4 The Analytical Process Chapter Outlook In this chapter, the implementation of an analytical measurement process from the uncollected, unmeasured, untreated sample to the required results, via the four major steps involved, namely preliminary operations, measurement and transducing of the analytical signal, acquisition and processing of data, and calibration, is out- lined. The principles and practical implementation of sampling are highlighted as a ley aspect of analytical processes, The significance of analytical separation tech niques in the context of sample treatment is emphasized. A global description of the measuring and transducing of the aralytcal signal, as well as @ general approach to the acquisition and processing of data, is provided. The main sclentifc and technical trends relating to analytical processes are described Chapter Outlook 37 45° Measuring and Tronsducing of the Analytical 4.1 A General Overview of Chemical Measurement Signal 55 Processes 38 46 Signal Acquisition and Data Processing 57 42. Preliminary Operations 39 47 Current Scientific and Technical Trends 59 43, Sampling 41 Questions and Problems 60 44 Sample Preparation 52 Recommended Reading 60 Atala Chenier: A Modem Approach Anal! Scien, Sead Bi Bi by Kale, J-M Mere Ot, Valet, Fo Wide Copght © 200 WLSVVCH Vetag Grab & Co. Kas, WeilFique 41. Main steps ofa chemical reasizement process (CMP) that, separates samples from results 4 The Anaiiel Procass Ruse ‘ek anal MEASUREMENT TaNARY PROCESS (CMP) NI MEASUREMENT myst wen, AND TRANSDUCING peonns ‘OP ANALYTICAL SIGNAL = MEASUREMENT ‘STANDARDS, 4.1 A General Overview of Chemical Measurement Processes ‘A chemical measurement process (CMP) can be defined as a set of operations that comes between uncollected, unmeasured, untreated samples and the results t pro- vides. Because it involves the use of at leat one instrument, itis also the material- ization of an analytical technique. On the other hand, a CMP materializes in an analytical method, the most detailed expression of which is an analytical procedure. ‘Chemical measucement processes use a variety of anaiytical tools in combination. Such tools can be physical (eg. instruments, apparatuses), chemical (eg. reagents, solvents, standards), mathematical (eg, chemometric treatments of signals), bio chemical (eg, immunoassay reagents, immobilized enzymes), or biological (eg. animal or plant material for constructing sensors). {As can be seen in Fig, 41, a CMP consists of four generic steps with samples and ‘measurement standards as the inputs, and information about the samples as the ‘output. The fist step can involve a variety of substeps, the main purpose of which is to make the sample ready for the measurement proper, interestingly, it rarely in- volves physical (eg. temperature, pressure, current intensity) measurements. The second step is the measurement and transducing of the analytical signal, which en- ‘ails the use of an instrument (eg. a gas chromatograph, spectrometer or lumin- ‘ometer), Data cquisition and processing, which constitute the third step, provide the results sought in accordance with the client's information needs. These three steps, Which have the sample as imput, constitute a simplistic approach to which there are obviously many exceptions. For example, instruments (e.g. a balance, volumetric glassware) are also used in the first step to measure the sample mass or volume. The three steps are frequently integrated, ether parly (e.g. sensors and gasliquid chro ‘matographs integrating the frst two steps) or completely (eg, clinical analyzers or strips forthe in situ deterraination of glucose in blood), “The fourth essential step of 2 CMP involves calibration operations and has mea- surement standards as input. Equipment calibration (sce Section 2.2.5) is intended ‘0 ensure correct performance of the instruments (eg. balances, volumetric glass ‘ware, spectrophotometers, chromatographs, pH-meters) and apparatuses (e.g. cen- twifuges, ovens) used in CMPs. On the other hand, method calibration (see Section 2.25) is carried out to establish unequivocal qualitative or quantitative relationships between the analytes) and the signal(s) provided by the analytical instruments used, mainly, in the socond step ofthe process.‘42 Preliminary Operations ‘The choice or design of a CMP for a specific purpose relies heavily on 2 number of factors, the most salient of which are as follows: 1. The particular problem addressed in terms of the specific information required by the client, the type of analysis (qualitative, quantitative, structural, surface, glotal) to be performed, and the quality compromises to be adopted (eg. to favor expeditiousness at the expense of accuracy of vice versa). 2. he characteristics of the target sample (e.g. nature, aggregation state, availability, stability). 3, The nature, number, and concentration of the analytes to be identified and/or determined. 4. The specific tools (instruments, standards, reagents) available in the laboratory that is to conduct the analyses. A CMP has two types of analytical features (see Section 3.1), ramely: () basic analytical properties (vz. precision, sensitivity, selectivity, and proper sampling), on swhich the capital properties attributed to analytical results (viz, accuracy and repre sentativeness) should rest; and (i) productivity xelated properties (viz. expeditious- ness, costeffectiveness and personnel elated factors) Because solving the analytical problem (see Chapter 5) inevitably involves adopting some quality compromise, one should always bear in mind the contradictory and complementary relationships among analytical properties discussed in Section 3.10, 42 Pr inary Operations So-called “preliminaty operations” encompass a wide variety of substeps of the an- alytical process that connect the uncollected, unmeasured, untreated sample to the main measuring step (see Fig. 4.1). In contrast to physical measurements, the pre- liminary operations of 2 CMP are highly relevant as they have 2 favorable impact on capital, basic, and produatvity-elated properties. In fact, they exert a direct infu. cence on accuracy (through systematic errors), representativeness (through proper sampling), precision (through random errors), and productivitytelated properties (expeditiousness, costeffectiveness, and personnelrelated factors). Also, they ind rectly enhance selectivity (through interference removal) and sensitivity (through preconcentration), as well as accuracy as a whole (through the individu effects of precision, sensitivity, and selectivity), Each analytical problem and, especially, each sample-analyte pair, calls for specific combinations ofa ide varity of preliminary operations. Figure 4.2 shows some of the more common substeps involved in such preliminary analytical actions. One of ‘the main problems faced in this contest is deciding whether to include sampling in the analytical processor to exchide it. Because itis extremely relevant tothe quality ‘of the results, sampling is dealt with as an integral part of the analytical process in this textbook. ‘The sequence depicted in Fig. 4.2 is not always that followed in practice; more cover, not all substeps axe always needed, while some processes require others not shown in the scheme. The figure makes a distinction based on the aggregation state of the sample on account of its high significance in this context. Solid samples usually require more preliminary processing (e.g. drying, sieving, dissolution, dis- aggregation} than do liquid or gas samples. The most frequently implemented pre- liminary operations ate highlighted in the figure.“ Figure 42. The many possible substeps ofthe preliminary ‘operations ofthe analytical process (CMP; those in chided bones are the Figure 43. Genera fetures of ¢ astute 9. @ cone TENE = HUMAN Varian ARC ATION CHARACTERISTICS, OF PRELIMINARY OPERATIONS. 7 oF ‘TO ® ERRORS CONTROL, o © Figure 43 depicts the most salient features of the frst step of the analytical pro- cess, which can be summarized as follows: (a) Preliminary operations are widely variable in nature. Differences between them arise from the factors potentially affecting their design. Thus, samples can be solid, liquid or gaseous, and can have an oxganic, inorganic or biological matrix. Analytes ‘ean also be inorganie, organic or biochemical, and are present at variable tration levels (viz. as macro or micro components, or as traces). This vara sulis in the need for @ specific approach for each individual sample-analyte pair and in an obvious scarcity of dedicated commercially available equipment. (b) The complexity of preliminary operations is one of their greatest hindrances. As ‘a nule, multi-step processes using @ number of analytical tools are required. (c} Preliminary operations involve intensive human participation and are generally Gifficut to automate. There are some useful automated approaches to offline (di- gesters, extractors) and ondine (continuous-flow manifolds) equipment coupled to instruments.43 Soming [4 (a) Preliminary operations constitute the mest severe bottleneck of CMPs as regards expeditiousness. Between 70 and 60% of te time taken to conduct them is spent on. precoperations. The fist step of a CMP is thus quite slow relative to the second and third (¢) Systematic contol of preliminary operations is not so affordable or convenient 4s that of an insteument through clibzation. Performance checks involve the pains taking testing of al tools in order to confirm that they operate as scheduled. There ate two main practical ways of ensuring cuality in these operations, namely (i) by applying the principles and practices of quality assurance systems within the framework of the standard [80 17025:1999, and (i) by global assessment of the CMP using certified reference materials [if their results (within their uncertainties) are consistent with the certified values, then one can conclude thatthe preliminary ‘operations were properly implemented). (£) Preliminary operations are, in general, the greatest sources of both systematic and random errors, which have a decisive influence on the quality ofthe results of a CMP. Typical errors in this context arise from non-representative samples, inappro- priate sample storage conditions, incomplete removal of inerferents, gains o¢ losses of trace analytes te, These errors stem both from technical complesity and from the socalled “human factor” (@) Preliminary operations constitute a potential source of human and environ: mental hazards. The feequent use of acids, organic solvents, high pressures or ter: peratures, et, can have adverse hygienic and health effects on laboratory personnel both in the short and long terms. These operations also produce variable amounts of toxic waste that requires careful handling and disposal in order to prevent environ mental damage For the aforementioned reasons, preliminary operations play a crucial role in MPs, 20 much so that they can be deemed their Achilles’ heel. On the other hand, they are indispensable with a view to obtaining quality results, 43° Sampling 43:1 Introduction Sampling can be regarded as the first substep of the preliminary operations of « CMP; some authors, however, consider sampling a separate step of the analytical process and use it to distinguish between the analytical processes that include it and analytical methods. ‘Sampling can be defined in various, complementary ways as 1. the practical procedure used to select a single or several portions (aliquots) fiom ‘the material (object) under study; 2, the link between the object and the other steps of the analytical process; and 43, the way representativeness of the analytical results is achieved as regards a spe- cific set of features of the objec, taking into account both the characteristics of the object and the information required about it. Sampling possesses an undeniable significance as the quality of the analytical results relies on both accuracy and representativeness. An accurate result that is not representative will bea poor result anyway. Frequently, sampling isnot cacied ‘out by analytical chemists, who receive previously collected samples for analysisFigute 44, Schematic view ofthe Principal bottlenecks of sampling procedures 4 The Anolyeal Process ‘MAIN SOURCES OF SAMPLING PROBLEMS. cansacrsummes [corona] ee Ce OO L___,] exes PROCEDURE TAIN OFT TOOLS Undoubtedly, ensuring quality in the analytical results entails having analytical chemists participate in the design, implementation, monitoring, and control of sampling procedures. In other words, sampling is an essential aspect of CMPs and as such should be conceived and managed. 43.2 Limiting Factors of Sampling Sampling is not an easy operation, In fact, proper sampling entails overcoming var ious problems that make it one of the most difficult operations of a CMP (Fig. 44), narnely: 1. Accurately and precisely defining the chemical information required to solve the ‘analytical problem (see Chapter 5) addressed and hence the aims of sampling. Thus, ‘the needs will vry depending on whether the information required from the object is of the global ype (e.g. the average hydrocarbon content in air) or includes spatial or temporal variability. Accurately defining the specific type of information to be extracted from the object is thus essential. Without a clear aim, sampling makes 10 2. The nature and properties of the target object are highly relevant to sampling. “Thus, a lack of spatial andjor temporal uniformity in the object is one of the greatest hindrances to this analytical operation. Ifthe target material is uniform, then any portion taken fiom it will be representative of the whole. However, objects are not ‘usually uniform ox homogencous, and so the collection of a number of samples is required in order to ensure representativeness. Also, an object that is homogeneous overall may not be uniform as regards a specific property. The aggregation sate of the object (solid liquid, gaseous or mixed) is also crucial as it dictates the type of sam. pling procedure to be used. Sampling is also strongly influenced by the type of ratriof the objet (inorganic, organic, biological) and by the nature and concentration. ofthe target analytes. Thus, a semiconductor and a biological tissue to be analyzed for metal traces will require different sampling procedures. Also, the sampling approach of choice strongly depends on the variability ofthe object with time, which is commonly referred to a8 stability, if the composition of the object is time: dependent, then the number of samples to be collected will be greater than if itisDSS EEE EEE eee EEE EEE EE EEE EEE EEE EERE eer eee eee eee eee ene ee ee ee cee ee eee eee eee ee 43 somelg | rot. There is also the need to consider the availability of the objec; thus, the amounts of samples that one can obtain frorn a painting by Rubens, horse urin, see, or a baby's blood will be rather diferent, and consequently so will the sampling proce- dare of choice in each case. Finally, the location of the object with respect tothe labo: ratory can also dictate the choice of sampling approach (consider, for example, the analysis of moon rocks by a NASA laboratory and that of dairy products by the manufacuser’s own laboratory} 3. The experimental sampling procedure should also be clearly established, Thus, one ‘must consider the difference between on-site analyzers operating far from the labo- ratory and conventional analyses implemented within them; the sampling approach of choice will obviously be rather different. Additional sources of problems here in- clude deciding on the location, mumber, and size of the sample object aliquots needed to achieve the required representativeness level, andthe lack of specific tools for implementing the most suitable approach. Finally, sampling should be done in | such a way as to ensute that the sample aliquet ultimately subjected to the other steps ofthe CMP is representative ofthe portion taken from the objet in this con- j text, sample stoge and transport operations can be after source of problems. 43.3. Sampling Approaches "The sampling plan is a well-defined procedure comprising several steps involving the selection, collection, storage, transport and preparation of the portions collected from the target abject. It should be designed with regard to both the objectives of the CMP and the characteristics of the object, and aimed at minimizing the potential problems depicted in Fig. 44, ‘The sampling plan should be a compromise between representativeness and cost plus efforts, and be realized in the number and size of samples to be taken from the target object. The plan should thus establish the smallest number of samples re ‘quired to ensure representativeness at the intended level. ‘A properly designed sampling protocol should be able to provide clear-cut answers to the following questions: + Where? (ie. the locations from which the samples are to be collected) + When? (ic. the frequency of sampling atthe previously defined places) «+ How many (ie, the number of samples to be collected from the object) «© What size? (Ie. the mass or volume of the aliquots to be taken) + How? (ie. the way ia which sampling and sample storage and transport are to be accomplished) Sampling approaches can be of two pes depending on whether they rely on probabilistic (statistical) or non-probabilistic criteria (Fig. 4.5). There are additional approaches such as those based on a protocol ot on stratified sampling, which, however, can be included in one of the previous two groups. In sampling approaches based on non-probabilistic criteria, several elements or parts of the object ate assumed to have zero probability of being collected. One can further distinguish between those based on intuitive sampling and oriented { sampling | ‘in intuitive sampling, the analyst, by personal choice based on his/her own experi cence, selects the object portions to be analyzed; such is the case when a texture or color change is observed in the studied material or when some isolated alteration in. a production process is suspected, On the other hand, oriented sampling is the pre: | fetred choice when the analytical problem requires well-defined, highly specific in- |M4] 4 The Antal Process Figure 45. Main types of sampling approaches: for details, see text [oromer cme | Sawn SAMPNG nor ais STRATEN APPROACHES PROTOCOL SAMPLING Tf} formation (e.g. the concentration of metal species in suspended particles of a spe- cific size in the analysis of natural water). Probabilistic sampling approzches rely on statistical procedures that allow one to establish specific rules for collecting parts of the object. They constitute the best choice for sampling when available information about the object is inadequate and assume that non-uniformity in the object composition conforms to a Gaussian dis- tribution characterized by 2 standard deviation directly representative of heteroge ncity in the object. ‘There are three main types of probabilistic sampling, namely random, systematic, and mixed sampling (see Fig, 4.5). Random sampling is carried out in such a way that any part ofthe object (a “lot” in statistical terms) has the same probability of being collected; ordinarily, this involves collecting a large number of samples by using (or not) a random standard based on computer software generating random data; this disadvantage, however, can be overcome by using object strata. In sjstematic sampling approaches, samples are collected over specific spatial or temporal intervals accurately defined in the sampling plan in accordance with the properties of the object and the information required fiom it. This is the most fre- {quently used sampling approach. Ordinarily the object is split into parts by using a template of variable shape (see Fig. 4.6). Thus, the quadrangular template (Figs. 4.68, 4B, and 4.60) is very frequently used to spit the object into regulely shaped portions; samples can be taken in a systematic manner at the grid nodes (Fig. 4.6A) or by using a mixed (systematicrandom) approach to collect either one sample from any point on the grid surface (Fig. 4.6B) or several samples from randomly selected srids (Fig, 4.6C). Environmental samples to be collected from large areas are fre: ‘quently obtained by using a W- or Xshaped template (Figs. 4.6D and 4.68, respec: tively). When the specific source (location) ofa given analyte (e.g. an environmental pollutant) is kuown, 2 template consisting of concentric circles (Fig. 4.6F) is usually ‘employed for collection, which is carried out near the source. ‘When the target object is dynamic in nature (ie. when its composition varies in a ‘clic or nom- figure 434, Main separation techniques used for analytical purposes, classified according tothe lggregation state ofthe two phases involved (inital and fral sample phases) for details, see tests Figue 415. Classfcation of analytical separation vechniques based fon 8 combination of thre criteria, namely principal operation mode, efficency/purpose, and relationship to the instrument involved inthe second step ofthe analytical process; for deta, se text 4 The Avolytical Process ‘THESECOND STEP CRITERIA —+ orrranion EFFICIENCY /PURPOSE (OF THE CNP, aS OS aac HY 8 corine = ‘inrneR é SEPARATION § fecunaves, i $ [commcos]}-2 interferents. In continuous separation techniques, the so-alled “mobile phase” isin continuous motion, while the other (the stationary phase) remains still throughout the separation process; this facilitates the establishment of multiple transfer equilibria One further essential distinction between analytical separation techniques con- cers various aspects related to their sims and efficiency. Thus, chromatographic ‘techniques (column and thin-layer chromatographies) are aimed at separating (ie. at discriminating in space andor time) most of the components of the sample matrix (both analytes and other species); they are implemented in a continuous manner and are usually ~ thin-layer approaches excepted ~ connected ondine to the instru- ment, which results in a typically very high efficiency. Non-chromatographic sepa ration techniques, which can be operated in a discrete or continuous fashion and connected both online and off to the instrument, are less efficient than their chro: ‘matographic counterparts. The most commonplace non-chromatographic separation techniques, which involve a variety of interfaces, are gas diffusion, distillation, dial ysis, liquid-liquid extraction, solid-phase extraction, precipitation, sublimation, and leaching. Flectrophoresis is non-chromatographic in nature but resembles chro- ‘matographic techniques in operation. ‘A detailed description of the separation techniques commonly used in CMPs is provided in Chapters 13-16. Also, the fundamentals of mass transfer equilibria are dealt with in Chapters 9 and 13-16. ‘The significance of analytical separation techniques stems from the fact that they cffciently enhance two basic analytical properties, viz. sensitivity (through pre concentration) and selectivity (through interference removal and clean-up), which are the comerstones for accuracy in the analytical results, Figure 4.16 illustrates these two crucial functions of analytical separation techniques. Preconcentration of the analyte through the use of a non-chromatographic separation technique (Fig. 4.16.1) is accomplished by transferring the whole analyte content from a high vol ture (Va) in the initial sample phase to a low volume (Va) in a second phase. The ratio of the analyte concentration in the final phase, [A] to that in the initial phase, [Ac], Constitutes the so-called, “preconcentration factor” % Ye % [Ad = ladl ys (43) In trace analysis, the insertion of sample aliquots containing a low concentration of the analyte, [Ag], frequently provides signals that are too weak to be distinguished from noise; however, by concentrating the initial sample, the signal can be raised ‘well above noise evel to facilitate the identification and/or quantitation of the analyte.45 Measuring and Transducng ofthe Anoicl Signal @ ® SAMPLE ital phase) ABCD.E, sano 2 rananae open See ag wa Gr \we OES Removing interferents (B, C, D, E ..) potentially disturbing the determination of the analyte (A) is the other essential aim of analytical separation techniques, Figure 4.162 illustrates the two major approaches to this goal. The more simple of the two (Fig, 4.16.2a) involves having the analyte accumulate in the second phase while the other components are sent to wast or vice versa, This can be efficiently accomplished by using a non-chromatographic continuous separation technique. Chromatographic and electrophoretic techniques (Fig. 416.26) allow one to isolate virtually every ‘component of the sample matrix (A, B, C, D, E...) in new mobile phase waits in such a way that they can reach the on-line coupled instrument one by one and yield discriminated signals that will constitute a chromatogram or electropherogram. ‘As can be seen in Fig. 4.2, the insertion of a treated sample aliquot into an in- strument is preceded by other preliminary operations, the most relevant of which are (bio)chemical reactions, whether analytical or non-analytical. Non-analytical re actions are those intended to facilitate the second step. Such is the case with the use of fluoride ion to mask Fe* by forming a stable, colorless complex (FeF~) and avoid its interference with the photometric determination of aluminum, and with the use ofthe Jones reductor (amalgamated zinc) to transform dissolved iron fons into Fe prior to ther titsimetric determination with standardized potassium di- chromate, The analytical (bio)chemical reactions used in the preliminary operations of CMPs are intended to convert the analyte into products with which the instru: ‘ment will be compatible (eg. the use of derivatizing reagents forming volatile com pounds with the analyte that can be separated and/or quantified with a gas chroma- tograph) or to which it will respond (e.g. the addition of 1,10phenanthroline as a ligand, 1, to form a colored chelate, Fels”, with iron to enable the spectrophoto- metric determination of iron traces) 45. Measuring and Transducing of the Analytical Signal Based on the scheme of Fig. 4.1, the second step of the analytical process involves the use of an instrument - which is the materialization of an analytical technique ~ 5 Figue 416, Main goals of analytical separation techniques: (1) preconcer tration. (2) leap A B,C, are sample components for details, ee6 Figure 417, Nonerclusive lassifce- ‘ion eter for instruments; for etal, see text 4 The Arai Pres TYPES OF INSTRUMENTS ‘CLASSIFICATION ‘CRITERIA qa seasons warure [7 2| wer Eeiomen, —_ Soaauves | 3 some (ormtin pee) ‘RELATIONSHIPS srweenoneiorece) 4 eran rota enn ae amano] 5 sean CAUTION quarries «| maumen. Sian ronrost Siero ata (BBs that receives an aliquot of the treated sample from the first step and measures and ‘ransduces an analytical signal related to the presence and/or amount of analyte. ‘This step coincides with that of physical measurements. The instruments involved can be dlassified according to six complementary, non-exclusive criteria (Fig. 417), namely: 1, The human body and, specifically, the brain and two senses (sight and smell) are used as instruments in classical qualitative analysis and manval ttimetres (eg. to read a titrant volume held in a burette). Most often, however, signals are measured with an instrument based on some physico-chemical principle. 2. The measured signal is a response of the instrument to chemical (reactivity) or physico;chemical properties of the analyte or its reaction product. This signal (and the corresponding instrument) can be of various types, including optical (eg. UV visible spectrophotometer, fluorimeter, atomic emission spectrometer), electro- chemical (eg, potentiometer, pH-meter, voltammeter), mass (e.g. balance, mass spectrometer, piezoelectric sensor), or thermal (cg. thermogravimetvic balance, dif: ferential thermal analyzes). The primary signal is transduced and amplified into another (usually electrical) signal, which is that actually measured (in volts or mill- volts) in practice. The output can be in analog, digital or printed form, but is usually siven in units related to the initial signal (e.g. absorbance in spectrophotometry, po- tential and/or millivolts in voltammetry). A detailed description of these instru- ‘ments can be found in many ofthe chapters ofthis textbook. 3. Instruments can be active or passive depending on the interaction between them and the analytes or their reaction products. In passive instruments, the analytical signal is not induced by the instrument, but arises directly from the physico- chemical properties of the analytes or reaction products; typical examples include ‘mass in balances and optical emission in chemi(biojiuminometers. On the other hhand, active instruments induce the analytical signal by imposing some type of energy (eg. optical, electrical, magnetic) on the analytes or their products. Such is46 Signal Acquistion ond Data Processing the case with UVjvisible and infrared spectroscopies, mnass spectrometry, or polar ography, for example 4, Depending on their relationships to previous and subsequent steps of the CMP, ‘measuring instruments can be of two types, namely: (i) stand-slone instruments (offline connected), which receive an aliquot of the treated sample that is manually cor automatically inserted in a discrete manner, and (ii) integrated instruments cou: pled online to one or more of the other steps of the CMP (e.g. a UYjvisible detector in a liquid chromatograph, and automatic signal acquisition and processing by ‘means of a computer). 5, The traceability inherent in chemical measurements dictates the type of calibra: tion to be used. Thus, primary instruments (the balance included) require equip. ‘ment calibration only (see Section 2.2.5). On the other hand, relative instruments, which operate by comparing signals from samples and standards, call for both equipment and method calibration (see Section 2.2.5) 6. Depending on the objectives of the analysis, instruments can provide signals to bbe used for qualitative, quantitative, structural or mixed purposes. Instruments for preferentially qualitative purposes provide a wealth of information that allows the reliable identification of the analytes; typical examples include mass and magnetic resonance spectrometers, which can also be used for quantitative purposes, however. Instruments primarily intended to obtain quantitative information provide reliable signal-analyte concentration (amount) relationships; such is the case with pH- meters and UVjvisible molecular absorption spectrometers. Some instruments (eg, atomic absorption and emission spectrometers) are frequently used for both purposes. 4.6 Signal Acquisition and Data Processing “The last step of a CMP is the acquisition of the analytical signals produced by in struments in the second step and their transformation into the analytical results in the required format. This involves two sequential substeps, namely: 1. Acquisition of transduced signals, which are rave (e.g. absorbance, mass, current in: tensity) data obtained in the preceding measurement step. Such data can be ac- quired in three main ways, namely: (i) by inspecting the color of a precipitate, read- ing off a burette scale locating the position of @ gauge on an analog scale, or reading the figures on a digital display; (i) semsi-automaticaly, with the instrument provid: ing an information output such as a spectrum, chromatogram or signal-time plot (fom which data can be manually extracied) for purposes such as identifying a ‘molecule from its infrared spectral bands or measuring the height of a chromato- ‘graphic peak or the slope of a kinetic curve; and (ii) automatically, with a computer processing one-, two: of three-dimensional information such as @ mass, a volume, and a signal-wavelength, signal-time or signal-wavelength-time relationship, respectively, 2, Processing of data through computations based on chemometric methods in order ‘to express the results as required and support the production of reposts within the framework of the analytical problem (see Chapter 5). There are two main sources of data here (see Fig, 4.18). Thus, there are experimental data (signals) from the second step of the analytical process derived from both samples and analytical standards ‘used in the calibration procedures, Also, there is a need to use stated or tabulated data to produce analytical results; such is the case with values assigned to chemical standards (e.g, the Faraday, atomic weights), physico-chemical constants (e.g. parti- ”*| Figure 418. The two main sources of data tobe processed in order to produce analjical esults a5 required Inthe tied step of a CMP Figure 419, Possible relationships between an instrument ard a computer in te tid step of the analytical process; for detalls, see test 4 The Anica! Process ‘STANDARDS Lamers a sAnerLes INSTRUMENT [oo ava conve caution RESULTS REFORTS tion coefficients in analytical separation techniques, acid-base and complexometric equilibrium constants), statistical values (eg. Student's Fvalues, which can be used to express the uncertainty intervals of the results), and conversion factors, which are dimensionless numbers (e.g, that used to convert protein nitrogen contents from primary results when determining various types of sample matrix) by which some ‘experimental data must be multiplied to be made consistent with well-established differences of the CMP (eg. incomplete extraction, partial conversion). The data processing substep depends strongly on the type of analytical method (primary, rel- ative) used, the aim of the analysis (qualitative, quantitative, structural), and the static or éynamic nature of the primary data. The use of computers has brought about a dramatic change in the third step of the CMP, where they play a central role st present. There are two main types of re lationships between instruments and computers (see Fig. 4.19). On the one hand, appropriate software is used to process data that can be acquired either manually (offline), by having the operator input the instrument's output data, or autora cally (ondine), by cect transfer of data via a passive electronic interface. On theBe cere eee eee eee eae 47 Cav Sif ond Tecra Tends | 39 Figue 420, Principal scenic nd technical tends in the design and pplication of new chemical mansurement processes ‘MAIN TRENDS IN ‘CHEMICAL MEASUREMENT PROCESSES (CPS) AUTOMATION. MINIATURIZATION SIMPLIFICATION other hand, the computer can be used to monitor and govern the fimetioning of the instrument, Le. the instrument can be operated from the computer via an active clectronic interface 4,7 Current Scientific and Technical Trends Current research and development activites in analytical sciences in general and MPs in paticular are aimed at improving existing methods and meeting the new chemical information demands of the clients of analytical laboratories. Many of these new developments share some basic trends (viz, automation, miniaturization and simplification] with ther scientific and technical disciplines (see Fig, 4.20) ‘Automating a CMP entails reducing or even completely avoiding human pat ticipation in it. There have been substantial practical advances in this direction over the past twenty years, 36 a result, a wealth of automated apparatuses and instr iments used in CMPs have been made commercially available. At the top of the ranking of integrated equipment for this purpose are automatic analyzers, fre ‘quently called “suteanalyzers”. The most salient advantage of automation in Anz Iytical Chemistry is improved baste (precision) and productivity-elated (expedi- iousness, costeffectiveness, reduced risks) properties. The different steps of the CMP have been automated to rather different degrees. Thus, instruments (second step) and data acquisition and processing (third) are now highly automated thanks to sdvances in microelectronics, micromechanics, and computer science. On the other hand, the preliminary operations (fst step) continue to be performed in a largely non-automated manner, mainly because of their intrinsic drawbacks (see Section 42), Reducing human intervention in CMPs continues to bea top priority in R&D in analytical sciences, Miniaturization also has a strong impact on the ability of CMPs to meet informa: tion needs. This has materialized in @ dramatic reduction in the size of material tools (eg. capillary elecirophocetic systems embedded in silicon chips that are only a few millimetees in size) and in the integration of modules that perform the steps and/or substeps of a CMP. Sovalled “micro total analytical systems” (wTAS) (see Chapter 32) have a highly promising futere in this context as they are expected to help break the batrers with which Analytical Chemisty has traditionally been confronted; dedicated R&D work is still required, howeves, with a view to their consolidation. | \4 The Anoiyia! Process ‘The simplification of some CMPs by the use of novel analytical tools such as re- sponsive sensors and portable NIR or NMR analyzers has brought about a revolu: tion in the traditional approach to the three steps of the CMP, which, however, are somehow implicitly developed during the process. Efforts in this direction are fo- ‘cussed on minimizing or avoiding pretiminary operations with a view to improving productivity related analytical properties. Simplified systems meet the requirements imposed by the need to process large numbers of samples or to obtain a rapid re- sponse, a global measure, or a binary (yes/no) response (see Chapter 35). There have been substantial advances in this context, even though a number of problems in various fields remain unaddressed, ‘As can be seen fiom Fig. 4.20, the previous three trends are inevitably related to ‘one another. Thus, simplification cntails both reducing human intervention and ‘Questions and Problems 11. Establish the relationships between the four main steps of the analytical process 2, What are the factors influencing the choice or design of an analytical process? 3. What are the tangible inputs of an analytical process? 4. Why is sampling an essential sub step of the preliminary operations of analytical processes? ‘What is the analytical property directly involved? 5. Comment on the inherent adverse connotations of the preliminary operations of analytical processes. Recommended Reading 1. Anderson, "Sample Pretreatment and Separation, Wiley, D. Shook, J. Leary, "“nstrumenal Anais, thea, ainiaturizng ~ particularly f autoanation and simplification ofthe CMP, tegration purposes ~ and miniaturization leads to ing from the | 6. What are the sampling problems object? ’ 7. Classify samples according to size and neamess to the target object. ¥ 8. Establish the relationship between sample size and random sampling errors, 9. What are the main roles of separation techniques in the analytical procesc? 10, Describe the separation techniques of choice when the sample is a liquid or is obtained by dissolving a : solid. : : Saunders Col. Publ, New York, 1992 1, Smith, G. V. Hames, "The Sampling of Bull Merial" Royal Society of Chemistry, Cambridge, 1981 1. alcitel, “Principles of Analytical Chemistry", Springer ‘Verlag, Heidelberg, 2000