Wat. Res. Vol. 21, No. 9, pp.

1109-1118, 1987
Printed in Great Britain. All fights reserved

0043-1354/87 $3.00+0.00
Copyright 1987 Pergamon Journals Ltd

EVALUATION OF SOLUBLE A N D INSOLUBLE

XANTHATE PROCESS FOR THE REMOVAL
OF HEAVY METALS FROM WASTEWATERS
VINOD TARE* and SANJEEV CHAUDHARI
Environmental Engineering Division, Department of Civil Engineering, Indian Institute of Technology,
Kanpur-208 016, India
(Received August 1986)
Abstract--The effectiveness of xanthate (water soluble and water insoluble) process for hexavalent
chromium removal has been evaluated. Insoluble xanthates were synthesized in the laboratory from
corn starch (ICSX), potato starch (IPSX) and cellulose powder (ICX), and their removal efficiency
for Cr(VI) is compared with soluble starch xanthate (SSX). In preliminary experiments various insoluble xanthates were tested for their effectiveness in removal of both metallic cation [Cd(II)] and metallic
anion (chromate). The results indicated that the metal binding capacity followed the sequence
q,(ICSX) > q,(IPSX)-~ q,(ICX). Comparison between ICSX and SSX revealed that ICSX has better
removal capacity for Cr(VI) on unit weight basis. However, based on chemical requirements for the
synthesis of ICSX and SSX, SSX appears to be better than ICSX. The removal of Cr(VI) decreased with
increase in pH while ionic composition of the aqueous phase had little effect on the removal for both
soluble and insoluble xanthates. The removal mechanism for Cr(VI) appears to be reduction and
complexation of the reduced chromium with xanthate groups. A comparative analysis of the traditional
reduction-precipitation process and xanthate process for hypothetical waste containing hexavalent
chromium revealed that xanthate process would be a worthwhile alternative.
Key words--insoluble starch xanthate, soluble starch xanthate, insoluble cellulose xanthate, heavy metals,
cadmium removal, Cr(VI) and Cr(III) removal, chromate removal, heavy metal-xanthate interaction

INTRODUCTION
Metallic cations and anions (e.g. chromate) appear in
the wastewaters of a variety of processes. These
metals may include cadmium, copper, lead, nickel,
zinc and chromium at concentrations ranging up to
50,000 mg 1 '. Metal bearing effluents are produced
by a broad spectrum of sources which include metal
processing and refining, metal plating, chloralkali,
storage battery manufacturing, pigment manufacturing, tanning, anodising and automative industries (Patterson, 1981). For many of these industrial
groups and waste constituents discharge limits have
been promulgated.
Various methods have been developed for the
removal and recovery of heavy metals from wastewaters. Comparisons have been made of several of
these methods (Weiner, 1967; Bryson and Dardis,
1980). Available methods include chemical treatment
with lime, caustic, oxidation and reduction, ion exchange, adsorption, reverse osmosis, solvent extraction, membrane filtration, electrochemical treatment
and evaporative recovery. Thus, solving the problem
of metals removal from industrial wastewaters entails
a choice between numerous traditional and advanced
technologies. Precipitation processes are most widely

*Author to whom all correspondence should be addressed.

used for metals removal (Patterson, 1981). However,

traditional precipitation process of metal hydroxide
cannot always give satisfactory metal removal
efficiency, for examples with complexed metals
(Karra et al., 1985), and besides they usually produce
high volumes of toxic sludges which are difficult to
dispose. One of the advanced precipitation processes
recently proposed is that of utilizing starch xanthate,
the derivative of one relatively economical and annually renewable substance, as metal precipitant (Wing
et al., 1974). This process has been claimed to have
very high metal removal efficiency for several metals
either separately or in combination, over a wide pH
range (Wing et al., 1974). The metal xanthate sludge
is easily dewaterable and its oxidation allows precious
metals recovery (Marani et al., 1980, 1981). Wing's
group at NRRC, Peoria, Ill., U.S.A. has further
developed several insoluble starch based products for
the removal and possible recovery of metallic cations
and anions (Wing et al., 1975, 1978; Rayford et al.,
1979; Wing and Doane, 1981). While Wing's group
advocate the use of insoluble starch products, especially xanthates, other group of researchers (Maraft1 et al., 1980, 1981) prefer the use of soluble
xanthates over insoluble xanthates.
A comparative study of soluble vs insoluble xanthates for the removal of heavy metals would greatly
facilitate the choice of one of these (soluble or
insoluble xanthate). It is this end that this research is

1109

1110

VINOD TARE and SANJEEV CHAUDHARI

attempted. Further, literature on the removal of

hexavalent chromium by starch xanthates is scanty.
Hence, in the present study efforts have been made to
study the removal of hexavalent chromium using
xanthates synthesized from starch and cellulose.
EXPERIMENTAL METHODOLOGY
In view of the major objective of the study to evaluate the
performance of soluble versus insoluble xanthate process for
heavy metals removal from wastewaters, experiments were
conducted using insoluble starch xanthate (ISX), insoluble
cellulose xanthate (ICX) and soluble starch xanthate (SSX).
Insoluble starch xanthates were prepared from two starch
sources e.g. corn starch (ICSX) and potato starch (IPSX).
Cadmium, and chromium in the form of hexavalent chromium were used to evaluate the metal removal efficiency of
different insoluble xanthates. The aqueous environment was
simulated to typical metal bearing wastewaters by adjusting
ionic strength and pH using appropriate salts and buffers
respectively. However, the experiments were restricted to
single metal to allow useful comparisons. The experiments
conducted with insoluble xanthates are classified under
sorption experiments as it involves transfer of solute molecules from aqueous phase to already existing solid phase
(ISX/ICX). The experiments with soluble xanthate are
considered as precipitation experiments since the solid phase
is formed after the interaction between soluble xanthate
molecules and metal ions. This classification is used for

Prepare slurry with lOOg of commercial

corn starch in 150mr H20 containing 1.5g
NoCt and .5.5mt epichLorohydrin

I Add 40mr H20 containing 6g KOH sLowLy

over 30 min
c.)

Add 50mr HzO and 2mL epichtorohydrin 1

and stir for 16h

Add 250mr H20 containing 48g

NoOH

Add

15ml. CSz near the bottom of the

reactor andstir for 2h

1
=

"

Table 1. Typical characteristics of the insoluble xanthates

Characteristics
ICSX
IPSX
ICX
Colour
Yellow
Pale yellow Whitish
Yield (g per 100g starch)
132
--Moisture content (%)
12
--Particle size (after
-710 to +425
--grinding and sifting)
Geometric
mean size
= 0.549 mm
Percentage of
starch/cellulose
77.52
Degree of substitution
0.127
Loss in weight at varying Not detectable
pH (4-8) in aqueous
system (contact time of
24 h at 80 rpm)
m

convenience in describing the experimental methodology

and results, and may not be appropriate in true sense of the
terminology used in literature.

Sorption experiments
Many factors affect transfer of solute molecules (sorbate)
from liquid phase (aqueous phase) to solid phase (sorbent)
and require control in sorption research. In this research,
characteristics of the sorbent and operational parameters of
the sorption process were kept constant in most of the
experiments. Emphasis was placed on the characteristics of
the liquid phase and the solute (metal ion) to be removed.
Sorbent characteristics. The sorbents used were insoluble
corn starch xanthate (ICSX), insoluble potato starch xanthate (IPSX) and insoluble cellulose xanthate (ICX). The
synthesis procedure and the chemicals used for the preparation of ICSX are schematically shown in Fig. I. This
procedure is similar to that given by Wing et aL (1975) with
minor modifications in washing and drying step. The synthesis was done at room temperature (15 + 3C) in a 1 litre
polyethylene beaker employing mechanical paddle stirrer to
allow uniform mixing. The IPSX and ICX were synthesized
in a similar way excepting that 30 g of potato starch and
I00 g of cellulose powder were used respectively instead of
100 g of corn starch. The xanthates prepared were kept in
closed bottles and stored at low temperature (6-8C). The
typical characteristics of the three insoluble xanthates synthesized are presented in Table I.
Sorption equilibria. The sorption equilibria were conducted in 300 ml corning glass stoppered bottles (200 ml liquid
volume) employing rotary shaker (at 20 rpm) for mixing.
The ionic strength of the aqueous solution was adjusted by
adding an appropriate quantity of potassium nitrate and the
pH was maintained by a suitable buffer. Metal concentrations were maintained by adding stock solutions of metal
salts. Before starting the sorption equilibria experiment, the
liquid phase was allowed to equilibrate for a few hours.
Weighed quantities of sorbent (ISX/ICX) were added in
different bottles at the time of initiation of the experiment.
After the appropriate equilibrium time (determined from
kinetic experiments), about 50ml of the samples were
filtered and stored for subsequent metal analysis. Metal
loading of the ISX/ICX was computed, based on the mass
balance through loss of metals from the aqueous phase. In
all experiments initial and final pH was measured. A
summary of the experimental conditions employed during
different sorption equilibria experiments is presented in
Table 2.

Precipitation experiments

Air dry in dessicator for 72h

at room temperature
Fig. 1. Procedure for synthesis of insoluble corn starch

xanthate (ICSX).

Like any other unit process, chemical precipitation is

influenced by several factors. The most important factors
which alter the precipitation reactions in wastewater are
aqueous phase composition and the characteristics of the
chemical precipitant used. Aqueous phase is characterized
by pH, ionic mobility (influenced by ionic strength, g) and

The removal o f heavy metals from wastewaters

1111

Table 2. Experimental conditions employed for sorption equilibria

experiments (equilibrium time = 3 h, temperature = 24-28C)

Table 4. Experimental conditions employed in various precipitation

experiments (reaction time = 2.0 h, temperature = 24-28C)

Metal and its

initial
concentration, C0
(rag 1-~)
Cadmium*
Co = 1.0-19.0
Chromium(VI)?
Co = 1.0-15.0

Metal and its

initial
concentration,
CO (mgl -I)

Co = 1.0-10.0
CO= 1.0-22.4
COffi 1.0-30.4
Co = 2.0-30.0
Co = 4.0-33.0
CO= 2.0-30.0
Co = 0.94-30.0
CO= 10.37
CO= 1.15-23.7
Co = 1.0-22.0
Co = 1.0-22.0

ISX and
its dosages,
(mgl-')
ICSX
203
IPSX
444
ICX
444
ICSX
444
ICSX
444
ICSX
444
ICSX
444
ICSX
444
ICSX
444
ICSX
230-5000
ICSX
444
ICSX
444
ICSX
444

pH
4.5~.7
5.0-5.3

Ionic
strength Buffer used
(#)
(g 1-~):~
0.0223 Acetate
(0.8)
0.016

Acetate
(0.216)
5.0-5.2
0.016
Acetate
(0.216)
4.0-4.4
0,026
Acetate
(0.83)
4.0-4.4
0.116
Acetate
(0.83)
5.0-5.6
0.016
Acetate
(0.216)
5.0-5.5
0.106
Acetate
(0.216)
6.0--6.5 0 . 0 1 2 Phosphate
(0.162)
5.9-6.3
0 . 1 0 2 Phosphate
(0.162)
7.1-7.7
0.0137 Phosphate
(0.162)
7.0~
0.1037 Phosphate
(0.162)
8.0~
0.015 Phosphate
(0.17)
8.0~
0.105
Phosphate
(0.17)

*Stock metal solution prepared using Cd(NO3)2.4H20.

?Stock metal solution prepared using K2Cr207.
:l:Total concentration of respective components viz., acetate and
phosphate.
pH variation not observed.

levels o f different cations and anions present. In the present

research soluble starch xanthate (SSX) is used as a precipitant for the removal o f hexavalent chromium. Synthesis,
purification and characterization o f SSX was done as described by Marani et al. (1980). The characteristics of the
SSX prepared in this study are reported in Table 3.

Experimental procedurefor precipitation experiments. The

required amount of experimental solution mixture was
prepared using distilled water, stock metal solution, buffer
(for maintaining pH) and potassium nitrate stock solution
(for maintaining ionic strength) in a coming glass volumetric
flask. Fifty ml o f the solution mixture was added to several
100ml polyethylene bottles. The required amount o f
purified xanthate solution was then added to these bottles
and agitated on a rotating shaker. Then the bottles were
kept for 2 h to allow the precipitation reaction to nearly
complete. The precipitate (solid phase) were separated by
centrifugation at I0,000 rpm for 30 rain. The supernatants
were stored in 100ml polyethylene sampling bottles and

Table 3. Characteristics of soluble starch xanthate

Molar ratio of the constituents
used
Quantity of starch used
Quantity of NaOh
Quantity of CS2
Quantity of viscose obtained
Percentage of starch
Viscose colour
Colour of purified SSX
Degree of substitution (D.S)*
Percentage impurities

Starch:NaOH:CS21 : 1:0.5
62 g
200 ml (75 g l- i;
density = 1.08)
13 ml (density = 1.26)
294.38 g
21-06

Orange
Colourless to pale yellow
0.23
39.5%

*D.S. defined as moles of SX groups per glucosidic unit with

MW = 162.

Precipitant
(SSX)
concentration
(mmol 1-l)

pH

Ionic
strength
(#)

Chromium(VI)*
Co = 9.3-8.0

0.1-0.8

3.0-3.3

0.024

Co = 9.6

0.1-0.8

4.0-4.4

0.077

C0 =9.5

0.1-1.2

4.0-4,4

0.167

Co ffi9.7

0.2-1.6

5.0-5.7

0.035

Co = 9.69

0.l-l.4

5.0-5.7

0,125

CO= 9.4

0.3-1.3

6.0-6.8

0.018

Co = 9.9

0.2-1.2

7.0-8.0

0.025

Buffer used
(gl-t)?
Phthalate
(1.67)
Acetate
(6.7)
Acetate
(6.7)
Acetate
(1.73)
Acetate

(1.73)
Phosphate
(I.30)
Phosphate
(I.29)

*Stock metal solution prepared using K2Cr207.

t'Total concentration of respective components viz., phthalate,
acetate and phosphate.
subjected to metal analysis. A summary o f the experimental
conditions employed for various precipitation experiments
is presented in Table 4.

Analytical techniques
Cadmium and chromium (hexavalent and trivalent) conc~ntrations in aqueous phase were estimated as per Standard
Methods (APHA, 1980). Cadmium was analysed using
atomic absorption spectrophotometry. Hexavalent and total
chromium estimations were done using diphenyl carbazide
and permanganate azide methods respectively. Trivalent
chromium was estimated from the difference in total and
hexavalent chromium.
RESULTS AND DISCUSSION

Metal-IX interaction
T h e m e t a l - I X i n t e r a c t i o n is c h a r a c t e r i z e d h e r e as
s o r p t i o n i n t e r a c t i o n . S o r p t i o n in a n y given s y s t e m
p r o c e e d s until the c o n c e n t r a t i o n o f solute ( s o r b a t e )
r e m a i n i n g in s o l u t i o n is in d y n a m i c e q u i l i b r i u m w i t h
t h a t o n t h e solid ( s o r b e n t ) p h a s e . A t this p o s i t i o n o f
e q u i l i b r i u m , t h e r e is a d e f i n e d d i s t r i b u t i o n o f solute
b e t w e e n the solid a n d liquid p h a s e . T h e d i s t r i b u t i o n
ratio is a m e a s u r e o f t h e p o s i t i o n o f e q u i l i b r i u m in t h e
s o r p t i o n process. T h e p r e f e r r e d f o r m f o r d e p i c t i n g
this d i s t r i b u t i o n is to e x p r e s s t h e a m o u n t o f solute
s o r b e d p e r u n i t w e i g h t o f s o r b e n t as a f u n c t i o n o f t h e
c o n c e n t r a t i o n o f solute r e m a i n i n g in s o l u t i o n u n d e r
e q u i l i b r i u m at c o n s t a n t t e m p e r a t u r e . A n e x p r e s s i o n
o f this t y p e is k n o w n as s o r p t i o n i s o t h e r m .
Metal binding capacity of various IX's. The s o r p tion i s o t h e r m s for C d ( I I ) a n d C r ( V I ) for v a r i o u s
i n s o l u b l e x a n t h a t e s are s h o w n in Fig. 2. T h i s indicates t h a t I C S X h a s b e t t e r b i n d i n g c a p a c i t y for
cadmium and chromium. Among the various IX's
used, c a d m i u m a n d c h r o m i u m r e m o v a l c a p a c i t y foll o w e d the s e q u e n c e I C S X > I P S X ~ I C X . I f t h e
m e t a l b i n d i n g c a p a c i t y o f I X is r e l a t e d to t h e n u m b e r
o f x a n t h a t e g r o u p s p e r u n i t w e i g h t o f I X , it c a n be
said t h a t t h e efficiency o f x a n t h a t i o n u n d e r t h e synthesis c o n d i t i o n s u s e d is b e t t e r for c o r n s t a r c h t h a n

l 112

VINOD TARE and SAN~w CHAUDHARI

O'I

"6
12 _ - - - o - - I C S X
-..~-.--o--

IS
IP
C
XX

Contact time" 12 hrs

E
200 "E x

IJ, = 0.016
pH = 5.0

i ~.-a~'--"-:"=~-~"
E
Aqueous phase Cr(VI)

"~
=~

.~

ICSX
IPSX

-~-

I
I
8
10
concentration,

-- 100
~o

I
12
14
C, (rag/I)

Contact time 12 hrs

600

--o--ICX~

60

.2E

20

E
i

pH =4.5

0~r~"

I
I
1
2
Aqueous phase

400

- 200 ~ ,,-

I
I
I
I
0
3
4
5
6
cadmium concentration, C, (mg/[)

dE

Fig. 2. Comparison of chromium and cadmium binding capacity of ICSX, IPSX and ICX.

~1

~1

I
:2

'

OI
2

:2

log C,

log Ce

p, = 0.026,

q, = 9.53 C:/2s3

X
03

x
(/1

40 _ - - e - - 1J,=0,116, q. = 10.9 C. '/3-43

- 800

"6

32 l_
O

24-

600

~00

---~

:}

o
t-

E
.o

eU

~6

- 200

cn

E
0

I
4

I
8

12

I
16

I
20

I
2&

280

E
=1_

Aqueous phase Cr(VI) conc., C , ( m g / I )

Fig. 3. Equilibrium distribution of chromium between aqueous phase and ICSX at pH 4.

The removal of heavy metals from wastewaters

1113

o=

log C.

log Ce
-

~ ^^ ,-1/2 82

200

# 10 _ ---o--- p,=0.012. %=z.out, e "

x"
- 4 - - p,= 0.102, qe= 3.20 C~39~
O1

150 ~
0

100 oE

50

~6
"6
E

4
8
12
16
20
24
280
~
Aqueous phase Cr(VI) conc., C= (rag/I)

Fig. 4. Equilibrium distribution of chromium between aqueous phase and ICSX at pH 6.

that for potato starch or cellulose powder. However,
at this stage it cannot be concluded that the potato
starch and cellulose powder would be less effective.
The optimum conditions for xanthation of corn
starch, potato starch and cellulose powder may be
different. Further, the final product (IX) yield may be
different for these three sources and hence the comparison should be made on overall basis considering
all these factors. In the present study, the synthesis
conditions were not changed and hence ICSX which
was found to be better from metal binding considerations was used for further studies.

Distribution of chromium between aqueous phase

and ICSX. Figures 3-5 are representative of the
sorption isotherm data for Cr(VI)-ICSX system.
Since straight line plots can be more readily extrapolated to concentrations outside the experimental
range and interpolated within a range, many investigators present isotherms plotted in a manner so
as to produce as straight a line as possible. The two
primary plotting schemes derive from the Langmuir
and Freundlich equations (Neely and Isacoff, 1982).
The present data gave a better fit to the Freundlich
equation as indicated by relatively high values of
coefficient of correlation, low values of standard error
of estimation and narrow confidence internal (Table
5). The Freundlich equation has the general form

q, = K:C~/".

(1)

Here, K/and n are constants, q, is the mass of sorbate

per unit weight of sorbent, and C, is the equilibrium
sorbate concentration in solution. The linearized

form of Freundlich equation is

log qe ----log Kf q- 1_.log Ce.

(2)

A plot of equation (2) is convenient to determine

sorption capacity, K: and the sorption intensity, 1/n.
The least-squares method is used to estimate these
isotherm parameters through equation (2). The estimated isotherm parameters along with the values of
coefficient of correlation, standard error of estimate,
and range of the 95% confidence interval for the
estimated isotherm parameters are presented in Table
5. The linearized plots along with 95% confidence
band for the estimated qe values are incorporated in
respective figures (Figs 3-5). The confidence interval
band assists in concluding whether the variation in qe
can be correlated to change in any system parameter
[e.g. pH, ionic strength (/z), etc.] or is due to experimental limitations. The wider the band, the higher the
uncertainty of prediction and vice versa.

Chromium binding capacity of ICSX under varying

aqueous phase composition. The sorbate-sorbent interaction in the sorption process is influenced by
solution (aqueous) phase composition. The change in
the aqueus phase composition leads to redistribution
of ions and the changes in the functional groups of
sorbents leading to a new equilibrium position. The
two important parameters which characterize the
aqueous phase composition are pH and ionic
strength, /z. The aqueous phase composition is
strongly dependent upon pH. pH also dictates the
extent of protonation of several functional groups on

I114

VZNODTAREandSANJEErCI-IAUDR~,RI
@

2~=

_I02

2~p.=0.102

0.012

0' 2

log Ce

@10

x"

log Ce
2oo x

---o-- tA=0.012, qe=2.10 C~/s2

- - e - - ~,=0.102, qe=l.61 Cle/3'B7

"6

~ 8

150

o~

E
100 "~
E= 4

o
i_

id

~50

v 2
"6
E 0

"6
o

I
I
I
I
I
I
4
8
12
IB
20
24
Aqueous phose Cr(VI) conc., Ce (rng/l)

0
28

~-

Fig. 5. Equilibrium distribution of chromium between aqueous phase and ICSX at pH 8.

the sorbent. The ionic strength controls the mobility
of ions and can influence the equilibrium constants by
influencing the activities of the ions. Figures 6 and 7
show the typical variation of chromium binding
capacity of ICSX with pH for two different ionic
strength values. The ionic strength has very little
effect, if any, on the chromium binding capacity.
However, the aqueous phase pH certainly influences
the chromium binding capacity of ICSX as the
variation is much more than that can be accounted
for by the uncertainties in estimations (95%
confidence band). From Figs 6 and 7, it is very clear
that the chromium binding capacity of ICSX decreases with increase in pH. The change in pH leads
to change in chromate species. At lower pH the
predominant species is acid chromate ion while at
higher pH the predominant species is chromate ions
(Figs 6 and 7, Stumm and Morgan, 1970). Both acid

chromate and chromate ions are quite stable and

have negligible complexing ability with the type of
ions present in the system. The pKo for the
xanthate-xanthic acid dissociation is reported to be
1.70 (Iwasaki and Cooke, 1958). Thus in the pH
range used, the characteristics of the interacting
surface group (xanthate) of the sorbent are unlikely
to change. This indicates that acid chromate ion has
more affinity for xanthate group compared to chromate ion.
Metal-SX interaction

The metal-SX interaction is characterized here as

precipitation reaction as it involves the formation of
a solid phase after the interaction between metal and
xanthate, both being in solution. The experimental
results from precipitation studies (Figs 8 and 9) show
that Cr(VI) can be removed from the waters below

Table 5. Estimated Freundlich isotherm parameters and relevant statstical information

95% confidence
interval for

Ionic
strength
pH

(~ )

K/

l /n

4.0

0.026
0.116
0.016
0.106
0.012
0.102
0.014
0.104
0.015
0.105

9.53
10.9
6.55
6.55
2.80
3.2
0.591
2.22
2.10
1.571

0.395
0.291
0.224
0.108
0.354
0.253
0.790
0.134
0.192
0.348

5.0
6.0
7.0
8.0

log K/
0.849-1.11
0.985-1.089
0.784-0.849
0.748-0.863
0.396-0.489
0.442-0.586
-0.272-0.183
0.32-0.37
0.218-0.426
0.072-0.464

l /n

Standard
error of
estimation

0.272-0.518
0.232-0.351
0.147-0.301
0.033-1.8
0.259-0.45
0.072-0.303
0.489-1.092
0.098-0.171
0.026-0.358
0.117-0.814

0.091
0.046
0.023
0.058
0.036
0.033
0.046
0.018
0.073
0.188

Coefficient
of correlation, r
0.993
0.994
0.991
0.940
0.994
0.990
0.970
0.990
0.951
0.899

The removal of heavy metals from wastewaters

100

CrTI=Io_{M I

50E

1115

CrO; 2
500

24

X
Ce = 1'0 rng/t

20

- 20

- 400 ~0

><

qe 10

16
c~

300 ~,
E

6~
E
- 200 oI_

12-

~"
E
'- 8E
,-=-
u Z.-

a.

Ce= 0.1 m g / l
o Ce= 1.0 m g / l

~
" ~ ~ ,

zx C.=IO.O mg/[

.=
v

- I00 ~"6

~0

pH

Fig. 6. Variation of chromium binding capacity of ICSX with pH ~ = 0.019 + 0.007).

given for Cr(VI)-ICSX interaction may be put forward to explain the effect of pH and ionic strength on
the precipitation of chromium-xanthate complex. It
was observed that the settling characteristics of
chromium-xanthate precipitate improve with the increase in ionic strength. This might indicate that the
precipitates are charged colloidal particles and the

the detectable limit (< 0.1 mg 1-5) by SSX, especially

at lower pH. As with Cr(VI)--ICSX interaction,
Cr(VI)-SSX system also indicated that ionic strength
of the aqueous phase has little effect on precipitation
of chromium-xanthate complex. Further, the Cr(VI)
removal and hence chromium-xanthate precipitation
decreased with increase in pH. Similar arguments as

I00

I/-I

CrT=IO- M
5O

Cr022

0
24
X

20

Ce= 1.0 rag/(

400 "
"6

qe 10

16

~,
12
P,

"=v
P

300
\
~

"3

\\
\%
~

5 6
pH

C. = 0.1 mg/[

c.: 1.o

g/l
mg/I

-~ 2 0 0

100

"6
E

~:

O.

~-T

E
:d_

,P

pH
Fig. 7. Variation 0f chromium binding capacity of ICSX with pH (/J = 0.109 + 0.007).

1116

VINOD TARE and SAN~r~EVCRAUDHAR[

SSX{Viscoss)
0

(g/I}
4

=o
~~iI

/ 15

=i

-I~oo
L

=o

4 FI

'~. 31-.-

: ;I.I:I:

= pH=5.O, {,.1,=O085
o pH=6.0, p,=0018

~ \
~ 1

x pH=Z0, 1.1,=0025

I , I '
04
08
12
16
2,0
SSX concentrotlon (mrnole/[)

<

Fig. 8. Variation of aqueous phase Cr(VI) concentration

with SSX concentration (# = 0.0475 + 0.0295).
increased ionic strength tends to decrease the electrical double layer surrounding the colloidal particles
(Weber, 1972).

Mechanism of Cr(VI)-xanthate interaction

The probable mechanisms for Cr(VI)-xanthate interaction could be electrostatic attraction, ion exchange and/or specific chemical reaction. The predominant species of Cr(VI) in the pH range

SSX (Viscose) (g/I)

1
I

2
I

9
8

3
I

4
I

o p.=0.167, pH=/-.0
= p.=0.125, pH=50
Initial conc = 1 0 0 m g / [

Q q ~

Relative effectiveness of ICSX and S S X for Cr(VI)

removal

~ ~ k

150

d 6
~
8
=

~
d

~oo ,;

so

<
i ^
o.2

o.~

o.6

SSX concentration

o.8

~.o
(mrnole/l)

investigated were either acid chromate ion or chromate ion. Both are negatively charged species. The
xanthate groups are unprotonated above pH 2.0 and
hence have a net negative charge. From this, the
electrostatic attraction between chromate species and
xanthate groups can be ruled out. There are no
exchangeable groups on xanthate for anions (Wing et
al., 1978) and hence it is unlikely that the chromate
species would be removed by ion exchange. There
may be specific chemical reaction between chromate
species and xanthate groups. In literature (Marani et
al., 1980) it is reported that metal ions could get
reduced by xanthate, thereby oxidizing xanthate to
xanthide and the reduced metal ion forming an
insoluble complex with remaining xanthate groups.
The same mechanism could be hypothesized for
chromate ion removal.
The standard oxidizing potentials (E ) relative to
the potential of a standard hydrogen electrode for
acid chromate ion and chromate ion are + 1.33 and
- 0 . 3 3 V respectively (Lurie, 1975). The corresponding value for a group similar to that of xanthate
(cystine/cysteiine) is - 0 . 3 4 V (Mahler and Cordes,
1971). These values do support the possibility of
chromate ions getting reduced by xanthate groups.
As reported earlier, chromium removal increases with
decrease in pH when the predominant species is
strongly oxidizing acid chromate ion. Thus this hypothesis supports the observed variation in chromate
ion removal with pH. The sludge formed with the
SSX-chromate reaction, and the ICSX after interaction with chromate ion had a greenish tinge, typical
of trivalent chromium compounds. This indicated
that chromium in trivalent form may have complexed
with the xanthate groups. The intermittent check for
trivalent chromium in aqueous phase gave traces of
the same. Further, the acidification of SSXchromium sludge released considerable amount of
Cr(III).

in
~.~

~.:

Fig. 9. Variation of aqueous phase Cr(VI) concentration

with SSX concentration (p = 0.146 + 0.021).

The choice between insoluble and soluble xanthate

process can be made only when their effectiveness for
metal removal is compared under similar conditions.
One basis for comparison would be to evaluate the
quantity of metal ion removed per unit weight of IX
or SX. Figure 10 shows the comparison of variation
in chromium loading of ICSX and SSX for two
different molarities (ionic strength) at pH 4.0 with
equilibrium Cr(VI) concentration. Figure 11 shows
the similar comparison for a fixed Cr(VI) equilibrium
concentration and varying pH. Both these figures
indicate that on a unit weight basis ICSX is better
compared to SSX for Cr(VI) removal. However, it
should be noted that ~ 100 g of corn starch yields
only 130 g of ICSX while ~ 62 g of corn starch yields
210 g of viscose (SSX). Thus a realistic comparison
should include the chemical requirements for the
synthesis of unit weight of ICSX or SSX. Such a

1117

The removal of heavy metals from wastewaters

I

pH =t,O

19

C= = 6 mglI

I/ - - - ~:261icsx
~:O116J

~a

- -

/--o

~ = 0077] s s x

~
~"= 0]C11/' 0 002] "-SX
- - o - - ~= 0.10~ 0.002J LL,

%,

600

15

~.=0.0520.02Zl

_.,._

i~=0.146O021JSSX

D50

300 u~

HCrO~r

(/I

`5 20 ~~m

/
/

z~ /

400 '5
tm

10

:
/

DH

200

loo

'

"6 10

I~
o

2 " ~-"~'=

200 "~
"6

I
/.

J
12

Aqueous

phose Cr(VII

I
16

I
20

I
24

capacity

at pH

Fig. I I. C o m p a r i s o n

4.

of I C S X

and

SSX

for c h r o m i u m

CONCLUSIONS

Based on the results of the present investigation

and the synthesis of the available scientific information derived from review of the relevant literature,
following conclusions may be drawn.

SSX treatment
2.5gl

] viscose
i.e.
5 3 0 m g l t starch
125mgl ~NaOH
0 . 1 1 m l l i CS 2

I C S X treatment
2.0gl

f ICSX
i.e.
1 5 0 0 m g l ' starch
800mgl ' NaOH
22mgl ' NaCI
0.07 ml I ~ Epichlorohydrin
0.3 ml I ' CS 2

*Dosages required in pure solutions. Adopted f r o m Chamberlin and D a y (1956) and

N e m e r o w (1971)

WR 21/~H

90

precipitation in the reduction-precipitation method is

not included in Table 6. This varies from waste to
waste and depends upon the buffering capacity of the
system. It may be as high as 8-10 g 1-l of lime (Tare
and Venkobachar, 1985). Further, the volume of the
sludge produced is much more for metal hydroxide
precipitates compared to metal xanthate precipitates.
In addition, the traditional hydroxide precipitation
suffers from the limitation that it may not be able to
achieve the desired effluent concentration due to
increased chromium solubility in complexed wastes
(Tare and Venkobachar, 1985).

Table 6. Relative effectiveness o f I C S X , SSX and traditional reduction-precipitation

method for hexavalent c h r o m i u m removal f r o m a hypothetical waste. Influent
concentration = 1 0 m g l t; expected effluent concentration ~< 0.1 m g l *: wastewater
p H = 4.0

66 m g I ~ SO~
or
160mgl tFeSO 4
or
ll0mgl ~ NaHSO 3
or
1 0 1 m g l i Na2S203
or
130 m g l ~N a 2 S O 3
and
6 0 m g l ] H2SO 4
+
95 m g I r C a ( O H ) 2

binding capacity at varying pH.

comparison for treating a hypothetical wastewater

containing 10 mg 1-1 of Cr(VI) to achieve a treated
effluent concentration of 0.1 mg1-1 or less is
presented in Table 6. This table also includes the
chemical requirements for traditional reductionprecipitation method.
It is very clear that from chemical requirements,
SSX is much better compared to ICSX for Cr(VI)
removal.
The
chemical
requirements
for
reduction-precipitation method appear to be lower
compared to SSX or ICSX treatment. However, it
should be kept in mind that the chemical requirements for reduction-precipitation treatment are for
pure system while the SSX and ICSX dosages are
estimated from a complex system which contains
background electrolytes and relatively higher concentrations of ligands like pthalate, acetate or phosphates (Tables 2 and 4). The amount of alkali
required to raise the pH for chromium hydroxide

Reduction-precipitation
treatment*

pH

conc, Ce (rng/I)

Fig. 10. Comparison of [CSX and SSX for chromium

binding

28

1118

VINOD TARE and SANJEEV CHAUDHARI

(1) The insoluble x a n t h a t e s c a n remove metallic

cation [Cd(II)] a n d a n i o n (chromate) from aqueous
phase. T h e removal capacity followed the sequence
I C S X > I P S X --~ ICX.
(2) The removal of c h r o m a t e ions by I C S X decreased with increase in p H a n d was f o u n d to be
negligibly influenced by ionic strength o f the a q u e o u s
phase.
(3) The soluble starch x a n t h a t e also r e m o v e d hexavalent c h r o m i u m , a n d the extent o f removal was
affected by ionic strength a n d aqueous phase p H in
a similar way to t h a t using ICSX.
(4) The SSX appears to be superior t h a n I C S X for
c h r o m a t e removal a n d in general the x a n t h a t e process seems to be a worthwhile alternative to the
traditional r e d u c t i o n - p r e c i p i t a t i o n method.
REFERENCES
APHA, AWWA, WPCF (1980) Standard Methdos for the
Examination o f Water and Wastewater, 15th edition.
American Public Health Association, Washington, D.C.
Bryson A. W. and Dardis K. A. (1980) Treatment of dilute
metal effluents in an electrolytic precipitator. War. SA 6,
85-87.
Chamberlin N. S. and Day R. V. (1956) Technology of
chrome reduction with sulphur dioxide. Proc. llth Annual
lndust. Waste Conf. Purdue Unit,. Lafayette, Ind., pp.
129-156.
Iwasaki I. and Cooke S. R. B. (1958) The decomposition of
xanthate in acid solution. J. Am. chem. Soc. 80, 285-288.
Karra S. B., Haas C. N., Tare V. and Allen H. E. (1985)
Kinetic limitations on the selective precipitation treatment of electronics wastes. Wat. Air Soil Pollut. 24,
253-265.
Lurie Ju. (1975) Handbook o f Analytical Chemistry. Mir,
Moscow.
Mahler H. R. and Cordes E. H. (1971) Biological Chemistry,
2nd edition. Harper and Row, New York.
Marani D., Mezzana M., Passino R. and Tiravanti G.
(1980) Starch xanthate and polycations in heavy metal

removal from wastewater. Envir. Teehnol. Lett. 1,

141-150.
Marani D., Mezzana M., Passino R. and Tiravanti G.
(1981) Treatment of industrial effluents for heavy metal
removal using the water soluble starch xanthate process.
Proc. Int. Conf. Heavy Metals in the Environment, Amsterdam, pp. 92-95.
Neely J. W. and Isacoff E. G. (1982) Carbonaceous Adsorbents for the Treatment of Ground and Surface Waters.
Marcel Dekker, New York.
Nemerow N. L. (1971) Liquid Waste o f lndustry : Theories,
Practiees, and Treatment. Addison-Wesley, Reading,
Mass.
Patterson J. W. (1981) Effect of carbonate ion on precipitation treatment of cadmium, copper, lead and zinc. Proe.
36th Annual Indust. Waste Conf. Purdue Univ. Lafayette,
Ind., pp. 579~02.
Rayford W. E., Wing R. E. and Doane W. M. (1979)
Carboxy-containing starch graft polymer: preparation
and use in heavy metal removal. J. appl. Polymer Sci. 24,
105-113.
Stumm W. and Morgan J. J. (1970) Aquatic Chemistry.
Wiley, New York.
Tare V. and Venkobachar C. (1985) Removal and recovery
of chromium from wastewaters of chrome tanning industry: a study on traditional and alternative methods.
Presented at the National Seminar on Pollution Control,
NEERI, Nagpur, India.
Weber JR W. J. (1972) Physicochemical Processes for Water
Quality Control. Wiley-lnterscience, New York.
Weiner R. F. (1967) Acute problems in effluent treatment.
Plating 54, 1354-1356.
Wing R. E. and Doane W. M. (1981) Wastewater treatment
of acid cadmium rinses. Plat. Surf Finish 68, 50-53.
Wing R. E., Doane W. M. and Russell C. R. (1975)
Insoluble starch xanthate: use in heavy metal removal. J.
appl. Polymer Sci. 19, 847-854.
Wing R. E., Rayford W. E., Doane W. M. and Russell
C. R. (1978) Preparation of insoluble cationic starches
and their use in heavy metal anion removal. J. appl.
Polymer Sci. 22, 1405-1415.
Wing R. E., Swanson C. L, Doane W. M. and Russell
C. R. (1974) Heavy metal removal with starch xanthate
cationic polymer complex. J. Wat. Pollut. Control Fed. 46,
2043 2047.