Electronic Spectra of the Azide Ion, Hydrazoic Acid, and Azido Molecules

1970 ◽  
Vol 52 (3) ◽  
pp. 1332-1340 ◽  
Author(s):  
J. R. McDonald ◽  
J. W. Rabalais ◽  
S. P. McGlynn
Keyword(s):  
Electronic Spectra ◽  
Hydrazoic Acid ◽  
Azide Ion

Thermochemistry and reactivity of the azides - I. Thermochemistry of the inorganic azides

1956 ◽  
Vol 235 (1200) ◽  
pp. 106-119 ◽  
Keyword(s):  
Heavy Metal ◽  
Alkali Metal ◽  
Alkaline Earth ◽  
Enthalpies Of Formation ◽  
Hydrazoic Acid ◽  
Explosive Decomposition ◽  
Dissociation Energies ◽  
Azide Ion ◽  
Heavy Metal Azides ◽  
Lattice Energies

The problems of structure and reactivity of the azides are of course closely related to their thermochemistry. Lattice energies, electron affinities and bond energies are especially important. Although numerous investigations have been made both into slow thermal decomposition and explosive decomposition of the azides interpretation has been hampered by lack of reliable thermochemical data. In the literature, only a collection of inconsistent and unreliable data for the heavy-metal azides is available; for the alkali-metal and alkaline-earth azides there are no data at all. This paper deals with the thermochemical relations of the azides and their application to reactivity. In part I the experimental determination of consistent enthalpy data for hydrazoic acid, the aqueous azide ion, the alkali metal, the alkaline-earth and heavy-metal azides is described. The values of the enthalpies of formation (∆ H o f in kcal mole -1 ) are: N - 3 Aq (55∙51 H 2 O), 65∙53; HN 3G , 71∙66; HN 3L , 64∙37; LiN 3 , 2∙58; NaN 3 , 5∙08; KN 3 , 0∙33; RbN 3 , -0∙07; CsN 3 , -2∙37; NH 4 N 3 , 26∙79; CaN 6 , 11∙03; SrN 6 , 1∙72; BaN 6 , -5∙32; CuN 3 , 67∙23; CuN 6 , 140∙4; AgN 3 , 74∙17; Hg 2 N 6 , 141∙5; T1N 3 , 55∙78; PbN 6 , 115∙5. From these and other measurements consistent values for free energies and entropies of the azides are derived. These primary thermodynamic data will be employed in part II of this paper to derive important thermochemical quantities not susceptible to direct measurement such as bond dissociation energies, lattice energies and the electron affinity of the azide ion.

THE REACTION OF NITROUS ACID WITH 4-SUBSTITUTED-THIOSEMICARBAZIDES

1957 ◽  
Vol 35 (8) ◽  
pp. 832-842 ◽  
Author(s):  
Eugene Lieber ◽  
C. N. Pillai ◽  
Ralph D. Hites
Keyword(s):  
Nitrous Acid ◽  
Relative Proportion ◽  
Chemical Degradation ◽  
Hydrazoic Acid ◽  
Melting Points ◽  
Pure Nitrogen ◽  
Competitive Reactions ◽  
Azide Ion ◽  
Lower Melting Point ◽  
Aryl Isothiocyanates

The reaction of nitrous acid with 4-alkyl- or 4-aryl-thiosemicarbazides, as well as the reaction of alkyl- or aryl-isothiocyanates with hydrazoic acid, leads to the identical 5-(substituted)amino-1,2,3,4-thiatriazole. This has been established by infrared absorption and chemical degradation studies. The reaction of the 5-(substituted)amino-1,2,3,4-thiatriazoles with aqueous bases leads to two competitive reactions: (1) degradation to an isothiocyanate and azide ion, and (2) isomerization to a 1-substituted-tetrazole-5-thiol, the extent of path (1) or (2) depending on the nature of the substituent. Path (1) predominates when the substituent is alkyl, whereas when the substituent is aryl both paths (1) and (2) occur, the relative proportion depending on the electrical nature of the aromatic group, path (2) increasing as the electronegativity increases. The 1-aryl-tetrazole-5-thiols were found to be thermally unstable at their melting points, degrading more or less violently to one mole proportion of pure nitrogen with the formation of sulphur and organic products of lower melting point as yet unidentified. Theories to account for these observations are presented and discussed.

ISOMERIC 5-(SUBSTITUTED)AMINOTHIATRIAZOLE AND 1-SUBSTITUTED-TETRAZOLINETHIONES

1959 ◽  
Vol 37 (1) ◽  
pp. 101-109 ◽  
Author(s):  
Eugene Lieber ◽  
J. Ramachandran
Keyword(s):  
Electrical Properties ◽  
Sodium Azide ◽  
Side Reactions ◽  
Hydrazoic Acid ◽  
Azide Ion ◽  
Rearrangement Mechanism

The reaction of organic isothiocyanates with sodium azide in ethanol and water has been investigated. Water is shown to be the more advantageous solvent for this reaction giving higher yields and initially purer 1-substituted-tetrazoline-5-thiones. A series of these latter compounds was made by this procedure. The yield of product appears to be dependent on the electrical properties of the substituent of the isothiocyanate, the yields decreasing as the electron-donating properties increase. A series of new 4-substituted-thiosemicarbazides has been prepared and converted by diazotization to the corresponding 5-(substituted)aminothiatriazoles. A theory to account for the differences in the mode of reaction of hydrazoic acid and azide ion is presented and discussed. The basic conversion of 5-(substituted)aminothiatriazoles to 1-substituted-tetrazolinethiones may involve a simple dearrangement–rearrangement mechanism complicated by side reactions. A summary of known isomeric 5-(substituted)aminothiatriazoles and 1-substituted-tetrazolinethiones is presented.

Electronic structure of hydrazoic acid and the azide ion from x-ray and ultraviolet electron spectroscopy

1975 ◽  
Vol 97 (17) ◽  
pp. 4845-4851 ◽  
Author(s):  
Ting Ho Lee ◽  
Richard J. Colton ◽  
Michael G. White ◽  
J. Wayne Rabalais
Keyword(s):  
Electronic Structure ◽  
Electron Spectroscopy ◽  
Hydrazoic Acid ◽  
X Ray ◽  
Azide Ion

ChemInform Abstract: ELECTRONIC STRUCTURE OF HYDRAZOIC ACID AND THE AZIDE ION FROM X-RAY AND ULTRAVIOLET ELECTRON SPECTROSCOPY

1975 ◽  
Vol 6 (43) ◽  
pp. no-no
Author(s):  
TING HO LEE ◽  
RICHARD J. COLTON ◽  
MICHAEL G. WHITE ◽  
J. WAYNE RABALAIS
Keyword(s):  
Electronic Structure ◽  
Electron Spectroscopy ◽  
Hydrazoic Acid ◽  
X Ray ◽  
Azide Ion

scholarly journals METHOD OF REGENERATION OF AZIDE ION

2017 ◽  
Vol 20 (7) ◽  
pp. 163-167
Author(s):  
E.L. Vikulina ◽  
E.E. Romashin ◽  
D.I. Fedorov ◽  
I.K. Kukushkin ◽  
A.M. Pyzhov ◽  
...  
Keyword(s):  
Quaternary Ammonium ◽  
Reaction Mass ◽  
Hydrazoic Acid ◽  
Organic Azides ◽  
Highly Active ◽  
Azide Ion ◽  
Liquid Wastes ◽  
First Time

In this article the results of research devoted to the development of methods of disposal and regeneration of azide ion contained in the liquid wastes are stated. As a rule, all existing methods of disposal of azide ion in the liquid wastes based on its destruction, which is not only economically impractical because it is irretrievably lost, but also dangerous, as this forms an extremely explosive and toxic hydrazoic acid, which significantly increases the risk of the process of disposal of liquid wastes. Researches carried out by the authors allowed for the first time to suggest an effective method of disposal of azide ion at producing organic azides that consists in deletion of azide ion from reaction mass in the form of azide of quaternary ammonium which is highly active azidating agent and can be effectively used in the processes of getting organic azides. In this case at getting organic azides before its finishing quaternary amonium chloride is added to the reaction mass.

The electronic spectra of diphenyl-sulphide and DI-2-pyridyl-sulphide. A CNDO/S treatment

1976 ◽  
Vol 73 ◽  
pp. 523-526 ◽  
Author(s):  
Vinicio Galasso ◽  
Giuseppe C. Pappalardo ◽  
Giuseppe Scarlata
Keyword(s):  
Electronic Spectra
Sign in / Sign up

Export Citation Format

Share Document