Int. J. Chem. Sci.

: 8(3), 2010, 1379-1388

STUDIES ON MANGANESE (II) CATALYZED OXIDATION OF N-METHYLANILINE BY PERIODATE ION

R. D. KAUSHIK*, MANMEET KAUR, RAJDEEP MALIK and ANUJ KUMAR
Department of Chemistry, Gurukul Kangri University, HARIDWAR - 249404 (U.K.) INDIA

ABSTRACT
The kinetics of the periodate oxidation of N-methylaniline (NMA) in acetone-water medium has been followed by monitoring the increase in the absorbance of reaction intermediate, C4, and the main reaction product is p-benzoquinone. Results under pseudo first order conditions, [IO4-] >> [NMA], are in agreement with the rate law: d[C]/dt = kK3K4Kw[MnII] [S] [IO4]0 [H+] /{K2 Kw + (Kw + Kb K2 )[H+] + Kb [H+]2} where kK3K4 is the empirical composite rate constant, Kw is ionic product of water, K2 is acid dissociation constant of H4IO6, Kb is base dissociation constant of NMA i.e. Substrate [S] and [IO4]0 represents the concentration of periodate that has been taken in excess in most of the kinetic runs. In agreement with the rate law, the 1/kcat versus [H+] profile passes through the minimum. Free radical scavengers do not affect the reaction rate. Thermodynamic parameters evaluated are: Ea = 5.2 kcal mol-1, A = 4.79 109 dm3 mol-1 s-1; S# = 16.3 cal mol-1, G# = 9.7 kcal mol-1 and H# = 4.6 kcal mol-1. Key words: Kinetics, MnII catalysed, Periodate, n-Methylaniline, p-Benzoquinone.

INTRODUCTION
Keeping in view our earlier studies on uncatalysed periodate oxidation1-8 and a few reports available on the kinetic studies for the MnII catalyzed non-Malapradian periodate oxidation of aromatic amines9-12, the kinetic-mechanistic studies have been made on Mn (II) catalysed periodate oxidation of N-methylaniline (NMA). The results of these studies in acetone-water medium are presented and discussed in this communication. The studies are important for their further expected use in developing methods for detection and treatment of the aromatic amines the chemicals enlisted as toxic13.
________________________________________
*

Author for correspondence; E-mail: rduttkaushik@yahoo.co.in

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EXPERIMENTAL
Reagents and chemicals
Sodium metaperiodate (Loba Chemie), NMA (Aldrich), acetone (E. Merck), manganese sulphate monohydrate (Aldrich) and all other chemicals of analytical reagent/ guaranteed reagent grade were used after redistillation/ recrystallization. Triply distilled water was used for preparation of the solutions. Thiel, Schultz and Koch buffer14, consisting of different volumes of 0.05 M oxalic acid, 0.02 M boric acid, 0.05 M succinic acid, 0.05 M sodium sulphate and 0.05 M borax, was used for maintaining the pH.

Kinetic procedure
The reaction was studied in a spectrophotometric cell and initiated by adding temperature equilibrated NaIO4 solution of known concentration to the reaction mixture containing the NMA, MnII and buffer and maintained at the desired temperature ( 0.10C). The progress of the reaction was followed by recording the absorbance on Schimadzu double beam spectrophotometer (UV Pharmaspec-1700), at 533 nm, i.e., the max of the violet color reaction mixture. max was not found to change with change in time under experimental conditions. Desired temperature was maintained with the help of a high precision thermostatic control.

Product analysis
Reaction mixture containing oxidant in excess was left overnight to ensure completion of the reaction. Initially, the solution turned violet, thereafter reddish brown and finally the solid product settled down on standing. It was filtered and the filtrate was extracted with petroleum ether (40-60oC). The extract was evaporated at room temperature to get a solid yellow residue that was found to be TLC single (using plate thickness of 0.5 mm, silica gel G as adsorbant, chloroform+ acetone+ benzene in the ratio 4 : 6 : 4 mL used as eluent and 30 minutes as the time for development). The remaining part of filtrate may be having other products of this reaction, which could not be separated and identified. The yellow crystalline compound was recrystallised in ethanol and characterized as pbenzoquinone on the basis of positive test for quinone15, M.P. 116oC (literature value 115117oC16), UV spectrum in ethanol giving absorption maxima at 240, 280 and 440 nm, suggested the presence of quinonoid structure in the compound (literature values 244, 280 and 436 nm 17). The IR spectrum of this compound (in KBr) showed the presence of bands at 1645 cm1 (s) (indicating the presence of C=O on benzoquinone pattern18), 3280 cm1(s) (may be due to overtones of C=O stretch as the frequency is about twice that of C=O stretch).

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Further, the bands at 1470 cm-1 (s) may be due to due to C=C ring stretch, 1365 cm1 (m) and 1100 cm1 (m) may be due to in plane C-H bending. The bands at 830 cm1 (m) (due to out of plane C-H bending in case of two adjacent H atoms) and 680 cm1 (m) (due to out of plane C=C bending mode) were also obtained.

Stoichiometry
Stoichiometry of the reaction was determined by allowing a known excess of NaIO4 to react with substrate. After completion of the reaction, the precipitated product was filtered out and in the filtrate, unconsumed NaIO4 was determined iodimetrically. The results indicated the stoichiometry to be 1 mol NMA : 2 moles periodate for the initial part of the reaction as in eq. (1).
C6H5NHCH3 + 2 IO4 + 2 H+ + H2O

Mn II

C6H4O2 + 2 HIO3 + NH3 + CH3OH

...(1)

RESULTS AND DISCUSSION

Preliminary observations
On mixing the reactants, the solution becomes violet, which later changes into reddish brown. On keeping for long time, it finally gives the product. These observations indicate the formation of more than one intermediate prior to the formation of final reaction product. The rapid scan of the violet solution showed the max of the intermediate, C4, to be 533 nm. The UV-visible spectra of IO4, NMA and MnII indicated that these do not show absorption in visible region. Hence, for following the kinetics, the absorbance changes were recorded at 533 nm at which only the intermediate C4 absorbs.

Rate law
The kinetics was studied under pseudo-first order conditions by keeping periodate concentration in excess. Guggenheims method was used for evaluation of pseudo-first order rate constants, kobs. Under these conditions, the kinetics was defined by the rate law (2). d[C]/dt = kcat [S] [IO4-]0 [MnII] ...(2)

where kobs = kcat [IO4-]0 [MnII] and kcat is the rate constant for MnII catalysed pathway. [IO4-]0 represents the initial concentration of periodate that has been taken in excess. In the absence of MnII, no significant reaction occurred. The values of kcat obtained for different [MnII], [IO4]0 and [S] are seen to be in good agreement and consistent with the rate law (2) (Table 1, Fig. 1).

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R. D. Kaushik et al.: Studies on Manganese.

Table 1: Values of kobs and kcat at 35 0.1oC

[NaIO4] (mol dm-3) 0.0002 0.0002 0.0002 0.0002 0.0002 0.003 0.004 0.005 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 [NMA] [Mn (II)] 107 (mol dm-3) (mol dm-3) 0.002 0.003 0.004 0.005 0.006 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003 1.456 1.456 1.456 1.456 1.456 6.0 6.0 6.0 1.456 2.912 4.368 5.824 7.280 1.456 1.456 1.456 1.456 1.456 1.456 1.456 1.456 1.456 1.456 1.456 1.456 1.456 Acetone [% (v/v)] 5.0 5.0 5.0 5.0 5.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 2.5 5.0 7.5 10.0 pH 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 6.0 6.0 6.0 6.0 kobs 104 (s-1) 3.99 5.60 7.06 8.32 9.47 24.6 31.5 37.6 5.37 10.05 16.00 21.30 26.60 3.11 4.22 4.57 4.68 5.37 9.15 6.29 4.40 3.93 7.68 6.83 5.99 5.37 kcat 10-7 (dm6 mol-2 s-1) 0.140 0.130 0.120 0.110 0.110 0.136 0.131 0.130 0.123 0.115 0.122 0.122 0.122 0.071 0.097 0.104 0.107 0.123 0.210 0.144 0.100 0.090 0.180 0.160 0.140 0.123

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0.0050 0.0045 0.0040

kobs

0.0035 0.0030 0.0025 0.0020

0.0000002

0.0000004

0.0000006

0.0000008

Mn (II)

Fig. 1: Effect of [Mn(II)] on reaction rate at [NMA] = 3.0 10-4 mol dm-3, [NaIO4] = 3.0 10-3 mol dm-3, pH = 6.0, Acetone = 10.0 % (v/v), Temp. = 35 0.1C

Effect of pH, ionic strength, acetone, free radical scavengers and temperature
The effect of pH was examined in the range 4.0-8.0. 1/ kcat [H+] profile indicates a minimum at pH = 6.5 (Table 1, Fig. 2), which could be due to change in the nature of species and their relative reactivity, when the pH is changed. An increase in ionic strength caused almost no effect on the rate. An increase in the acetone (2.5-10.0%) led to about 39% decrease in the rate. Free radical scavengers, viz., acrylamide and allyl alcohol had no effect on the reaction rate. By determining the rate constants at four different temperatures (35.0 to 50.0oC), the values of different thermodynamic parameters were found and these are given in Table 2. Preliminary examinations reveal that faster colour changes in the reaction mixture relative to the separation of product on standing for long time indicates the formation of the colored intermediate on a time scale of minutes and that of the final product on a time scale of hours. The overall reaction appears to involve several steps and possibly several transient intermediates, in addition to comparatively stable one C4, during the oxidation of NMA into p-benzoquinone. Further, the kinetic order of one in periodate against the requirement of two periodate molecules for each NMA molecule in the stoichiometry (Eq. 1) requires the involvement of only one periodate in the rate determining step and second IO4 ion to be consumed in a fast step leading to the formation of the intermediate, C4. Since the concentration of C4 increases continuously with time and reaches a limiting value, its

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R. D. Kaushik et al.: Studies on Manganese.

concentration can not be in steady state. Finally, 1/ kcat [H+] profile indicates the presence of at least three differently reactive reactant species in the pH region chosen for study. Finally, the observation that free radical scavengers have no effect on reaction rate rules out the involvement of free radicals in the oxidation mechanism. Table 2: Activation parameters
[NMA] =3.0 10-4 mol dm-3, [NaIO4] = 3.0 10-3 mol dm-3, [MnII] = 1.456 10-7 mol dm-3, Acetone = 10.0 % (v/v), pH = 4.5 Temp. (oC) 35 40 45 50 104 kobs 10-7 kcat (dm6 mol-2 s-1) (s-1) 4.22 4.84 5.53 6.29 0.097 0.111 0.127 0.144 5.2 4.8 109 - 16.3 9.7 4.6 Ea (kcal mol-1) A (dm3 mol-1 s-1) S# (cal mol-1) G# (kcal mol-1) H# (kcal mol-1)

14 12

1/kcat x 10

10 8 6 4

200
+

400
7

600
-3

800

1000

[H ] x 10 mol dm

Fig. 2: Effect of [H+] on the rate at Acetone = 10% (v/v), [NMA] =3.0 10-4 mol dm-3, [NaIO4] = 3.0 10-3 mol dm-3, [MnII] = 1.456 10-7 mol dm-3 and Temp.= 35 0.1oC Construction of a mechanism requires discussion on the speciation of NMA and periodate. In aqueous solutions, periodate exists in the three forms governed by the equilibria (3 4).

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H5IO6 H4IO6-

H4IO6 + H+ , K1 = 2.3 10-2 H3IO62 + H+ , K2 = 4.35 10-9

...(3) ...(4)

The value of K1 indicates that in the pH range 4.0 8.0, species H5IO6 shall be practically non-existent and hence, only species H4IO6 and H3IO62 need be considered for explaining observed pH - dependence. In aqueous solution, NMA19, undergoes the following acid base equilibrium with Kb = 7.1 10-10. C6H5NHCH3 + H2O C6H5N+H2CH3 + OH ...(5)

Since in the studied pH-range, both C6H5NHCH3 and C6H5N+H2CH3 exist, these species have been taken into account. The pH effect may be explained by assuming the unprotonated amine and periodate monoanion to be reactive. This requires the reaction rate to decrease when the concentration of either of these or both decreases on changing the pH. Based on the observed kinetic rate law (Eq. 2) and pH- dependence, the following mechanism, which assumes, C6H5NHCH3 and H4IO6 to be the reactive species, is proposed. C6H5NHCH3 + Mn2+ [C1] + [IO4 ] [C2]
k

K3 K4

[C1] [C2] (fast)

...(6) ...(7) ...(8) ...(9)

[C3] + H2O + HIO3 + Mn2+ (slow) [C4] + H2O + HIO3 (fast)

[C3] + IO4- + H+

In steps (6 9), [C1], [C2], [C3] and [C4], are intermediates, out of which [C4] appears to undergo very slow reorganization/ hydrolysis to yield the reaction product, C5. [C4] [C5] (Product) ...(10)

In the mechanism for simplicity, H4IO6 has been written as IO4. Since the elementary reactions in liquid phase are a rarity, the formation of intermediates [C1] and [C2] in a rapid step having low values of equilibrium constants, K3 and K4, is assumed in the proposed gross mechanism. In the detailed mechanism (Scheme 1), the catalytic role of Mn2+ appears to be due to the formation of a ternary complex, [(NMA) Mn (H4IO6)]+, in which Mn acts as a conduit for electron transfer.

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R. D. Kaushik et al.: Studies on Manganese.

Scheme 1
CH3NH II + Mn

..

II CH3NH Mn

..

CH3

H II O Mn O I O O H+ Slow CH3 N II O + Mn OH2 I O O

K3
[C1] O

K4 + IO 4
[C2] I O OH2 O H2O Fast
+

CH3 N: II + HIO3 + H2O + Mn [C3] H H O H CH3 N Fast

II Mn

+ IO 4 Fast
CH3

O H CH3 N:

..

:N

:NCH3

O H H O .. O I O

O O O H H O
+

O O

OH H O H+ I O

I O

O O

:NCH3
Slow H2O

:NCH3
HIO3 H2O

O [C5]

O [C4]

O OH2 O O

O ..

1,4-Benzoquinone

The proposed mechanism (6 9) leads to the rate law (11). d[C4 ]/dt = kK3K4 [MnII][IO4 ] [C6H5NHCH3] ...(11)

On substituting the values of concentrations of the reactive species [C6H5NHCH3] and [IO4] in terms of equilibria (3-4) and (5), respectively, in eq. (2), the complete rate law including [H+] - dependence becomes:

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d[C]/dt = kK3K4[MnII]{([S] [OH]/( [OH] + Kb)}{([IO4-]0 [H+] /(K2 + [H+])}

...(12)

On replacing the term, [OH][H+], by Kw in numerator, and [OH] by Kw/ [H+] in denominator, and on rearranging, the Eq. (12) becomes Eq. (13). d[C]/dt = kK3K4[MnII]Kw[S][IO4]0 [H+] /{K2 Kw +(Kw + Kb K2)[H+] + Kb[H+]2} ...(13) On comparing eqs.(2) and (13), we get kcat = k K3K4 Kw[H+]/{K2 Kw + ( Kw + Kb K2 ) [H+] + Kb [H+]2} Eq. (14) on rearranging becomes eq. (15). 1/kcat = (K2 / kK3K4 [H+]) + {(Kw + Kb K2) / kK3K4 Kw} + Kb[H+] / kK3K4 Kw ...(15) The nature of the rate law (15) shows that a plot of 1/kcat versus [H+] shall pass through a minimum20. On differentiating 1/kcat with respect to [H+] in eq. (15), we get the values of d2[1/kcat] / d[H+]2. The value of second derivative is found to be positive showing the plot of 1/kcat versus [H+] to pass through a minimum. Thus, on setting d[1/kcat] / d[H+] equal to zero for obtaining hydrogen ion concentration at which the 1/kcat vs [H+] profile will pass through minimum, we obtain, [H+]min = (K2 Kw / Kb)1/2 On substituting the values of K2, Kw and Kb, we get [H+]min = 2.48 10-7 mol dm-3 It is noteworthy that the calculated value of [H+]min is in satisfactory agreement with the experimental value of [H+]min of 3.16 10-7 mol dm-3 obtained from 1/kcat versus [H+] plot (Fig. 2) and this provides strong support to the proposed mechanism. ...(16) ...(14)

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R. D. Kaushik, D. Kumar, A. Kumar and R. Malik, Asian J. Chem., 22, 2155 (2010). R. D. Kaushik, R. Malik, Manila and A. Kumar, Asian J. Chem., 22, 2090 (2010). R. D. Kaushik, P. Sundriyal, Tarun Kumar and Prabha Singh, Asian J. Chem., 22, 2136 (2010). R. D. Kaushik, Manila, D. Kumar and Prabha Singh, Oxid. Commun., 31, (2010) (In Press). R. D. Kaushik, R. Malik and Ajay Kumar, J. Indian Chem. Soc., 87, 317 (2010). I. F. Dolmanova, V. P. Poddubienko and V. M. Peshkova, Zh. Anal. Khim., 25, 2146 (1970). R. D. Kaushik, A. K. Chaubey and R. P. Singh, Indian J. Environ. Ecoplan., 7, 29 (2003). R. D. Kaushik, Amrita and S. Devi, J. Curr. Sci., 3, 197 (2003). R. D. Kaushik, Shashi, Amrita and S. Devi, Asian J. Chem., 16, 818 (2004). H. M. Pinheiro, E. Touraud and O. Thomas, Dyes and Pigments, 61, 121 (2004). H. T. S. Britton, Hydrogen Ions, D. Von Nostrand Co., (1956) p. 354. B. S. Furniss, A. J. Hannaford, P. W. G. Smith and A. R. Tatchell, Vogels Text Book of Practical Organic Chemistry, 5th Ed., Addison-Wesley Longman LTD., (1998) p. 1221. J. Buckingham, (Ed.), Dictionary of Organic Compounds, 5th Ed., Chapman and Hall, N. York, 1, (1982) p. 578. O. H. Wheeler and L. A. Kaplan, Organic Electronic Spectral Data, Interscience Publishers, N. York, 3, (1956-1957) p. 56. P. S. Kalsi, Spectroscopy of Organic Compounds, 2nd Ed., New Age International Ltd., N. Delhi, (1996). J. A. Dean, Langes Handbook of Chemistry, 13th Edn., McGraw-Hill Book Company, N. York, (1985) p. 5-46. K. S. Gupta and Y. K. Gupta, J. Chem. Edu., 61, 972 (1984).

16. 17. 18. 19. 20.

Accepted : 22.04.2010