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Kinetics and mechanism of oxidation of monoethanolamine by chloramine-T catalysed by Cu(II) ions
1185
No~s
Table 2. Force constant, lattice frequenceis and Debye temperatu~ of isotopic lithium hydride crystal Lattice frequency in 10-~2/sec.
Force constant (f x 10 -4) Crystals 6LiH 7LiH 6LiD 7LiD
Debye O°K
Pot. I
Pot. 2
Pot. 3
Pot. 1.
Pot. 2
Pot. 3
Pot. I
Pot. 2
Pot. 3
0.1276 (I.1161 0.1231 0.09405
0.5834 0.5784 0.5864 0.5735
0.9643 0.%55 0.9752 0.9711
6.120 5.777 4.546 3.901
13.087 12.896 9.922 9.637
16.826 12.732 12.795 12.540
293.798 277.339 218.217 187.291
628.699 619.027 476.280 462.600
807.691 611.140 614.203 601.963
Table 3. Gruneisen parameter (3'), Anderson---Gruneisen parameter (8) of isotopic lithium hydride crystal Anderson-Gruneisen parameter (8)
Gruneisen parameter (3') Crystals
Pot. 1
Pot. 2
Pot. 3
3' (Exptl.)
Pot. I
Pot. 2
6LiH 7LiH 6LiD 7LiD
6.643 4.161 6.931 8.946
1.159 1.165 1.162 1.200
0.7959 0.7958 0.7956 0.7967
1.085 1.187 0.948 1.109
12.619 7.655 13.197 17.227
1.653 0.9251 1.663 0.9252 1.658 0 . 9 2 4 6 1 . 7 3 4 0.9267
Gruneisen parameter and pseudo Gruneisen parameter. The Gruneisen parameter 3' is given by Slater[12], r0$1I,Jo,
Government Postgraduate College Pithoragarh India
8 Exptl. 1.990 1.994 2.000 2.020
UMA RAN1 PANT
(6)
where d, Jr~ and $~lt refer to the second and third derivatives of The values of 3' have been calculated using this expression. The Anderson--Gruneisen parameter has been computed using Chang's relation [13]. RESULTS AND DISCUSSION
The computed values of the cohesive energy are reported in Table I. The experimental values of B and w[15, 16] are also listed. The agreement is satisfactory. The values of the force constant, lattice frequency and Debye temperature are listed in Table 2. The values of 3' and B are given in Table 3 with the experimental values of 3' and fl for these crystals [ 15]. The logarithmic potential is successful in calculations of all the lattice properties of the isotopic lithium hydride crystals and as such may be considered a suitable ionic potential for such crystals. J. D. PANDEY
Department of Chemistry University of Allahabad Allahabad-211 002 India
Pot. 3
RE~NCES
I. E. S. Rittner, J. Chem. Phys. 19, 1030 (1951). 2. Y. P. Varshni, Trans. Faraday Soc. 53, 132 (19571. 3. Y. P. Varshni, Rev. Mod. Phys. 29, 644 (19571; 31,839 (1959). 4. Y. P. Varshni and R. C. Shukla, J. Chem. Phys. 35. 582 (19511. 5. Y. P. Varshni and R. C. Shukla, Rev. Mod. Phys. 35, 130 (1%3). 6. Y. P. Varshni and R. C. Shukla, J. Mol. Spect. 16, 63 (1%5). 7. M. M. Patel, V. B. Gohel and M. D. Trivedi, Ind. J. Phys. 41, 235 (19671. 8. K. P. Thankur, Ind. J. Pure and Appl. Phys. !1,549 (19731. 9. K. P. Thakur, Ind. J. Chem. 12, 374 (19741. I0. K. P. Thakur and J. D. Pandey, J. Chem. Phys. 71,850 (19741. 11. K. S. Krishnan and S. K. Roy, Proc. R. Soc., (London) 2ff'/A, 447 (19511. 12. J. C. Slater, Introduction to Chemical Physics. McGraw-Hill, New York (19391. 13. Y. A. Chang, Phys. Chem. Solids 28, 697 (19671. 14. L. Das and S. C. Saxena, J. Chem. Phys. 43, 1747 (1%51. 15. S. P. Srivastava and R. S. Saraswat, J. Phys. Chem. Solids 36, 351 (1975).
£ inorg, nucl. Chem. Vol. 40. pp. 1185-1187 © Pergamon Press Ltd., 1978. Printed in Great Britain
0022-1902/'78/0601-1185/$02.00/0
Kinetics and mechanism of oxidation of monoethanolamine by chloramine-T catalysed by Cu(ll) ions (First received 4 May 1977; in revised [orm 25 September 1977) The Cu(II) ion catalysed oxidation of monoethanolamine by chloramine-T has not received any attention to-date, though its oxidation by other reagents, such as K2S208, K3Fe(Cn)6 has been reported[l--4]. The oxidation of monoethanolamine by chloramine-T is very slow, so Co(II) ion has been used as a catalyst. OsO4 has been widely employed as a catalyst in oxida-
tion reactions in alkaline medium [5-8]. However, very few cases of catalysis by Cu(II) ions in this redox system are reported in literature. Recently, Wilson et al. [9--I 1] have investigated the role of Cu(lI) ions in the oxidation of cystine and related thiols, and hydroxylamine by alkaline hexacyanoferrate (III). The present paper summarises the results of our kinetic oxidation of mono-
1186
Notes Table 1. Chloramine-T dependence [Monoethanolamine] = 1.0 x 10- 2M,' [NaOH] = 0.4M, [CuSO4] = 1.0 x 10-4M, Temp. = 40°C [Chloramine-T] x 103M Irx 10~M(min.-m) Irxl02/[chloramine-T]
1.0 0.52 0.52
1.5 2.0 2.5 3.0 0.73 1.18 1.45 !.70 0.48 0.59 0.58 0.56
4.0 5.0 2.17 2.6 0.54 0.52
Table 2. Monoethanolamine dependence [Chloramine-T] = 2.5 x 10-3M, [CuSO4]= 1.0 x 10-4M, [NaOH] = 0.40M, Temp. = 40°C [Monoethanolamine] x 103M IRxl0~M(min. -~) IRxl02/[Monoethanolamine]
0.50 0.80 1.00 1.50 5.00 8.00 0.14 0.21 0.29 0.44 1.62 1.80 0.28 0.26 0.29 0.29 0.32 0.22
ethanolamine by alkaline chloramine-T in the presence of Cu(II) as catalyst. The fact that only initial rates have been studied limits the applicability of any mechanism to this initial period. Such a mechanism may not apply through out most of the reaction: EXPERIMENTAL Materials and method. E. Merck (Pro analysis) chloramine-T was used; solution strengths were checked iodometrically[12]. All other chemicals used were either A.R. grade or extra pure quality. The storage and reaction vessels were coated with black varnish to exclude photo-chemical effects. The solution of sodium hydroxide was always standarised before use. The kinetics of the reaction were followed by estimating the unconsumed chloramine-T iodometrically. The results are interpreted in terms of the initial rate of the reaction. RESULTSAND DISCUSSION On the basis of qualitative and quantitative results the stoichiometric equation of the reaction is 3CHr C6H4.SO2.N.NaCI + NH2'CH2.CH2.OH + 3H20 = 3CH3"C6H4"SO2.NH2 + 2HCOOH + NH3 + 3NaCI The formic acid was detected in the distillate of the reaction mixture by the cromotropic acid reaction test[13]. Kinetics. Some preliminary experiments were performed to identify suitable conditions of temperature and concentration of reactants for measurable rates of oxidation. The results are interpreted in terms of initial rate of the reaction to avoid the complexities which may arise due to interference by the products. These rates are obtained from the gradients of chloramine-T reacted vs time plots. The effects of varying (i) chloramine-T, (ii) monoethanolamine concentration, (iii) alkali concentration, and (iv) catalyst concentration on the reaction were investigated and the kinetic data are presented in Tables 1-4. The results show that the reaction is first order with respect to all the reacting substances. Salts like NaCI, KCI, K2SO4, CH3COONa have negligible effect on the reaction rate. Addition of different numbers of glass
Table 4. Cu(II) dependence [Chloramine-T] = 2.5 x 10-3M, [NaOH] = 0.40 M, [Monoethanolamine] = 1.0 x 10-2M, Temp. = 40°C [CuSO4] x 104M IR x 105 M (min. -z) IR/[CuSO4]
1.00 1.44 0.14
1.50 2.00 2.50 3.00 1.74 2.30 2.40 3.00 0.11 0.11 0.096 0.10
beads to the reaction mixture showed that surface/volume ratio plays no role in the reaction. Arrhenius parameters were also calculated from the rate study measurements carded out at different temperatures. Values abstained are EA (kcal/mole), 23.97; AH*, (kcallmole), 23.34; AS*, (cal per degree per mole) -13.25. Mechanism. The oxidising properties of chloramine-T may be due to four oxidising species, viz. chloroamine-T itself, ptoluenesulphochloramide, dichloramine-T or hypochlrite ion which are the hydrolytic product of the parent material/14/. The amount of each species depends on the pH of the solution/15/. At high alkali concentration, dichloramine-T does not exist and p-toluenesulphochloramide being a fairly strong acid/16/ (pKo =4.55) exists in traces only. The two oxidising species left are thus chloramine-T and hypochlorite ion. The possibility of hypochlorite ion as the oxidising species is ruled out as it would imply an interaction between two negatively charged ions. (anion of the amine and hypochlorite ion) which would correspond to a high negative entropy of activation, high energy of activation and a positive salt effect. The observed data and the thermodynamic parameters do not indicate such a reaction path. Thus it is concluded that chloramine-T is the only oxidising species. The mechanism of the oxidation of monoethanolamine by chloramine-T, may therefore be summarised as follows: kl
NH2.CHz.CHz.OH + OHk-i
NHH2"CH2'CH~O-+ H20
(i)
NH2.CH2-CH2.O- + CAT?
Table 3. Hydroxyl ion dependence [Chloramine-T] = 2.5 x 10-3M, [CuSO4] = 1.0 x 10-4M, [Monoethanolamine] = 1.0 x 10-2M, Temp. = 40°C [NaOH]M IR x 105 M (rain. -~) IR x 10S/[NaOI-I]
0.10 0.47 4.70
?CAT is written for chloramine-T.
0.16 0.20 0.30 0.40 0.65 0.82 1.15 1.45 4.00 4.10 3.83 3.62
Intermediate (slow and R.D.)
(ii)
Intermediate + Cu2+ - - ~ p*
(iii)
k~
P* + H20 -*Products
(iv)
In view of the stoichiometry, steps (iii and iv) do not form the final products of the reaction, and it seems likely that these steps generate intermediate products which react in a sequence of
Notes reactions which are very rapid relative to NH~.CH2.CH20-. The rate of the disappearance of chloramine-T is given as: d [CAT1 = klk:k3 [NH2.CH2.CH2OH] [OH-] [chloramine-T] [Cu. . z÷]• ,k-lk-~[H~O] + k3lCuz+] [k-iIH20] + k2[CAT]I
_ _
Under the experimental conditions, we may make the steady state approximation that k3[Cu÷÷] '~ k_, the derived rate equation d - ~ [CAT] = k~k:k3[NH2.CH2.CH2OH] [OH-] [Cu2÷] [chloramine-T] k_lk-2[H20] The above rate law equation is thus in complete accordance with the experimentally observed results. The rate" determining step (ii) of the proposed mechanism involves the interaction between a neutral molecule and a charged ion which is supported by the insignificant effect of a large variation of ionic strength. Acknowledgements--The authors thank C.S.I.R., New Delhi for the award of Junior Research Fellowship (M. C.), Dr. A. K. Bhattacharya for his keen interest and the Agra College authorities for provision of facilities. Chemical Laboratories Agra College Agra India
J I N C Vol. 40, N o , 6 - - Q
MUNESH CHANDRA O.P. BANSAL
,
1187
REFERENCES 1. O. A. Chaltykhan and N, M. Beileryan, Dokl. Akad. Nauk. Arm. SSR, 160, 31, 73; Khim. Nauk. 14, 7 (1961). 2. W. H. Dennis, L. H. Hull and D. H. Rosenblatt, J. Org. Chem. 32, 3783 (1967). 3. D. G. Dahlgren and E. M. Rand, J. Phys. Chem. 1955, 71, (i%7). 4. K. S. Shukla, Ph.D. Thesis, Agra University, Agra (19731. 5. U. S, Mahrotra and S. P. Mushran, J. Ind. Chem. Soc. 45. 526 (1%8). 6. V. N. Singh, H. C. Singh and B. B. L. Saxena, J. Am. Chem. Soc. 91, 2643 (1%9). 7. S. P. Mushran, V. K. Jindal and M C. Agarwal, J. Chem. Soc. (A), 622 (1971). 8. P. C. Mathur and S. S. Srivastava, J. Ind. Chem. Soc. 53, 576 (1976). 9. G. L Bridgart, M. W. Fulter and I. R. Wilson, J. Chem. Soc. (Dalton Trans.) 12, 1274 (1973). 10. G. J. Bridgart and I. R. Wilson, J. Chem. Soc. (Dalton Trans) 12, 1281 (1973). I1. Co. J. Bridgart, W. A. Water and I. R. Wilson, J. Chem. Soc. (Dalton Trans.) 15, 1282 (1973). 12. A. I. Vogel, A Test Book of Quantitative Inorganic Analysis 3rd. Edn, p. 392, Wiley, New York (1961). 13. F. Feigl, Spot Test in Organic Analysis, 6th Edn, p. 368 (1960). 14. R. Dietzel and K. Tanfel, Apoch. Zig. 44, 989 (1929). 15. E. Bishup and V. J. JennigS, Talanta 31, 197. 16. J. C. Morria, J. A. Salaza and M, A. Wineman, J. Chem. Soc. 70, 2038 (1948).
No~s
Table 2. Force constant, lattice frequenceis and Debye temperatu~ of isotopic lithium hydride crystal Lattice frequency in 10-~2/sec.
Force constant (f x 10 -4) Crystals 6LiH 7LiH 6LiD 7LiD
Debye O°K
Pot. I
Pot. 2
Pot. 3
Pot. 1.
Pot. 2
Pot. 3
Pot. I
Pot. 2
Pot. 3
0.1276 (I.1161 0.1231 0.09405
0.5834 0.5784 0.5864 0.5735
0.9643 0.%55 0.9752 0.9711
6.120 5.777 4.546 3.901
13.087 12.896 9.922 9.637
16.826 12.732 12.795 12.540
293.798 277.339 218.217 187.291
628.699 619.027 476.280 462.600
807.691 611.140 614.203 601.963
Table 3. Gruneisen parameter (3'), Anderson---Gruneisen parameter (8) of isotopic lithium hydride crystal Anderson-Gruneisen parameter (8)
Gruneisen parameter (3') Crystals
Pot. 1
Pot. 2
Pot. 3
3' (Exptl.)
Pot. I
Pot. 2
6LiH 7LiH 6LiD 7LiD
6.643 4.161 6.931 8.946
1.159 1.165 1.162 1.200
0.7959 0.7958 0.7956 0.7967
1.085 1.187 0.948 1.109
12.619 7.655 13.197 17.227
1.653 0.9251 1.663 0.9252 1.658 0 . 9 2 4 6 1 . 7 3 4 0.9267
Gruneisen parameter and pseudo Gruneisen parameter. The Gruneisen parameter 3' is given by Slater[12], r0$1I,Jo,
Government Postgraduate College Pithoragarh India
8 Exptl. 1.990 1.994 2.000 2.020
UMA RAN1 PANT
(6)
where d, Jr~ and $~lt refer to the second and third derivatives of The values of 3' have been calculated using this expression. The Anderson--Gruneisen parameter has been computed using Chang's relation [13]. RESULTS AND DISCUSSION
The computed values of the cohesive energy are reported in Table I. The experimental values of B and w[15, 16] are also listed. The agreement is satisfactory. The values of the force constant, lattice frequency and Debye temperature are listed in Table 2. The values of 3' and B are given in Table 3 with the experimental values of 3' and fl for these crystals [ 15]. The logarithmic potential is successful in calculations of all the lattice properties of the isotopic lithium hydride crystals and as such may be considered a suitable ionic potential for such crystals. J. D. PANDEY
Department of Chemistry University of Allahabad Allahabad-211 002 India
Pot. 3
RE~NCES
I. E. S. Rittner, J. Chem. Phys. 19, 1030 (1951). 2. Y. P. Varshni, Trans. Faraday Soc. 53, 132 (19571. 3. Y. P. Varshni, Rev. Mod. Phys. 29, 644 (19571; 31,839 (1959). 4. Y. P. Varshni and R. C. Shukla, J. Chem. Phys. 35. 582 (19511. 5. Y. P. Varshni and R. C. Shukla, Rev. Mod. Phys. 35, 130 (1%3). 6. Y. P. Varshni and R. C. Shukla, J. Mol. Spect. 16, 63 (1%5). 7. M. M. Patel, V. B. Gohel and M. D. Trivedi, Ind. J. Phys. 41, 235 (19671. 8. K. P. Thankur, Ind. J. Pure and Appl. Phys. !1,549 (19731. 9. K. P. Thakur, Ind. J. Chem. 12, 374 (19741. I0. K. P. Thakur and J. D. Pandey, J. Chem. Phys. 71,850 (19741. 11. K. S. Krishnan and S. K. Roy, Proc. R. Soc., (London) 2ff'/A, 447 (19511. 12. J. C. Slater, Introduction to Chemical Physics. McGraw-Hill, New York (19391. 13. Y. A. Chang, Phys. Chem. Solids 28, 697 (19671. 14. L. Das and S. C. Saxena, J. Chem. Phys. 43, 1747 (1%51. 15. S. P. Srivastava and R. S. Saraswat, J. Phys. Chem. Solids 36, 351 (1975).
£ inorg, nucl. Chem. Vol. 40. pp. 1185-1187 © Pergamon Press Ltd., 1978. Printed in Great Britain
0022-1902/'78/0601-1185/$02.00/0
Kinetics and mechanism of oxidation of monoethanolamine by chloramine-T catalysed by Cu(ll) ions (First received 4 May 1977; in revised [orm 25 September 1977) The Cu(II) ion catalysed oxidation of monoethanolamine by chloramine-T has not received any attention to-date, though its oxidation by other reagents, such as K2S208, K3Fe(Cn)6 has been reported[l--4]. The oxidation of monoethanolamine by chloramine-T is very slow, so Co(II) ion has been used as a catalyst. OsO4 has been widely employed as a catalyst in oxida-
tion reactions in alkaline medium [5-8]. However, very few cases of catalysis by Cu(II) ions in this redox system are reported in literature. Recently, Wilson et al. [9--I 1] have investigated the role of Cu(lI) ions in the oxidation of cystine and related thiols, and hydroxylamine by alkaline hexacyanoferrate (III). The present paper summarises the results of our kinetic oxidation of mono-
1186
Notes Table 1. Chloramine-T dependence [Monoethanolamine] = 1.0 x 10- 2M,' [NaOH] = 0.4M, [CuSO4] = 1.0 x 10-4M, Temp. = 40°C [Chloramine-T] x 103M Irx 10~M(min.-m) Irxl02/[chloramine-T]
1.0 0.52 0.52
1.5 2.0 2.5 3.0 0.73 1.18 1.45 !.70 0.48 0.59 0.58 0.56
4.0 5.0 2.17 2.6 0.54 0.52
Table 2. Monoethanolamine dependence [Chloramine-T] = 2.5 x 10-3M, [CuSO4]= 1.0 x 10-4M, [NaOH] = 0.40M, Temp. = 40°C [Monoethanolamine] x 103M IRxl0~M(min. -~) IRxl02/[Monoethanolamine]
0.50 0.80 1.00 1.50 5.00 8.00 0.14 0.21 0.29 0.44 1.62 1.80 0.28 0.26 0.29 0.29 0.32 0.22
ethanolamine by alkaline chloramine-T in the presence of Cu(II) as catalyst. The fact that only initial rates have been studied limits the applicability of any mechanism to this initial period. Such a mechanism may not apply through out most of the reaction: EXPERIMENTAL Materials and method. E. Merck (Pro analysis) chloramine-T was used; solution strengths were checked iodometrically[12]. All other chemicals used were either A.R. grade or extra pure quality. The storage and reaction vessels were coated with black varnish to exclude photo-chemical effects. The solution of sodium hydroxide was always standarised before use. The kinetics of the reaction were followed by estimating the unconsumed chloramine-T iodometrically. The results are interpreted in terms of the initial rate of the reaction. RESULTSAND DISCUSSION On the basis of qualitative and quantitative results the stoichiometric equation of the reaction is 3CHr C6H4.SO2.N.NaCI + NH2'CH2.CH2.OH + 3H20 = 3CH3"C6H4"SO2.NH2 + 2HCOOH + NH3 + 3NaCI The formic acid was detected in the distillate of the reaction mixture by the cromotropic acid reaction test[13]. Kinetics. Some preliminary experiments were performed to identify suitable conditions of temperature and concentration of reactants for measurable rates of oxidation. The results are interpreted in terms of initial rate of the reaction to avoid the complexities which may arise due to interference by the products. These rates are obtained from the gradients of chloramine-T reacted vs time plots. The effects of varying (i) chloramine-T, (ii) monoethanolamine concentration, (iii) alkali concentration, and (iv) catalyst concentration on the reaction were investigated and the kinetic data are presented in Tables 1-4. The results show that the reaction is first order with respect to all the reacting substances. Salts like NaCI, KCI, K2SO4, CH3COONa have negligible effect on the reaction rate. Addition of different numbers of glass
Table 4. Cu(II) dependence [Chloramine-T] = 2.5 x 10-3M, [NaOH] = 0.40 M, [Monoethanolamine] = 1.0 x 10-2M, Temp. = 40°C [CuSO4] x 104M IR x 105 M (min. -z) IR/[CuSO4]
1.00 1.44 0.14
1.50 2.00 2.50 3.00 1.74 2.30 2.40 3.00 0.11 0.11 0.096 0.10
beads to the reaction mixture showed that surface/volume ratio plays no role in the reaction. Arrhenius parameters were also calculated from the rate study measurements carded out at different temperatures. Values abstained are EA (kcal/mole), 23.97; AH*, (kcallmole), 23.34; AS*, (cal per degree per mole) -13.25. Mechanism. The oxidising properties of chloramine-T may be due to four oxidising species, viz. chloroamine-T itself, ptoluenesulphochloramide, dichloramine-T or hypochlrite ion which are the hydrolytic product of the parent material/14/. The amount of each species depends on the pH of the solution/15/. At high alkali concentration, dichloramine-T does not exist and p-toluenesulphochloramide being a fairly strong acid/16/ (pKo =4.55) exists in traces only. The two oxidising species left are thus chloramine-T and hypochlorite ion. The possibility of hypochlorite ion as the oxidising species is ruled out as it would imply an interaction between two negatively charged ions. (anion of the amine and hypochlorite ion) which would correspond to a high negative entropy of activation, high energy of activation and a positive salt effect. The observed data and the thermodynamic parameters do not indicate such a reaction path. Thus it is concluded that chloramine-T is the only oxidising species. The mechanism of the oxidation of monoethanolamine by chloramine-T, may therefore be summarised as follows: kl
NH2.CHz.CHz.OH + OHk-i
NHH2"CH2'CH~O-+ H20
(i)
NH2.CH2-CH2.O- + CAT?
Table 3. Hydroxyl ion dependence [Chloramine-T] = 2.5 x 10-3M, [CuSO4] = 1.0 x 10-4M, [Monoethanolamine] = 1.0 x 10-2M, Temp. = 40°C [NaOH]M IR x 105 M (rain. -~) IR x 10S/[NaOI-I]
0.10 0.47 4.70
?CAT is written for chloramine-T.
0.16 0.20 0.30 0.40 0.65 0.82 1.15 1.45 4.00 4.10 3.83 3.62
Intermediate (slow and R.D.)
(ii)
Intermediate + Cu2+ - - ~ p*
(iii)
k~
P* + H20 -*Products
(iv)
In view of the stoichiometry, steps (iii and iv) do not form the final products of the reaction, and it seems likely that these steps generate intermediate products which react in a sequence of
Notes reactions which are very rapid relative to NH~.CH2.CH20-. The rate of the disappearance of chloramine-T is given as: d [CAT1 = klk:k3 [NH2.CH2.CH2OH] [OH-] [chloramine-T] [Cu. . z÷]• ,k-lk-~[H~O] + k3lCuz+] [k-iIH20] + k2[CAT]I
_ _
Under the experimental conditions, we may make the steady state approximation that k3[Cu÷÷] '~ k_, the derived rate equation d - ~ [CAT] = k~k:k3[NH2.CH2.CH2OH] [OH-] [Cu2÷] [chloramine-T] k_lk-2[H20] The above rate law equation is thus in complete accordance with the experimentally observed results. The rate" determining step (ii) of the proposed mechanism involves the interaction between a neutral molecule and a charged ion which is supported by the insignificant effect of a large variation of ionic strength. Acknowledgements--The authors thank C.S.I.R., New Delhi for the award of Junior Research Fellowship (M. C.), Dr. A. K. Bhattacharya for his keen interest and the Agra College authorities for provision of facilities. Chemical Laboratories Agra College Agra India
J I N C Vol. 40, N o , 6 - - Q
MUNESH CHANDRA O.P. BANSAL
,
1187
REFERENCES 1. O. A. Chaltykhan and N, M. Beileryan, Dokl. Akad. Nauk. Arm. SSR, 160, 31, 73; Khim. Nauk. 14, 7 (1961). 2. W. H. Dennis, L. H. Hull and D. H. Rosenblatt, J. Org. Chem. 32, 3783 (1967). 3. D. G. Dahlgren and E. M. Rand, J. Phys. Chem. 1955, 71, (i%7). 4. K. S. Shukla, Ph.D. Thesis, Agra University, Agra (19731. 5. U. S, Mahrotra and S. P. Mushran, J. Ind. Chem. Soc. 45. 526 (1%8). 6. V. N. Singh, H. C. Singh and B. B. L. Saxena, J. Am. Chem. Soc. 91, 2643 (1%9). 7. S. P. Mushran, V. K. Jindal and M C. Agarwal, J. Chem. Soc. (A), 622 (1971). 8. P. C. Mathur and S. S. Srivastava, J. Ind. Chem. Soc. 53, 576 (1976). 9. G. L Bridgart, M. W. Fulter and I. R. Wilson, J. Chem. Soc. (Dalton Trans.) 12, 1274 (1973). 10. G. J. Bridgart and I. R. Wilson, J. Chem. Soc. (Dalton Trans) 12, 1281 (1973). I1. Co. J. Bridgart, W. A. Water and I. R. Wilson, J. Chem. Soc. (Dalton Trans.) 15, 1282 (1973). 12. A. I. Vogel, A Test Book of Quantitative Inorganic Analysis 3rd. Edn, p. 392, Wiley, New York (1961). 13. F. Feigl, Spot Test in Organic Analysis, 6th Edn, p. 368 (1960). 14. R. Dietzel and K. Tanfel, Apoch. Zig. 44, 989 (1929). 15. E. Bishup and V. J. JennigS, Talanta 31, 197. 16. J. C. Morria, J. A. Salaza and M, A. Wineman, J. Chem. Soc. 70, 2038 (1948).