摘要:

Abstract—The intensity of the (0, 0) (1Σ+g‐3Σ‐g) emission band of oxygen near 7600Å (which system is observed also in the night air‐glow) has been used to investigate the formation and removal of 02(1Σ+g) in the products of an r.f. discharge in dry oxygen at total pressures of 0.8–6 mm Hg and at 300†K. The concentration of O2(1Σ+g) was found to be about 10‐4mm Hg in a total pressure of 1 mm Hg. No change of concentration of O2(1Σ+g) withtime, nor with oxygen atom concentration (for the same discharge conditions), could be observed. The results show that considerable amounts of metastable O2(1Σ+g) molecules are formed within the discharge, and that virtually no formation of this species occurs by recombination of ground state oxygen atoms in the afterglow. 02(1Σ+g) may also be formed from other metastable species in the afterglow [such as O2(lΔg], if the rates of production and removal of O2(1Σ+g) are equal.Ozone removed O(1Σ+g), and simultaneously O(3P) atoms were formed, suggesting that the exothermic reaction 03+02(1Σ+g) = 0(3P)

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09286.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—The temperature dependence and the absolute emission intensity of the 6340 Å band of molecular oxygen have been measured. The results indicate that the emitting pair of molecules is not bound and possesses a radiative half life of about 25 msec. The implications of these results on some chemiluminescent reactions are discuss

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09287.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—The only detectable emission from discharged oxygen was a band system at 7619 Å. However, when a film of mercuric oxide was interposed between the discharge and the observation position, the intensity of this band was greatly enhanced and additional bands were observed at 6340, 7030 and at 12,700 Å, in agreement with the findings of Bader and Ogryzlo. A linear relationship, however, was found between the intensities at 6340 and at 12,700 Å, instead of the quadratic dependence reported by these authors.A rapid reaction was found to occur between O3, and O2>(1Σ+g) molecules but the reappearance of the 7619 Å, emission after all the O3had been reacted indicates a production process of O2(1Σ+g) molecules, probably from O2(1Δg).The value of the rate constant for the reaction 02(1Σ+g) + O3→2O2+ Ois approximately 6times10‐13cm3/molecule per sec. The rate constant for the comparable reaction with O2(1Δg) molecules is probably lower than this by a facto

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09288.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—Investigations of the systems O—CH4and, O—n‐C4H10have been made, using techniques for producing atomic oxygen in the presence and absence of ground state molecular oxygen. The results indicated that the initial rate of removal of atomic oxygen from both systems was accelerated by the presence of molecular oxygen, whereas the initial rate of removal of hydrocarbon, for n‐butane, was affected little if at all.The relative concentrations of atomic oxygen, hydrocarbon and molecular oxygen appeared to govern the overall stoichiometry. It is concluded that rate constants observed in the absence of O2and when [RH] ≥ [O], are probably a more reliable measure of the primary step:O +

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09289.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—A spectroscopic investigation has been made of the chemiluminescent emission from atomic flames produced by the addition of volatile silicon compounds to active nitrogen. Of seven such additives, SiCI6proved to be the most intense source for SiN emission. The two electronic systems of SiN, theB2Σ‐X2ΣandC‐A2II, were detected both in the reaction vessel glow and also in an intense glow from a liquid nitrogen trap.An analysis of the relative vibration populations in the B2Σ electronic state of SiN showed large population inversions with a maximum population in thev= 5 level. A strong rotational perturbation of theB2Σ‐X2Σ SiN system atv'= 4 in theK' =13, 14, 19 and 21 levels indicated a leakage occurring from these perturbed levels into those of the perturbing state.The finding that bands of theC‐A2II system of SiN in the trap glow were enhanced in intensity relative to theB2Σ‐X2Σ system has made a reinvestigation of the system possible. New bands of this system are reported and an analysis shows the need to increase the original numbering ofv“by one.Two new and unidentified spectra have been recorded which result from the addition of silicon compounds to active nitrogen—a green system in the 5180 to 6020 Å region. produced by SiCI4, and an orange chemiluminescence, 5540 to 7250 Å. throu

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09290.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—New additional experimental data were obtained to give further information pertinent to the mechanism for the chemiluminescent NO—O‐atom reaction. Results were obtained for the change of emission intensities from 10 to 300 microns pressure. Some studies were also made of the effect of various third bodies. The results support a simple two body recombination for the mechanism for the light emission: NO+O+N

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09291.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—The rapid bimolecular reaction SO + O3= SO2+O2+ 106 kcal/moleyields electronically excited SO2in the3B1and1B2states with some vibrational excitation, as well as SO2in its electronic ground state. It is shown thatk1= 1.5x1012exp (‐2100/RT) cm2mole‐1s‐1and that the formation of electronically excited SO2involves higher activation e

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09292.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—Methods for the absolute measurement of the spectral sensitivity of phototubes are reviewed in detail. Several experimental arrangements are described for the independent determination of these values to insure the elimination of systematic error. On the basis of these measurements a rapid, simple technique is described for measuring the average absolute spectral sensitivity of a phototube over a defined emission spectrum, thus obviating the original tedious point‐by‐point methods and allowing frequent re‐Standardization. The application of these standardized phototubes to the measurement of the absolute quantum yields of the chemiluminescence of luminol and the bioluminescence of luminous bacteria and the firefly is described. An absolute low‐level light emission standard in the form of the luminol chemiluminescence reaction, either in aqueous or in the non‐aqueous solvent dimethylsulfoxide is proposed for general use and the conditions for its use are described in detail. It should therefore be possible for any researcher to obtain an absolute calibration, in his own experimental geometry, in the blue region of t

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09293.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—The total radiant flux from a solution containing a radioactive compound, hexadecme‐l‐14C, plus an appropriate scintillator, has been determined. The procedure used involves comparison of its luminescent emission with the light scattered by glycogen illuminated with a monochromatic homogeneous light beam of known photon flux. These standards are particularly convenient for use with chemiluminescent and bioluminescent reactions, since the geometry of the emission may be duplicated ex

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09294.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY

摘要:

Abstract—A methodology for the determination of chemiluminescence quenching terms is given. By using the oxidation of tetrakis(dimethylamino)ethylene as an example, it is shown how the nature and magnitude of the quenching terms help to elucidate the reaction mechanism, or how ignoring them can lead to false impressions. It is shown that chemiluminescence quenching effects need not be the same as those for photoluminescence of the same electronically excited specie

ISSN:0031-8655    

DOI:10.1111/j.1751-1097.1965.tb09295.x

出版商:Blackwell Publishing Ltd    

年代:1965

数据来源: WILEY