scholarly journals Kinetics of periodate oxidation of polyoxyethylene – 300, a biodegradable pharmaceutical polymer

2019 ◽  
Vol 10 (4) ◽  
pp. 2830-2836
Author(s):  
Koteswara Rao K.V.S ◽  
Venkata Nadh R ◽  
Venkata Ratnam K

Polyoxyethylene Oxide – 300 (POE) is a well-known biodegradable pharmaceutical polymer. In order to understand the stability of POE and to derive the reaction rate law, the title reaction was carried out in aqueous alkaline medium, Reaction was found to be first order dependent on the concentration oxidant (periodate) and independent of substrate (POE) concentration. A retardation of reaction rate with an increase in hydroxide concentration shows an inverse fractional order in it. Based on the studies of the temperature dependence of reaction, evaluated the activation parameters.

1971 ◽  
Vol 26 (10) ◽  
pp. 1010-1016 ◽  
Author(s):  
Renate Voigt ◽  
Helmut Wenck ◽  
Friedhelm Schneider

First order rate constants of the reaction of a series of SH-, imidazole- and imidazole/SH-compounds with FDNB as well as their pH- and temperature dependence were determined. Some of the tested imidazole/SH-compounds exhibit a higher nucleophilic reactivity as is expected on the basis of their pKSH-values. This enhanced reactivity is caused by an activation of the SH-groups by a neighbouring imidazole residue. The pH-independent rate constants were calculated using the Lindley equation.The kinetics of DNP-transfer from DNP-imidazole to SH-compounds were investigated. The pH-dependence of the reaction displays a maximum curve. Donor in this reaction is the DNP-imidazolecation and acceptor the thiolate anion.The reaction rate of FDNB with imidazole derivatives is two to three orders of magnitude slower than with SH-compounds.No inter- or intra-molecular transfer of the DNP-residue from sulfure to imidazole takes place.


Author(s):  
K. V. S. KOTESWARA RAO ◽  
R. VENKATA NADH ◽  
K. VENKATA RATNAM

Objective: To study the kinetics of periodate oxidation of polyethylene glycol-600 (PEG-600), a familiar non-toxic polymer used in pharmaceutical and other fields of industry. Methods: Reactions were carried out in alkaline medium and measured the kinetics by iodometry. One oxygen atom loss or two electrons transfer was observed per each molecule of periodate i.e., the rate of reaction was measured periodate converts to iodate because the formed iodate species is unable to oxidize the substrate molecules. Results: Based on log (a-x) versus t plots, order w. r. t. oxidant (periodate) is unity. Reactions were found to be independent of substrate (PEG-600) concentration. A decrease in rate with an increase in alkali concentration [OH–] was found and order was inverse fractional. Temperature dependence of reaction rate was studied and then calculated the corresponding Arrhenius parameters. Conclusion: An appropriate rate law was proposed by considering the above experimental results.


2001 ◽  
Vol 56 (3) ◽  
pp. 281-286 ◽  
Author(s):  
Ceyhan Kayran ◽  
Eser Okan

Abstract The kinetics of the thermal substitution of norbornadiene (nbd) by 2,2'-bipyridine (2,2'-bipy) in (CO)4Mo(C7H9) was studied by quantitative FT-IR and UV-VIS spectroscopy. The reaction rate exhibits first-order dependence on the concentration of the starting complex, and the observed rate constant depends on the concentration of both leaving nbd and entering 2,2'-bipy ligand. The mechanism was found to be consistent with the previously proposed one, where the rate determining step is the cleavage of one of the two Mo-olefin bonds. The reaction was performed at four different temperatures (35 -50 °C) and the evaluation of the kinetic data gives the activation parameters which now support states.


1978 ◽  
Vol 33 (6) ◽  
pp. 657-659 ◽  
Author(s):  
M. P. Singh ◽  
A. K. Singh ◽  
Mandhir Kumar

Abstract The present paper deals with the kinetics of oxidation of D-galactose by Nessler's reagent in alkaline medium. The reaction is zero order with respect to Hg(II) and first order with respect to reducing sugar. The direct proportionality of the reaction rate at low hydroxide ion concentrations shows retarding trend at higher concentrations. The reaction rate is inversely proportional to iodide ion concentration. A mechanism has been proposed taking HgI3- as the reacting species


2011 ◽  
Vol 8 (4) ◽  
pp. 1728-1733 ◽  
Author(s):  
N. M. I. Alhaji ◽  
S. Sofiya Lawrence Mary

The kinetics of oxidation of isoleucine withN-bromophthalimide has been studied in perchloric acid medium potentiometrically. The reaction is of first order each in [NBP] and [amino acid] and negative fractional order in [H+]. The rate is decreased by the addition of phthalimide. A decrease in the dielectric constant of the medium increases the rate. Addition of halide ions or acrylonitrile has no effect on the kinetics. Similarly, variation of ionic strength of the medium does not affect the reaction rate. The reaction rate has been determined at different temperatures and activation parameters have been calculated. A suitable mechanism involving hypobromous acid as reactive species has been proposed.


2019 ◽  
Vol 2019 ◽  
pp. 1-10
Author(s):  
Weiping Du ◽  
Guiming Zhang ◽  
Song Wang ◽  
Lianjiang Tan ◽  
Huifang Chen

An optical polythiourethane based on m-xylylene diisocyanate (XDI) and 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol (BES) has been studied. Triethylamine was adopted as a catalyst, and the solid-state isothermal cure reaction was carried out using FTIR spectroscopy, in the temperature range of 75°C-105°C. The -NCO absorption band of XDI was used to monitor the conversion of diisocyanate into polythiourethane. The reaction rate enhanced with an increase in the content of the catalyst, and the gel time determined by swelling test was shorter for the system with higher catalyst content. Kinetic parameters were calculated from the infrared spectrum data, and the results showed that the curing reaction of polythiourethane accords with first-order kinetic characteristics. The activation parameters obtained from the evaluation of kinetic data were △H∗=97.22 kJ mol−1, △S∗=−6.77 J K−1 mol−1, and Ea=100.23 kJ mol−1. The observed negative entropy of activation value supported the formation of a transition state in the cure reaction.


1992 ◽  
Vol 57 (2) ◽  
pp. 326-331 ◽  
Author(s):  
Refat M. Hassan

The kinetics of hexachloroiridate(IV) oxidation of tin(II) in aqueous perchlorate media at a constant ionic strength of 2.0 mol dm-3 have been studied spectrophotometrically. The reaction was found to follow second-order overall kinetics and first order with respect to each of the reactants. The results showed hydrogen ion dependence where the reaction rate increased with increasing hydrogen ion concentration. The activation parameters were evaluated and a tentative reaction mechanism has been discussed.


2005 ◽  
Vol 2005 (3) ◽  
pp. 197-201 ◽  
Author(s):  
G.C Hiremath ◽  
R.M Mulla ◽  
S.T Nandibewoor

The kinetics of oxidation of isonicotinate ion by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 0.60 mol dm−3 was studied spectrophotometrically. A mechanism involving the formation of an intermediate complex between the diperiodatocuprate(III) as the oxidant species and isonicotinate ion is proposed. The reaction constants involved in the different steps of mechanism have been calculated. The activation parameters with respect to the slow step of the mechanism have been computed and discussed and thermodynamic quantities were also determined.


2005 ◽  
Vol 70 (4) ◽  
pp. 585-592 ◽  
Author(s):  
J.H. Shan ◽  
S.Y. Huo ◽  
S.G. Shen ◽  
H.W. Sun

The kinetics of oxidation of 1,2-propanediol and 1,2,3-propanetriol by dihydroxyditelluratoargentate(III) (DDA) were studied spectrophotometrically between 298.2 K and 313.2 K in alkaline medium. The reaction rate showed first order dependence on DDA and 1 < nap < 2 order on the reductant. It was found that the pseudo-first order rate constant kobs increased with increasing concentration of OH-1 and decreasing concentration of TeO42-. There is a negative salt effect and no free radicals were detected. In view of this, the dihydroxymonotelluratoargentate(III) species is assumed to be the active species. A plausible mechanism involving a two-electron transfer is proposed and the rate equations derived from the mechanism can explain all the experimental results. The activation parameters, as well as the rate constants of the rate-determining step were calculated.


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