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Analyst, August, 1974, Vol. 99, $p. 519-522 519

A Titrimetric Method for the Determination of
Sulphate in Fertilisers
BY A. D. CAMPBELL, D. P. HUBBARD AND N. H. TIOH
(Department of Chemistry, University of Otago, Box 56, Dunedin, New Zealand)
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A method is described for the determination of sulphate in fertilisers in

which the sulphate is precipitated with barium chloride from an acidified
EDTA solution. The precipitate is filtered off by using membrane filters and
is dissolved in ammoniacal EDTA ; the excess of EDTA is then titrated against
a solution of magnesium ions with Eriochrome black T as theindicator. No
interference is encountered from iron, aluminium, fluoride or phosphate ions.

THEfertiliser industry has long been interested in accurate, rapid and simple methods for the
determination of sulphate in superphosphate fertilisers. The procedure most often used is
gravimetric, involving the precipitation of barium sulphate. However, this method is time
consuming and subject to interferences1 The direct titrimetric methods for sulphate deter-
mination suffer from interferences from phosphate, iron and aluminium, etc., and require
extra separation stages, which lengthen the time taken for analysis.
Excellent reviews of both gravimetricl and titrimetric methods1s2 have been given.
Belcher, Gibbons and West3 reported an indirect titrimetric method, which entails the
precipitation of barium sulphate, its dissolution in ammoniacal EDTA and finally back-
titration with a solution of magnesium ions. Subsequently, this basic method has been suc-
cessfully applied to the determination of sulphur in steel4 and organic compounds5 and of
sulphate in urine.6 It seemed to us that this procedure could well be adapted to the deter-
mination of sulphate in fertilisers. With minor modifications to the established method we
have been able to analyse both actual and synthetic superphosphate samples with excellent
accuracy and precision.

EXPERIMENTAL
REAGENTS AND SOLUTIONS-
All reagents were of analytical-reagent grade quality unless otherwise stated.
Ammonia solution, sp. gr. 0.88.
Barium chloride solution, 5 per cent. m/V.
Standard magnesium chloride solution, 0.025 M-Dissolve 5.08 g of magnesium chloride,
MgCl,. 6H20, in distilled water and dilute to 1 litre with distilled water. Standardise the
solution against 0-04 M EDTA solution with Eriochrome black T as indicator.
EDTA solution, 0.04 M-This and other EDTA solutions at different concentrations,
together with various concentrations of dilute hydrochloric and sulphuric acids, were prepared
by suitable dilution of Volucon standard volumetric solution concentrates obtained from May
and Baker Ltd.
Bufer solfition,p H 10-Dissolve 70.0 g of ammonium chloride in a mixture of 250 ml of
water and 570 ml of ammonia solution (sp. gr. 0-88), and dilute the solution to 1 litre.
Indicator solution-Dissolve 0-40g of Eriochrome black T in a mixture of 30ml of
triethanolamine and 10 ml of absolute ethanol.

APPARATUS-
Circles of Metricel filter (25 mm in diameter, 0.45 pm pore size) were cut from sheets of
filter obtained from Gelman Instruments Co., Ann Arbor, Michigan, U.S.A. In use, the filters
were clamped in a demountable Pyrex microanalysis filter holder (Millipore Corp., Bedford,
Mass., U.S.A.) that incorporated a glass funnel of 15 ml capacity and a filter area of approxi-
mately 2-5 cm2.

0 SAC and the authors.

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520 CAMPBELL, HUBBARD AND TIOH: A TITRIMETRIC METHOD FOR [ArtaZyst, Vol. 99
The tip of the burette was coated with picene wax, which was then drawn out with a wire
to give a small orifice, thus allowing the delivery of smaller drops.
PREPARATION
OF SYNTHETIC SUPERPHOSPHATE SAMPLES-
In view of the unavailability of standard superphosphate f ertiliser samples of accurately
known sulphate content, and in order to assess carefully the accuracy of the method, synthetic
superphosphate solutions were prepared as follows by the method recommended by P. J.
Gallaher (personal communication). Weigh out 0.62 g of Christmas Island rock (Note 1) and
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add an accurately known volume of 0.500 M sulphuric acid [between 6 and 8 ml (Note 2)].
Warm the mixture for a few minutes in order to complete the reaction. Add 10 ml of con-
centrated hydrochloric acid and heat nearly to dryness, then re-dissolve the residue in 100 ml
of 2 M hydrochloric acid and filter the solution through a membrane filter. Dilute the filtrate
to 250 ml with distilled water, take a 25-ml aliquot and continue as described in the method
recommended below.
RECOMMENDED PROCEDURE FOR THE DETERMINATION OF SULPHATE IN SUPERPHOSPHATE-
Dissolve 1.00 g of finely powdered superphosphate (ground to pass through a 250-mesh
sieve) in 10 ml of concentrated hydrochloric acid and evporate the solution nearly to dryness.
Re-dissolve the residue in 100 ml of 2 M hydrochloric acid and filter the solution through a
0-45-pm membrane filter, rinsing thoroughly with distilled water. Transfer the filtrate into
a 250-ml calibrated flask and dilute it to the mark with distilled water. Transfer a 25-ml
aliquot into a Taylor flask and add to it 10 ml of 0.05 M EDTA solution.
Boil the solution for about 2 minutes and then add 100 ml of 0.05 M hydrochloric acid.
Allow it to stand for a few minutes and slowly add 50ml of 5.0 per cent. barium chloride
solution. Then, after allowing it to stand for 5 to 10 minutes, filter the precipitate on a
0-45-pm membrane filter (Note 3) and wash it with 25 ml of 0.05 M hydrochloric acid, followed
by 50 ml of distilled water. Transfer the precipitate to the original flask, using forceps to
handle the filter, ad rinse any barium sulphate remaining on the glass funnel into the flask with
distilled water. Add 20 ml of 0-04M EDTA and 4 ml of ammonia solution (sp. gr. 0.88).
Dilute the mixture to about 150 ml with distilled water and heat it for 15 minutes. Finally,
allow it to cool, add 5 ml of buffer solution and titrate against standard 0.025 M magnesium
chloride solution with Eriochrome black T as the indicator.

XOTES-
1. The choice of this rock ensures that the main possible interferences are likely to be present in
relatively high concentrations. The only possible difference between this type of synthetic super-
phosphate and the commercial product could be a higher fluoride level as a result of its reduced evolution
during reaction. However, only a small proportion of the fluoride is evolved from Christmas Island
rock during superphosphate manufacture so that the standard solution will not be very different from
that of a commercial product.
2. The stated volume of sulphuric acid ensures that the amount of sulphate in the synthetic
superphosphate samples closely resembles the amount in actual samples, i.e., of the order of 30 per cent.
of sulphate (10 per cent. as sulphur). I n addition, the total amount of added sulphate plus rock is
close to 1 g, which again agrees with the recommended mass of sample for commercial superphosphate
in the method that follows.
3. It is known that aged barium sulphate is much more difficult to dissolve than the freshly
precipitated variety.5 However, precipitation in the cold and the short time of standing produce a very
fine precipitate, hence the use of the fine pore filter. This precipitate dissolves readily in ammoniacal
EDTA.

RESULTSAND DISCUSSION

I t was to be expected that ions such as PO,3 -, F -, Fe3+ and A13+, which interfere in the
precipitation of barium sulphate, 7 would also interfere in the proposed titrimetric method.
All of these ions are likely to be present in superphosphate samples. However, in preliminary
experiments, we found no evidence of interference from either phosphate (11-5mg) or fluoride
(0.95 mg) in the determination of sulphate (12.0 mg) when following the recommended
procedure with the slight modification that the initial precipitation was carried out in the
absence of EDTA, Le., basically the method of Belcher et aL3 However, in the presence of
phosphate (23.0 mg), both iron (3.52 mg) and aluminium (1.70 mg) gave a positive error of
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August, 19741 THE DETERMINATION OF SULPHATE I N FERTILISERS 521

2-4 per cent. in the determination of 24.0 mg of sulphate. A solution containing phosphoric
acid, sodium fluoride, iron(II1) chloride or aluminium chloride was added to a standard volume
of sulphuric acid and subjected to the described procedure in studies of these interferences.
Pi-ibil and Maricovas have shown that if barium sulphate is precipitated in the presence
of EDTA, then the co-precipitation of moderate amounts of many ions is prevented. Modi-
fication of the procedure accordingly eliminated the interference of iron(II1) ions ; however, a
slight interference from aluminium remained. It is well known that aluminium complexes
only slowly with EDTA but that boiling speeds up the reactiong9lo. The time of boiling needed
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to complete complexation is dependent on several factors, such as pH and previous treatment

of the ~ o l u t i o n . ~Milner and Woodheadlo recommend boiling for about 2 minutes and the
aluminium interference was eliminated under these conditions.
The results obtained all show a very small positive bias, which may or may not be
significant. This bias is not serious.
During the development of the method it was noted that phosphate caused an inter-
ference in the determination when the precipitation of barium sulphate was carried out in the
presence of EDTA. This interference was eliminated by washing the precipitate with dilute
hydrochloric acid. It was also necessary to increase the amount of barium chloride used in
order to achieve the complete precipitation of barium sulphate when EDTA was present.
Washing the precipitate with EDTA in addition to dilute acid made no difference to the
recovery of sulphate and was therefore discontinued.

I
TABLE
ANALYSIS
OF SYNTHETIC SUPERPHOSPHATE SOLUTIONS
Amount of sulphate Amount of sulphate Mean recovery,
added/mg* recovered/mgT per cent.
317.0 317.7, 317.7, 317.3, 316.8 100-1
369.9 371.0, 370.5, 371.4, 370.5 100-3
317.0 317.7, 317.7, 317.7, 316.8 100.1
313.2 314.7, 314.2, 313.8, 313.8 100.3
* Amounts added to approximately 0.625 g of Christmas Island phosphate rock.
t Four separate, 25-ml aliquots of each synthetic superphosphate stock solution were taken through the
recommended procedure.
Much has been written about the suitability of Eriochrome black T as an indicator.11
We have found that the final colour change to pink is, in fact, very distinct against a white
background, and that reproducible titrations can be obtained. In Table I the recoveries of
sulphate added to Christmas Island rock that had been shown to contain no natural sulphate
are shown. The accuracy of the method is within that required by the fertiliser industry
(within 0.5 per cent.) and the precision is excellent. In Table I1 the results obtained for four
actual superphosphate fertiliser samples are given.

TABLEI1
ANALYSIS
OF ACTUAL SUPERPHOSPHATE SAMPLES

Sample Nominal sulphur Sulphur content

number content, per cent.* determined, per cent.
1 11-17 11-20, 11.19, 11.21
2 10.16 10.18, 10.17, 10.18
3 10.42 10.45, 10.45, 10.46
4 11.11 11.12, 11.13, 11.13
* Values supplied by The New Zealand Fertiliser Manufacturers' Research Association, obtained by use
of a calibrated gravimetric procedure.

CONCLUSIONS
It has been shown, via the analysis of both actual and synthetic superphosphate solutions,
that the indirect method, first proposed by Belcher et u Z . , ~ for the determination of sulphate can,
with modification, be applied to sulphate in phosphate fertilisers. The method involves the
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522 CAMPBELL, HUBBARD AND TIOH

precipitation of the sulphate with barium chloride from an acidified EDTA solution to prevent
the co-precipitation of various ions. The precipitate is filtered off and dissolved in ammoniacal
EDTA and the excess of EDTA titrated against standard magnesium solution with Erio-
chrome black T as the indicator. Excellent agreement with available data for the actual
samples and virtually 100 per cent. recoveries of sulphate for the synthetic samples demon-
strate the reliability of this procedure. The method is straightforward, relatively fast (several
samples could be analysed simultaneously within 1 hour) and accurate.
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The authors thank the Research Committee of the New Zealand Grants Committee, for
financial assistance, and also Mr. P. J. Gallaher, of the New Zealand Fertiliser Manufacturers’
Research Association, for his valuable advice.

REFERENCES
1. Haddock, L. A., in Wilson, C. L., Editor, “Comprehensive Analytical Chemistry,” Volume lc,
Elsevier Publishing Co., Amsterdam, 1962, p. 282.
2. Schwarzenbach, G., and Flaschka, H., “Complexometric Titrations,” Second English Edition,
Methuen and Co. Ltd., London, 1969, p. 315.
3. Belcher, R., Gibbons, D., and West, T. S., Chem. 6 Ind., 1954, 850.
4. - - -, Analyst, 1955, 80, 751.
5. Belcher, R:, Bhasin, R. L., Shah, R. A., and West, T. S., J . Chenz. S O ~ .1958,
, 4054.
6. Lewis, D. A., Analyst, 1962, 87, 566.
7. Vogel, A. I., “Quantitative Inorganic Analysis,” Third Edition, Longmans, Green and Co. Ltd.,
London, 1961, p. 462.
8. Pribil, R., and Maricova, D., Chemicke‘ Listy, 1952, 46, 542.
9. Schwarzenbach, G., and Flaschka, H., “Complexometric Titrations,” Second English Edition,
Methuen and Co. Ltd., London, 1969, p. 185.
10. Milner, G. W. C., and Woodhead, J. L., Analyst, 1954, 79, 363.
11. West, T. S., “Complexometry with EDTA and Related Reagents,” BDH Chemicals Ltd., Poole.
1969, p. 191.
Received February Sth, 1974
Accepted March 8th, 1974