Journal of Colloid and Interface Science 256, 237–248 (2002)
doi:10.1006/jcis.2002.8681
Surface Chemical Studies on Sphalerite and Galena Using Extracellular
Polysaccharides Isolated from Bacillus polymyxa
D. Santhiya, S. Subramanian,1 and K. A. Natarajan
Department of Metallurgy, Indian Institute of Science, Bangalore 560 012, India
Received September 12, 2001; accepted September 4, 2002
Adsorption, electrokinetic, microflotation, and flocculation stud-
ies have been carried out on sphalerite and galena minerals using ex-
tracellular polysaccharides (ECP) isolated from Bacillus polymyxa.
The adsorption density of ECP onto galena is found to be higher
than that onto sphalerite. The adsorption of ECP onto sphalerite
is found to increase from pH 3 to about pH 7, where a maximum
is attained, and thereafter continuously decreases. With respect to
galena, the adsorption density of ECP steadily increases with in-
creased pH. The addition of ECP correspondingly reduces the neg-
ative electrophoretic mobilities of sphalerite and galena in absolute
magnitude without shifting their isoelectric points. However, the
magnitude of the reduction in the electrophoretic mobility values
is found to be greater for galena compared to that for sphalerite.
Microflotation tests show that galena is depressed while sphalerite
is floated using ECP in the entire pH range investigated. Selec-
tive flotation tests on a synthetic mixture of galena and sphalerite
corroborate that sphalerite could be floated from galena at pH 9–
9.5 using ECP as a depressant for galena. Flocculation tests reveal
that in the pH range 9–11, sphalerite is dispersed and galena is
flocculated in the presence of ECP. Dissolution tests indicate re-
lease of the lattice metal ions from galena and sphalerite, while
co-precipitation tests confirm chemical interaction between lead or
zinc ions and ECP. Fourier transform infrared spectroscopic stud-
ies provide evidence in support of hydrogen bonding and chem-
ical interaction for the adsorption of ECP onto galena/sphalerite
surfaces. C 2002 Elsevier Science (USA)
Key Words: sphalerite; galena; extracellular polysaccharides;
Bacillus polymyxa; bioflotation and bioflocculation.
INTRODUCTION
The processing of complex sulfides containing base metals
such as copper, lead, and zinc continues to pose a challeng-
ing task. This is mainly due to the finer dissemination of the
metal values and their intimate association with the gangue
minerals, resulting in a complex mineralogy. Conventional tech-
niques of mineral processing do not yield adequate selectivity of
separation, leading to misplacement of values. In recent times,
1 To whom correspondence should be addressed. Fax: +91-80-3600472;
3600683. E-mail: ssmani@metalrg.iisc.ernet.in.
237
biomineral processing of such complex ores has gained atten-
tion. Mycobacterium phlei has been used to selectively separate
coal from pyrite and ash by flocculation and flotation (1–2).
This organism has also been reported to flocculate and float
hematite and apatite (3–5). The effectiveness of Bacillus sub-
tilis as a depressant for dolomite from apatite has been evalu-
ated by Zheng et al. (6). Natarajan and co-workers have carried
out beneficiation studies on bauxite and some iron ore miner-
als using Bacillus polymyxa and its metabolic products (7–9).
Thiobacillus ferrooxidans has been found to depress galena from
sphalerite (10), pyrite from chalcopyrite (11), and pyrite from
galena (12). Similarly, Bacillus polymyxa has been shown to
depress pyrite but not chalcopyrite (13, 14). The isolation and
characterization of a novel polysaccharide-producing Bacillus
polymyxa has been studied (15, 16). The utility of Thiobacillus
thiooxidans and Bacillus polymyxa in achieving the selective
separation of galena from sphalerite has been recently reported
by us in a series of papers (17–19).
In an ongoing research program, the interaction of Bacillus
polymyxa and its metabolic products with various sulfide and ox-
ide minerals is being studied. The present investigation is aimed
at gaining a better insight into the surface chemical changes that
are brought about due to mineral–microbe interactions. In this
context, it becomes pertinent to evaluate the contributions of the
components of the metabolic products of Bacillus polymyxa in
altering the surface properties of the minerals.
In the present study, the extracellular polysaccharides (ECP)
produced by Bacillus polymyxa have been isolated, purified,
and interacted with galena and sphalerite. The surface chemical
changes have been examined by adsorption, electrokinetic, flota-
tion, and flocculation experiments. The bulk solution interac-
tions have been ascertained by dissolution and co-precipitation
tests.
EXPERIMENTAL
Materials
Mineral samples of sphalerite and galena were obtained from
Gregory, Bottley, and Lloyd, U.K. Mineralogical studies as well
as X-ray powder diffraction data indicated that the samples
were of high purity. The above samples were dry ground using
0021-9797/02 $35.00

C 2002 Elsevier Science (USA)
All rights reserved.
238 SANTHIYA, SUBRAMANIAN, AND NATARAJAN
a porcelain ball mill and then sieved through 105-, 63-, and
37-µm BSS sieves. The −37 µm size fraction was ground further
in a Retsch mortar grinder. The mean (d50 ) particle size of this
fraction was found to be ≈5 µm using a Malvern Mastersizer-
Model 3000 particle size analyzer. This fraction was used for the
adsorption, electrokinetic, flocculation, and dissolution studies.
For the microflotation experiments, the −105 +63 µm fraction
of galena and sphalerite was used. The BET nitrogen-specific
surface areas of the ≈5-µm fraction of sphalerite and galena
were respectively found to be 1.43 and 0.99 m2 /g.
The strain of Bacillus polymyxa (NCIM 2539) used in this
study was obtained from the National Collection of Industrial
Microorganisms (NCIM), National Chemical Laboratory, Pune.
The bacteria were subcultured in the laboratory using the mod-
ified Bromfield medium as per the procedure previously descri-
bed (20).
The starch sample used in this study for the calibration of the
extracellular polysaccharide fraction was obtained from BDH
Limited, Poole, England.
Potassium nitrate was used to maintain the ionic strength,
while nitric acid and potassium hydroxide were used as pH
modifiers. All the reagents used in this study were of analytical
grade. Deionized double distilled water with a final conductivity
of <1.5 µmho was used for all the tests.
Methods
Separation of Metabolite from the Bacterial Culture
The bacterium Bacillus polymyxa was grown by adding 10%
v/v of an active inoculum to the Bromfield medium and incu-
bated at 30◦ C on a Remi rotary shaker at 240 rpm for 48 h. The
growth conditions and the composition of the medium have been
kept fixed in all experiments. Precautions were taken to prevent
contamination by undesirable microorganisms by maintaining
aseptic conditions. This fully grown culture was centrifuged at
10,000 rpm for 10 min at 10◦ C to separate the cells from the ex-
tracellular materials. The supernatant (metabolite) obtained was
filtered through a sterile Millipore membrane filter paper of pore
size 0.2-µm using a Tarsons membrane filter holder and used
for the isolation of the extracellular polysaccharides (ECP).
Isolation and Characterization of Extracellular
Polysaccharides (ECP) from Metabolite
The polysaccharide component of the metabolite was isolated
as an ethanol precipitate from the cell-free supernatant solution.
The precipitate was separated by centrifugation and dissolved
in sterile double distilled water. The ethanol precipitation was
repeated two or three times for further purification of the ECP.
The solidified portion was weighed and stored in a refrigerator.
The ECP solution was prepared fresh each day by dissolving
a known weight in cold water. The components of the purified
ECP were qualitatively analyzed for α-amino acids and aro-
matic amino acids by the ninhydrin reaction and the xanthopro-
teic reaction respectively, following the procedures described by
Plummer (21). Furthermore, the amounts of total sugar, neutral
sugar, and uronic acid present in the ECP were also quantitatively
estimated by the phenol–sulfuric acid reaction, the anthrone re-
action, and the carbazole–sulfate reaction, respectively (22). The
molecular weight of the purified ECP of Bacillus polymyxa was
determined to be 17,000 by high performance liquid chromatog-
raphy (HPLC), using dextran as a standard.
Adsorption Studies
For the adsorption tests, 1 g of the mineral powder of mean
(d50 ) size ≈5 µm was taken and pulped to 50 ml. This was
followed by the addition of ECP of desired concentration and
preadjusted pH equivalent to that of the suspension pH. The ionic
strength was kept at 10−3 M using KNO3 and the total volume
was made up to 100 ml. The suspension was agitated for 4 h
at 200 rpm in a Remi orbital shaking incubator at 27◦ C ± 2◦ C.
Subsequently, the suspension was centrifuged at 5000 rpm using
a Sorvall RC-5B refrigerated high-speed centrifuge for 10 min
and filtered through a Whatman 42 filter paper. The clear super-
natant solution was analyzed for the residual ECP concentration
using a Shimadzu UV-260 spectrometer as per the procedure
described by Dubois et al. (23).
Electrokinetic Measurements
Electrophoretic mobilities of sphalerite as well as galena were
determined in the presence and absence of ECP using a Malvern
3000 model Zetasizer. A known concentration of the ECP so-
lution at a desired pH was added slowly to the suspension con-
taining 10 mg of the solids under agitated conditions at the same
pH and made up to 100 ml. In all these experiments, the pH of
the suspension was adjusted to a desired value using AR grade
nitric acid or potassium hydroxide and the ionic strength was
maintained at 10−3 M KNO3 . The suspension was allowed to
equilibrate for 1 h and ultrasonicated for 30 s before measuring
its electrophoretic mobility. The effects of pH and ECP concen-
tration on the electrophoretic mobilities of the minerals were
determined.
Microflotation Studies
Microflotation tests were carried out using a modified
Hallimond tube (24). Potassium isopropyl xanthate (10−4 M),
was used as a collector for both sphalerite and galena, while
10−6 M CuSO4 was used as an activator for sphalerite. For the
flotation tests, 1 g of mineral sample of size −105 +63 µm
was pulped to a final volume of 200 ml with double-distilled
water after conditioning with the chosen reagents at a desired
pH for 15 min using a magnetic stirrer. The sample was then
transferred to the Hallimond tube and nitrogen gas was passed
at 40 ml per minute. After flotation for 3 min, the concentrate and
the tailing fractions were separately filtered, dried, and weighed.
The recoveries are expressed on a weight basis. In experiments
where ECP was used as a depressant, the sample was further
conditioned with it for 15 min at a given pH prior to flotation.
 SURFACE CHEMICAL STUDIES ON SPHALERITE AND GALENA USING ECP 239

Differential Flotation Tests plasma emission spectrometer and the residual ECP concentra-
tion by adopting the method of Dubois et al. (23). Additionally,
In these experiments, 0.5 g each of galena and sphalerite (1 : 1)
control experiments were also carried out by agitating 100 ml
mixture, of particle size −105 +63 µm was interacted with ECP
of solution of the desired metal ions or the ECP of chosen ini-
in the pH range of 9–9.5 for 15 min prior to flotation. The same
tial concentration for 1 h as a function of pH and the residual
procedure as adopted for the flotation of the individual minerals
concentrations were analyzed.
was followed. The lead and zinc contents in the concentrate and
tailing fractions were separately analysed using a Jobin Yvon
JY 24 inductively coupled plasma emission spectrometer. FTIR Spectroscopic Studies
Fourier transform infrared spectra of ECP were recorded at
Flocculation Tests different pH values using a Perkin–Elmer Model FT Spectrum
The flocculation test procedure was standardized as follows: 1000 instrument, operating in the range 4000-400 cm−1 . In ad-
0.5 g of galena or sphalerite of ≈5 µm size was suspended in dition to this, difference FTIR spectra of the mineral samples
a volume of 50 ml and adjusted to a desired pH value in the after interaction with ECP at different pH values, namely ≈3.5,
range of 3–11 in a 100-ml measuring jar. This was followed by ≈6.5, and ≈9.5, were also recorded. Approximately 2 mg of
the addition of 50 ppm concentration of ECP at a preadjusted the desired sample was thoroughly mixed with 200 mg of spec-
pH, equivalent to that of the mineral suspension pH, such that troscopic grade KBr and pressed into pellets for recording the
the total volume was 100 ml. The measuring jar was gently spectra.
tumbled 10 times and allowed to stand for 2 min. Exactly 90 ml
of the supernatant was siphoned out into a clean 100-ml beaker
RESULTS AND DISCUSSION
and filtered through a Whatman 42 filter paper and the residue
was dried and weighed. The percentage weights of the solids The results of the adsorption, electrokinetic, flotation, floccu-
dispersed as well as those settled were determined. lation, dissolution, and co-precipitation experiments carried out
with the isolated and partially purified extracellular polysaccha-
Selective Flocculation Tests
rides (ECP) are discussed.
In these experiments, 0.25 g each of galena and sphalerite
(1 : 1) of particle size ≈5 µm was initially mixed and interacted Chemical Analysis of ECP
with 50 ppm of ECP at pH 9–9.5 for 2 min in a 100-ml mea-
The results of the chemical analysis of ECP are summarized in
suring jar. The same procedure as described for the flocculation
Table 1. Additionally, the ninhydrin and xanthoproteic tests did
of the individual minerals was adopted. The lead and zinc con-
not show any color change, indicating the absence of α-amino
tents in the dispersed and flocculated portions were analyzed
acids and aromatic amino acids.
using a Jobin Yvon JY24 inductively coupled plasma emission
spectrometer.
Adsorption Studies
Dissolution Studies
Kinetics
Sphalerite/galena, 1 g, was dispersed in 100 ml of distilled
The adsorption density of ECP onto sphalerite and galena as
water of desired pH in the range of 3–11 and agitated in a Remi
a function of time is depicted in Fig. 1. The adsorption density
orbital shaking incubator at 200 rpm and at 27◦ C ± 2◦ C for 24 h,
steeply increases with time up to about 2 h and thereafter attains a
in the absence and presence of 100 ppm of ECP. This was fol-
saturation value in the case of galena. With respect to sphalerite,
lowed by centrifugation and filtration of the suspension. The
the adsorption density follows a similar trend reaching a plateau
dissolved lead/zinc concentration in the clear supernatant solu-
region after 2 h, though the magnitude of the adsorption density
tion was analysed using a Jobin Yvon JY 24 inductively coupled
is significantly lower relative to that onto galena. In all further
plasma emission spectrometer.
adsorption experiments, the equilibration time was maintained
Co-precipitation Studies at 4 h.

In these studies, a known amount of Pb(NO3 )2 /Zn(NO3 )2 so-

lution was mixed with ECP solution in a such a way that the
TABLE 1
final concentration of lead or zinc was 50 ppm and that of the
Analysis of the Components of the ECP
polysaccharide was 100 ppm, in 100 ml solution. The pH was
adjusted to a desired value in the range of 3–11 by adding either Components % (w/w)
nitric acid or potassium hydroxide solution. After agitation for
1 h in a Remi orbital shaker, the solution was centrifuged and fil- Total sugar 98.58
tered. The clear supernatant solution was then analyzed for lead Neutral sugar 80.00
Uronic acid 16.51
or zinc content using a Jobin Yvon JY24 inductively coupled
240 SANTHIYA, SUBRAMANIAN, AND NATARAJAN

respectively (25, 26). From Fig. 2, it is readily evident that the

adsorption density of ECP onto galena is about 6 to 8 times
higher than the maximum observed on sphalerite. A higher ad-
sorption of polysaccharides onto galena vis-à-vis sphalerite was
also observed earlier (25, 26).

Isotherms
The adsorption isotherms of ECP onto sphalerite and galena
are shown in Figs. 3a and 3b respectively. In the case of spha-
lerite, the adsorption density is very low at ≈pH 11 (Fig. 3a). At
≈pH 3.5, the adsorption density steadily increases with increase
in concentration up to 200 ppm and thereafter sharply increases.
At ≈pH 7, there is a steep increase in the adsorption density up
to about 75 ppm equilibrium concentration followed by a slight
decrease in the slope of the isotherm up to about 220 ppm. In
the case of galena, the adsorption density steeply increases with
increase in concentration up to about 50 ppm and thereafter a
slight decrease in the slope is observed at all the pH values
FIG. 1. Adsorption density of ECP onto sphalerite and galena as a function
of time.

Effect of pH
The effect of pH on the adsorption of ECP onto galena and
sphalerite is portrayed in Fig. 2. The adsorption density is found
to increase from pH 3 to about pH 7, when a maximum is at-
tained and thereafter continuously decreases up to pH 11 in
the case of sphalerite. On the contrary, the adsorption density
steadily increases from pH 3 to pH 11 for galena and does not
exhibit a distinct adsorption maximum. It is noteworthy that de-
tailed investigations of the adsorption of polysaccharides such as
dextrin and guar gum onto galena and sphalerite have revealed
adsorption maxima at pH 7.5 and 11.5 for sphalerite and galena

FIG. 2. Adsorption density of ECP onto sphalerite and galena as a function FIG. 3. Adsorption isotherms of ECP onto (a) sphalerite and (b) galena at
of pH. different pH values.
 SURFACE CHEMICAL STUDIES ON SPHALERITE AND GALENA USING ECP 241

The results of electrophoretic mobility measurements on

galena as a function of pH are portrayed in Fig. 4b. The isoelec-
tric point of galena is found to lie at pH 2.1. Consequent to the
addition of ECP, the negative electrophoretic mobility is reduced
in absolute magnitude in proportion to the concentration of ECP
added. Here, again, there is no change in the isoelectric point of
galena after addition of ECP. A careful examination of Figs. 4a
and 4b indicates that the magnitude of the electrophoretic mo-
bility is diminished to a greater extent after the addition of ECP
in the case of galena vis-à-vis that of sphalerite. This could be
attributed to the higher adsorption density of ECP onto galena
compared to that onto sphalerite (Fig. 2).
It is apparent that since the electrophoretic mobility is reduced
in absolute magnitude under all pH conditions, the primary effect
of the ECP seems to be to shift the slipping plane further away
from the interface. These results suggest that some conforma-
tional rearrangements of the polymer take place with increasing
extension of the looping chain, when the ECP concentration is
further increased. Similar trends have been observed for galena
and sphalerite after the interaction of varying concentrations of
natural polysaccharides such as guar gum and dextrin (25, 26).

Microflotation Tests
The flotation recoveries of sphalerite and galena as a function
of pH under different conditions are shown in Fig. 5. In the case
of galena and sphalerite, over 90% floatability is observed in the
pH range 4.5 to 8.5 in the presence of collector (PIPX)/activator
(CuSO4 ). Beyond pH 9, slight decreases in flotation recovery are
observed. It is noteworthy that after the addition of ECP, galena
is significantly depressed and its flotation recovery drops below
10% in the pH range 6–11. On the contrary, the floatability of
sphalerite is only marginally affected in the pH range 5.5–7.5,
FIG. 4. Electrophoretic mobilities of (a) sphalerite and (b) galena as a func-
while over 90% recovery is observed in the pH range 8–11. In
tion of pH in the absence and presence of different concentrations of ECP.

studied (Fig. 3b). On a comparative basis, the adsorption density

of ECP onto galena is significantly higher than that onto spha-
lerite. The isotherms depicted in Figs. 3a and 3b resemble the
S1 type of the Giles classification (27). Further, the pH trend
observed for the isotherms for both the minerals (Figs. 3a and
3b) corroborates that depicted in Fig. 2.

Electrokinetic Studies
Figure 4a shows the electrophoretic mobility of sphalerite as
a function of pH both in the absence and in the presence of dif-
ferent concentrations of ECP. The isoelectric point of sphalerite
is located around pH 2.2 and it becomes increasingly negatively
charged with pH increase up to pH 11. The electrophoretic mo-
bility of sphalerite becomes proportionally less negative with
increase in concentration of ECP from 1 to 100 ppm in the en-
tire pH range investigated. However, there is no apparent change
in the isoelectric point of sphalerite consequent to interaction FIG. 5. Effect of pH on the flotation recovery of sphalerite and galena before
with ECP. and after interaction with ECP.
242 SANTHIYA, SUBRAMANIAN, AND NATARAJAN

both cases, the change in the sequence of addition of the collector TABLE 2
and ECP does not alter the flotation recoveries. The decrease in Selective Flotation Test Results on Sphalerite–Galena
the flotation recovery of sphalerite in the pH range 5.5 to 7.5 may System Using ECP
be attributed to the higher adsorption of ECP in this pH range
PbS (%) ZnS (%)
(Fig. 2). It has been well documented that the interaction of Experimental conditions
polysaccharides with the hydroxylated sulfide mineral surfaces at pH 9–9.5; ECP (50 ppm) Float Sink Float Sink S.I.
takes place through a chemical interaction process (25, 28–31). It
Flotation in the presence of 10−4 M PIPX 98.6 1.2 94.1 2.0 0.6
is also pertinent (32) that zinc hydroxide decomposes to soluble and 10−6 M CuSO4 (without ECP) 98.2 1.4 96.3 2.4
zincate ions at highly alkaline pH values, while lead hydroxide
Flotation after interaction with 5.1 94.1 6.7 92.4 1.2
is stable up to ≈pH 12. Further, the significant differences in the ECP (No collector/activator) 4.9 94.8 6.2 93.1
adsorbabilities of ECP onto galena and sphalerite (Fig. 2) result Flotation in the presence of 10−4 M PIPX 2.4 96.3 93.8 4.5 31.8
in the pronounced depression of galena and good floatability and 10−6 M CuSO4 after interaction 1.9 97.2 94.7 3.9
of sphalerite, particularly in the pH range 9–11. These findings with ECP
are in good agreement with those observed earlier for galena and
sphalerite in the presence of polysaccharides such as dextrin and
guar gum (25, 26).
Figure 6 depicts the flotation recoveries of galena and spha- Differential Flotation Tests
lerite as functions of the concentration of ECP. These flotation
tests were carried out at pH 9–9.5 and corroborate the results The results of differential flotation tests carried out on a
shown in Fig. 5. It is evident that over 90% recovery of spha- (1 : 1) synthetic mixture of galena and sphalerite at pH 9–9.5
lerite is obtained irrespective of the concentration of ECP. On in the absence and presence of 50 ppm ECP are summarized in
the other hand, the flotation recovery of galena decreases from Table 2. The selectivity index was calculated using Gaudin’s for-
about 30% with 5 ppm ECP to below 5% after the addition of mula (33).
50 ppm ECP and remains at that value up to 150 ppm ECP ad- From the data presented in the table the following inferences
dition. Thus, at and beyond 50 ppm ECP concentration, galena can be drawn:
is almost completely depressed while sphalerite is floated in the 1. In the presence of collector and activator without the ad-
pH range investigated. It is also apparent that the change in the dition of ECP, over 98% galena and about 95% sphalerite are
sequence of addition of collector/activator and ECP does not floated. As can be expected, no selectivity is obtained.
affect the flotation recoveries. 2. Flotation tests carried out with ECP alone in the absence
Based on the results of these tests carried out on individual of collector and activator, result in the depression of both galena
minerals it becomes of interest to assess the feasibility of se- and sphalerite. In this case also hardly any selectivity is observed.
lective separation of galena from sphalerite from a synthetic 3. Flotation studies carried out at pH 9–9.5 using collector/
mixture of the two. activator and ECP highlight that over 96% of galena is depressed
while about 94% of sphalerite is floated. These results indicate
that good separation of galena from sphalerite can be achieved
with a high selectivity index (S.I. = 31.8).

FIG. 6. Effect of ECP concentration on the flotation recovery of sphalerite
and galena at pH 9–9.5.
Flocculation Tests
Settling tests were carried out on galena and sphalerite sus-
pensions in the absence and presence of 50 ppm ECP as a func-
tion of pH (Fig. 7). In these tests, the suspension was allowed
to settle for 2 min prior to the determination of the percent-
age of solids settled. Without the addition of ECP, the percent-
age galena settled increases from about 30% at pH 3 to about
57% at pH 11. The amount of galena settled significantly in-
creases as a function of pH after the addition of ECP. For ex-
ample, 85% of galena is settled at pH 3 and almost 98% floc-
culation is observed at pH 10. With respect to sphalerite, in
the absence of ECP the percentage of solids settled decreases
from about 35% at pH 3 to about 10% at pH 11. In the pres-
ence of ECP, the amount of sphalerite settled is close to about
35% in the pH range 3–7 and thereafter steadily decreases to
about 10% at pH 10.5. It is worthy of observation that in the
 SURFACE CHEMICAL STUDIES ON SPHALERITE AND GALENA USING ECP 243

Bulk Solution Studies

The results of the adsorption, electrokinetic, flotation, and
flocculation tests reveal a higher affinity of ECP toward galena
compared to that onto sphalerite. In order to gain a better un-
derstanding of the mechanisms of ECP adsorption onto galena
and sphalerite, the direct interaction of the corresponding metal
ions, namely lead and zinc, with ECP in the bulk solution was
assessed. In this context, dissolution and co-precipitation studies
have been carried out.

Dissolution Tests
The dissolution characteristics of sphalerite and galena as a
function of pH in the absence and presence of 100 ppm ECP
are portrayed in Figs. 8a and 8b, respectively. In the absence
of ECP, the amount of dissolved zinc species continuously de-
creases from about 35 ppm at pH 3 to about 3 ppm at pH 6 and
more or less remains at that value up to pH 11 (Fig. 8a). After
FIG. 7. Effect of pH on the settling of sphalerite and galena in the absence
and presence of ECP.

pH range 9–10 galena is almost completely flocculated, while

good dispersion of sphalerite takes place. The translation of
these tests carried out on individual suspensions of galena and
sphalerite to a synthetic mixture of the two minerals was next
attempted.

Selective Flocculation Tests

The results of the selective flocculation tests carried out at pH
9–9.5 on a 1 : 1 synthetic mixture of galena and sphalerite are
given in Table 3. In the absence of ECP, about 70% of sphalerite is
dispersed while 72% of galena is flocculated. After the addition
of ECP, the amount of sphalerite dispersed is only marginally
altered to about 75%, while the amount of galena flocculated
is significantly improved to about 95%. A careful examination
of the results indicates that about 25% of sphalerite is floccu-
lated even in the presence of ECP, indicating partial selectivity
of separation. On a comparative basis, the results of the selec-
tive flotation process (Table 2) attest to better selectivity than
achieved in the selective flocculation tests (Table 3).

TABLE 3
Selective Flocculation Test Results on Sphalerite–Galena
System Using ECP

ZnS (%) PbS (%)

Experimental conditions Dispersed Flocculated Dispersed Flocculated

Blank at pH 9–9.5 70.5 27.8 27.0 71.7

70.3 29.5 27.0 72.3
In the presence of ECP 75.3 23.7 5.6 93.7
FIG. 8. Amount of zinc and lead species dissolved from (a) sphalerite and
(50 ppm) at pH 9–9.5 72.6 26.8 4.2 95.2
(b) galena respectively in the absence and presence of ECP a function of pH.
244 SANTHIYA, SUBRAMANIAN, AND NATARAJAN

the addition of ECP, the amount of dissolved zinc in solution

is relatively low when compared to that observed for sphalerite
alone, especially in the pH range 3–5. Beyond pH 6 there is not
much of a difference in the dissolved zinc content, either in the
absence or in the presence of ECP. These results are sugges-
tive of chemical interaction between the zinc species and ECP,
particularly in the pH range 3–5.
Figure 8b shows the amount of dissolved lead species as a
function of pH for galena both in the absence and in the presence
of ECP. A trend similar to that observed for sphalerite is obtained
in this case also. However, the amount of lead species dissolved
is almost 4 to 5 times that of the zinc species dissolved. For
example, at pH 3, over 160 ppm lead is dissolved compared to
35 ppm of zinc (Figs. 8a and 8b). The lesser amount of lead
dissolved in the presence of ECP further testifies to its chemical
interaction with ECP.

Co-precipitation Tests
Figure 9a depicts the residual concentrations of zinc and ECP
as functions of pH. It must be noted that the initial concen-
trations of zinc and ECP were 50 ppm and 100 ppm respec-
tively. It is interesting to observe from Fig. 9a that the residual
concentration of zinc in the absence of ECP steeply decreases
from about 50 ppm at pH 3 to about 1 ppm at pH 6, remains
at that value up to pH 7, and thereafter steadily increases to
about 44 ppm in the pH range 10–11. The very low concen-
tration of residual zinc in the pH range 6–7 may be attributed
to precipitation of the hydroxide, while the increase in the pH
range 8–11 may be attributed to the formation of soluble zincate
species. It has been reported that zinc hydrolyzes only spar-
ingly in acidic media to produce Zn(OH)+ and Zn2 OH3+ before
precipitation commences in the neutral region. In the basic me-
dia, Zn(OH)2− 2−
4 and Zn2 (OH)6 are presumably formed (32).
The increase in zinc concentration in the high alkaline range
can be attributed to the redissolution of zinc hydroxide or ox-
ides by the formation of anionic complex ions, namely zincates.
Consequent to the addition of ECP, the residual zinc concentra-
tion is marginally decreased in the entire pH range investigated
when compared to the trend observed in the case of zinc nitrate
alone. These results are in good agreement with those observed
in Fig. 8a. The ECP concentration remains unaltered in the en-
tire pH range studied in the absence of zinc nitrate (Fig. 9a).
However, when zinc nitrate is added, the residual ECP concen- FIG. 9. Effect of pH on the residual concentrations of ECP and (a) zinc and
tration markedly decreases and reaches a minimum of about (b) lead species.
65 ppm in the pH range 6–7 and thereafer again increases in
the pH range 8–11. Strong interaction between ECP and zinc the absence of ECP, the residual lead concentration decreases
species is clearly borne out, particularly in the pH range 5–8. from about 50 ppm at pH 4 to about 10 ppm at pH 6.5,
A close parallelism thus exists between the adsorption maxi- while it is almost negligible in the pH range 7–9.5 and there-
mum of ECP onto sphalerite in the pH range 6–8 (Fig. 2) and after steeply increases to about 45 ppm at pH 11. The forma-
strong interaction between zinc species and ECP at an identi- tion of mononuclear (PbOH+ ) and polynuclear (Pb4 (OH)4+ 4 ,
−
cal pH range as revealed by the co-precipitation experiments Pb6 (OH)4+8 , Pb(OH) 3 , and Pb(OH) 2−
6 ) complexes of lead has
(Fig. 9a). been reported (32), depending on the pH. In the presence of
The results of the co-precipitation tests carried out with lead ECP, the residual lead concentration is relatively lower in the
nitrate and ECP as a function of pH are portrayed in Fig. 9b. In pH range 3–6 when compared to the trend observed with lead
 SURFACE CHEMICAL STUDIES ON SPHALERITE AND GALENA USING ECP
nitrate alone. The lead concentration is negligible in the pH range
7–10 and increases to about 12 ppm around pH 11. These results
closely follow the trend observed in Fig. 8b. When lead ions are
interacted with ECP, the residual ECP concentration is signifi-
cantly reduced from about 90 ppm at pH 3.5 to about 20 ppm in
the pH range 8–11. The strong interaction between lead species
and ECP in this pH range is clearly evident. It may be recalled
that the adsorption density of ECP onto galena was also higher
in this pH range (Fig. 2). As observed in Fig. 9a, the ECP con-
centration remains unaltered at 98 ppm in the entire pH range
investigated in the absence of lead nitrate. Similar observations
have been reported earlier for the interaction of polysaccharides
with lead and zinc species (25, 26).
FTIR Spectroscopic Studies
Sphalerite–ECP System at pH 6.8–7.2
Figure 10a shows the FTIR spectrum of ECP before interac-
tion while the difference spectrum of ECP after interaction with
sphalerite at pH 6.8–7.2 is shown in Fig. 10b. The broad absorp-
tion band centered around 3274 cm−1 due to –O–H stretching
vibrations of the unadsorbed ECP (Fig. 10a) appears at a lower
FIG. 10. (a) FTIR spectrum of ECP and (b) difference FTIR spectrum of
ECP after interaction with sphalerite at pH 6.8–7.2.
245
wavenumber, viz. 3254 cm−1 after adsorption (Fig. 10b). This
could be attributed to hydrogen bonding between the –O–H of
ECP and the hydroxylated sphalerite surface. The weak shoul-
der observed at ≈2885 cm−1 due to –C–H stretching of the ECP
is found to be unaltered after adsorption. The medium band of
the ECP at 1673 cm−1 due to asymmetric COO− stretching and
ring stretching of pyranose is shifted to lower wavelength and
appears at 1642 cm−1 after interaction with the sphalerite sam-
ple indicating the existence of hydrogen bonding. The band at
1428 cm−1 of the adsorbed ECP can be assigned to symmetrical
COO− stretching (Fig. 10b) and appears slightly shifted from
that of ECP at about 1440 cm−1 , due to hydrogen bonding. The
broad band at 1109 cm−1 due to –C–O stretching modes of the
unadsorbed ECP is split into a doublet and appears at 1113 cm−1
and 1065 cm−1 after adsorption. This reveals the existence of
chemical as well as hydrogen bonding between the –C–O group
of ECP and the hydroxylated sphalerite surface. The weak shoul-
der at 986 cm−1 in the case of free ECP due to –C–H bending
appears at a slightly higher wavenumber, viz. 1001 cm−1 , after
adsorption. The absorption at 927 cm−1 due to antisymmetrical
ring vibration appears slightly altered at 932 cm−1 in the differ-
ence spectrum of ECP. The weak shoulder at 823 cm−1 due to
–C–H deformation in the case of ECP is increased in intensity
and appears at a slightly higher wavenumber at 828 cm−1 in the
adsorbed state. The peak at ≈617 cm−1 due to –O–H out-of-
plane vibration is found to be more or less unaltered after ECP
adsorption onto sphalerite.
Sphalerite/Galena–ECP System at pH 9–9.5
Figure 11a depicts the FTIR spectrum of ECP at pH 9–9.5,
while the difference spectrum of ECP after interaction with spha-
lerite at pH 9–9.5 is shown in Fig. 11b. The difference spectrum
reveals that most of the characteristic peaks of the ECP depicted
in Fig. 11a are not conspicuous. This could be attributed to the
lower adsorption of the ECP onto sphalerite at pH 9–9.5. The
weak broad band at 3250 cm−1 is assignable to O–H stretching
of the adsorbed ECP. The asymmetric and symmetric stretching
vibrations of the –COO− group are significantly reduced in in-
tensity and appear as very weak bands at 1612 and 1387 cm−1
respectively. The sharp peak assignable to –C–O stretching of
the free ECP at 1126 cm−1 is appreciably shifted to a lower
wavenumber, namely 1114 cm−1 , after adsorption due to hydro-
gen bonding between ECP and the sphalerite surface. The O–H
out-of-plane vibration of the unadsorbed ECP at ≈618 cm−1 is
found to be almost unaltered after adsorption.
The difference FTIR spectrum of ECP after interaction with
galena at pH 9–9.5 is portrayed in Fig. 11c. The broad band
centered around 3385 cm−1 due to the –O–H group in the case
of ECP is shifted to a lower wavenumber, viz. 3371 cm−1 , af-
ter interaction with galena, consequent to hydrogen bonding.
The two weak peaks at 2935 and 2885 cm−1 originating due to
–C–H stretching of the –CH2 group of ECP appear at 2935 and
2875 cm−1 in the case of adsorbed ECP (Fig. 11c). The band
at 1649 cm−1 due to asymmetric –COO− stretching is shifted
246 SANTHIYA, SUBRAMANIAN, AND NATARAJAN

tense peak due to –O–H out-of-plane vibration of the ECP at

617 cm−1 is found to be further intensified and appears more or
less unaltered.

Galena–ECP System at pH 3–3.5

The FTIR spectrum of ECP before interaction and the dif-
ference spectrum of ECP after interaction with galena, both at
pH 3.0–3.5 are depicted in Figs. 12a and 12b, respectively. The
broad band centered around 3390 cm−1 due to –O–H stretching
of the free ECP is shifted to 3373 cm−1 after adsorption due to
hydrogen bonding. The –C–H stretching vibrations of the ECP,
appearing as weak shoulders at 2977 and 2933 cm−1 , are shifted
to lower wavenumbers, namely, 2959 cm−1 and 2912 cm−1 , af-
ter interaction with the mineral. This attests to the existence of
hydrogen bonding between –C–H of ECP and the hydroxylated
galena surface. The band due to –C==O stretching of the –COOH
group of the unadsorbed ECP at 1641 cm−1 is found to be shifted
to a slightly higher wavenumber, namely at 1647 cm−1 , after
adsorption onto galena, due to chemical interaction. The com-
bination band at 1430 cm−1 due to –C–O stretching and –O–H
deformation of the –COOH group of ECP is unaltered after ad-
sorption. The vibrational frequency for –O–H stretching of the

FIG. 11. (a) FTIR spectrum of ECP, (b) difference FTIR spectrum of ECP
after interaction with sphalerite, and (c) difference FTIR spectrum of ECP after
interaction with galena at pH 9–9.5.

to a lower wavenumber, namely 1634 cm−1 , after adsorption

due to hydrogen bonding. The weak shoulder at 1406 cm−1 cor-
responding to –COO− symmetrical stretching of ECP before
adsorption is slightly intensified and shifted to 1411 cm−1 after
adsorption, suggestive of chemical interaction. The sharp peak
at 1126 cm−1 of the free ECP, assigned to –C–O stretching, is
observed as an intense peak at 1117 cm−1 after adsorption. The
slight reduction in the wavenumber indicates the presence of
hydrogen bonding. The weak shoulder due to –C–H bending at
991 cm−1 of the free ECP is slightly shifted to 986 cm−1 after
adsorption. The weak shoulder at 932 cm−1 due to asymmetric
ring stretching is marginally shifted to 922 cm−1 in the adsorbed
sample. The weak shoulder at 843 cm−1 observed due to –C–H FIG. 12. (a) FTIR spectrum of ECP and (b) difference FTIR spectrum of
deformation of the polymer is found to be unaltered. The in- ECP after interaction with galena at pH 3–3.5.
 SURFACE CHEMICAL STUDIES ON SPHALERITE AND GALENA USING ECP 247

–COOH group of ECP at 1337 cm−1 is intensified and appears at of polysaccharides with various sulfides and oxides has been
1347 cm−1 after adsorption, as a result of chemical interaction. extensively studied by Laskowski and co-workers and a chemi-
Two weak peaks at 1130 cm−1 and 1059 cm−1 due to –C–O cal complexation mechanism has been proposed (29–31). More
stretching of the –COOH group and primary alcoholic group, recently, an acid–base interaction model has been suggested by
respectively, appear at 1125 and 1061 cm−1 after adsorption. them (28). These mechanisms have been corroborated by the
The weak shoulder at 1001 cm−1 due to –C–H bending of the work of Rath and Subramanian (25, 26, 37) for the interaction
ECP appears at a slightly lower wavenumber, viz., 996 cm−1 , of polysaccharides such as dextrin and guar gum with several
after interaction with galena. The weak shoulder due to asym- sulfides.
metrical ring stretching at 937 cm−1 is slightly shifted to a lower In line with the proposed mechanisms, the hydroxyl groups in
wavenumber, viz., 932 cm−1 , in the case of the adsorbed sam- polysaccharides interact with the mineral surface metal hydrox-
ple. The weak peak at 828 cm−1 in the case of the ECP assigned ide by both hydrogen bonding and chemical forces. According
to –C–H deformation is shifted to 838 cm−1 after interaction to the acid–base interaction model the hydroxylated mineral sur-
with galena. The sharp peak at 617 cm−1 due to the –O–H out- face would behave as a Brønsted base, with the hydroxyl groups
of-plane vibration remains unaltered in the adsorbed spectrum. in the polysaccharides behaving as a Brønsted acid (28). It can be
The spectral assignments correlate well with those reported ear- expected that stronger the basicity, the greater will be the interac-
lier for other polysaccharides (34–37). tion with the polysaccharides. It is thus logical to expect that lead
hydroxide, being strongly basic, will have a higher affinity for
Interaction Mechanisms ECP compared to hydroxylated sphalerite, which is amphoteric.
The basicity of the surface hydroxyl groups will be dependent on
From the results of the adsorption, flotation, flocculation, and
the valence states, ionic radii, and coordination numbers of the
co-precipitation experiments carried out on sphalerite and galena
lead and zinc ions on the corresponding mineral surfaces. For
using ECP the following facts emerge:
equivalent valence states and coordination numbers, ionic radii
1. The adsorption density of ECP onto galena is higher than of zinc are less than those of lead (38). Consequently, the surface
that onto sphalerite. Additionally, the amount of ECP adsorbed hydroxide groups on galena exhibit more basicity, resulting in
onto galena continuously increases with increase of pH. How- stronger interaction with ECP. This facilitates selective depres-
ever, in the case of sphalerite an adsorption maximum is ob- sion and flocculation of galena from sphalerite, especially in
served around pH 7. the alkaline pH range. It is understandable that the carboxylate
2. Flotation and flocculation tests reveal depression of galena ions will be relatively much fewer than the hydroxyl groups. A
and dispersion of sphalerite respectively. schematic representation of hydrogen bonding and chemical in-
3. Co-precipitation tests confirm strong interaction between teraction forces between the hydroxylated mineral surface and
Zn species and ECP at around pH 7, while in the case of Pb ECP is depicted in Fig. 13.
species and ECP significant interaction is observed in the pH
range 7–11. On a comparative basis, the interaction between
lead species and ECP is significantly higher, as attested to by
the very low residual ECP concentration (<20 ppm).
4. It is noteworthy that the pH of maximum adsorption of
ECP onto sphalerite coincides with the pH of maximum co-
precipitation for the zinc–ECP system. Similarly, close paral-
lelism exists between the pH of maximum adsorption and sig-
nificant co-precipitation in the case of the lead–ECP system,
although a distinct adsorption maximum is not observed in this
case.
5. The FTIR spectral results indicate the presence of func-
tional groups such as –OH, –CH, –C–OH, and –CH2 groups.
Additionally, the presence of –COO− groups arising from uronic
acid is also observed (34). The presence of uronic acid has also
been independently confirmed (Table 1).
It is well known that sulfide minerals get hydroxylated as
a function of pH. In this context, it is pertinent to recall that
the solubility product of lead hydroxide is over three orders of
magnitude less than that of zinc hydroxide (38). Further, zinc
hydroxide is amphoteric while lead hydroxide is highly basic
(39). Thus in the alkaline pH range, zinc hydroxide decomposes FIG. 13. Schematic representation of hydrogen bonding and chemical in-
to ZnO2− 2 ions while lead hydroxide is stable. The interaction teraction forces between the hydroxylated mineral surface and ECP.
248 SANTHIYA, SUBRAMANIAN, AND NATARAJAN
CONCLUSIONS
Based on the results of the present investigation the following
conclusions can be arrived at:
1. The adsorption density of the ECP onto galena is signifi-
cantly higher than that onto sphalerite. The adsorption density of
ECP onto galena steadily increases with increase of pH, whereas
the amount of ECP adsorbed onto sphalerite shows a distinct ad-
sorption maximum at pH 7.
2. The electrophoretic mobility of the minerals becomes less
negative consequent to ECP adsorption, without any apparent
shift in the isoelectric point. The reduction in the magnitude of
the electrophoretic mobility after the addition of ECP is found
to be greater in the case of galena vis-à-vis that of sphalerite.
3. Dissolution tests indicate release of zinc species from spha-
lerite and lead species from galena and the amount of lead species
dissolved is found to be more compared to that of zinc species,
particularly at acidic pH.
4. Co-precipitation tests confirm metal ion–ECP interaction
in the bulk solution.
5. Microflotation tests demonstrate that galena is signifi-
cantly depressed in the pH range 6–11 after the addition of ECP.
On the other hand, the floatability of sphalerite is unaffected in
the presence of ECP especially in the pH range 7.5–11. Dif-
ferential flotation tests on a synthetic mixture of sphalerite and
galena reiterate the above findings.
6. Individual flocculation tests on galena and sphalerite in
the presence of ECP show that galena is almost completely floc-
culated, while good dispersion of sphalerite takes place in the
pH range 9–10. Selective flocculation tests at pH 9–9.5 on a
1 : 1 synthetic mixture of the two sulfide minerals do not yield
adequate selectivity of separation.
7. FTIR spectroscopic studies provide evidence in support of
hydrogen bonding as well as chemical interaction between the
hydroxylated mineral surface and ECP.
ACKNOWLEDGMENTS
The authors gratefully acknowledge financial support for this investigation
received from the Indo-Swedish (STINT) program.
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