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1 Object of Analytical Chemistry

Analytical chemistry is one of the oldest scientiˇc disciplines. Its history can be traced back to the ancient Egyptians, about four to ˇve thousand years ago (Szabadvary [1966], Malissa [1987], Yordanov [1987]). But notwithstanding its long history, analytical chemistry is always an essential factor in the development of modern scientiˇc and industrialised society. The development of chemistry itself has progressed signiˇcantly by analytical ˇndings over several centuries. Fundamental knowledge of general chemistry is based on analytical studies, the laws of simple and multiple proportions as well as the law of mass action. Most of the chemical elements have been discovered by the application of analytical chemistry, at ˇrst by means of chemical methods, but in the last 150 years mainly by physical methods. Especially spectacular were the spectroscopic discoveries of rubidium and caesium by Bunsen and Kirchhoff, indium by Reich and Richter, helium by Janssen, Lockyer, and Frankland, and rhenium by Noddack and Tacke. Also, nuclear ˇssion became evident as Hahn and Strassmann carefully analyzed the products of neutron-bombarded uranium. In recent times, analytical chemistry has stimulated not only chemistry but many ˇelds of science, technology and society. Conversely, analytical chemistry itself has always been heavily in uenced by ˇelds like nuclear engineering, materials science, environmental protection, biology, and medicine. Figure 1.1 shows by which challenges analytical chemistry has been stimulated to improved performances within the last half century. Wilhelm Ostwald [1894], who published the ˇrst comprehensive textbook on analytical chemistry, emphasized in it the service function of analytical chemistry. This fact has not changed until now. Interactions with all the ˇelds of application have always had a promoting in uence on analytical chemistry.

1.1 Deˇnition of Analytical Chemistry
In the second half of the twentieth century, analytical chemistry was deˇned as the chemical discipline that gains information on the chemical composition and structure of substances, particularly on the type of species, their amount,

e. instruments.2 1 Object of Analytical Chemistry Fig. Lewenstam and Zytkow [1987]). have the same feature: it is the dependence of signal on analyte . Zolotov [1984] characterized chemical. however. physicochemical and physical methods of analytical chemistry as follows: \All of them. and strategies to obtain information on the composition and nature of matter in space and time" (Kellner et al. and structural relationships between the constituents (see. [1987]. Eckschlager and Danzer [1994].g. However. that of WPAC [1993]: \Analytical chemistry is found to be a scientiˇc discipline that develops and applies methods. Danzer et al. not really helpful. The ˇrst deˇnition that is focused directly on the role of analytical signals was given by Pungor who characterizes analytical chemistry as \a science of signal production and interpretation" (Veress et al. [1998]). [1976]). 1.1. and physical chemists) as well as physicists and bioscientists also obtain information on inanimate or living matter using and developing high-performance analytical instruments just as analytical chemists do.g. e. organic. there exists a wide range of diverse deˇnitions. Chemists of other branches (inorganic. One of the most appropriate is that of Reilley [1965]: \Analytical chemistry is what analytical chemists do" which is. Consequently. now and then analytical chemists feel uneasy with such kinds of deˇnitions which do not re ect completely the identity and independence of analytical chemistry. however. Economic and social challenges and stimuli for the development of some important branches of analytical chemistry possible temporal and spatial changes. Sometimes the development of methods and instruments is included or is central to such deˇnitions.

energetic state and geometrical arrangement of atoms and molecules in general or within any given sample volume. Danzer [1992]. . Green [1992]. is the chemical metrological science" (Valcarcel [1992]) \. . present in particular state. an international competition was organized in 1992 by noted European analytical chemists and the Fresenius Journal of Analytical Chemistry to characterize analytical chemistry as an autonomous ˇeld of science by a topical and proper deˇnition. computer science. followed by problem. . . is a branch of science which comprises the theory and practice of acquiring information about chemical characteristics of any matter of system. .and matterrelated signal processing and signal interpretation in order to provide 1 Note of the author: this interpretation is not reversible: physical chemistry is not theoretical analytical chemistry . behaviour in chemical reaction systems at all levels of the chemical organisation of matter" (Zuckerman [1992]) \. Valcarcel [1992]. . In analytical chemistry. The important task of analytical chemistry is therefore the discovery and implantation of these dependencies into analytical procedures" (Lewenstam and Zytkow [1987]). into information and ordered knowledge". can also be considered applied physical chemistry"1 (Cammann [1992]) \. " (Zhou Nan [1992]) \. . . Zhou Nan [1992]. . To overcome the unsatisfactory situation in the understanding the meaning of analytical chemistry at the end of the last century. Ortner [1992]. structure and state. Other remarkable aspects expressed in the published contributions of the competition are the following: Analytical chemistry . uses chemical. and engineering" (Koch [1992]) \. Cammann [1992]. is a multidiscipline.1 Deˇnition of Analytical Chemistry 3 concentration. . . Koch [1992]. . number. derived mostly from speciˇc interaction between matter and energy. \. . mathematics. Stulik and Zyka [1992]. composition.1. . Kuznetsov [1992]). special techniques are used to transform measured chemical signals. . from its bulk or from a speciˇed region . The title of this competition was \Analytical Chemistry { today's deˇnition and interpretation" and 11 out of 21 contributions were published in Fresenius J Anal Chem (Fresenius and Malissa [1992]. steric and inner relations. comprising various ˇelds of chemistry with special understanding of physics. The ˇrst prize winner { Cammann [1992] { deˇned analytical chemistry \as the self-reliant chemical sub-discipline which develops and delivers appropriate methods and tools to gain information on the composition and structure of matter. Perez-Bustamante [1992]. and physical or even biological methods for analytical signal production. is a science devoted to the analytical cognition of substances: their properties. . Zuckerman [1992]. . physicochemical. especially concerning type. . .

How bound? (Speciation). How structured? (Structure analysis). . concentration). ions. modiˇcations. complexes. functional groups. and binding state (oxidation state. wide agreement can be stated about the aim to obtain information on matter via representative samples and the inclusion of structural information. . such as that from Murray [1991] who characterized analytical chemistry brie y and aptly as \the science of chemical measurements". . or even being an autonomous science. simple. or complex bound). On the other hand. Some others { with originality { could be added. is the science of the creative derivation of information using proper methods to answer the following four basic questions which also resemble the relevant fundamental ˇelds of analytical chemistry: What and how much? (Bulk analysis). Its object is the generation. physics and applied mathematics. . the following object characterization is proposed: Analytical Chemistry is the science of chemical measurement. . isotopes. and occasionally sum parameters. the aim of which is the handling of any type of matter in order to separate. occasionally called Analytics or Analytical Sciences. . . organic. viz. How distributed? (Topochemical analysis)" (Ortner [1992]) \. Considering the recent development of analytical chemistry and the signiˇcance of analytical signals for which reasons will be given in Chap. compounds. embraces that domain of the physical sciences that allows the interaction of molecules and matter to be understood and their composition to be determined. 3. Principle goals are the identiˇcation and recognition of sample constituents with regard to their type (elements. their amount (absolute or relative: content." (Green [1992]) All these deˇnitions express essential aspects of analytical chemistry and the analytical work. macromolecular or biomolecular. to establish a congruent trinomium involving: chemical species { instrumentation and metrology { data handling and processing (chemometrics)" (Perez-Bustamante [1992]) \. too). treatment and evaluation of signals from which information is obtained on the composition and structure of matter.4 1 Object of Analytical Chemistry reliable (quality assured) qualitative. quantitative and/or structural information about a sample" (Koch [1992]) \. identify. quantify and speciate its components by extracting the pertinent information of analytical interest contained in a representative sample" (Perez-Bustamante [1992]) \. Remarks on the general importance of analytical signals can be repeatedly found. binding form and type: inorganic. is the branch of chemistry. . Different opinions can be found about the status of analytical chemistry as being a branch of chemistry independent from other chemical disciplines or being a physical discipline (Green [1992]). is based upon the symbiotic knowledge and application of chemistry. .

The analytical chemist is considered as a \problem solver" (Lucchesi [1980]) and the concept is represented in the form of the \analytical trinity" (Betteridge [1976]) as shown in Fig. according to Betteridge [1976] The opinions about the status of analytical chemistry { being an independent or an auxiliary science { have varied over many decades. and principles (e. The analytical trinity. various respectable sciences like mathematics.2.g. Therefore. it is not really a desirable to be independent among the scientiˇc or chemical disciplines and is not a disadvantage to be thought of as an auxiliary science.1. analytical chemistry has a large variety of methods. Nowadays. techniques. physics. Therefore. 1.2 Repertoire of Analytical Chemistry 5 Fig. 1. ash . In contrast to classical analysis. 1.g. In Fig. However. the question about independence is relative and of secondary importance. and biology have a service function. The progress was caused by the development of completely new methods. techniques and apparatus at its disposal and is able to play its \instruments" with high virtuosity. the wide range of performance which analytical chemistry can achieve is extremely varied and extends from simple binary decisions (qualitative analysis) to quantitative analysis at the ultratrace level. Performance parameters have rapidly and drastically improved by the high demands of the main focuses of development. too. the concept of modern analytical chemistry has changed in so far as the problem that has to be solved is included in the analytical process.3 it is shown how the efˇciency of analytical methods has successively improved in the last 50 years. from structure elucidation and species identiˇcation to studies of the dynamics and the topology of multispecies systems by means of temporally and spatially high-resolving techniques.2. microprobe techniques) as well as the introduction of new system components into common instruments (e.2 Repertoire of Analytical Chemistry The continual progress of analytical chemistry is attributed to the increasing demands from science and technology as well as from society. 1. In some respects.

On the other hand.g. single component and multicomponent analysis are distinguished. ultra trace analysis). According to the demands of the analysis. and time expenditure/time resolution t excitation. and trace components (trace analysis. micro analysis. On the other hand. One has to perform dynamic analysis or process analysis on the one hand and distribution analysis. This kind of analysis is denoted as bulk analysis (average analysis). sample areas (cross-section) l .6 1 Object of Analytical Chemistry Fig. investigation of stoichiometry). limit of detection LD . analytical problems are differentiated according to the number of analytes involved. Accordingly. analytical investigations can particularly be directed to characterize temporal or local dependences of the composition or structure of samples. capillary columns) and methods (e.3. precision analysis. Additionally. Analytical investigations usually concern samples which are temporally and locally invariant. minor components. and nano analysis on the other. analytical chemistry can be classiˇed into analysis of major components (major component analysis. enrichment techniques. Technical progress in analytical chemistry with regard to sample mass m . hyphenated methods). . local analysis. the use of chemometric procedures has considerably improved the power and range of analytical methods. 1.

1. In any case. The latter is the process of determining if a particular analyte is present in a sample (Prichard et al.2 Repertoire of Analytical Chemistry 7 Fig.1.5 the repertoire of analytical chemistry is classiˇed more in detail according to element and structure analysis and according to the extent of quantiˇcation.3 it will be shown that there is a . [2001]). Further structure investigations concern near-orders in solids and liquids (e. The tetrahedron represents the basic analytical repertoire in a simpliˇed way. glass). identiˇcation is the process of ˇnding out what unknown substance(s) is or are present (Eckschlager and Danzer [1994]). On the other hand.g. structure analysis can be considered as distribution analysis in atomic dimensions. The tetrahedron of the analytical repertoire In principle. The relations between the questions that are answered by analytical chemistry are shown in Fig. The different ways of species analysis { qualitative and quantitative { are well known. identiˇcation is not the same as qualitative analysis. 1.1 and 9. However. they can also be differentiated between qualitative and quantitative ways according to the type and amount of information obtained (Eckschlager and Danzer [1994]). In Fig. Qualitative analysis seeks to answer the question of whether certain components are present in a sample or not.4. from the practical point of view it makes sense to deal separately with structure analysis and to differentiate between molecular structure analysis and crystal structure analysis. In Sects 9. However.4. 1. in structure analysis. It can be seen that all the analytical treatments are connected with each other. Identiˇcation of a sample or a given constituent may have an intermediate position between species and structure analysis.

ICP-MS. i.8 1 Object of Analytical Chemistry Fig. The application of combinatorial principles in chemical synthesis. By the way. Notwithstanding the formal classiˇcation given in Fig. and chromatography are the work-horses in today's analytical chemistry. ultimate lines.5. requires analytical methods with high throughput (von dem Bussche-Hunnefeld et al. 1. A rough gradation of analyte amounts has been done by de Gramont [1922] who investigated 82 elements in minerals. 1. [1997]). Screening techniques can be used to analyse a large number of test samples in a short . particularly in the search for active substances. In each case a speciˇc signal is generated which may be evaluated to meet any component of the following logical sequence: Detection ! Assurance ! Semiquantifying ! Quantifying This chain of information can be broken and applied at each point according to the special demands. ores and alloys by means of atomic spectroscopy using so-called \raies ultimes" (last lines. such lines which disappear at deˇnite concentrations). Especially spectroscopic and chromatographic methods are able to detect and determine a large number of species simultaneously. even the detection limit involves a numerical estimation. such methods like ICP-OES. Survey of element and structure analytical standard procedures clear difference between the information contents of qualitative analysis and identiˇcation.e.5 there is no fundamental difference between qualitative and quantitative analysis. Another aspect of modern analytical chemistry is the possibility of multicomponent analysis. TXRF. Therefore.

from the philosophical point of view. diagnosis.6. criminalogy and law as well as from chemical synthesis to materials sciences and engineering. Methods of screening must be inexpensive with regard to both time and cost. The characteristics of molecules are then linked with those of crystals and elementary cells. On the other hand. The ˇelds of application of analytical chemistry extend from research to service. from science to technology and society. and space ight.6. and process control. the relative amounts (contents. 1. from chemistry to biology. analytical chemistry plays an important role in every ˇeld of our life. microelectronics. Structure elucidation of a compound follows another logical sequence: Constituents ! Gross composition ! Sum formula ! Constitution ! Conˇguration ! Conformation ! Quantitation: Intramolecular Dimensions This strengthens the case for treating structure analysis as a particular ˇeld of analytical chemistry despite the fact that. In brief. structure analysis can be considered as distribution analysis (topochemical analysis) of species in atomic dimensions. Structure analysis of solids follows a similar scheme like that given above. 1. The ˇeld of operation covers over 30 orders of magnitude and more when the amount of lots is included. respectively) is low. Absolute masses of samples and analytes (a) and relative analyte amounts (b) relevant in analytical investigations time. . concentrations) with which the analyst has to do covers 20 orders and more because single atom detection has become reality now.1. environmental protection. production. A quantiˇcation of the repertoire of analytical chemistry is shown in Fig. Naturally they must be reliable enough that the risk of erroneous decisions (false positive and false decisions.2 Repertoire of Analytical Chemistry 9 Fig. health services.

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