The Influence of Irradiation Temperature on U.V. Induced Defect Creation in Dry Silica

1985 ◽  
Vol 61 ◽  
Author(s):  
R. A. B. Devine ◽  
C. Fiori ◽  
J. Robertson
Keyword(s):  
Oxygen Vacancy ◽  
Peroxy Radical ◽  
Irradiation Temperature ◽  
Threshold Temperature ◽  
Peroxy Radicals ◽  
Oxygen Hole ◽  
Spin Resonance ◽  
Dependent Growth ◽  
Dose Dependent ◽  
Annealing Curve

ABSTRACTElectron spin resonance measurements have been carried out on samples of Suprasil Wl (dry silica) subjected to ultraviolet laser radiation (λ = 248 nm, E = 5 eV/photon). Studies have been made for fixed irradiation temperature (room) variable accumulated ultraviolet dose and fixed accumulated dose (3000 J/cm2) at various irradiation temperatures in the range 110 K to 335 K. Three principal defect centers are observed. Non-bridging oxygen hole centers are created at all temperatures in the range studied with slightly higher efficiency at room temperature (ration 300 K/150 K ∼ 2.5). Comparison of the dose dependent growth curve of the 4.8 eV absorption and its isochronal annealing curve with those for the oxygen hole center clearly identify the origin of the absorption band with this defect. A threshold temperature ∼ 200 K is found for oxygen vacancy creation consistent with results on single crystalline quartz. Post irradiation annealing at 593 K eliminates the vacancy centers and the peroxy radical resonance appears. Its growth as a function of accumulated ultraviolet dose and irradiation temperature supports the hypothesis that peroxy radicals form by the trapping of diffusing, molecular oxygen at the oxygen vacancy center.

Formation of radicals in the amine inhibited decomposition of t-butyl hydroperoxide

1969 ◽  
Vol 47 (2) ◽  
pp. 295-299 ◽  
Author(s):  
K. Adamic ◽  
K. U. Ingold
Keyword(s):  
Aromatic Amines ◽  
Peroxy Radical ◽  
Nitroso Compounds ◽  
Peroxy Radicals ◽  
Tertiary Amines ◽  
Chain Initiation ◽  
Butyl Hydroperoxide ◽  
Spin Resonance ◽  
Butoxy Radical ◽  
Radical Signal

The radicals formed in the amine inhibited, α,α′-azo-bis-isobutyronitrile initiated, decomposition of t-butyl hydroperoxide at 65° have been examined by electron spin resonance. In the absence of amine a strong peroxy radical signal is obtained. Amines with structures that do not correspond to those of conventional antioxidants (i.e. primary and secondary aliphatic amines and tertiary amines) generally have little or no effect on this signal. Nitroxide radicals are generated from secondary aromatic (diaryl and alkaryl) amines. The rate of conversion of these amines to nitroxides reached a maximum of 50–60% of the rate of chain initiation for some diphenylamines. A maximum concentration of nitroxide of about half the initial amine concentration was obtained with 4,4′-dimethyldiphenylamine.N,N,N′,N′-Tetramethyl-p-phenylenediamine is very rapidly oxidized by t-butyl hydroperoxide to give Wurster's Blue cation and, presumably, a t-butoxy radical. This amine is therefore an initiator of oxidation rather than an inhibitor as has commonly been supposed.Primary aromatic amines do not appear to form simple aryl nitroxides. It is proposed that arylamino radicals [Formula: see text] are directly oxidized to nitroso compounds by peroxy radicals.

Formation of diphenyl nitroxide in diphenylamine inhibited autoxidations

1969 ◽  
Vol 47 (2) ◽  
pp. 287-294 ◽  
Author(s):  
K. Adamic ◽  
M. Dunn ◽  
K. U. Ingold
Keyword(s):  
Electron Spin Resonance ◽  
Oxygen Atom ◽  
Electron Spin ◽  
Peroxy Radical ◽  
Peroxy Radicals ◽  
Alkoxy Radical ◽  
Oxygen Atom Transfer ◽  
Lower Efficiency ◽  
Alkoxy Radicals ◽  
Spin Resonance

The formation of diphenyl nitroxide in diphenylamine inhibited, α,α′-azo-bis-isobutyronitrile initiated, autoxidations at 65° has been studied by electron spin resonance. Diphenylamine is oxidized to a diphenylamino radical which is then converted to the nitroxide by an oxygen atom transfer from a peroxy radical. The initial rates of conversion of diphenylamine to diphenyl nitroxide and the maximum nitroxide concentrations attained are generally greater for oxidations with tertiary peroxy radicals than for oxidations with primary or secondary peroxy radicals. The lower efficiency of nitroxide formation by primary and secondary peroxy radicals is attributed to a cage disproportionation between alkoxy radical and nitroxide which leads to the formation of a carbonyl compound and diphenyl hydroxylamine. This reaction cannot occur with tertiary radicals. The rate of formation of diphenyl nitroxide is greater for tertiary peroxy radicals which give stable tertiary alkoxy radicals. Nitroxide formation is inhibited by secondary, but not by tertiary, hydroperoxides.

Absolute rate constants for hydrocarbon autoxidation. VI. Alkyl aromatic and olefinic hydrocarbons

1967 ◽  
Vol 45 (8) ◽  
pp. 793-802 ◽  
Author(s):  
J. A. Howard ◽  
K. U. Ingold
Keyword(s):  
Hydrogen Atom ◽  
Steric Hindrance ◽  
Rate Constants ◽  
Peroxy Radical ◽  
Electron System ◽  
Chain Termination ◽  
The Self ◽  
Hydrogen Atom Abstraction ◽  
Peroxy Radicals ◽  
Absolute Rate

Absolute rate constants have been measured for the autoxidation of a large number of hydrocarbons at 30 °C. The chain-propagating and chain-terminating rate constants depend on the structure of the hydrocarbon and also on the structure of the chain-carrying peroxy radical. With certain notable exceptions which are mainly due to steric hindrance, the rate constants for hydrogen-atom abstraction increase in the order primary < secondary < tertiary; and, for compounds losing a secondary hydrogen atom, the rate constants increase in the order unactivated < acyclic activated by a single π-electron system < cyclic activated by a single Π-system < acyclic activated by two π-systems < cyclic activated by two π-systems. The rate constants for chain termination by the self-reaction of two peroxy radicals generally increase in the order tertiary peroxy radicals < acyclic allylic secondary  [Formula: see text] cyclic secondary  [Formula: see text] acyclic benzylic secondary < primary peroxy radicals < hydroperoxy radicals.

scholarly journals Diel peroxy radicals in a semi industrial coastal area: nighttime formation of free radicals

2012 ◽  
Vol 12 (8) ◽  
pp. 19529-19570 ◽  
Author(s):  
M. D. Andrés-Hernández ◽  
D. Kartal ◽  
J. N. Growley ◽  
V. Sinha ◽  
E. Regelin ◽  
...  
Keyword(s):  
Boundary Layer ◽  
Trace Gases ◽  
Peroxy Radical ◽  
Industrial Area ◽  
Diurnal Variations ◽  
Peroxy Radicals ◽  
Industrial Emissions ◽  
Air Masses ◽  
Volatile Organic ◽  
Organic Trace

Abstract. Peroxy radicals were measured by a PeRCA (Peroxy Radical Chemical Amplifier) instrument in the boundary layer during the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) campaign at a coastal, forested site influenced by urban-industrial emissions in Southern Spain in late autumn. Total peroxy radicals (RO2* = HO2 + ΣRO2) generally showed a daylight maximum between 10 and 50 pptv at 13:00 UTC, with an average of 18 pptv over the 15 days of measurements. Emissions from the industrial area of Huelva often impacted the measurement site at night during the campaign. The processing of significant levels of anthropogenic organics leads to an intense nocturnal radical chemistry accompanied by formation of organic peroxy radicals at comparable levels to those of summer photochemical conditions with peak events up to 60–80 pptv. The RO2 production initiated by reactions of NO3 with organic trace gases was estimated to be significant but not sufficient to account for the concentrations of RO2* observed in air masses carrying high pollutant loading. The nocturnal production of peroxy radicals seems therefore to be dominated by ozonolysis of volatile organic compounds. RO2* diurnal variations were consistent with other HO2 measurements available at the site. HO2/RO2* ratios generally varied between 0.3 and 0.4 in all wind directions. Occasional HO2/RO2* ≥ 1 seemed to be associated with periods of high RO2* variability and with RO2 interferences in the HO2 measurement in air masses with high RO2 load.

scholarly journals Peroxy radical partitioning during the AMMA radical intercomparison exercise

2010 ◽  
Vol 10 (21) ◽  
pp. 10621-10638 ◽  
Author(s):  
M. D. Andrés-Hernández ◽  
D. Stone ◽  
D. M. Brookes ◽  
R. Commane ◽  
C. E. Reeves ◽  
...  
Keyword(s):  
Trace Gases ◽  
Geographical Area ◽  
Peroxy Radical ◽  
Peroxy Radicals ◽  
Intercomparison Exercise ◽  
Additional Information ◽  
Multidisciplinary Analysis ◽  
Photolysis Rates ◽  
Photolysis Frequencies ◽  
Wing Tip

Abstract. Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis) campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE) and total peroxy radicals (RO2* = HO2+ΣRO2, R = organic chain) by two similar instruments based on the peroxy radical chemical amplification (PeRCA) technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously. Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

scholarly journals Characterization of ozone production in San Antonio, Texas, using measurements of total peroxy radicals

2019 ◽  
Vol 19 (5) ◽  
pp. 2845-2860 ◽  
Author(s):  
Daniel C. Anderson ◽  
Jessica Pavelec ◽  
Conner Daube ◽  
Scott C. Herndon ◽  
Walter B. Knighton ◽  
...  
Keyword(s):  
San Antonio ◽  
Peroxy Radical ◽  
Ozone Production ◽  
Peroxy Radicals ◽  
Entire Region ◽  
Volatile Organic ◽  
In Situ Observations ◽  
Study Sites

Abstract. Observations of total peroxy radical concentrations ([XO2] ≡ [RO2] + [HO2]) made by the Ethane CHemical AMPlifier (ECHAMP) and concomitant observations of additional trace gases made on board the Aerodyne Mobile Laboratory (AML) during May 2017 were used to characterize ozone production at three sites in the San Antonio, Texas, region. Median daytime [O3] was 48 ppbv at the site downwind of central San Antonio. Higher concentrations of NO and XO2 at the downwind site also led to median daytime ozone production rates (P(O3)) of 4.2 ppbv h−1, a factor of 2 higher than at the two upwind sites. The 95th percentile of P(O3) at the upwind site was 15.1 ppbv h−1, significantly lower than values observed in Houston. In situ observations, as well as satellite retrievals of HCHO and NO2, suggest that the region was predominantly NOx-limited. Only approximately 20 % of observations were in the VOC-limited regime, predominantly before 11:00 EST, when ozone production was low. Biogenic volatile organic compounds (VOCs) comprised 55 % of total OH reactivity at the downwind site, with alkanes and non-biogenic alkenes responsible for less than 10 % of total OH reactivity in the afternoon, when ozone production was highest. To control ozone formation rates at the three study sites effectively, policy efforts should be directed at reducing NOx emissions. Observations in the urban center of San Antonio are needed to determine whether this policy is true for the entire region.

scholarly journals Radicals in the marine boundary layer during NEAQS 2004: a model study of day-time and night-time sources and sinks

2009 ◽  
Vol 9 (9) ◽  
pp. 3075-3093 ◽  
Author(s):  
R. Sommariva ◽  
H. D. Osthoff ◽  
S. S. Brown ◽  
T. S. Bates ◽  
T. Baynard ◽  
...  
Keyword(s):  
Boundary Layer ◽  
New England ◽  
Gas Phase ◽  
Marine Boundary Layer ◽  
Peroxy Radical ◽  
Chemical Mechanism ◽  
Physical Parameters ◽  
Peroxy Radicals ◽  
Night Time ◽  
Aerosol Composition

Abstract. This paper describes a modelling study of several HOx and NOx species (OH, HO2, organic peroxy radicals, NO3 and N2O5) in the marine boundary layer. A model based upon the Master Chemical Mechanism (MCM) was constrained to observations of chemical and physical parameters made onboard the NOAA ship R/V Brown as part of the New England Air Quality Study (NEAQS) in the summer of 2004. The model was used to calculate [OH] and to determine the composition of the peroxy radical pool. Modelled [NO3] and [N2O5] were compared to in-situ measurements by Cavity Ring-Down Spectroscopy. The comparison showed that the model generally overestimated the measurements by 30–50%, on average. The model results were analyzed with respect to several chemical and physical parameters, including uptake of NO3 and N2O5 on fog droplets and on aerosol, dry deposition of NO3 and N2O5, gas-phase hydrolysis of N2O5 and reactions of NO3 with NMHCs and peroxy radicals. The results suggest that fog, when present, is an important sink for N2O5 via rapid heterogeneous uptake. The comparison between the model and the measurements were consistent with values of the heterogeneous uptake coefficient of N2O5 (γN2O5)>1×10−2, independent of aerosol composition in this marine environment. The analysis of the different loss processes of the nitrate radical showed the important role of the organic peroxy radicals, which accounted for a significant fraction (median: 15%) of NO3 gas-phase removal, particularly in the presence of high concentrations of dimethyl sulphide (DMS).

THE BIOASSAY OF GROWTH HORMONE IN SNELL'S DWARF MICE: EFFECTS OF THYROXINE AND PROLACTIN ON THE DOSE—RESPONSE CURVE

1973 ◽  
Vol 56 (2) ◽  
pp. 235-243 ◽  
Author(s):  
M. WALLIS ◽  
JENNIFER A. DEW
Keyword(s):  
Growth Hormone ◽  
Response Curve ◽  
Growth Response ◽  
Growth Promotion ◽  
Promoting Effect ◽  
Pituitary Growth Hormone ◽  
Growth Promoting ◽  
Dependent Growth ◽  
Dwarf Mice ◽  
Dose Dependent

SUMMARY Pituitary growth hormone has a dose-dependent growth promoting effect in pituitary dwarf mice (Snell's strain), and this effect can be used as the basis of a bioassay for the hormone. Prolactin and thyroxine also promote growth in these animals, and the effects of these hormones in combination with growth hormone were studied, in order to see whether their presence might enhance the precision or sensitivity of the growth hormone assay. When prolactin and/or thyroxine were administered with growth hormone, the growth response observed was no greater than the sum of the effects of the hormones given separately; in some cases it was less. Neither prolactin nor thyroxine increase the sensitivity or precision of the growth hormone bioassay. The implications of these results for theories about the mechanisms of growth promotion by these hormones are considered.

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