Kinetics and Mechanistic study of oxidation of L-Alanine by Using N-Bromophalimide in presence of Chloro– Complex of Pd (II) as Homogenous Catalyst in Aqueous Acetic acid medium

 

Jaishree Gawai1, Mazahar Farooqui2, Narayan Lawale3 , MilindUbale4

1Jawaharlal Nehru Engineering College, N-6 CIDCO, Aurangabad, India

2Dr. Rafiq Zakaria College for Women, Aurangabad, India

3Moreshwar Arts, Commerce and Science College, Bhokardan Dist Jalna , India

4Vasantrao Naik College, India

*Corresponding Author E-mail: drmilindubale@gmail.com

 

ABSTRACT:

Spectrophotometric study of oxidation of Palladium chloride catalyzed L-Alanine in aqueous acetic acid medium has been studied at different temperatures. Present research work focus on effect of various parameters on oxidation of L- Alanine . Parameters varies during the study of reaction is concentration of L-Alanine, Palladium chloride and effect of salts on oxidation phenomenon. As a conclusion oxidation reaction was found as first order reaction with respect to L Alanine, N bromopthalamide Palladium chloride ,Perchloric acid and Kcl.

 

KEYWORDS:L-Alanine, NBP, Perchloric acid (HClO4), Mercuric Acetate (Hg(AO)2, Acetic acid (CH3COOH).

 

 


INTRODUCTION:

N-halogeno compounds are versatile in nature and due to their ability to act as sources of halonium ions, hypohalite species and nitrogen anions they act as both bases and nucleophbiles. N-halocompounds have been used widely as oxidizing and halogenating reagent in organic compounds [1-5]. N-halocompounds, a group of mild oxidizing agents, have been extensively used for catalyzed [6-8] and uncatalyzed [9-12] oxidation of variety of organic compounds. N-bromophthalimide (NBP) has recently been developed as an oxidimetric titrant for the determination of certain pharmaceuticals by Abou Ouf et. al. [13, 14].

 

Literature survey shows that a large amount of  work has been done on NBP [15-17]  and  is extremely stable in solid state in the absence of light and moisture. Amino acids study  is one of the most exciting fields of organic chemistry. Amino acid plays a significant role in a number of metabolic reactions like biosynthesis of polypeptide, protein and nucleotides. A survey of most recent literature on kinetic study reveals that there is a lots of scope for the study of oxidation process involving various oxidants. There are different system reported in the literature such as oxidation of    L- Alanine by Alkaline Permanganate Ion.

 

The  investigation reports that the oxidation of L-Alanine by NBP under pseudo first order condition occurs in Acidic medium.

 

 

 

 

EXPERIMENTAL:

Material and Methods

Analytical reagent grade chemicals and triple distilled water were used throughout the investigation. The solution of NBP (Lancaster, 98% ) was prepared in 70% acetic acid  and stored in a black-coated flask to prevent any photochemical deterioration . The prepared solution of NBP was standardized by reported method [18]. The Pd(II) chloride solution was prepared by dissolving  a known weight of palladium (II) chloride (S.D.fine) in HCl of known strength and stored in  a black coated bottle to prevent any photochemical deterioration. Standard solution of  KCl, Pthalimide was  prepared with distilled water. Mercuric Acetate solution was prepaired in 20 % acetic acid and perchloric acid(GR) was diluted with triple distilled water for the present investigation.

Kinetic investigations were carried out  under pseudo first order conditions with excess of L- Alanine over, the oxidant at 250C to 450C. Required amount of solution of substrate, Perchloric acid were equilibrated. A measured amount of N-Bromophalimidewas added to the reaction mixture with constant stirring. The time of initiation of the reaction was recorded when half of the content of pipette were released. The solution was taken in a cuvette and absorbance was measured at 330 nm using double beam spectrophotometer SL 210.

L-Alanine (2x10-3M), NBP (2x10-4M) and Perchloric acid  (0.5M) and water volume 100 ml kept a side for 24hrs. The unconsumed NBP was determined spectrophotometrically and the product was verified by TLC. The stichiometry is determined to be 2:1.

 

Product Analysis

Product study was made under acidic condition in presence of Palladium chloride (II). Keeping concentration of NBP, mercuric acetate and acetic acid  in excess over L-Alanine, the two solutions were mixed and Perchloric acid was also added. The reaction mixture was set a side for about 72hr, to ensure completion of the reaction. The reaction mixture was then evaporated and extracted with ether. The ether layer was washed with water many times to remove exess of ether . The ether layer was kept in a water bath for the evaporation of ether and cooled in ice-bath to obtain the solid product.

The product was dissolved in Acetonitrile and a TLC analysis was done. Formation of product was further confirmed by mixing the product with pure solution  and identified  that there was no change in the melting point.

Present study is result of our continuous efforts taken to understand kinetics of various oxidation reactions [19-25].

 

RESULTS AND DISCUSSION:

1: Effect of variation of N-Bromophalimide(NBP)

To study the effect of variation of NBP concentration, the experimental sets were prepared in which concentration of NBP varied from 0.714 x10-5Mto 7.14 x10-5M keeping constant concentration of L-Alanine and Perchloric acid (HClO4). As the reaction has been studied under pseudo first order condition it was observed that O.D. decreases with time (Fig -1). The rate constant was determined using an equation

 

 

 

Which was modified as

 

 

 

 

The Pseudo first order rate constant so obtained is represented in [table-2]. When rate constant is plotted against concentration of N-Bromophalimide [Fig-2] the trend found to be almost straight line with negative slope indicating first order reaction at low concentration of N-Bromophalimide. This has been further confirmed when log [FOR] versus Conc of [NBP] is plotted. [Fig-3]. Hence the reaction under pseudo first order rate depends on the concentration of oxidant. Secondly, from results, it is clear that Initial rate increases with increase in concentration of N-Bromophalimide [Fig-4].


 

Table-1: Effect of Variation of concentration of N-Bromophalimideon initial rate and rate constant of L-Alanine.

Sr. no

NBP Concentration (M)

Initial Rate mole/lit/sec

log [FOR]

Rate constant  (k)(sec-1)       

L-Alanine

1

0.714×10-5 M

3.749

1.570

0.04530

2

1.42×10-5 M

3.794

1.572

0.04530

3

2.14×10-5 M

4.123

1.578

0.04510

4

2.85×10-5 M

4.526

1.583

0.04500

5

3.57×10-5 M

4.626

1.585

0.04497

6

4.28×10-5 M

4.658

1.592

0.04480

7

5×10-5 M

4.763

1.594

0.04478

8

5.71×10-5 M

5.112

1.595

0.04470

9

6.42 ×10-5 M

5.285

1.598

0.04466

10

7.14×10-5 M

5.308

1.601

0.04460

 

 

Table-2: Average rate determination of oxidation of L-Alanine

Time(s)

10-5 Conc (mole/dm3)

10-5< c >

10-5 ∆c

∆t

10-8<rate> mole/dm3/s

log <c >

log <rate>

0

37.5534

3

37.5406

37.5470

0.0128

3

4.2630

1.5746

0.6297

6

37.5214

37.5310

0.0192

3

6.4043

1.5744

0.8065

9

37.5150

37.5182

0.0064

3

2.1217

1.5742

0.3267

12

37.5022

37.5086

0.0128

3

4.2630

1.5741

0.6297

15

37.4868

37.4945

0.0154

3

5.1484

1.5740

0.7117

18

37.4766

37.4817

0.0101

3

3.3776

1.5738

0.5286

21

37.4638

37.4702

0.0128

3

4.2630

1.5737

0.6297

 

 


2: Effect of variation of L-Alanineconcentration (Substrate)To study the effect of variation of concentration of substrate, the sets were prepared in which the concentration of L-Alanine was varied from 0.714 x10-5M to 7.14 x10-5 M, keeping constant concentration of [NBP] = 2 x10-4 M, [Perchloric Acid] = 0.5 M, KCl =1x10-5 and Pd(II)=4.2x10-5M [Fig-5] as the reaction has been studied under pseudo first order condition pseudo first order rate constants were calculated [Table-3]. It is clear that pseudo first order rate constants were found decrease with increases in concentration of [L-Alanine] in irregular way. When initial rate is plotted against concentration of L-Alanine, [Fig-6] the trend line is linear with positive slope. When     log[FOR] versus [L-Alanine] is plotted it confirms the fractional order of reaction. Hence the reaction under pseudo first order rate depends on the concentration of substrate. The average rate is also calculated [Table-4] and the graph between rate constant against [L-Alanine] is straightline with negative slope [Fig-8].


Table-3: Effect of Variation in concentration of L-Alanine on initial rate and Rate constant

Sr. no

L-Alanine

concentration M

Initial Rate mole/lit/sec

log [FOR]

Rate constant  (k)(sec-1) Alanine

1

0.714×10-5 M

3.59

1.483

0.0446

2

1.42×10-5 M

4.279

1.482

0.0474

3

2.14×10-5 M

4.408

1.484

0.0474

4

2.85×10-5 M

4.618

1.486

0.0473

5

3.57×10-5 M

5.198

1.489

0.0472

6

4.28×10-5 M

5.442

1.491

0.0471

7

5×10-5 M

5.537

1.498

0.047

8

5.71×10-5 M

6.101

1.505

0.0469

9

6.42×10-5 M

6.011

1.509

0.0468

10

7.14×10-5 M

6.242

1.515

0.0466

 

Table-4: Average rate determination of oxidation of L-Alanine

Time(s)

10-5 Conc (mole/dm3)

10-5< c >

10-5∆c

∆t

10-8 <rate> mole/dm3/s

log <c >

log <rate>

0

30.7975

3

30.7789

30.7882

0.0187

3

6.2196

1.4884

0.7938

6

30.7578

30.7683

0.0211

3

7.0361

1.4881

0.8473

9

30.7416

30.7497

0.0162

3

5.4031

1.4878

0.7326

12

30.7162

30.7289

0.0254

3

8.4659

1.4875

0.9277

15

30.7042

30.7102

0.0119

3

3.9733

1.4873

0.5992

18

30.6856

30.6949

0.0187

3

6.2196

1.4871

0.7938

21

30.6594

30.6725

0.0262

3

8.7459

1.4867

0.9418

 

 

 

 

 

 

 


 

 

3: Effect of variation of Perchloric acid concentration

To study the effect of variation of concentration of Perchloric acid (HClO4), [Fig-9] in the experimental sets the concentration of HClO4 is varied from 0.714 x10-5 M to 7.14 x10-5 M, keeping constant concentration i.e. [L-Alanine]= 2 x 10-3M and [NBP]=2x10-4 M ,Hg(OA)2=3x10-4 M, KCl =1x10-5M and Pd(II)=4.2x10-5 M. As the reaction has been studied under pseudo first order condition for varying [HClO4] was made and pseudo first order rate constants were calculated in [Table-5]. It is clear from that pseudo first order rate constants decreases with change in concentration of HClO4[Fig-10] confirming the first order dependence with respect to acid. Hence the reaction under pseudo order rate depends on the concentration of acid. [Fig-11] . The average rate determination data confirm that the order with respect to acid concentration is unity [Table-6] and [Fig-12].

 


 

 

Table-5: Effect of Variation in concentration of Perchloric acid (HClO4) on initial rate and rate constant of [L-Alanine] oxidation

     [NBP]=2 x 10-4 M                        [L-Alanine] = 2 x 10 –3 M                     [HClO4] = 0.5 M

 

Sr. No.

Perchloric Acid

(0.5 M) Concentration

Initial Rate of Alanine

log [FOR] Alanine

Rate constant  (k)(sec-1) Alanine

1

0.714 ×10-5 M

6.541

1.042

0.0592

2

1.42×10-5 M

5.265

1.048

0.059

3

2.14×10-5 M

4.958

1.054

0.0588

4

2.85×10-5 M

5.138

1.06

0.0586

5

3.57×10-5 M

5.103

1.067

0.0584

6

4.28×10-5 M

5.563

1.073

0.0582

7

5×10-5 M

5.443

1.081

0.058

8

5.71×10-5 M

4.457

1.091

0.0576

9

6.42×10-5 M

4.483

1.098

0.0571

10

7.14×10-5 M

3.354

1.107

0.0575

 

Table-6: Average rate determination of oxidation of L-Alanine

Time(s)

10-5Conc (mole/dm3)

10-5< c >

10-5 ∆c

∆t

10-8<rate> mole/dm3/s

log <c >

log <rate>

0

31.2100

3

31.2051

31.2076

0.0049

3

1.6396

1.4943

0.2147

6

31.1904

31.1977

0.0148

3

4.9188

1.4941

0.6919

9

31.1658

31.1781

0.0246

3

8.1981

1.4938

0.9137

12

31.1510

31.1584

0.0148

3

4.9188

1.4936

0.6919

15

31.1412

31.1461

0.0098

3

3.2792

1.4934

0.5158

18

31.1215

31.1313

0.0197

3

6.5585

1.4932

0.8168

21

31.1117

31.1166

0.0098

3

3.2792

1.4930

0.5158

                                                                                                                        

 

 


4: Effect of Variation in concentration of Palladium chloride (II) [Pd (II)] on initial rate and Rate constant of [L-Alanine] oxidation.

To study the effect of variation of concentration of [Pd(II)] , in the experimental sets the concentration of [Pd(II)]   is varied from 0.714 x10-6 to 7.14 x10-6 M, keeping constant concentration i.e.  [L-Alanine]= 2 x 10-3M and [NBP] = 2x10-4M ,Hg(OA)2=3x10- KCl =1x10-5M and [Pd(II)]=4.2x10-5M.[Fig-13]. As the reaction has been studied under pseudo first order condition for varying [Pd (II)] was made and pseudo first order rate constants were calculated [Table-7]. It is clear from that pseudo first order rate constants decreases with change in concentration of [Pd(II)]   confirming the first order dependence with respect to acid[Fig-14]. Hence the reaction under pseudo order rate depends on the concentration of acid [Table-8]. The average rate determination data confirm that the order with respect to salt concentration is unity [Fig-15 and Fig-16].


 

 

Table-7: Effect of Variation in concentration of catalyst Pd(II) on initial rate and rate constant of [L-Alanine] oxidation

Sr. no

[Pd(II)]

Concentration M

Initial Rate

log [FOR]

Rate constant  (k)(sec-1)

1

0.714×10-6 M

3.861

1.488

0.04727

2

1.42×10-6 M

4.084

1.49

0.04723

3

2.85×10-6 M

4.496

1.487

0.04731

4

3.2×10-6 M

4.566

1.486

0.04733

5

3.57×10-6 M

4.511

1.486

0.04731

6

4.28×10-6 M

4.807

1.487

0.0473

7

5×10-6 M

4.922

1.488

0.04728

8

5.71×10-6 M

5.118

1.487

0.04729

9

6.42×10-6 M

5.408

1.486

0.04729

10

7.14×10-6 M

5.544

1.485

0.04728

 

Table-8: Average rate determination of oxidation of L-Alanine

Time(s)

10-5Conc (mole/dm3)

10-5<c>

10-5∆c

∆t

10-8<rate> mole/dm3/s

log<c>

log <rate>

0

31.2100

3

31.2051

31.2076

0.0049

3

1.6396

1.4943

0.2147

6

31.1904

31.1977

0.0148

3

4.9188

1.4941

0.6919

9

31.1658

31.1781

0.0246

3

8.1981

1.4938

0.9137

12

31.1510

31.1584

0.0148

3

4.9188

1.4936

0.6919

15

31.1412

31.1461

0.0098

3

3.2792

1.4934

0.5158

18

31.1215

31.1313

0.0197

3

6.5585

1.4932

0.8168

21

31.1117

31.1166

0.0098

3

3.2792

1.4930

0.5158

 

 


5:  Effect of variation of Salt ( KCl ) Concentration on L- Alanine

To study the effect of variation of salt, the concentration of salt KCl was varied from 0.714 x 10-6 to 7.14 x 10-6 M,[Fig-17] keeping constant concentration of reactants such as [NBP] = 2 x 10-4 M, [L-Alanine] = 2 x10-3 M, [HClO4] = 3x 10-4 M  and Hg(OA)2=3x10-4 M,[KCl] =1x10-5M and [Pd(II)]=4.2x10-5M. From the obtained results,[Table-9] it is clear that pseudo first order rate constant kobs increases with the increase in concentration of salts[Fig-18]. A plot of log kobsVS µ, according to extended Bronsted Debye-Huckel equation was found to be linear with positive slope of salt effect [Fig-19]. On the other hand pseudo first order rate constant decreased with increase in concentration of salts. A plot of log kobs versus µ was found to be linear with negative slopes (KCl), indicating negative salt effect. The first order is also confirms on the basis of dependence of rate and rate constant on KCl [Fig-19 and Fig-20].

 


 

Table-9: Effect of Variation in concentration of salt [KCl] on initial rate and Rate constant of [L-Alanine] oxidation

Sr. no

[KCl]

Concentration   M

Initial Rate

log[FOR]

Rate constant  (k)(sec-1)

Log K

õX10-6

1

0.714×10-6 M

3.064

1.464

0.0479

-1.3196

0.8449

2

1.42×10-6 M

3.942

1.466

0.0478

-1.3205

1.1916

3

2.14×10-6 M

3.855

1.468

0.0477

-1.3214

1.4628

4

2.85×10-6 M

3.937

1.471

0.0477

-1.3214

1.6881

5

3.57×10-6 M

4.019

1.473

0.0476

-1.3223

1.8894

6

4.28×10-6 M

4.277

1.476

0.0476

-1.3223

2.0688

7

4.99×10-6 M

4.33

1.478

0.0475

-1.3233

2.2338

8

5.712×10-6 M

4.47

1.479

0.04749

-1.3242

2.3899

9

6.42×10-6 M

4.524

1.48

0.04746

-1.3236

2.5337

10

7.14×10-6 M

4.585

1.48

0.04745

-1.3237

2.6721

 

Table no -10: Average rate determination of oxidation of L-Alanine

Time(s)

10-5  Conc (mole/dm3)

10-5  < c >

10-5 ∆c

∆t

10-8<rate> mole/dm3/s

log <c >

log <rate>

0

29.4521

3

29.3979

29.4250

0.0542

3

18.0671

1.4687

1.2569

6

29.3851

29.3915

0.0128

3

4.2792

1.4682

0.6314

9

29.3801

29.3826

0.0050

3

1.6558

1.4681

0.2190

12

29.3633

29.3717

0.0168

3

5.5909

1.4679

0.7475

15

29.3568

29.3600

0.0065

3

2.1805

1.4678

0.3386

18

29.3409

29.3488

0.0159

3

5.2958

1.4676

0.7239

21

29.3309

29.3359

0.0100

3

3.3282

1.4674

0.5222

54

29.1802

29.1894

0.0183

3

6.1132

1.4652

0.7863

57

29.1727

29.1765

0.0075

3

2.5108

1.4650

0.3998

 

 

 

 

 


6: Effect of Temperature on Kinetics of phthalamide oxidation

The effect of temperature was studied at temperature 30,35,40 and 45 oc [Fig 21] and keeping the other parameter constant [Table-11]. A Arrhenius plot [Fig-22] is straight line with negative slope. From which Energy of Activation was calculated [Fig- 23] it was found to be Ea= -210.886 J mole-1. The ∆G, ∆S and ∆H values were also calculated and found to be ∆G= 34616.2437 J mole-1, ∆S= -121.3875 J mole-1 and                ∆H = -2771.59 J mole-1 respectively.

 

 

 


 

Table no-11: Effect of Temperature on Kinetics of phthalamide Oxidation of Alanine in Acedic media

Alanine=  (0.714 X10-5M   Perchloric acid=o.5 M        NBP=7.14 X10-5M

 

Sr. No.

Time sec.

Temperature ( K )

298o ( K)

303o (K)

308o(K)

313o(K)

3180o(K)

O.D

O.D

O.D.

O.D

O.D

1

0

0.6261

0.6232

0.6218

0.6194

0.6196

2

3

0.6257

0.6228

0.6214

0.6189

0.6190

3

6

0.6253

0.6226

0.6211

0.6186

0.6187

4

9

0.6250

0.6223

0.6208

0.6182

0.6183

5

12

0.6245

0.6220

0.6203

0.6176

0.6178

6

15

0.6242

0.6217

0.6200

0.6173

0.6173

7

18

0.6238

0.6214

0.6197

0.6169

0.6168

8

21

0.6233

0.6210

0.6192

0.6164

0.6165

 

Table no -12 :

Effect of Temp on Alanine

Alanine=  (0.714X10-5)M   Perchloric acid=o.5 M        NBP=0.714X10-5M

Rate k

t°C

T °K

1/T

logk

3+logk

0.04739

25

298

0.0033557

-1.32431329

1.675686709

0.04747

30

303

0.00330033

-1.32358077

1.676419232

0.04753

35

308

0.00324675

-1.32303219

1.676967814

0.04761

40

313

0.00319489

-1.32230182

1.677698181

0.04763

45

318

0.00314465

-1.32211942

1.677880582

 

 

Table no. 13: Effect of Temp. on Alanine

Alanine = (0.714x10-5)M         Perchloric acid = 0.5M           NBP = 0.714x10-5M

Ea# = -210.886622 J mole-1    Slope = -11.0140 kJ/mole

 

Temp

T

K

DH# (J mole-1)

DS# (J mole-1)

DG# (J mole-1)

250C

298

0.04739

-2688.4586

-121.2894

33455.7951

300C

303

0.04747

-2730.0286

-121.3384

34035.4946

350C

308

0.04753

-27741.5986

-121.3880

34615.9021

400C

313

0.04761

-2813.1686

-121.4353

35196.0841

450C

318

0.04763

-2854.7386

-121.4864

35777.9425

Average

 

 

-2771.5986

-121.3875

34616.2437

 


ACKNOWLEDGEMENT:

I am thankful to Dr. Mazahar Farooqui, Incharge Dean Faculty of Science, Dr.Babasaheb Ambedkar Marathwada University, Aurangabad for providing laboratory and library facilities to carry out this work.

 

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Received on 01.06.2017         Modified on 05.11.2017

Accepted on 08.12.2017         © AJRC All right reserved

Asian J. Research Chem. 2018; 11(2):369-378.

DOI:10.5958/0974-4150.2018.00067.6