Progress of sequential reactions under linear heating conditions

Gontkovskaya, V. T.; Ozerkovskaya, N. I.; Barzykin, V. V.; Pestrikov, S. V.

doi:10.1007/bf00756245

Cited by 2 publications

(1 citation statement)

References 3 publications

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“…Obviously, mathematical models for polymer formation -or for sequential reactions in general -are widely available in literature [6][7][8][9][10][11][12][13][14][15], including models for enzymatic polymerization [16,17,12,18].…”

Section: Introductionmentioning

confidence: 99%

Chain length distribution and kinetic characteristics of an enzymatically produced polymer

Mulders¹,

Beeftink

2013

E-Polymers

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Non-processive enzymatic polymerization leads to a distribution of polymer chain lengths. A polymerization model was developed to investigate the relation between the extent of this distribution on one hand, and the polymerization start conditions and reaction kinetics on the other hand. The model describes changes in concentration of chains of length n as the result of two elongation reactions: elongation by monomer addition to length n-1 and elongation by monomer addition to length n. Polymerization reactions were assumed to be zero order in monomer concentration and to obey Michaelis-Menten kinetics with respect to polymer concentrations. In addition, the amount of enzyme available for each individual reaction (n n+1) is assumed to be proportional to the concentration of polymer substrate of length n. The development of the shape of the chain length distribution was found to be independent of the value of the overall reaction rate constant; only the rate at which these shapes developed was influenced by the 1 st -order rate constant. The value of the Michaelis parameter did affect the form of the chain length distribution curve since it affects the reaction order. An increase in reaction order was found to promote widening of the chain length distribution. Differences in kinetic parameters between the subsequent polymerization reactions, if any, were also found to have a large effect on the development of the chain length distribution. An increase in rate constants with chain length entailed a wider distribution; a more narrow distribution would require a decrease in rate constants with chain length.

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Section: Introductionmentioning

confidence: 99%

Chain length distribution and kinetic characteristics of an enzymatically produced polymer

Mulders¹,

Beeftink

2013

E-Polymers

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Thermal ignition behaviour of ammonium perchlorate in presence of fuel-rich compounds

Sundararajan

Jain

1983

Journal of Thermal Analysis

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The thermal ignition behaviour of ammonium perchlorate has been investigated in the presence of fuel-rich compounds such as tetramethylammonium perchlorate, trimethylammonium nitrate, carbon and cellulose. The ignition characteristics, as studied by differential thermal analysis, have been found to be strongly influenced by self-decomposition and other physicochemical properties of the additives. For a simple system, an analytical model proposed on the basis of the coupling of two exothermic decomposition reaction kinetics and a heat-balance equation, appears to explain to some extent the observed trend in peak ignition temperature when the composition is varied. The salient features of the analysis, as regards its application to fuel-oxidizer interactions in general, have been pointed out.The importance of thermal ignition studies on condensed fuel-oxidizer systems arises mainly because of their extensive application in the field of propellants and explosives. Of the condensed systems, the mixtures involving ammonium perchlorate (AP) are of special interest due to their wide use in solid propellants. The thermal ignition behaviour of AP is known to be modified in the presence of catalysts, impurities and additives [1]. A systematic study of the differential thermal analysis (DTA) of AP in the presence of structurally similar, fuel-rich compounds, viz. methylammonium perchlorates (MAPs), was recently carried out in our laboratory [2]. It was observed that although AP shows two exotherms due to partial and complete decomposition at around 300 ~ and 400 ~ respectively [1] in DTA, it ignites in asingle step at around its partial decomposition temperature in the presence of small amounts of mono-, di-, tri-or tetramethylammonium perchlorate. Interestingly, the critical concentration of a MAP needed to cause ignition in a single step corresponds to a unique composition of the mixture, expressed in terms of its elemental stoichiometric coefficient, ~e [3]. However, some of the features in the DTA of the mixtures of AP and tetramethylammonium perchlorate (TMAP), such as the shift of the terminal exotherm to lower temperatures as a function of concentration, were not clearly explained.

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Progress of sequential reactions under linear heating conditions

Cited by 2 publications

References 3 publications

Chain length distribution and kinetic characteristics of an enzymatically produced polymer

Chain length distribution and kinetic characteristics of an enzymatically produced polymer

Thermal ignition behaviour of ammonium perchlorate in presence of fuel-rich compounds

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