Lewis Basicity and Affinity Scales (PDF)
Data and Measurement
(Sprache: Englisch)
The Lewis concept of acids and bases is discussed in every general,
organic and inorganic chemistry textbook. This is usually just a
descriptive treatment, as it is not possible to devise a single
numerical scale suitable for all occasions. However...
organic and inorganic chemistry textbook. This is usually just a
descriptive treatment, as it is not possible to devise a single
numerical scale suitable for all occasions. However...
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The Lewis concept of acids and bases is discussed in every general,
organic and inorganic chemistry textbook. This is usually just a
descriptive treatment, as it is not possible to devise a single
numerical scale suitable for all occasions. However quantitative
Lewis acid-base chemistry can be developed by compiling
reaction-specific basicity scales which can be used in specific
branches of chemistry and biochemistry.
Lewis Basicity and Affinity Scales: Data and
Measurementbrings together for the first time a comprehensive
range of Lewis basicity/affinity data in one volume. More than 2400
equilibrium constants of acid-base reactions, 1500 complexation
enthalpies, and nearly 2000 infrared and ultraviolet shifts upon
complexation are gathered together in 25 thermodynamic and
spectroscopic scales of basicity and/or affinity. For each scale,
the definition, the method of measurement, an exhaustive database,
and a critical discussion are given. All the data have been
critically examined; some have been re-measured; literature gaps
have been filled by original measurements; and each scale has been
made homogeneous.
This collection of data will enable experimental chemists to
better understand and predict the numerous chemical, physical and
biological properties that depend upon Lewis basicity.
Chemometricians will be able to apply their methods to the data
matrices constructed from this book in order to identify the
factors which influence basicity and basicity-dependent properties.
In addition, measured experimental basicities and affinities are
essential to computational chemists for the validation, calibration
and establishment of reliable computational methods for quantifying
and explaining intermolecular forces and the chemical bond.
Lewis Basicity and Affinity Scales: Data and Measurement
is an essential single-source desktop reference for research
scientists, engineers, and students in academia, research
institutes and industry, in all areas of chemistry from fundamental
to applied research.
"The book is a noteworthy piece of work and represents a
timely and vast accumulation of knowledge regarding Lewis bases
that brings together accurate thermodynamic and spectroscopic
data on typical reference Lewis acids. As such, it should serve as
a useful and general guide to basicity." J. AM. CHEM.
SOC. 2011, 133, 642
organic and inorganic chemistry textbook. This is usually just a
descriptive treatment, as it is not possible to devise a single
numerical scale suitable for all occasions. However quantitative
Lewis acid-base chemistry can be developed by compiling
reaction-specific basicity scales which can be used in specific
branches of chemistry and biochemistry.
Lewis Basicity and Affinity Scales: Data and
Measurementbrings together for the first time a comprehensive
range of Lewis basicity/affinity data in one volume. More than 2400
equilibrium constants of acid-base reactions, 1500 complexation
enthalpies, and nearly 2000 infrared and ultraviolet shifts upon
complexation are gathered together in 25 thermodynamic and
spectroscopic scales of basicity and/or affinity. For each scale,
the definition, the method of measurement, an exhaustive database,
and a critical discussion are given. All the data have been
critically examined; some have been re-measured; literature gaps
have been filled by original measurements; and each scale has been
made homogeneous.
This collection of data will enable experimental chemists to
better understand and predict the numerous chemical, physical and
biological properties that depend upon Lewis basicity.
Chemometricians will be able to apply their methods to the data
matrices constructed from this book in order to identify the
factors which influence basicity and basicity-dependent properties.
In addition, measured experimental basicities and affinities are
essential to computational chemists for the validation, calibration
and establishment of reliable computational methods for quantifying
and explaining intermolecular forces and the chemical bond.
Lewis Basicity and Affinity Scales: Data and Measurement
is an essential single-source desktop reference for research
scientists, engineers, and students in academia, research
institutes and industry, in all areas of chemistry from fundamental
to applied research.
"The book is a noteworthy piece of work and represents a
timely and vast accumulation of knowledge regarding Lewis bases
that brings together accurate thermodynamic and spectroscopic
data on typical reference Lewis acids. As such, it should serve as
a useful and general guide to basicity." J. AM. CHEM.
SOC. 2011, 133, 642
Inhaltsverzeichnis zu „Lewis Basicity and Affinity Scales (PDF)“
Preface Chapter 1 Lewis basicity and affinity measurement: definitions and context 1.1 The Brönsted definition of acids and bases 1.2 Scales of Brönsted basicity and affinity in solution 1.3 Scales of Brönsted basicity and affinity in the gas phase 1.4 The Lewis definition of acids and bases 1.5 Quantum chemical descriptions of Lewis acid-base complexes 1.6 Measurement of Lewis basicity 1.7 Measurement of Lewis affinity 1.8 The role of the solvent 1.9 Spectroscopic scales of basicity (affinity) 1.10 Polybasic compounds 1.11 Attempts at a quantitative formulation of the Lewis definition of acids and bases 1.12 Concluding remarks and contents of Chapters 2-7 References Chapter 2 The Donor Number or SbCl5 affinity scale 2.1 Structure of SbCl5 complexes 2.2 Definition of the Donor Number scale 2.3 Experimental determination of the Donor Number 2.4 The Donor Number scale: data 2.5 Critical discussion References Chapter 3 The BF3 affinity scale 3.1 Structure of BF3 complexes 3.2 Definition of the BF3 affinity scale 3.3 Experimental determination of the BF3 affinity scale 3.4 The BF3 affinity scale: data 3.5 Discussion 3.6 Conclusion References Chapter 4 Thermodynamic and spectroscopic scales of hydrogen-bond basicity and affinity 4.1 Structure of hydrogen-bonded complexes 4.2 Hydrogen-bond basicity scales. Early works 4.3 The 4-fluorophenol basicity scale 4.4 Hydrogen-bond affinity scales. Early works 4.5 The 4-fluorophenol affinity scale 4.6 Comparison of 4-fluorophenol affinity and basicity scales 4.7 Spectroscopic scales 4.8 Conclusion References Chapter 5 Thermodynamic and spectroscopic scales of halogen-bond basicity and affinity 5.1 Structure of halogen-bonded complexes 5.2 The diiodine basicity scale 5.3 Is the diiodine basicity scale a general halogen-bond basicity scale? 5.4 The diiodine affinity scale 5.5 Spectroscopic scales 5.6 Conclusion References Chapter 6 Gas-phase cation basicity and affinity scales 6.1 Cations as Lewis acids in the gas phase 6.2
... mehr
Structure of cation/molecule adducts 6.3 Experimental techniques for measuring gas-phase cation affinities and basicities 6.4 Ion thermochemistry conventions 6.5 Lithium, sodium, potassium, aluminum, manganese, cyclopentadienylnickel, copper and methylammonium cation affinity and basicity scales 6.6 Significance and comparison of gas-phase cation scales References Chapter 7 The measurement of Lewis basicity and affinity in the laboratory 7.1 Calorimetric determination of the BF3 affinity of pyridine by gas/liquid reaction 7.2 Calorimetric determination of the BF3 affinity of pyridine by liquid/liquid reaction 7.3 Determination by FTIR spectrometry of the complexation constants of 4-fluorophenol with isopropyl methyl ketone and progesterone 7.4 Determination by FTIR spectrometry of the complexation enthalpy and entropy of 4-fluorophenol with cyclopropylamine 7.5 FTIR determination of the OH shift of methanol hydrogen-bonded to pyridine, mesitylene and N-methylmorpholine 7.6 Solvatochromic shifts of 4-nitrophenol upon hydrogen bonding to nitriles 7.7 Determination by visible spectrometry of the complexation constant of diiodine with iodocyclohexane 7.8 Determination by visible spectrometry of the complexation enthalpy and entropy of diiodine with dimethyl sulfoxide 7.9 FTIR determination of the shift of the I-C stretching frequency of iodine cyanide upon halogen bonding to phosphine chalcogenides 7.10 Blue shift of the visible diiodine band upon halogen bonding to pyridines 7.11 Mass spectrometric determination of the gas-phase lithium cation basicity of dimethyl sulfoxide and methyl phenyl sulfoxide by the kinetic method References Index
... weniger
Autoren-Porträt von Christian Laurence, Jean-François Gal
Professor Christian Laurence, UFR Sciences et Techniques, UMR CEISAM 6230 CNRS-Université de Nantes, FranceChristian Laurence is Professor Emeritus of Chemistry at the University of Nantes. He was head of the laboratory of spectrochemistry of the Faculty of Sciences of Nantes for 23 years, where he published more than 140 scientific papers in the field of physical organic chemistry.
Professor Jean-François Gal, Laboratoire de Radiochimie, Sciences Analytiques et Environnement, Institut de Chimie de Nice (FR CNRS 3037), Université de Nice-Sophia Antipolis- Parc Valrose, France
Jean-François Gal is Professor Emeritus of Chemistry at the University of Nice-Sophia Antipolis. He supervised, for more than 25 years, a group working on mass spectrometry and, specifically, on ion/molecule reactions, gas-phase acidity and basicity, and metal cation reactions.
Bibliographische Angaben
- Autoren: Christian Laurence , Jean-François Gal
- 2009, 1. Auflage, 476 Seiten, Englisch
- Verlag: John Wiley & Sons
- ISBN-10: 0470681896
- ISBN-13: 9780470681893
- Erscheinungsdatum: 15.12.2009
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