The combustion of the butane-2,3- and 1,4-diol dinitrates and some aldehydenitrogen dioxide mixtures

Powling, J.; Smith, W.A.W.

doi:10.1016/0010-2180(58)90006-3

Cited by 24 publications

(10 citation statements)

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“…The thermal decomposition mechanism proposed by Powling and Smith would account for this product. 7 However, the formation of a small amount of tetrahydrofuran (30%) suggests that molecular fragmentation may be stepwise rather than concerted. Loss of NO 2 produces an alkoxy-nitrate radical, which can decompose to ethylene, NO 2 , and formaldehyde or be reduced to the nitrate-alcohol, which then ring closes to tetrahydrofuran (Fig.…”

Section: Resultsmentioning

confidence: 99%

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Thermal decomposition of nitrate esters

Hiskey¹,

Brower²,

Oxley³

1991

J. Phys. Chem.

106

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Rates of thermal decomposition and solvent rate effects have been measured for a series of nitrate esters. The alkoxy radicals formed by homolysis together with some of their further degradation products have been stabilized by hydrogen donation. Internal and external return of nitrogen dioxide has been demonstrated by solvent cage effects and isotope exchange. Radicalstabilizing substituents favor β-scission. Dinitrates in a 1,5 relationship behave as isolated mononitrates. Dinitrates in a 1,3 or 1,4 relationship exhibit intramolecular reactions. Tertiary nitrate esters in diethyl ether undergo elimination rather than homolysis. IntroductionThe esters of nitric acid have long been used as explosives and propellants, and their thermal decomposition products and kinetics have been studied as a means to evaluate the thermal hazards of these compounds. The thermal decomposition of ethanolnitrate was examined by a number of researchers, and it was proposed that the first, and rate-determining, step was the reversible loss of NO2: [2][3][4][5] RCH2O-NO2 <--> RCH2O . + NO2

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Section: Resultsmentioning

confidence: 99%

“…7 They found that 1,4-butanediol dinitrate, following cleavage of one NO2 moiety, decomposed to formaldehyde, nitrogen dioxide, and ethylene, whereas 2,3-butanediol dinitrate gave acetaldehyde in place of formaldehyde and ethylene. A similar intramolecular decomposition to gaseous products has been proposed for nitroglycerin.…”

Section: Introductionmentioning

confidence: 99%

Thermal decomposition of nitrate esters

Hiskey¹,

Brower²,

Oxley³

1991

J. Phys. Chem.

106

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“…Heats of explosion of catalyzed and noncat •y~d prgpellants were measurg by several investigatorsiT55du 7 l Lenchitz and Haywood measured heat of explosion at various pressures with great precision. They found in the superrate region (p -10 atm) that the heat of explosion ("%530 cal/g at low pressure) of propellant modified with lead stearate is 40 cal/g higher (about 8% higher) than that of non-modified propellant, whereas the burning rate of the modified propellant is approximately twice that of the nonmodified propellant.…”

Section: B Observations Of the Gas Phase Zone Of Catalyzed Prospellamentioning

confidence: 99%

“…C-6 Close-up of strand burner for measuring burning rates at subatmospheric pressures C13 C- 7 Strand burner for gas phase observations C14 C-8…”

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confidence: 99%

The mechanism of super-rate burning of catalyzed double base propellants

Kubota

Ohlemiller

Caveny

et al. 1975

Symposium (International) on Combustion

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“…However, the ratio is less than that of a noncatalyzed propellant i•the plateau and mesa-burning regimes (Lenchitz 7 …”

Section: S3mentioning

confidence: 99%

The Mechanism of Super-Rate Burning of Catalyzed Double Base Propellants

Kubota¹,

Ohlemiller²,

Caveny³

et al. 1973

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of. the-Navy,-Washinricton,D.C.!1i)stuy isdirected -at-understanding-howv'o.rgai la -ats(4 the 1%level) -`alter the 'burn'ing-mechanisms of--double base proppllXants --to produce large (up to 300%) burning rate increases (super-rate burning) Sand domains of reduced burning rate pressure and temperature sensitivity-*I(plateau burning). Investigations wore carried out with nitrocelluose-. and trimethylolethane trinitrate (TMETN) double base propellants withSsystematic variations in additives (including -lead-powder, -lead-oxide,--lead salicylate, copper powder, copper ealicylate, finely divided carbon Fl'and oxainide),, particle size,.and degree of dispersion. Diagnostic experSiments (from 0.*1 to 100 atm) .examined burning -rate behavior, gasa-phase stutr, burning-surface structure, -temperature profiles interac ton zones, and global efet. -fhe micro -thermo couple experiments.-re~vealed that 1% lead salts have lest -than a 10% effect on surface temapera n ueadsraeha ees u produce significant increases (70 to 4'-1 1 j~100%) in the fizz zone temperature gradi~ents. Lead salts decompose andd1 T Sdircl affect the surface reaction layer (ru 20Vi thick at 20 atm). The -----------------------------------------lead salts' decomposition products react with the nitrate esters to proSduce an increased amount of solid carbon. 'The portion of decomposed organic molecules which appears at the surface in the form of carbon Srather than readily oxidizable dl ehydes reduce the effective fuel to Soxidizer ratio (aldehyde to NO 2 ) 1 (Ad,, thus,, shifts the equivalence ratio AFý toward, the stoichiometric 'value; thid.accelera~tes the reaction rates in ;ýr fizz zone and produces super rate burning. P' DD IoSS 473-___________ 50iRIS14f. Also, the authors thank Professor W. A. Sirignano for his review and comments concerning the gas phase reactions.The experimental work was accomplished with the capable support of the Technician Staff.In particular, Mr. C. R. Felsheim was responsible for the specialized processing of the propellants used in this study, Mr. E. R. Crosby participated in the photographic work, and Mr. J. H. Semler assisted in the experiments using the delicate micro-thermocouples. ABSTRACTThis study is directed at uwderstanding how organic lead salts used as catalysts a!;er the burning mechanisms of double base propellants (i.e., two nitrate esters interdiffused) to produce burning rate increases (known as super-. rate burning) and domains of reduced burning rate pressure sensitivity (known as plateau burning).Simultaneously, these same lead salts greatly reduce the temperature sensitivity of burning rate in the super-rate range. These effects are of great practical interest since they provide design flexibility and yield performance which is largely. constant over a prescribed range of operating I.ressures and initial temperatures.The experimental investigations were carried out with particulate nitrocellulose (PNC) and trimethylolethane-trinitrate (TMETN) double base propellants instead of with the more hazardous-t...

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The combustion of the butane-2,3- and 1,4-diol dinitrates and some aldehydenitrogen dioxide mixtures

Cited by 24 publications

References 3 publications

Thermal decomposition of nitrate esters

Thermal decomposition of nitrate esters

The mechanism of super-rate burning of catalyzed double base propellants

The Mechanism of Super-Rate Burning of Catalyzed Double Base Propellants

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