Thin Layer Chromatographic Characterisation and Quantitative Densitomery of… 137

TLC Characterisation and Quantitative Densitometry of

Red Mud Constituents
P.A. Mohamed Najar* and K.V.Ramana Rao
Jawaharlal Nehru Aluminium Research Development and Design Centre,
Amaravati Road, Nagpur

ABSTRACT: Alumina (Al2O3) is commercially produced from bauxite using Bayer process. After digestion, the
bauxite residue known as red mud is separated, washed and disposed off. It contains six major oxides such as Fe ,
Al, Ti, Si, Na, Ca along with several minor and trace elements. Based on the principles of thin layer
chromatography, a new analytical method has been developed for the characterization of some of the major
constituents in red mud. The chromatographic characteristics of the separated constituents were studied and the
respective chromatograms were quantitatively evaluated by scanning densitometry. The results were compared
with classical wet analytical method.

1. INTRODUCTION nature, red mud has to be treated as a separate

The commercial production of aluminium
involves two main process steps such as Bayer’s
chemical process (Bayer, 1887, 1892) and Hall-
Heroult electrolytic process (Hall, 1889). The
refining of bauxite ore to alumina tri-hydrate by
Bayer’s process generates red mud as a waste
product. The effective utilization of red mud is
found to be entirely dependent on its chemical
composition. Conventional wet chemical analysis
and instrumental methods such as XRD/XRF are
commonly used for the qualitative and quanti-
tative determination of red mud constituents.
A detailed characterization of red mud is
reported by various authors (Mahapatra et al,
2000; Solymar et al. 1992; Sahin, 1998; Wang et
al, 1998). Chemical analysis of red mud reveals
that it contains silica, aluminum, iron, calcium,
titanium along with minor constituents like Na,
K, Cr, V, Ni, Ba, Cu, Mn, Pb, Zn etc. The
compositional range of major constituents varies
within the weight percentage Al2O3:10-20;
Fe2O3:30-60; SiO2:3-50; Na2O:2-10; CaO:2-8 and
TiO2: trace-25.
Our recent studies on the thin layer
chromatographic (TLC) analysis of bauxite
revealed the possibility of separating co-existing
Al-Fe-Ti as well as the detection of silicon in
bauxite (Najar and Rao,2002; Najar et al.,2005;
Najar et al.,2005;Najar and Rao, 2006) and red
mud (Najar et al.,2004). From these studies, it
has been realised that due to its highly complex
entity for chromatographic characterization.
Chromatograms of Al3+, Fe2+, Ti4+ and Si4+ in
red mud samples were obtained at the optimised
chromatographic conditions and the quantitative
estimation has been achieved by peak area
measurements of the respective densitograms.
This communication reports the develop-
ment of a microanalysis method for the major
constituents of red mud and exploring the
possibility of using combination of TLC with
scanning densitometry for quantitative deter-
mination with acceptable error limits.
2. EXPERIMENTAL
2.1 Reagents and Test Solutions
1% test samples of red mud (Plant Origin) were
prepared by the standard sample preparation
method (Aluterv, Budapest, 1970; Indian Bureau
of Mines 1979).1% alkali and other salt solutions
(Analytical grade) were prepared with in double
distilled water.
2.2 Instrumentation
Systronics pH meter model 335 was used for pH
measurements. Photometric measurements were
carried out by a dual wavelength scanning
densitometer (Shimadzu CS-9301PC) equipped
with Quanta Scan 2D quantitative software.
138  Mineral Processing Technology (MPT 2007)
2.3 Procedure
The chromatographic plates were prepared by
standard TLC procedure (Touchstone, 1992). Test
solution of approximate 1-2 µL was applied
using a micropipette about 1.5 cm above the
lower edge of TLC plates (10 x 5 cm 2 ) coated
with silica gel H (S1) impregnated with 0.2%
HCOONa. The spots were dried at room
temperature and the plates were developed in
developing chambers (20 x 10 cm2) containing
mobile phase M1 (8:2 v/v mixture of 10%
solutions of NaCl and HCOOH) by ascending
technique. In all experimental runs the mobile
phase ascend was fixed at 7 cm from the point of
sample application. The developed plates were
subjected for spot visualization and characteri-
zation based on RF values. Al3+ was detected (RF:
0.98) by spraying aqueous solution of 0.1%
aluminon (tri-ammonium aurin tri-carboxilate
[C22H23N3O9]. Saturated potassium ferrocyanide
[K4Fe(CN)6] was used for the detection of Fe2+
(RF: 0.69) and Ti4+ (RF: 0.08) was detected by
0.5% tiron (Yoes reagent, C6H4Na2O8S2). Si4+ was
detected (RF: 0.60) on TLC plates coated with
microcrystalline cellulose (S2) developed with
5% v/v of HCl (M2).1% aqueous sodium
molybdate (Na2MoO4.2H2O) in acid medium was
used as the detection reagent. Na+ (RF: 0.90) and
Ca2+ (RF: 0.86) were detected on cellulose coated
plates. The spots appeared as florescent bands by
spraying 8-hydroxyquinoline followed by
exposure on shortwave IR radiation at 254nm.
2.4 Quantitative Studies
The sample solutions of red mud for the TLC
study was prepared with red mud of plant origin
and their chemical composition was determined
by wet analytical procedure (Aluterv, Budapest,
1970; Indian Bureau of Mines 1979). The TLC-
Scanning densitometric evaluation of Al3+, Fe2+,
Ti4+ in red mud was carried out by spotting the
red mud solution on TLC plates (10 x 10 cm 2)
coated with S1 and developed with M1. Si4+ was
detected on S2 coated plates developed with M2.
The individual ions (viz. Al3+, Fe2+, Ti4+, Si4+)
were detected on separate plates and the spots
were subjected for densitometry at the respective
λmax values (530-520 nm for Al, 628-520 nm for
Fe, 410-400 nm for Ti and Si).
3. RESULTS AND DISCUSSION
The important parameters like sample concen-
ration, pH effect and presence of impurity
elements etc. which have a direct impact of
chromatographic characteristics were separately
studied.
3.1 Effect of Other Elements
Calcium and sodium in red mud have been
treated as impurity elements during the densito-
metric determination of Al2O3, Fe2O3, TiO2 and
SiO2. In order to study their effect on the TLC
detection, a synthetic sample of red mud solution
was prepared without calcium and sodium. The
TLC-densitometric experiments were simulta-
neously carried out with the synthetic and red
mud samples of plant origin. The recovery
percentage is found to remain the same for plant
and synthetic samples.
3.2 Effect of pH
pH of sample and mobile phase plays an
important role in the TLC detection and
resolution of the cations (Touchstone, 1992). In
the case of red mud samples it has been noticed
that a change in pH from neutral to alkaline
results the decomposition of sample due to the
precipitation of iron and titanium. Therefore the
study has been carried out by changing mobile
phase pH. It was noticed that a decrease in pH of
mobile phase harm the separation possibility due
to tailing of Fe2+ from the point of sample
application. Detection and separation of Ti 4+ was
largely affected by the pH variation. The sample
solution needs to be acidified to pH 0.3-0.4, prior
to loading on TLC plate for achieving the
detection of Si4+.
3.3 Effect of Sample Constituents
The concentration of Fe2+ in the sample matrix is
very high compared to other constituents except
Al3+. The simultaneous determination of all the
four (Al3+, Fe2+, Ti4+ and Si4+) elements in the
same matrix is not possible due to the variation
of high concentration range among the consti-
tuents as well as chromatographic characteristics.
Thin Layer Chromatographic Characterisation and Quantitative Densitomery of…
3.4 Limit of Detection
The coloured spots on the TLC plates were
detected and subjected for densitometric
scanning at the respective λmax values. The
procedure was repeated with successive lowering
of the amount of cation until no peaks were
detected. The lowest detection range goes down
to 8ppm for Fe2+, 5ppm for Si4+, 12ppm for Al3+
and 8ppm for Ti4+.
3.5 Densitometry
139
The recovery percentage of Al2O3, Fe2O3, TiO2
and SiO2 in red mud were determined by
scanning densitometry at the optimised chroma-
tographic conditions. The results of the study are
shown in Table- 1. The trials were repeated with
red mud samples of unknown chemical compo-
sition and peak area of the constituents obtained
were compared with that of standard red mud
samples. The concentration of the constituents in
unknown samples was determined by wet
analysis and the results were compared with
densitometric peak analysis data. The percentage
error for concentration of Al3+, Fe2+, Ti4+, Si4+ with
reference to the data recorded by wet chemical
analysis is 98±2.

Table 1: Comparative wet analysis and densitometry of red m

Experimental conditions for densitometry

Medium Acid digested Alkali Fused
Constituents Al2O3 Fe2O3 TiO2 SiO2*
Concentration 1% 0.1% (buffered**) 0.4 in NaOH
Volume loaded 2µl 2µl 2µl 3µl
Scanning at λmax 527nm 625nm 405nm 380nm
% Composition of red mud constituents (Wet analysis)
Sl No. Al2O3 Fe2O3 TiO2 SiO2 LOI Na2O CaO
A 15.64 64.00 2.59 3.41 10.04 2.65 0.01
B 19.04 50.49 4.56 5.68 12.71 6.02 0.53
C 10.49 58.90 4.93 7.01 12.80 3.46 1.19
D 12.48 61.00 5.25 7.11 8.02 4.29 1.09
E 12.12 60.48 5.06 7.35 7.53 4.50 0.99
% Composition of red mud constituents by densitometry **
Al2O3 Error Fe2O3 Error TiO2 Error SiO2
A 15.62 0.12 64.30 0.46 2.55 1.54 3.41
B 19.11 0.36 50.33 0.31 4.61 1.10 5.66
C 10.22 2.57 59.02 0.20 5.02 1.83 7.00
D 12.39 0.72 61.41 0.67 5.14 2.09 7.09
E 12.70 4.78 60.32 0.26 4.99 1.38 7.39
*** Mean 1.71% Mean 0.38% Mean 1.58% Mean

*All measurements have been taken for yellow sodium molybdosilicate complex;
**Concentration with respect to peak area measurement is average of three consecutive trials;
*** Mean % error is average for the five samples with respect to the respective wet analytical data.

4. CONCLUSSIONS An improved and rapid quantitative methodology

for the analysis of major constituents in industrial
140  Mineral Processing Technology (MPT 2007)
wastes such as red mud is investigated. The
investigations also showed that TLC procedure
can be successfully modified and coupled with
suitable instrumentation methods for the quail-
tative and quantitative determination of trace
elements in highly complex matrices.
5. ACKNOWLEDGEMENT
The authors thank Dr. J. Mukhopadhyay, Director
JNARDDC for his constant encourage-ment,
useful suggestions and permission for publishing
the work
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