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1.
R. K. Patil S. T. Nandibewoor S. A. Chimatadar 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2012,86(3):369-374
The kinetics of ruthenium(III) catalyzed oxidation of atenolol by diperiodatocuprate(III) in aqueous alkaline medium at a
constant ionic strength of I = 0.10 M has been studied spectrophotometrically at 27°C. The reaction between diperiodatocuprate(III) and atenolol in alkaline
medium in presence of ruthenium(III) exhibits 2: 1 stoichiometry (atenolol: diperiodatocuprate(III)). The main products were
identified by spot test, IR, NMR, and LC-MS. The reaction is of first order in DPC concentrations and has less than unit order
in both ATN and alkali concentrations. The order in ruthenium(III) was unity. Intervention of free radicals was observed in
the reaction. Increase in periodate concentration decreases the rate. The oxidation reaction in alkaline medium has been shown
to proceed via a ruthenium(III)-atenolol complex, which reacts with monoperiodatocuprate(III) in a rate determining step followed
by other fast steps to give the products. Probable mechanism is proposed and discussed. The activation parameters with respect
to the slow step of the mechanism and thermodynamic quantities were determined and discussed. 相似文献
2.
The kinetics of ruthenium(III) catalyzed oxidation of chloramphenicol (CHP) by diperiodatocuprate(III) (DPC) in aqueous alkaline
medium at a constant ionic strength of 0.1 mol l−1 was studied spectrophotometrically. The reaction between DPC and CHP in alkaline medium exhibits 1: 2 stoichiometry (CHP:
DPC). The main oxidation products were identified by spot test, IR, NMR, and GC-MS spectral studies. The reaction is first
order with respect to ruthenium(III) and DPC concentrations. The order with respect to chloramphenicol concentration varies
from first order to zero order as the chloramphenicol concentration increases. As the alkali concentration increases the reaction
rate increases with fractional order dependence on alkali concentration. Increase in periodate concentration decreases the
rate. A mechanism adequately describing the observed regularities is proposed. The reaction constants involved in the different
steps of the mechanism were calculated. The activation parameters with respect to limiting step of the mechanism are computed
and discussed. Thermodynamic quantities are determined. 相似文献
3.
The kinetics of oxidation of vanillin (VAN) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.50 mol dm?3 was studied spectrophotometrically. The reaction between DPC and vanillin in alkaline medium exhibits 1:2 stoichiometry (vanillin: DPC). The reaction is of first order in [DPC] and has less than unit order in both [VAN] and [alkali]. Intervention of free radicals was observed in the reaction. Increase in periodate concentration decreases the rate. The oxidation reaction in alkaline medium has been shown to proceed via a monoperiodatocuprate(III)–vanillin complex, which decomposes slowly in a rate‐determining step followed by other fast steps to give the products. The main products were identified by spot test, IR, and MS studies. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. © 2007 Wiley Periodicals, Inc. 39: 236–244, 2007 相似文献
4.
The kinetics of oxidation of atenolol (ATN) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.10 mol dm−3 was studied spectrophotometrically. The reaction between DPC and ATN in alkaline medium exhibits 1:2 stoichiometry (ATN:DPC). The reaction is of first order in [DPC] and has less than unit order in both [ATN] and [alkali]. However, the order in [ATN] and [alkali] changes from first order to zero order as their concentration increase. Intervention of free radicals was observed in the reaction. Increase in periodate concentration decreases the rate. The oxidation reaction in alkaline medium has been shown to proceed via a monoperiodatocuprate(III)–ATN complex, which decomposes slowly in a rate-determining step followed by other fast steps to give the products. The main oxidative products were identified by spot test, IR, NMR and LC–ESI-MS studies. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. 相似文献
5.
Shweta J. Malode Nagaraj P. Shetti Sharanappa T. Nandibewoor 《Journal of solution chemistry》2010,39(3):417-430
The oxidation of ketorolac (KET) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength
of 0.10 mol⋅dm−3 was studied spectrophotometrically at 298 K. The reaction is of first order in [DPC] and has less than unit order in both
[KET] and [alkali], and negative fractional order in [periodate]. The oxidation reaction in alkaline medium has been shown
to proceed via a DPC-ketorolac complex, which decomposes slowly in a rate determining step followed by other fast steps to
give the products. The main products were identified by spot test, IR and GC-MS spectral studies. The reaction constants involved
in the different steps of the mechanism were calculated at different temperatures, which yielded thermodynamic quantities
for different steps of the reaction scheme. The activation parameters with respect to the slow step of the mechanism were
computed and discussed; thermodynamic quantities were also determined. 相似文献
6.
Shweta J. Malode Jyothi C. Abbar Sharanappa T. Nandibewoor 《Monatshefte für Chemie / Chemical Monthly》2011,34(6):469-479
Abstract
The kinetics of the oxidation of ruthenium(III)-catalyzed oxidation of pentoxifylline (PTX) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.30 mol dm−3 was studied spectrophotometrically. The reaction between PTX and DPC in alkaline medium in the presence of Ru(III) exhibits 1:2 stoichiometry (PTX:DPC). The reaction was of first order in DPC, less than the unit order in [PTX] and [OH−] and negative fractional order in [IO4 −]. The order in [Ru(III)] was unity. Intervention of free radicals was observed in the reaction. The main products were identified by TLC and spectral studies including LC-MS. The oxidation reaction in alkaline medium has been shown to proceed via a Ru(III)-PTX complex, which reacts with monoperiodatocuprate(III) to decompose in a rate determining step followed by a fast step to give the products. The reaction constants involved in different steps of the mechanism were calculated. The activation parameters with respect to the slow step of the mechanism were computed and discussed, and thermodynamic quantities were also determined. The active species of catalyst and oxidant have been identified. 相似文献7.
The kinetics of oxidation of L-cystine (L-CYS) by diperiodatocuprate (III) (DPC) in aqueous alkaline medium at a constant
ionic strength of 0.20 mol/1 was studied spectrophotometrically at 298 K. The reaction between DPC and L-cystine in alkaline
medium exhibits 1: 4 stoichiometry (L-cystine: DPC = 1: 4). The reaction is of first order in [DPC] and has less than unit
order in [L-CYS] and [alkali], negative fractional order in [periodate] and intervention of free radicals was observed in
the reaction. The oxidation reaction in alkaline medium has been shown to proceed via a monoperiodatocuprate(III)-L-ystine
complex, which decomposes slowly in a rate determining step followed by other fast steps to give the products. The main products
were identified by spot test, IR and GC-MS. The reaction constants involved in the different steps of the mechanism are calculated.
The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities
were also determined. 相似文献
8.
T. S. Kiran D. C. Hiremath S. T. Nandibewoor 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2007,81(12):2070-2077
The kinetics of oxidation of L-lysine by diperiodatocuprate (III) (DPC) in alkaline medium at a constant ionic strength of
0.15 mol/dm3 was studied spectrophotometrically. The reaction between DPC and L-lysine in an alkaline medium had a 1: 2 stoichiometry
(L-lysine: DPC). The reaction was first order in [DPC] and less than first order in [L-lysine] and [alkali]. The addition
of periodate had no effect on the rate of the reaction. The intervention of free radicals was observed in the reaction. The
oxidation reaction in alkaline medium was shown to proceed via a DPC-L-lysine complex. The main products were identified by
spot test and spectral studies. The reaction constants involved in different steps of the mechanism were calculated. The activation
parameters with respect to the slow step of the mechanism were computed and discussed, and thermodynamic values were also
determined.
The article is published in the original. 相似文献
9.
D. S. Munavalli R. K. Patil S. A. Chimatadar S. T. Nandibewoor 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2009,83(13):2210-2214
The kinetics of ruthenium(III) catalyzed oxidation of sulfanilic acid by diperiodatocuprate(III) (DPC) in alkaline medium
at a constant ionic strength of (0.50 mol dm−3) has been studied spectrophoto-metrically. The reaction between sulfanilic acid and DPC in alkaline medium exhibits 1: 4
stoichiometry (sulfanilic acid: DPC). The reaction is first order with respect to [DPC] and [RuIII] and has less than unit order both in [sulfanilic acid] and [alkali]. The active species of catalyst and oxidant have been
identified. Intervention of free radicals was observed in the reaction. The main products were identified by spot test and
IR. Probable mechanism is proposed and discussed. The reaction constants involved in the different steps of the mechanism
are calculated. The activation parameters with respect to the slow step of the mechanism are computed and discussed. Thermodynamic
quantities are also determined. 相似文献
10.
Ragunatharaddi R. Hosamani Rajesh N. Hegde Sharanappa T. Nandibewoor 《Monatshefte für Chemie / Chemical Monthly》2010,33(8):1069-1076
Abstract
Oxidation of the amino acid l-phenylalanine by diperiodatocuprate(III) in alkaline medium at constant ionic strength of 0.25 mol dm−3 was studied spectrophotometrically at different temperatures (298–313 K). The reaction between diperiodatocuprate(III) and l-phenylalanine in alkaline medium exhibits 1:2 stoichiometry. Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidence, a mechanism involving monoperiodatocuprate(III) as the reactive oxidant species has been proposed, proceeding through the formation of a complex and reaction of the intermediate of l-phenylalanine with monoperiodatocuprate(III) to give the products. The products were identified by spot test, infrared (IR), and gas chromatography-mass spectrometry (GC-MS). The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to the slow step of the mechanism were computed and are discussed. The thermodynamic quantities were determined for different equilibrium steps. The isokinetic temperature was also calculated and found to be 331 K. 相似文献11.
The kinetics of oxidation of sarcosine by diperiodatocuprate(III) (DPC) was studied with spectrophotometry in a temperature range of 292.2–304.2 K. The reaction between diperiodatocuprate(III) and sarcosine in alkaline medium exhibits 1:1 stoichiometry (DPC:sarcosine). The reaction was found to be first order with respect to both DPC and sarcosine. The observed rate constant (kobs) decreased with the increase of the [IO?4], decreased with the increase of the [OH?], and then increased with the increase of the [OH?] after a turning point. There was no salt effect, and free radicals were detected. Based on the experimental results, a mechanism involving the diperiodatocuprate(III) (DPC) as the reactive species of the oxidant has been proposed. The activation parameters, as well as the rate constants of the rate‐determining step, have been calculated. 相似文献
12.
Nagaraj P. Shetti Rajesh N. Hegde Sharanappa. T. Nandibewoor 《Central European Journal of Chemistry》2009,7(4):929-937
Oxidation of an amino acid, L-tyrosine (L-Tyr) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength
of 0.1 mol dm−3 was studied spectrophotometrically at different temperatures (288.1–313.1 K). The reaction between DPC and L-Tyr in alkaline
medium exhibits 1:4 stoichiometry (L-Tyr:DPC). Intervention of free radicals was observed in the reaction. Based on the observed
orders and experimental evidence, a mechanism involving monoperiodatocuprate(III) (MPC) as the reactive oxidant species has
been proposed. A suitable mechanism is proposed through the formation of a complex and free radical intermediate. The products
were identified by spot test and characterized by spectral studies. The reaction constants involved in the different steps
of the mechanism were calculated. The activation parameters with respect to slow step of the mechanism were computed and are
discussed. The thermodynamic quantities were determined for different equilibrium steps. Isokinetic temperature was also calculated
and found to be 252.3 K.
相似文献
13.
Shekappa D. Lamani Praveen N. Naik Sharanappa T. Nandibewoor 《Journal of solution chemistry》2010,39(9):1291-1310
The kinetics of the osmium(VIII) (Os(VIII)) catalyzed oxidation of diclofenac sodium (DFS) by diperiodatocuprate(III) (DPC)
in aqueous alkaline medium has been studied spectrophotometrically at a constant ionic strength of 1.0 mol⋅dm−3. The reaction showed first order kinetics in [Os(VIII)] and [DPC] and less than unit order with respect to [DFS] and [alkali].
The rate decreased with increase in [periodate]. The reaction between DFS and DPC in alkaline medium exhibits 1:2 [DFS]:[DPC]
stoichiometry. However, the order in [DFS] and [OH−] changes from first order to zero order as their concentration increases. Changes in the ionic strength and dielectric constant
did not affect the rate of reaction. The oxidation products were identified by LC-ESI-MS, NMR, and IR spectroscopic studies.
A possible mechanism is proposed. The reaction constants involved in the different steps of the mechanism were calculated.
The catalytic constant (K
C) was also calculated for Os(VIII) catalysis at the studied temperatures. From plots of log 10
K
C versus 1/T, values of activation parameters have been evaluated with respect to the catalytic reaction. The activation parameters with
respect to the slow step of the mechanism were computed and discussed, and thermodynamic quantities were also determined.
The active osmium(VIII) and copper(III) periodate species have been identified. 相似文献
14.
The kinetics of oxidation of isoniazid (INH) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic
strength of 0.05 mol dm−3 has been studied spectrophotometrically. The reaction showed first order kinetics both in [DPC] and [INH] and negative less
than unit order, both in alkali and periodate concentrations under the experimental conditions. Intervention of free radicals
was observed in the reaction. Products of the reaction, isonicotinic acid and copper(II) have no effect on the rate of reaction.
Ionic strength and dielectric constant did not affect the rate of reaction. Based on the observed orders and experimental
evidences, a mechanism involving the monoperiodatocuprate(III) (MPC) as the reactive oxidant species has been proposed. The
main products were identified by I.R, N.M.R. and GC-MS spectral studies. The reaction constants involved in the mechanism
were evaluated. Investigations at different temperatures allowed the determination of the activation parameters with respect
to the slow step of proposed mechanism. The mechanism proposed and the derived rate laws are consistent with the observed
kinetics. 相似文献
15.
K. Sharanabasamma Manjali S. Salunke Suresh M. Tuwar 《Journal of solution chemistry》2008,37(9):1217-1225
The diperiodatocuprate(III) (DPC) oxidation of DL-methionine, a sulfur containing amino acid, was studied spectrophotometrically
in alkaline solution. The reaction rate was first order in the concentration of DPC and fractional order in the concentration
of DL-methionine. Increasing the OH− concentration decreased the rate of reaction, whereas adding IO4− enhanced the rate. The reaction was preceded by a small initiation period of about 0.8 minutes. This initiation time decreased
when the concentration of IO4− or DPC increased. Adding the reaction products did not alter the rate of reaction. A mechanism including the intervention
of a DL-methionine free radical is proposed and the corresponding rate law is derived. The reaction rate constants are evaluated
as well as the activation parameters. 相似文献
16.
The kinetics of oxidation of the anti-ulcer drug, ranitidine hydrochloride (RNH) by diperiodatocuprate(III) (DPC) in alkaline
medium was studied spectrophotometrically. The reaction exhibits 1:2 stoichiometry (ranitidine:DPC). The reaction is of first
order in [DPC] and has less than unit order in [RNH] and negative fractional order in [alkali]. The involvement of free radicals
was observed in the reaction. The oxidation has been found to proceed via a DPC-ranitidine complex, which decomposes slowly
in a rate-determining step followed by other fast steps to give the products, which were identified as ranitidine sulfoxide
by spot test and spectroscopic studies.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
17.
The kinetics of Ru(III) catalysed oxidation of l-leucine by diperiodatoargentate(III) (DPA) in alkaline medium at 298 K and a constant ionic strength of 0.60 mol dm−3 was studied spectrophotometrically. The oxidation products are pentanoic acid and Ag(I). The stoichiometry is [l-leucine]:[DPA] = 1:2. The reaction is of first order in Ru(III) and [DPA] and has less than unit order in both [l-leu] and [alkali]. The oxidation reaction in alkaline medium has been shown to proceed via a Ru(III)–l-leucine complex, which further reacts with one molecule of monoperiodatoargentate(III) (MPA) in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test and spectral studies. The reaction constants involved in the different steps of the mechanism are calculated. The catalytic constant (Kc) was also calculated for the Ru(III) catalysed reaction at different temperatures. From the plots of log Kc versus 1/T, values of activation parameters with respect to the catalyst have been evaluated. The activation parameters with respect to the slow step of the mechanism are computed and discussed, and thermodynamic quantities are also determined. The active species of catalyst and oxidant have been identified. 相似文献
18.
The kinetics of oxidation of a non-steroidal analgesic drug, aspirin (ASP) by diperiodatocuprate(III)(DPC) in the presence and absence of osmium(VIII) have been investigated at 298 K in alkaline medium at a constant ionic strength of 0.10 mol dm−3 spectrophotometrically. The reaction showed a first-order in [DPC] and less than unit order in [ASP] and [alkali] for both the osmium(VIII) catalysed and uncatalysed reactions. The order with respect to Os(VIII) concentration was unity. The effects of added products, ionic strength, periodate and dielectric constant have been studied. The stoichiometry of the reaction was found to be 1:4 (ASP:DPC) for both the cases. The main oxidation product of aspirin was identified by spot test, IR, NMR and GC–MS. The reaction constants involved in the different steps of the mechanisms were calculated for both reactions. Activation parameters with respect to slow step of the mechanisms were computed and discussed for both the cases. The thermodynamic quantities were also determined for both reactions. The catalytic constant (KC) was also calculated for catalysed reaction at different temperatures and the corresponding activation parameters were determined. 相似文献
19.
Jyothi C. Abbar Shweta J. Malode Sharanappa T. Nandibewoor 《Journal of molecular catalysis. A, Chemical》2009,313(1-2):88-99
The oxidation of dl-ornithine monohydrochloride (OMH) by diperiodatocuprate(III) (DPC) has been investigated both in the absence and presence of ruthenium(III) catalyst in aqueous alkaline medium at a constant ionic strength of 0.20 mol dm−3 spectrophotometrically. The stiochiometry was same in both the cases, i.e., [OMH]/[DPC] = 1:4. In both the catalyzed and uncatalyzed reactions, the order of the reaction with respect to [DPC] was unity while the order with respect to [OMH] was < 1 over the concentration range studied. The rate increased with an increase in [OH−] and decreased with an increase in [IO4−] in both cases. The order with respect to [Ru(III)] was unity. The reaction rates revealed that Ru(III) catalyzed reaction was about eight-fold faster than the uncatalyzed reaction. The oxidation products were identified by spectral analysis. Suitable mechanisms were proposed. The reaction constants involved in the different steps of the reaction mechanisms were calculated for both cases. The catalytic constant (KC) was also calculated for catalyzed reaction at different temperatures. The activation parameters with respect to slow step of the mechanism and also the thermodynamic quantities were determined. Kinetic experiments suggest that [Cu(H2IO6)(H2O)2] is the reactive copper(III) species and [Ru(H2O)5OH]2+ is the reactive Ru(III) species. 相似文献
20.
碱性介质中二过碘酸合铜(III)配离子氧化四氢糠醇的动力学及机理 总被引:7,自引:0,他引:7
本文采用分光光度法研究了二过碘酸合铜(III)配离子在碱性介质中氧化四氢糠醇的动力学及机理. 结果表明反应对[Cu(III)]是一级, 对四氢糠醇是1.3级. 反应速率随体系中[OH^-]的增大而增大, 随过碘酸浓度的增大而减小, 反应体系加入硝酸钾盐时,速率增大, 有正盐效应. 在氮气保护下, 体系能够诱发丙烯酰胺聚合. 提出了一种含有自由基过程的反应机理, 据此导出了一个能够解释本文全部实验事实的速率方程. 求得了速率控制步骤的速率常数, 并给出了相应的活化参数. 相似文献