Kinetic study of iridium(III)catalyzed oxidation of ethylenediamine by

chloramine-T in acidic medium

Ajaya Kumar Singh1*, Bhawana Jain1, Reena Negi1,Yokraj Katre2

Department of Chemistry, Govt. V. Y .T. PG. Autonomous College, Durg (C.G.), India
Department of Chemistry,Kalyan PG College Bhilai, Sect-7,Bhilai,Durg,CG

Phone: 91-7882223421, Email: ajayaksingh_au@yahoo.co.in

Abstract

1
 The kinetics of iridium(III) chloride-catalyzed oxidation of ethylenediamine

(EDA) by chloramine-T (CAT) was studied in aqueous perchloric acid medium at 308K.

The results showed first-order kinetics with respect to [CAT] and fractional order with

respect to [Ir(III)chloride] and [EDA]. The rate of reaction decreased with increase in the

proton concentration. RNH2(p-toluene sulphonamide),Chloride ion, Ionic strength (I)

and dielectric constant of the medium (D) had no significant effect on the reaction rate.

Activation parameters of the reaction were determined by studying the reaction at

different temperatures (298-313K). A reaction scheme of the oxidation of EDA by CAT

in presence of Ir(III) chloride was proposed, which was found to be in agreement with the

rate law and the reaction stoichiometry.

Keywords: Kinetics, oxidation, ethylene diamine, Ir(III) chloride, chloramine-T.

Introduction

The chemistry of aromatic sulfonyl haloamines (N-haloamines) is of interest due to their

diverse behavior. Their versatile nature is due to their abilities to exist as halonium

2
cations and nitrogen anions, which act both as base and nucleophile [1-5]. As a result,

these compounds react with a wide range of functional groups and affect a variety of

molecular changes. The prominent members of this class of compounds are Sodium-N-

chloro-4-methyl benzensulfonamide, p-CH3C6H4SO2NclNa.3H2O, generally known as

chloramine-T (CAT), which has long been used as an analytical reagent. CAT is used

for disinfection and as an algicide. It contains active chlorine so it is used as a source of

electrophile in organic synthesis. There are excellent reviews covering their oxidizing

action, by Ozerassi, Filler, Mathur and Narang, Mukherji, and Campbell and Johnson [6-

8]. There are number of publications on the mechanistic aspects of the redox reactions in

acidic media in which one of the species, RNHCl (R = CH 3C6H4SO2), HOCl, or H2OCl+,

has been considered as reactive species of CAT [9].

Ethylenediamine is most widely used for production of many industrial

chemicals. It form derivative with carboxylic acid, nitriles, alcohol, aldehyde and ketones

because of its bifunctional nature. EDA is well known chelating ligand for co-ordination

compound. Literature survey revealed that there is limited work done on EDA [10]. The

mechanism of catalysis is quite complicated due to the formation of different

intermediate complexes, free radical and different oxidizing state of Ir(III). Iridium (III)

chloride is the most important platinum group metal ion and has been widely used as

homogenous catalyst in various redox reaction [11,12]. To the best of our knowledge,

there is no report available for the oxidation of EDA by CAT in the presence of

iridium(III). This has encouraged us to investigate mechanistic aspect of EDA by CAT.

Preliminary result indicate that in the absence of the Ir(III) chloride catalyst in acidic

medium was very sluggish but reaction become facile in the presence of small amount of

3
iridium. Objectives of the present study are : (i) to ascertain the reactive species of Ir(III)

chloride as catalyst and CAT as an oxidant in acidic medium, (ii) to identify the oxidation

products, (iii) to elucidate a plausible mechanism, (iv) to deduce an appropriate rate law.

2. Experimental

2.1 Material

AR grade chemicals and double distilled water used throughout the investigation. Stock

solution of CAT (Loba) was prepared in doubly distilled water and standardized

iodometrically. A solution of Ir(III) chloride was prepared by dissolving a known weight

of IrCl3 (S. D. fine) in HCL of known strength. Stock solution of EDA (Fluka) was

prepared by dissolving appropriate amount of sample in double distilled water. Standard

solution of KCl and NaClO4 were prepared with double distilled water and perchloric

acid (GR) was used as a source of H+ ions and acetonitrile as a solvent.

2.2 Kinetic Procedure

All the kinetic measurement were carried out in a black-coated vessel at constant

temperature (308 K) and performed under pseudo first-order condition with [EDA] >>

[CAT]. The reaction was initiated by the rapid addition of known amounts of oxidant to

the reaction mixture containing the required amounts of EDA, perchloric acid, Ir(III)

chloride and water in glass stoppered Pyrex boiling tubes; thermosttated at the same

temperature. Progress of reaction was monitored by iodometric determination of

unconsumed [CAT] in known aliquots of the reaction mixtures at different time intervals.

Each kinetic run was studied for ~80 % reaction. Runs were repeated twice and had <

5% standard deviation. The rate of reaction (-d[CAT]/dt) in each kinetic run was

determined by the slope of tangent drawn at fixed [CAT].

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2.3. Stoichiometry and Product Analysis

Varying different ratio of CAT to EDA were equilibrated at 308 K in presence of

requisite amount of all reactant under the condition of [CAT]>> [EDA], for 48 h.

Determination of unconsumed CAT revealed that for the oxidation of each mole of EDA,

two moles of CAT was required. Accordingly, the following stoichiometric equation

could be formulated:

NH2-CH2-CH2-NH2 + 2CAT + 2 H2O → 2 NH2-CH2-COOH + 2 RNH2 + NH3 +

Na+ + Cl-

The reaction products were neutralize with NaOH and extracted with ether. The organic

products were subjected to spot test and chromatographic analysis which revealed the

formation of glycine was the major product[13].

3.Kinetic measurements & Results

3.1 Kinetics

Initially, the kinetics of the oxidation of EDA by CAT in the presence of Ir(III) chloride

under all acidic conditions were studied at several initial concentrations of all the

reactants at 308 K. For the variation of [CAT], the reaction rate was calculated by the

slope of tangent drawn at fixed time. In the variation of concentration of other reactants,

tangents were drawn at constant [CAT] ([CAT]*) (Fig. 1). The pseudo-first-order rate

constant k1 was calculated as

- (dc/dt)
k1 =
[CAT]*

The order of reaction in each reactant was determined using log-log plot of (-dc/dt)

versus concentration of reactant. Considering CAT, EDA, perchloric acid and

5
iridium(III) chloride as the main reactants, the general form of the rate equation for the

oxidation of EDA by CAT can be written as

rate = k1 [CAT]α [EDA]β [Ir(III)]γ [H+]δ

Uniform pseudo-first-order rate constant (k1) values for the variation of [CAT] clearly

indicate that the order with respect to [CAT] is unity. This is also obvious from the plot

of (-dc/dt) versus [CAT] (Fig 1; Table 1). The reactions have been studied for EDA from

0.5 x 10-2 to 3.5 x 10-2 mol dm-3 keeping other reactants constant at constant temperature.

The rate of reaction calculated at different [EDA], this was showing fractional order

kinetics with respect to [EDA] (Fig 2; Table 1). The reaction follows first-order kinetics

with respect to [Ir(III)] chloride at a low range of concentration and tends to zero-order

at high concentration range. This result was further confirmed by the plot of -dc/dt

versus [Ir(III)] (Fig 3; Table 1). The reaction rate decreased with increasing [HClO4].

This indicates that negative effect of proton concentration on the oxidation rate (Fig.4;

Table 1). The variation of [Cl-], solvent and ionic strength of medium did not affect the

reaction velocity. The effect of temperature on the reaction rate was determined by

keeping constant concentration of other constituents of the solution. The values of

different activation parameters such as activation energy, Ea, enthalpy of activation,

(ΔH#), entropy of activation (∆S#) and Gibb’s free energy of activation ((∆G#) were

calculated from Arrhenius plot (Fig.5; Table-2).

3.2 Test for free radicals

To test the presence of free radicals in the reaction, the reaction mixture

containing CAT, EDA, Ir(III) chloride and perchloric acid with acryl amide was placed in

6
an inert atmosphere for 24 h. When the reaction mixture was diluted with methanol, it

was found that there was no precipitate in the reaction mixture. This clearly showed free

radicals were not formed in the redox reaction under present investigation.

4.Discussion

4.1Reactive species of CAT

CAT acts as a mild oxidant in both acidic and alkaline media. In general, CAT undergoes

a two-electron change in its reactions forming the reduction products, PTS

(p-CH3C6H4SO2NH2 or TsNH2) and sodium chloride. The oxidation potential of CAT-

TsNH2 redox couple varies with pH of the medium (Eo is 1.14 V at pH 0.65, 0.778 V at

pH 7.0, 0.614V at pH 9.7 and 0.50 V at pH 12) and decrease with increase in pH of the

medium. The existence of similar equilibria in acid and alkaline solution of CAT has

been reported by Morris et al. [14], Ruff and Kucsman [15], Bishop and Jennings [16],

Hardy and Johnston [17], and Higuchi et al. [18]. Aqueous solution of chloramine-T

(TsNClNa) behaves as a strong electrolyte [15] and depending on the pH, it furnishes

different types of reactive species. The possible oxidizing species in acidified CAT

solution are the conjugate free acid (TsNHCl), dichloramine-T (TsNCl2), hypochlorous

acid (HOCl) and possibly H2OCl+, and in alkaline solutions TsNHCl, HOCl, TsNCl- and

OCl-.

4.2Reactive species of iridium:

It is known that IrCl3 in hydrochloric acid gives [IrCl6]3- species [19]. It has also been

reported that iridium (III) and iridium (I) ions are the stable species of iridium [20].

7
 Further the aquation of [IrCl6]3- gives [IrCl5H2O]2-, [IrCl4(H2O)2]- and [IrCl3(H2O)3]

species [21-23]. This equilibrium may be shown by general equation.

k1
IrCl63- + H 2O [IrCl5 (H2O)]2- + Cl-
k-1

in the negligible effect of chloride ions on the reaction rate in the present study indicate

that [IrCl5(H2O)]2- can be considered as the reactive species [24-25]. Therefore,

considering our experimental results, [IrCl5(H2O)]2- has been considered to be the reactive

species of iridium (III) chloride in the present study.

4.3 Rate law and mechanism

Considering the reactive species of catalyst, oxidant and with the help of above

experimental findings, the probable reaction mechanism is proposed (Scheme I) and

considering the fact that 1 mole of EDA is oxidized by 2 moles of CAT.

Rate = 2 k [C1] (1)

On the basis of steps (i) to (v), Eq. (2) can be obtained in the following forms,

respectively:
+
2 k K 1K 2 [H2NCH2CH2NH2] [TsNH2Cl] [Ru(III)]
Rate = (2)
+
[H ]

Applying steady state approximation

dC1
0 = = k2 [TsNHCl] [NH2CH2CH2NH2] - k-2 [C1] - k [C1] [Ir(III)] (3)
dt

8
 +
kk 2K 1 [TsNH2Cl] [NH2CH2CH2NH2] [Ir(III)]
Rate = (4)
[H+] k-2 - k [Ir(III)]

At any time of the reaction, the total concentration of CAT, i.e. [CAT]T can be shown as

+
[CAT]T = [TsNH2Cl] + [TsNHCl] + [C1] (5)

On substituting the value of [C1] in Eq. (5) we get Eq. (6)

+ +
+ K 1 [TsNH 2Cl] K 1k 2 [TsNH2Cl] [NH2CH2CH2NH2]
= [TsNH 2Cl] + + (6)
+ [H++]] [CAT] k - k [Ir(III)]+
[H T -2 [H ] k-2 - k [Ir(III)] (7)
[TsNH2Cl] =
k -2K 1 + K 1k 2 [NH2CH2CH2NH2] + k [Ir(III)]

kk 2K 1 [NH2CH2CH2NH2] [Ir(III)] [CAT]T

Rate = (8)
k-2K 1 + K 1k 2 [NH 2CH2CH2NH2] + k [H+] [Ir(III)]
Rate kk 2K 1 [NH2CH2CH2NH2] [Ir(III)]
= k obs = (9)
[CAT] T k -2K 1 + K 1k 2 [NH2CH2CH2NH 2] + k [H +] [Ir(III)]

The rate expression obtained in equation (8) can be re-written as

1 k -2 1 [H+]
= + + (10)
k obs kk 2 [NH2CH2CH2NH2] [Ir(III)] k [Ir(III)] K 1k 2 [NH2CH2CH2NH2]

Eq. (10), indicates that if a plot is made between [CAT]T]/rate(1/kobs) and 1/[EDA] or [H+]

or 1/[Ir(III)], a straight line with positive intercept on y-axis will be obtained (Fig. 6&7),

on one hand proves the validity of the rate law (8) and on the other hand the proposed

reaction scheme on the basis of which the rate law (8) has been derived. The values of k,

k2K1, kK2 and k-2 were calculated from the slope and intercept of the plot and found to be

0.33s-1, 4.54 x 10-3mol dm-3s-1, 1.00 x 10-7 mol-1 dm3 s-1 and 2.59 x 10-13 s-1 respectively.

9
Conclusion

Oxidation of EDA by CAT in perchloric acid medium was found to be very

sluggish, but became facile in the presence of a micro- quantity of iridium(III) chloride

catalyst. Among the various species of Ir(III) chloride in acidic medium, [IrCl5(H2O)]2-

was determined to be the catalytic species. Oxidation products were identified and

activation parameter have been calculated.

10
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[9] Shailendra Jha, P.D. Sharma, and Y.K. Gupta, Inorg. Chem. 22 (1983) 1393-1395.

[10] A. Kumar, Vaishali, P. Ramamurthy, Int. J. Chem. Kinet., 32 (2000) 286-293.

[11] V. Uma, B. Sethuram, T. N. Rao, Reac. Kinett. Catal. Letter, 18 (1981), 283.

[12] A. K. Singh, Reena Negi, Y. R. Katre, S. P. Sing, J. Mol. Cataly A:chem., 302

(2009) 36-42.

[13] F. Feigl, Spot Tests in Organic Analysis, 7th ed., Elsevier, Amsterdam,

(1966) 501.

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2036-2041.

[15] F. Ruff, A. Kucsman, J. Chem. Soc., Perkin Trans. II (1975) 509-519.

[16] E. Bishop, V.J. Jennings, Talanta 1 (1958) 197-212.

11
[17] F.F. Hardy, J.P. Johnston, J. Chem. Soc., Perkin Trans. II (1973) 742-746.

[18] T. Higuchi, K. Ikeda, A. Hussain, J. Chem. Soc. B (1967) 546-549.

[19] J. C. Chang, C. S. Garner, Inorg. Chem. 4 (1965) 209.

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Chemistry Wiley Interscience (1999) p. 1039.
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[22] I. A. Poulsen, C. S. Garner, J. Am. Chem. Soc. 84 (1962) 2032.
[23] A. P. J. Domingos, A. M. T. S. Domingos, J. M. P. Gabral, J.Inorg. Nucl. Chem.
31 (1969) 2568.
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Figure Captions

Fig. 1 Plot of rate versus [CAT] at T = 308K.

[EDA] = 2.00 x 10-2 mol dm-3, [HClO4] = 0.50 mol dm-3 and

[Ir(III)]= 3.34 x 10-6 mol dm-3.

Fig. 2 Plot of rate versus [EDA] at T = 308K.

[CAT] = 1.00 x 10-3 mol dm-3, [HClO4] = 0.50 mol dm-3 and

[Ir(III)]= 3.34 x 10-6 mol dm-3.

Fig. 3 Plot of rate versus [Ir(III)] at T = 308K.

[CAT] = 1.00 x 10 -3 mol dm-3, [EDA] = 2.00 x 10-2 mol dm-3, [HClO4] = 0.50

mol dm-3.

Fig. 4 Plot of rate versus [H+] at T = 308K.

[CAT] = 1.00 x 10-3 mol dm-3, [EDA] = 2.00 x 10-2 mol dm-3 and

[Ir(III)]= 3.34 x 10-6 mol dm-3.

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 Fig. 5 Arrhenius plot of log k versus 1/T

[CAT] = 1.00 x 10-3 mol dm-3, [EDA] = 2.00 x 10-2 mol dm-3 and

[Ir(III)]= 3.34 x 10-6 mol dm-3.[H+]=0.5 mol dm-3

Fig. 6 Plot of [CAT]/rate versus [1/EDA] at 308 K.

[CAT] = 1.00 x 10-3 mol dm-3, [Ir(III)]= 3.34 x 10-6 mol dm-3.

[H+]=0.5 mol dm-3

Fig. 7 Plot of [CAT]/rate versus [H+] at 308 K.

[CAT] = 1.00 x 10-3 mol dm-3, [EDA] = 2.00 x 10-2 mol dm-3 and

[Ir(III)]= 3.34 x 10-6 mol dm-3

Table 1. Effect of [CAT], [EDA], [Ir(III)] and [H+] on the rate of oxidation of EDA at 308 K.

13
 [CAT] x 103 [EDA] x 102 [Ir(III)] x106 [H+] -dc/dt x 107 k1 x 104
mol dm-3 mol dm-3 mol dm-3 mol dm-3 mol dm-3s-1 s-1
(Cal)
0.25 2.00 3.34 0.50 1.10 5.36
0.50 2.00 3.34 0.50 2.04 5.78
0.75 2.00 3.34 0.50 3.50 5.20
1.00 2.00 3.34 0.50 4.61 5.00
2.00 2.00 3.34 0.50 10.00 5.47

1.00 0.50 3.34 0.50 2.00 2.50

1.00 1.00 3.34 0.50 3.12 3.90
1.00 1.50 3.34 0.50 3.91 4.87
1.00 2.00 3.34 0.50 4.60 5.75
1.00 3.00 3.34 0.50 5.09 6.37
1.00 3.50 3.34 0.50 5.12 6.40

1.00 2.00 0.33 0.50 0.40 0.5

1.00 2.00 1.60 0.50 1.92 2.40
1.00 2.00 2.60 0.50 3.21 4.01
1.00 2.00 3.34 0.50 4.62 5.57
1.00 2.00 6.68 0.50 5.65 7.06

1.00 2.00 0.10 10.65 13.31

3.34
1.00 2.00 0.20 9.62 12.02
3.34
1.00 2.00 0.30 7.21 9.01
3.34
1.00 2.00 0.50 4.60 5.75
3.34
1.00 2.00 0.70 3.00 3.75
3.34
1.00 2.00 0.90 2.65 3.30
3.34

Table 2. Effect of temperature and corresponding activation parameter on the rate of oxidation

14
of EDA.

Temperature -dc/dt x 107

(K)
mol dm-3s-1

298 2.62
303 4.12
308 4.60
313 6.25
Ea ( kJ mol -1) 42.69
∆H( kJ mol -1) 40.13
∆S (JK-1 mol -1) -59.07
∆G( kJ mol -1) 58.32
log A 9.72
kr x 10-3 0.3749
( s-1)

Solution conditions: [CAT] = 1.00 x 10-3 mol dm-3, [EDA] = 2.00 x 10 -2 mol dm-3,
[H+] = 0.50 mol dm-3 , [Ir(III)] = 3.34 x 10-6 mol dm-3.

15