Journal of Applied Geochemistry
Vol. 18, No.2 (2016). pp. 137-140
METHOD DEVELOPMENT FOR FeO ANALYSIS FOR IRON ORE
AND REDUCED PRODUCTS
S.K. Saraf, P. Sharma and B.C. Hajela
R&D Centre, NMDC Ltd., Hyderabad
Email: [Link]@[Link], sksaraf@[Link]
Abstract
Several different techniques have been worked upon for the establishment of FeO analyses. In the technique, dissolution is carried
out in a nitrogen atmosphere to prevent oxidation by atmospheric oxygen. The Indian Standard Method IS: 1493-1959 describes
that the iron ore sample is attacked in a covered platinum crucible, with sulphuric acid and hydrofluoric acid in an atmosphere of
carbon dioxide, the solution thus obtained is analysed by titration method. The above analytical method needs a sophisticated
apparatus which is designed suitably so that FeO does not react with the oxygen content of the material under study.
It needs a careful study of the XRD phases associated with the sample. A NIST traceable standard is utilised for the purpose. The
experiment is carried out by applying different national and international standard methods. The results are compared by applying
a statistical technique and established by prevailing ILC practices.
Keywords: Inter Laboratory Comparison (ILC), X Ray Diffraction (XRD), Inter Laboratory Comparison, National Institute of
Standards and Technology (NIST)
1. Introduction the conical flask is drawn through a source of CO2 gas at
a pressure of 2 bar. The sample is digested for at least
Iron Ore is most often found in the form of
half an hour in an oxygen absant environment. The
hematite and magnetite, though goethite, limonite and
solution is allowed to cool to room temperature. 20 mL of
siderite types are also common. Approximately 98 percent
ortho-phosphoric acid is added followed by 2-3 drops of
of the iron ore produced in the world is used for producing
diphenyl ammonium sulphonate indicator. Finally the
steel. Hematite ore has the chemical formula Fe2O3 and
solution is titrated against pre-standardised 0.0893 N
has a very high iron content.
Potassium dichromate standard solution to an end point
Iron ore is the most important raw material for of violet color. The method depends upon the quantitative
the manufacture of steel and hence accurate analysis of oxidation of ferrous salts in cold acid solutions (Sulphuric
FeO content is most important with respect to the quality acid).
of steel. One of the important steps in steel manufacturing
The following reaction takes place:
is sintering process. Characteristics of FeO during
sintering is always examined mainly in terms of chemical 6 FeCl2+K2Cr2O7+14HCL=6 FeCl3+2 CrCl3+2KCl+7 H2O
composition and the melting characteristics of iron ores.
3. Research
Statistical regression and X-ray diffraction were used to
further explain the specific effect of iron ore characteristics In one of the techniques of FeO determination,
in terms of FeO. The results indicate that LOI (loss on the dissolution and titration procedures are carried out in
ignition) in iron ores has a positive influence on FeO by a nitrogen atmosphere (Shaeffer, 1966) to prevent
promoting the sintering process of Fe2O3 decomposition oxidation by atmospheric oxygen. The experiment is a
and reduction. Silica contents as well as melting tedious one and leads to a low value of % FeO (Fritz and
characteristics of iron ores play a significant role in Popp, 1985). In subsequently modified techniques
constraining the final content of FeO in the sinter. (Whipple, 1974), the system does not require an oxygen-
free atmosphere. The sample is oxidized in the presence
2. Experimental Studies
of a known amount of an oxidizing agent. The excess
Sample of Iron powder is weighed accurately oxidizing agent is then titrated with a ferrous-bearing
and digested in 1:1 30 ml of sulphuric acid. The inlet of solution, and the Fe2+ content of the sample calculated.
137
S.K. Saraf et al.,
In colorimetric determination (Shapiro, 1960) of FeO, the with α-Fe2O3 at low temperatures on the O-rich side
sample is dissolved by a mixture of HF and H2SO4 in the indicated in the graph between [20–22], 2 theta
presence of o-phenanthroline. values(Fig.1). Also, λ-Fe2O3 is a common constituent in
This organic reagent prevents oxidation of the tropical soils and may be dispersed in the matrix,
sample’s ferrous iron during dissolution by selectively structurally appearing more as a modification of Fe3O4.
complexing with the released ferrous iron during acid From X-ray diffraction analysis, it can be safely
attack, and it forms an orange-colored complex with Fe2+ suggested that the ore sample is observed to be hematitic
whose intensity is directly proportional to the ferrous in nature. The sample contains 2.1% magnetite and 11.4%
content of the digested sample (Fritz and Popp, 1985). hematite. Results of chemical analysis by the present
This procedure is relatively tolerant of atmospheric oxygen modified method reflects its magnetite content.
and thus obviates the need for dissolution under oxygen-
The Thermo Gravimetric Analyzer (TGA) is an
free conditions.
essential laboratory tool used for material characterization.
4. Results Thermo gravimetric analysis is carried out in an inert
X-Ray Diffraction study (Mohapatra and Saraf, atmosphere preferably in the absence of air but in the
2003), of the sample was undertaken for qualitative presence of Nitrogen Gas.
analysis using a PANalytical X’Pert PRO XRD System The aim of this work is to apply thermo-analytical
with Kα-1 Cu-radiation(1.54060 AO) and Kα-2 Cu- technique to evaluate iron ore types during
radiation(1.54443 AO) and Kβ Cu-radiation(1.39225 AO) decomposition of the LOI matter and determine the
operated at 40 kV and 30 mA. It was operated at a scan associated decomposition temperature. Three distinctive
speed of 0.5 with increments of 0.02° from 4° to 82° 2 temperature ranges of decomposition of iron ore LOI
theta range. matter were detected (Fig.2). The first region was
The peaks of λ-Fe 2 O 3 and Fe 3 O 4 were associated with dehydration of hygroscopic moisture at
overlapping with those of α-Fe2O3 at 2θ of about 26°, 36° a temperature range between 100°C and 150 °C and a loss
and 57°–63°. This may be due to the fact that, according of 0.73 % is observed. A total loss of 5.75% occurred at
to the Fe-O phase diagram, Fe3O4 coexists with α-Fe2O3 the second region at a temperature range between 260°C
below 570°C on the Fe-rich side and is in equilibrium and 425 °C, during which strongly bonded water is
Source: GSI, Bangalore
Fig.1. XRD Pattern for Iron Ore Sample 3360
138
Method Development for FeO.................... Ore and Reduced Products
Table 1. Analysis of FeO sample by modified
method
Sl. No Standard Analysed Difference
sample used sample
(%FeO) (%FeO)
BCS 174/2
1 6.57 7.07 -0.50
2 6.57 7.07 -0.50
3 6.57 7.20 -0.63
4 6.57 6.82 -0.25
5 6.57 6.17 0.40
6 6.57 6.04 0.53
7 6.57 6.82 -0.25
Fig. 2. TGA Graph for Iron Ore Sample 3360 8 6.57 7.07 -0.50
9 6.57 7.20 -0.63
10 6.57 6.30 0.27
released and the OH groups associated with primarily
11 6.57 6.82 -0.25
iron oxy-hydroxides were fractured. The third range, which
12 6.57 6.94 -0.37
occurred at a temperature range of 530°C and 605°C and a
loss of 6.14 %, is related to decomposition of alumino- 13 6.57 7.07 -0.50
silicate clay materials which is also confirmed by the XRD 14 6.57 6.82 -0.25
data constituent of 42% Quartz. The total loss for the Average 6.82
sample is calculated to be 8.15% which may be attributed SD 0.38
to various metal oxides and water molecules.
A NIST standard sample is also analyzed by the other wet chemical techniques. Inter Laboratory
modified method and the result shown below describe comparison and z-score data reveals that the procedure
that there is very close correlation of data (Table-1). The is well validated. Further the method is accredited by the
Z-score is calculated for various laboratories which is National Accreditation Board of Laboratories for NMDC,
represented at (Table-2). (R&D Centre, Chemical Laboratory) for FeO analysis.
Table 2. Sample Analysis by modified method and comparison with various Laboratory
results and Z-Score
Sample Sample Analysed Analysed Analysed Z-Score Z-Score Z-Score
No. Result By M/s By M/s By M/s M/s SGS M/s S K M/s Ita Lab
(%FeO) SGS Labs, S K Mitra Ita Lab 3 Labs Mitra Labs
India India India
(%FeO) Labs 2 (%FeO)
(%FeO)
3360 2.64 2.57 2.16 2.63 0.31 -1.49 0.57
5. Conclusion References
The method described here can be used to Mohapatra, B.B and Saraf, S.K., (2003) Polymetallic
complexes Part LXXXII. Bis-Bidentate and Bis-
determine absolute amounts of FeO. The technique gives
Tridentate Complexes, [Link].v. 80,
results that, in general, are in reasonable agreement with pp. 696-699.
139
S.K. Saraf et al.,
Shaeffer, H. N., (1966) The determination of iron (II) oxide Steven F. Fritz and Robert K. Popp (1985) A single
in silicate and refractory materials. Analyst, v. 9, dissolution technique for determining Feo and
Fe2O3 in rock and mineral samples, American
pp.763-790.
Mineralogist, v. 70, pp.961-968
Shapiro, L. (1960) A spectro-photometric method for the
Whipple, W. E. (1974) A study of Wilson’s determination
determination of FeO in rocks. U.S. Geological of ferrous iron in silicates, Chemical Geology, v.
Survey Professional Paper, v. 1.400B, pp.496-497 14, pp. 223-238.
Received on 23-11-15; Revised Ms accepted on 16-02-16
140
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