Kinetics and Reaction Mechanism of

Fenton's-Reagent-Initiated Graft Copolymerization

of Acrylonitrile onto Sodium Alginate
S. 6. SHAH, C. P. PATEL, and H. C. TRIVEDI*
Department of Chemistry, Sardar Patel University, Vallabh Vidyanagar-388120, Cujarat, India

SYNOPSIS

The kinetics and mechanism of grafting of acrylonitrile (AN) onto sodium alginate (SA)
using Fenton's reagent ( Fe2+-H202)has been studied. The experimental results are found
to be in good agreement with the proposed kinetic scheme. 0 1994 John Wiley & Sons, Inc.

INTRODUCTION
In our previous studies we have reported Cericinduced' as well as Fenton's-reagent-initiated'
grafting of acrylonitrile (AN) onto sodium alginate
( SA ) and investigated the biodegradable behavior
of sodium alginate-graft-acrylonitrile by studying
its interactions with different microorganism^.^ This
note is a report on the kinetics and mechanism of
grafting of AN onto sodium alginate using Fenton's
reagent as an initiator.

EXPERIMENTAL
In order to discover the optimal conditions for
grafting of acrylonitrile onto sodium alginate using
Fenton's reagent as an initiator, polymerization was
carried out under various conditions as described
earlier.' The variables studied included sulfuric acid
concentration, concentrations of initiator components, monomer concentration, reaction time, temperature, and amount of sodium alginate. The results
of our previous study' have been used in the present
work.

RESULTS AND DISCUSSION

Kinetics and Mechanism

In a system containing HzOz, ferrous ammonium

sulfate (FAS), and sodium alginate, H202may react
with FAS ( Fe2+)to form 'OH. The hydroxyl radical
thus formed abstracts hydrogen from the hydroxyl
groups present on the reactive sodium alginate (SAOH) backbone to produce sodium alginate macroradicals (SA-0'), which react with the monomer
( M ) to initiate grafting. The following reaction
mechanism scheme is proposed for this graft copolymerization:

Fe2+ HO-OH

2 Fe3++ HO-

+ 'OH

(1)

The free radicals ('OH) formed in the above

manner attack sodium alginate (SA-OH) , giving
rise to sodium alginate macroradicals (SA-0') .

(SA-OH)

'0 OR

....;om
OZ

'0

* To whom correspondence should be addressed,

Journal of Applied Polymer Science, Vol. 52, 857-860 (1994)
0 1994 John Wiley & Sons, Inc.
CCC 0021-6995/94/070857-04

H (SA-6)

(SA-6)
+H,O

(2)
857

858

SHAH, PATEL, AND TRIVEDI

(iv) Oxidation

(i)Initiation

C0,Na

ki

'0

**.'"

Of + CH,=CH -*
I
GN

....om

(SA-6)

of (3)

The lives of the growing polymers are relatively

short and hence the steady-state approximations
may be applied to these radicals. The following
equations thus follow:

(SA-0-M;

d [ SA-0-M;]
dt

(ii)Propagation

ki [ SA-0'1 [MI
-

Kp[ SA-0-Mi] [MI

- K,[ SA-0-M;]

HC-H,C-O
I
NC

''..o

- $[
H&H,CfHC-H,CjO
I
I
NC
NC

H
(SA-0-M;

*}

(7)

d [ SA-0-Mi]
= kp[SA-O-Mi][M]
dt

(MI

{ [ SA-O-M;]

+ [SA-0-Mi] + -

CN

(SA-0-M;

(6)

'0

(M)

H&H,C-O
I
NC

16 oxidation
products

SA-0-Mi] [MI

k,[ SA-0-Mi] { [ SA-O-M;]

+ [SA-0-Mi] +

* *

-}

(8)

d [ SA-0-M',]
dt
= Kp[ SA-O-M',-I] [MI
fHC-H,C-t;;O
I
NC

H
(SA-O-M,'_)

Of + H,C=CH
I
CN

kP

(MI

. * * . " P o f (4b)
HC-H,C~-HC-H,C~~O
i
NC

K,[ SA-0-M',] { [ SA-0-Mi I

of

(9)

2 [SA-0-M',l2

(10)

The [SA-0-M',] is the concentration of the

longest polymeric radical and as it is small, its concentration can be neglected. Therefore, we get

1)

ki[ SA-0'1 [MI - k,

.*.

HC-H,C+HC-H,C~,O
I
NC

*}

Ki [ SA-0'1 [MI - Kp[ SA-0-M',] [MI

1)

- K,

(SA-0-M

Adding Eqs. (7), (81, and (9), we get

(iii)Termination

NC

(SA-0-M

NC

Kp[ SA-0-M',] [MI

+ [SA-0-Mi] + -

C0,Na

I
NC

I
NC

2 [SA-0-M',]

2 [ SA-0-Mi]

\/"
k,

=0

[SA-0.1 [MI

(11)

(SA-0-M

A)
graft
copolymer

(5)

Similarly for 'OH radical the following equation

can be written:

KINETICS AND REACTION MECHANISM OF FENTONS REAGENT

-d[oH1 -

k1[H202][Fe2+]- kd[SA] [OH]

859

dt

Further, we can write

d [ SA-01
=

dt

kd[SA][OH] - ki[SA-O][M]

005 006 007

(yo,@

OO9

Figure 2 Plot of In Rp vs. [ H202]

0.5. (Data taken from
Ref. 2 ) .

or

Putting Eq. ( 12 in ( 13), we get

[ H202]I2[ Fe2+]1 / 2
X {ki[M1 + k0[H2021}~~

Substituting Eq. ( 14) in (11) , we get

In Rp = C1

2 [SA-0-Mi]

+ f ln[H202]+ f ln[Fe2+]

+ $ l n [ M ] - f In $[MI [ 1 +
+

where C1 = In kp f In ki f In kl - f In k , . Since
ki 9 k o and [MI 9 [ H202], then k o [H202] ki[ MI
and let x = ko[H202]/ki[M]

The rate of polymerization, R p , is given by

Rp = kp[M] 2 [SA-0-Mi]

(16)

02

04

06

08

$0

$2

+ f In [ H202]+ f In [ Fe2+]+ $ In [ MI
4 In ki[M] f l n ( 1 + x )
In Rp = C1 + f ln[H202]+ f ln[Fe2+]
+ l n [ M ] - f In ki - f ln[M]

In Rp = C1

Upon substituting Eq. ( 15) in ( 16), we get

k:i;gl]

-In[M1

Figure 1 Plot of In Rp vs. In [MI. (Data taken from

Ref. 2.

002003ooc0.05006007
(FAS

Figure 3 Plot of In Rp vs. [ FAS] 0.5. (Data taken from

Ref. 2.

860

SHAH, PATEL, AND TRIVEDI

Since the value of x is very small, the terms involving x 2 , x 3 ) etc. can be neglected and we get,

+ f In [ H20,] + f In [Fez+J

In Rp = Cl
In Rp = C2

+:ln[M] f ln[H202]

f lnki - f ln[M] (20)

+ f ln[Fe2+]+ ln[M]

(21)

where C2 = C1 - f In hi.
According to Eq. (21) the plots In Rp versus
In [ M I , In Rp versus In [ H202]' I 2 , and In Rp versus
In [ Fe2+]' I 2 should be linear and are found to be so
)

as shown in Figures 1, 2, and 3, respectively, thus

confirming the validity of the above reaction scheme.

REFERENCES
1. S.B. Shah, C. P. Patel, and H. C. Trivedi, High Performance Polym., 4,151 (1992).
2. S . B. Shah, C. P. Patel, and H. C. Trivedi, J. Appl.
Polym. Sci., to appear.
3. S . B. Shah, C. P. Patel, and H. C . Trivedi, Communicated to J . Polym. Mat., to appear.
Received July 26, 1993
Accepted October 20, 1993