State-to-state rate constants for the rotational relaxation of CH(B 2Σ−,v=0,J) in inelastic collisions with Ar

2001 ◽  
Vol 114 (14) ◽  
pp. 6160-6165 ◽  
Author(s):  
M. Kind ◽  
F. Stuhl
1996 ◽  
Vol 207 (1) ◽  
pp. 193-201 ◽  
Author(s):  
R.G. Sharafutdinov ◽  
A.E. Belikov ◽  
M.L. Strekalov ◽  
A.V. Storozhev

1996 ◽  
Vol 74 (10) ◽  
pp. 1774-1778 ◽  
Author(s):  
Robin A. Cox

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.


2003 ◽  
Vol 118 (10) ◽  
pp. 4477-4486 ◽  
Author(s):  
B. Maté ◽  
F. Thibault ◽  
A. Ramos ◽  
G. Tejeda ◽  
J. M. Fernández ◽  
...  

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

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