x t 1.517C ( n = 6 and r = 0.9997 1

where C is the us.rn1-l of sulfide and A A is the change in

absorbance for the catalyzed reaction minus that of the
uncatalyzed reaction at the same fixed time. Higher
concentrations of sulfide ( > 0 . 5 0 0 ug.ml-l) can be studied by
the above method using lower concentration of azide.
 DETERMINATION OF SULFIDE 163

TABLE 1
Effect of Various Ions On The Determination of
Sulfide At The Optimum Conditions
Species Tolerance Limit
(Wion/Wsu 1 f ide )
____________________-------__--_____-__-----------_-_____-__
NO3-, B4072-, C lo3-, C 104-, POq3-,
Br03-, SOq2-, NH4+, Na', K+,
Citrate, Ca(I1). Mg(I1) 10000*
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C032-, F-, C1-, Br-. Bog-, Ba(I1).

~2042-, NO^-, MO(VI ) , ~i (I I I 1 ,
Acetate, Phthalate, Tartarate 1000

Cr(V1). As(II1). V(V), V(II1) 1

_______________-__--____________________-------__-----_-__--
*, Maximum concentration of species that were tested

The experimental limit of detection is 0.008 ug.ml-l

whereas the theoretical limit of detection21 is 0 . 0 0 3 ug.ml-'
of sulfide.
The relative standard deviation for ten replicate
determinations was 2.2% and 1.0% for 0.050 and 0 . 4 0 0 ug.ml-l
of sulfide.

Interference Study
The effect of potential interferences which generally
accompany sulfide has been studied for sulfide concentration
 164 ENSAFI A N D SAMIMIFAR
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5. Apparatus used for the removal of sulfide from the

matrix of the sample.

of 0.100 ug.ml-l at the optimum conditions. The tolerance

limit was taken as the amount of species required to cause
-
+1.5% error in sulfide recovery. The results are shown in
Table 1. Cations such as Zn(I1). Cu(11). Mn(I1) and Co(I1)
interfere because of precipitation with sulfide ion. Other
species such as Cr(V1). V(V), Ce(IV) and SzO8’- interfere
due to oxidation of sulfide and azide. Other anions such as
S032- and S2052- interfere due to reaction with iodine.

Removal of Interferins Ions

In this reaction, cations and anions that react with
sulfide and/or with iodine and/or with azide can interfere.
For the elimination of the interferences, we used a suitable
separation system (Fig. 5 ) . that can release the total
sulfide content from the matrix of the samples as the
hydrogen sulfide. The sample was placed in the flask and 10
ml of 6 M hydrochloric acid were added from a separating
funnel. The absorption tube was loaded with 30 - 50 ml of
 DETERMINATION OF SULFIDE 165

TABLE 2

Species Sulfide Sulfide Found RSD

Added (n=7)
............................................................
Spring Water -- 21.00 ug .m1-1 1.3%
Spring Water 2.00 ug.ml-1 23.00 , II 1.2%
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Spring Water 5.00 , 26.00 69 , 18 1.1%

Steel No. 1 0.035%* 0.0354% 1.4%

Steel No. 2 0.112%* 0.1127% 1.5%

0.10 M NaOH (depending on the amount of sulfide or sulfur).

Flask no. 1 was heated ( 10 min boiling ) and the hydrogen
sulfide evolved was absorbed in the NaOH solution ( in the
flasks no. 2 and 3 , Fig. 5 1 . Then the delivery tube was
disconnected and rinsed with 2 or more small volumes of
0.001 M NaOH. The solutions from flasks no. 2 and no. 3 were
mixed and the sulfide content wus then determined by the
recommended procedure.

Determination of Sulfide in Sprins Water and Sulfur in Steel

In order to check the validity of the proposed method
for the determination of sulfide in real samples. spring
water and steel were selected for the determination of
sulfide and sulfur contents.
For the determination of sulfide in a sample of spring
water, sulfide contents were initially removed from the 50.0
 166 ENSAFI AND SAMIMIFAR

ml of the sample by the recommended procedure. Then the

sulfide was determined by the proposed method.
For the determination of sulfur in steel, synthetic
samples were made . A sample between 1.00 to 2.50 g was
placed in the flask no. 1. and 20 ml of 6.0 M hydrochloric
acid were added. The flask was heated 10 min after
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dissolution was completed. The hydrogen sulfide evolved was

absorbed in a 0.10 M sodium hydroxide solution in the
absorption flasks (the absorption flasks were loaded with
10-50 ml of NaOH solution, depending on the amounts of
sulfur). Then the delivery tube was disconnected and rinsed

with 2-3 small volumes of 0.001 M NaOH solution. The

adsorption flask contents were mixed, and the sulfide
contents was determined by the recommended procedure (Table

2 ).

CONCLUSION
The results of the present investigation show that the
azide-iodine system can be successfully used for the
quantitative determination of ultra-trace amounts of
sulfide and sulfur. The rapidity, simplicity and sensitivity
attained using this method encourage the application of the
proposed method in routine analysis of sulfide in natural
water and sulfur in steel without any preconcentration.

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Received May 2 4 , 1993

Accepted August 2 4 , 1993