Colloids and Surfaces, 24 (1987) 33-42

Elsevier Science Publishers B.V., Amsterdam -

33
Printed in The Netherlands

Adsorption Thermodynamics of Carbofuran on

Sn (IV) Arsenosilicate in H+, Na+ and Ca2+ Forms

ASIF A. KHAN,* and R.P. SINGH

Analytical Laboratories, Chemistry Section, Z.H. College of Engineering and Technology,
Aligarh Muslim University, Aligarh-202001 (India)
Section of Plant Pathology and Nemutology, Botany Department, Aligarh Muslim University,
Aligarh-202001 (India)
(Received 27 March 1986; accepted in final form 8 October 1986)

ABSTRACT
The adsorption thermodynamics of carbofuran was studied on Sn(IV) arsenosilicate cation
exchanger in the H + , Na + and Ca2+ forms at 25 and 50 C. The adsorption isotherms of carbofuran were found to follow the Freundlich adsorption model and yield s and L class isotherms.
The order of adsorption of carbofuran on the different forms of cation exchanger is H + >
Na + > Ca2+. The thermodynamic equilibrium constant ( KO), standard free energy @Go),
enthalphy ( AHo) and entropy ( ASo) changes were also been calculated to predict the nature of
adsorption.

INTRODUCTION

Pesticides have a judicious use in agriculture; therefore their adsorption

behaviour is an important aspect of study. The adsorption of a pesticide on an
inorganic ion exchanger is also of great significant as our laboratories have
shown that antimony(V) silicate [ 1 ] has an enhanced adsorption potential
for carbofuran ( 2,3-dihydro-2,2-dimethyl-7-benzofuramyl
methyl carbomate)
as compared to soils [ 21. The present study demonstrates differences in the
behaviour of an inorganic ion exchanger when three different ionic forms are
examined. Sn (IV) arsenosilicate in H+ , Na+ and Ca2+ forms was used as the
adsorbent since it has shown good chemical stability [ 31 and carbofuran was
selected because it is the least studied pesticide.
*To whom all correspondence should be addressed.

0166-6622/87/$03.50

0 1987 Elsevier Science Publishers B.V.

34
MATERIALS AND METHODS

Reagents and chemicals

Stannic chloride is a Polish product (I.P.H. Polskee Odezynnik Chemwas obtained from Rallis India Ltd, Bombay. All other chemicals and reagents (B.D.H.) were of A.R. grade.

iezne) . Carbofuran (Furodan3G)

Apparatus
A waterbath incubator-shaker having a temperature variation of +O.lC
was used for all the equilibrium studies and a Bausch and Lomb spectronic-20
spectrophotometer was used for the spectrophotometric studies.
Synthesis of Sn(IV)

arsenosilicate

0.1 M Solutions of stannic chloride pentahydrate ( SnC1,*5H20), disodium

hydrogen
arsenate
( NaPHAsOl*7Hz0)
and
sodium
metasilicate
(NazSi08*5H,0) were mixed in a volume ratio of 1:l:l with constant stirring
and the pH was adjusted to 1 by adding nitric acid. The slurry was allowed to
stand overnight and then filtered, and the product was washed to remove the
unreacted materials. It was dried at 40 C and converted into H+ form by keeping it in 1 M HN03 for 24 h. Finally, the product was washed several times
with demineralized water until the effluent was neutral. The ion exchange
capacity of the dried Sn (IV) arsenosilicate was found to be 0.95 meq/g dry
material. The material was also converted into Na+ and Ca2+ forms by passing
1.0 M NaNO, on 1.0 M Ca( NO,)2 solutions through columns of Sn( IV)
arsenosolicate.
Adsorption studies
Aliquots of 0.2 g of all three forms of the exchanger (H+, Na+, Ca2+) were
placed in various stoppered conical flasks at the desired temperatures (25 and
50 QC ) followed by the addition of the carbofuran solutions ( 2000 ,ug ml- ) in
varing amounts (0 to 10 ml). The total volume was brought to 20 ml by adding
demineralized water and equilibrium was attained in 2 h as shown in Fig. 1.
The supernatant liquid was then analyzed spectrophotometrically [ 41.
RESULTS AND DISCUSSIONS

The adsorption of carbofuran by the three forms of Sn (IV) arsenosilicate

ion exchanger is represented by the isotherms in Fig. 2. The shape of the isotherms varies with the nature of exchangeable cations. The isotherms for the

35

ts
20

ul
I2,
16
c 0
ax
k
12
B
5

15

04

H+Form

Na+Form

Ca++Form

30

45

60
Minutes-

90

105

120

Fig. 1. Plots of adsorbed carbofuran versus time on Sn (IV ) arsenosilicate.

c, V Ce FOR H*

Equilibrium

10 12 IL 16 18 20 22 24 26 28 30 32 36 36 38 LO
ce X 10-7FOR SO?
concentration
of carbofuran in m.molesI ml x 10-8FOR 25OC

Fig. 2 (a). Adsorption isotherms of carbofuran on Sn (IV) arsenosilicate (H+ ) cation exchanger
at25and50C.

ii

il

x10

-5
C,

36 c

or-,
0

V Ce FOR Na+

10 12

lb

CeEquilibrium

16 18 20

concentration

22 24

26

26 30
X l$ FOR 50C
X10-FOR
25C
of carbofuran
in m.moles/ml

Fig. 2 (b) . Adsorption isotherms of carbofuran on Sn (IV) arsenosilicate (Na+ ) cation exchanger
at 25 and5OC.
C, V Ce FOR Ca++

s
2
5
u-l

a
4
0

10 12

CeEquilibrium

concentration

14 16

18

20 22 24 28
X lo- FOR 5OC
X lfi* FOR 25C
of carbofuran
in m.mo\es/m\

Fig. 2 (c) . Adsorption isotherms of carbofuran on Sn (Iv) arsenosilicate

at 25 and 50C.

( Ca2+) cation exchanger

H+ and Na+ forms are of the L class at 25 C and of the S class at 50 C. For
the Ca2+ form of the ion exchanger, it is of S class at both temperatures [ 51.
The L-shaped isotherms suggest that initially more sites on the exchanger
are occupied by carbofuran. With time, it becomes increasingly difficult for
carbofuran to find vacant sites. The S-shaped isotherms suggest that the

37
TABLE 1
Freundlich isotherm co&ants K and l/n for the adsorption of carbofuran on Sn (IV) arsenosilicate cation exchangers
Forms of Sn (IV)
arsenosilicate

H+ form
Na+ form
Ca2+ form

25C

50C

l/n

IIn

59.84x lo2
74.82 X 10
14.94

1.14
1.1313
1.5177

0.1942
10.15
5.83

0.572
0.8874
0.868

adsorption of carbofuran is enhanced at higher concentrations. This may be

due to a marked localization of the forces of attraction over the carbonyl group
(>C=O) of carbofuran leading to an interaction with the exchanger cations.

where X stands for the Sn (IV) arsenosilicate cation exchanger and M is Na+
or Ca+. In all cases the adsorption is higher at 25 C than at 50 C. It is probably due to the fact that the attractive forces are weaker at a higher temperature.
The adsorption behaviour of carbofuran on the different forms of the
exchanger can be represented by the Freundlich equation.

x/m = KC/

(1)

where x/m is the surface concentration of carbofuran in mmoles per gram of

the exchanger, C is the concentration of carbofuran in equilibrium suspension
in mmol ml-, and K and l/n are are constants determined from the intercept
and slope, respectively of the straight lines (Fig. 3) fitted to the points by the
least squares method. The values are listed in Table 1. The values of K are
generally greater at 25 C than at 50 C. The results are in accordance with the
work of Singal and Singh [ 61 and Van Bladal and Moreale [ 71.
Thermodynamic parameters are calculated from the variation of the ther-

38

- 3.0 -

0)

,o

-4.5

-5.0 L
-8-O

-7.5

-7.0

- 6.5
log

-6.0

-5.5

I
-5-o

Ce -

Fig. 3 (a). Freundlich isotherms of carahofuran adsorption on Sn (IV) arsenosilicate

exchanger.

-3.0

(H+ ) cation

25%

5oc
t
v1 - 4.0
0 -;)_

9,

VI
o

-&5

-5.0
-8.0

-7.5

-7-o

-6.5
log Ce-

-6.0

-5.5

- 5.0

Fig. 3 (b 1.Freundlich isotherms of carbofuran adsorption on Sn (IV ) arsenosilicate

exchanger.

( Na+ ) cation

modynamic equilibrium constant KO (or the thermodynamic distribution coefficient) with changes in temperature. I-C,,for the adsorption reaction can be
defined:

K,==vc,
a, v, C,

(2)

where a, is the activity of the adsorbed solute, a, the activity of the solute in

39

-3.5

3 -4.0
0
-4.5

-5.0

+577

log Ce-

Fig. 3 (c) . Freundlich isotherms of carbofuran adsorption on Sn (IV) arsenoeilicate ( Ca2+ ) cation
exchanger.

the equilibrium solution, C, the surface concentration of carbofuran in mmoles

per gram of exchanger and C, the concentration of carbofuran in equilibrium
suspension in mmol ml-, u, the activity coefficient of the adsorbed solute, and
ye the activity coefficient of the solute in the equilibrium solution.
As the concentration of the solute in the solution approaches zero, the activity coefficient v approaches unity. Equation (2) may then be written as:
lim cB=aS=K
cad0 c, a,

(3)

Values of K. are obtained by plotting In (CJC,) versus C, and extrapolating to

zero C, [ 81. First, a straight line is fitted to the points based on least squares
analysis; its intersection with the vertical axis then gives the value of K. (Fig.
4). Standard free energy changes ( AGo) for interactions are calculated [ 91
from the relationship:
dG = -RT

In K.

(4)

where R is the universal gas constant and T is the temperature in degrees

Kelvin. The standard enthalpy changes (AH) are then calculated from the
well-known Vant Hoff isochore equation:

(5)
and standard entropy changes ( ASo) are calculated using the equation:

40
TABLE 2
Values of various thermodynamic
exchangers
Forms of Sn (IV)
arsenosilicate

parameters for the adsorption of carbofuran on Sn (IV) arsenosilicate cation

Thermodynamic

parameters
dc0 (Cal mol-)

&

H+ form
Na+ form
Ca*+ form

AGo =dH

25C

50C

25C

50C

851.9
825.5
160.3

136.6
50.4
27.1

-4001.1
-3983.1
- 2565.2

-3161.1
- 2520.0
-2120.1

AH
(cd mol-)

AS
(calmoldeg.-)

- 14023.12
-21417.03
- 7862.1

- 34.02
- 59.2
- 18.0

- TdS

(6)

The valuesobtained are shown in Table 2, the negative free energy changes
(AGO) indicate that the reactions are spontaneous with a high affinity for carbofuran. The values of the standard free energy (AGO) also confirm that the

7-

25Oc

6-

2-

l-

I
0

10

12 14

CsxlO
Fig. 4 (a).

16618

20

22 24

26

28

30 32

34

36 38

Plots of In CJC, versus C, on Sn (IV) arsenosilicate ( H + ) cation exchanger.

40

41

7-

25?

IJ

0
6-

I
:
siu

50

L.

5o"c

08

000
3-

2-

l-

101214;6

182022242628303234

cs x10-

Fig. 4 (b) . Plots of In C,/C, versus C. on Sn (IV) arsenosilicate

(Na+ ) cation exchanger.

Cd

6r

lo5 12

CsxlO

14

16

18

20 22

Fig. 4 (c ) . Plots of In C./C. versus C, on Sn (IV) arsenosilicate

( Ca2+ ) cation exchanger.

42

maximum adsorption is obtained with the H+ form of the exchanger followed

by the Na+ and Ca 2+ forms. Negative values of standard enthalpy changes
( AHo) indicate that the carbofuran exchanger interactions are exothermic and
the products are energetically stable with a high binding of carbofuran to the
exchanger sites. The negative entropy changes, dSo, indicate a greater order
of reaction during the adsorption of carbofuran in all three systems at both
temperatures. It may be due to the fixation of carbofuran to the exchanger
sites resulting in a decrease in the degree of freedom of the system.
ACKNOWLEDGEMENTS

The authors are thankful to Prof. A.U. Malik for providing research facilities
and the University Grants Commission (India) for financial assistance.

REFERENCES
K.G. Varshney, S. Rani and R.P. Singh, Ecotoxicol. Environ. Saf., 11 (1986).
R.P. Singh, K.G. Varshney and S. Rani, Ecotoxicol. Environ. Saf., 10 (1985) 309.
K.G. Varshney, A.A. Khan, A. Maheshwari, S. Anwer and U. Sharma, Indian J. Technol., 22
(1984) 99.
M.S. Mithyantha and N.S. Perur, Curr. Sci., 43 (1979) 578.
C.H. Giles, T.H. MacEwan, S.N. Nakhwan and D. Smith, J. Chem. Sot., (1960) 3973.
J.P. Singal and N. Singh, Soil Sci., 125 (1978) 301.
R. Van Blade1 and A. Moreale, Soil. Sci. Sot. Am. Proc., 38 (1974) 244.
J.W. Biggar and M.W. Cheung, Soil Sci. Sot. Am. Proc., 37 (1973) 863.
S. Glasstone, Text Book of Physical Chemistry, Van Nostrand, New York, 1960, pp. 815-883.