STUDIES ON RDX AND RELATED COMPOUNDS: IV. THE BACHMANN OR COMBINATION PROCESS

1951 ◽  
Vol 29 (8) ◽  
pp. 642-645 ◽  
Author(s):  
H. L. Williams ◽  
C. A. Winkler

The effect of varying the concentrations of nitric acid and ammonium nitrate on the yield of RDX has been determined at 35°C., using hexamine, hexamine mononitrate, and hexamine dinitrate. The activation energies for the formation of RDX from hexamine, hexamine mononitrate, and hexamine dinitrate were found to be approximately 11 kcal., 12.5 kcal., and 16.5 kcal., respectively.

1952 ◽  
Vol 30 (10) ◽  
pp. 734-742 ◽  
Author(s):  
S. Epstein ◽  
C. A. Winkler

The reactions to form RDX and HMX in Bachmann-type mixtures are comparable in respect of optimum nitric acid concentrations and in the fact that optimal amounts of acetic anhydride and ammonium nitrate are necessary for maximum yields of either explosive. The activation energies for formation of RDX and HMX were also found to be comparable, at 15 ± 1 kcal. per mole. However, withholding ammonium nitrate from the reaction mixture was found to have a more deleterious effect on RDX production than on HMX production. A mechanism is proposed which attempts in a general way to represent the relation between RDX and HMX production in the type of reaction mixtures used.


1953 ◽  
Vol 31 (3) ◽  
pp. 201-203
Author(s):  
R. H. Betts ◽  
R. S. Stuart ◽  
C. A. Winkler

An electrometric method for determination of nitric acid in RDX(B) liquors has been developed. The method is not largely affected by ammonium nitrate and acetic anhydride. A precision of ± 0.5% may be readily obtained. Acetic anhydride in RDX(B) liquors may be determined by direct titration with standard aniline–toluene solution at 0 °C., using calcium hypochlorite as an external indicator. In routine analysis, a precision of ± 2% may be obtained.


1949 ◽  
Vol 27b (6) ◽  
pp. 503-519 ◽  
Author(s):  
A. F. McKay ◽  
R. H. Meen ◽  
George F Wright ◽  
W. J. Chute ◽  
G. S. Myers

When hexamethylenetetramine is nitrolyzed with nitric acid and an anhydride in absence of ammonium nitrate the synthesis of cyclic nitramines is decreased and the yields of esterified linear tetramethylenetrinitramines are increased. The two remaining carbon atoms and one nitrogen atom in hexamine can be accounted as esterified dimethylolnitramide. The isolation of a trace of linear pentamethylenetetranitramine from a normal nitrolysis of hexamethylenetetramine shows that in all of these reactions a common intermediate, dimethylolaminomethyldinitrotriazacyclohexane, must be present. This has never been isolated, but its reactions can be deduced from the behavior of methylene-bis-3,5-dinitro-1,3,5-triazacyclohexane.


1951 ◽  
Vol 29 (5) ◽  
pp. 377-381 ◽  
Author(s):  
A. Gillies ◽  
H. L. Williams ◽  
C. A. Winkler

This reaction at 35°C. exhibits a behavior indicative of the presence of an intermediate in the reaction. Reaction of paraformaldehyde and ammonium nitrate in glacial acetic acid resulted in the isolation of hexamine dinitrate. Evidence is presented to indicate that formation of hexamine dinitrate, accompanied by the production of nitric acid, is responsible for the production of RDX in the acetic anhydride system.


Author(s):  
Ralph Dlugi ◽  
Lucia Kins ◽  
Thomas Seiler ◽  
Winfried Seidl ◽  
Peter Seifert ◽  
...  

1950 ◽  
Vol 28b (11) ◽  
pp. 715-719 ◽  
Author(s):  
C. A. Winkler ◽  
M. Kirsch

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.


2010 ◽  
Vol 3 (1) ◽  
pp. 187-208 ◽  
Author(s):  
V. Wolff ◽  
I. Trebs ◽  
C. Ammann ◽  
F. X. Meixner

Abstract. The aerodynamic gradient method is widely used for flux measurements of ammonia, nitric acid, particulate ammonium nitrate (the NH3-HNO3-NH4NO3 triad) and other water-soluble reactive trace compounds. The surface exchange flux is derived from a measured concentration difference and micrometeorological quantities (turbulent exchange coefficient). The significance of the measured concentration difference is crucial for the significant determination of surface exchange fluxes. Additionally, measurements of surface exchange fluxes of ammonia, nitric acid and ammonium nitrate are often strongly affected by phase changes between gaseous and particulate compounds of the triad, which make measurements of the four individual species (NH3, HNO3, NH4+, NO3− necessary for a correct interpretation of the measured concentration differences. We present here a rigorous analysis of results obtained with a multi-component, wet-chemical instrument, able to simultaneously measure gradients of both gaseous and particulate trace substances. Basis for our analysis are two field experiments, conducted above contrasting ecosystems (grassland, forest). Precision requirements of the instrument as well as errors of concentration differences and micrometeorological exchange parameters have been estimated, which, in turn, allows the establishment of thorough error estimates of the derived fluxes of NH3, HNO3, NH4+, and NO3−. Derived median flux errors for the grassland and forest field experiments were: 39% and 50% (NH3), 31% and 38% (HNO3), 62% and 57% (NH4+), and 47% and 68% (NO3−), respectively. Additionally, we provide the basis for using field data to characterize the instrument performance, as well as subsequent quantification of surface exchange fluxes and underlying mechanistic processes under realistic ambient measurement conditions.


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