Analytica Chimica Acta.

107 (1979) 231-243

o Elsevier Scientific Publishing Company, Amsterdam

Printed in The Netherlands

THE ACCURATE DETERMINATION

OF TOTAL SULPHUR AND
DISULPHIDE AND POLYSULPHIDE COMPOUNDS IN PETROLEUM
PRODUCTS BY METAL REDUCIION AND FLAME EMISSION
SPECIROMETRY

J. F. ALDER*

and K. KARGOSHA

Chemistry Department,
(Gt. Britain)

Imperial College of Science and Technology.

London,

SW7 2AY

(Received 3rd October 1978)

SUMMARY
Conditions for the determination of total sulphur and disulphide/polysulphide
in petroleum products are described_ The sulphur is reduced by heating with sodium or Devardas
alloy under reflux with subsequent liberation of H,S and measurement of the chemiluminescent S, emission intensity in a hydrogen-argon
diffusion flame. The precision and
accuracy are good. Applications to light distillates and waxy residues are discussed.

Sulphur is present in petroleum products in many forms including sulphur,

mercaptans, sulphides, polysulphides, thiophenes and related compounds.
These,may impart both desirable and undesirable properties. The oxides of
sulphur formed on combustion are corrosive and unpleasant; many sulphur
compounds are catalyst poisons and thus present problems in the refining
processes, whereas polysulphides may influence the viscosity characteristics
of heavy residues. Certain natural sulphur compounds or sulphur-containing
additives act as oxidation or corrosion inhibitors in lubricating oils or impart
extreme pressure properties to cutting oils. Because of its many roles, sulphur
is an important element in industrial processes involving petroleum products
and its determination and speciation are of great significance.
Several metal reduction methods are available for the determination of
total sulphur in petroleum products. Acid reduction with zinc under reflux
has been used for the determinat.ion of disulphides [l] ; Raney nickel [ 21,
potassium [ 31 and magnesium [ 41 have been used in the analysis of various
materials for total sulphur.
In previous work [ 51, it was shown that a modified Lassaigne fusion could
be employed for the rapid determination of sulphur in oils and fuels. The
product was fused with sodium and the hydrogen sulphide, liberated in the
subsequent hydrolysis of the sodium sulphide formed, was passed into a cool
argon-hydrogen diffusion flame. The emission from the Sz species was monitored by using a simple filter photometer. This provided a rapid but rather

232

imprecise method for the determination of sulphur The reasons for the
imprecision probably lay mainly in the loss of volatile sulphur species - the
recovery of sulphur from the samples was later estimated to be 50-60% and inadequate control of the heating and fusion procedures. The present
study was concerned in part with estimating the recovery of sulphur species
by this method, and with optimization of the pretreatment conditions in
order to maximize recovery and improve both precision and accuracy.
Disulphides and polysulphides play many very important roles in the wool,
synthetic polymer, rubber, petroleum and protein industries_ Most of these
roles are connected with the S-S bond and the presence of cross-linking sites.
The analytical difficulties which arise in the determination of disulphides and
polysulphides arise more from the type of samples encountered than from the
measurement techniques available. Many different quantitative methods have
been reported for the determination of disulphide and polysulphide in the
presence of other sulphur compounds [63 . These can be largely divided into
chromatographic (t.1.c. and g-c.) methods [7] and metal reduction followed
by chemical separation and determination
[8] _
The method of Wronski [9], which is probably the most recent chemical
separation-metal
reduction method, is based on conversion of disulphides
by sodium aluminium bis( 2-methoxyethoxy)dihydride
in benzene solution
to hydrogen sulphide and thiols which can be either directly titrated, after
dilution with alcohol, or separated by extraction and determined in the presence of each other by selective masking with acrylonitrile. This is a simple
and sensitive method: sulphur at the O-l-ppm level in hydrocarbons can be
determined with a relative standard deviation of 0.5-1.510, but the recovery
for di-t-butyl disulphide is only 75%. Metals such as zinc and sodium, and
hydrides such as sodium borohydride and lithium aluminium hydride, which
have been used for the reduction of disulphides and polysulphides to mercaptan
[lo],
suffer from poor reduction efficiency for tertiary disulphides, except for
the zinc reduction method under reflux conditions which is expected to yield
8%90% recoveF1 for di-t-butyldisulphide.
This recovery is, however, achieved
only by heating the sample for 1.5 h and purging for 3 h.
In the present study the metal reduction method worked out previously
was modified in order to differentiate between some of the various species of
sulphur found in petroleum products and to permit their determination by
chemiluminescent
flame photometry.
EXPERRUENTAL

Apparatus

and reagents

The hydrogen--argon
diffusion flame and burner assembly and generating
cell [5] are outlined in Fig. 1. The emitted radiation is passed through a
circular variable wavelength filter (Barr and Stroud, Glasgow) with a band
pass of about 20 nm at 348 nm. The filtered light is focused onto an E.M.I.
9781A photomultiplier
and the signal is passed via an amplifier and backing-off

233

r-l

H2/Ar/HZS

I I

Photomultplier
1 holnlng

Chimney

Senturn

Fd:er
**heel

Fig. 1. (A) Burner assembly and (B) generating cell.

unit to a strip-chart recorder. Samples are introduced by a variable-volume

(50-250 ~1) ejection pipette (Finpipette, Jencons Ltd.). Figure 2 is a schematic
diagram of the sample introduction system_
Aqueous standards were prepared from analytical-reagent grade sodium
sulphide nonahydrate (B.D.H.). Organic standards were prepared from di-tbutyl disulphide (Aldrich Chemical Co.), diphenyl sulphide, ethanethiol,
benzene potassium sulphonate, dimethyl sulphoxide, diphenyl disulphide,
diphenyl trisulphide and 1,3dithiane, all of which were of the highest purity
available, made up in white spirit or liquid paraffin.

I
I

Bypass

IF----Y

y!!
i-rgm

Ar

1
3.3

0.6

0.9

1.2

1.5

I.8

Flow robs (1 mm-)

Fig. 2. Schematic diagram of sample introduction

system.

Fig. 3. Optimization of flow rates. H, pressure, 1 p.s.i.; Ar pressure, 1.5 p.s.i. When one
curve was being obtained the other flow rates were at their optimum setttings.

234

The sodium sulphide solution was stabilized initially with a pH 11 borateNaOH buffer but a better method was to use aqueous 20% (w/v) NaOH. The
stock lOOO-ppm solutions thus prepared were stable for up to one week
(Table 1) but were standardized by iodimetric titration [ll]
before use.
Organic solutions were prepared fresh daily (Table 1). Refrigeration of the
organic solutions was unnecessary when solutions were prepared daily.
Improvement of the sodium fusion method for total sulphur determination
In the previous method for the estimation of total sulphur by sodium fusion
[5], the initial reduction of the sample was carried out in an open tube over
a flame. Although this permitted rapid analyses, results were not reproducible
and recoveries were poor. Attempts were therefore made to improve this opentube method and the subsequent liberation of H2S from the sodium sulphide
formed- Although recoveries of about 80% were obtainable, this did not give
good reproducible analyses. The poor recovery of sulphur in the reduction
process is due to the conflicting processes of sample vaporization on heating
the sample and of the reduction of the sulphur species which needs elevated
temperatures for reasonably rapid reaction.
To improve recovery, precison and duration of the reduction process, a
reflux method was devised_ The apparatus comprised a lo-ml three-neck flask
fitted with a nitrogen purge; the Liebig condenser was of single-surface type
(10 cm long) with a delivery tube which passed the purge gas into a lo-ml
round-bottom flask containing the absorbing solution_
A l-ml aliquot of a standard solution of di-t-butyl disulphide in liquid
paraffin or white spirit was placed in the reflux flask with a freshly chopped-up
2-mm cube of sodium. The flask was fitted to the condenser and the delivery
TABLE

Stabilityof standardsolutions
Aqueous

solutions

(initial

concentration,

100 ppm

S as Na,S)

In aqueous
solution

S found
(ppm) 2 s-d.=

In 20% (w/v)
NaOH solution

S found
(ppm) + s.d.

after 8 h
after 24 h

89 2 1
75 f 1

after 3 days
after 7 days

99.5
99.0

Organic

standard

solutions

In liquidparaffin
S added (ppm)
260
195
130
Talculated

for 4-6

(S added

as di-t-butyl

S found (ppm) 2 s-da

Fresh

After 24 h

262 2 3
194 + 2
129 2 2

202 * 2
160 +- 1
107 2 2

analyses.

f 1
t 1

disulphide)

In white spirit
S added (ppm)

S found (ppm) 5 s-d.

Fresh

After 24 h

260
195
130

257 2 2
192 f 2
129 * 2

202 * 2
152 f 2
104 f 1

tube immersed in 8 ml of 5% (w/v) sodium hydroxide in the collector flask.

The whole system was purged with nitrogen at a rate of 4 ml min-*. The contents of the flask were refluxed under predetermined conditions of temperature and time_ The reflux was stopped, the flask was allowed to cool and then
removed, and the contents were transferred to a 25-ml beaker (to remove the
possibility of explosion). The contents of the absorber flask were diluted to
10 ml with 5% sodium hydroxide solution and used to rinse the reflux flask;
the washings were then transferred to the beaker. The mixture was carefully
stirred and transferred to a separating funnel, shaken for 1 min and allowed
to stand until the lower (aqueous) phase cleared. The lower layer was transferred to a IO-ml graduated flask. The sulphide concentration was then determined after acidification of a sample of the solution in the generation vessel
(Fig. lB), by liberation of the H,S into the diffusion flame and measurement
of the Sz emission intensity [ 5]_
Purging the reflux system ensures complete removal of any H2S formed, or
present in the sample, from the condenser and it is then trapped in the sodium
hydroxide. The amount of sulphur trapped in the sodium hydroxide is small;
two samples of light distillates containing 300 and 260 ppm sulphur were
refluxed in this manner. The contents of the absorber flask were analysed by
standard addition and found to contain only 2 and 1 ppm sulphur, respectively.
Optimization of reflux conditions
Duplicate l-ml aliquots of di-t-butyl disulphide were refluxed as described
above at 272, 345, and 380% for liquid paraffin solvent, and at 157,173
and
190C for white spirit solvent, for 20-, 30- and 40-min periods. After subtraction of the solvent blank signal, the recorded S, emission signal intensity was
compared with aqueous samples containing the same original sulphide concentration and the recoveries were calculated (Table 2). As can be seen, there
is little difference between 345 and 380C or 173 and 190C for the recoveries
TABLE

Optimization

of temperature and duration of refluxing

Temperature
(C)
Liquid paraffin
380

345

272

Heating time
(min)

S recovery
W)

20
30
40
20
30
40
20
30
40

63
95
70
61
94
70
15
50
47

Temperature
(C)

S recovery

Heating time
(min)

(S)

20
30
40
20
30
40
20
30
40

67
89
73
66
90
74
30
60
40

White spirit

190
173

157

from liquid paraffm and white spirit, respectively. In both cases, therefore,
the lower temperatures were chosen for the analyses, so as to minimize loss
of volatile sulphurcontaining species. The reason for the decrease in yield
after about 30 min is the formation of an emulsion on mixing of the reduced
sample with aqueous sodium hydroxide and subsequent difficulty in separating
the aqueous layer.
Optimization of gas flows and stirring
The argon flows through the cell and into the flame, and the hydrogen
flow to the flame were optimized (Fig. 2). Hydrogen sulphide was generated
continuously by hydrolysis of a crystal of sodium sulphide with dilute hydrochloric acid. The results are illustrated in Fig. 3, which shows that the flow
rates are quite critical for maximum emission intensity from the flame.
The rate of stirring of the mixture in the gas generating cell was found to
be important. The stirring affects the rate of mixing of the analyte solution
and the hydrochloric acid in the vessel and the subsequent generation and
release of hydrogen sulphide. The recovery reaches a maximum just before
the onset of splashing in the cell and for optimum recovery the stirring speed
should be maintained just below this critical value.
Calibration curves
Calibration solutions were made up from di-t-butyl disulphide in white
spirit and liquid paraffin to represent low and high boiling petroleum products,
respectively, and from sodium sulphide in 20% NaOH. The solvent blanks
were 1.5 and 0.5 ppm S for the white spirit and liquid paraffin, respectively;
these were subtracted before plotting.
The calibration curves are shown in Fig. 4. The linear portion of the curves
lie in the range 5-70 ppm S in the original sample, corresponding to 0.5-7.0
r.cg
of sulphide in the loo-p1 aliquot taken. The shape of the curves is similar to
those obtained by other workers [12] ; the curves do not coincide because of
the different recoveries of sulphur. As the origin of the emission is chemiluminescent, it is not easy to say what causes the non-linearity. It may be due
to quenching effects in the higher concentration and kinetic effects in the
lower region where the S + S recombination may be incomplete; these points
have been discussed elsewhere 112,131 but warrant further investigation. The
recovery (and relative standard deviation) of the method compared to aqueous
solutions on 10 replicate analyses of samples containing 150 ppm sulphur was
95% (i7%) for liquid paraffin.solvent, and 90% (*S%) for white spirit solvent.
Analysis of petroleum products
Samples provided by B. P. Research Ltd. and previously analyzed by x-ray
fluorescence (x-r-f.) were analyzed by the reflux method. The samples had to
be diluted with white spirit for the light distillates and liquid paraffin for the
waxy residues, to bring the final solution into the correct concentration
range (Table 3). The results, obtained from calibration curves established

237

1.5-

3-

-5 -

2-

.5 -

I-

I
2

1.5

log cotxentrotlon

1.5

log concentrot8on

(ppm)

I
2
(ppm)

Fig. 4. Calibration curves for organic (A) and aqueous (B) solutions- Curve (a) is for liquid
paraffin solutions and curve (b) for white spirit.
TABLE

Analysis of petroleum
Sample
Light

8014
7935
8136
7914
7956
9143
9142

products

% S found (A s-d.)

9b S presenta

Sample

0.01
0.24
0.03
0.2
O-26
0.95
0.11

9246
9245
8630
8634
7990
7927
8635

distillates

Waxy

0.01 f 0.002
0.20 f 0.015
0.025 2 0.002
0.18 ? 0.01
0.2 +_0.025
1.05 + 0.06
0.14 + 0.01

% S found (+- s-d.)

X S presenta

residues

0.63 + 0.02
0.79 f 0.065
3.65 +_0.3
1.5 + 0.1
2.29 + 0.15
2.2 2 0.18
3.3 * 0.2

0.62
0.75
3.7 3
1.39
2.24
2.11
3.33

aData supplied by B. P. Research_

with organic solutions taken through the procedure, compare most favourably
with those obtained by x.r.f.
Determination

of dkulphide

and polysulphide

The reduction conditions with sodium are so drastic that all organic sulphurcontaining compounds appear to be converted to sulphides. Whereas total

sulphur is a very useful quantity in many applications, particularly where the

petroleum product is to be used as a fuel, there are many cases where more
discerning methods for sulphur determination are required. One of these is
the determination of disulphide and polysulphide, which play an important
role in lubricant and polymer technology.
Several reducing agents were therefore studied for their suitability as specific
reductants for the disulphide and polysulphide linkages_ After preliminary
experiments, described later, to obtain the best conditions for each reducing
agent, a series of comparative tests were carried out; the results are summarized
in Table 4. The apparatus described above was used; 100 mg of the metal
was placed in the reflux flask and 1 ml of a solution of di-t-butyl disulphide,
(0.032% w/v) in liquid paraffin was added. The flask was purged with nitrogen
(4 ml min-) and the contents heated to 320C on a calibrated isomantle for
40 min. The flask was cooled and to the contents were added 2 ml of concentrated hydrochloric acid. The contents were heated again under reflux for 20
min at 120C. The liberated H?S was collected in 10 ml of cooled 5% (w/v)
sodium hydroxide solution. A O-l-ml aliquot of this sample was treated as
described above to liberate H,S in the generating cell and pass it into the cool
hydrogen diffusion flame_ The signal due to the SZ chemiluminescent emission
was recorded and compared to that from standardized aqueous sodium sulphide
solutions to obtain the amount of sulphide (as S) in the sample.
RESULTS

Reducing agents
Magnesium_ Commercially

available magnesium

powder

was employed

(B.D.H_ Ltd.). The addition of concentrated hydrochloric acid to the flask

after the initial reduction step resulted in an uncontrollably vigorous reaction.
The use of (1 + 9) HCl gave a more moderate reduction, but the recoveries
obtained were very low.
TABLE

Results from different reducing agents

(The sample contained 0.032% S as di-t-butyl disulphide in liquid paraffin; l-ml aliquots
were used_ The normalized

data for 0.032% S are intercomparable

for Tables 4-8.)

Reductant

Signal intensity
(ax.)

Reductant

Mg
Zn
Zn
Zn

Unsuccessful
19
79
81

Zn amalgam
50% Zn-50%
SnClz
Cu (foil clippings)
Devardas alloy
(50% Cu, 45% Al, 5% Zn)

(fine powder)
(powder)
(granular)
(foil clippings)

aNormalized

to 100.

Signal intensity
(ax.)
81
10
23

loo=

Zinc. Powdered zinc gave low recoveries (Table 4) and was not studied
further. Granular zinc was much better and gave similar results to the zinc
amalgam and zinc foil. (The amalgam was made by grinding granular zinc in
liquid nitrogen, washing with water and treating with 2% (w/v) HgCl, solution;
it was stored under water.) The Zn--SnCl* mixture, which is a powerful
reducing agent, gave poor results.
Copper and Deuardas alloy. Copper clippings (<40 mesh) gave low results
but Devardas alloy (50% Cu, 45% Al, 5% Zn) was most efficient and was
therefore used in subsequent work_ Different weights of the alloy were
employed in the reduction of 1 ml of the sample solutions, and 100 mg proved
to be the optimum.
Temperature

and duration

of heating

The conditions of reduction particularly in the first part with the alloy
alone and then in the presence of hydrochloric acid are quite critical, In the
first step the reduction is thought to proceed via partial reduction of the S-S
bond and formation of metal sulphides. Extending the duration of the heating
at 320C during the first part of the reduction results in increased recovery
up to about 40 min (Fig. 5); to obtain this curve, the heating time during the
second stage was kept constant at 20 min.
The second stage of reduction which involves the alloy and hydrochloric
acid is thought to occur through two processes: decomposition of metal sulphides and also reduction of some S-S and S-H bonds to hydrogen sulphide
by hydrogen [lo] :
(t-Bu)-- -S-S-(t-Bu)

O.
0

10

20

U-U

--f 2(t-Bu)-SH

30

Heatmgttme

40

U-U

2(t-Bu)H

+ H,S

50

hnl

Fig. 5. Effect of duration of heating on the sulphur recovery:

(0) first stage; (c)

secondstage.

240

The optimum period of heating the solution during the second stage was
determined in the usual way and found to be 20 min at 120C. The amount
of concentrated hydrochloric acid employed in this step was varied in order to
obtain the optimum recovery of S. The concentration of the sodium hydroxide solution in the absorber was also varied in order to optimize the conditions;
this concentration should not be so high that the solution must be rendered
acid in the subsequent step, and the minimum concentration compatible with
good recovery is best. These experiments indicated the use of 2 ml of concentrated hydrochloric acid and 10 ml of 5% (w/v) sodium hydroxide in the
absorbing flask (Table 5).
During the heating process, the sodium hydroxide solution becomes warm
as the purge nitrogen passes through. This leads to loss of HIS (about 5-770)
and must be minimized. The flask was hherefore kept cool in an ice bath
thoughout the esperiment.

Optimization

of other parameters

When nitrogen was bubbled through the solution in the flask, lower recoveries (about 5%) were found, possibly because of more rapid removal of the
hydrogen from the solution. Passing the purge gas over the surface of the liquid
improved the recoveries; this use of purge gas is not always essential, but is
advisable in many cases to avoid atmospheric oxidation_
The order of addition of reagents in the reduction process was also investigated as well as the effect of omitting the Devardas alloy. The results obtained
(Table 6) show that the last method is by far the most efficient; this underlines the role that the reducing alloy plays in the initial reduction of the S-S
bond.
To check whether any H,S passed through the absorbing flask a second
flask was put in series containing the same 5% sodium hydroxide solution;
no sulphide was detected in this flask.

TABLE

Effect of amount of acid and concentration

(Sample as for Table 4)

Amount
HCI (ml)

0.5
1-O
1.5
2.0
2-5

of

of sodium hydroxide

in absorbing solution

Intensity (a-u.)
30
absorber

Aq. 2% NaOH
absorber

Aq. 5% NaOH
absorber

24
29
16
6
8

24
56
86
95
85

24
24
87
100
lOOa

aNonnalizedto 100, all other signalsreferredto this.

241
TABLE

The effect of order of addition of reagents on signal intensity

(Sample as for Table 4)
Intensity (au.)

Method
Add
Add
Add
Add

2 ml 11
100 mg
2 ml 11
100 mg

M HCI; heat 60 min

Devardas alloy + 2 ml 11 M HCl: heat 60 min
M HCI; heat 20 min; add 100 mg ahoy; heat 40 min
alloy; heat 40 min; add 2 ml 11 M HCI; heat 20 min

<2=
8
19
1OOb

=NaOH absorbing solution became acid.

bSignal normalized to 100 and others referred to it.

Interference

studies

Several other sulphur-containing organic compounds were tested by this

method. The compounds were dissolved in liquid paraffin, where possible, to
give solutions containing 0.032% S. The results, summarized in Table 7, show
that thiols and, of course, dissolved hydrogen sulphide interfere, as does
elemental sulphur (Table 8). In view of the proposed mechanism of the
reduction of the S-S bonds it is not surprising about the effect of thiols. The
interference can, however, be easily removed by previously shaking 5 ml of
the analyte solution with 5 ml of aqueous 1 M silver nitrate. The silver mercaptide precipitates, is centrifuged out and can be determined separately if
required. The sulphur can be removed by then shaking the solution with
mercury (2 g for 10 ml of sample) which forms mercury sulphide; this too
can be readily centrifuged out and determined separately. Recovery tests of
the disulphide from solutions containing other sulphur compounds are shown
in Table 8.
The determination of disulphide in the presence of monosulphide
In order to test the applicability of the method for the determination of
the disulphide species in the presence of monosulphide, solutions containing
32 ppm S as di-t-butyl disulphide were made up in liquid paraffin in the presence of 300-400
ppm S as dimethyl sulphide and diphenyl sulphide. The
effect on the recovery is illustrated in Fig. 6. It can be seen that there is only
a modest interference by these other species.
Recovery from light distillates
Recovery tests were carried out on di-t-butyl disulphide and diphenyl trisulphide light distillate fractions diluted with white spirit to bring their
sulphur levels down to between 300 and 1000 ppm. These samples had previously been analysed for total sulphur by x.r.f. and some also by the proposed
method (Table 3). The samples were first shaken with 1 M silver nitrate and
then mercury to remove any mercaptans or sulphur. As can be seen from
Table 9, the recovery is good for both the disulphide and trisulphide species.

242

TABLE

Potential interference of sulphur containing compounds on disulphide determination

(All species sulphur-containing compounds were present at a level of 0.032% sulphur by
weight calculated on their molecular formula_ and made up in liquid paraffin_ The signal
for di-t-butyl disulpbide was normalized to 100 and all other signals referred to that.)
Compound

Intensity
(au_)

Compound

Liquid paraffin
Di-t-butyl disulphide
Ethylmercaptan
Diphenyl trisulphidea
Diphenyl sulphide

<l
100
110
95
<1

Dimethyl sulphide
Dimethyl sulphoxide
Benzene potassium sulphonatea
1 ,3-Dithianea

aDissolved fist
TABLE

Intensity
(a.u.)
2

0.03
2
1

in a little benzene and then diluted with liquid paraffin.

Recovery of disulphide sulphur (0.032%

compounds

S) in presence of lOO-fold amounts of interfering

Intensity
(a-u.)

Interferent

1ooa
>350
110
130
145

[Di-t-butyl disulphide]
Ethyl mercaptan
Ethyl mercaptanb
Diphenyl sulphide
Dimethyl sulphide

Intensity
(au.)

Interferent

Dimethyl sulphoxide
Benzene potassium sulphonate
1,3-Dithiane
Elemental sulphurC
Elemental sulphurc* d

96
96
100
> 350
98

aThe signal is normalized to 100.

u5 ml of sample washed with 5 ml of 1 M AgNO, prior to analysis.
=Dissolved fii
in a little aniline and then in liquid paraffin_
d10 ml of sample shaken with 2 g of mercury prior to analysis.

- loo

b--e--:

go-.A-.-&-.-&

3 B

s2=)-

70

Knxl

2000
Sulphde-S

3ooo

4000

(ppd

Fig. 6. Interference of monosulphides

(0) diphenyl sulphide.

on disulphide determination.

(A) Dimethyl sulphide;

Conclusions

This work has shown that the combination of metal reduction of sulphur
compounds to sulphides in petroleum products coupled with release of
hydrogen sulphide into a cool flame and measurement of the S, emission
provides a useful method for the determination of total sulphur and for the
separate determination of sulphur species. The method is capable of good

243
TABLE

Recovery tests from light distillates diluted with white spirit

Original
sample

S in
diluted
sample
(ppm)

Di-t-butyl
Added
(ppm)

Recovery
(X)

Added
(ppm)

Recovery
(a)

7866
7914
7956
7957
8110
9142
9143

400
800
520
330
450
300
950

320
420
250
200
180
150
120

90
92
91
93
90
90
91

320
410
240
200
180
150
120

89
90
92
92
91
91
90

disulphide

Diphenyl trisulphide

precision and accuracy as well as versatility. With selective separation of the

species, mercaptans with acrylonitrile
[14] , hydrogen sulphide with silver
nitrate and sulphur with mercury, these species could all be analysed separately
and thus provide S, -SH, H2S, (S, and S,) in the same sample.
The authors are grateful to B. P. Research, Sunbury, for the provision of
the analyzed samples and to the Reza Pahlavi Cultural Foundation
for support
of K. K.
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1
2
3
4
5
6
7
8
9
10
11
12
13
14

J. H. Karchmer and M. T. Walker, Anal. Chem., 30 (1958) 85.

I. Honarkhah, BuU. Iran. Petrol. Inst., 50 (1973) 21.
A. D. Campbell, M. J. Brown and D. J. Hannah, Anal. Chim. Acta, 78 (1975) 234.
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