Online citations, reference lists, and bibliographies.
← Back to Search

Bulk Gas-phase Acidity.

D. Himmel, Sascha K. Goll, I. Leito, I. Krossing
Published 2012 · Chemistry, Medicine

Cite This
Download PDF
Analyze on Scholarcy
Share
The capability of a gaseous Brønsted acid HB to deliver protons to a base is usually described by the gas-phase acidity (GA) value of the acid. However, GA values are standard Gibbs energy differences and refer to individual gas pressures of 1 bar for acid HB, base B(-), and proton H(+). We show that the GA value is not suited to describe the bulk acidity of a gaseous acid. Here the pressure dependence of the activities of HB, H(HB)(n)(+), and B(HB)(m)(-) that result from gaseous autoprotolysis have to be considered. In this work, the pressure-dependent absolute chemical potential of the proton in the representative gaseous proton acids CH(4), NH(3), H(2)O, HF, and HCl was worked out and the general theory to describe bulk gas phase acidity--that can directly be compared with solution acidity--was developed.
This paper references
10.1016/0009-2614(95)00838-U
Auxiliary basis sets to approximate Coulomb potentials (Chem. Phys. Letters 240 (1995) 283-290)
Karin Eichkorn (1995)
10.1002/(SICI)1096-987X(19960115)17:1<30::AID-JCC3>3.0.CO;2-1
Superacidity of neutral Brönsted acids in gas phase
P. Burk (1996)
10.1021/jp905449k
Gas-phase Brønsted superacidity of some derivatives of monocarba-closo-borates: a computational study.
Lauri Lipping (2009)
10.1016/J.THEOCHEM.2010.06.029
Gas phase acidities and associated equilibrium isotope effects for selected main group mono- and polyhydrides, carbon acids, and oxyacids: A G4 and W1BD study
S. Rayne (2010)
10.1002/cphc.200800305
Boratabenzene Anions C5B(CN)6(-) and C5B(CF3)6(-) and the superacidic properties of their conjugate acids.
Agnes Kütt (2009)
10.1039/B515623H
Accurate Coulomb-fitting basis sets for H to Rn.
F. Weigend (2006)
10.1021/JA036611J
True stabilization energies for the optimal planar hydrogen-bonded and stacked structures of guanine...cytosine, adenine...thymine, and their 9- and 1-methyl derivatives: complete basis set calculations at the MP2 and CCSD(T) levels and comparison with experiment.
P. Jurečka (2003)
10.1016/S0009-2614(02)01423-9
On the convergence of the (ΔECCSD(T)−ΔEMP2) term for complexes with multiple H-bonds
P. Jurečka (2002)
10.1002/chem.201003164
Anchor points for the unified Brønsted acidity scale: the rCCC model for the calculation of standard Gibbs energies of proton solvation in eleven representative liquid media.
D. Himmel (2011)
10.1103/PHYSREVA.38.3098
Density-functional exchange-energy approximation with correct asymptotic behavior.
Becke (1988)
10.1016/S0009-2614(02)01084-9
An efficient implementation of second analytical derivatives for density functional methods
P. Deglmann (2002)
10.1103/PHYSREVB.33.8822
Density-functional approximation for the correlation energy of the inhomogeneous electron gas.
Perdew (1986)
10.1063/1.469408
Efficient molecular numerical integration schemes
Oliver Treutler (1995)
10.1021/J100076A029
Thermodynamics of the Electron and the Proton
J. Bartmess (1994)
10.1021/ja908964h
Investigating the weak to evaluate the strong: an experimental determination of the electron binding energy of carborane anions and the gas phase acidity of carborane acids.
Matthew M. Meyer (2009)
10.1002/ANGE.201000252
Eine vereinheitlichte pH‐Skala für alle Phasen
D. Himmel (2010)
10.1080/00268970412331333429
A ‘universal’ B3LYP-based method for gas-phase molecular properties: bond dissociation enthalpy, ionization potential, electron and proton affinity and gas-phase acidity
J.S. Wright * (2005)
10.1021/jp104917a
Gas-phase basicities around and below water revisited.
I. Leito (2010)
10.1016/J.IJMS.2007.02.018
Gas-phase acidities of the 20 protein amino acids
C. M. Jones (2007)
10.1103/physrevb.34.7406
Erratum: Density-functional approximation for the correlation energy of the inhomogeneous electron gas
Perdew (1986)
10.1039/B508541A
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy.
F. Weigend (2005)
10.1021/jp903780k
Revision of the gas-phase acidity scale below 300 kcal mol(-1).
I. Leito (2009)
By chance, scaling factors for BP86/def-TZVP frequencies are very close to unity
10.1021/jp100888k
Experimental and theoretical gas-phase acidities, bond dissociation energies, and heats of formation of HClO(x), x = 1-4.
Matthew M. Meyer (2010)
10.1016/J.THEOCHEM.2007.03.017
Anions N[C(CN)2]3- and P[C(CN)2]3- and the superacidic properties of their conjugate acids
I. Leito (2007)
10.1021/JP072431A
Basis set limit coupled cluster study of h-bonded systems and assessment of more approximate methods.
A. D. Boese (2007)
10.1016/0020-7381(80)85015-7
Non-ideal behaviour of weakly ionized gases
T. Mcmahon (1980)
10.1016/S0009-2614(00)00566-2
Critical test of performance of B3LYP functional for prediction of gas-phase acidities and basicities
P. Burk (2000)
10.1080/00268979909482993
The MP2 limit correction applied to coupled cluster calculations of the electronic dissociation energies of the hydrogen fluoride and water dimers
W. Klopper (1999)
10.1016/j.jasms.2008.06.026
Determination of gas-phase acidities of dimethylphenols: Combined experimental and theoretical study
P. Madeira (2008)
10.1063/1.1523393
Efficient characterization of stationary points on potential energy surfaces
P. Deglmann (2002)
10.1021/JP063552Y
Aqueous solvation free energies of ions and ion-water clusters based on an accurate value for the absolute aqueous solvation free energy of the proton.
C. Kelly (2006)
10.1021/JA0000753
Gas-Phase Acidities of Some Neutral Brønsted Superacids: A DFT and ab Initio Study
I. Koppel (2000)
10.1021/JA00086A038
The Gas-Phase Acidities of Very Strong Neutral Bronsted Acids
I. Koppel (1994)
10.1002/anie.201000252
A unified pH scale for all phases.
D. Himmel (2010)
10.1016/0009-2614(89)85118-8
ELECTRONIC STRUCTURE CALCULATIONS ON WORKSTATION COMPUTERS: THE PROGRAM SYSTEM TURBOMOLE
R. Ahlrichs (1989)
10.1063/1.463096
Fully optimized contracted Gaussian basis sets for atoms Li to Kr
A. Schaefer (1992)



This paper is referenced by
10.1016/J.JCAT.2018.01.035
Ab initio study of CO 2 hydrogenation mechanisms on inverse ZnO/Cu catalysts
Thomas Reichenbach (2018)
10.1038/s41598-017-10156-w
Predicting the Ionic Product of Water
E. Perlt (2017)
10.1002/cphc.201402906
Absolute Brønsted Acidities and pH Scales in Ionic Liquids.
D. Himmel (2015)
10.1002/chem.201500034
Protic anions [H(B12X12)]- (X = F, Cl, Br, I) that act as Brønsted acids in the gas phase.
Carsten Jenne (2015)
10.1021/jo400915f
Theoretical study on the acidities of chiral phosphoric acids in dimethyl sulfoxide: hints for organocatalysis.
Chen Yang (2013)
10.1039/C3QO00070B
Computation of standard equilibrium acidity of C–H acids in ionic media: shedding light on predicting changes of chemical behavior by switching solvent system from molecular to ionic
Xiao-Song Xue (2014)
10.1021/ja511639b
Scales of Lewis basicities toward C-centered Lewis acids (carbocations).
H. Mayr (2015)
10.1007/s10870-019-00773-w
Insights into the Structure of Halide-Rich Hydrochloric and Hydrobromic Acid: A Structural and Quantum-Chemical Investigation of the [H6X4O2]2− (X = Cl, Br) Anions
Philipp Bertocco (2019)
10.1002/anie.201709057
Basic Remarks on Acidity.
D. Himmel (2018)
10.1039/c5cs00672d
Reactive p-block cations stabilized by weakly coordinating anions
Tobias A Engesser (2016)
10.1039/c4dt02822h
From unsuccessful H2-activation with FLPs containing B(Ohfip)3 to a systematic evaluation of the Lewis acidity of 33 Lewis acids based on fluoride, chloride, hydride and methyl ion affinities.
H. Böhrer (2015)
10.1021/jo402605n
Computational study on the pKa shifts in proline induced by hydrogen-bond-donating cocatalysts.
Xiao-Song Xue (2014)
10.1002/chem.201302473
The protoelectric potential map (PPM): an absolute two-dimensional chemical potential scale for a global understanding of chemistry.
V. Radtke (2014)
10.1002/ANGE.201709057
Grundlegende Bemerkungen zur Azidität
D. Himmel (2018)
Semantic Scholar Logo Some data provided by SemanticScholar