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1.1.
GENERAL ASPECTS
A
large
macromolecule
number
or
of
smaller
polymer.
This
molecules
unite
chemical
process
to
form
is
called
The
polymerization
and
addition
polymerization.
In
The
free-radical
polymerization
involves
chain
reaction,
kp
+
M
kp
M
kp
RM2
RM3
RM4
By recombination
(ii)
kt
R- CH2-CHX-XHC-CH2R
By disproportionation
R-CH2-CHX + XCH-CH2-R
kt
R-CH2-CH2X + R-CH=CH-X
(iii)
By metal
(iv)
kt
By primary radical
R-CH2-CHX + R
kt
R- CH2-CHXR
complex
In the
of
AAM
manganese(III)
acetate,
and
methacrylamide
Santappa
et
al.40-42
initiated
proposed
that
by
the
Jayakrishnan and
Mahadevan60 investigated the polymerization of AN initiated by Mn(III)cyanoacetic acid and Mn(III)-2-butanone redox systems and suggested
that the initiation was through the complex formed between Mn(III) and
reducing agent and termination by the mutual combination of growing
chains. Though the above authors suggested the complex formation,
the complex formation constant had not been evaluated.
Nayak et al.61 investigated the polymerization of AN with a series
of organic acids as reducing agents and found that the order of
reactivity varied as citric > tartaric > ascorbic > oxalic > succinic >
glutaric > adipic acid. Similarly in the polymerization of MMA, initiated
by Mn(III)-alcohol redox systems62, the reactivity of alcohols was found
to vary in the order : 1-propanol > glycerol > ethylene glycol > isobutyl
alcohol > 1-butanol > 1,2-propanediol > cycloheptanol > cyclohexanol >
cyclopentanol. The kinetics of polymerization of AN, initiated by Mn(III)
Elayaperumal
the
foregoing
survey,
it
becomes
evident
that
the
CHEMISTRY OF CERIUM
Cerium belongs to the group of inner transition elements with the
acidic,
more
easily
hydrolysed
and
more
susceptible
to
complexation than Ce(III). The salts of quadrivalent cerium are noted for
10
their strong oxidizing power and are largely used in analysis and
synthesis. Oxidation of a substrate by Ce(IV) occurs through transfer of
a single electron from the substrate to the oxidant
Ce(IV) + e-
Ce(III)
Ce(OH)3+ + H2O
70
Ce(OH)22+ + H+
11
species
upto
concentration
of
0.01M
H2SO4.
Hardwick
and
Robertson73 have studied the association of ceric ions with sulphate ion
spectrophotometrically and proposed the existence of complexes of the
type Ce(SO4)2+, Ce(SO4)2 and (Ce(SO4)3)2- In nitric acid medium
Blaustein and Gryder74 identified the existence of the following dimers
and
2 Ce(IV)
(Ce(IV))2
Ce(IV) + Ce(III)
(Ce(IV) Ce(III))
12
kd
Complex
R + Ce(III) + H+
fast
R + Ce(IV)
products + Ce(III) + H+
acid
media
was
made
by
Saldick86
in
1956.
Later
13
14
when
compared
to
non-redox
system.
This
would
permit
15
followed
similar
kinetics
with
the
rate
of
monomer
16
17
The
18
The termination
systems,
the
rate
of
polymerization
was
proportional
to
19
20
beyond this concentration, the rate was found to have decreased. The
half order on the [IBA] and 3/2 order on the [MMA] suggested the
mutual termination of growing polymeric radicals.
Fernanda et al.120 investigated the polymerization of MMA,
initiated by ceric ammonium nitrate-methanol redox system, in
aqueous nitric acid medium. The concentration of nitric acid in the
reaction medium was varied from 1.0 x 10-3 N to 1.0 N. An increase in
the acid concentration from 1 x 10-3 N to 9 x 10-2 N caused an
increase in the rate of polymerization, but for acid concentrations
above 9x10-2N the Rp values decreased progressively. At the high
concentration of nitric acid, the protonation of methanol did not favour
the complex formation between ceric ion and methanol.
Fernandez and Guzman121 reported the effects of nitric acid and
nitrate ion concentration on the polymerization of MMA initiated by
ceric ammonium nitate-2-propanol and 2-butanol redox systems. In
these systems, the Rp values initially increased rapidly on increasing the
nitric acid concentration upto 0.1 M and then decreased with further
increase of acid concentration. It was shown that ceric ions in acid
solution consist of different species such as Ce4+, Ce(OH)3+ and
(Ce-O-Ce)6+, whose relative amounts depend on the acid concentration,
according to the equilibria (1) and (2).
21
Ce4+ + H2O
(CeOH)3+ + H+
(1)
2(CeOH)3+
(Ce-O-Ce)6+ + H2O
(2)
of
malonic
acid
systems.
During
Ce(IV)-EDTA
redox
spectrophotometric
system
process.
The
in
aqueous
radicals
medium
which
through
initiated
the
Ce(IV) - EDTA
Complex C
kd
Ce(IV) EDTA
Complex C
EDTA + Ce(III) + H+
R
22
23
The rate of ceric ion consumption RCe was first order with respect to
Ce(IV) concentration in the concentration range (0.5 - 5.5) x 10-3 M and
0.5 order with respect to reducing agent concentration in the
concentration ranges (0.0480 - 0.2967 M) and (0.0500 - 03912 M) for
Ce(IV) - MEK and Ce(lV)-acetone initiator systems respectively.
Nalla Mohamed128 has studied the polymerization of acrylamide
initiated by Ce(IV) -iminodiacetic acid (IDA) redox system in aqueous
solution. Polymerisation behaviour as a function of the concentration of
Ce(IV), IDA and acrylamide as well as temperature has been studied.
The rate of polymerization has been found to be first order with respect
to the concentration of monomer. The complex formation constant (K)
and disproportionation constant (kd) of Ce(lV) IDA complex were
evaluated.
complex
The
effect
(initiator)
of
excess
concentrations
of
Ce(IV),
was
mineral
studied.
acid
Evaluation
and
of
24
and
Kishore131
have
studied
catalytic
oxidative
polymerization
of
acrylonitrile,
initiated
by
Tristrinitratocerium(IV)paraperiodate-propane-l,2-diol133,
the
system
has
been
and
acrylamide
initiated
by
the
redox
system
25