STUDIES ON RDX AND RELATED COMPOUNDS: VI. THE HOMOGENEOUS HYDROLYSIS OF CYCLOTRIMETHYLENETRINITRAMINE (RDX) AND CYCLOTETRAMETHYLENETETRANITRAMINE (HMX) IN AQUEOUS ACETONE, AND ITS APPLICATION TO ANALYSIS OF HMX IN RDX(B)

1951 ◽  
Vol 29 (9) ◽  
pp. 731-733 ◽  
Author(s):  
S. Epstein ◽  
C. A. Winkler
Keyword(s):  
Reaction Time ◽  
Alkaline Hydrolysis ◽  
Activation Energies ◽  
Aqueous Acetone ◽  
Second Order ◽  
Alkali Concentration ◽  
Calibration Curves ◽  
Hydrolysis Of ◽  
Related Compounds ◽  
Homogeneous Hydrolysis

Measurements of the rates of alkaline hydrolysis of cyclotrimethylenetrinitramine (RDX) and cyclotetramethylenetetranitramine (HMX) in aqueous acetone show these two reactions to involve consecutive steps, the first of which is second order and rate controlling. Activation energies were estimated as 14 and 25 kcal. respectively. By establishing calibration curves, and controlling temperature, alkali concentration relative to concentration of explosive, and reaction time, the differential hydrolysis permits analysis of the HMX content of RDX(B) with an error of approximately ±0.2% HMX.

KINETICS OF THE AQUEOUS ALKALINE HOMOGENOUS HYDROLYSIS OF HIGH EXPLOSIVE 1, 3,5,7-TETRAAZA- 1, 3,5,7-TETRANITROCYCLOOCTANE (HMX)

1994 ◽  
Vol 30 (3) ◽  
pp. 53-61 ◽  
Author(s):  
Harro M. Heilmann ◽  
Michael K. Stenstrom ◽  
Rolf P. X. Hesselmann ◽  
Udo Wiesmann
Keyword(s):  
Temperature Dependence ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Elevated Temperatures ◽  
Second Order ◽  
Order Rate ◽  
Subsequent Calculation ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Order Rate Equation

In order to get basic data for the design of a novel treatment scheme for high explosives we investigated the kinetics for the aqueous alkaline hydrolysis of 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane (HMX) and the temperature dependence of the rate constants. We used an HPLC procedure for the analysis of HMX. All experimental data could be fit accurately to a pseudo first-order rate equation and subsequent calculation of second-order rate constants was also precise. Temperature dependence could be modeled with the Arrhenius equation. An increase of 10°C led to an average increase in the second-order rate constants by the 3.16 fold. The activation energy of the second-order reaction was determined to be 111.9 ±0.76 kJ·moJ‒1. We found the alkaline hydrolysis to be rapid (less than 2.5% of the initial HMX-concentration left after 100 minutes) at base concentrations of 23 mmol oH‒/L and elevated temperatures between 60 and 80°C.

Studies on Sulphamic Acid and Related Compounds. II. Kinetics and Mechanism of Hydrolysis of Trimethylamine- and of Triethylamine Sulphur Trioxide Addition Compounds

1962 ◽  
Vol 15 (2) ◽  
pp. 251 ◽  
Author(s):  
BE Fleischfresser ◽  
I Lauder
Keyword(s):  
Rate Constant ◽  
Order Rate Constant ◽  
Aqueous Acetone ◽  
Second Order ◽  
Fluoride Ions ◽  
Order Rate ◽  
Mechanism Of Hydrolysis ◽  
Reaction With Water ◽  
Sulphamic Acid ◽  
Hydrolysis Of

The kinetics of hydrolysis of trimethylamine- and of triethylaminesulphur trioxide addition compounds have been studied in water and in aqueous acetone. Reaction occurs according to the equation,������������� f - + R,N.SO,+H,O-tR,XH+HSO~.The solvolysis reactions are first-order and are not catalyzed by acids. The halide ions, Cl', Br', and 1', show only a normal salt effect on the rate of hydrolysis of + - (CH,),N.SO, but in the presence of fluoride ions, the rate constant for the production + - of acid from (C,H,),N.SO, in water at 95 OC is about one-seventh of that in the absence of fluoride under the same conditions. It is suggested that the fluorosulphonate ion is formed rapidly, and that this ion then undergoes slow hydrolysis :�In the presence of alkali, using water as the solvent, second-order kinetics are observed, the equation for the reaction being,�������������� + - R,N.SO,+~OH-+R,X+SO~= +H,O. Assuming the reaction with water is bimolecular, the ratio of the (bimolecular) rate constants at 35 OC, ko~-/k~,o is approximately lo8 for each complex. In aqueous acetone, at low water concentrations, the hydrolysis reactions of the trialkylaminesulphur trioxide complexes show second-order kinetics. At 35 OC for the hydrolysis of + - (CH,),N.SO, the ratio of the second-order rate constant in aqueous acetone to the + - (calculated) second-order rate constant in water is approximately 550 ; for (C,H,),N.SO, the same ratio is 6900. It is considered that hydrolysis occurs in water and in aqueous acetone via a bi- molecular attack at sulphur.

Influence of the Polarity of the Medium on the Alkaline Hydrolysis of n-Butyl Acetate in Hydroalcoholic Mixtures

1977 ◽  
Vol 32 (5) ◽  
pp. 496-500
Author(s):  
M. S. Celdrán ◽  
M. V. Ramón ◽  
P. Martínez
Keyword(s):  
Reaction Mechanism ◽  
Alkaline Hydrolysis ◽  
Rate Constants ◽  
Butyl Acetate ◽  
Activation Energies ◽  
Free Energies ◽  
Kinetics Of ◽  
Hydrolysis Of

Abstract The kinetics of the alkaline hydrolysis of n-butyl acetate have been studied in water and in hydroalcoholic mixtures. The rate constants, activation energies, frequency factors, entropies, Gibbs free energies and enthalpies of activation have been determined. The radii of the activated com­ plexes have been calculated and related to their degree of solvation. A possible reaction mechanism is formulated.

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