Table 1

[LA]

= 0.2 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

10-7 [-d [Ce(IV)]/dt] mol. dm-3. sec-1

[Ce(IV)] mol. dm-3

300C

350 C

0.00314

6.9079

5.3289

0.00418

7.6974

7.5

0.00523

8.2895

8.8816

0.00627

8.8816

10.8553

0.0732

10.0658

12.2368

0.00783

10.8553

12.3434

14

35oC
10-7[-d[Ce(IV)]/dt] mol. dm-3.Sec-1

12

30oC

10
8
6
4
2
0

-23--33

0.01

0.02

0.03

0.04

[Ce(IV)] mol. dm-3

Fig.1

0.05

0.06

0.07

0.08

Table 2
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

10-7 [-d [Ce(IV)]/dt] mol. dm-3. Sec-1

-3

10-7 [-d [Ce(IV)]/dt] mol. dm-3.

Sec-1

[LA] mol. dm

300C

350C

0.02

14.013

14.605

0.03

15.395

15.395

0.04

15.987

16.974

0.05

16.579

17.961

0.055

17.566

19.145

0.06

17.961

20.132

25

35oC

20

30oC
15

10

0
0

0.01

0.02

0.03

0.04

0.05

[LA] mol. dm-3

Fig.2

0.06

0.07

Table 3
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

-1

106 [-d [Ce(IV)]/dt]-1mol. dm-3. Sec-1

-3 -1

[LA] (mol. dm )

300C

350C

50

0.7136

0.6847

33.33

0.6496

0.6496

25

0.6255

0.5891

20

0.6032

0.5568

16.67

0.5693

0.5223

14.29

0.5568

0.4967

30oC

0.7

35oC

106 [-d [Ce(IV)]/dt]-1mol. dm-3.

Sec-1

0.8

0.6
0.5
0.4
0.3
0.2
0.1
0
0

10

20

30

40

[LA]-1 (mol. dm-3)-1

Fig.3

50

60

Table 4
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[LA]

= 0.2 mol. dm-3

Temperature = 300C & 350C.

-1

106 [-d [Ce(IV)]/dt]-1 mol. dm-3. Sec-1

-3 -1

106 [-d [Ce(IV)]/dt]-1 mol. dm-3.

Sec-1

[H2SO4] (mol. dm )

300C

350C

20

1.2992

1.1783

3.33

1.1259

1.1014

1.818

1.034

1.0555

1.25

0.9559

0.9744

0.952

0.8587

0.9212

0.769

0.7795

0.8587

30oC

1.4
1.2

35oC

1
0.8
0.6
0.4
0.2
0
0

10

15

[H2SO4]-1 (mol. dm-3)-1

Fig.4

20

25

Table 5
[LA]

= 0.2 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300c & 350c.

[M]

= 0.02 mol.dm-3
10-4 [-d [Ce(IV)]/dt] mol. dm-3. Sec-1

-3

[Ce(IV)] mol. dm

300C

350C

0.00314

3.1578

4.9342

0.00418

6.1184

8.6842

0.00523

6.5131

9.0789

0.00627

9.0789

11.6447

0.00732

10.0657

12.6315

0.00784

10.6578

13.0263

10-4 [-d [Ce(IV)]/dt] mol. dm-3.

Sec-1

16

35oC

14
12

30oC

10
8
6
4
2
0
0

0.001

0.002

0.003

0.004

0.005

0.006

[Ce(IV)] mol. dm-3

Fig.5

0.007

0.008

0.009

Table 6
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3
10-3 [-d [Ce(IV)]/dt] mol. dm-3. Sec-1

-3

[LA] mol. dm

300C

350C

0.02

1.1644

1.6578

0.03

1.3223

1.6973

0.04

1.3618

1.7763

0.05

1.3815

1.8552

0.055

1.4802

1.8947

0.06

1.5789

1.9539

10-3 [-d [Ce(IV)]/dt] mol. dm-3.

Sec-1

2.5

35oC

1.5

30oC

0.5

0
0

0.01

0.02

0.03

0.04

0.05

[LA] mol. dm-3

Fig.6

0.06

0.07

Table 7
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[LA]

= 0.02 mol.dm-3
10-4 [-d [Ce(IV)]/dt] mol. dm-3. Sec-1

-3

10-4 [-d [Ce(IV)]/dt] mol. dm-3.

Sec-1

[M] mol. dm

300C

350C

0.0004

4.9342

3.9473

0.0005

5.3289

4.3421

0.0006

6.1184

4.7368

0.0007

3.9473

5.1315

0.0008

5.9210

6.1184

0.0009

7.3026

6.9078

8
7
6

30oC

5
4

35oC

3
2
1
0
0

0.0002

0.0004

0.0006

[M] mol. dm-3

Fig.7

0.0008

0.001

Table 8
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3

-1

103 [-d [Ce(IV)]/dt]-1 mol. dm-3. sec-1)-1

-3 -1

103 [-d [Ce(IV)]/dt]-1 mol. dm-3.

sec-1)-1

[LA] (mol. dm )

300C

350C

50

0.8588

0.6032

30.33

0.7562

0.5892

25

0.7343

0.5629

20

0.7238

0.5390

18.18

0.6756

0.5278

16.66

0.6333

0.5118

1
0.9

30oC

0.8
0.7

35oC

0.6
0.5
0.4
0.3
0.2
0.1
0
0

10

20

30

40

[LA]-1 (mol. dm-3)-1

Fig.8

50

60

Table 9
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[LA]

= 0.2 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3

-1

103 [-d [Ce(IV)]/dt] -1 (mol. dm-3. Sec-1)-1

-3 -1

103 [-d [Ce(IV)]/dt] -1 (mol. dm-3.

sec-1)-1

[H2SO4] (mol. dm )

300C

350C

20

0.7562

0.7238

3.333

0.7451

0.7451

1.8181

0.7343

0.7136

1.25

0.7037

0.7037

0.9523

0.6667

0.6496

0.7692

0.6414

0.6255

0.9

30oC

0.8
0.7

35oC

0.6
0.5
0.4
0.3
0.2
0.1
0
0

10

15

[H2SO4]-1 (mol. dm-3)-1

Fig.9

20

25

Table 10
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3

-1

107 [-d [M]/dt]-1 (mol. dm-3. Sec-1)-1

-3 -1

107 [-d [M]/dt]-1 (mol. dm-3. sec1 -1

)

[LA] (mol. dm )

300C

350C

50

9.2311

0.8541

33.33

4.6153

0.7224

25

3.7509

0.6707

20

0.8889

0.5522

18.18

0.6956

0.5217

16.66

0.6476

0.4580

10

30oC

8
6
4
2

35oC
0
0

-2

[LA]-1 (mol. dm-3)-1

Fig.10

Table 11
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[LA]

= 0.2 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3
-1

107 [-d [M]/dt] -1 (mol. dm-3. sec-1)-1

-3 -1

107 [-d [M]/dt] -1 (mol. dm-3. sec1 -1

)

[H2SO4] (mol. dm )

300C

350C

20

0.7224

0.9884

3.333

0.4472

0.8163

1.8181

0.3683

0.7224

1.25

0.3354

0.6956

1.9523

0.3183

0.6956

0.7692

0.2981

0.6030

1.2

35oC

0.8

30oC

0.6
0.4
0.2
0
0

10

15

[H2SO4]-1 (mol. dm-3)-1

Fig.11

20

25

Table 12
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[LA]

= 0.2 mol. dm-3

Temperature = 300C & 350C.

[H2SO4]

= 5 mol.dm-3
Rp x 10-7

-3

[M] mol. dm

300C

350C

0.0004

1.8655

1.5112

0.0005

2.3488

2.0239

0.0006

2.8537

2.6232

0.0007

3.3288

3.1013

0.0008

3.8259

3.6859

0.0009

4.4411

4.2285

30oC

4.5
4

35oC

Rp x 10-7

3.5
3
2.5
2
1.5
1
0.5
0
0

0.0002

0.0004

0.0006

[M] mol. dm-3

Fig.12

0.0008

0.001

Table 13
[LA]

= 0.2 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

= 0.02 mol.dm-3

[M]

Rp x 10-7

-3

[Ce(IV)] mol. dm

300C

350C

0.00314

2.9076

2.6588

0.00418

2.9243

2.8360

0.00523

2.9423

2.9068

0.00627

3.0297

2.9423

0.00732

3.0658

2.9778

0.00784

3.1017

3.0133

3.15

30oC

3.1
3.05

35oC

Rp x 10-7

3
2.95
2.9
2.85
2.8
2.75
2.7
2.65
2.6
0

0.001

0.002

0.003

0.004

0.005

0.006

[Ce(IV)] mol. dm-3

Fig.13

0.007

0.008

0.009

Table 14
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3
Rp x 10-8

-3

[LA] mol. dm

300C

350C

0.02

0.3607

3.8981

0.03

0.7214

4.6083

0.04

0.8878

4.9634

0.05

3.7455

6.0288

0.055

4.7859

6.3806

0.06

5.1327

7.2663

35oC

Rp x 10-8

30oC

5
4
3
2
1
0
-1

0.01

0.02

0.03

0.04

0.05

[LA] mol. dm-3

Fig.14

0.06

0.07

Table 15
[LA]

= 0.2 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3

[-CD] = 0.02 mol.dm-3

10-4 [-d [Ce(IV)/dt] mol. dm-3. sec-1

-3

[Ce(IV)] mol. dm

300C

350C

0.00314

1.7763

1.1842

0.00418

3.3553

2.1711

0.00523

4.3421

3.5526

0.00627

6.1184

4.3421

0.00732

6.9079

4.9342

0.00784

8.4868

5.7237

9
8
7
y = 934.56x - 1.6414
6

R2 = 0.9863

5
4

y = 1342.2x - 2.4368

R2 = 0.9835

2
1
0
0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

0.009

Table 16
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[M]

= 0.02 mol.dm-3

[-CD] = 0.02 mol.dm-3

10-3 [-d [Ce(IV)/dt] mol. dm-3. sec-1

-3

[LA] mol. dm

300C

350C

0.02

2.6447

2.9605

0.03

2.5658

2.9211

0.04

2.5066

2.8026

0.05

2.4474

2.7434

0.055

2.3882

2.6645

0.06

2.2895

2.5461

y = -9.8467x + 3.1915

3.5

R2 = 0.943

3
2.5
2

y = -8.0594x + 2.8162
R2 = 0.9553

1.5
1
0.5
0
0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

Table 17
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300C & 350C.

[LA]

= 0.2 mol.dm-3

[-CD] = 0.02 mol.dm-3

10-4 [-d [Ce(IV)/dt] mol. dm-3. sec-1

-3

[M] mol. dm

300C

350C

0.0004

0.5921

2.5658

0.0005

1.5789

3.75

0.0006

2.5658

5.1316

0.0007

3.75

6.1184

0.0008

5.1316

7.6974

0.0009

6.1184

8.4868

10
9
8

y = 12124x - 2.2556

R2 = 0.9953

6
5
4
3

y = 11278x - 4.0414

R2 = 0.9967

1
0
0

0.0002

0.0004

0.0006

0.0008

0.001

Table 18
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

= 0.02 mol.dm-3

[-CD] = 0.02 mol.dm-3

& 350c.
[M]

103[-d (Ce(IV)/dt]-1 (mol. dm-3. sec-1)-1

-3 -1

[Ce(IV)] (mol. dm )

300c

350c

50

0.3781

0.3378

33.33

0.3897

0.3423

25

0.3989

0.3568

20

0.4085

0.3645

18.18

0.4187

0.3753

16.66

0.4368

0.3928

0.5

y = -0.0015x + 0.4448

0.45

R2 = 0.7794

0.4
0.35
0.3

y = -0.0014x + 0.3995

0.25

R2 = 0.7345

0.2
0.15
0.1
0.05
0
0

10

20

30

40

50

60

Table 19
[Ce(IV)]

= 0.0209 mol.dm-3

= 1.1 mol.dm-3

[LA]

= 0.2 mol. dm-3

Temperature = 300c & 350c.

[M]

= 0.02 mol.dm-3

[-CD]

-1

= 0.02 mol.dm-3

103 (-d [Ce(IV)/dt)-1 (mol. dm-3. sec-1)-1

-3 -1

[H2SO4] (mol. dm )

300c

350c

20

0.3543

0.3423

3.3333

0.3698

0.3494

1.8181

0.3726

0.3543

1.25

0.3868

0.3989

0.9523

0.3989

0.4053

0.7692

0.4119

0.4187

y = -0.002x + 0.3919

0.45

R2 = 0.5291

0.4
0.35
0.3

y = -0.0027x + 0.3908

0.25

R2 = 0.381

0.2
0.15
0.1
0.05
0
0

10

15

20

25

Table 20
[Ce(IV)]

= 0.0209 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300c & 350c.

[M]

= 0.02 mol.dm-3

[-CD]

-1

= 1.1 mol.dm-3
= 0.02 mol.dm-3

107 [-d [Ce(IV)/dt]-1 (mol. dm-3. sec-1)-1

-3 -1

[LA] (mol. dm )

300c

350c

50

0.3261

0.3435

33.33

0.2577

0.3319

25

0.3159

0.3210

20

0.2967

0.3108

18.18

0.2511

0.2923

16.66

0.2331

0.2683

0.4

y = 0.0018x + 0.2305
R2 = 0.3709

0.35
0.3
0.25

y = 0.0018x + 0.2618
R2 = 0.7089

0.2
0.15
0.1
0.05
0
0

10

20

30

40

50

60

Table 21
[Ce(IV)]

= 0.0209 mol.dm-3

[LA]

= 0.2 mol. dm-3

Temperature = 300c & 350c.

[M]

= 0.02 mol.dm-3

[-CD]

-1

= 1.1 mol.dm-3
= 0.02 mol.dm-3

107 [-d [Ce(IV)/dt]-1 (mol. dm-3. sec-1)-1

-3 -1

[H2SO4] (mol. dm )

300c

350c

20

0.2879

0.2758

3.3333

0.3159

0.2923

1.8181

0.3435

0.3159

1.25

0.3497

0.3319

0.9523

0.3626

0.3626

0.7692

0.3839

0.3996

0.45
0.4
y = -0.0037x + 0.3581

0.35

R2 = 0.6801

0.3
0.25
0.2
0.15

y = -0.004x + 0.3484
R2 = 0.4342

0.1
0.05
0
0

10

15

20

25

Table 22.
[Ce(IV)]

= 0.0209 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300c & 350c.

[LA]

= 0.2 mol.dm-3

[-CD]

= 1.1 mol.dm-3
= 0.02 mol.dm-3
Rp x 10-7

-3

[M] mol. dm

300c

350c

0.0004

1.3475

1.4041

0.0005

1.6924

1.7288

0.0006

2.2950

2.0231

0.0007

2.8757

2.2809

0.0008

3.4223

2.4251

0.0009

4.0049

2.6274

y = 5445x - 0.9329
R2 = 0.9956

4.5
4
3.5
3
2.5
2
1.5

y = 2418.1x + 0.5098
R2 = 0.9815

1
0.5
0
0

0.0002

0.0004

0.0006

0.0008

0.001

Table 23
[LA]

= 0.2 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300c & 350c.

[M]

= 0.02 mol.dm-3

[-CD]

= 1.1 mol.dm-3
= 0.02 mol.dm-3
Rp x 10-7

-3

[Ce(IV)] mol. dm

300c

350c

0.00314

1.9379

2.1422

0.00418

2.0911

2.1759

0.00523

2.1759

2.2273

0.00627

2.2781

2.2612

0.00732

2.4651

2.2950

0.00784

2.6013

2.3631

y = 132.09x + 1.5102

R2 = 0.9715

2.5
2
1.5

y = 43.316x + 1.9988
R2 = 0.9628

1
0.5
0

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008

0.009

Table 24
[Ce(IV)]

= 0.0209 mol.dm-3

[H2SO4]

= 5 mol. dm-3

Temperature = 300c & 350c.

[M]

= 0.02 mol.dm-3

[-CD]

= 1.1 mol.dm-3
= 0.02 mol.dm-3
Rp x 10-7

-3

[LA] mol. dm

300c

350c

0.02

1.0209

0.9691

0.03

1.2921

1.0029

0.04

0.0540

0.0371

0.05

1.1223

1.0712

0.055

1.3259

1.1389

0.06

1.4280

1.2410

1.6
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

C.M.Patra et.al (1994) was investigated the influence of N-acetylglycine on the

kinetics of graft copolymerization of acrylonitrile (AN) and methyl methacrylate (MMA)
onto chemically modified jute fibers was studied in the temperature range 40-600C. The
optimum conditions for grafting have been determined by the effects of concentrations of
monomers, Ce(IV), and N-acetylglycine on the rate of grafting. The effect of time,
temperature, and concentration of the acid, the amount of jute fibers and some organic
solvents and inorganic salts on the rate of grafting has been reported. On the basis of
experimental results findings out, a kinetic scheme has been proposed. Infrared spectra of
chemically modified jute and grafted jute have been investigated. More than 185% graft
yield could be achieved with the present system. Grafting has improved the thermal
stability of jute fibers.
H.K.Das, et.al (1993) was investigating the effects of toluene on the kinetics of
polymerization of acrylonitrile (AN) initiated by the Ce(IV) / sucrose redox system in the
presence of an emulsifier, N-cetyl-trimethylammonium bromide (NCTAB) in the
temperature range 35-450C. The effects of concentration of metal ion, monomer, sulfuric
acid, substrate (sucrose), emulsifier, toluene, some inorganic salt, and organic solvent on
Rp have been investigated. The remarkable features of the investigation involve the
derivation of the rate expression for the above system with the calculation of activation
energy (Ea).
B.K. Patel et.al(1993) was investigating the Graft copolymerization of
acrylonitrile onto Sodium salt of partially carboxy methylated starch using ceric

ammonium nitrate (CAN) has been carried out in the presence of triethylamine,
diethylamine, ammonia and pyridine. The percentage of grafting varied with the nature
and concentration of the amines. All the amines with exception of diethylamine have
been found to suppress grafting. The relative reactivity of different amines towards
grafting has been determined and found to follow the order :DEA > TEA > ammonia >
pyridine.
Nesrin Oz et.al (2001) was investigating the Ethoxylated nonyl phenols,
ethoxylated fatty alcoholos, and ceric ammonium nitrate redox systems were used for the
polymerization of vinyl and acrylic monomers such as acrylonitrile, styrene, and acrylic
acid. The initiating radical was formed on reducing organic compound which in turn
initiated polymerization to give polymers containing chain ends of ethoxylated nonyl
phenols and ethoxylated fatty alcohols that showed much higher water absorption. The
effects of the concentration of Ce+4 salt, ethoxylated nonyl phenols, and monomers on
both the yield and the molecular weight of corresponding polymers were studied.
M.Patra et.al (1996) studying the polymerization of acrylonitrile (AN) the Ce(IV)
Citric Acid (CA) redox system as an initiator in aqueous nitric acid solution, in the
presence of an anionic surfactant, sodium dodecyl sulfate (SDS) has been kinetically
reported at a temperature range of 25-450C. The rate of polymerization (Rp) and
disappearance of Ce(IV) (-Rce) increase with increasing concentration of SDS above its
critical micelle concentration (CMC) when the surfactant molecules are organized, Rp
was found to be proportional to [AN]1.5 and [CA]0.5 with other organic substrates Rp

follows the increasing order of sorbitol > mannitol > glycerol > CA. It was found to
decrease considerably in the presence of cationic surfaetant (CTAB), and nonionic
surfactant (Trition - X 100) had no effect on the rate. Rce various linearly with
[Ce(IV)] and [CA]. Both Rp and Rce increase with increasing temperature. The overall
activation energy was found to be 18.31 and 13.72 k.cal mol in the absence and presence
of 0.015 MSDS, respectively. The chain length of the polyacrylonitrile has also increased
with increasing SDS concentration.
Femeozturk et.al (2007) was studying the present review gives a comprehensive
account on the synthesis of block copolymers via redox initiating systems. Redox
polymerization systems for the synthesis of block copolymers have been reported. The
mechanism of initiation by a radox process is a method which is used to obtain block
copolymers by various transition metals, such as Ce(IV), Mn(III), Cu(II), and Fe(III)
redox polymerization has found wide applications in initiating polymerization reactions
in initiating polymerization reactions and has been specifically of industrial importance.
As it follows from the Contents in addition to the above mentioned metals other redox
polymerization systems such as hydrogen peroxide and vanadium are described as well.
P.L.Nayak et.al (2011) was studying the grafting of acryonitrile onto chitosan
was studied using ceric ammonium nitrate as the redox initiation in aqueous media. The
percentage of grafting and the efficiency of the process were calculated as function of the
concentration of initiator and monomer the reaction time and temperature. The
percentage of grafting was found to depend on the relative amount of monomer to

chitosan, initiator and volume of the aqueous phase as well as the reaction temperature.
By using optimized combinations of the reaction variables a grafting efficiency up 88%
and a percentage of grafting of nearly 220% were reached. Evidence of grafting was
obtained from comparison of SEM, XRP, and FTIR of the grafting and non-grafted
chitosan as well as solubility characteristics of the product. The antibacterial and
angifungal activities of the grafted polymer have also been investigated.

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