652 SHORTCOMMUNICATIONS

REFERENCES
5. A. Saito and S.’Himeno, Nippon Kagaku Kaishi, 1974,
1. H. Dahms, J. Electroanal. Chem., 1964, 8, 5. 2340.
2. G. C. Barker and J. A. Bolzan, Z. Anal. Chem., 1965, 6. I. M. Kolthoff and S. E. Khalafalla, Reo. Polarogr.,
216, 15. 1963, 11, 11.
3. W. H. Reinmuth and K. Balasubramanian, J. Elec- 7. F. Stmad, Collection Czech. Chem. Commun., 1939, 11,
troanal. Chem., 1972, 38, 79. 391.
4. R. Guidelli, ibid., 1968, 18, 5.

Talanto, Vol. 24, pp. 652654. Pergamon Press, 1977. Printed in Great Bntain

DETERMINATION OF SILICA IN SILICATES BY FORMATION OF

1ZMOLYBDOSILICIC ACID AND REDOX TITRATION OF MOLYBDENUM(II1)

0. A. OHLWEILER and J. 0. MEDITSCH

Instituto de Quimica, Universidade Federal, Porto Alegre, Brasil

(Received 17 January 1977. Accepted 16 April 1977)

Summary-An indirect titrimetric method for the determination of silica in silicates is described. A
boron trioxide-lithium carbonate (1O:l) mixture is used as flux and the melt is dissolved in an acidic
molybdate solution to form 12-molybdosilicic acid. The yellow complex is extracted with methyl isobu-
tyl ketone (MIBK) and, after removal of the co-extracted molybdate reagent, is decomposed with
alkali. The resultant aqueous phase is acidified and passed through a Jones reductor to convert the
molybdenum(V1) into molybdenum(III), which is then titrated with potassium permanganate. The
method has high precision and accuracy. Phosphorus, titanium, zirconium and vanadium, in amounts
that may occur in silicate rocks, do not interfere; at least 5% P,O,, 5% TiO,, 2% ZrO, and 0.5%
V,O, are permissible. Fluorine (at least 2%) can also be tolerated when lithium metaborate is used
as flux.

Indirect amplification methods have been published for the Procedure

determination of silicon by atomic-absorption spectro-
metry of the twelve molybdenum atoms associated with
each silicon atom in 12-molybdosilicic acid, after its selec-
tive extraction into an organic solvent.‘-4
This paper describes an indirect titrimetric method for
the determination of silica in silicates, by formation of
IZmolybdosilicic acid, its selective extraction with methyl
isobutyl ketone (MIBK), washing of the organic extract
with dilute hydrochloric acid to remove excess of molyb-
date, decomposition of the lbmolybdosilicic acid with
dilute ammonia solution and transfer of the molybdenum
to the alkaline aqueous phase, acidification with sulphuric
acid, reduction to molybdenum(II1) in a Jones reductor,
then titration with potassium permanganate. A similar pro-
cedure has been used by Kirkbright et al. for the deter-
mination of phosphorus.5
EXPERIMENTAL
Reagents
Iron(III) phosphate solution. Prepare 1 litre of solution
containing 48.5 g of NH,Fe(SO,), ‘12Hz0, 40 ml of 85%
phosphoric acid and 50 ml of concentrated sulphuric acid.
Apparatus
Ultrasonic generator. Operating frequency, 20 kHz; cavi-
tation bath, 16cm diameter, 1Ocm height; power density
in the cavitation bath, 2 W/cm2.
Jones reductor. Prepare and store conventionally.6 If the
reductor has been standing idle, pass 1OOml of sulphuric
acid (1 + 19) through it and then a little cold water.
Transfer 0.100&0.1500 g of the finely powdered sample
(<200 mesh), containing 5&70mg of silica, to a 30-ml
platinum crucible. Add l.OOg of boron trioxide and O.lOg
of lithium carbonate and mix intimately with a short glass
rod with rounded ends. Heat carefully with a small flame
until any water is completely expelled, then cover the cru-
cible and heat with a strong flame (ca. 1000”). After fusion
for 30 mitt, allow the crucible to cool to room temperature.
Weigh out 8.Og of sodium molybdate,
Na,Mo0,.2H,O, transfer to a lOOO-ml beaker and dis-
solve in about 700 ml of distilled water. Add, with stirring,
6.0mI of concentrated hydrochloric acid and then place
the crucible in the solution contained in the beaker. Rinse
the cover of the crucible into the beaker with distilled
water. Put the beaker in the cavitation bath of the ultra-
sonic generator until the cake becomes detached from
the crucible (ca. 1 mm). Then stir magnetically (Teflon-
coated stirrer bar) until the melt dissolves (about 20 min)
forming a yellow molybdosilicic acid solution. Remove and
rinse the crucible with distilled water. Transfer the yellow
solution to a lOOO-ml volumetric flask and dilute to
volume with distilled water.
Transfer a 50-ml aliquot to a 250-ml separating-funnel
and add 16.0 ml of concentrated hydrochloric acid to make
the solution about 3M in HCl. Then add 75 ml of MIBK
and shake for 5 min. Allow adequate time for the layers
to separate and transfer the aqueous phase (containing
most of the molybdate excess and any unextracted
1Zmolybdosilicic acid) to a second 250-ml separating fun-
nel, retaining the organic phase in the first one. Rinse the
organic phase with a 2-3 ml of water. Add 50 ml of MIBK
 SHORT CQMMUNlCATIONS 653

to the second separating-funnel, shake for 5 min and dis-
card the aqueous phase.
Add 25 ml of 1M hydrochloric acid to each of the separ-
ating-funnels, shake both for 30sec and allow the layers
to separate. Take the first funnel, discard the aqueous
phase, and rinse the funnel tip with distilled water (do
this after all transfers of aqueous phases). Transfer the
aqueous phase from the second funnel to the fist. Shake
the first funnel for 30 set and then discard the aqueous
phase. Shake the organic phase in the second funnel with
25 ml of IM hydrochloric acid for 30 set and transfer the
aqueous phase to the first funnel. Shake this for 3Osec,
allow the layers to separate, and discard the aqueous
phase. Transfer the organic phase from the second funnel
to the first. Add 30ml of 1W ammonia solution to the
funnel and shake for 30 sec. Drain the aqueous phase into
a IOO-ml beaker. Add another 30 ml of 1M ammonium
hydroxide, shake for 30 set, drain the aqueous phase into
the beaker and rinse the funnel with distilled water into
the beaker.
Add 6 ml of concentrated sulphuric acid to the solution
containing the molybdenum. Transfer 35 ml of iron(II1)
phosphate solution to the receiver of the Jones reductor,
and then enough water so that the tip of the reductor
dips well beneath the surface of the solution. Draw the
cold solution of molybdenum through the reductor. Wash
the beaker and reductor successively with 50 ml of sul-
phuric acid (1 + 19) and then transfer the two 5Gml ali-
quots of distilled water. Titrate the solution in the receiver
with 0.05N potassium permanganate.
Make a blank deter~nation, passing successively
through the reductor 150ml of sulphuric acid (1 + 19) and
100 ml of distilled water.
RESJJXS AND DISCUSSION
The attack on the sample and the preparation of the
solution must ensure the conversion of all silica into the
monomeric silicic acid in order to form 1Zmolybdosilicic
acid. A fusion technique employing a boron trioxidolith-
ium carbonate (10: 1) flux was chosen for its speed, simpli-
city and effectiveness in silicate decomposition as shown
in previous studies. ‘-’ The dissolution of the cake in an
acidic molybdate solution ensures the complete depolymer-
ization of silica and the formation of the 1Zmolybdosilicic
acid. In the dissolution step, sufficient hydrochloric acid
is added to lower the pH to 1.3. The correct amount of
acid was empirically determined, as the presence of molyb-
date alters the pH of the solution. The complete formation
of the yellow molybdosilicate complex is obtained by the
presence of a relatively high excess of molybdate reagent.
An aliquot for analysis should contain no more than
3.5 mg of SiO,; otherwise the extraction of 12-molybdo-
silicic acid with the organic solvent is hindered.
Extraction of 1Zmolybdosilicic acid with MIBK was
used to permit the separation of other molybdoheteropoly
acids eventually present and also the subsequent removal
of the co-extracted molybdate. The extractability of molyb-
doheteropoly acids in MIBK was studied recently.iO
Molybdosilicic acid has a maximum distribution ratio of
approximately 720 from 0.084.0&f hydrochloric acid and
thus can be quantitatively extracted over this range.
12-Molybdosilicic acid can be selectively extracted in the
presence of molybdophosphoric and molybdoarsenic acids
at an acidity >2.5M hydrochloric acid. Three washings
are needed to remove the excess of molybdate from the
extract.
The method was tested with analysed samples (Table
1). The relative errors are less than 0.1%. The six results
for the soda feldspar gave a standard deviation of 0.02,%.
Synthetic samples were prepared with a soda feldspar
containing 65.49% of SiOz, to which amounts of the fol-
lowing potentially interfering elements were added: phos-
phorus, arsenic, titanium, zirconium, vanadium, niobium,
tantalum and fluorine. Particular attention was given to
phosphorus, titanium, and zirconium because small
mounts of these elements may occur in silicate minerals
and rocks, and they might be expected to interfere with
the method by virtue of their tendency to hydrolyse or
form the heteropoly acids.“-i4.
The results obtained with synthetic samples (Table 2)
indicate that phosphorus, titanium, zirconium and vana-

Table 1. Results obtained in the determination of silica in silicate standard samples

SiO, found, Relative

Sample Composition, % % error, y0

Soda feldspar SiOa, 68.66; Al,O,, 19.06; 68.62 - 0.06

(U.S.N.B.S., No. 99) Fe,O,, 0.067; MgO, 0.053; 68.60 -0.09
CaO, 0.36; Na,O, 10.73; 68.62 -0.06
K,O, 0.41; TiO,, 0.017; 68.64 - 0.03
P,Os, 0.142; MnO, <O.OOl; 68.60 0.00
BaO, 0.01 68.66 - 0.09
Plastic clay SiO,, 59.11; Al,O,, 25.54; 59.07 -0.07
(U.S.N.B.S., No. 98) Fe,O,, 2.05; TiO,, 1.43;
ZrO,, 0.041; P,O,, 0.08;
V,Os, 0.025; Cr,O,, 0.021;
CaO, 0.21; MgO, 0.72; K,O,
3.17; Na,O, 0.28; SO,, 0.07;
MnO, 0.005; CuO, 0.009
Flint clay SiO*, 42.87; Al,O,, 38.77; 42.83 -0.09
(U.S.N.B.S., No. 97) Fe,Os, 0.98; TiOa, 2.38;
ZrO,, 0.25; P,O,, 0.08; V,O,,
0.040; Cr,O,, 0.079; CaO,
0.10; MgO, 0.26; K,O, 0.54;
NarO, 0.33; SOa, 0.042; MnO,
0.002: cue, o&O3
Burst refractory Si02,. 54.69; A&O,, 37.67 ; 54.64 -0.09
(U.S.N.B.S., No. 76) FeaO,, 2.38; TiO,, 2.21;
ZrO,, 0.07; MgO, 0.58; CaO,
0.27; K,O, 1.37; Na,O, 0.38;
P,O,, 0.069; v,o,, 0.021
654 SHORT COMMUNICATIONS

Table 2. Results obtained in the determination of silica in synthetic mixtures

prepared with a soda feldspar containing 65.49% of SiO,

Additions SiOz found, % Relative error, %

2% TiO, 65.43 -0.09

5% TiOZ 65.42 -0.11
5% P205 65.46 -0.05
2% P,O, + 5% TiO, 65.41 -0.03
5% P,Os + 5% TiOz 65.46 -0.05
5% P,O, + 5 TiOz + 1% ZrO, 65.46 -0.05
5% P,O, + 5 Ti02 + 2% ZrO, 65.41 -0.12
0.5% v,os 65.41 -0.12
1.0% v,05 65.32 -0.26
5% As,05 65.43 -0.09
2% Nb,O, 64.34 - 1.79
2% Ta,O, 65.01 -0.61
2% F (fusion with B,O,-Li,CO, 1O:l) 64.34 - 1.76
2% F (fusion with LiB02) 65.44 -0.08

dium, in amounts that usually occur in silicate rocks, do
not interfere: at least 5% P20s, 5% TiO,, 2% ZrO, and
0.5% Vz05 are permissible. (The presence of 5% As,O,
is also admitted.) Niobium and tantalum interfere. The
presence of fluorine yields low results when the sample
is fused with boron trioxide-lithium carbonate (10: 1) mix-
ture, because some silicon is lost while fluorine volatilizes;
but good results are obtained by using a lithium metabor-
ate flux to decompose the sample.
The association of twelve molybdenum atoms with each
atom of silicon in l-2-molybdosilicic acid and the reduction
of the molybdenum(V1) to molybdenum(II1) before titra-
tion of the latter with standard potassium permanganate
gives an amplification factor of 36. Ordinarily, an amplifi-
cation method is not used for the determination of major
constituents, but in this instance it allows the use of a
small aliquot and, hence, the separation of interferents by
extraction of 12-molybdosilicic acid under selective condi-
tions. The complete analysis can be performed in less than
4 hr.
REFERENCES
1. T. R. Hurford, and D. F. Boltz, Anal. Chem., 1968,
40, 379.
2. G. F. Kirkbright, A. M. Smith and T. S. West, Analyst,
1967, 92, 411.
3. W. S. Zaugg and R. Knox, Anal. Chem., 1966,38, 1759.
4. T. Kumamaru, Y. Otani and Y. Yamamoto, Bul[.
Chem. Sot. Japan, 1967, 40, 427.
5. G. F. Kirkbright, A. M. Smith and T. S. West, Analyst,
1968, 93, 224.
6. A. S. T. M., 1960 Book of A.S.T.M. Methods for Chemi-
cal Analysis of Metals, Philadelphia, 1960.
7. 0. A. Ohlweiler, J. 0. Meditsch, C. L. P. da Silveira
and S. Silva, Anal. Chim. Acta, 1972, 61, 57.
8. 0. A. Ohlweiler, J. 0. Meditsch, S. Silva and J. A.
Oderich, ibid., 1974, 69, 224.
9.. 0. A. Ohlweiler, J. 0. Meditsch and C. M. S. Piatnicki,
ibid., 1976, 84, 431.
10. S. J. Simon and D. F. Boltz, Awl. Chem., 1975, 47,
1758.
11. G. F. Kirkbright, A. M. Smith and T. S. West, Analyst,
1968, 93, 292.
12. G. F. Kirkbright, A. M. Smith, T. S. West and R.
Wood, ibid., 1969, 94, 754.
13. H. N. Johnson, G. F. Kirkbright and T. S. West, ibid.,
1972, 97, 696.
14. Y. F. Shkaravskii, Russ. J. Inorg. Chem., 1963,8, 1339.