Handbook of Solvents

Preface
1 INTRODUCTION
Christian Reichardt, Department of Chemistry, Philipps University, Marburg, Germany
2 FUNDAMENTAL
PRINCIPLES GOVERNING SOLVENTS USE
2.1 Solvent effects on chemical systems Estanislao Silla, Arturo Arnau and 2.1 Iñaki Tuñón, Department of Physical Chemistry, University of Valencia, Burjassot (Valencia), Spain
2.1.1 Historical outline
2.1.2 Classification of solute-solvent interactions
2.1.2.1 Electrostatic
2.1.2.2 Polarization
2.1.2.3 Dispersion
2.1.2.4 Repulsion
2.1.2.5 Specific interactions
2.1.2.6 Hydrophobic interactions
2.1.3 Modelling of solvent effects
2.1.3.1 Computer simulations
2.1.3.2 Continuum models
2.1.3.3. Cavity surfaces
2.1.3.4 Supermolecule models
2.1.3.5 Application example: glycine in solution
2.1.4 Thermodynamic and kinetic characteristics of chemical reactions in solution
2.1.4.1 Solvent effects on chemical equilibria
2.1.4.2 Solvent effects on the rate of chemical reactions
2.1.4.3 Example of application: addition of azide anion to tetrafuranosides

2.1.5 Solvent catalytic effects
2.2 Molecular design of solvents Koichiro Nakanishi, Kurashiki Univ. Sci. & the Arts, Okayama, Japan
2.2.1 Molecular design and molecular ensemble design
2.2.2 From prediction to design
2.2.3 Improvement in prediction method
2.2.4 Role of molecular simulation
2.2.5 Model system and paradigm for design Appendix. Predictive equation for the diffusion coefficient in dilute solution
2.3 Basic physical and chemical properties of solvents George Wypych, ChemTec Laboratories, Inc., Toronto, Canada
2.3.1 Molecular weight and molar volume
2.3.2 Boiling and freezing points
2.3.3 Specific gravity
2.3.4 Refractive index
2.3.5 Vapor density and pressure
2.3.6 Solvent volatility
2.3.7 Flash point
2.3.8 Flammability limits
2.3.9 Sources of ignition and autoignition temperature
2.3.10 Heat of combustion (calorific value)
2.3.11 Heat of fusion
2.3.12 Electric conductivity
2.3.13 Dielectric constant (relative permittivity)
2.3.14 Occupational exposure indicators
2.3.15 Odor threshold
2.3.16 Toxicity indicators
2.3.17 Ozone-depletion and creation potential
2.3.18 Oxygen demand
2.3.19 Solubility
2.3.20 Other typical solvent properties and indicators

3 PRODUCTION METHODS, PROPERTIES, AND MAIN APPLICATIONS

3.1 Definitions and solvent classification
3.2 Overview of methods of solvent manufacture
3.3 Solvent properties
3.3.1 Hydrocarbons
3.3.1.1 Aliphatic hydrocarbons
3.3.1.2 Aromatic hydrocarbons
3.3.2 Halogenated hydrocarbons
3.3.3 Nitrogen-containing compounds (nitrates, nitriles)
3.3.4 Organic sulfur compounds
3.3.5 Monohydric alcohols
3.3.6 Polyhydric alcohols
3.3.7 Phenols
3.3.8 Aldehydes
3.3.9 Ethers
3.3.10 Glycol ethers
3.3.11 Ketones
3.3.11 Acids
3.3.12 Amines
3.3.13 Esters
3.3.14 Comparative analysis of all solvents
3.4 Terpenes Tilman Hahn, Konrad Botzenhart, Fritz Schweinsberg, Institut fuer Allgemeine Hygiene und Umwelthygiene, University of Tuebingen, Tuebingen, Germany
3.4.1 Definitions and nomenclature
3.4.2 Occurrence
3.4.3 General
3.4.4 Toxicology
3.4.5 Threshold limit values
4 GENERAL PRINCIPLES GOVERNING DISSOLUTION OF MATERIALS IN SOLVENTS
4.1 Simple solvent characteristics Valery Yu. Senichev, Vasiliy V. Tereshatov, Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
4.1.1 Solvent power
4.1.2 One-dimensional solubility parameter approach
4.1.3 Multi-dimensional approaches
4.1.4 Hansen's solubility
4.1.5 Three-dimensional dualistic model
4.1.6 Solubility criterion
4.1.7 Solvent system design
4.2 Effect of system variables on solubility Valery Yu. Senichev, Vasiliy V. Tereshatov, Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
4.2.1 General considerations
4.2.2 Chemical structure
4.2.3 Flexibility of a polymer chain
4.2.4 Crosslinking
4.2.5 Temperature and pressure
4.2.6 Methods of calculation of solubility based on thermodynamic principles

4.3 Polar solvation dynamics: Theory and simulations Abraham Nitzan, School of Chemistry,The Sackler Faculty of Sciences, Tel Aviv University, Tel Aviv, Israel
4.3.1 Introduction
4.3.2 Continuum dielectric theory of solvation dynamics
4.3.3 Linear response theory of solvation dynamics
4.3.4 Numerical simulations of solvation in simple polar solvents: The simulation model
4.3.5 Numerical simulations of solvation in simple polar solvents: Results and discussion
4.3.6 Solvation in complex solvents
4.3.7 Conclusions
4.4 Methods for the measurement of solvent activity of polymer solutions Christian Wohlfarth, Martin-Luther-University Halle-Wittenberg, Institute of Physical Chemistry, Merseburg, Germany
4.4.1 Introduction
4.4.2 Necessary thermodynamic equations
4.4.3 Experimental methods, equipment and data reduction
4.4.3.1 Vapor-liquid equilibrium (VLE) measurements
4.4.3.1.1 Experimental equipment and procedures for VLE-measurements
4.4.3.1.2 Primary data reduction
4.4.3.1.3 Comparison of experimental VLE-methods
4.4.3.2 Other measurement methods
4.4.3.2.1 Membrane osmometry
4.4.3.2.2 Light scattering
4.4.3.2.3 X-ray scattering
4.4.3.2.4 Neutron scattering
4.4.3.2.5 Ultracentrifuge
4.4.3.2.6 Cryoscopy (freezing point depression of the solvent)
4.4.3.2.7 Liquid-liquid equilibrium (LLE)
4.4.3.2.8 Swelling equilibrium
4.4.4 Thermodynamic models for the calculation of solvent activities of polymer solutions
4.4.4.1 Models for residual chemical potential and activity coefficient in the liquid phase
4.4.4.2 Fugacity coefficients from equations of state
4.4.4.3 Comparison and conclusions
Appendix 4.4A

5 SOLUBILITY OF SELECTED SYSTEMS AND INFLUENCE OF SOLUTES

5.1 Experimental methods of evaluation and calculation of solubility parameters of polymers and solvents. Solubility parameters data Valery Yu. Senichev, Vasiliy V. Tereshatov, Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
5.1.1 Experimental evaluation of solubility parameters of liquids
5.1.1.1 Direct methods of evaluation of the evaporation enthalpy
5.1.1.2 Indirect methods of evaluation of evaporation enthalpy
5.1.1.3 Static and quasi-static methods of evaluation of pair pressure
5.1.1.4 Kinetic methods
5.1.2 Methods of experimental evaluation and calculation of solubility parameters of polymers
5.2 Prediction of solubility parameter Nobuyuki Tanaka, Department of Biological and Chemical Engineering Gunma University, Kiryu, Japan
5.2.1 Solubility parameter of polymers
5.2.2 Glass transition in polymers
5.2.2.1 Glass transition enthalpy
5.2.2.2 Cp jump at the glass transition
5.2.3 Prediction from thermal transition enthalpies
5.3 Methods of calculation of solubility parameters of solvents and polymers Valery Yu. Senichev, Vasiliy V. Tereshatov, Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia,
5.4 Mixed solvents, a way to change the polymer solubility Ligia Gargallo and Deodato Radic, Facultad de Quimica Pontificia Universidad Católica de Chile, Santiago, Chile
5.4.1 Introduction
5.4.2 Solubility-cosolvency phenomenon
5.4.3 New cosolvents effects. Solubility behavior
5.4.4 Thermodynamical description of ternary systems. Association equilibria theory of preferential adsorption
5.4.5 Polymer structure of the polymer dependence of preferential adsorption. polymer molecular weight and tacticity dependence of preferential adsorption
5.5 The phenomenological theory of solvent effects in mixed solvent systems Kenneth A. Connors, School of Pharmacy, University of Wisconsin, Madison, USA
5.5.1 Introduction
5.5.2 Theory
5.5.2.1 Principle
5.5.2.2 The intersolute effect: solute-solute interactions
5.5.2.3 The solvation effect: solute-solvent interaction
5.5.2.4 The general medium effect: solvent-solvent interactions
5.5.2.5 The total solvent effect
5.5.3 Applications
5.5.3.1 Solubility
5.5.3.2 Surface tension
5.5.3.3 Electronic absorption spectra
5.5.3.4 Complex formation
5.5.3.5 Chemical kinetics
5.5.3.6 Liquid chromatography
5.5.4 Interpretations
5.5.4.1 Ambiguities and anomalies
5.5.4.2 A modified derivation
5.5.4.3 Interpretation of parameter estimates
5.5.4.4 Confounding effects Solute-solute interactions Coupling of general medium and solvation effects The cavity surface area The role of interfacial tension
5.5.5 Notes and References
6 SWELLING
6.1 Modern views on kinetics of swelling of crosslinked elastomers in solvents E. Ya. Denisyuk, Institute of Continuous Media Mechanics; V. V. Tereshatov Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
6.1.1 Introduction
6.1.2 Formulation of swelling for a plane elastomer layer
6.1.3 Diffusion kinetics of plane layer swelling
6.1.4 Experimental study of elastomer swelling kinetics
6.2 Equilibrium swelling in binary solvents Vasiliy V. Tereshatov, Valery Yu. Senichev, Institute of Technical Chemistry; E. Ya. Denisyuk, Institute of Continuous Media Mechanics, Ural Branch of Russian Academy of Sciences, Perm, Russia
6.3 Swelling data on crosslinked polymers in solvents Vasiliy V. Tereshatov, Valery Yu. Senichev, Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
6.4 Influence of structure on equilibrium swelling Vasiliy V. Tereshatov, Valery Yu. Senichev, Institute of Technical Chemistry, Ural Branch of Russian Academy of Sciences, Perm, Russia
7 SOLVENT TRANSPORT PHENOMENA
7.1 Introduction to diffusion, swelling, and drying George Wypych, ChemTec Laboratories, Inc., Toronto, Canada
7.1.1 Diffusion
7.1.2 Swelling
7.1.3 Drying References
7.2 Bubbles dynamics and boiling of polymeric solutions Semyon Levitsky, Negev Academic College of Engineering, Israel; Zinoviy Shulman, A.V. Luikov Heat and Mass Transfer Institute, Belarus
7.2.1 Rheology of polymeric solutions and bubble dynamics
7.2.1.1 Rheological characterization of solutions of polymers
7.2.1.2 Dynamic interaction of bubbles with polymeric liquid
7.2.2 Thermal growth of bubbles in superheated solutions of polymers
7.2.3 Boiling of macromolecular liquids
7.3 Drying of coated film Seung Su Kim, SKC Co., Ltd., Chon-an City, Korea; Jae Chun Hyun, Department of Chemical Engineering, Korea University, Seoul, Korea
7.3.1 Introduction
7.3.2 Theory for the drying
7.3.2.1 Simultaneous heat and mass transfer
7.3.2.2 Liquid-vapor equilibrium
7.3.2.3 Heat and mass transfer coefficient
7.3.2.4 Prediction of drying rate of coating
7.3.2.5 Drying regimes: constant drying rate period (CDRP) and falling drying rate period (FDRP)
7.3.3 Measurement of the drying rate of coated film
7.3.3.1 Thermo-gravimetric analysis
7.3.3.2 Rapid scanning FT-IR spectrometer analysis
7.3.3.3 High-airflow drying experiment using flame ionization detector (FID) total hydrocarbon analyzer
7.3.3.4 Measurement of drying rate in the production scale dryer
7.3.4 Miscellaneous
7.3.4.1 Drying of coated film with phase separation
7.3.4.2 Drying defects
7.3.4.2.1 Internal stress induced defects
7.3.4.2.2 Surface tension driven defects
7.3.4.2.3 Defects caused by air motion and others
7.3.4.3 Control of lower explosive level (LEL) in a multiple zone dryer
8 INTERACTIONS IN SOLVENTS AND SOLUTIONS
Jacopo Tomasi, Benedetta Mennucci, Chiara Cappelli, Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Italy
8.1 Solvents and solutions as assemblies of interacting molecules
8.2 Basic simplifications of the quantum model
8.3 Cluster expansion
8.4 Two-body interaction energy: the dimer
8.4.1 Decomposition of the interaction energy of a dimer: variational approach The electrostatic term The induction term The exchange term The charge transfer term The dispersion term The decomposition of the interaction energy through a variational approach: a summary
8.4.2 Basis set superposition error and counterpoise corrections
8.4.3 Perturbation theory approach
8.4.4 Modeling of the separate components The electrostatic term The induction term The dispersion term The exchange (or repulsion) term The other terms A conclusive view
8.4.5 The relaxation of the rigid monomer constraint
8.5 Three- and many-body interactions Screening many-body effects Effective interaction potentials
8.6 The variety of interaction potentials
8.7 Theoretical and computing modeling of pure liquids and solutions
8.7.1 Physical models
8.7.1.1 Integral equation methods
8.7.1.2 Perturbation theories
8.7.2 Computer simulations
8.7.2.1 Car-Parrinello direct QM simulation
8.7.2.2 Semi-classical simulations Molecular dynamics Monte Carlo QM/MM
8.7.3 Continuum models
8.7.3.1 QM-BE methods: the effective Hamiltonian
8.8 Practical applications of modeling Dielectric constant Thermodynamical properties Compressibilities Relaxation times and diffusion coefficients Shear viscosity
8.9 Liquid surfaces
8.9.1 The basic types of liquid surfaces
8.9.2 Systems with a large surface/bulk ratio
8.9.3 Studies on interfaces using interaction potentials

9 MIXED SOLVENTS
Y. Y. Fialkov, V. L. Chumak, Department of Chemistry, National Technical University of Ukraine, Kiev, Ukraine
9.1 Introduction
9.2 Chemical interaction between components in mixed solvents
9.2.1 Processes of homomolecular association
9.2.2 Conformic and tautomeric equilibrium. Reactions of isomerization
9.2.3 Heteromolecular association
9.2.4 Heteromolecular associate ionization
9.2.5 Electrolytic dissociation (ionic association)
9.2.6 Reactions of composition
9.2.7 Exchange interaction
9.2.8 Amphoterism of mixed solvent components
9.2.8.1 Amphoterism of hydrogen acids
9.2.8.2 Amphoterism of L-acids
9.2.8.3 Amphoterism in systems H-acid-L-acid
9.2.8.4 Amphoterism in binary solutions amine-amine
9.3 Physical properties of mixed solvents
9.3.1 The methods of expression of mixed solvent compositions
9.3.1.1 Permittivity
9.3.1.2 Viscosity
9.3.1.3 Density, molar volume
9.3.1.4 Electrical conductivity
9.3.2 Physical characteristics of the mixed solvents with chemical interaction between components
9.3.2.1 Permittivity
9.3.2.2 Viscosity
9.3.2.3 Density, molar volume
9.3.2.4 Conductivity
9.3.3 Chemical properties of mixed solvents
9.3.3.1 Autoprotolysis constants
9.3.3.2 Solvating ability
9.3.3.3 Donor-acceptor properties
9.4 Mixed solvent influence on the chemical equilibrium
9.4.1 General considerations
9.4.2 Mixed solvent effect on the position of equilibrium of homomolecular association process
9.4.3 Mixed solvent influence on the conformer equilibrium
9.4.4 Solvent effect on the process of heteromolecular association
9.4.4.1 Selective solvation. Resolvation
9.4.5 Mixed solvent effect on the ion association process
9.4.6 Solvent effect on exchange interaction processes Systems with non-associated reagents Systems with one associated participant of equilibrium Systems with two associated participants of equilibrium
9.4.7 Mixed solvent effect on processes of complex formation
9.5 The mixed solvent effect on the chemical equilibrium thermodynamics

10 ACID-BASE INTERACTIONS
10.1 General concept of acid-base interactions George Wypych, ChemTec Laboratories, Inc., Toronto, Canada
10.2 Effect of polymer/solvent acid-base interactions: relevance to the aggregation of PMMA S. Bistac, M. Brogly, Institut de Chimie des Surfaces et Interfaces, ICSI - CNRS, Mulhouse, France
10.2.1 Recent concepts in acid-base interactions
10.2.1.1 The nature of acid-base molecular interactions
10.2.1.1.1 The original Lewis definitions
10.2.1.1.2 Molecular Orbital (MO) approach to acid-base reactions
10.2.1.1.3 The case of hydrogen bonding
10.2.1.2 Quantitative determination of acid-base interaction strength
10.2.1.2.1 Perturbation theory
10.2.1.2.2 Hard-Soft Acid-Base (HSAB) principle
10.2.1.2.3 Density functional theory
10.2.1.2.4 Effect of ionocity and covalency: Drago's concept
10.2.1.2.5 Effect of amphotericity of acid-base interaction: Gutmann's numbers
10.2.1.2.6 Spectroscopic measurements: Fowkes' approach
10.2.2 Effect of polymer/solvent interactions on aggregation of stereoregular PMMA
10.2.2.1 Aggregation of stereoregular PMMA
10.2.2.2 Relation between the complexing power of solvents and their acid-base properties
10.2.3 Influence of the nature of the solvent on the and -relaxations of conventional PMMA
10.2.3.1 Introduction
10.2.3.2 Dielectric spectroscopy results
10.2.4 Concluding remarks References10.3 Solvent effects based on pure solvent scales Javier Catalán, Departamento de Química Fisíca Aplicada, Universidad Autónoma de Madrid, Madrid, Spain Introduction 10.3.1 The solvent effect and its dissection into general and specific contributions
10.3.2 Characterization of a molecular environment with the aid of the probe/homomorph model
10.3.3 Single-parameter solvent scales: the Y, G, ET(30), , Z, R, , and S' scales
10.3.3.1 The solvent ionizing power scale or Y scale
10.3.3.2 The G values of Allerhand and Schleyer
10.3.3.3 The ET(30) scale of Dimroth and Reichardt
10.3.3.4 The Py scale of Dong and Winnick
10.3.3.5 The Z scale of Kosower
10.3.3.6 The R scale of Brooker
10.3.3.7 The scale of Dubois and Bienvenue
10.3.3.8 The S' scale of Drago
10.3.4 Solvent polarity: the SPP scale
10.3.5 Solvent basicity: the SB scale
10.3.6 Solvent acidity: the SA scale
10.3.7 Applications of the pure SPP, SA and SB scales
10.3.7.1 Other reported solvents scales
10.3.7.2 Treatment of the solvent effect
10.3.7.2.1 Spectroscopy
10.3.7.2.2 Kinetics
10.3.7.2.3 Electrochemistry
10.3.7.2.4 Thermodynamics
10.3.7.3 Mixtures of solvents. Understanding the preferential solvation model
10.4 Acid-base equilibria in ionic solvents (ionic melts) Victor Cherginets, Institute for Single Crystals, Kharkov, Ukraine
10.4.1 Acid-base definitions used for the description of donor-acceptor interactions in ionic media
10.4.1.1 The Lewis definition
10.4.1.2 The Lux-Flood definition
10.4.2 The features of ionic melts as media for acid-base interactions
10.4.2.1 Oxygen-less media
10.4.2.2 Oxygen-containing melts
10.4.2.3 The effect of the ionic solvent composition on acid-base equilibria
10.4.3 Methods for estimations of acidities of solutions based on ionic melts
10.4.4 On studies of the homogeneous acid-base reactions in ionic melts
10.4.4.1 Nitrate melts
10.4.4.2 Sulphate melts
10.4.4.3 Silicate melts
10.4.4.4 The equimolar mixture KCl-NaCl
10.4.4.5 Other alkaline halide melts
10.4.5 Reactions of melts with gaseous acids and bases
10.4.5.1 High-temperature hydrolysis of molten halides
10.4.5.2 The processes of removal of oxide admixtures from melts

11 ELECTRONIC AND ELECTRICAL EFFECTS OF SOLVENTS
11.1 Theoretical treatment of solvent effects on electronic and vibrational spectra of compounds in condensed media
Mati Karelson, Department of Chemistry, University of Tartu, Tartu, Estonia
11.1.1 Introduction
11.1.2 Theoretical treatment of solvent cavity effects on electronic-vibrational spectra of molecules
11.1.3 Theoretical treatment of solvent electrostatic polarization on electronic-vibrational spectra of molecules
11.1.4 Theoretical treatment of solvent dispersion effects on electronic-vibrational spectra of molecules
11.1.5 Supermolecule approach to the intermolecular interactions in condensed media
11.2 Dielectric solvent effects on the intensity of light absorption and the radiative rate constant
Tai-ichi Shibuya, Faculty of Textile Science and Technology, Shinshu University, Ueda, Japan
11.2.1 The Chako formula or the Lorentz-Lorenz correction
11.2.2 The generalized local-field factor for the ellipsoidal cavity
11.2.3 Dielectric solvent effect on the radiative rate constant
12 OTHER PROPERTIES OF SOLVENTS, SOLUTIONS, AND PRODUCTS OBTAINED FROM SOLUTIONS
12.1 Rheological properties, aggregation, permeability, molecular structure, crystallinity, and other properties affected by solvents
George Wypych, ChemTec Laboratories, Inc., Toronto, Canada
12.1.1 Rheological properties
12.1.2 Aggregation
12.1.3 Permeability
12.1.4 Molecular structure and crystallinity
12.1.5 Other properties affected by solvents
12.2 Chain conformations of polysaccharides in different solvents
Ranieri Urbani and Attilio Cesaro, Department of Biochemistry, Biophysics and Macromolecular Chemistry, University of Trieste, Italy
12.2.1 Introduction
12.2.2 Structure and conformation of polysaccharides in solution
12.2.2.1 Chemical structure
12.2.2.2 Solution chain conformation
12.2.3 Experimental evidence of solvent effect on oligosaccharide conformational equilibria
12.2.4 Theoretical evaluation of solvent effect on conformational equilibria of sugars
12.2.4.1 Classical molecular mechanics methods
12.2.4.2 Molecular dynamic methods
12.2.5 Solvent effect on chain dimensions and conformations of polysaccharides
12.2.6 Solvent effect on charged polysaccharides and the polyelectrolyte model
12.2.6.1 Experimental behavior of polysaccharides polyelectrolytes
12.2.6.2 The Haug and Smidsrød parameter: description of the salt effect on the chain dimension
12.2.6.3 The statistical thermodynamic counterion-condensation theory of Manning
12.2.6.4 Conformational calculations of charged polysaccharides
16 RESIDUAL SOLVENTS IN PRODUCTS
16.1 Residual solvents in various products
George Wypych, ChemTec Laboratories, Inc., Toronto, Canada
16.2 Residual solvents in pharmaceutical substances
Michel Bauer, International Analytical Department, Sanofi-Synthelabo, Toulouse, France; Christine Barthélémy, Laboratoire de Pharmacie Galenique et Biopharmacie, Faculte des Sciences Pharmaceutiques et Biologiques, Universite de Lille 2, Lille, France
16.2.1 Introduction
16.2.2 Why should we look for RS?
16.2.2.1 Modifying the acceptability of the drug product
16.2.2.2 Modifying the physico-chemical properties of drug su