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Specific ion effects are important in numerous fields of science and technology. This book summarizes the main ideas that came up over the years. It presents the efforts of theoreticians and supports it by the experimental results stemming from various techniques.
Electrolyte solutions play a central role in life and technological processes because of their complexity. This complexity is yet to be described by a predictive theory of the specific effects that different ions induce in solution. The vast majority of investigations of specific-ion effects have been conducted in aqueous solutions. These studies have revealed that amongst the complexity, the effectiveness of the ions often follow trends that are apparent across a number of very different experiments, revealing an underlying order (e.g. the Hofmeister series). It is often assumed that water itself is intricately involved in these trends. Here I investigate specific-ion effects in non-aqueous solvents rather than water. By extending the investigation to a number of non-aqueous solvents, the role of the solvent in specific-ion effect trends can be elucidated and a better understanding of the general phenomenon gained. Firstly, a more definite terminology is developed for describing the specific-ion effects trends in order to address the current confusion in the literature and provide a basis for the following investigations. An extensive investigation of the scarce literature demonstrates that water is by no means a special solvent with regards to ion-specificity, and that within the complexity there is universality. An investigation of electrostriction under the conditions of infinite dilution shows that the same fundamental specific ion trends are observed across all solvents, demonstrating that ion-specificity arises from the ions themselves. In this regard the influence of solvents, surfaces and real concentrations of electrolytes can be seen as perturbations to this fundamental series. Further work shows that for systems that are perturbed, the trends in non-aqueous protic solvents can be expected to follow the same trend in water; and in aprotic solvents the cations are more likely to adhere to the trend in water than the anions. My experimental work focuses on specific-anion effects of seven Hofmeister sodium salts in the solvents: water, methanol, formamide, dimethyl sulfoxide and propylene carbonate. Two very different experiments were performed; the elution of electrolytes from a size-exclusion chromatography column and an investigation of the electrolyte moderated swelling of a cationic brush (PMETAC) using a Quartz Crystal Microbalance (QCM). The trends observed are consistent across these experiments. A forward or reverse Hofmeister series is observed in practically all salt-solvent combinations, and the reversal is attributed to the polarisability of the solvent. Finally, a qualitative model of ion specific trends is formulated, where the specific-ion effects are fundamentally a property of the ion, and the associated trends correspond to the Hofmeister series for anions and the lyotropic series for cations. When the concentration is increased, or surfaces introduced, the effects of ion-ion interactions and ion-surface interactions can perturb the fundamental series. The perturbation of the series is related to the proticity of the solvent for ion-ion interactions, whereas the polarisability of the solvent and ion are important when a surface is present. This work for the first time individuates the principal properties of the solvent that affect their ordering: proticity and polarisability.
The book starts with an exposition of the relevant properties of ions and continues with a description of their solvation in the gas phase. The book contains a large amount of factual information in the form of extensive tables of critically examined data and illustrations of the points made throughout. It covers: the relevant properties of prospective liquid solvents for the ions the process of the transfer of ions from the gas phase into a liquid where they are solvated various aspects of the solutions of the ions, such as structural and transport ones and the effects of the ions on the solvent dynamics and structure what happens in cases where the solvent is a mixture selective solvation takes place applications of the concepts expounded previously in fields such as electrochemistry, hydrometallurgy, separation chemistry, biophysics, and synthetic methods
This comprehensive, widely-read anthology presents cogent and provocativearticles from differing political perspectives on major issues in post-World WarII America. The fourth edition is considerably expanded to include newselections on the AIDS epidemic, gay rights, the women's movement, and theClinton-Gore administration. In addition to articles by leading historians theeditors have chosen first-person accounts by participants in each of the issuesunder discussion, from Martin Luther King, Jr.'s "Letter from the BirminghamJail" to Al Gore's speech on environmentalism. With lively introductions to eachsection providing a context for the articles, this book helps students makesense of the tumultuous world of our time.
The aim and purpose of this book is a survey of our actual basic knowledge of electrolyte solutions. It is meant for chemical engineers looking for an introduction to this field of increasing interest for various technologies, and for scientists wishing to have access to the broad field of modern electrolyte chemistry.
pH Measurements is a seven-chapter simplified text on obtaining a high degree of accuracy in practical pH measurement. The introductory chapter of this book relates the principles of pH measurements to the actual measurement. This chapter specifically tackles the factors involved in the measurement and what magnitude of effect does each factor have on the measurement. These topics are followed by discussions on the components of pH equipment and technique, including the electrodes and buffers. A chapter considers the general approach of pH measurements and illustrates with examples of some common difficult samples. The concluding chapter shows the isolation and correction a pH equipment malfunction. pH equipment operators and users will find this book rewarding.
Considering the properties of inorganic and organic ions pertaining directly, as well as indirectly, to their behaviour in solutions, this work aims to enable the specialist and non-specialist alike to comprehend ion behaviour in ongoing and developing studies and applications. The companion disk is for use with Microsoft Access 2.0.
This book addresses the use of ionic liquids in biotransformation and organocatalysis. Its major parts include: an overview of the fundamentals of ionic liquids and their interactions with proteins and enzymes; the use of ILs in biotransformations; non-solvent applications such as additives, membranes, substrate anchoring, and the use of ILs in organocatalysis (from solvents to co-catalysts and new reactivities, as well as non-solvent applications such as anchoring and immobilization).
The book starts with an exposition of the relevant properties of ions and continues with a description of their solvation in the gas phase. The book contains a large amount of factual information in the form of extensive tables of critically examined data and illustrations of the points made throughout. It covers: the relevant properties of prospective liquid solvents for the ions the process of the transfer of ions from the gas phase into a liquid where they are solvated various aspects of the solutions of the ions, such as structural and transport ones and the effects of the ions on the solvent dynamics and structure what happens in cases where the solvent is a mixture selective solvation takes place applications of the concepts expounded previously in fields such as electrochemistry, hydrometallurgy, separation chemistry, biophysics, and synthetic methods
Liquid Chromatography: Fundamentals and Instrumentation, Third Edition offers a single source of authoritative information on all aspects of the practice of modern liquid chromatography. The book gives those working in academia and industry the opportunity to learn, refresh, and deepen their understanding of the field by covering basic and advanced theoretical concepts, recognition mechanisms, conventional and advanced instrumentation, method development, data analysis, and more. This third edition addresses new developments in the field with updated chapters from expert researchers. The book is a valuable reference for research scientists, teachers, university students, industry professionals in research and development, and quality control managers. - Emphasizes the integration of chromatographic methods and sample preparation - Provides important data related to complex matrices, sample preparation, and data handling - Gives background information to facilitate the choice of LC sub-technique and experimental conditions, mobile and stationary phases, detectors, data processing, and more - Offers comprehensive updates to all chapters - Includes new chapters on chiral recognition, co-solvents and mobile phase additives, physicochemical measurements, and identification and quantitation in mass spectrometry