Calculated R.R.K.M. unimolecular dissociation rate constants for hydrazine

Setser, D. W.; Richardson, William C.

doi:10.1139/v69-428

Cited by 6 publications

(1 citation statement)

References 4 publications

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“…= 1 X 10 -xø cm 3 s -x. On the other hand, theoretical studies, such as the RRKM calculations of Sester and Richardson [1969], indicated that the high pressure limit was attained only above 1000 torrs, an indication agreeing well with the fact that the thermal decomposition of hydrazine also has a high pressure limit [Benson and O'Neal, 1970]. A recent experimental investigation of Miller [1973] confirms the theoretical expectations, and K•.…”

Section: Photolysis Of Ammonia B•y the Solar Radiations With 2 >mentioning

confidence: 52%

The photochemistry of ammonia in the Jovian atmosphere

Prasad

Capone

1976

J. Geophys. Res.

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To resolve the discrepancy between the Jovian albedo in the IR and UV, a model of ammonia photochemistry was recently proposed by Strobel (1973) which led to a severe depletion of the ammonia concentration with altitude. Some features of this photochemistry, for example, the use of a pressure‐independent rate coefficient for NH2 recombination and the formation of hydrogen and nitrogen molecules in photodissociation of N2H4, were inconsistent with several laboratory and theoretical results. The treatment of the reaction between H and N2H3 was also controversial. When these shortcomings are removed and the basic photochemistry proposed by Strobel is made relatively more consistent with the available theoretical and laboratory data, as far as possible within the limits set by the present paucity of data, then only a moderate ammonia depletion is obtained. The discrepancy between the Jovian albedo in the IR and UV therefore may still be an open question. However, if condensation nuclei were present to such an extent that N2H4 condensed before it reacted or photodissociated, then a new solution of the discrepancy could be possible. Alternatively, existence of a stratospheric ‘cold trap’ may also explain the decreased ammonia abundance. We have also identified and stressed the specific needs for laboratory measurement.

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Section: Photolysis Of Ammonia B•y the Solar Radiations With 2 >mentioning

confidence: 52%

The photochemistry of ammonia in the Jovian atmosphere

Prasad

Capone

1976

J. Geophys. Res.

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Absolute rate constants for reactions of free radicals in the high‐temperature photolysis of formamide vapor. II. Amino radicals

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Yokota

1973

Int J of Chemical Kinetics

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The rotating-sector method has been applied to the photoinitiated radical-chain decomposition of formamide at 300°C to measure the rate constant for the bimolecular disappearance of NH2 radicals. The decomposition is propagated by the reactionsConditions were chosen so that reaction (1) was rate controlling and NH? the terminating radical. A flow system was employed with CZFG as a carrier qas at a pressure of 300 Torr, and the chain reaction was initiated by the photolysis of either formamide or NH3. A value of 4.7( K2.0) X 10'O (M .sec)-l was estimated for the termination reactionand a value of 8.4 x 1 0 6 (M.sec)-l for reaction ( I ) in the same system, both at 300°C.

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Thermal stability of primary amines

Tsang

1978

Int J of Chemical Kinetics

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Tertiary-amyl amine has been decomposed in single-pulse shock-tube experiments. Rate expressions for several of the important primary steps areThe present and earlier comparative rate single-pulse shock-tube data when combined with high-pressure hydrazine decomposition results (after correcting for fall off effects through RRKM calculations) gives [k?(tCSH1 1.,NHP.)/kr(tCSH1l-,tC5H11.) k,(NHz.,NH2-)]1/z -2 a t 1lOOOKwhere k,(--) is the recombination rate involving the appropriate radicals. This suggests that in this context amino radical behavior is analogous to that of alkyl radicals. If this agreement is exact, then km(N2H4 -2NHz-) = 1016-25 exp(-32,300/T) sec-'

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Calculated R.R.K.M. unimolecular dissociation rate constants for hydrazine

Cited by 6 publications

References 4 publications

The photochemistry of ammonia in the Jovian atmosphere

The photochemistry of ammonia in the Jovian atmosphere

Absolute rate constants for reactions of free radicals in the high‐temperature photolysis of formamide vapor. II. Amino radicals

Thermal stability of primary amines

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