Photolysis of methyl nitrite in the presence of nitric oxide, nitrogen dioxide, and oxygen

Wiebe, H. A.; Villa, Alberto; Hellman, T. M.; Heicklen, Julian

doi:10.1021/ja00782a002

Cited by 54 publications

(21 citation statements)

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“…Although the experiment~al values do not agree exactly, the net uncertainty in log k7, is only about =t0. 3. This point will be discussed in more detail later.…”

Section: Introductionmentioning

confidence: 90%

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

Barker

Benson

Golden

1977

Int J of Chemical Kinetics

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The decomposition of dimethyl peroxide (DMP) was studied in the presence and absence of added NO, to determine rate constants k l and k z in the temperature range of 391-432OK:The results reconcile the studies by Takezaki and Takeuchi, Hanst and Calvert, and Batt and McCulloch, giving log kl(sec-1) = (15.7 f 0.5) -(37.1 f 0.9)/2.3 RT and k , = 5 X 104MM-'sec-1. The disproportionation/recombination ratio k7t,/k7, = 0.30 f 0.05 was also determined: Me0 + NO, (+ &I) % MeONOz (+ M ) M e 0 + NO, 3 CH,O + HONO When 0 2 was added to DMP mixtures containing NO,, relative rate constants klZ/k?a CH,O + 0 2 3 CHIO + HOZ were obtained over the temperature range of 396-442'K: A review of literature data produced kTa = 109.s*~.~M-1~sec-1, giving log k12(M-1.sec-1) = (8.5 f 1.5) -(4.0 =k 2.8)/2.3 RT, where most of the uncertainty is due to the limited temperature range of the experiments. *Present address:

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“…Although the experiment~al values do not agree exactly, the net uncertainty in log k7, is only about =t0. 3. This point will be discussed in more detail later.…”

Section: Introductionmentioning

confidence: 90%

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

Barker

Benson

Golden

1977

Int J of Chemical Kinetics

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“…160 quadrupole mass spectrometer. Complete details of the apparatus and procedure have been described previously (7). The leak-rate of the first pinhole was sufficiently small so that the pressure drop in the reaction vessel was negligible during the time of the experiment ( 5 600 s).…”

Section: Methodsmentioning

confidence: 99%

The Reaction of O(³P) with C₂Cl₄

Sanhueza¹,

Heicklen²

1974

Can. J. Chem.

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EUGENIO SANHUEZA and JULIAN HEICKLEN. Can. J. Chem. 52,3870 (1974). The reaction of 0(3P), prepared from Hg photosensitization of N 2 0 with C2C14 was studied at 25 "C. The exclusive products of the reaction in the absence of 0, were CC1,O and polymer (as well as N, from the N,O). The quantum yield of CCI20 production, @{CC120), was 0.19 independent of the C2CI4 pressure or the absorbed intensity, I,. There was no evidence for CO, m Clz, c-C3CI,, CC13CC1(0), or CCI2CCI20 production. The reaction mechanism is 112~1 o (~P ) + c2c14 + CCIZO + cc12[I261 + C2C140* with klZo/k12 = 0.19. The CC12 radical dimerizes and the energetic C2CI,0* intermediate polymerizes. By competitive kinetics, the ratio kl2/kl3 was found to be 0.10, where k12 = klzy + k12, and k,, is the rate coefficient of the O(,P) + CzF4 reaction.In the presence of O,, a chain process is involved in which CC13CCI(0) and CC120 are the major products. They are formed in a ratio of 2.0 independent of reaction conditions, but the chain length is proportional to [C2C14]/Za"Z. Also produced is CO with a quantum yield of -0.18. The ratio @{CCI3CC1(0)}/@{CCl20) = 2.0 is similar to that of 2.5 found in the C1 atom initiated oxidation. This result is interpreted to mean that chlorine atoms are involved in the chain. The reaction which initiates monoradicals in the system is Chem. 52,3870 (1974). On a Ctudie, a 25 "C, la reaction de C2CI, avec 0(3P) prepare par photosensibilisation au mercure du N 2 0 . Les seuls produits formes au cours de la reaction, en absence d'oxygene, sont le CC1,O et un polymere (il se forme aussi du N, a partir du N20). Le rendement quantique pour la production de CCI20, @{CCI20), est de 0.19 et est indipendant de la pression de C2CI4 ou de l'intensite absorbCe, I,. On n'a trouve aucune indication concernant la production de CO, En presence d'oxygene, un processus en chaine est implique dans lequel CC13CC1(0) et CCI,(O) sont les produits predominants. Ils se forment dans un rapport de 2.0 qui est indtpendant des conditions de la reaction mais la longueur de la chaine est proportionnelle a la quantite [C2C14]/Z,"2. Du CO est aussi produit avec un rendement quantique d'environ 0.18. Le rapport @{CC13CCl(0))/~{CC120} = 2.0 est semblable a la valeur de 2.5 trouve pour les reactions d'oxydation initiies par des atomes de chlore. On interprete ce resultat comme signifiant que les atomes de chlore sont impliquks dans la chaine. La reaction qui provoque la formation initiale de monoradicaux dans ce systeme est

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“…(i) The pressure dependence of both reactions (2) and (2'): This may be the reason for the variation in the ratio observed by other workers [12,18,211. However, we took considerable care to examine and remove this effect.…”

Section: Discussionmentioning

confidence: 89%

“…Baker and Shaw determined a value of 2.7 at 403 K [18], whereas Phillips and Shaw found a value of 1.8 at 363 K [21]. The work of Wiebe and co-workers [12] led to a value of 1.3 a t room temperature. Barker, Benson, and Golden decided that this apparent temperature dependence was an artifact and concluded that the ratio was 2 f 1 independent of temperature.…”

Section: Dirnethyl Peroxide and Nitric Oxidelnitrogen Dioxide Mixturesmentioning

confidence: 99%

The reaction of methoxy radicals with nitric oxide and nitrogen dioxide

Batt

Rattray

1979

Int J of Chemical Kinetics

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By allowing dimethyl peroxide ( 10-4M) to decompose in the presence of nitric oxide (4.5 X lOW5M), nitrogen dioxide (6.5 X 10-5M) and carbon tetrafluoride (500 Torr), it has been shown that the ratio kzlkz, = 2.03 f 0.47: CH30 + NO -CH30NO (reaction 2) and CH30 + NO2 -CH30N02 (reaction 2'). Deviations from this value in this and previous work is ascribed to the pressure dependence of both these reactions and heterogeneity in reaction (2). In contrast no heterogeneous effects were found for reaction (2') making it an ideal reference reaction for studying other reactions of the methoxy radical. We conclude that the ratio kz/k2, is independent of temperature and from kl = 10'0.2*0.4M-1 sec-' we calculate that kz, = 109.9i0.4M-1 sec-1. Both kz and kz. are pressure dependent but have reached their limiting high-pressure values in the presence of 500 Torr of carbon tetratluoride. Preliminary results show that k4 = 10.9.0i0.6 10-4.5*1.1/8M-' sec-' (8 = 2.303RT kcal mole-') and by kq, = 108.6i0.6 10-2.4i1.1/8M-1 sec-': CH30 + 0 2 -CHzO + HOz (reaction 4) and CH30 + t-BuH -CH30H + (t-Bu) (reaction 4').Of particular interest to us were their decomposition [reaction (3)] [9] and the reaction with oxygen, especially the methoxy radical [reaction (4)][lo]:

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Photolysis of methyl nitrite in the presence of nitric oxide, nitrogen dioxide, and oxygen

Cited by 54 publications

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The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

The Reaction of O(³P) with C₂Cl₄

The reaction of methoxy radicals with nitric oxide and nitrogen dioxide

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Photolysis of methyl nitrite in the presence of nitric oxide, nitrogen dioxide, and oxygen

Cited by 54 publications

References 0 publications

The decomposition of dimethyl peroxide and the rate constant for CH3O + O2 → CH2O + HO2

The decomposition of dimethyl peroxide and the rate constant for CH3O + O2 → CH2O + HO2

The Reaction of O(3P) with C2Cl4

The reaction of methoxy radicals with nitric oxide and nitrogen dioxide

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The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

The decomposition of dimethyl peroxide and the rate constant for CH₃O + O₂ → CH₂O + HO₂

The Reaction of O(³P) with C₂Cl₄