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MICROCHEMICAL JOURNAL 53, 168–174 (1996)

ARTICLE NO. 0024

A Simple Spectrophotometric Method for the Determination of

Hydrogen Sulfide Based on Schiff’s Reaction

KRISHNAMOORTHY SHANTHI AND NATESAN BALASUBRAMANIAN1

Department of Chemistry, Indian Institute of Technology, Madras 600 036, India
Received February 9, 1995; accepted April 13, 1995
A simple and sensitive spectrophotometric method for the determination of trace amounts of
hydrogen sulfide after fixation in a zinc acetate trapping solution is described. The fixed sulfide was
made to react with formaldehyde to form a hydrosulfide adduct which reacts with pararosaniline in
an acid medium to form a colored product. The product was stabilized with gelatin and thiocyanate
for the absorbance measurement at 520 nm with a Beer’s law range of 0–20 mg hydrogen sulfide. The
relative standard deviation for ten determinations at 10 mg H2S is 2.4%. The effect of various
interfering gases was overcome by the use of a simple collection procedure. The method was applied
to the determination of residual amounts of H2S present in a laboratory fume hood and the results
were compared with those of the standard methylene blue method. © 1996 Academic Press, Inc.

INTRODUCTION

Increasing emphasis on clean air has resulted in the development of fairly effective
control methodology and sensitive analytical techniques for H2S determination. Most of
the analytical methods, including the widely used methylene blue method (1) and redox
methods (2, 3), have a long way to go toward meeting the desired analytical requirements
such as high sensitivity, freedom from interference, good color stability, and ease of
operation. The use of Schiff’s reaction for SO2 (4) suffers serious interference from
sulfides, thiols, and thiosulfates, which give virtually identical reactions. The possibility
of using Schiff’s reaction for the determination of H2S was investigated in detail.
In the present study, H2S is trapped in 1% zinc acetate solution (5) and the fixed sulfide
was treated with pararosaniline and formaldehyde in acid medium to form a colored
product which was stabilized by gelatin and thiocyanate. To eliminate serious interference
from many interfering gases, including SO2, a simple collection procedure (6) was
adopted.

EXPERIMENTAL

Apparatus

All absorbance measurements were made with a Carl Zeiss PMQII spectrophotometer
with 10-mm glass cells. Fritted glass bubblers with a 60-mm maximum pore diameter frit
and an air suction pump were used for trapping H2S from air. The flow rate of the air was
measured using a rotameter.

1
To whom correspondence should be addressed.

168
0026-265X/96 $18.00
Copyright © 1996 by Academic Press, Inc.
All rights of reproduction in any form reserved.
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SPECTROPHOTOMETRY OF HYDROGEN SULFIDE 169

Reagents
All chemicals used were of analytical reagent grade and distilled water was used for
preparing the reagent solutions.
Standard H2S solution (200 µg ml−1). Prepared by dissolving 0.1412 g of Na2S·9H2O
in 100 ml of water and standardizing the solution iodimetrically. Dilute a suitable volume
of this solution to a solution containing 2 mg ml−1 of H2S with 1% zinc acetate solution.
This solution must be prepared on the day of use.
Zinc acetate trapping solution (1%). Prepared by dissolving 10 g of zinc acetate
dihydrate in 950 ml of water, adding 2 drops of glacial acetic acid, and bringing up to
1000 ml.
Pararosaniline solution (PRA). Prepared by dissolving 0.2 g of pararosaniline hydro-
chloride (BDH, England), adding 57ml of HCl (specific gravity 1.18), and bringing up to
1000 ml.
Formaldehyde solution (2% v/v). Prepared by diluting 5.3 ml of 38% formaldehyde
solution to 100 ml with water.
Ammonium thiocyanate (1% m/v). Prepared by dissolving 1 g of NH4SCN in 100 ml of
water.
Gelatin (0.25% m/v). Prepared by dissolving 0.25 g of gelatin in 100 ml of hot water.
This solution must be prepared on the day of use.
Hydrochloric acid (4.5 M). Prepared by diluting 40 ml of HCl (specific gravity 1.18)
to 100 ml with water.

PROCEDURE
Sampling
Air samples were collected by drawing air through fritted glass bubblers containing 10
ml of 1% zinc acetate solution at a flow rate of 0.5 liter min−1. The volume of the solution
was brought up to 25 ml with the trapping solution prior to determination.

Determination
To a 10-ml aliquot of 1% zinc acetate solution containing not more than 20 mg H2S, 1.5
ml of 5% potassium alum was added. The solution was centrifuged. The precipitate was
washed once with 5 ml of water. The precipitate obtained was made into a slurry using two
5 ml portions of 1% zinc acetate solution. This was then transferred into a 25 ml calibrated
flask. To this were added 5 ml of PRA, 3.5 ml of formaldehyde, 1 ml of gelatin, and 2 ml
of NH4SCN. After 15 min, 1 ml of 4.5 M HCl was added and the solution was brought
up to 25 ml with water. The absorbance of the solution at 520 nm was measured against
the reagent blank carried through the procedure. The concentration of H2S was established
by reference to a calibration graph prepared by treating 0–10 ml of standard H2S solution
(0–20 mg H2S) with 10–0 ml of zinc acetate solution and following the above procedure.

RESULTS AND DISCUSSION

Initial studies were carried out using 10 ml of 0.1 M NaOH as the trapping solution for
H2S. To a 10-ml aliquot of 0.1 M NaOH containing 10 mg H2S were added 5 ml of 0.02%
PRA in 1 M HCl and 4 ml of 2% formaldehyde. The resulting solution after 15 min was
brought up to 25 ml with water and the absorbance was measured at 520 nm against the
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170 SHANTHI AND BALASUBRAMANIAN

reagent blank. The system obeyed Beer’s law in the range 0–40mg H2S with high blank
absorbance of 0.150 A and the color was stable for 10 min.
Attempts were made to stabilize the color system. Since the formed product was
cationic in nature, the addition of bulky anionic species to stabilize the color system by
forming ion pairs was attempted. As it is well known that zinc and cadmium (5,7) salt
solutions find widespread use as trapping solutions for H2S, addition of some anionic
complexes of zinc and cadmium to stabilize the color system was investigated.
Use of [Zn(NCS)4]2−, [Cd(SCN)4]2−, and [CdI4]2− at low concentration levels had
increased the stability of the color system. The use of these reagents in excess increased
blank absorbance due to the formation of ion pairs between PRA and these species and
caused slow precipitation of the product. To prevent this precipitation, gelatin solution
was added and under these conditions the color system was stable for 60 min.
Zinc acetate is widely used as a trapping solution for H2S and does not require any
precaution to prevent the photo-oxidation of fixed sulfide (8). Therefore, experiments
were carried out with sulfide prepared in 1% zinc acetate solution instead of 0.1 M NaOH.
The use of zinc acetate as the trapping solution for H2S instead of NaOH stabilized the
color from 10 min to 15 min. Low concentration of NH4SCN (1%) solution was added to
increase the stability further. However on standing, slow precipitation was observed in
both the blank and the sample. This precipitation was prevented by the addition of 1 ml
of 0.5% gelatin prior to the addition of NH4SCN. Under these conditions, the color system
was stable for 60 min after the reaction time of 15 min.
Even though the modification improved the color stability, still the blank absorbance
was high (0.150 A). Since blank color was due to a Schiff’s base formed between free
PRA and formaldehyde, an attempt was made to selectively reduce the blank by the
addition of a slight excess of hydrochloric acid, 1 ml 4.5 M in a final volume of 25 ml,
(overall acidity 4 0.31 M) which selectively reduced the blank absorbance to 0.050 A
with color stability for 60 min. Further increase in acidities greater than 0.35 M was found
to decrease the stability of the color system, even though the blank absorbance was
negligible.
Systematic optimization studies were carried out with 10 mg H2S in 1% zinc acetate
solution to get optimum reagent concentrations. The optimum acidity for the reaction of
the formaldehyde–hydrosulfide adduct with PRA was found to be 0.15 ± 0.02 M HCl. This
was achieved by the addition of 5 ml of 0.02% PRA in 0.65 M HCl. However, final acidity
during the absorbance measurement was fixed at 0.32 ± 0.05 M HCl. Similar studies
revealed that the use of 5 ml of 0.02% PRA in 0.65 M HCl, 3.5 ml of 2% formaldehyde,
1 ml of 0.25% gelatin, 2 ml of 1% NH4SCN and 1 ml of 4.5 M HCl with a minimum
standing time of 12 min was essential to get maximum sample absorbance with low blank
value. These values were incorporated into the recommended procedure.
The absorption spectrum of the color system showed a broad absorption maximum from
510 to 550 nm and a corresponding blank maximum at 560 nm when measured against
water (Fig. 1). However, measurement of the absorbance at 520 nm is recommended
because at this wavelength, the blank absorbance is low, 0.050. A linear calibration graph
was obtained over the range 0–20 mg H2S in a final volume of 25 ml. The molar
absorptivity was found to be 2.55 × 104 liter mol−1 cm−1. The relative standard deviation
for 10 determinations at 10 mg H2S was 2.4%.
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SPECTROPHOTOMETRY OF HYDROGEN SULFIDE 171

FIG. 1. Absorption spectra measured against water. (a) Reagent blank, (b) H2S 10 mg, (c) H2S 20 mg.

Nature of Species Responsible for Color

The reaction of the hydrosulfide adduct of formaldehyde and H2S with PRA and its
complexation with zinc and thiocyanate under the experimental conditions was respon-
sible for the observed color.
The hydrosulfide adduct formed between formaldehyde and H2S attacked the amino
nitrogens of PRA, resulting in a product. The poor stability of this product might be due
to the oxidation of the thiol moiety to form stable disulfide. In the presence of Zn2+ ion,
the thiol moiety was stabilized by complex formation. The addition of the thiocyanate ion
further stabilized the complex by replacing the water molecules coordinated to the Zn2+
ion. Based on this, the structure shown in Fig. 2 was proposed and was supported by a
composition study of the colored complex by the mole ratio method, which gave the
S2−:Zn2+:SCN molar ratio as 1:1:3.
As the formation of the complex indicated the presence of a sulfur–zinc bond, attempts
were made to get additional evidence of this from the IR spectrum of the complex. The
complex was prepared on a macroscale to isolate milligram amounts of the product. The
procedure used for this purpose was similar to the procedure recommended for analytical
determination except that all the reagent concentrations were increased by a factor of 10.
Subsequent to color development the product was extracted with 4 × 25 ml portions of
amyl alcohol from an aqueous volume of 250 ml. The organic layer was washed with
water and the solvent was removed by vacuum distillation. The isolated product was
recrystallized from methanol. The infrared spectrum of the product was taken in the range
400–200 cm−1 (polyethylene pellet) and in the range 4000–400 cm−1 (KBr pellet). A
medium band at 300 cm−1 indicated the presence of a sulfur–metal bond (9). A sharp band
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172 SHANTHI AND BALASUBRAMANIAN

FIG. 2. Nature of species responsible for color.

at 2070 cm−1 confirmed the presence of thiocyanate in the product (9). These observations
further confirmed the proposed structure of the complex (Fig. 2).

Effect of Interfering Gases

The effect of common air pollutants on the determination of H2S was investigated. Up
to 1000 mg of carbon disulfide did not interfere with the determination of 10 mg of H2S,
when introduced as an aqueous solution prepared in zinc acetate. Nitrogen dioxide, when
present in excess of 8 mg, caused a low recovery of H2S. The negative interference of up
to 1000 mg of nitrogen dioxide was eliminated by the incorporation of 1 ml of 0.4%
solution of sulfamic acid into the reagent solutions. Sulfur dioxide and ethanethiol, which
gave similar color reactions under the experimental conditions, interfered seriously. This
interference was overcome by adopting a simple collection procedure (6). To the collected
sulfide in zinc acetate trapping solution, 1.5 ml 5% potassium alum was added. The
aluminum hydroxide formed acted as a collector precipitate and it collected the zinc
sulfide quantitatively. The solution was centrifuged and the centrifugate was discarded.
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SPECTROPHOTOMETRY OF HYDROGEN SULFIDE 173

TABLE 1
Determination of Residual H2S in Laboratory Fume Hood

Amount of H2S (mg) in 25 ml Amount of H2S (ppb) b

Sample Vol. of air Methylene Proposed Methylene Proposed

no.a sampled (liter) blue method method blue method method
1 30 9.70 9.75 232.5 233.7
2 30 4.38 4.45 105.0 106.7
3 60 8.83 8.75 105.8 104.9
4 60 14.38 14.38 172.3 172.3
5 120 36.90 36.25 221.1 217.2
6 120 15.33 15.63 91.9 93.6

Note. Sampling solution—10 ml of 1% zinc acetate. Sampling rate—0.5 liter min−1. Sampled solution was
brought up to 25 ml before analysis.
a
Samples collected on different days.
b
Amount of H2S in ppb at 25°C 4 H2S (mg) × 719/(Vol. of air sampled in liters). 719 is the conversion factor
to convert mg/l of H2S into ppb at 25°C and 760 mm pressure.

The precipitate was washed once with 5 ml of water. Then it was made into a slurry using
two 5-ml portions of 1% zinc acetate solution. This solution was transferred to a 25-ml
calibrated flask and the color was developed following the given procedure. The collection
procedure described above virtually eliminated the interference from 75 mg SO2, 100 mg
ethanethiol, and 1000 mg nitrite.

Application

The proposed method has been applied for the determination of residual amounts of
H2S in a laboratory fume hood where H2S was used as a precipitating agent for the
qualitative analysis of metal ions. Air samples were collected in 10 ml of 1% zinc acetate
solution at an air flow rate of 0.5 liter min−1 in a fritted glass bubbler. The sampled
solution was brought up to 25 ml with the trapping solution. Suitable aliquots were
analyzed by the proposed method and standard methylene blue method. The results
obtained are shown in Table 1, from which it can be seen that the concentrations of H2S
obtained with both methods are comparable.

CONCLUSION

The proposed method is the first of its kind reported for the determination of H2S by
Schiff’s reaction. The method is simple, sensitive, and rapid and can be used to determine
0–20 mg of H2S. It is comparable in sensitivity to the standard methylene blue method.
The collection procedure used virtually eliminates interferences from other gases and
makes the method more selective.

REFERENCES
1. Lodge, Jr., James P., Ed. Methods of Air Sampling and Analysis, 3rd ed. pp. 486–492. Lewis Publishers,
Chelsea, MI, 1989.
2. Balasubramanian, N.; Kumar, B.S. M. Analyst, 1990, 115, 859–863.
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174 SHANTHI AND BALASUBRAMANIAN

3. Kumar, B.S. M.; Balasubramanian, N. J. AOAC Intl., 1993, 76(4), 730–734.

4. Dasgupta, P. K.; DeCesare, K.; Uilrey, J. C. Anal. Chem., 1980, 52, 1912–1922.
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8. Bamesberger, W. T.; Adams, D. F. Environ. Sci. Technol., 1969, 3, 258–261.
9. Nakamoto, Kazuo. IR and Raman Spectra of Inorganic and Coordination Compounds 4th ed. pp. 283–287.
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