QUANTITATIVE METHODS OF D E T E R M I N I N G FERROUS OXIDE

IN M I N E R A L RAW M A T E R I A L S

A. L. K o n d r a s h e v a

All Union Refractories Institute

Translated from Ogneupery, No. 10,
pp. 475-478, October, 1963

The chief trend in analytical chemistry in modern conditions is the development of accurate, rapid, and sellsitive
methods of determining very low contents of elements in minerals, alloys, and pure metals.

Modern problems of analytical chemistry have produced new methods of analysis.

tn addition to the development of new methods the old c!assicat methods have been improved: both gravim-
etric and volumetric. As in other spheres of analytical chemistry there is an intermixing and combination of methods.

The correct quantitative determination of ferrous oxide in minerals and rocks is accompanied by dfficulties
which c o m m e n c e with the preparation of the sample for analysis. Grinding the powder containing Fe (II) in air re-
duces the amount of Fe (II) and correspondingly increases the content of Fe (III).

Oxidation of FeO by oxygen of the air is possible when decomposing the sample and when titrating the solution.
The sources of errors in the accurate quantitative determination of FeO. elimination of which is difficult, include
also the presence in the sample of organic substances, soluble sulfides, vanadium (III), peroxide compounds, metallic
iron, etc. Everything new which appears in the literature on the quantitative determination of FeO in minerals appears
to be an attempt to e l i m i n a t e some error or other,

In the last ten years many papers have been published in Soviet and foreign literature dealing with the quantita-
tive determination of ferrous oxide in minerals.

For the quantitative determination of FeO in iron ores the solution of the sample is most often done in HF, more
rarely in HC1 or H2SO4, A paper [1] deals with the accurate determination of FeO in iron ores containing arsenic,
organic materials, sulfur and vanadium. In the presence of organic materials, the author dissolved the sample in
HsPO4 (1 : 1) the solution was diluted and the Fe (II) titrated with NH4VOs solution.

In the presence of S2- ions the sample is dissolved in phosphoric acid to which a saturated solution of HgC1 z has
been added. The Fe (II) so formed is titrated with a m m o n i u m vanadate. In the presence of arsenic, orgamcs and Sa-
ions, a saturated solution of HgC12, a 10~ solution of NazSO3, HaPO4 (1 ; 1) are added. The solution is boiled. After
cooling, the Fe (II) is titrated with NH4VOa.
The FeO can be determined by this method only if no vanadium is present in the sample.

In another paper [2] a method was also developed for determining FeO (and F%Oa) in iron ores with a high sulfur
content.
The ore sample is mixed for an hour at room temperature in 20 ml of methanol containing 2 m! of bromine,
the solution is filtered through a Gooch crucible. The insoluble residue is carefully washed, first with methanol then
with water and treated with 40 ml HC1 (1 : 1) for 40 min while COz is being passed continuously through the solution.
The resulting solution is used to determine the Fe 0ID content by permanganatometrie titration. The filtered solution
is boiled almost to dryness and treated with 20 mi HC1 (1 : 1). With the solution obtained, after treating it when SnC12,
HgClz, and MnSO4, the total content of iron is determined with permanganate. From the difference between the total
content of iron and of FeO it is possible to find the Fe~Os content.

The literature contains a proposal [a] for the chemical rational analysis of iron ores. The quantitative determ-
ination of different forms of iron (bonded with sulfates, carbonates, ilminite, sulfides, disulfides; contained in the form
of free oxides, in the composition of silicates, magnetites, chrome spinels) is based respectively on the solubility of the
ferrous sulfate in water, the decomposibility of the iron carbonates by acetic acid, the separation of i l m e n i t e by mag-
netic separation; the determination of sulfide and disulfide forms of sulfur; the reduction of free oxides with hydrogen
and subsequent determination of the m e t a l l i c iron with an existing method; the solubility of iron silicate in a mixture
of HF and HC1. etc.

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 It is proposed that FeO be determined in aggIomerates of iron ores and silicates by the gravimetric method
based on the capacity of the FeO to oxidize during calcination in a stream of oxygen or air to Fe203 [4]. The author
determined that complete oxidation occurs in two minutes at 1000-1100~ The FeO content Was determined by the
change in weight of the specimen.

Some work has dealt with FeO determination in ilmenite. Japanese workers tested a method of dissolving the
sample in HzSO4 (1 : 1) and HF (40%) in carbon dioxide [5]. The ions of Fe (II) formed in solution were titrated with
permanganate.

Ferruginous sands and ilmenite were tested also by decomposing them with phosphoric acid and a m m o n i u m
vanadate [6]. The Fe (II) ions were titrated with KMnO4. Reproducible results were obtained.

In a Chinese paper [7] it is proposed to modify the method given by Shein. Instead of expensive vanadium
pentoxide, HsPO4 and K2Cr207 were used. Accurate and highly reproducible results are obtained. Decomposition of
the sample takes 10 minutes.

The Shein method is the most widespread for quantitative determination of FeO in chromites, c h r o m e - m a g -
nesites and chrome ores.

In the case of c o n t a m i n a t i o n of the sulfo-phosphoric mixture by impurities of reducing substances, the corrections
to the blank experiment are usually high and this reduces the accuracy of the determination. To oxidize these sub-
stances the mixture used to decompose the sample is subjected to preliminary treatment with KMnO4 solution [8]. A
description is given of a method for preparing the specially treated acid mixture.

Paper [9] notes that if the mixture of HaPO4-H2SO4 containing vanadium and used for decomposition of chromite
is specially treated with an addition of Fe (III) and Cr (III), then some of the vanadium is reduced at 250~ This
must be remembered in the quantitative determination of FeO. This is very important. It substantiates the need for
using chromite with an accurately known FeO content when doing the blank test.

In paper [9] a proof was made on Shein's [10] previous dry method for FeO in chromite, based on the calculation
of the oxygen consumption used on the oxidation of FeO into Fe203 by change in weight of the mineral after c a l c i n a -
tion in oxygen at ll00~

The authors found that calcining the sample at this temperature is not optimum for all minerals. Curves should
be drawn for the change in weight of the sample in relation to the temperature for a given mineral and the optimum
temperature should be established for each mineral.

Further, it is necessary to consider that oxidation of FeO does not go to completion and the results are about
1.8~ too Low.
Shein's method has been modified [11]. As an oxidizing agent, selectively oxidizing Fe (II) to Fe (III) and not
reacting with the Cr (III) in chromite-solubility conditions, instead of VzOs the authors used Ce(SQ) z. The sample
of chromite was treated for 90 min at 290-300~ with a mixture of phosphoric and sulfuric acids in the presence of
a given in amount of cerium sulfate. The FeO content in the chromite was found by the difference between the
amom~ts of added and titrated Ce(SO4)~. Reproducible results were obtained.

The use of cerium sulfate in place of V~Os for the determination of FeO in chrome ore is d e a r with also in
paper [12]. A mixture of 0.2 g of chrome ore and 0.2 g of Ce(SO4) z was dissolved at 280-300~ in a mixture of acids
(1 : 4), sulfuric and 85% H3PO,~. The solution was diluted with water and ~itrated potemiometrically with a 0.05 N
solution of Mohr's saR. A blank was done simultaneously. The rime of the analysis was 2-3 h.

In paper [12] for determining FeO in chrome ores and ehrome-magnesites a method is proposed in which the
sample of 3 g is heated for 2 h at 900-950~ in a quartz boat, and the amount of evolved H20 and CO2 absorbed in
tubes fitled with CaC1 a and soda asbestos is determined. Then the sample is calcined for another 5 h at 1100~
From the increase in the weight of the sample, taking into account the HzO and CO 2 content as determined, it is
possible to calculate the FeO content.

In papers [13, 14], for determining FeO in chrome ores the authors use a modified vanadate method of Shein
with an amperometric etad to the titration. The sample of chromite or chrome-magnesite was decomposed by a hot
mixture of (1 : 2) concentrated HaPO4 and HzSO4 to which had been added a given amount of V205. The solution was
titrated amperometrically with Mohr's salt with an emf equal to 1 V.
 Investigators [15] used the potentiometrie end titration. For the determination of FeO in chrome ores by the
method of H2SO4 (1 : 1) solution, they used a glass tube sealed at one end. The sample was decomposed for 10 h in
a furnace at 250~ The Fe (II) formed was titrated potentiometrically with KMnO4 solution.

Accurate resuIts were obtained with the use of HsPO4-VzO5 systems for dissolving the sample. The sample was
mixed with a given amount of V205 in a glass test tube C'Fiolax" glass), HsPO4 was added (d = 1.9), heated for 5-15
rain, cooled, the HzSO4 was added, heated to 80~ and titrated potentiometrica!ly with KMnO4. Determining FeO by
oxidation of chromite in a current of oxygen at 1000~ showed that often about 3% of the FeO remained unoxidized.

Shein's method has been proved, supplemented and changed by other workers [ 16].

The method of decomposing materials that are difficult to decompose (including chromites) by fusing with
sodium metafluoroborate [18] has been altered. The decomposition is carried out in a platinum boat in carbon
dioxide [17]. Titrating the Fe (II) is done according to Hey [19] by using iodine chloride and concentrated HC1.

The quantitative determination of FeO in ores and agglomerates in various rocks and minerals has been discussed
in a number of papers.

Agglomerate is decomposed in a platinum crucible in a current of COz, with a mixture of HFand H2SO4 [20].
This gives excellent results, but the test requires the use of platinum and a long time (30-40 rain).

A rapid gravimetric method has been used for FeO by measuring the increase in weight in calcination in a
porcelain boat in a tube furnace. The authors found that fayalite does not change in these conditions.

Paper [21] gives a detailed account of the trilonometric determination of iron in ores and agglomerate which
makes it possible to determine both Fe (HI) and Fe (II); the Fe (III) is titrated with a solution of trilone B in the
presence of sulfosalicyl acid as indicator at a pH of 1-3; Fe (II) is determined on the same sample. If the titration
liquid is cooled it is again heated to g0-70~ and a m m o n i u m or sodium persulfate is added. In the absence of Fe (/I)
the color of the liquid does not change, in the presence of Fe (II) it becomes violet, which, with subsequent titration
with trilone B, changes to yellow.

The complexiometric determination of di- and trivalent iron is dealt with in paper [22]. Trivalent iron is titra-
ted with a complex III in the presence of sulfosalicylic acid, Fe (II) is determined from the difference between the
total amount of iron and the amount of Fe ('IH).

Paper [23] states that in the rapid method of analyzing silicate rocks and minerals, for the quantitative determ-
ination of FeO the sample is dissolved in a mixture of HF and H2SO4 (minerals difficult to decompose are fused with
sodium metafluomborate in CO2) and Fe (II) is determined on the resulting solution by titrating with KzCr207 using
sodium diphenylaminesulfonate as an indicator.

Some articles [24, 25] give rapid methods for determining the amount of FeO in acid and basic slags.

Paper [26] deals with a method for determining FeO in rocks and minerals based on the oxidation of Fe fiI) by
metavanadate and decomposing the specimen with HF and then titrating the excess VOW. It is shown that NH4VO~
is stable in cold 40% HF. The sample and vanadate weighing are treated for 18 h with 20% HF in a polyethylene of
platinum vessel, 10N H2SO4 is added together with a saturated solution of HsBO8 and the indicator solution; after solu-
tion of the residues of calcium and magnesium fluorides the liquid is titrated with a solution of Mohr's salt.

A polarographic method of determining Fe (II) and Fe(III) in minerals for ceramics based on the measurement
of the cathode wave of reducing Fe (III) and anodic wave of oxidizing Fe (II) in citrate-containing solution has been
proposed [27].
The determination of Fe (II) in carbonate rocks containing MnO2 is dealt with in paper [28]. To the sample of
the rock is added oxalic acid and H~SO4 (1: 4), the mixture is heated to decomposition after cooling to below 12~ the
indicator is added (diphenylamine in H2SO4) and it is titrated with KMnO4.

A number of papers deal with the quantitative determination of different degrees of valency of the element of
iron when they are combined. The proposed methods have so far been used only on artificial mixtures [29-33].

Paper [29] gives a detailed method of separation of a mixture of Fe, FeO, and FezO s. The author analyzed
artificial mixtures and iron ores. To resolve the problem he used the method of sequential removal of the valence
forms based on their different soIubilities in certain solutions. They were selected according to their complex forma-
tion and for oxidizing-reducing reactions.

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 Paper [30] also deals with the quantitative determination of ferric, ferrous oxides,and iron in the combined
state. Experiments showed that the addition of excess Hg (II) for preventing the formation of dispersed particles of
Hg (0) together with the addition of HC1 gives satisfactory results.

Paper [31] describes a scheme for the rational analysis of artificial mixtures of ferric oxalate, ferrous oxide,
ferric oxide, and m e t a l l i c iron.

Researchers [32, 33] proposed a new method of determining the contents of Femet, FeO,and Fe20 a when c o m -
bined in ferruginous materials. To d e t e r m i n e the content of Feme t the sample was dissolved in an acid mixture (in
an inert gas) and the amount of H% evolved was measured by the method of gas-liquid chromatography.

The total F e m e t and FeO was determined by permanganate titration using the Zimmerman-Reinhardt reagent;
the amount of FeO was c a l c u l a t e d from this total by difference.

The content of Fe20 a was determined from the difference between the total content of iron and total Feme t
and FeO.

This method is used in the analysis of dust, agglomerates,and different materials containing 0-70% Fe.

Paper [34] deals with a new indicator in vanadate analysis (vanadatometry). It is shown that copper phthalo-
c y a n i n e t e t r a s u l f o - a c i d is an exceIlent internal indicator when titrating Fe (II) with vanadate in 12N H2SO4 and in the
presence of syrupy HaPO4, The indicator correction with this is less than with phenylanthranyl acid.

Article [35] describes a new method of decomposing minerals that are difficult to dissolve and its use for d e t e r m -
ining the content of ferrous oxide (and also alkalis),

It is proposed to decompose zircon, corundum, futile, tourmaline, and other minerals by heating in a mixture of
concentrated HF and H2SO4 (1 : 1) at high temperatures and pressures.

The sample of 0.3 g is placed in a cartridge of teflon, wetted with water, 5 ml HaSO4 is added (1 : 1), then 5 ml
of cone HF. The cartridge is closed with a lid and placed in a bomb of stainless steel. The closed bomb is placed in
a vertical e l e c t r i c furnace and heated to 240~ After 3 - 4 h the cartridge is removed from the cooled bomb. The
contents of the cartridge are transferred to a crucible with 300 ml of water and 10 m l of saturated HoBOa solution and
titrated with 0.1N KMnO4.

The drawbacks of the method are the c o m p l e x i t y of the apparatus and the time needed.

As a result of the work done in the last 10 years on improving methods of quantitative determination of ferrous
oxide in mineral raw materials, methods have been found to e l i m i n a t e some of the sources of error in FeO analysis;
some of the old methods have been modified for determining the content of ferric oxide and applied to certain types
of mineral raw materials; many proofs have been made of classical methods of analysis for different materials, some
of their drawbacks have been clarified, and new methods of decomposing the sample have been evolved; finally new
methods of titrating the Fe (II) ions in solution have been found.

In practice iron is found in all rocks and it is a component of hundreds of minerals; therefore, methods of d e t e r m -
ining the content of ferrous oxide in minerals will be improved.

LITERATURE CITED

1. Ik4gami and Kammori, Morita Jour. Iron and Steel Inst. Japan, 39, No. 12 (1958).
2. I. Okura, Buns4ki Kagaku, Japan Analyst, 9, No. 10 (1960).
3. A . T . Chernyi and K. V. Podoinikova, Zavodskaya Laboratoriya, No. 3 (1951).
4. Yu. I. Usatenko, Author's dissertation for scientific degree of Dr. Chemistry (1954).
5. Midzoguti, Journ. Japan Welding Soc.,No. 5 (1953).
6. Vakamatsu, Journ. Iron and Steel Inst. Japan, 44, No. 10 (1958).
7. Li Chzhi-Chan, Lyu Chzhi-Tsin, and Kyasyu4 Shitsze, No. 3 (1959).
8. S . T . Balyuk and V. M. Mirak'yan, Zavodskaya Laboratoriya, No. 8 (1949).
9. Sasuga and Iida, Japan Analyst, 7, No. 4 (1958).
10. A . V . Shein, Zavodskaya Laboratoriya, No. 4, 10 (1987).
11. Gosvali, Sci. and Culture, 22, No. 7 (1957).
12. B~ezny Bohuslay, Huth. listy, 15, No. 7 (1960).

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13. E.G. Kondrak.hina and O. A. Songina, Tr. In-ta, Stroitel'stva; Stroimaterialov AN, KazSSfL 1 (1958).
14. E.G. Kondrakhina, et a1., Izc. AN. Kaz. SSP,, Series Chemistry, No. I (1957),
15. Skalla and Reishl', Radex Rundschau, No. 6 (1956). ~

16. D.N. Finkel'shtein and V. A. Boretskaya, Methods of analyzing mineral raw materials, Moscow, Geoltekhizdat
[in Russian] (1958).
17. A.V. Grovs, Analysis of Silicates, Publication of Foreign Literature Press (1953).
18. H . P . Rouledge, Journ. Roy. Soc. W. Australia, 20 (1934).
19. M.H. Hey, Analytical notes I, I. Mineralogical Soc. (June 23, 1949).
20. N . Z . Plotkin, et al., Zavodskaya Laboratoriya, No. 8 (1949).
21. N.G. Fesenko, Zavodskaya Laboratoriya, No. 1 (1958).
22. K0udelka, Voda, 35, No. 11 (1956).
23. Raili, Analyt. Chim acta, t9, No. 5 (1958).
24. Kitakhara and Tanino, Reports Sci. Res. Inst.,S2, No. 1, 2, 4 (1956).
25. VanDo-Kui and Sym Chzhi-Tszya, Khuasyu4 pitsze, No. 11 (1955).
26. Wilson, Bull. Geol. Survey, Gr. Brit.,No. 9 (1955).
27. Bin and Goldberg, Analyt. Chem.,No. 1 (1956).
28. U, D. Bregvadze0 Report of AN Gruz. SSR, 15, No. 9 (1954).
29. A . K . Lavrukhina, Trans. of the Commission on Analytical Chemistry, Vol. III (VI) (1951).
30. A~ S. Andreev and S. M. Rabovskaya, Zavodskaya Laboratoriya, 19, No, 4 (1953).
31. V. V, Boldyrev, Tram. Tomsk University, 126 (19 54).
32. StoI1, Norbert, Wagner, and Armand, Rev, univers, mines. 16, No. 10 (11960).
33. Stoli, Norbert, Wagner, and Armand, Rev, Techn., Luxembourg, No. 3 (1961).
34. Gopala-Rao and Sastri, Zeitsch. analyt. Chem., No. 1, 167 (1959).
35. tto ]un, Scient. Papers Coll. Gen. Edue. Univ. Tokyo, No. 1 (1961).

A l l a b b r e v i a t i o n s of p e r i o d i c a l s in t h e a b o v e b i b l i o g r a p h y are l e t t e r - b y - l e t t e r t r a n s l i t e r -
a t i o n s of t h e a b b r e v i a t i o n s a s g i v e n in the o r i g i n a l R u s s i a n j o u r n a l Some or all of t h i s p e r i -
o d i c a l l i t e r a t u r e m a y w e l l be a v a i l a b l e in E n g l i s h t r a n s l a t i o n . A c o m p l e t e l i s t o f the c o v e r - t o .
c o v e r E n g l i s h t r a n s l a t i o n s a p p e a r s at t h e b a c k o f t h i s i s s u e .

518