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Evaluated Gas Phase Basicities and Proton Affinities Of

By Lias, Sharon G.

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Book Id: WPLBN0000659442
Format Type: PDF eBook
File Size: 8.18 MB.
Reproduction Date: 2005
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Title: Evaluated Gas Phase Basicities and Proton Affinities Of  
Author: Lias, Sharon G.
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Language: English
Subject: Technology., Reference materials, Technology and literature
Collections: Techonology eBook Collection
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Lias, S. G. (n.d.). Evaluated Gas Phase Basicities and Proton Affinities Of. Retrieved from http://hawaiilibrary.net/


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Technical Reference Publication

Excerpt
Introduction: The gas phase basicity and proton affinity of a molecule, M, are both defined in terms of the hypothetical reaction: The gas phase basicity is the negative of the free energy change associated with this reaction, while the proton affinity is the negative of the corresponding enthalpy change. Proton transfer reactions are of considerable importance in chemistry. Acid-base reactions have been studied extensively in solution for decades, but it is only in the past twenty years or so that experimental techniques have been devised to permit the quantitative study of the thermochemistry of proton transfer reactions in the gas phase. Particularly in the years since 1971, when the first gas phase ion-molecule equilibrium studies on proton transfer appeared, there has been a burgeoning of data in the literature, and consequently, a great interest in using information from such gas phase studies to distinguish between the chemical effects of solvation and the effects of intrinsic molecular properties.

Table of Contents
Contents 1. Introduction ......................................................... 696 1.1. Definitions ................................... . ....... 696 1.2. Proton Affinities and Gas Phase Basicities: An Overview ......................... 696 2. Types of Experiment Leading to Proton Affinity/Gas Basicity Data ..................... 696 2.1. Absolute Proton Affinity Values from Ionization Thresholds .............................. 697 2.2. Proton Affinity Values from Thermochemica1 Informatioll Dcrivcd from IIydridc Transfer Equilibrium Constant Determinations .................................................. 697 2.3. Relative Gas Basicity Values from Proton Transfer Equilibrium Constants .............. 697 2.4. Relative Gas Basicity/Proton Affinity Values from Bracketing ...................... 697 2.5. Other Sources of Proton Affinity/Cas Basicity Data ............................................ 698 3. Description of the Evaluation ............................ 698 3.1. Thermodynamic Ladders ........................ 698 3.1.1. Entropy Changes ...................... 698 3.1.2. Temperature .......................... 698 3.2. Assignment of Absolute Values to the Scale. R e f c r e n ~ cS tandards ..................... 699 3.2.1. Ammonia ................................... 699 3.2.2. Ketene ....................................... 700 3.2.3. Isobutene ................................... 700 3.2.4. Propylene .................................. 700 3.2.5. Formaldehyde ........................... 701 3.2.6. Water ......................................... 701 3.2.7. Ethylene .................................. 702 3.2.8. Carbon monoxide .. .... . . . .. .. . .. .. . .. 702 3.2.9. Carbon dioxide ......................... 702 3.2.10. Oxygen atom ............................. 702 3.2.1 1. Molecular oxygen ............. ........ 702 3.3. Summary of Thermochemical Data on Cumparisml Stadalds To1 Proton AIT1nit.y Scale ........................................................ 703 4. Experimental Error Limits ................................. 704 5. Explanation of the Tables ................................... 704 5.1. Explanation of Table 1 .......................... .. 704 5.1.1. List of Symbols Used in Table 1 ...... 707 5.2. Explanation of Table 2 ............................ 708 5.2.1. Conventions Used. ................. ... 708 5.2.2. Heats of Formation of Neutral Molecules .............. ............... ... 708 5.2.3. References ................................. 710 6. Literature Coverage ............................................ 710 7. References ...................... ,~ ................ ......... .. 7 11 List of Tables 1. Gas phase basicities and proton affinities .......... 713 Annotated references ro Table 1 ........................ 772 2. Proton affinities and heats of formation of @ 1984 by the U.S. Secretary of Commerce on behalf of the United States. This copyright is assigned to the American Institute of Physics and the molecules and corresponding protonated Americsn Chemical Socistv. species ............................... . ........................... 782 ~~-~ ~ - - - Reprints available from ACS; see Reprint List at back of issue. References to Table 2 ......................................... 806 0047-2689/84/030695-99/$12.00 695 J. Phys. Chem. Ref. Data, Vol. 13, No

 

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