STUDIES OF RDX AND RELATED COMPOUNDS: XI. THE CONVERSION OF PHX TO AcAn

1953 ◽  
Vol 31 (6) ◽  
pp. 602-614 ◽  
Author(s):  
R. A. Marcus ◽  
C. A. Winkler
Keyword(s):  
Experimental Data ◽  
Activation Energy ◽  
Acetic Acid ◽  
Nitric Acid ◽  
Reaction Rate ◽  
Salt Effect ◽  
Quantitative Agreement ◽  
Kcal Mole ◽  
First Order ◽  
Related Compounds

The formation of AcAn from PHX, nitric acid, and acetic anhydride has been investigated at various temperatures. The effects of added acetic acid and added salts have been determined. While the reaction is first order with respect to PHX, it is of an order 2.6 with respect to nitric acid. The reaction rate is significantly decreased by small concentrations of sodium nitrate. The reaction is also characterized by a secondary salt effect and a low apparent activation energy of about 2 kcal. mole−1. A mechanism has been suggested in qualitative, and to some extent quantitative, agreement with the experimental data. It is postulated that the conversion of PHX involves a rate-controlling ionic reaction between PHX and nitric acid, and that this is followed by a rapid acetylation of the acidic intermediate to AcAn.

STUDIES ON RDX AND RELATED COMPOUNDS: II. THE NITROLYSIS OF HEXAMINE IN ACETIC ACID

1950 ◽  
Vol 28b (11) ◽  
pp. 715-719 ◽  
Author(s):  
C. A. Winkler ◽  
M. Kirsch
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Deleterious Effect ◽  
Reaction Rate ◽  
Harmful Effect ◽  
Maximum Yield ◽  
Related Compounds

Acetic acid has a harmful effect on the reaction rate and on the yield of RDX at 1 °C. and at 30 °C. for a given nitric acid – hexamine ratio below a certain optimum value. At the optimum, however, the maximum yield of 80% is obtained at both temperatures. The deleterious effect of acetic acid may be explained by assuming that the concentration of the active nitrolyzing agent (nitracidium ion) is decreased by reaction between acetic acid and nitric acid.

Aromatic oxidation by cobaltic acetate in acetic acid

1969 ◽  
Vol 47 (3) ◽  
pp. 387-392 ◽  
Author(s):  
Koichiro Sakota ◽  
Yoshio Kamiya ◽  
Nobuto Ohta
Keyword(s):  
Activation Energy ◽  
Electron Transfer ◽  
Acetic Acid ◽  
Bond Energy ◽  
Hydrogen Abstraction ◽  
Steric Factor ◽  
Benzyl Acetate ◽  
Kcal Mole ◽  
First Order ◽  
Reversible Electron Transfer

A detailed kinetic study of oxidation of toluene and its derivatives by cobaltic acetate in 95 vol% acetic acid is reported. The reaction was found to be profoundly affected by a steric factor and rather insensitive to the C—H bond energy. The order of reactivities of various alkylbenzenes is quite reversal to that of hydrogen abstraction reactions. The reaction was of first-order with respect to toluene, of second-order with respect to cobaltic ion and of inverse first-order with respect to cobaltous ion. The oxidation by cobaltic ion seems to proceed via an initial reversible electron transfer from toluene to cobaltic ion, yielding [Formula: see text] which is oxidized into benzyl acetate by another cobaltic ion. The apparent activation energy for toluene was found to be 25.3 kcal mole−1, and the same activation energy was found for ethylbenzene, cumene, diphenylmethane, and triphenylmethane.

scholarly journals Pyrolysis of phenylmercaptoacetic acid

1968 ◽  
Vol 46 (2) ◽  
pp. 191-197 ◽  
Author(s):  
A. T. C. H. Tan ◽  
A. H. Sehon
Keyword(s):  
Carbon Dioxide ◽  
Activation Energy ◽  
Carbon Monoxide ◽  
Acetic Acid ◽  
Rate Constant ◽  
Order Reaction ◽  
First Order Reaction ◽  
Kcal Mole ◽  
Dissociation Process ◽  
First Order

The pyrolysis of phenylmercaptoacetic acid was investigated by the toluene-carrier technique over the temperature range 760–835 °K. The main products of the decomposition were phenyl mercaptan, carbon dioxide, acetic acid, phenyl methyl sulfide, carbon monoxide, and dibenzyl.The overall decomposition was a first-order reaction with respect to phenylmercaptoacetic acid and could be represented by the two parallel steps:[Formula: see text]Reaction [1] was shown to be a homogeneous first-order dissociation process, and its rate constant was represented by the expression[Formula: see text]The activation energy of this reaction, i.e. 58 kcal/mole, was identified with D(C6H5S—CH2COOH).

THE OXIDATION OF MERCAPTANS BY POTASSIUM PERSULPHATE IN HOMOGENEOUS SOLUTION

1948 ◽  
Vol 26b (7) ◽  
pp. 527-540 ◽  
Author(s):  
C. A. Winkler ◽  
R. L. Eager
Keyword(s):  
Activation Energy ◽  
Acetic Acid ◽  
Rate Constant ◽  
Salt Effect ◽  
Homogeneous Solution ◽  
Ion Concentration ◽  
Potassium Persulphate ◽  
First Order ◽  
Homogeneous Oxidation ◽  
Wide Range

In the homogeneous oxidation of mercaptans by potassium persulphate in concentrated acetic acid, the rate of disappearance of potassium persulphate during an experiment is first order with respect to the measured persulphate concentration. The rate constant is independent of the kind of mercaptan used, and is independent of mercaptan concentration over a wide range of mercaptan concentrations. The rate constant falls off, however, at low mercaptan concentrations, this falling-off being less pronounced if the rate is reduced by the addition of salts. The mercaptan concentration at which the rate constant, calculated from persulphate disappearance, becomes independent of mercaptan concentration increases as the temperature is increased. A salt effect prevails, the rate constant being decreased with increased potassium ion concentration. The equivalent conductance of solutions of potassium persulphate in the solvent used shows a behavior on dilution which indicates that potassium persulphate is incompletely ionized in the solvent. A mechanism is proposed for the reaction, in which it is assumed that dissociation of persulphate ions into sulphate free radicals is rate-controlling, with an activation energy of the order 26,000 cal. per mole.

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

scholarly journals Microwave-Assisted Transesterification of Kusum Oil: Parametric, Kinetic and Thermodynamic Studies

2020 ◽  
Vol 32 (11) ◽  
pp. 2893-2903
Author(s):  
SHEETAL N. NAYAK ◽  
MILAP G. NAYAK ◽  
CHANDRAKANT P. BHASIN
Keyword(s):  
Activation Energy ◽  
Reaction Rate ◽  
Frequency Factor ◽  
Molar Ratio ◽  
Pseudo First Order Reaction ◽  
Time Intervals ◽  
First Order ◽  
Microwave Assisted ◽  
Lower Heat ◽  
Kinetic And Thermodynamic Studies

Microwave-assisted transesterification of non-edible oil to produce biodiesel is gaining attention due to lower heat loss as well as rapid conversion. In this study, esterified kusum oil as a feedstock was transesterified in the presence of Ba(OH)2. At 800 W microwave power and constant magnetic stirring the effect of important process parameters such as solvent methanol molar ratio, Ba(OH)2, temperature, and time on biodiesel yield were evaluated. The parametric study suggested that 9:1 M methanol, 65 ºC reaction temperature, 2.5 wt% Ba(OH)2 catalyst and 3.5 min of transesterification time gave close to 96% biodiesel yield. At the above conditions of methanol and catalyst, the reaction kinetics and thermodynamic study were performed using different time intervals. The microwave-assisted transesterification followed pseudo-first-order reaction rate with 34.57 kJ/mol K activation energy and 205664 min-1 frequency factor. The reduction in activation energy and increase in the frequency factor reveal the non-thermal effect associated with microwave heating. The thermodynamic properties evaluated using the Eyring equation suggests non-spontaneity and endothermic nature of transesterification.

Bisulfite Degrades Aflatoxin: Effect of Temperature and Concentration of Bisulfite

1978 ◽  
Vol 41 (10) ◽  
pp. 774-780 ◽  
Author(s):  
M. P. DOYLE ◽  
E. H. MARTH
Keyword(s):  
Rate Constant ◽  
Aflatoxin B1 ◽  
Reaction Rate ◽  
Reaction Rates ◽  
Reaction Rate Constant ◽  
Effect Of Temperature ◽  
Kcal Mole ◽  
First Order ◽  
Potassium Acid Phthalate ◽  
Acid Phthalate

Bisulfite reacted with aflatoxin B1 and G1 resulting in their loss of fluorescence. The reaction was first order with rate depending on bisulfite (or the bisulfite and sulfite) concentration(s). Aflatoxin G1 reacted more rapidly with bisulfite than did aflatoxin B1. In the presence of 0.035 M potassium acid phthalate-NaOH buffer (pH 5.5) plus 1.3% (vol/vol) methanol at 25 C, the reaction rate constant for degradation of aflatoxin G1 was 2.23 × 10−2h− and that for aflatoxin B1 was 1.87 × 10−2h− when 50 ml of reaction mixture contained 1.60 g of K2SO3. Besides bisulfite concentrations, temperature influenced reaction rates. The Q10 for the bisulfite-aflatoxin reaction was approximately 2 while activation energies for degrading aflatoxin B1 and aflatoxin G1 were 13.1 and 12.6 kcal/mole, respectively. Data suggest that treating foods with 50 to 500 ppm SO2 probably would not effectively degrade appreciable amounts of aflatoxin. Treating foods with 2000 ppm SO2 or more and increasing the temperature might reduce aflatoxin to an acceptable level.

Kinetics of the addition of acids to olefins with and without boron fluoride catalysis

1967 ◽  
Vol 45 (1) ◽  
pp. 11-16 ◽  
Author(s):  
G. A. Latrèmouille ◽  
A. M. Eastham
Keyword(s):  
Activation Energy ◽  
Acetic Acid ◽  
Apparent Activation Energy ◽  
Trifluoroacetic Acid ◽  
Similar Rate ◽  
Ethylene Dichloride ◽  
Kcal Mole ◽  
Rate Law ◽  
Boron Fluoride ◽  
Kinetics Of

Isobutene reacts readily with excess trifluoroacetic acid in ethylene dichloride solution at ordinary temperatures to give t-butyl trifluoroacetate. The rate of the reaction is given, within the range of the experiments, by the expression d[ester]/dt = k[acid]2[olefin], and the apparent activation energy is about 6 kcal/mole. The rate of addition is markedly dependent on the strength of the reacting acid and is drastically reduced in the presence of mildly basic materials, such as dioxane. The boron fluoride catalyzed addition of acetic acid to 2-butene can be considered to follow a similar rate law, i.e. d[ester]/dt = k[acid·BF3]2[olefin], but only if some assumptions are made about the position of the equilibrium [Formula: see text]since only the 1:1 complex is reactive.

STUDIES ON RDX AND RELATED COMPOUNDS: X. ANALYSIS FOR NITRIC ACID IN ACETIC ACID – ACETIC ANHYDRIDE MEDIA

1953 ◽  
Vol 31 (3) ◽  
pp. 214-215 ◽  
Author(s):  
R. A. Marcus ◽  
C. A. Winkler
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Acetic Anhydride ◽  
Analytical Method ◽  
Potassium Acetate ◽  
Standard Solution ◽  
Related Compounds

An analytical method has been developed for the estimation of nitric acid in acetic acid – acetic anhydride media, with a precision of 0.3%. The procedure involves the addition of a solution of potassium acetate in acetic acid to the sample. The excess is back-titrated conductometrically with a standard solution of nitric acid in acetic acid.

Pseudo-Homogenous Kinetics Model for the Synthesis of Dimethyl Carbonate from Urea and Methanol with Heterogeneous Catalyst

2011 ◽  
Vol 233-235 ◽  
pp. 481-486
Author(s):  
Wen Bo Zhao ◽  
Ning Zhao ◽  
Fu Kui Xiao ◽  
Wei Wei
Keyword(s):  
Experimental Data ◽  
Activation Energy ◽  
Dimethyl Carbonate ◽  
Side Reaction ◽  
Order Reaction ◽  
Zero Order ◽  
Kinetics Model ◽  
First Order ◽  
Zero Order Reaction ◽  
Kinetics Of

The synthesis of dimethyl carbonate (DMC) from urea and methanol includes two main reactions: one amino of urea is substituted by methoxy to produce the intermediate methyl carbamate (MC) which further converts to DMC via reaction with methanol again. In a stainless steel autoclave, the kinetics of these reactions was separately investigated without catalyst and with Zn-containing catalyst. Without catalyst, for the first reaction, the reaction kinetics can be described as first order with respect to the concentrations of methanol and methyl carbamate (MC), respectively. For the second reaction, the results exhibit characteristics of zero-order reaction. Over Zn-containing catalyst, the first reaction is neglected in the kinetics model since its rate is much faster than second reaction. After the optimization of reaction condition, the macro-kinetic parameters of the second reaction are obtained by fitting the experimental data to a pseudo-homogenous model, in which a side reaction of DMC synthesis is incorporated since it decreases the yield of DMC drastically at high temperature. The activation energy of the reaction from MC to DMC is 104 KJ/mol while that of the side reaction of DMC is 135 KJ/mol.

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