Vacuum ultraviolet chemiluminescence from the reactions of active nitrogen with I2, IBr, ICI, and ICN

1968 ◽  
Vol 46 (8) ◽  
pp. 1429-1434 ◽  
Author(s):  
L. F. Phillips
Keyword(s):  
Energy Transfer ◽  
Emission Intensity ◽  
Vacuum Ultraviolet ◽  
Nitrogen Molecule ◽  
Emission Lines ◽  
Kcal Mole ◽  
Active Nitrogen ◽  
Excitation Mechanisms ◽  
Excited Nitrogen ◽  
Cl Atoms

Numerous emission lines from excited I, Br, and Cl atoms have been observed between 1261 and 2062 Å. For the flames with I2, IBr, and ICl it is possible to assign excitation mechanisms on the basis of the dependence of emission intensity on either [N] or [N]2. In the case of dependence on [N] the emission is the result of energy transfer from an excited nitrogen molecule, which is produced by reaction of N with NI, has an energy of 185 ± 3.5 kcal/mole, and is identified with the predicted 3Δu species. The dissociation energy of NI is found to lie between 35.6 and 40 + 3.5 kcal/mole. It is proposed that excited nitrogen molecules can be produced as well as removed very rapidly by processes of the type[Formula: see text]

INTENSITIES OF EMISSION LINES IN FLAMES OF METAL HALIDES WITH ACTIVE NITROGEN

1963 ◽  
Vol 41 (8) ◽  
pp. 2060-2066 ◽  
Author(s):  
L. F. Phillips
Keyword(s):  
Energy Transfer ◽  
Energy Transfer Process ◽  
Nitrogen Molecule ◽  
Spectral Lines ◽  
Emission Lines ◽  
Metal Halides ◽  
Kcal Mole ◽  
Active Nitrogen ◽  
Atom Concentration ◽  
Excitation Mechanisms

The intensities of spectral lines emitted by flames of a number of metal halides with active nitrogen have been found to vary as the square of the nitrogen atom concentration. When the total energy required for simultaneous dissociation of the halide and excitation of the metal atom is less than about 200 kcal/mole the energy transfer process is too efficient to be attributed to the termolecular reaction of a halide molecule with a pair of nitrogen atoms. The observations are consistent with the hypothesis that in this case energy is transferred to the halide molecule during collision with a nitrogen molecule in the 5Σg+ state. Possible excitation mechanisms are discussed for less intense lines which would require up to 276 kcal/mole for simultaneous dissociation and excitation.

THE CHEMILUMINESCENT REACTION OF ACTIVE NITROGEN WITH THALLOUS HALIDES

1963 ◽  
Vol 41 (3) ◽  
pp. 732-738 ◽  
Author(s):  
L. F. Phillips
Keyword(s):  
Energy Transfer ◽  
Light Emission ◽  
Bimolecular Reaction ◽  
Emission Lines ◽  
Kcal Mole ◽  
Third Order ◽  
Active Nitrogen ◽  
Simultaneous Production ◽  
Chemiluminescent Reaction ◽  
Overall Efficiency

Energy transfer from active nitrogen to gaseous thallous halides leads to dissociation of the halide molecules with simultaneous production of excited thallium atoms. Thallium emission lines have been observed to correspond to the transfer of up to 221 kcal/mole to the TlX molecule. The process is kinetically third order but the high overall efficiency of light emission and thallous halide destruction requires a mechanism which involves a bimolecular reaction of TlX with an excited N2 formed during N-atom recombination.

Spectroscopic study of the reaction of active nitrogen with some organometallic compounds

1967 ◽  
Vol 45 (16) ◽  
pp. 1891-1896 ◽  
Author(s):  
R. E. March ◽  
H. I. Schiff
Keyword(s):  
Energy Transfer ◽  
Spectroscopic Study ◽  
Organometallic Compounds ◽  
Initial Energy ◽  
Emission Lines ◽  
Kcal Mole ◽  
Vibrationally Excited ◽  
Active Nitrogen ◽  
Metal Atoms

Transfer of energy from constituents in active nitrogen to gaseous organometallic compounds leads to dissociation of the organometallic and excitation of CN and (or) metal atom. Organometallic compounds of aluminium, zinc, and boron were used in this investigation. The observed emission lines from metal atoms and highly vibrationally excited CN correspond to an initial energy transfer in excess of 200 kcal/mole. The possible role of N2(5Σg+) molecules as excitors is discussed in the light of the results obtained.

Vacuum ultraviolet emission by active nitrogen. III. The absolute rates of population of N 2 (a 1 Π g ) and CO(A 1 Π)

1972 ◽  
Vol 330 (1580) ◽  
pp. 109-120 ◽  
Keyword(s):  
Energy Transfer ◽  
Vacuum Ultraviolet ◽  
Rate Coefficients ◽  
Simple Pattern ◽  
Ultraviolet Emission ◽  
Active Nitrogen ◽  
The Absolute ◽  
Detailed Kinetics ◽  
Individual Rate ◽  
Co Concentrations

A study of the detailed kinetics and particularly the CO 2 quenching of CO fourth positive emission from active nitrogen has yielded individual rate coefficients for the energy transfer from N 2 (a 1 Π g ), v = 0, 1 and 2 to CO(A 1 Π), v = 0 - 4. These do not follow any simple pattern. At high CO concentrations, an additional population of CO(A 1 Π), v = 1 and 6 from high levels of N 2 (a 1 Π g ) and (a' 1 ∑ u - ) occurs via the intermediacy of CO(I 1 ∑ - ).

scholarly journals An application of the Stern-Gerlach experiment to the study of active nitrogen

1930 ◽  
Vol 127 (806) ◽  
pp. 678-689 ◽  
Keyword(s):  
Dissociation Energy ◽  
Ground State ◽  
Excited Molecule ◽  
Nitrogen Molecule ◽  
Triple Collision ◽  
Chemical Activity ◽  
Active Nitrogen ◽  
Excited Nitrogen ◽  
Energy Relations ◽  
Normal Nitrogen

Many theories have been put forward at one time or another to explain the chemical activity of “active nitrogen” and the mechanism of the production of the yellow “after-glow.” Reunion of nitrogen atoms to form molecules, metastable molecules and interactions between atoms and molecules have all been drawn upon to explain the after-glow. At the time the work described in the present paper was commenced the theory holding the field was that of Sponer. According to this theory two normal nitrogen atoms collide in a triple collision with a normal nitrogen molecule with the resultant formation of one normal nitrogen molecule and one excited molecule. Since the carrier of the after-glow is known to be an excited nitrogen molecule with about 11⋅5 volts energy, and since the dissociation energy was then believed to be 11⋅5 volts, the theory seemed to explain the energy relations of active nitrogen satisfactorily. The comparative rareness of such a triple collision was in agreement with the long life of the after-glow. On this theory the chemical activity would be attributed to the nitrogen atoms (in their ground state). A support for this theory would have been obtained if it could have been shown that nitrogen atoms in their ground state, which is known to be a 4 S state, are present in active nitrogen. Later work has, however, shown that the dissociation energy of the nitrogen molecule is about 9⋅1 volts and not 11⋅5 volts as supposed by Sponer, and hence the theory cannot be valid.

Vacuum ultraviolet emission by active nitrogen. I. The formation and removal of N 2 (a 1 Π g )

1972 ◽  
Vol 330 (1580) ◽  
pp. 79-95 ◽  
Keyword(s):  
Ground State ◽  
Vibrational Relaxation ◽  
Emission Intensity ◽  
Vacuum Ultraviolet ◽  
Ultraviolet Emission ◽  
Active Nitrogen ◽  
Parallel Processes

The emission of the Lyman-Birge-Hopfield bands of N 2 (a 1 Π g ) - X 1 ∑ g + ), v ' ≤ 6 in active nitrogen is shown to originate from the recombination of ground state nitrogen atoms. Two parallel processes occur: ( а ) A two-body inverse predissociation populates rotational levels J > 13 of N 2 (a 1 Π g ), v ' = 6, from which there is rapid rotational and vibrational relaxation; this gives an emission intensity proportional to [N] 2 . ( b ) The reaction N( 4 S) + N 2 (B 3 Π g ) = N 2 (a 1 Π g ) + N( 4 S) (5) populates mainly lower levels of the a a 1 Π g state giving emission proportional to [N] 3 which is enhanced by argon carriers. Some measurements on N 2 (a' 1 ∑ u - ), v ' = 0 are also reported.

EFFECT OF ADDED AMMONIA ON THE REACTIONS OF ACTIVE NITROGEN WITH CH4, C2H6, AND C2H4

1962 ◽  
Vol 40 (7) ◽  
pp. 1291-1295 ◽  
Author(s):  
A. N. Wright ◽  
C. A. Winkler
Keyword(s):  
Nitrogen Molecule ◽  
Reaction Vessel ◽  
Active Nitrogen ◽  
Flame Emission ◽  
Excited Nitrogen

The small HCN yield from the CH4 and C2H6 reactions in an unheated, cylindrical reaction vessel is greatly reduced in the presence of added NH3. The addition of NH3 completely quenches the flame emission from the CH4 reaction, and greatly reduces that from the C2H6 and C2H4 reactions. Both flame emission and HCN production from the CH4 and C2H6 reactions appear to be initiated, at reaction temperatures of about 83 °C, by an excited nitrogen molecule similar to that responsible for NH3 decomposition.

THE STUDY OF VIBRATIONALLY EXCITED N2 MOLECULES WITH THE AID OF AN ISOTHERMAL CALORIMETER

1963 ◽  
Vol 41 (4) ◽  
pp. 903-912 ◽  
Author(s):  
J. E. Morgan ◽  
H. I. Schiff
Keyword(s):  
Microwave Discharge ◽  
Reaction Vessel ◽  
Kcal Mole ◽  
Collision Efficiency ◽  
Vibrationally Excited ◽  
Active Nitrogen ◽  
First Case ◽  
Nitrogen Stream ◽  
Excited Nitrogen ◽  
Isothermal Calorimeter

Vibrationally excited nitrogen molecules produced both by a microwave discharge in nitrogen and also by the reaction[Formula: see text]have been examined using an isothermal calorimetric probe.In the first case the energy associated with an 'active' nitrogen stream, due to vibrationally excited N2, was found to be 6.03 kcal mole−1 of total nitrogen. The subsequent relaxation of this species was found to occur almost entirely on the walls of the reaction vessel, with a collision efficiency of 4.5 × 10−4. The addition of other gases greatly accelerated the homogeneous relaxation rate. Collisional efficiencies of N2O, CO2, and Ar were found to be 0.8 × l0−4, 2.3 × 10−5, and 1.0 × 10−6 respectively.The vibrationally excited nitrogen produced by the N/NO reaction was found to possess 20 ± 4 kcal mole−1 of energy compared with the maximum of 75 kcal mole−1 allowed by the exothermicity of the reaction.

scholarly journals Down-Shifting in the YAM: Ce3+ + Yb3+ System for Solar Cells

Materials ◽  
2021 ◽  
Vol 14 (11) ◽  
pp. 2753
Author(s):  
Bartosz Fetliński ◽  
Sebastian Turczyński ◽  
Michał Malinowski ◽  
Paweł Szczepański
Keyword(s):  
Energy Transfer ◽  
Emission Intensity ◽  
Potential Application ◽  
Single Photon ◽  
Solar Spectrum ◽  
Excitation Power ◽  
Photovoltaic Devices ◽  
Photoluminescence Properties ◽  
System A ◽  
Down Conversion

In this work, we investigate Ce3+ to Yb3+ energy transfer in Y4Al2O9 (YAM) for potential application in solar spectrum down-converting layers for photovoltaic devices. Photoluminescence properties set, of 10 samples, of the YAM host activated with Ce3+ and Yb3+ with varying concentrations are presented, and the Ce3+ to Yb3+ energy transfer is proven. Measurement of highly non-exponential luminescence decays of Ce3+ 5d band allowed for the calculation of maximal theoretical quantum efficiency, of the expected down-conversion process, equal to 123%. Measurements of Yb3+ emission intensity, in the function of excitation power, confirmed the predominantly single-photon downshifting character of Ce3+ to Yb3+ energy transfer. Favorable location of the Ce3+ 5d bands in YAM makes this system a great candidate for down-converting, and down-shifting, luminescent layers for photovoltaics.

The afterglow and energy transfer mechanisms of active nitrogen

1970 ◽  
Vol 33 (1) ◽  
pp. 269-306 ◽  
Author(s):  
J Anketell ◽  
R W Nicholls
Keyword(s):  
Energy Transfer ◽  
Active Nitrogen ◽  
Transfer Mechanisms
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