scholarly journals Cure Kinetics of an Optical Polythiourethane with Amine Catalyst by IR Analysis

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.

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.


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.


2011 ◽  
Vol 295-297 ◽  
pp. 1236-1239
Author(s):  
Yin Hai Lang ◽  
Min Jie Wang ◽  
Nan Nan Wang

In this study, reductive dechlorination of DDT compounds by zero-valent iron in Jiangxi red soil was investigated. DDT compounds were effectively dechlorinated by zero-valent iron. The pseudo-first-order kinetic model for 2,4¢-DDT and 4,4¢-DDT reduction with zero-valent iron was proposed. The reaction rate constants for 2,4¢-DDT and 4,4¢-DDT were 1.19´10-2(min-1) and 1.44´10-2(min-1), respectively. The dechlorination of 2,4¢-DDT and 4,4¢-DDT were mainly affected by the specific surface area of iron. The data from the variable-pH experiments (between 3.6 and 8.8) suggested that pH does not play a role in the rate-determination step.


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.


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 4 (1) ◽  
pp. 55-61
Author(s):  
R. Sridharan ◽  
N. Mathiyalagan

Kinetics of Oxidation of Benzoin by N. Bromosuccinimide[NBS] 80% aqueous acetic acid has been investigated. The reaction follows first-order kinetics with respect to both[NBS] and [benzoin]. The effect of varying ionic strength and dielectric constant indicate the reaction is dipole-dipole type. Addition of succinimide(>NH), has a retarding effect on the rate of oxidation. The product of oxidation is benzil. By studying the effect of temparature on the reaction rate, the Arrhenius and the activation parameters have been calculated. A suitable mechanism has been proposed and a rate low explaining the experiment results is derived.


2009 ◽  
Vol 74 (2) ◽  
pp. 171-182 ◽  
Author(s):  
Govindasamy Rajarajan ◽  
Natesan Jayachandramani ◽  
Subramanian Manivarman ◽  
Jayaraman Jayabharathi ◽  
Venugopal Thanikachalam

The kinetics of the oxidation of aldonitrones (nitrone) by quinolinium chlorochromate (QCC) was determined in 50 % DMF-water in the absence and presence of oxalic acid in order to study the effect of oxalic acid. It was considered worthwhile to investigate whether it undergoes co-oxidation or just functions as a catalyst in the reaction. The reaction was followed iodometrically. Under the employed experimental conditions, the reaction is first order each with respect to concentration of nitrone, QCC, and oxalic acid and fractional order with respect to H+ concentration. There was no discernible effect with increasing in ionic strength but the rate of oxidation decreased with decreasing dielectric constant of the medium. Addition of MnSO4 had a significant and acrylonitrile no effect on the reaction rate. A mechanism involving protonated nitrone and QCC as the reactive oxidant is proposed. The activation parameters were calculated and are presented.


2014 ◽  
Vol 28 (2) ◽  
pp. 231-237 ◽  
Author(s):  
Lech W. Szajdak ◽  
Jerzy Lipiec ◽  
Anna Siczek ◽  
Artur Nosalewicz ◽  
Urszula Majewska

Abstract The aim of this study was to verify first-order kinetic reaction rate model performance in predicting of leaching of atrazine and inorganic compounds (K+1, Fe+3, Mg+2, Mn+2, NH4 +, NO3 - and PO4 -3) from tilled and orchard silty loam soils. This model provided an excellent fit to the experimental concentration changes of the compounds vs. time data during leaching. Calculated values of the first-order reaction rate constants for the changes of all chemicals were from 3.8 to 19.0 times higher in orchard than in tilled soil. Higher first-order reaction constants for orchard than tilled soil correspond with both higher total porosity and contribution of biological pores in the former. The first order reaction constants for the leaching of chemical compounds enables prediction of the actual compound concentration and the interactions between compound and soil as affected by management system. The study demonstrates the effectiveness of simultaneous chemical and physical analyses as a tool for the understanding of leaching in variously managed soils.


1992 ◽  
Vol 57 (7) ◽  
pp. 1451-1458 ◽  
Author(s):  
Refat M. Hassan

The kinetics of oxidation of arsenic(III) by hexachloroiridate(IV) at lower acid concentrations and at constant ionic strength of 1.0 mol dm-3 have been investigated spectrophotometrically. A first-order reaction in [IrCl62-] and fractional order with respect to arsenic(III) have been observed. A kinetic evidence for the formation of an intermediate complex between the hydrolyzed arsenic(III) species and the oxidant was presented. The results showed that decreasing the [H+] is accompanied by an appreciable acceleration of the rate of oxidation. The activation parameters have been evaluated and a mechanism consistent with the kinetic results was suggested.


1976 ◽  
Vol 29 (2) ◽  
pp. 443 ◽  
Author(s):  
MA Haleem ◽  
MA Hakeem

Kinetic data are reported for the decarboxylation of β-resorcylic acid in resorcinol and catechol for the first time. The reaction is first order. The observation supports the view that the decomposition proceeds through an intermediate complex mechanism. The parameters of the absolute reaction rate equation are calculated.


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