732 ANALYTICAL CHEMISTRY

sponsorship of the Bureau of Ships, Navy Department, which LITERATURE CITED

initiated this investigation. Thanks are expressed to James (1) Bureau of Ships, Navy Department, ~ p e c i f i c a t i o n51-S-47(IXTT)
McCambridge and Leonard Zoole, under whose supervision this (Oct. 1, 1947).
work was conducted, for their continued interest. (2) Hanawalt, J. D., Rinn, H. W., and Frevel, L. K., ISD. ENG.
The views expressed by the authors are their own and are not CHEY.,ANAL.ED.,10, 467-513 (1938).
to be construed as representing the official views of the Navy
Department. 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 micro-
grams. The procedure is convenient for occasional as well as frequent use.

T HE determination of hydrogen sulfide in gases has usually

been accomplished by iodometric methods (2,6). These give
accurate results on appropriate samples but are often too insensi-
precision at such high concentration is somewhat poorer than a t
about 100 to 200 micrograms, where it is *3%.
APPARATUS
tive for samples containing very little hydrogen sulfide. A much
more sensitive method is that of Field and Oldach ( S ) , in which the The list of apparatus includes the items necessary for taking
sulfide is converted to bismuth sulfide which is determined photo- two samples simultaneously and thereafter treating them con-
metrically while in suspension. This method, although very secutively.
sensitive (1.4 micrograms), is not well suited for the occasional
user, because very rigid control of technique is said to be neces- Two 250-ml. coarse sintered-glass type gas washing bottles.
(Those made by Corning Glass Works are suggested.)
sary and all solutions must be protected against oxygen. Two test meters, either wet or dry type.
The method described herein is a refinement of the methylene One pipet, 25-ml.
blue method (1, 5, 7 ) . The technique has been improved by use Two pipets, 5-ml.
of optimum conditions for the principal reaction and by applying One graduated cylinder, 250-ml.
One glass tubing cross, 8-mm.
modern spectrophotometry to the measurement of concentration. Three tubing clamps, screw type.
The manipulation is simple and the results are not affected by Ten meters of 7-mm. Tygon tubing.
minor variations. The method has been in successful use in the Three volumetric flasks, 250-ml.
form given for several pears. One spectrophotometer or filter photometer.

The hydrogen sulfide is absorbed from a stream of gas in a sus-
pension formed by adding sodium hydroxide to a solution of zinc
acetate. The stripped gas is then suitably metered. The suspen-
sion then containing the absorbed sulfide as zinc sulfide is treated
with an acid solution of p-aminodimethylaniline, followed by the
addition of a small amount of ferric chloride solution. Bfter time
has been allowed for the formation of the methylene blue, the
solution is diluted in a volumetric flask and an aliquot is trans-
ferred to the spectrophotometer for measurement. The corre-
spondin quantity of sulfide is then determined from a previously
preparef calibration curve, plotted from similar measurements
on methylene blue solutions prepared in the same manncr with
known amounts of sodium sulfide or hydrogen sulfide.
REAGENTS
KO especial care need be taken in the preparation of the rea-
gents. Deviations up to 5y0 in the concentrations given are al-
lowable. 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 hydro-
chloric acid.
p-Aminodimethylaniline sulfate, Eastman white label, 0.5
gram in 500 ml. of 5.5 molar hydrochloric acid.
SAMPLING

The method is sensitive to about 3.5 micrograms of sulfide when
used as given. Greater sensitivity could be obtained fairly easily
by appropriate reductions in the volumes of solutions used. The
upper limit of the method as given is about 500 micrograms. The
1 Present addreas, Chemistry Department, University of Southern Cali-
fornia, Los Angeles, Calif.
A dual sampling procedure in which two samples are obtained
simultaneously is recommended. The absorption should be done
if possible directly a t the source. Gas samples brought into the
laboratory in metal or rubber vessels usually give low results due
to the reaction of hydrogen sulfide with the metal or its oxide or to
its solubility in rubber. The pressure a t the source must be a t
V O L U M E 2 1 , N O . 6, J U N E 1 9 4 9
least 50 mm. of mercury above atmospheric or a pump must be
used to draw the sample through the absorption bottle.
One arm of a glass cross is connected to the source with Tygon
tubing. A 5-cm. length of tubing is attached to another arm and
a screw clamp is placed on the tubing. Each absorber is then
charged with 130 ml. of 1% zinc acetate solution and 5 ml. of 12%
sodium hydroxide solution, and the solutions are mixed by swirl-
ing. The parts of the bottles are assembled with petrolatum and
fastened with rubber bands. The inlets of the bottles are con-
nected to the remaining arms of the cross and screw clamps are
placed on the connecting tubing. A test meter is then connected
to the outlet of each absorber.
M'ith all screw clamps open, the gas is turned on a t the source
a t a rate considerably in excess of the sampling rate. Then the
clamp on the bleeder arm is slowly closed until gas passes through
the gas washing bottles a t a rate of about 170 liters per hour (6
cubic feet per hour). The rates through the two bottles may be
equalized by adjusting the screw clamps on the connecting tub-
ing. The amount of sample to be taken should be that which
will contain betiveen 35 and 350 micrograms. Where it is neces-
sary to use samples smaller than 50 liters, the sampling rate
should be reduced correspondingly.
If the method is being used to determine the amount of hydro-
gen sulfide resulting from the conversion of other sulfur com-
pounds to hydrogen sulfide for analysis (4), only one gas washing
bottle is used and the test meter can be replaced by a simple
flowmeter.
PROCEDURE
After the sample has been passed through the gas-washing bot-
tle, the inlet and outlet of the bottle are closed by slipping the
ends of a 25-em. length of tubing over them. Just before begin-
ning 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 concen-
trated 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.
WAVE LENGTH-MILLIMICRONS
Figure 1. Transmittancy of Methylene Blue Solution
157 microgram. of sulfur i n 250 m l . Spectral band width, 2 to 3 millimicrons.
Cell thickneae, 1.00 cm.
733
Table I. Specimen Calibration Data
(Coleman Universal spectrophotometer, wave length 650 millimicrons)
Sulfide Inserted,
Micrograms/2SO M I . Optical Density
64.8 0.21
64.5 0.22
129.6 0.41
129.6 0.43
2 59 0.80
239 0.82
389 1.12
359 1.16
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 meas-
ured, 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 dilut-
ing to 250 ml. with distilled water. This solution should be al-
lowed to age for about 30 minutes before use in the spectropho-
tometer; 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 de-
termined 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 670-
millimicron nave length. Light of 750-millimicron wave length
may be used if the solution is unusually opaque.
CA LIBR 4TION
If the measurement of the optical density of the test solution is
to be useful, a calibration curve must be prepared by making up
several standards in the manner described above but using care-
fully measured quantities of sodium sulfide solution or hydrogen
sulfide in place of the sample. A solution of sodium sulfide con-
taining about 20 micrograms of sulfur per milliliter is satisfactory.
The lumps of sodium sulfide should be thoroughly washed imme-
diately before making the solution, in order to remove any so-
dium sulfite. Oxvnen-free distilled water should be used in mak-
I -
ing the solution. The solution is standardized
iodometrically. Care must be taken throughout
the preparation of the standards t o protect the
sodium sulfide solution from more than a mini-
mum amount of contact with oxygen.
The calibration is completed bv measuring
the optical densities of the standard methylene
blue solutions and plotting the values obtained
against the corresponding mass of sulfide used
in preparing the 250-ml. solution. The result-
ing curve should be nearly linear in the lower
half of the useful range of concentrations. Speci-
men calibration data are given in Table I. Once
made the calibration may be used indefinitely.
Data should be obtained a t 670 millimicrons and
also if possible a t 710 and 750 millimicrons. The
apparent peak absorption wave-length may vary
somewhat from 670 millimicrons when instru-
ments of low spectral purity are used. For ex-
ample, with the Coleman Universal spectro-
photometer the apparent peak is a t 650 milli-
microns; this is apparently due to this instru-
ment's band width of about 35 millimicrons.
The absorption spectrum for a methylene blue
solution compared to a blank solution with a
Beckman Model DU spectrophotometer using a 2
to 3 millimicron band width is shown in Figure 1.
EXPERIMENTAL
The amount of methylene blue finally formed
in the reactions involved is a function of the tem-
934 ANALYTICAL CHEMISTRY

Then solutions were prepared with greater amounts of sulfide and

Table 11. Effect of Temperature on Yield of Methylene these solutions were diluted with blank solution sufficiently so
. Blue
that the diluted solution should have corresponded to the one in
Temperature, C. 5 20 25 30 40 55 75
Relative yield, % 76 99 100 98 79 64 43 which complete conversion was assumed. Invariably the optical
densities of the diluted solutions were found to be less than that of
the reference solution, indicating a loss. The results of these ex-
Table 111. Effect of Acid Concentration of Diamine periments are given in Table \-. Because corresponding losses
Reagent on Optical Density of Methylene Blue Solutions" occur in preparing the calibration curve, this effect is not consid-
Molarity (HC1) of ered to be important for methylene blue solutions representing
diamine reagent' 2 4 5 5.5 6 7 8 10 less than 470 micrograms of sulfide in 250 ml. of solution. This
Optical density a t
660 millimicrons 0.33 0.66 0.69 0.71 0.70 0.66 0.63 0.57 effect accounts for the deviation of the calibration curve from
a -411 solutions contained 222 micrograms of sulfide per 250 ml. Beer's law.

perature and other variables. A t higher temperatures the reac- Table IV. Recovery of Hydrogen Sulfide as Rlethylene
Blue
tion is rapid but greater amounts of hydrogen sulfide escape from
Sulfide inserted,
the acid solution into the vapor space of the gas-washing bottle micrograms 35 122 243 366 487 610 730 855
before reacting; a t low temperatures little hydrogen sulfide Recovery, % 100 99 98 97 96 94 88 80
escapes but the methylene blue reaction becomes so slow that side
reactions occur to a greater extent. The over-all effect of tempera-
ture on the relative yields of methylene blue fromidentical reaction
The reaction time of 30 minutes allowed in the procedure in-
mixtures is shown in Table I1 Fortunately, the maximum yield
cludes a considerable safety factor. Periodic determinations of
occurs a t about 24" C. and a reasonable tolerance may be allowed.
the optical density of a solution during the reaction period indi-
The effect of final acid concentration on the optical density of
cated that the reaction was just completed after 10 minutes-that
a methylene blue solution formed from a given amount of hydro-
is, no further increase in the optical density was detected after 10
gen sulfide was investigated by preparing the solutions as de-
minutes. After about 20 hours a decrease due to fading may be-
scribed above but with diamine reagents of various acid concen-
gin to be measurable.
trations. All the solutions contained 222 micrograms of sulfide
per 280 ml.; the results are given in Table 111. The effect is be- LITERATURE C I T E D
lieved to be due largely to the influence of acidity on the absorp-
tion spectrum of methylene blue rather than to influence on the (1) Almy, J . Am. Chem. Soc., 47, 1381 (1925).
(2) Calif. Natural Gasoline Assoc.. Los Angeles, Calif., "Determina-
yield of the reaction. tion of Hydrogen Sulfide in Natural Gas," Bull. TS 413, 1943.
When the diamine reagent is added to the suspension contain- (3) Field and Oldach, IND. EKG.CHEX.,A N ~ LED.,. 18, 665 (1946).
ing zinc sulfide, hydrogen sulfide is formed. Some of it escapes (4) Fog0 and Popowsky, ATAL.CHEM.,21,734 (1949).
into the vapor space of the bottle and is lost. The amount which ( 5 ) Mecklenburger and Rosenkranzer, 2 . anorg. Chem., 86, 143
(1914).
escapes is a function of the solubility and the total amount pres- (6) Shaw, ISD.ENG. CHEM..ANAL.ED.,12, 668 (1940).
ent. When only small amounts of sulfide were present no hydro- (7) Sheppard and Hudson, Ibid., 2, 73 (1930).
gen sulfide was detectable over the solution and this was arbitrar-
ily assumed to indicate complete conversion to methylene blue. RECEIVED
August 30, 1948.

Conversion of Sulfur Compounds to Hydrogen

Sulfide
In Air, Fuel Gas, or Mixtures

JAMES K. FOG01 AND MILTON POPOWSKY

Southern California Gas Company, Los Angeles, Calif.

T HE sulfur content of fuel gases is usually determined either

by oxidation or by hydrogenation. Oxidation methods
(5, 8, I O , 1 1 ) are capable of accurate results on gases containing
( 2 , 4,6, 9 ) have some advantages but are limited in scope by the
interference of oxygen, which is plentiful in certain types of gases.
Even the oxidation methods cannot be applied to explosive
as little as 114 micrograms of sulfur per cubic meter (0.005 grain mixtures or nonflammable gases. A method that can be used
per 100 cubic feet), but the technique is cumbersome and the on any mixture of air and fuel gas became necessary for this labo-
apparatus is likely t o be capricious. Hydrogenation methods ratory in order to determine whether the natural gas present in
1 Present address, Chemistry ~ ~ ~university
~ of~ southern
t tali-
~ ~ Soil~gasest was , that normally present in the soil of certain areas
fornia, Los Angeles, Calif. or leakage from gas distribution lines which carry natural gas