Absorption Spectra of the Halogen Monoxides

Durie, R.A.; Ramsay, D. A.

doi:10.1139/p58-005

Cited by 152 publications

(80 citation statements)

References 2 publications

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“…The first photoelectron band of BrO, prepared from reaction ͑1͒, is vibrationally resolved and allows the first AIE of BrO to be measured as (10.46Ϯ0.02) eV, in good agreement with previous measurements from photoionization mass spectrometry. 18 Assuming BrO(X 2 ⌸) dissociates to Br( 2 P) and O( 3 P) and BrO ϩ (X 3 ⌺) dissociates to Br ϩ ( 3 P) and O( 3 P), then D 0 0 (BrO) of (2.39Ϯ0.03) eV 42 and the first ionization energy of atomic bromine of 11.81 eV 24,29 can be combined with the first ionization energy of BrO of (10.46 Ϯ0.02) eV measured in this work to yield D 0 0 (BrO ϩ ,X 3 ⌺ Ϫ ) of (3.74Ϯ0.05) eV.…”

Section: Discussionmentioning

confidence: 99%

A study of the BrO and BrO2 radicals with vacuum ultraviolet photoelectron spectroscopy

Dyke

Gamblin

Hooper

et al. 2000

The Journal of Chemical Physics

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The BrO radical, prepared by the BrϩO 3 reaction, has been investigated by ultraviolet photoelectron spectroscopy. Two vibrationally resolved bands were observed corresponding to the ionizations BrO ϩ (X 3 ⌺ Ϫ )←BrO(X 2 ⌸) and BrO ϩ (a 1 ⌬)←BrO(X 2 ⌸). These assignments are supported by the results of complete active space self-consistent field/multireference configuration interaction ͑CASSCF/MRCI͒ calculations performed as part of this work. The adiabatic ionization energies of these bands were measured as (10.46Ϯ0.02) and (11.21Ϯ0.02)eV, respectively. Measurement of the vibrational separations in these bands led to estimates of the vibrational constants in the ionic states of (840Ϯ30) cm Ϫ1 and (880Ϯ30) cm Ϫ1 , and Franck-Condon simulations of the vibrational envelopes gave values of the ionic state bond lengths of (1.635Ϯ0.005) and (1.641Ϯ0.005) Å for the X 3 ⌺ Ϫ and a 1 ⌬ states of BrO ϩ , respectively. The OϩBr 2 reaction was found to give a band at (10.26Ϯ0.02) eV associated with a reaction product. Comparison of the results obtained for the BrϩO 3 reaction showed that it could not be assigned to ionization of BrO. Calculations of the first adiabatic ionization energies and Franck-Condon simulations of the vibrational envelopes of the first photoelectron bands of BrO 2 and Br 2 O and their isomers demonstrated that this band corresponds to the first ionization of OBrO, the BrO 2 ϩ (X 1 A 1 )←BrO 2 (X 2 B 1 ) ionization. FranckCondon simulations were performed with the experimental geometry of BrO 2 (X 2 B 1 ) but with different cationic state geometries. The simulated envelope which most closely matched the experimental envelope gave geometrical parameters of r e ϭ1.6135 Å and ЄOBrOϭ117.5°for the ionic state.

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Section: Discussionmentioning

confidence: 99%

A study of the BrO and BrO2 radicals with vacuum ultraviolet photoelectron spectroscopy

Dyke

Gamblin

Hooper

et al. 2000

The Journal of Chemical Physics

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“…The photolysis of Cl 2 in the presence of 0 2 was studied primarily as a check on the new apparatus,_since the system has been intensively studied for more than 20 years [2,[5][6][7][8][9][10][11]. During the course of the study, it became apparent that there remained disagreement between different investigators of the low pressure region for the reaction, 2CIO~Cl 2 +0 2 • Porter [6] was the first to report the existence of the ClO radical in a mixture of chlorine and oxygen after flash photolysis by observing intense vibronic bands from 3100 to 2577 A.· Since its discovery, ClO has been observed in the same ultraviolet region by many investigators, [5,[7][8][9][10][11][12][13][14][15] with various methods of production. The electron spin resonance of the radical has been observed both in rigid solution [16] and in the gas phase [17,18].…”

Section: Discussionmentioning

confidence: 99%

Molecular Modulation Mass Spectrometry Kinetic Study of the ClO Free Radical

Johnston

1972

Bulletin des Soc Chimique

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In complex photochemical reactions the effective mechanism may be different at low and at high light intensities, since the ratio of radicals to reactants may approach unity at high light intensities and may be 10−4 or less at low light intensities (such as sunlight). The method of flash photolysis has been highly successful in measuring the spectra and kinetics of free radicals in systems of high light intensities. In this laboratory a method named “molecular modulation spectrometry” has been developed, which measures the spectra and lifetimes of free‐radicals in lowintensity photochemical systems. Previous versions have utilized infrared and ultraviolet spectrometry. In this article the method is extended to ion‐counting mass spectrometry. The molecular‐modulation mass spectrometer was used to re‐investigate the kinetics of the CIO radical at low pressure and at low light intensities. Studies by flash photolysis have shown that the CIO radical decays by simple, second‐order kinetics This study confirms the previous result found in low intensity photolysis of CI2 and O2 that the decay process is complex and dependent on inert gas The change in rate law between high and low light intensities and trends exhibited by the parameters, k′ and k″, show that we still do not have a complete understanding of the mechanism of this reaction.

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“…Koref [ 23 ] (-190°to 0°C) and Westrum and Pitzer [52] (l6°to 530°K) measured the heat capacity of potassium fluoride, KF. Westrum and Pitzer [ 52 ] used an adiabatic calorimeter for the range 16°to 323°K and a ''drop" calorimeter for the range 298°to 530°K.…”

Section: !Yomentioning

confidence: 99%

“…Westrum and Pitzer [ 52 ] used an adiabatic calorimeter for the range 16°to 323°K and a ''drop" calorimeter for the range 298°to 530°K. Their KF sample was prepared by thermal decomposition of KHF 2 first at 300°C and finally at 295°C.…”

Section: !Yomentioning

confidence: 99%

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Preliminary report on the thermodynamic properties of selected light-element and some related compounds:

1962

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This is the seventh semi-annual report on the current experimental, theoretical, and evaluative program, at the National Bureau of Standards, on the thermodynamic properties of selected light-element compounds of primary interest in high-temperature research. In this connection the chemical elements principally involved are H, Li, Be, B, C, N, 0, F, At, Cl, and Zr, with more secondary interest in the compounds of Mg, Si, K, Ti, Br, I, W, Hg, and Pb. The emphasis in the NBS work has been on the simpler compounds of these elements.This report includes some recent NBS measurements under the program: The heat of formation of nitronium perchlorate, and the high-temperature heat capacity of aluminum carbide. As discussed in the report, precise measurements are essentially completed on the heat of combustion of aluminum in fluorine and on the low-temperature heat capacities and absolute entropies of LiH, and LiAlH^; however, these data are not yet presented, pending the resolution of small discrepancies needed to put the results on a final basis. Tables of thermodynamic functions are given for four gases omitted from earlier reports (H 2 > 02> H , and electron gas), and, on the basis of improved data, for the condensed phases of two substances (BeF 2 and At^C^) . A contribution from those areas in which elaborate apparatus development is still progressing is a description in the report of a new fast-opening large-aperture shutter for high-speed photography. This development will be important in the study of combustions at very high temperatures and pressures.Also included are several up-to-date literature surveys in the field.One describes recent additions to the literature on the chemistry of numerous light-element compounds. A second describes alloys and intermetallic compounds of aluminum and beryllium with titajaium and zirconium; while a third survey covers low-temperature heat capacities aud entropies of various substances, particularly the oxides of eight light elements. The fourth report is a comprehensive and critical assembly of the available values for the heats of formation of a large number of compounds. IntroductionNitronium perchlorate is a v;hite, crystalline material, stable at temperatures up to 120°C. It is extremely hygroscopic, reacting rapidly with water to form nitric and perchloric acids. Aqueous solutions of potassium hydroxide were used in this investigation, as the potassium salts of the acids provided more suitable reference substances. The heats of solution of KN0_(c) and KClO/c) in KOH(aq) were also determined. Constants and Conversion FactorsThe results of this investigation are given in joules and calories, with 1 cal = 4*1840 joules. All weights are corrected to vacuum. The molecular weights are calculated from the 1957 International Table of Atomic Weights [l]. For N02C10/(c) an estimated heat capacity of 36 cal/deg mole was used; other auxiliary data were taken where possible from [2].3. MaterialsThe KNO^(c) and KC10/(c) were reagent-grade materials, dried at 120°...

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Absorption Spectra of the Halogen Monoxides

Cited by 152 publications

References 2 publications

A study of the BrO and BrO2 radicals with vacuum ultraviolet photoelectron spectroscopy

A study of the BrO and BrO2 radicals with vacuum ultraviolet photoelectron spectroscopy

Molecular Modulation Mass Spectrometry Kinetic Study of the ClO Free Radical

Preliminary report on the thermodynamic properties of selected light-element and some related compounds:

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