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732
sponsorship of the Bureau of Ships, Navy Department, which
initiated this investigation. Thanks are expressed to James
McCambridge and Leonard Zoole, under whose supervision this
work was conducted, for their continued interest.
The views expressed by the authors are their own and are not
to be construed as representing the official views of the Navy
Department.
LITERATURE CITED
RECEIVED
September 15, 1948.
Spectrophotometric Determination of
Hydrogen Sulfide
Methylene Blue Method
JAJlES K . FOGO' AND MILTON POPOWSKY
Southern California Gas Company, Los Angeles, Calif.
Hydrogen sulfide is absorbed from gases and precipitated as zinc sulfide. The
precipitate is then redissolved and allowed to react with p-aminodimethylaniline
in the presence of ferric chloride. The optical density of the resulting methylene
blue solution is measured at 670-millimicron wave length and the corresponding
quantity of sulfide is read from a previously prepared calibration curve. The
method is sensitive to about 3 micrograms and the range up to about 500 micrograms. The procedure is convenient for occasional as well as frequent use.
KO especial care need be taken in the preparation of the reagents. Deviations up to 5y0 in the concentrations given are allowable. If the diamine used produces a dark colored solution, a
fresh supply should be obtained.
Zinc acetate, c.P.,1% solution in distilled Kater.
Sodium hydroxide, c.P., 12y0solution in distilled water.
Ferric chloride, c.P.,0.023 molar solution in 1.2 molar hydrochloric acid.
p-Aminodimethylaniline sulfate, Eastman white label, 0.5
gram in 500 ml. of 5.5 molar hydrochloric acid.
SAMPLING
V O L U M E 2 1 , N O . 6, J U N E 1 9 4 9
733
After the sample has been passed through the gas-washing bottle, the inlet and outlet of the bottle are closed by slipping the
ends of a 25-em. length of tubing over them. Just before beginning the methylene blue reaction the temperature of the bottle
and contents is adjusted to 24" * 3 " C.; the temperature of the
diamine reagent should be similarly adjusted. Then the top of
the gas-washing bottle is rai;ed and 25 ml. of diamine reagent are
pipetted into the bottle. The bottle is closed quickly and the
contents are snirled until all the precipitate is dissolved. Then
by alternately applying slight pressure and suction on the inlet, a
small amount of the solution is forced back and forth through the
sinter in order to dissolve any zinc sulfide that may have concentrated there. When all the sulfide is dissolved, the top is again
raised and 5 ml. of ferric chloride reagent are pipetted into the
bottle, followed by mixing as before. The use of pipets designed
for short delivery time rather than great accuracy is recommended.
Table I.
After the closed bottle is allowed to stand for 10 minutes the blue
solution is transferred to a 250-ml. volumetric flask and diluted to
the mark with distilled water. Before the optical density is measured, the solution should be allowed to stand a t least 20 minutes
but not more than 20 hours in a place out of direct sunlight.
A blank solution is made by mixing the same amounts of the
four solutions used above in a 250-ml. volumetric flask and diluting to 250 ml. with distilled water. This solution should be allowed to age for about 30 minutes before use in the spectrophotometer; the solution may be stored for several days in a dark or
dimly lighted place.
The optical density or transmittance of the test solution is determined by making the initial adjustment of the instrument
while the cell is filled with the blank solution. Sormally, and for
highest sensitivity, the measurements are made with light of 670millimicron nave length. Light of 750-millimicron wave length
may be used if the solution is unusually opaque.
CA LIBR 4TION
WAVE LENGTH-MILLIMICRONS
EXPERIMENTAL
ANALYTICAL CHEMISTRY
934
5
76
20
99
25
100
30
98
40
79
55
64
75
43
5.5
0.33
0.66
0.69
0.71
0.70
0.66
0.63
10
0.57
Table IV.
perature and other variables. A t higher temperatures the reaction is rapid but greater amounts of hydrogen sulfide escape from
the acid solution into the vapor space of the gas-washing bottle
before reacting; a t low temperatures little hydrogen sulfide
escapes but the methylene blue reaction becomes so slow that side
reactions occur to a greater extent. The over-all effect of temperature on the relative yields of methylene blue fromidentical reaction
mixtures is shown in Table I1 Fortunately, the maximum yield
occurs a t about 24" C. and a reasonable tolerance may be allowed.
The effect of final acid concentration on the optical density of
a methylene blue solution formed from a given amount of hydrogen sulfide was investigated by preparing the solutions as described above but with diamine reagents of various acid concentrations. All the solutions contained 222 micrograms of sulfide
per 280 ml.; the results are given in Table 111. The effect is believed to be due largely to the influence of acidity on the absorption spectrum of methylene blue rather than to influence on the
yield of the reaction.
When the diamine reagent is added to the suspension containing zinc sulfide, hydrogen sulfide is formed. Some of it escapes
into the vapor space of the bottle and is lost. The amount which
escapes is a function of the solubility and the total amount present. When only small amounts of sulfide were present no hydrogen sulfide was detectable over the solution and this was arbitrarily assumed to indicate complete conversion to methylene blue.
Sulfide inserted,
micrograms
Recovery, %
35
100
122
99
243
98
366
97
487
96
610
94
730
88
855
80
The reaction time of 30 minutes allowed in the procedure includes a considerable safety factor. Periodic determinations of
the optical density of a solution during the reaction period indicated that the reaction was just completed after 10 minutes-that
is, no further increase in the optical density was detected after 10
minutes. After about 20 hours a decrease due to fading may begin to be measurable.
LITERATURE C I T E D
(1) Almy, J . Am. Chem. Soc., 47, 1381 (1925).
(2) Calif. Natural Gasoline Assoc.. Los Angeles, Calif., "Determination of Hydrogen Sulfide in Natural Gas," Bull. TS 413, 1943.
(3) Field and Oldach, IND.
EKG.CHEX.,A N ~ LED.,
. 18, 665 (1946).
(4) Fog0 and Popowsky, ATAL.CHEM.,21,734 (1949).
( 5 ) Mecklenburger and Rosenkranzer, 2 . anorg. Chem., 86, 143
(1914).
(6) Shaw, ISD.ENG.
CHEM..ANAL.ED.,12, 668 (1940).
(7) Sheppard and Hudson, Ibid., 2, 73 (1930).
RECEIVED
August 30, 1948.
AND
MILTON POPOWSKY
~university
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of~ southern
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