Applied Mechanics and Materials Vols 110-116 (2012) pp 3086-3091 Online: 2011-10-24

© (2012) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/AMM.110-116.3086

Study of Determining the Concentration of Hydrogen Sulfide in Air by

Methylene Blue Spectrophotometric Method
Tai Ling*1, Zhou Ying-xue2
1
Yun Cheng University,
Yun Cheng,
2
Xi’an Polytechnic University
Xi’an, China
tailing08@126.com

Key words: hydrogen sulfide, nitrogen, zinc sulfide, standard curve, the slope

Abstract. Determination of methylene blue concentrations of hydrogen sulfide in the air is sensitive
and rapid ect. However, the standard curve tend to appear low line slope, leading to measurement
errors. In the preparation of ZnS colloidal process, it is nitrogen as the carrier gas and protective
gas. Its direct impact on the ventilation conditions colloidal particle size and uniformity of the
precision for the calibration concentration have the significant impact, particles size appropriate
uniform colloidal solution and the concentration can be more stable and accurate calibration by the
standard curve. It was drawn to meet the requirement that is possible, too large or too small
particles on the experimental results will lead to a greater impact. This article is related to the
verification experiment of nitrogen ventilation conditions (uniform or not) with aeration velocity on
the slope of the curve standard. The experiment we have come to: In this study, ZnS colloidal
preparation on passing the nitrogen should be uniform, and the ventilation rate is smaller and
needed to continuously bubbling one by one, in which the case of the experimental results, it is
required by the standard curve that is drawn 0.1489, spiked recovery rate of 97.5% and 99.0%.

Introduction
Hydrogen sulfide (H2S) is the stench of air pollutants and a toxic nerve agents, as well as
suffocating and irritating gases, which is mainly from steel (iron), oil refining, paper, dyes,
pharmaceuticals and leather production process. The main target of its toxicity control are the
central nervous system and respiratory system, the H2S concentration in the air is higher than 1 ×
10-6 pm nausea, eye irritation, headaches and dizziness and other symptoms. It is higher than 1 ×
l0-3 that can lead to instant death; the soil concentration of H2S will plant more than a certain death
by poison; oxidation of hydrogen sulfide in air after the impact on the climate; t is harmful to many
industrial catalysts; while H2S is also severe corrosion of equipment [1 - 5]. Therefore, in the
production process, it must be rapid H2S gas monitoring.
For hydrogen sulfide (H2S) in the presence of air, its characteristics of many domestic and
foreign scholars have conducted in-depth analysis of research [6-9]. Determination of H2S gas
present are iodometric method, methylene blue spectrophotometric method, passive detection tube
method, atomic absorption spectrometry, ion chromatography and gas chromatography, etc. [10-13].
In sulfuric acid, hydrogen sulfide and dimethyl amino aniline solution and the role of ferric chloride
solution produce methylene blue colorimetric quantitative basis for the determination of hydrogen
sulfide (H2S) in the methylene blue spectrophotometric method. This method is sensitive, rapid and
selective, etc., are widely used in petrochemical, light industry sources and fugitive emissions
monitoring, "air and exhaust gas monitoring and analysis methods" (Fourth Edition) as the method
of the main determination of hydrogen sulfide [14-17]. However, the method is accurate, poor
stability, while hydrogen sulfide standard solution method is more complicated, especially when the
standard curve of hydrogen sulfide in the drawing, it often has low standard curve slope, leading to
measurement errors.
In this experiment, nitrogen as the carrier gas and protective gas, preparation of ZnS colloid, it
passes the nitrogen uniform ventilation rate that is smaller, needed to continuously one by one, in
which case, the accuracy of the calibration standard curve was drawn to meet the requirements and
test satisfactory results.

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 Applied Mechanics and Materials Vols. 110-116 3087

Experimental Methods
The Main Instruments and Reagents. UV-7504 UV-visible spectrophotometer (Shanghai
Precision Scientific Instrument Co., Ltd.); KC-6D-type air sampler (Qingdao Laoshan Instrument
Factory); the amount of cadmium sulfate, ammonium hydroxide and polyvinyl alcohol,
respectively, dissolved in a small amount of water, mixing the preparation of absorbent; ferric
chloride; diammonium phosphate; sodium thiosulfate standard solution (c (Na2S2O3) = 0.0100mol
• L-1); iodine standard solution (c (1 / 2I2) = 0.0010 mol • L-1); starch solution; the amount of
concentrated sulfuric acid and the amino-dimethylaniline hydrochloride stock solution preparation
and use of liquid; temporary use, press 1.00mL Aminodiphenylamine use 1 drop of liquid and
(0.04mL) mixture of ferric chloride solution, the ratio of mixed reagent preparation; sodium sulfide;
zinc acetate; hydrochloride; analysis are used in accordance with national standards on analytical
grade or equivalent purity reagents and distilled water.
Preparation of ZnS Colloidal Solution. According to Figure 1, it accesses to high-purity nitrogen
blowing 5min with 0.25g sodium sulfide (Na2S • 9H2O crystals) into the first bottle and quickly
stopper, through nitrogen of about 5min, the solution to be the third bottle was slightly turbid
(colloidal solution of zinc sulfide generated)to stop ventilation. By the speed of the solution after
the calibration of the quantitative filter paper. The ZnS colloidal solution can be stored in a cold
dark stable three to seven days.

Fig.1 Preparation installation of Hydrogen sulfide colloidal solution

When you use this, take a certain amount of the 5.00µg·mL-1 solution, boil and cool with new
water and make into 5.00 solution of hydrogen sulfide.
The Standard Curve Method of Hydrogen Sulfide. Take seven 10mL colorimetric tube with
stopper according to Table 1 with the preparation of the standard of Israel, the first increase
absorption solution and standard solution add immediately reverse the mix. Add to each tube
reagent 1.00mL, immediately seal, invert slowly mixing, placing 30min, add a drop of diammonium
phosphate solution and mix to eliminate the influence of ferrousion. At the wavelength of 665nm
with a 2.0cm cuvette with distilled water as reference, measure absorbance. (µg)The absorbance of
the hydrogen sulfide content(standard curve)
Table1 Standard series of H2S
Pipe No. Absorption solution(mL) Standard solution(mL) Content

0 10.00 0.00 0.00

1 9.90 0.10 0.50
2 9.80 0.20 1.00
3 9.60 0.40 2.00
4 9.40 0.60 3.00
5 9.20 0.80 4.00
6 9.00 1.00 5.00
3088 Mechanical and Aerospace Engineering, ICMAE2011

Results and discussion

Nitrogen Ventilation Conditions of the Experiment. In the preparation of ZnS colloidal process,
it is with nitrogen as the carrier gas and protective gas, the direct impact of their ventilation
colloidal particle size and uniformity of the precision of the calibration concentration have a
significant impact. The record of table 2 records on the process of preparation of colloidal is ZnS,
nitrogen ventilation conditions on the calibration of the situation.
Table2 Effect of N2 ventilation situation on accuracy
Serial number of N2 ventilation Amount of Average Turbid or
Range
ZnS colloid situation Na2S2O3/mL deviation not
1 non-even 15.40, 16.05, 15.90 0.26 0.65 Y
2 non-even 16.60, 15.75, 16.20 0.29 0.85 Y
3 even 15.68, 15.60, 15.69 0.06 0.09 N
4 even 15.59, 15.60, 15.62 0.01 0.03 N
From the above table,we can know through nitrogen in the case of non-uniform, prepare for ZnS
colloid concentration in the calibration, there are larger average deviation and the poor situation.
With an average deviation of 0.26,0.29, 0.65,0.85 range through nitrogen in the case of uniform
average deviation and the lower range, the average deviation was 0.06,0.01, and the range is
0.09,0.03. Analysis result is not high precision for two reasons: Firstly, since nitrogen through
uneven, the preparation of colloidal particle size of ZnS is inevitable uneven, so uneven
concentration of colloidal solution; Secondly, the larger micelle solution under the action of
hydrogen ions is more likely to coagulation, turbidity endpoint solution makes it difficult to master.
The blank solution is by adding zinc sulfide standard solution, so nitrogen ventilation situation is on
the blank solution and it did not affect the titration.
Nitrogen Gas Velocity Impact Experiment. To ensure the uniformity in the case of ventilation
with different rates of ventilation, we can prepare ZnS colloids, calibration of its concentration, and
the standard curves was drawn, the specific data are as follows:
Ventilation rate of the first 0.5L/min Preparation of ZnS colloidal twice, respectively, after drawing
the standard calibration curve, as is shown in Table 3 and Figure 2, Table 4 and Figure 3.

Table3 Standard series of H2S (with speed of N2 be Table4 Standard series of H2S (with speed of N2 be
0.5L/min) 0.5L/min)
Serial Serial
0 1 2 3 4 5 6 0 1 2 3 4 5 6
number number
H2S
H2S
Content 0.00 0.50 1.00 2.00 3.00 4.00 5.00
Content 0.00 0.50 1.00 2.00 3.00 4.00 5.00
(µg)
(µg)
After
After
deducting 0.000 0.070 0.134 0.235 0.380 0.505 0.610
deducting 0.000 0.064 0.130 0.257 0.387 0.506 0.617
the blank
the blank
Regression line equation is Y = 0.1244X +0.0047 Regression line equation was Y=0.1226X+0.0047
Correlation coefficient r = 0.9996 correlation coefficient r = 0.9992

Fig.3 Standard curve of H2S (speed of N2 is

Fig.2 Standard curve of H2S (speed of N2 is 0.5L/min)
0.5L/min)
 Applied Mechanics and Materials Vols. 110-116 3089

The slope of the above two criteria are not met the requirements of the standard method, it
indicates that the actual amount of hydrogen sulfide content is less than calibration. The actual
cause may be due to low level: nitrogen aeration rate is too large, preparation of ZnS colloidal
particle size is small, unstable and susceptible to loss, even if an accurate calibration, but the size is
too small, not very stable.Therefore, the slope of the standard curve drawn is low.
Thus, the ventilation rate reduces the nitrogen, one by one discontinuous bubbling .Preparation
of colloidal zinc sulfide standard curve after calibration, the results is shown in Table 5 and
Figure 4.
Table5 Standard series of H2S
(with the ventilate of N2 be not bubbled continuously
one by one)
Serial
0 1 2 3 4 5 6
number
H2S
Content 0.00 0.50 1.00 2.00 3.00 4.00 5.00
(µg)
After
deducting 0.000 0.059 0.128 0.226 0.365 0.479 0.592
the blank
Regression line equation was Y=0.1188X+0.0011 r =
0.9995

Fig.4 Standard curve of H2S

(ventilate of N2 is not bubbled continuously one by one)
We see the result from the table that the ventilation rate control in one by one when the
discontinuous bubble, preparation of colloidal slope of standard curve drawn by a lower, or less
than the national standard method in the request. ZnS colloidal solution in the calibration process,
the phenomenon of colloidal solution appeared slightly cloudy phenomenon occurs due to:
ventilation rate is too slow to produce large micelles of zinc sulfide in the hydrogen ion that is more
likely to occur under the action of coagulation. Therefore, larger size particles may be caused by the
low slope of the main reasons.
Rubber particle size is only appropriate uniform colloidal solution, the concentration can be
stable, the accurate calibration of the standard curve was drawn to meet the requirements that is
possible. So once again a little aeration rate of nitrogen transfer large one by one continuous
bubbling and accurately calibrated by the standard curve, this time meets the requirements of the
experimental results, the specific result is in Table 6, Figure 5.
Table6 Standard series of H2S
(with the ventilate of N2 be bubbled continuously one by
one)
Serial
0 1 2 3 4 5 6
number
H2S
Content 0.0 0.50 1.00 2.00 3.00 4.00 5.00
(µg)
After
deducting 0.000 0.073 0.158 0.297 0.462 0.595 0.739
the blank
Regression line equation is Y=0.1483X+0.0036
r=0.9997

Fig.5 Standard curve of H2S

(ventilate of N2 is bubbled continuously one by one)
Quality Control. Continuous bubbling nitrogen is through the system one by one by taking the ZnS
colloidal solution, the standard curve is drawn up to the national standard method of slope
requirements, we adopt for the recovery of standard addition to its reliability test of standard
addition recovery as is shown in table 7 .
3090 Mechanical and Aerospace Engineering, ICMAE2011

Table7 Recoveries
Recoveried Recovery Average recoveries
Serial
Added （µg ） （%）
number （%）
1 2.00 1.97 98.5 ——
2 2.00 1.93 96.5 97.5
3 2.00 1.95 97.5 ——
4 4.00 3.96 99.0 ——
5 4.00 3.98 99.5 99.0
6 4.00 3.94 98.5 ——

Parallel does spike recovery, the recovery rate are 97.5% and 99.0%, the quality of experiment is
reliable.

Conclusion
By the experiment in the preparation process of zinc sulfide colloids, particles size is appropriate
uniform colloidal solution, the concentration can be more stable, the accuracy of the calibration
standard curve was drawn to meet the requirements, particles are too large or too small .The result
of the experiment has great impact. With nitrogen as carrier gas and protective gas, to study the
ventilation situation on the colloidal particle size and uniformity of the impact, and the ventilation
rate of the size on the slope of the standard that it is preparation of ZnS colloid, passes the nitrogen
uniform ventilation rate is small, and it is needed to continuously bubbling one by one, the precision
of the calibration concentration is essential, in which case the experimental results, as required by
the standard curve is drawn 0.1483, and the recovery are 97.5% and 99.0%.

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Mechanical and Aerospace Engineering, ICMAE2011
10.4028/www.scientific.net/AMM.110-116

Study of Determining the Concentration of Hydrogen Sulfide in Air by Methylene Blue

Spectrophotometric Method
10.4028/www.scientific.net/AMM.110-116.3086