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796 BAGSHAWE AND PILL: AN IMPROVED BARIUM SULPHATE METHOD [VOl. 80

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An Improved Barium Sulphate Method for the

Determination of Sulphur in Steel
BY B. BAGSHAWE AND A. L. PILL
The conventional barium sulphate method for sulphur in steel is critically
reviewed with particular reference to its performance on chromium steels.
It is shown that serious error can occur firom loss of sulphur by co-precipitation
with basic chromium compounds formed during the baking treatment to
remove residual nitrate, and because of this and the difficulty of ensuring
effective control of the baking operation the reliable range of the method
is limited to comparatively simple steels.
A modified and simplified procedure is described, in which the critical
baking treatment is dispensed with altogether and hydroxylamine hydro-
chloride is used to decompose residual nitrate. This modified procedure is
applicable, without loss of accuracy, in all ranges of chromium content and to
all classes of highly alloyed steel, with the single exception of steels of high
titanium content. The precision of determination is within 0.002 per cent.
of sulphur in all normal sulphur ranges.

ALTHOUGH determination of sulphur by high-t emperature combustion is now the generally

recognised procedure for routine control purposes in steelworks laboratories, the gravimetric
barium sulphate method must still be used as the primary basis of standardisation. This
method, however, is liable to errors that may be surprising in view of its long history and
almost universal acceptance. None the less, increasing recognition of this in recent years
has led to various modifications and suggestions for improvement. For example, Nydahll
makes a preliminary isolation of the sulphur from interfering ions by selective chromato-
graphic adsorption on aluminium oxide, whilst Belcher, Gibbons and West2 first separate
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Nov., 19551 FOR THE DETERMINATION O F S U L P H U R I N STEEL 797

the iron by extraction with isoamyl acetate and subsequently evaluate the barium sulphate
titrimetrically with ethylenediaminetetra-acetic acid.3 It seemed to us, however, that if
a simple adaptation of the classical procedure could be successfully applied this would be
preferable in general works practice.
EXPERIMENTAL
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Examination of the existing British Standard* barium sulphate method indicated that
it is reasonably satisfactory for carbon steels, but not entirely so, and very much less satis-
factory for alloy chromium steels. It is recognised, of course, that the method is prescribed
for carbon steels only, but the need for extending its useful scope is really a pressing
consideration.
The main features affecting its performance are-
(a) Retention of nitric acid after the prescribed baking period; this causes low
results. 1

(b) The formation of basic iron and chromium compounds during baking. When
these compounds are formed, they always include basic sulphates and this is another
cause of low results. Error from this source is greatest when the conditions are most
favourable for complete removal of nitrates, i.e., at high baking temperatures. The
conditions are often so critical, particularly with steels of high chromium content,
that there is no controllable margin between error from retained nitrates and error
from basic-salt formation. A further point is that basic salts tend to pass through
the filter in colloidal form when silica is removed and they subsequently contaminate
the barium sulphate precipitate. There is, therefore, when this occurs, some degree
of fortuitous compensation.
(c) The method of adding the solvent acid as a mixture is not always favourable
for the solution of chromium steels, and the difficulty of removing nitric acid is increased
by the use of an insufficient allowance of hydrochloric acid in the mixture.
The performance of the method in the presence of chromium is shown by the following
results, which were obtained on 5-g samples of plain carbon steel, containing 0.050 per cent.
of sulphur, to solutions of which various amounts of chromium solution were added (the
chromium solution was prepared by dissolving pure chromium in hydrochloric acid to ensure
the expulsion of nearly all the sulphur, so that only traces remained)-
Chromiumadded, g None None 0.1 0.1 0.25 0.25 0.50 0.50 1.00 1.00 1.00
Sulphur found, yo 0.050 0.050 0.048 0.046 0.047 0.045 0.043 No result* Noresult* 0-047 No result*
* These tests were not completed, owing t o serious contamination with chromium compounds.
I t was obvious during the operation of these tests that control of baking conditions
was the really critical feature. The British Standard procedure specifies a baking temperature
of approximately 300"C, but gives no indication of how this is to be interpreted. It is
notoriously difficult to measure the surface temperature of a hot-plate and still more so
in a manner that successfully interprets the required conditions for the baking of residues.
Tests have shown that the observed temperature of a given hot-plate measured a t a particular
point may vary by as much as 200"C, depending on the method of measurement adopted.
Other factors, such as variation of temperature across the hot-plate and air temperature
above the surface of the hot-plate, which depend on the efficiency of extraction conditions
within the fume chamber, also complicate the problem of interpreting baking conditions in
a reliable and reproducible manner.
In view of these difficulties it is clear that the British Standard direction may be seriously
misinterpreted. In any case a baking temperature of 300" C, as determined by the most
reliable methods of temperature measurement, is too high for chromium steels. With plain
steels, there is a fairly wide margin in that some degree of overheating can be tolerated
without inducing basic-salt formation. With chromium steels the margin is critically
narrowed and everything depends on a correct interpretation of hot-plate temperature.
It is difficult to give a quantitative value for the safe baking of chromium steels, as the
tolerance margin depends on the chromium content. As a general indication, it can be said
that basit chromium salts are almost certain to be formed above 280" C , and some contamina-
tion may be evident at as low as 250" C with high-chrome rustless steels containing 12 per
cent. or more of chromium. Below 250" C there is no certainty that nitrates will be eliminated
from the residue.
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798 BAGSHAWE AND PILL: AN IMPROVED BARIUM SULPHATE METHOD [VOl. 80

I n view of these practical difficulties we have examined various alternative means of
kemoving residual nitrates, as follows.
ALTERNATIVE SOLVENTS-
Replacement of nitric acid altogether by means of alternative solvents based on bromine
and bromine in admixture with hydrobromic or hydrochloric acids. Many steels dissolve
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completely in concentrated bromine, but others, particularly very high chromium rustless
+
types, do not. Mixtures of bromine and hydrobromic acid (1 1) gave very rapid initial
action, but in the later stages of dissolution some of the high-chromium steels became passive.
+
This was also true of bromine - hydrochloric acid (1 l), but in this case the initial action
was less vigorous. The use of bromine mixtures was therefore abandoned. In any case
they were found to be very objectionable.
USE OF PERCHLORIC ACID-
I n the preliminary tests small additions of perchloric acid were made after the initial
solution in nitric and hydrochloric acids. It was considered that this acid might ensure the
expulsion of nitric acid and at the same time prevent the formation of basic salts. Results
obtained on two plain steels, which are shown in Table I, indicate correct values for the
I
TABLE:
EFFECT
OF PERCHLORIC ACID
Sulphur found in B.C.S. Sulphur found in a
Perchloric acid carbon steel, carbon steel
added, (0.041 per cent of sulphur), (0.058 per cent of sulphur),
ml % O/
/O

5 0.042 0.059
10 0-038 0.054
15 0.038 0.053

TABLEI1
IXFLUENCE
OF ZINC REDUCTION ON CHROMIUM INTERFERENCE
5 g of zinc used in each test
Sulphur found in B.C.S. Sulphur found in a
carbon steel carbon steel
Chromium added, (0.041 per cent. of sulphur), (0.058 per cent. of sulphur),
equivalent % % %
None 0.042 0.060
20.0 0-015 0.010

5-ml perchloric acid addition, but low recoveries were obtained with the 10 and 15-ml
additions. For the 5-ml addition, baking conditions were normal; for the 10 and
15-ml additions, there was very little true baking, as most of the 30-minute “baking” interval
was taken up in removing the perchloric acid by heating. Further tests with much larger
additions of perchloric acid, e.g., replacing baking altogether by fuming with 35 ml of per-
chloric acid, failed entirely, as precipitation of barium sulphate was very much retarded
and in some instances little or no precipitation occurred after overnight standing. We
attributed this surprising effect to solubility in ferric perchlorate, as it is known that barium
sulphate can be quantitatively precipitated in the presence of perchloric acid. Subsequent
tests showed that, if the iron was reduced to the ferrous condition before precipitation, a
nearly quantitative yield could be obtained from a steel solution.
REDUCTION WITH ZINC-
Reduction of the acid extract with zinc, after a normal baking operation, is a well known
and often practised expedient. It suffers from the disadvantage that it materially increases
the salt concentration of the solution, as quite large amounts are required for the effective
reduction of 5-g steel samples. Our tests with zinc revealed a further disadvantage. With
plain steels performance is satisfactory, but seriously low recoveries can be obtained in the
presence of high chromium contents. This is shown by the results in Table 11. So much
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Nov., 19551 FOR T H E DETERMINATION O F SULPHUR I N S T E E L 799

acid is destroyed in the process of zinc reduction that basic chromium compounds are pre-
cipitated, with attendant loss of sulphur. The silica precipitates filtered off after zinc
reduction of high chromium solutions are distinctly green, owing to hydrolysis and the
formation of basic salts. If the reduction with zinc is carried out a t a higher initial acidity
to prevent this, too much zinc is consumed and the solution contains a large amount of
zinc chloride.
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REDUCTION WITH HYDROXYLAMINE HYDROCHLORIDE-

In considering possible organic reducing agents, the choice is very restricted, as only
one or two of the likely ones are available in sufficiently high purity grades for sulphur deter-
minations. AnalaR grade hydroxylamine hydrochloride was found to have an extremely

-
TABLE111
HYDROXYLAMIKE
TREATMENT UNDER VARIOUS EXTRACTION CONDITIONS
Sulphur in carbon steel
containing 0.043 per cent.
of sulphur

(Chromium (1 g of chrom-
absent), ium present),
Test Conditions % 70 Remarks
Dry residue was extracted with 30 in1 0.038 0.035
of diluted HCl (1 + 1) and 5 g of
NH,OH.HCI were added
Residue was extracted with 30 in1 0.044 21'0 result* Increased amount of NH,OH.HCl
of diluted HC1 ( 1+ 3) and 10 g of appeared to assist in breaking up
XH,OH.HCl were added the residue, but chromium test was
contaminated. Good reduction of
iron
As b, but residue was extracted with 0.042 0.042 Extraction better than in b ; reduc-
30 ml of diluted HCl (1 + 1) tion of iron not so good
Residue was extracted with 35 in1 0-043 0.043 Extraction conditions much im-
of conc. HC1; 6 g of NH,OH.HCl proved. Less iron was reduced on
were added and the solution was extraction with concentrated HCI
evaporated to a paste. The paste
was dissolved in a mixture of 10ml
of concentrated HCl and 30 ml of
water
As d , but 10 g of SH,OH.HCl were 0.044 0-042 Similar to d.
added
Residue was extracted as in d , and 0.042 0.037 Very heavy gassing, owing to reduc-
solution was evaporated to a paste. tion of iron in the dilute solution
The paste was dissolved in 10 ml of
conc. HC1, l o g of NH,OH.HCl
were added and the solution was
diluted with 20 ml of water
* Xot completed, owing to serious contamination with chromium compounds.
low sulphur blank, and preliminary tests with this reagent showed that it would decompose
nitric acid and reduce ferric iron under conditions adaptable for sulphur determinations
in steel.
Further tests with this reagent showed that it was so effective that the critical baking
operation could be dispensed with altogether. By eliminating baking, the formation of basic
chromium salts is prevented and it thus becomes possible, in addition to the general simpli-
fication of operational technique that this step affords, to apply the method to chromium
steels a t all levels of chromium content, with the same facility and accuracy as with carbon
steels.
Reduction with hydroxylamine hydrochloride is achieved without loss of acid concen-
tration, which is the main disadvantage of zinc; there is, in fact, an increase of acid
concentration resulting from iron reduction, vix.-
+
NH20H.HC1 HNO, + 2N0 +
HCl 2H20 +
SNH,OH.HCl +4FeC1, -+4FeC1, +
6HC1+ N,O H20. +
This ensures perfect solution of iron and chromium salts in the reduced extract, which can
afterwards be adjusted, by suitable evaporation and dilution, t o give optimum conditions
for barium sulphate precipitation.
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800 BAGSHtlWE AND PILL: AN IMPROVED BARIUM SULPHATE METHOD [VOl. 80

Barium sulphate precipitates obtained from solutions treated in this way are invariably
pure and free of discoloration. The residues are, in fact, purer for all classes of steel, plain
or chromium, than they have previously been with conventional baking procedures.
The best conditions for applying the hydroxylamine treatment were derived from a
series of tests (Table 111)in which the solutions were all heated just to dryness and extracted
and treated with hydroxylamine under slightly varied conditions.
The general impression gathered- from these tests was that conditions for effective
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removal of nitrates were not at all critical, but reduction of iron was more complete in the
weaker acid extracts. There is no evidence, however, that complete reduction of iron is
necessary. It is important to note (see test f) that unless hydroxylamine is destroyed by
evaporating the concentrated extract after treatment, subsequent dilution results in further
reduction of iron, accompanied by heavy gassing at the silica filtration stage and afterwards
when the solution is being digested for barium sulphate precipitation. The conditions given
in test e appeared to give the best combination of requirements and these were adopted in
the final method.
METHOD
REAGENTS-
+
Diluted hydrochloric acid (0-5 99-5)-Dilute 5.0 ml of concentrated hydrochloric acid
to 1litre with water.
Barium chloride, 10 per cent. w/v--Dissolve 100 g of barium chloride, BaC1,.2H,O, in
1 litre of water. Filter before use.
Dilute barium chloride, wash solution-Dissolve 1 g of barium chloride crystals in 1 litre
+
of dilute hydrochloric acid (2 98). Filter before use.
PROCEDURE-
Weigh 6 g (Note 1) of millings or drillings into a dry 600-ml squat beaker. Cover with
a watch-glass, and add 0.1 g of potassium nitrate and 35 ml of concentrated nitric acid.
Add 50 ml of concentrated hydrochloric acid in increments of 5 to 10 ml, swirling the contents
of the beaker before each new addition.
Digest until solution is complete (Note 2), and then evaporate (without removing the
cover) until the residue is completely dry (Note 3), but do not bake thereafter. When this
condition is reached remove the beaker from the hot-plate a t once.
Add 35 ml of concentrated hydrochloric acid and warm the beaker gently until all or
nearly all the residue has dissolved. Rinse the underside of the watch-glass with water,
and then add a 10-g portion of AnalaR hydroxylamine hydrochloride. Evaporate briskly
to low volume, and then more slowly until heavy crystallisation occurs and the concentrate
becomes semi-solid. Remove the beaker from the hot-plate, whereupon, after cooling
slightly, the mass should solidify. Drench thme residue with 10ml of concentrated hydro-
chloric acid, warm gently, dilute with 30 ml of hot water and boil for 1 or 2 minutes to ensure
complete extraction of soluble salts (Note 4).
Filter through a paper-pulp pad and washt with diluted hydrochloric acid (0.5 + 99.5).
h'ot less than 50 ml will be required altogether for effective washing. Discard the siliceous
residue, which should be quite free from basic iron or chromium compounds, but there may
be traces of residual carbides. To the filtrate (volume about 120 ml) contained in a 250-ml
conical beaker add 20 ml of 10 per cent. w/v barium chloride solution (Note 5) and digest
on a steam-bath for 1 hour. Remove the beaker from the bath and set aside overnight.
Filter through a tightly packed paper-pulp pad and wash with dilute barium chloride
wash solution until the filter is free from iron salts and finally several times with cold water
until free from chlorides. Ignite the filter and precipitate in a porcelain crucible a t a low
temperature until free from carbonaceous matter and finally a t about 850" C. Cool and
weigh the residue of barium sulphate, and callculate to percentage of sulphur in the steel,
using the factor 13.74.
A simultaneous blank determination on all reagents should be carried through all stages
of the process and an appropriate correction tjhould be made.

EOTES-
1. For steels of high tungsten content weigh 6 g of sample. For sulphur contents between
0.1 and 0.3 per cent. weigh 2 g, and for contents above 0.3 per cent. 1 g .
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Nov., 19551 FOR T H E DETERMINATION O F SULPHUR I N S T E E L 801

2. Some types of very highly alloyed steel may not dissolve entirely with the amount
of hydrochloric acid specified. With such steels make the minimum further addition necessary
to effect solution.
3. Complete dryness is interpreted as being when the viscous paste first becomes
superficially dry and then firm and immobile. This point would usually be taken as the
commencement of true baking in the conventional method.
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4. For steels of high tungsten content (6-g sample), cool and transfer the solution to a
120-ml calibrated flask, dilute to the mark and mix. Allow the precipitated tungstic acid
to settle and then collect a 100-ml aliquot (equivalent to 5 g of sample) by filtration through
a dry fluted filter-paper. Transfer to a 250-1111 conical beaker and precipitate with barium
chloride, and continue as described in the procedure.
5. For samples that are likely to have a very low sulphur content, e.g., < 0.015 per
cent., it is desirable to add a standard amount of a soluble sulphate, e.g., potassium sulphate,
equivalent to 10mg of barium sulphate, just before the barium chloride addition.

RESULTS
Results obtained by the method on a synthetic chromium series, plain carbon steel with
a range of chromium additions, are shown in Table IV. It will be seen that the chromium
TABLEIT.:
PERFORMANCE
OF HWROXYLAMINE MODIFICATION O N 5-g SAMPLE OF
(0-050per cent. of sulphur) IN THE PRESENCE
CARBON STEEL OF CHROMIUM
Chroniiuin added, Chromium added, Sulphur found,
g % %
None - 0.05 1
None - 0.050
0.1 2.0 0.060
0.1 2-0 0.049
0.26 5.0 0.050
0.26 5.0 0.050
0.5 10.0 0.049
0.6 10.0 0.048
1.0 20.0 0.049
1.0 20.0 0-051
1.0 20.0 0-048
interference markedly shown in the results on p. 797 has been eliminated by the modified
conditions, and that correct results, within acceptable tolerance limits (within about 0.002 per
cent.), can be obtained over the complete chromium range up to 20 per cent. Further,
there would seem to be no real reason why the method should not be applied with equal
success at still higher chromium levels. Table V shows results by the method on a

RESULTS ON A RANGE O F SAMPLES

Accepted value
for sulphur, Sulphur found,
01
O/ O
/
/O

E.C.S. 232, carbon steel -. .. .. .. 0*067* 0.069

R.C.S. 240, carbon steel .. .. ,. .. 0.041* 0.042
l3.C.S. 169,cast iron . . .. . . . . . . 0.031* 0.033
B.C.S. 219, Ni-Cr-I1Io .. .. .. . . 0.044* 0-045
B.C.S. 220 IV - Mo high-speed: 7'3; of W; 4% of RIo 0-039* 0.039
Stainless steel: 13% of Cr ., .. .. .. 0-040t 0.041
Stainless steel: lSoh of Cr; 8% of Xi .. .. 0-015t 0.014
Stainless steel: 18% of Cr; 8% of Ni .. .. 0-026t 0-025
Stainless steel: l8yo of Cr; 9% of Ni .. .. 0-052t 0.054
Stainless steel: 13y0 of Cr, free cutting .. .. 0-64t 0.63
Stainless steel: 3076 of Xi; 20% of Cr; 1-2O/; of Ti o-olst 0.011$
Silicon steel: 4% of Si .. .. .. .. 0.031t 0.030
* Certified values.
t By combustion.
t Low result, owing t o loss of sulphur in titanis hydrolysis product.
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802 BAGSHAWE AND PILL [Vol. 80

miscellaneous assortment of steels. For some steels the comparison may be of rather limited
value, particularly where the comparison relates to the combustion method, which itself
is dependent on cross standardisation against some other steel. None the less, the results
give a good indication of performance on a representative selection of “difficult” steels.
The steel containing 4 per cent. of silicon shown in this series (Table V) was included
in view of the possibility that in the absence of a baking treatment there might conceivably
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be some interference from residual silica. Duplicate tests on this steel gave 0.029 and 0.030
per cent. of sulphur, and in each case the barium sulphate residues were tested for silica and
found to contain only 0.1 and 0.2 mg, respectively. Determinations of soluble silica in the
barium sulphate filtrate, i.e., the silica remaining as a result of omitting the normal baking
operation, showed 3.0 and 4.9mgJ respectively. It is clear therefore that all but a few
milligrams of silica are rendered insoluble merely by evaporating the initial solution to
dryness, and the small amount that remains in solution does not contaminate the barium
sulphate.
It should be noted that the method is not satisfactory for steels containing much titanium,
as the titania hydrolysis product removed with the silica always includes some co-precipitated
sulphur. This, of course, applies equally to all conventional forms of the barium sulphate
procedure. Tungsten hydrolysis residues do not appear to occlude sulphur as titania residues
do, but large tungsten residues are difficult to manipulate in a sulphur method and fractional
filtration is usually necessary.
CONCLUSIONS
The accuracy and scope of the traditional barium sulphate method for steel is adversely
influenced by the critical nature of the baking operation. Unless the baking conditions can
be precisely defined and correctly interpreted within a close margin of tolerance, results on
chromium steels may be seriously in error.
Use of hydroxylamine hydrochloride as a means of decomposing residual nitrates has
the following advantages-
(a) the operational procedure is shortened and simplified,
(b) there is no risk of basic-salt formation, which causes loss of sulphur aqd also
contaminates the barium sulphate .precipitate, and
(c) the range of application is considerably widened and, with the exception of titanium
steels, all classes of steel, including high chromium types, can be analysed to the
same accuracy limits-within about 0.002 per cent. of sulphur in normal ranges.
The authors thank Dr. C. Sykes, F.R.S., for permission to publish this paper.
Acknowledgment is also made to Mr. R. Postlethwaite of Messrs. Samuel Fox & Co. Ltd.,
Stocksbridge, who kindly provided some of the test samples and also assisted in carrying
out confirmatory tests of the method.

REFERENCES
1 . Nydahl, F., Anal. Chem., 1954, 26, 580.
2. Belcher, R.,Gibbons, D., and West, T. S., private coiiimunication.
3.---- , Chew. & Ind. 1954, 127.
4. British Stindard 1111: Part I : 1943.
THE BROWN - FIRTHRESEARCH L A \ ~ ~ ~ . i ~ ~ ~ ~ ~ ~ ~
PRINCESS STREET,SHEFFIELD