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)

“…Appropriate empirical COI-rections were applied for loss by solubility in the filtrate. The resulting R D X was analyzed for HR4X by the method of differential homogeneous hyclrolysis ( 2 ) .…”

Section: Methodsmentioning

confidence: 99%

Studies of RDX and Related Compounds: Vii Relation Between RDX and HMX Production in the Bachmann Reaction

Epstein¹,

Winkler²

1952

Can. J. Chem.

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-\BSTRACT The reactions t o form R D X and H M X in Rachmann-type ~n i s t i~r e s are c o~n parable in respect of optimum nitric acid concentrations and in the fact t h a t optimal amounts of acetic anhydride and ammonium nitrate are necessary for masimum yields of either explosive. The activation energies for formation of R D X and H M X were also found to be comparable, at 15 f 1 kcal. per mole. However, withholdinganimo~~iuninitratefrom thereaction mixture \\.as found t o have a more tleleterious effect on R D X production than on H M X production. A n~e c h a n i s n~ is proposed which attempts in a general way t o represent the relation between R D X a n d H h I X production in the type of reaction mixtures used. INTRODUCTIONAn accurate method for analysis of HNIX (cyclotetramethylenetetranitramine) in RDX (cyclotrimethylenetrinitramine), produced by the Bachmailil reaction (I), was described in a preceding paper (2). In the present investigation the method was applied to a study of the relative rates of formation of R D X and H M X , and of the influence of certain factors on the relative yields of R D S and H M X in Bachmann type reaction mixtures. EXPERIMENTALThe materials employed were all of commercial grade. The hexamine, acetic acid, acetic anhydride, and ammonium nitrate were 99.0, 99.3, 95.0, and 99% pure respectively, while the nitric acid was 97y0 HNO3.Ammoilium nitrate of accurately weighed amount was placed in 250 cc. Erlenmeyer flasks and the desired molar ratio of nitric acid added to bring the ammonium nitrate into solution. The ammonium nitrate was then reprecipitated as fine crystals by addition of acetic acid to the dilution required. -Acetic anhydride of a designated amount was then added and the flask and its contents shaken in a constant temperature bath, the temperature of which was controlled within =t 0.2' C. After some minutes, the reaction was initiated by adding 5 cc. of 1 M hexamine -acetic acid solution, which caused any solid anlmonium nitrate present to dissolve almost immediately.By this sequence of addition and by using large proportions of acetic acid, any effect due to rate of solution of anlmonium nitrate was practically eliminated and the total amounts of all reagents were brought together initially in a virtually homogeneous reaction medium. In this manner, satisfactory reproducibility of results was realized.The reaction was stopped a t the desired time by addition of approximately 30 cc. of water. Nitric acid (5 cc.) was then added and the resulting mixture simmered on a hot water bath for approximately four hours I1'1rYKLER: RDX. 171 733 t o destroy any B S S (1,7-diacetoxytetramet1~ylene-2,4,6-tr1nitra1n111e) present (1). Blanli experiments with the product fro111 reaction mixtures containing no amrnoniu~n nitrate showed that a three hour simmer was sufficient to clestroy all the solids present. The Aask was then filled to the 11ecli with water and permitted to stand a t room temperature for taro clays to ensure complete precipitation of RDX. The precipitate w...

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“…The observed rates of degradation for TNT in aqueous systems are summarized in Table 1. Similarly to TNT, the hydrolysis of RDX in alkaline solutions has been observed for quite some time (Epstein andWinkler 1951, Jones 1954), although early efforts were focused on developing methods for quality assurance analysis of finished RDX. The end products of alkaline hydrolysis of RDX were observed by Hoffsommer et al (1977) to be nitrite, nitrous oxide, ammonia, nitrogen, formaldehyde, and formate, with the relative amounts being determined by the reaction pH.…”

Section: Foundations Of Alkaline Hydrolysismentioning

confidence: 99%

“…Aqueous octohydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) undergoes an alkaline decomposition similar to RDX, though this reaction has been observed to be slower (Epstein and Winkler 1951). Heilmann et al (1996) observed a first order reaction rate for the alkaline degradation of HMX that was two orders of magnitude slower than that observed for RDX.…”

Section: Foundations Of Alkaline Hydrolysismentioning

confidence: 99%

Management of Munitions Constituents in Soil Using Alkaline Hydrolysis: A Guide for Practitioners

Johnson¹,

Felt²,

Martin³

et al. 2011

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This report summarizes the state of the practice for the effective management of munitions constituents using alkaline amendments. It includes the wide variety of laboratory results that delineate the reaction kinetics and transformation products of alkaline hydrolysis. It also describes the field demonstrations that have proven the worth of alkaline amendments on both active training ranges and former defense facilities. Alkaline hydrolysis has been extensively studied for the degradation of secondary explosives in aqueous and soil systems. Laboratory studies have determined that the end products of alkaline hydrolysis are mostly small compounds that are readily biodegradable in natural systems. A well-mixed application of hydrated lime has been shown to reduce the concentration of explosives in soil and the concentration of explosives leaving soil lysimeters as both leachate and runoff. Field studies have proven the technology at both active training ranges and formerly used facilities. The total of the work performed to date has demonstrated alkaline hydrolysis to be a safe, effective, and cost-efficient method of managing or treating munitions constituents in soil. It has gained regulatory acceptance for soil remediation activities, and is a valuable technique for Army environmental practitioners.

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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)

Cited by 21 publications

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Environmental Fate Studies of HMX Screening Studies. Phase 1

Environmental Fate Studies of HMX Screening Studies. Phase 1

Studies of RDX and Related Compounds: Vii Relation Between RDX and HMX Production in the Bachmann Reaction

Management of Munitions Constituents in Soil Using Alkaline Hydrolysis: A Guide for Practitioners

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