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

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.

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

Canadian Journal of Chemistry ◽

10.1139/v51-045 ◽

1951 ◽

Vol 29 (5) ◽

pp. 377-381 ◽

Cited By ~ 2

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.

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

Canadian Journal of Chemistry ◽

10.1139/v52-088 ◽

1952 ◽

Vol 30 (10) ◽

pp. 734-742 ◽

Cited By ~ 9

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.

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STUDIES ON LIGNIN AND RELATED COMPOUNDS: IV. THE NITRATION OF GLYCOL-LIGNIN

Canadian Journal of Research ◽

10.1139/cjr30-051 ◽

1930 ◽

Vol 3 (2) ◽

pp. 130-139 ◽

Cited By ~ 2

Author(s):

Harold Hibbert ◽

Leo Marion

Keyword(s):

Nitric Acid ◽

Acetic Anhydride ◽

Nitro Group ◽

Nitroso Compound ◽

Initial Oxidation ◽

Percentage Composition ◽

Acidic Component ◽

Fuming Nitric Acid ◽

Related Compounds

Glycol-lignin at temperatures below 0 °C., dissolves completely in a mixture of four parts of acetic anhydride and one part of fuming nitric acid, giving rise to a 125% yield of a product (nitrated-lignin) which has undergone nitration and acetylation. The nitrogen in the product is present partly in the form of a nitro group, an ester of nitric acid, a nitroso compound and in another form not yet determined. A further treatment of this nitrated-lignin with a nitrating liquor of the same composition, followed by heating at 80 °C. causes a short initial oxidation, and yields a substance differing slightly from the first and having a C:H ratio almost 1:1. Repetition of the treatment does not seem to alter the percentage composition appreciably, until after the fourth treatment.Nitrated-lignin can be methylated, the methoxyl content of the product being more than double that of the original nitrated-lignin. It can also be reduced, the resulting product diazotized and coupled with β-naphthol disulphonic acid.The soluble products of the nitration reaction contain an acidic component which has not been identified.

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

Canadian Journal of Chemistry ◽

10.1139/v53-031 ◽

1953 ◽

Vol 31 (3) ◽

pp. 214-215 ◽

Cited By ~ 5

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.

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

Canadian Journal of Chemistry ◽

10.1139/v51-072 ◽

1951 ◽

Vol 29 (8) ◽

pp. 642-645 ◽

Cited By ~ 2

Author(s):

H. L. Williams ◽

C. A. Winkler

Keyword(s):

Nitric Acid ◽

Ammonium Nitrate ◽

Activation Energies ◽

Combination Process ◽

Related Compounds

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.

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NITROLYSIS OF HEXAMETHYLENETETRAMINE: V. 1,7-DINITROXY-2,4,6-TRINITRO-2,4,6-TRIAZAHEPTANE AND RELATED COMPOUNDS

Canadian Journal of Research ◽

10.1139/cjr49b-052 ◽

1949 ◽

Vol 27b (6) ◽

pp. 503-519 ◽

Cited By ~ 8

Author(s):

A. F. McKay ◽

R. H. Meen ◽

George F Wright ◽

W. J. Chute ◽

G. S. Myers

Keyword(s):

Nitric Acid ◽

Nitrogen Atom ◽

Ammonium Nitrate ◽

Cyclic Nitramines ◽

Related Compounds

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.

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

Canadian Journal of Research ◽

10.1139/cjr49b-053 ◽

1949 ◽

Vol 27b (6) ◽

pp. 520-544 ◽

Cited By ~ 13

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.

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NITROLYSIS OF HEXAMETHYLENETETRAMINE: II. NITROLYSIS OF l,5-ENDOMETHYLENE-3,7-DINITRO-1,3,5,7-TETRAZA-CYCLOÖCTANE (DPT)

Canadian Journal of Research ◽

10.1139/cjr49b-048 ◽

1949 ◽

Vol 27b (5) ◽

pp. 462-468 ◽

Cited By ~ 12

Author(s):

A. F. McKay ◽

George F Wright ◽

H. H. Richmond

Keyword(s):

Nitric Acid ◽

Acetic Anhydride ◽

Ammonium Nitrate ◽

Acid Anhydride ◽

Nitrogen Pentoxide ◽

Linear Poly ◽

Acetyl Nitrate ◽

Nitrate Mixture

When 1,5-enedomethylene-3,7-dinitro-1,3,5,7-tetrazacycloöctane (DPT) is nitrolyzed with nitric acid – ammonium nitrate mixture the products are cyclic trimeric and tetrameric methylenenitramines (RDX and HMX). When the ammonium nitrate in this nitrolysis mixture is replaced by anhydrides such as nitrogen pentoxide or acetic anhydride then terminally esterified linear poly-methylenenitramines such as 1,9-dinitroxy-2,4,6,8-tetranitro-2,4,6,8-tetrazanonane and the 1,9-diacetoxy analogue respectively are obtained. Replacement of this nitric acid – anhydride mixture by acetyl nitrate does not produce the same type of nitrolysis. It is therefore concluded that nitric acid and an anhydride act independently, the former as a nitrolyzing agent and the latter as an esterifying agent. Alternatively the presence of ammonium nitrate serves to promote esterification and/or promote demethylolation.

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Electrometric Method for the Determination of Chloride in Serum and Other Biologic Fluids

Clinical Chemistry ◽

10.1093/clinchem/4.2.159 ◽

1958 ◽

Vol 4 (2) ◽

pp. 159-169 ◽

Cited By ~ 9

Author(s):

David Seligson ◽

Gerald J McCormick ◽

Kenneth Sleeman

Keyword(s):

Spinal Fluid ◽

Electrometric Method ◽

Direct Titration ◽

Titration Procedure

Abstract A direct titration procedure for chloride in serum, spinal fluid, urine, and other biologic materials has been described. It can be applied to tissues. It is recommended for its accuracy, precision, speed, and versatility.

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