Gas-phase Lewis acid-base interactions. An experimental determination of cyanide binding energies from ion cyclotron resonance and high-pressure mass spectrometric equilibrium measurements

1988 ◽  
Vol 110 (23) ◽  
pp. 7604-7609 ◽  
Author(s):  
J. W. Larson ◽  
J. E. Szulejko ◽  
T. B. McMahon
Keyword(s):  
High Pressure ◽  
Gas Phase ◽  
Lewis Acid ◽  
Cyclotron Resonance ◽  
Mass Spectrometric ◽  
Binding Energies ◽  
Ion Cyclotron Resonance ◽  
Acid Base ◽  
Cyanide Binding

Solvation of Cl− and O2− with H2O, CH3OH, and CH3CN in the gas phase

1973 ◽  
Vol 51 (15) ◽  
pp. 2507-2511 ◽  
Author(s):  
R. Yamdagni ◽  
J. D. Payzant ◽  
P. Kebarle
Keyword(s):  
High Pressure ◽  
Temperature Dependence ◽  
Gas Phase ◽  
Experimental Technique ◽  
Equilibrium Constants ◽  
Ion Source ◽  
Mass Spectrometric ◽  
Mass Spectrometric Detection ◽  
Free Energies

Determination of the temperature dependence of the equilibrium constants Kn,n−1 for the reactions A −Bn = A −Bn−1 + B where A− equals Cl− and O2− and B is HOH, CH3OH, or CH3CN leads to the corresponding ΔH0n−1, ΔG0n−1,n, and ΔS0n−1,n values. The experimental technique is based on mass spectrometric detection of ions escaping from a high pressure ion source. At n = 1, Cl− is solvated most strongly by methanol, then CH3CN and HOH. At higher n a cross over is observed with water becoming the best solvent. These results are in agreement with the positive transfer enthalpies and free energies for Cl− from the liquid solvents HOH → CH3OH and HOH → CH3CN reported in the literature.O2− is solvated more strongly than Cl− appearing thus as an ion of "size" intermediate between Cl− and F− Again CH3OH gives the highest interaction for n = 1, however for n > 1 water gives stronger interactions.

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