Separation Techniques in Analytical Chemistry
Description
The separation of a mixture into its individual components is one of the most fundamental procedures in analytical and industrial chemistry. This classic book in analytical chemistry provides a comprehensive yet systematic outline of all known separation methods. Through its detailed treatment of the basic principles of separation possibilities, it not only covers what is currently known, but also represents a treasure trove of methods that are still awaiting further development. It is clearly structured and contains interesting examples, further reading and a detailed index. An indispensable book for advanced students of natural sciences (chemistry, biochemistry, food chemistry, pharmacy, clinical chemistry, environmental sciences) and technology (chemical engineering, chemical-physical measurement & biotechnology), as well as teachers of these disciplines.
Reviews / Votes
From Reviews of the German Edition:
"Subject: This textbook summarizes separation methods in analytical and technical chemistry. The first edition of this book by Prof. Bock was published in 1974. This new version has been revised by Prof. Nießner and supplemented by the analytical achievements of the last 40 years. Furthermore, the classical, systematic classification of separation methods of the original work is retained. The book provides a detailed overview of the separation of individual components from sometimes complex mixtures. The intended readership should be found primarily in advanced students of science and chemical engineering, as well as in teachers of these disciplines.
Contents: The book contains 23 chapters and is structured in three parts. After the introduction in the first part, the second deals with separations due to different distribution between two immiscible phases, and Part III deals with separations due to different migration rates in one phase.
In the specific part of the textbook, separation processes are evaluated (Chapter 1) and classified (Chapter 2). Chemical reactions in separations (Chapter 3), analytical applications of incomplete separations (Chapter 4), and in overview of concentration data (Chapter 5) round out the introduction. Part II includes an extensive introduction (Chapter 6), partitioning between two liquids (e.g., partition chromatography, Chapter 7), solubility of gases in liquids (including a subchapter on gas chromatography, Chapter 8), adsorption and absorption of gases on solids (Chapter 9), adsorption of solutes on solids (e.g. e.g., thin-layer chromatography, Chapter 10), ion exchange (Chapter 11), precipitation methods (Chapter 12), extraction and phase analysis (Chapter 13), crystallization (Chapter 14), distillation (Chapter 15), sublimation (Chapter 16), and condensation (Chapter 17). In Part III, after a brief introduction (Chapter 18), mass spectrometry (Chapter 19), electrophoresis (Chapter 20), diffusion (Chapter 21), sedimentation (Chapter 22), and crossed force field separation of particles (Chapter 23) are described. Each chapter of separation techniques begins with the historical development, definitions as well as theory and ends with a list of literature used or further reading.
Critical review: The systematic classification of all described separation techniques according to distribution between two phases or separation by different migration velocities may seem unusual at first, but turns out to be a highly effective way of structuring a textbook. On the one hand, the reader can expect a reference work, and on the other hand, a textbook on separation processes. Thus, a detailed summary of separation processes in use today, as well as those that have been superseded in the meantime, is provided. On the back cover of the book, it is appropriately described as a "treasure trove of methods" "which are still awaiting further development". The authors deliberately do not evaluate any of these methods, which is why a certain amount of prior knowledge is already required, although mainly basic principles are taught. However, the lack of advantages and disadvantages of the respective methods is disadvantageous especially for readers with less previous knowledge.
The reader should by no means expect a textbook that focuses only on modern methods. For example, application examples are completely missing. The attempt to bring a 40 year old textbook up to date does not always work in detail, but very well in general, which makes the book quite exciting for the interested reader. The chapter on mass spectrometry, for example, is well done, as it also explains new techniques, while capillary electrophoresis, UHPLC or detectors in LC are (almost) not mentioned in the book. Numerous well-done and schematic illustrations complement the book and explain the subject matter very clearly. While the theory is thereby didactically prepared, on the other hand, somewhat more detailed graphics on the devices, apparatus or setups are missing.
Summary: Separation Methods in Analytical Chemistry provides a systematic, albeit non-judgmental, introduction to separation methods that are of great importance to analytical chemistry and process engineering. Most enjoyable will be advanced readers who are already familiar with some separation methods."
Franz Berthiller, Rudolf Krska, Universität für Bodenkultur Wien, Department für Agrarbiotechnologie (IFA-Tulln), Analytikzentrum, Konrad-Lorenz-Str. 20, 3430 Tulln, Austria, e-mail: rudolf.krska@boku.ac.at
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Persons
Reinhold Nießner, Institute of Hydrochemistry/ Chair of Analytical Chemistry, Technical University of Munich. Co-editor of the ACS journal "Analytical Chemistry". Author of nearly 500 scientific publications. Awards: Emanuel Merck Prize for Analytical Chemistry (1990), Smoluchowski Prize for Aerosol Research of the Society for Aerosol Research (1991), Fritz Pregl Medal of the Austrian Society for Analytical Chemistry (1996), Fresenius Prize for Analytical Chemistry of the Society of German Chemists (2000).
Content
Part I: Introduction
1 Evaluation of separation processes
1.1 Ideal and real separations
The aim of a separation operation is to separate a mixture of - in the simplest case - two substances A and B as completely as possible. If the separation is complete, the mixture is divided into two parts, one of which contains exclusively substance A, the other exclusively B.
However, such a complete partitioning is not achievable in practice; there will always still be some B as impurity in the part with substance A, and correspondingly some A in the part with B (cf. Fig 1.1).
? = Separation operation.
Fig. 1.1: Separation of a two-substance mixture.
1.2 Separation factor - enrichment factor - depletion factor
The result of a separation operation can be expressed by specifying the impurities in A and in B or by specifying the yields of A and B; thus, to unambiguously characterize the efficiency, two numbers are required for the separation of two substances (correspondingly more for systems with more than two components). To arrive at a simpler description, one uses the separation factor ß (probably first given by Chlopin), which is defined as follows:
(1)ß=concentrationofA/concentrationofBinpart1concentrationofA/concentrationofBinpart2.The separation factor is a measure of the effectiveness of the separation of two substances. If, after separation, the concentration ratio in both parts is the same, i.e. [A]/[B] in part 1 = [A]/[B] in part 2, then ß = 1; no separation has taken place.
For an (ideal) complete separation, either the numerator or the denominator of the double fraction would have to become zero, so that ß would take the values 0 or 8. ß and 1ß thus denote the same separation effect, since the choice of numerator and denominator is arbitrary. However, it is common to write the fraction so that ß = 1, so that the separation factor increases with an improvement in separation.
Instead of the separation factor, the term enrichment factor is sometimes used. For example, the enrichment factor f for substance A (cf. Fig 1.1) is defined as the concentration ratio in Part 1 after separation divided by the concentration ratio in the starting material before separation:
f=A/Binpart1A/BafterseparationAccordingly, one obtains the depletion factor f´ for A:
(2)f´=A/Binpart2A/BbeforeseparationThe depletion factor becomes smaller as the separation improves (decreasing concentration of A in part 2); more illustrative is the reciprocal value d of this factor, which increases as the efficiency of the separation increases. Referring again to the depletion of A (Fig. 1.1):
(3)d=A/BbeforeseparationA/Binpart2The quantity d is used above all in radiochemistry when the effectiveness of the removal of interfering radioactive substances is to be described; d is then referred to as the decontamination factor.
1.3 Separation factors required for analytical separations
In analytical chemistry, the term quantitative separation is generally used. This is usually understood to mean the 100 percent separation of the substance sought. According to what has been said so far, complete separations cannot be achieved in practice, and one must therefore define the term quantitative arbitrarily.
If a separation is to be sufficient for analytical purposes, it will normally be required that at least 99.9% of substance A is in part 1 and at least 99.9% of substance B is in part 2 after the separation operation (cf. Fig 1.1). The separation factor ß is then
ß=99,9:0,10,1:99,9?106.Such a high separation factor is a requirement that can be modified depending on the needs present in the specific case, but on the whole it should be justifiable.
1.4 Limits of applicability of the separation factor - selectivity and specificity of separations
A value of about 106 for the separation factor is a necessary but not sufficient condition for analytical applications. If one component of the mixture to be separated is present to an extreme extent in one part after separation, a very large separation factor can be achieved without the other component having to be sufficiently separated.
If, for example, the iron is precipitated with ammonia from a solution containing 100 mg Fe3+ and 100 mg Zn2+ ions, 10 mg Zn2+ ions may be entrained by the iron precipitate and, on the other hand, 0.0003 mg Fe3+ ions may be dissolved in the filtrate. The separation factor would then be 3 · 106, thus clearly exceeding the minimum value of 106 given above, although only 90% of the zinc was separated from the iron and the separation would therefore be insufficient for analytical purposes.
The separation factor is therefore of limited applicability, and one must specify the yields of both components of the mixture or their impurities for definite statements.
If the analytical sample contains more than two substances (which is usually the case), several separation factors must be specified according to the number of components, which can make the labeling of the separation effect quite complicated.
Therefore, when evaluating a separation process, the selectivity must also be taken into account, i.e. the number of substances from which the component sought is separated at the same time. The greater this number, the more efficient the process obviously is. Ideally, even all the impurities in question are sufficiently removed in a single separation operation; then there is a specific separation. Some examples of separations that have historically been considered specific are given in Tab. 1.1 (some of these separations require additional masking reactions).
Nowadays, the term specific appears to be of little value in the light of the high detection sensitivity of modern analytical methods. Even supposedly highly pure reagents or solvents still contain detectable trace substances.
Tab. 1.1:Known specific separations (examples).
Separated element Compound formed Separation process F (C2H)3SiF Shake out with CHCl3 a. o. Ge GeCl4 Shake out with CHCl3 a. o. H H2 Diffusion through palladium Hg 2-Methylthiophene-5-mercury acetate Shake out with CHCl3 a. o. Pd Dimethylglyoxime compound Shake out with CHCl3 a. o. Tl Tl(C5H5) Shake out with CH2Cl2 etc.It is much used in immunology; there it tries to describe the (almost) exclusive interaction of antigens with antibodies. But even there, the concept of so-called cross-reactivity is better used to describe the achievable selectivity or specificity.
General literature
R.E. Langman, The specificity of immunological reactions, Molecular Immunology 37, 555-561 (2000).
B.-A. Persson & J. Vessman, The use of selectivity in analytical chemistry - some considerations, TrAC Trends in Analytical Chemistry 20, 526-553 (2001).
D. Thevenot, K. Tóth, R. Durst & G. Wilson, Electrochemical biosensors: recommended definitions and classification, Pure and Applied Chemistry 71, 2333-2348 (1999).
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