Dye laser flash photolysis kinetics study of the reaction of ground-state atomic oxygen with hydrogen peroxide

Davis, Deborah Winders; Wong, Wah Hun; Schiff, Robert

doi:10.1021/j100597a033

Cited by 18 publications

(1 citation statement)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In this context, the reactions of OH with the terpenes will always compete against the reactions of OH with CO and CH4. [Greiner, 1970;Davis et al, 1974;Margitan et al, 1974;Zellner and Steineft, 1976]. Consequently, during the periods of maximum terpene concentration, the reaction of OH with the terpenes will be approximately 25% that of OH with CO and CH4.…”

Section: The Plot Of Ozone Versus C(monoterpene Carbon)/nox For the Dmentioning

confidence: 99%

Measurement of monoterpene hydrocarbons at Niwot Ridge, Colorado

Roberts¹,

Fehsenfeld²,

Albritton³

et al. 1983

J. Geophys. Res.

View full text Add to dashboard Cite

Measurements of atmospheric monoterpene hydrocarbons were made at a site in the Colorado mountains. The research was undertaken to examine the influence of the compounds on the photochemistry of the troposphere. A sampling technique was developed using Tenax GC porous polymer traps with analysis by capillary gas chromatography and detection by flame ionization and mass spectrometry. Positive identification of six monoterpene hydrocarbons, •-pinene, camphene, ]•-pinene, myrcene, A-3carene, and d-limonene, was obtained, as well as tentative identification of •-thujene and ]•-phellandrene. A definite seasonal trend was evident in the average monoterpene mixing ratios. The summertime average was 0.30 ppbv for the sum of the five major identified monoterpenes, ]•-pinene, •-pinene, A-3carene, camphene, and d-limonene, with a high degree of constancy in relative ratios of each throughout the summer months. Wintertime measurements gave mixing ratios below the detection limits (0.001 ppbv of an individual compound). Simultaneous measurements of ozone, NO, NO2, and monoterpene hydrocarbons allowed examination of the contribution of monoterpene photooxidation to ozone production. Based on reported modeling studies, monoterpenes were estimated to be a small source of ozone, insufficient to account for the relatively high ozone mixing ratios (> 80 ppbv) sometimes observed at this sampling site. sphere [Dirnitriades, 1981; Graedel, 1979]. Estimates made from a review of biogenic hydrocarbon emission data indicate that isoprene and monoterpenes are a major source of carbon emitted to the atmosphere. The global emission rates were estimated to be 3.5 x 10 •'• and 4.8 x 10 •'• g C/yr of isoprene and monoterpenes, respectively [Zimmerman et al., 1978]. The total of isoprene and monoterpene inputs roughly equal those of methane 5.3-12.1 x 10 •'• g C/yr [Ehhalt and Schmidt, 1978; Sheppard et al., 1982] and anthropogenic hydrocarbons • 1.0 x 10 •'• g C/yr [Duce, 1978]. This has lead to the assertion that the photooxidation of isoprene and monoterpenes produces significant amounts of CO and H 2 in the atmosphere [Zimmerman et al., 1978]. Reaction rates of monoterpene hydrocarbons with ozone and hydroxyl radicals yield daytime atmospheric lifetimes of several hours or less for the removal of the monoterpenes. Studies of the reaction mechanisms of olefins with ozone [Herton and Huie, 1979] and hydroxyl radicals [Niki et al., 1978] show that oxidant molecules (HO2, RO:, R = organic group) can be produced. This conversion of monoterpenes to oxidant species results in ozone formation in the presence of NOx and may be partially responsible for the imbalance in the / NO/NO: "photostationary state" observed at a rural site [Kelly et al., 1980]. Since the initial observations of biogenic hydrocarbons in the atmosphere [Went, 1960], laboratory studies have shown that monoterpenes contribute to aerosol formation and participate in photochemical oxidant production [Ripperton et al., 1971; Westberg and Rasmussen, 1972; Lillian, 1972; Arnts and Gay...

show abstract

Section: The Plot Of Ozone Versus C(monoterpene Carbon)/nox For the Dmentioning

confidence: 99%

Measurement of monoterpene hydrocarbons at Niwot Ridge, Colorado

Roberts¹,

Fehsenfeld²,

Albritton³

et al. 1983

J. Geophys. Res.

View full text Add to dashboard Cite

show abstract

Atmospheric Chemical Kinetics Data Survey

Series

1976

1976, Chemistry and Physics of the Stratosphere

View full text Add to dashboard Cite

Stratospheric Ozone: An Introduction to Its Study

Series

1976

1976, Chemistry and Physics of the Stratosphere

View full text Add to dashboard Cite

An analysis is made of the varions re actions in which ozone and atomic oxyge n are involve d in the stratosphère. At the présent time, hydrogen. nitrogen. and chlorine compounds in the ranges parts per million, parts per billion, and parts per I rillion may have significant chemical effects. I n the upper stratosphère, above the ozone peak. where there is no slrong departure from photochemical equilibrium conditions, the action of hydroxyl arid hydroperoxyl radicals of nitrogen dioxide and chlorine monoxide on atomic oxygen and of atomic chlorine on ozone can be introduced. A précise détermination of their ex act effects requires Knowledge of (1) the vertical distribution of the HjO. CH,. and Hj dissociation by reaction of thèse molécules with electronically excited oxygen atom OCf): (2) the ratio of the OH and HOj concentrations and their absolute values, which dépend on insufficiently known rate coefficients: (3) the various origins of nitric oxide production, with their vertical distributions relaled to latitude and season; and (4) the various sources giving différent chlorine compounds lhat may be dissociated in the stratosphère. I n the lower stratosphère, below the ozone peak. there is no important photochemical production of Oj, but there exist various possibilities of transport. The prediclability of the action of chemical reactions dépends strongly on important interactions between OH and HOj radicals with CO and NO. respectively. which affect the ratio n(OH)/n(\\Oi) at the tropopause level; between OH and NOj. which lead to the formation of nitric acid with its downward transport toward the troposphère; between NO and HO2. which lead to NO? and its subséquent photodissociation; between CI O and NO. which also lead to NOj and become more important than the reaction of CI O with O; and between Cl and various molécules, such as CH. and Hj, which lead to HCl with its downward transport toward the troposphère. Ail thèse chemical processes are subjeci to many changes since they occur in the lower stratosphère where seasonal. latiludinal, and even daytoday variations of the ozone concentrations are observed in associa tion with advective and dynamic transports, which dépend on meteorological conditions as indicated by variations of tropopause heights.

show abstract

Dye laser flash photolysis kinetics study of the reaction of ground-state atomic oxygen with hydrogen peroxide

Cited by 18 publications

References 0 publications

Measurement of monoterpene hydrocarbons at Niwot Ridge, Colorado

Measurement of monoterpene hydrocarbons at Niwot Ridge, Colorado

Atmospheric Chemical Kinetics Data Survey

Stratospheric Ozone: An Introduction to Its Study

Contact Info

Product

Resources

About