STUDIES OF RDX AND RELATED COMPOUNDS: III. THE REACTION TO FORM RDX FROM AMMONIUM NITRATE AND FORMALDEHYDE IN ACETIC ANHYDRIDE

1951 ◽  
Vol 29 (5) ◽  
pp. 377-381 ◽  
Author(s):  
A. Gillies ◽  
H. L. Williams ◽  
C. A. Winkler
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Acetic Anhydride ◽  
Ammonium Nitrate ◽  
Glacial Acetic Acid ◽  
Related Compounds

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.

scholarly journals STUDIES ON RDX AND RELATED COMPOUNDS: IX. DETERMINATION OF NITRIC ACID AND ACETIC ANHYDRIDE IN BACHMANN LIQUORS

1953 ◽  
Vol 31 (3) ◽  
pp. 201-203
Author(s):  
R. H. Betts ◽  
R. S. Stuart ◽  
C. A. Winkler
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Ammonium Nitrate ◽  
Routine Analysis ◽  
Calcium Hypochlorite ◽  
Electrometric Method ◽  
Direct Titration ◽  
Related Compounds ◽  
External Indicator

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.

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.

NITROLYSIS OF HEXAMETHYLENETETRAMINE: VI. RECOMBINATION OF FRAGMENTS DURING HEXAMETHYLENETETRAMINE NITROLYSIS IN ACETIC ANHYDRIDE

1949 ◽  
Vol 27b (6) ◽  
pp. 520-544 ◽  
Author(s):  
E. Aristoff ◽  
J. A. Graham ◽  
R. H. Meen ◽  
G. S. Myers ◽  
G. F Wright
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Acetic Anhydride ◽  
Ammonium Nitrate ◽  
Degradation Products ◽  
Stepwise Synthesis ◽  
Alternative Hypotheses ◽  
Enhanced Yield ◽  
By Products

Alternative hypotheses can account for the yield of more than one equivalent of Cyclonite from hexamine when the Bachmann reagents, ammonium nitrate, nitric acid, and acetic anhydride are used. In the nitrolysis, evidence for a stepwise synthesis from unit fragments is presented as the enhanced yield when methylenedinitramine is added with paraform to ammonium nitrate and acetic anhydride according to the Schiessler–Ross method for Cyclonite synthesis. However, this evidence is discounted because the expected by-product, 1,5-diacetoxy-2,4-dinitro-2,4-diazapentane is not found. Alternatively it is believed that the Bachmann reaction is actually a combination of the direct nitrolysis of hexamine with nitric acid, concurrent with a resynthesis of hexamine from the fragments produced by the nitrolysis. On this basis all by-products from the hexamethylenetetramine nitrolysis must be accounted as degradation products of hexamethylenetetramine and not capable of synthesis from unit fragments like formaldehyde, ammonia, and acetic acid. No exception has been found; the addition of acylamides to the Bachmann reaction mixture increases the yield of two by-products, 1-acyl-3,5-dinitro-1,3,5-triazacyclohexane and 1-acyl-3,5,7-trinitro-1,3,5,7-tetrazacycloöctane. It has been shown that these can be formed only from degradation products of hexamethylenetetramine such as 1,5-diaceto-3,7-endomethylene-1,3,5,7-tetrazacycloöctane and acetaminomethylhexamethylenetetramine nitrate.

STUDIES OF RDX AND RELATED COMPOUNDS: VII RELATION BETWEEN RDX AND HMX PRODUCTION IN THE BACHMANN REACTION

1952 ◽  
Vol 30 (10) ◽  
pp. 734-742 ◽  
Author(s):  
S. Epstein ◽  
C. A. Winkler
Keyword(s):  
Nitric Acid ◽  
Acetic Anhydride ◽  
Ammonium Nitrate ◽  
Deleterious Effect ◽  
Activation Energies ◽  
Related Compounds

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.

scholarly journals Nitration of Jharia basin coals, India: a study of structural modifications by XRD and FTIR techniques

2021 ◽  
Author(s):  
Prabal Boral ◽  
Atul K. Varma ◽  
Sudip Maity
Keyword(s):  
Acetic Acid ◽  
Nitric Acid ◽  
Linear Relationship ◽  
Glacial Acetic Acid ◽  
Vitrinite Reflectance ◽  
Aqueous Media ◽  
Interlayer Spacing ◽  
Acetic Acid Medium ◽  
X Ray ◽  
The Media

AbstractFour coal samples from Jharia basin, India are treated with nitric acid in glacial acetic acid and aqueous media to find out the chemical, petrographic and spatial structure of the organic mass by X-ray diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) techniques. X-ray parameters of coal like interlayer spacing (d002), crystallite size (Lc), aroamticity (fa), average number of aromatic layers (Nc), and coal rank (I26/I20) have been determined using profile-fitting software. Considerable variation is observed in treated coals in comparison to the demineralized coals. The d002 values of treated coals have increased in both the media showing increase in disordering of organic moieties. A linear relationship has been observed between d002 values with the volatile matter of the coals. Similarly, the d002 values show linear relationship with Cdmf contents for demineralized as well as for the treated coals in both the media. The Lc and Nc values have decreased in treated coals corresponding to demineralized coals. The present study shows that nitration in both the media is capable of removing the aliphatic side chains from the coals and aromaticity (fa) increases with increase in rank and shows a linear relationship with the vitrinite reflectance. The corresponding I26/I20 values are least for treated coals in glacial acetic acid medium followed by raw and then to treated coals in aqueous medium. FTIR studies show that coal arenes of the raw coals are converted into nitro-arenes in structurally modified coals (SMCs) in both the media, the corresponding bands at 1550–1490 and 1355–1315 cm−1 respectively. FTIR study confirms that nitration is the predominant phenomenon, though, oxidation and nitration phenomena takes place simultaneously during treatment with nitric acid to form SMCs. In comparison to raw coals, the SMCs show higher aromaticity and may be easily converted to coal derived products like activated carbon and specialty carbon materials.

scholarly journals Oxidation of 3-Carene with Red Lead in Glacial Acetic Acid and Acetic Anhydride

1974 ◽  
Vol 23 (7) ◽  
pp. 420-422
Author(s):  
Yoshiharu MATSUBARA ◽  
Yoshihito FUJIHARA ◽  
Yutaka SAKAI ◽  
Makoto SANO
Keyword(s):  
Acetic Acid ◽  
Acetic Anhydride ◽  
Glacial Acetic Acid ◽  
Red Lead

1,4-Dinitroimidazole and Derivatives. Structure and Thermal Rearrangement

1989 ◽  
Vol 42 (8) ◽  
pp. 1281 ◽  
Author(s):  
MR Grimmett ◽  
ST Hua ◽  
KC Chang ◽  
SA Foley ◽  
J Simpson
Keyword(s):  
Molecular Structure ◽  
Acetic Acid ◽  
Acetic Anhydride ◽  
Glacial Acetic Acid ◽  
Crystal And Molecular Structure ◽  
Direct Methods ◽  
Thermal Rearrangement

Nitration of 4-nitroimidazole in acetic anhydride/glacial acetic acid gives 1,4-dinitroimidazole. The crystal and molecular structure of this compound have been determined by direct methods. Crystals are orthorhombic; P212121, a 5.853(3), b 9.591(8), c 10.392(5) � , V 583.4(7) � 3 , Dm 1 .76 g cm-1, Dc, 1 .80 g cm-1 (Z = 4); λ 0.71069 � ; T 173 K. The structure was refined to R = 0.048 for 926 reflections [I > 2 σ(1)]. Both 2-methyl-4-nitro- and 5-methyl-4-nitro-imidazoles N-nitrate under the same conditions. When heated in solution at 100-140�C 1,4-dinitro- and 2-methyl-1,4-dinitro-imidazoles rearrange to give C-nitro isomers and some denitration products, but 5(4)-methyl-1,4(5)-dinitroimidazole failed to give identifiable products.

STUDIES ON THE FORMATION OF HEXAMINE

1952 ◽  
Vol 30 (9) ◽  
pp. 687-693 ◽  
Author(s):  
T. R. Ingraham ◽  
C. A. Winkler
Keyword(s):  
Activation Energy ◽  
Acetic Acid ◽  
Acid Solution ◽  
Induction Period ◽  
Ammonium Nitrate ◽  
Sodium Acetate ◽  
Glacial Acetic Acid ◽  
Initial Rate ◽  
Acetic Acid Solution ◽  
Rate Data

Rate curves have been determined for the reaction of ammonium nitrate with formaldehyde in glacial acetic acid solution at 25 °C., 35 °C., 45 °C., and 55 °C. over a range of Initial mole ratios (formaldehyde: ammonia) of 0.75:1 to 9.0:1. Data obtained at 25 °C. show a definite induction period in the formation of hexamine. The length of the induction period is not changed by increasing ammonium nitrate concentrations above the theoretical (1.5:1), but may be appreciably shortened by initial additions of excess formaldehyde or of sodium acetate. From 35 °C. upward, the induction period is not apparent. The order of the reaction with respect to formaldehyde has been determined from initial rate data, and an activation energy calculated. The reactions in general appear analogous to those found in slightly acid aqueous systems.

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.

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