Kinetics of esterification of monoisopropylphenols with phosphoryl trichloride

1989 ◽  
Vol 54 (5) ◽  
pp. 1311-1317
Author(s):  
Miroslav Magura ◽  
Ján Vojtko ◽  
Ján Ilavský
Keyword(s):  
Liquid Phase ◽  
Rate Constants ◽  
Reaction Rates ◽  
Activation Energies ◽  
The Individual ◽  
Kinetics Of

The kinetics of liquid-phase isothermal esterification of POCl3 with 2-isopropylphenol and 4-isopropylphenol have been studied within the temperature intervals of 110 to 130 and 90 to 110 °C, respectively. The rate constants and activation energies of the individual steps of this three-step reaction have been calculated from the values measured. The reaction rates of the two isomers markedly differ: at 110 °C 4-isopropylphenol reacts faster by the factors of about 7 and 20 for k1 and k3, respectively. This finding can be utilized in preparation of mixed triaryl phosphates, since the alkylation mixture after reaction of phenol with propene contains an excess of 2-isopropylphenol over 4-isopropylphenol.

Esterification kinetics of phenol with phosphoryl trichloride

1989 ◽  
Vol 54 (3) ◽  
pp. 608-615 ◽  
Author(s):  
Miroslav Magura ◽  
Ján Vojtko ◽  
Eva Zemanová ◽  
Alexander Kaszonyi ◽  
Ján Ilavský
Keyword(s):  
Liquid Phase ◽  
Linear Regression ◽  
Rate Constants ◽  
Optimization Method ◽  
Activation Energies ◽  
System Of Differential Equations ◽  
Consecutive Reactions ◽  
Esterification Rate ◽  
The Given ◽  
Kinetics Of

The liquid-phase esterification kinetics of phenol with POCl3 has been studied at isothermal conditions within the temperature interval from 90 to 110 °C. The esterification rate constants of the first, second, and third esterification steps and the activation energies of these steps have been calculated. The given system of competitive consecutive reactions can be described by a system of differential equations which has been solved by the Gauss-Newton optimization method of non-linear regression in the Marquardt modification. In the sequence of the first, second, and third step the esterification rate constants have been found to gradually decrease, whereas the activation energies uncrease in the same sequence.

Kinetics of esterification of diisopropylphenols with phosphoryl trichloride

1989 ◽  
Vol 54 (8) ◽  
pp. 2099-2104
Author(s):  
Miroslav Magura ◽  
Ján Vojtko ◽  
Ján Ilavský
Keyword(s):  
Liquid Phase ◽  
Differential Equations ◽  
Rate Constants ◽  
Activation Energies ◽  
The Other ◽  
Kinetics Of

The title liquid-phase isothermal esterification kinetics have been measured in the temperature intervals of 110-125 and 110-160 °C for 2,4- and 2,6-diisopropylphenols, resp. The values measured have been used to calculate the rate constants of the respective three steps and to determine the activation energies. 2,6-Diisopropylphenol has been found to react only to the first degree, and the rate constants of the other two reaction steps (k2, k3) were only calculated from the differential equations given by means of a computer.

Kinetics of the successive chlorination of 1,2-dichloroethane in the liquid phase

1969 ◽  
Vol 22 (6) ◽  
pp. 1177 ◽  
Author(s):  
DS Caines ◽  
RB Paton ◽  
DA Williams ◽  
PR Wilkinson
Keyword(s):  
Liquid Phase ◽  
Rate Constants ◽  
Relative Rate ◽  
Stirred Tank ◽  
Continuous Stirred Tank Reactor ◽  
Alternative Pathways ◽  
Tank Reactor ◽  
Relative Rate Constants ◽  
Continuous Stirred Tank ◽  
Kinetics Of

Liquid 1,2-dichloroethane has been chlorinated by dissolved chlorine to a succession of chloroethanes up to the ultimate hexachloroethane. The results of both batch and continuous stirred tank reactor systems have been analysed by computer techniques to give a set of relative rate constants from which one can predict the product composition for a given chlorine uptake, the aim in this work being to optimize the production of tetrachloroethanes. An unusual feature of the kinetics is that 1,1,1,2- and 1,1,2,2-tetrachloroethanes provide alternative pathways between 1,1,2-trichloroethane and pentachloroethane.

THE REACTION OF 2,2-DIPHENYL-1-PICRYLHYDRAZYL WITH SECONDARY AMINES

1958 ◽  
Vol 36 (12) ◽  
pp. 1729-1734 ◽  
Author(s):  
J. E. Hazell ◽  
K. E. Russell
Keyword(s):  
Secondary Amine ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Hydrogen Abstraction ◽  
Activation Energies ◽  
Major Product ◽  
The Other ◽  
Secondary Amines ◽  
First Order ◽  
Kinetics Of

The reaction of DPPH (2,2-diphenyl-1-picrylhydrazyl) with N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, diphenylamine, and methylaniline has been studied and has been shown to be primarily a hydrogen abstraction process. Two moles DPPH react with 1–1.15 moles secondary amine to give 1.7–1.8 moles 2,2-diphenyl-1-picrylhydrazine and further products.The reaction between DPPH and N-phenyl-1-naphthylamine is first order with respect to each reactant. The reaction of DPPH with the other amines is retarded by the major product 2,2-diphenyl-1-picrylhydrazine and the kinetics of the over-all reaction are complex. However second-order rate constants and activation energies have been obtained using initial rates of reaction. Possible reaction mechanisms are discussed.

scholarly journals Kinetics of the Toluene Reaction with OH Radical

Research ◽  
2019 ◽  
Vol 2019 ◽  
pp. 1-19 ◽  
Author(s):  
Rui Ming Zhang ◽  
Donald G. Truhlar ◽  
Xuefei Xu
Keyword(s):  
High Pressure ◽  
Low Temperature ◽  
Atmospheric Chemistry ◽  
Temperature Regime ◽  
Rate Constants ◽  
Chemical Activation ◽  
Reaction Rates ◽  
State Theory ◽  
Partition Functions ◽  
Kinetics Of

We calculated the kinetics of chemical activation reactions of toluene with hydroxyl radical in the temperature range from 213 K to 2500 K and the pressure range from 10 Torr to the high-pressure limit by using multistructural variational transition state theory with the small-curvature tunneling approximation (MS-CVT/SCT) and using the system-specific quantum Rice-Ramsperger-Kassel method. The reactions of OH with toluene are important elementary steps in both combustion and atmospheric chemistry, and thus it is valuable to understand the rate constants both in the high-pressure, high-temperature regime and in the low-pressure, low-temperature regime. Under the experimental pressure conditions, the theoretically calculated total reaction rate constants agree well with the limited experimental data, including the negative temperature dependence at low temperature. We find that the effect of multistructural anharmonicity on the partition functions usually increases with temperature, and it can change the calculated reaction rates by factors as small as 0.2 and as large as 4.2. We also find a large effect of anharmonicity on the zero-point energies of the transition states for the abstraction reactions. We report that abstraction of H from methyl should not be neglected in atmospheric chemistry, even though the low-temperature results are dominated by addition. We calculated the product distribution, which is usually not accessible to experiments, as a function of temperature and pressure.

Kinetics of oxidation of thiocyanate by aqueous iodine

1973 ◽  
Vol 26 (9) ◽  
pp. 1863 ◽  
Author(s):  
GT Briot ◽  
RH Smith
Keyword(s):  
Rate Constants ◽  
Activation Energies ◽  
Stopped Flow ◽  
Kinetics Of Oxidation ◽  
Rate Law ◽  
General Base ◽  
Present Rate ◽  
Rapid Equilibrium ◽  
Ph Range ◽  
Kinetics Of

The kinetics of oxidation of thiocyanate to sulphate by aqueous iodine in the pH range 9.2-12.5 have been studied using a spectrophotometric stopped flow technique. The reaction is general base-catalysed, having the rate law ��������������������� -d[I2]a/dt = ([SCN-][I3-]/[I-]2)Σ kB[B] where [I2]a is the total analytical concentration of iodine, [B] is the concentration of base, and where the summation is taken over all bases present. Rate constants, kB, and activation energies have been measured for the bases, OH-, PO43- and CO32-. ��� A mechanism involving the initial steps ����������������� I2+SCN- ↔ ISCN+I- �����������������(rapid equilibrium) ������������� ISCN+H2O+B → HOSCN+I- + HB+ �����������(rate determining) followed by rapid reactions of HOSCN with itself or with iodine is proposed.

Kinetics of 1-butanol, di-(1-butyl) ether and 1-butene reactions on aluminas partially deactivated by sodium

1989 ◽  
Vol 54 (11) ◽  
pp. 2985-2997 ◽  
Author(s):  
František Krampera ◽  
Ludvík Beránek
Keyword(s):  
Vapour Phase ◽  
Reaction Rates ◽  
Product Formation ◽  
Sodium Content ◽  
Butyl Ether ◽  
Deactivation Kinetics ◽  
Two Factors ◽  
Best Fitting ◽  
The Individual ◽  
Kinetics Of

The initial rates of six reactions taking place in 1-butanol dehydration at 260 °C in vapour phase were measured on aluminia samples differing in sodium content. The reactants were 1-butanol, di-(1-butyl) ether and 1-butene, resp. The parameters of the best fitting rate equation for each reaction were evaluated. The reaction rates as well as the rate constants and adsorption coefficients of the individual reactions show different sensitivity to datalyst acidity. Therefore, the selectivity of product formation can be influenced by sodium content of the catalyst. The selectivities (with the exception of 1-butene izomerization) strongly depend also on the partial pressure of the starting reactants. Thus, these two factors can be used to control the selectivity for preparative purposes. The results of this paper clearly demonstrate the nonseparability of the deactivation kinetics in 1-butanol dehydration on sodium poisoned aluminas.

THE KINETICS OF THE DECOMPOSITION AND SYNTHESIS OF SOME DITHIOCARBAMATES

1962 ◽  
Vol 40 (2) ◽  
pp. 246-255 ◽  
Author(s):  
D. M. Miller ◽  
R. A. Latimer
Keyword(s):  
Kinetic Study ◽  
Rate Constants ◽  
Reaction Mechanisms ◽  
Dissociation Constants ◽  
Activation Energies ◽  
Spectral Evidence ◽  
Kinetics Of

Rate constants, activation energies, and dissociation constants were determined in a kinetic study of the synthesis and decomposition of a number of N-substituted dithiocarbamates. These data combined with certain spectral evidence are evaluated and reaction mechanisms suggested.

scholarly journals THE PHOTOINITIATED ADDITION OF MERCAPTANS TO OLEFINS: III. THE KINETICS OF THE ADDITION OF THIOPHENOL TO STYRENE AND TO 1-OCTENE

1957 ◽  
Vol 35 (7) ◽  
pp. 723-733 ◽  
Author(s):  
R. H. Pallen ◽  
C. Sivertz
Keyword(s):  
Free Radical ◽  
Rate Constants ◽  
Chain Transfer ◽  
Kinetic Studies ◽  
Activation Energies ◽  
Reverse Reaction ◽  
Kinetics Of

Kinetic studies were made of the free radical photoinitiated addition of thiophenol to 1-octene and to styrene in the absence of oxygen. In addition to the usual attack, chain transfer, and termination steps, it is found that a reverse reaction accompanies the attack step, [Formula: see text] The rate constants for the thiophenol–styrene reaction were calculated to be [Formula: see text]kt = 2 × 107 liters.moles−1sec.−1. The over-all activation energies for the two reactions were found to be E (1-octene) = 1.2 kcal., E (styrene) = 2.4 kcal.; suggestions are submitted as to why these activation energies are so low. These reactions are compared with n-butyl mercaptan – olefin reactions.

Kinetics of Triplet Sublevel Selective Photochemical Reactions in the Solid State

1981 ◽  
Vol 36 (7) ◽  
pp. 743-750
Author(s):  
Manfred Gehrtz ◽  
Christoph Bräuchle ◽  
Jürgen Voitländer
Keyword(s):  
Solid State ◽  
Reaction Rates ◽  
Photochemical Reactions ◽  
Solid State Reactions ◽  
Physical Activation ◽  
Zero Field ◽  
Excited Triplet ◽  
The Individual ◽  
Activation Rates ◽  
Kinetics Of

Abstract A detailed description of the overall kinetics of photochemical reactions has to deal with photo-physical activation and de-activation rates as well as with true photochemical rates. Based on the hypothesis that for photoreactions involving the lowest excited triplet state the chemical reaction rates of the individual triplet zero-field levels have different values, a method is presented for the evaluation of these rates from bulk measurements under steady state illumination conditions. The complications arising from the detection of solid state reactions are discussed, and a simple solution is given, illustrated by a numerical example.

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