Rotational relaxation of HF in a free‐jet expansion of dilute HF–He mixtures: Information content on state‐to‐state rate constants

1983 ◽  
Vol 78 (7) ◽  
pp. 4486-4493 ◽  
Author(s):  
T. E. Gough ◽  
R. E. Miller
Keyword(s):  
Information Content ◽  
Rate Constants ◽  
Rotational Relaxation ◽  
Free Jet ◽  
State Rate

State-to-state rate constants and rotational relaxation time in nitrogen

1996 ◽  
Vol 207 (1) ◽  
pp. 193-201 ◽  
Author(s):  
R.G. Sharafutdinov ◽  
A.E. Belikov ◽  
M.L. Strekalov ◽  
A.V. Storozhev
Keyword(s):  
Relaxation Time ◽  
Rate Constants ◽  
Rotational Relaxation ◽  
State Rate ◽  
Rotational Relaxation Time

The decomposition of aliphatic N-nitro amines in aqueous sulfuric acid. Bisulfate as a nucleophile

1996 ◽  
Vol 74 (10) ◽  
pp. 1774-1778 ◽  
Author(s):  
Robin A. Cox
Keyword(s):  
Sulfuric Acid ◽  
Water Molecule ◽  
Rate Constants ◽  
Activation Parameters ◽  
Standard State ◽  
Aqueous Sulfuric Acid ◽  
Alkyl Groups ◽  
Different Temperatures ◽  
State Rate ◽  
Acid Catalyzed

In aqueous sulfuric acid, aliphatic N-nitro amines decompose to N2O and alcohols. An excess acidity analysis of the observed rate constants for the reaction shows that free carbocations are not formed. The reaction is an acid-catalyzed SN2 displacement from the protonated aci-nitro tautomer, the nucleophile being a water molecule at acidities below 82–85% H2SO4, and a bisulfate ion at higher acidities. Bisulfate is the poorer nucleophile by a factor of about 1000. Twelve compounds were studied, of which results obtained for nine at several different temperatures enabled calculation of activation parameters for both nucleophiles. The reaction appears to be mainly enthalpy controlled. The intercept standard-state rate constants are well correlated by the σ* values for the alkyl groups; the slopes are negative, with a more negative value for the slower bisulfate reaction. Interestingly the m≠m* slopes also correlate with σ*, although the scatter is bad. Key words: N-nitro amines, excess acidity, bisulfate, nucleophiles, acid-catalyzed, kinetics.

scholarly journals Experimental and theoretical determination of rotational-translational state-to-state rate constants for N2:He collisions at low temperature (3

2003 ◽  
Vol 118 (10) ◽  
pp. 4477-4486 ◽  
Author(s):  
B. Maté ◽  
F. Thibault ◽  
A. Ramos ◽  
G. Tejeda ◽  
J. M. Fernández ◽  
...  
Keyword(s):  
Low Temperature ◽  
Rate Constants ◽  
Theoretical Determination ◽  
State Rate

scholarly journals State-to-state rotational relaxation rate constants for CO+Ne from IR–IR double-resonance experiments: Comparing theory to experiment

2004 ◽  
Vol 120 (16) ◽  
pp. 7483-7489 ◽  
Author(s):  
David A. Hostutler ◽  
Tony C. Smith ◽  
Gordon D. Hager ◽  
George C. McBane ◽  
Michael C. Heaven
Keyword(s):  
Relaxation Rate ◽  
Rate Constants ◽  
Double Resonance ◽  
Rotational Relaxation

Substituent effects on homolytic versus heterolytic photocleavage of (1-naphthylmethyl)trimethylammonium chlorides

1987 ◽  
Vol 65 (7) ◽  
pp. 1599-1607 ◽  
Author(s):  
B. Foster ◽  
B. Gaillard ◽  
N. Mathur ◽  
A. L. Pincock ◽  
J. A. Pincock ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Hydrogen Atom ◽  
Charge Distribution ◽  
Rate Constants ◽  
Bond Cleavage ◽  
Substituent Effects ◽  
Hydrogen Atom Transfer ◽  
Singlet Excited State ◽  
State Rate

Singlet excited state rate constants have been measured for both the heterolytic and homolytic photocleavage of 3- and 4-methoxy and 3- and 4-cyano (1-naphthylmethyl)trimethylammonium chlorides, 6–10. The results are interpreted in terms of the meta effect or changes in charge distribution upon excitation and the competition between bond cleavage, electron transfer, and hydrogen atom transfer in the contact pairs resulting from the two types of cleavage.

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