Chemical measurement

In the following sections, we will deal with only some of the more common techniques used to evaluate the chemical nature of CVD films. We will be interested in the composition of the thin films, both as an average over the film thickness as well as a function of position in the film. We will also consider the chemical state of the atoms in terms of the bonds they can form within the film. 

---

Taylor, J. K. Quality Assurance of Chemical Measurements. Lewis Publishers Ghelsea, MI, 1987. 

The aroma of fmit, the taste of candy, and the texture of bread are examples of flavor perception. In each case, physical and chemical stmctures ia these foods stimulate receptors ia the nose and mouth. Impulses from these receptors are then processed iato perceptions of flavor by the brain. Attention, emotion, memory, cognition, and other brain functions combine with these perceptions to cause behavior, eg, a sense of pleasure, a memory, an idea, a fantasy, a purchase. These are psychological processes and as such have all the complexities of the human mind. Flavor characterization attempts to define what causes flavor and to determine if human response to flavor can be predicted. The ways ia which simple flavor active substances, flavorants, produce perceptions are described both ia terms of the physiology, ie, transduction, and psychophysics, ie, dose-response relationships, of flavor (1,2). Progress has been made ia understanding how perceptions of simple flavorants are processed iato hedonic behavior, ie, degree of liking, or concept formation, eg, crispy or umami (savory) (3,4). However, it is unclear how complex mixtures of flavorants are perceived or what behavior they cause. Flavor characterization involves the chemical measurement of iadividual flavorants and the use of sensory tests to determine their impact on behavior. 

Quahty control testing of siUcones utilizes a combination of physical and chemical measurements to ensure satisfactory product performance and processibihty. Eor example, in addition to the usual physical properties of cured elastomers, the plasticity of heat-cured mbber and the extmsion rate of TVR elastomers under standard conditions are important to the customer. Where the siUcone appHcation involves surface activity, a use test is frequently the only rehable indicator of performance. Eor example, the performance of an antifoaming agent can be tested by measuring the foam reduction when the sihcone emulsion is added to an agitated standard detergent solution. The product data sheets and technical bulletins from commercial siUcone producers can be consulted for more information. 

Limits on emissions are both subjective and objective. Subjective limits are based on the visual appearance or smell of an emission. Objective limits are based on physical or chemical measurement of the emission. The most common form of subjective limit is that which regulates the optical density of a stack plume, measured by comparison with a Ringelmann chart (Fig. 25-1). This form of chart has been in use for over 90 years and is widely accepted for grading the blackness of black or gray smoke emissions. Within the past four decades, it has been used as the basis for "equivalent opacity" regulations for grading the optical density of emissions of colors other than black or gray. 

For the physico-chemical measurements and practical utilisation in some cases the purification of nanotubules is necessary. In our particular case, purification means the separation of filaments from the substrate-silica support and Co particles. 

The traditional view of molecular bonds is that they are due to an increased probability of finding electrons between two nuclei, as compared to a sum of the contributions of the pure atomic orbitals. The canonical MOs are delocalized over the whole molecule and do not readily reflect this. There is, furthermore, little similarity between MOs for systems which by chemical measures should be similar, such as a series of alkanes. The canonical MOs therefore do not reflect the concept of functional groups. 

One of the chief reasons for the recent extensive work in this field has been the recognition that ion-molecule reactions are highly relevant to radiation chemistry. The possibility that certain simple reactions, such as the formation of H3+, participate in the mechanism of product formation was appreciated much earlier 14), but wider applicability of this concept required that the generality of such reactions be demonstrated by an independent, unequivocal method. Mass spectrometry has been the predominant means of investigating ion-molecule reactions. The direct identification of reactant and product ions is appealing, at least in part, because of the conceptual simplicity of this approach. However, the neutral products of ion-molecule reactions cannot be determined directly and must be inferred. Gross chemical measurements can serve as an auxiliary technique since they allow identification of un-... 

Functions of Standards. Fluorescent standards can be used for three basic functions calibration, standardization, and measurement method assessment. In calibration, the standard is used to check or calibrate Instrument characteristics and perturbations on true spectra. For standardization, standards are used to determine the function that relates chemical concentration to Instrument response. This latter use has been expanded from pure materials to quite complex standards that are carried through the total chemical measurement process (10). These more complex standards are now used to assess the precision and accuracy of measurement procedures. 

If the sample and standard have essentially the same matrices (e.g., air particulates or river sediments), one can go through the total measurement process with both the sample and the standard in order to (a) check the accuracy of the measurement process used (compare the concentration values obtained for the standard with the certified values) and (b) obtain some confidence about the accuracy of the concentration measurements on the unknown sample since both have gone through the same chemical measurement process (except sample collection). It is not recommended, however, that pure standards be used to standardize the total chemical measurement process for natural matrix type samples chemical concentrations in the natural matrices could be seriously misread, especially since the pure PAH probably would be totally extracted in a given solvent, whereas the PAH in the matrix material probably would not be. All the parameters and matrix effects. Including extraction efficiencies, are carefully checked in the certification process leading to SRM s. 

Section 4.5). Of these, mesocosms have stimulated the greatest interest. In these, replicated and controlled tests can be carried out to establish the effects of chemicals upon the structure and function of the (artihcial) communities they contain. The major problem is relating effects produced in mesocosms to events in the real world (see Crossland 1994). Nevertheless, it can be argued that mesocosms do incorporate certain relationships (e.g., predator/prey) and processes (e.g., carbon cycle) that are found in the outside world, and they test the effects of chemicals on these. Once again, the judicious use of biomarker assays during the course of mesocosm studies may help to relate effects of chemicals measured by them with similar effects in the natural environment. 

Ramsey, J. M., Miniature chemical measurement systems, in Widmer E., Verpoorte, E., Banard, S. (Eds.),... 

Measurement of exposure can be made by determining levels of toxic chemicals in human serum or tissue if the chemicals of concern persist in tissue or if the exposure is recent. For most situations, neither of these conditions is met. As a result, most assessments of exposure depend primarily on chemical measurements in environmental media coupled with semi-quantitative assessments of environmental pathways. However, when measurements in human tissue are possible, valuable exposure information can be obtained, subject to the same limitations cited above for environmental measurement methodology. Interpretation of tissue concentration data is dependent on knowledge of the absorption, excretion, metabolism, and tissue specificity characteristics for the chemical under study. The toxic hazard posed by a particular chemical will depend critically upon the concentration achieved at particular target organ sites. This, in turn, depends upon rates of absorption, transport, and metabolic alteration. Metabolic alterations can involve either partial inactivation of toxic material or conversion to chemicals with increased or differing toxic properties. 

May W, Paeeis R, Beck C, Fassett, Greenberg R, Kramer R, Wise S, Giles T, Colbert J, Gettings R, and MacDonald B (2000) Definitions of Terms and Modes used at NIST for Value Assignment of Reference Materials for Chemical Measurements. NIST Special Publication 260-136, Gaithersburg, MD12 pp. 

Since the early 1970 s there has been a growing belief that chemical measurements must not only be done correctly, but that data, the product of the measurement process, must be seen to be accurate, precise, and reliable. Analytical data have become another manufactured product and like all manufactured products, the customers demand that Quality Assurance (QA) must be built in. 

It should be recognized that, in some cases, it is not difficult to set up a traceable measurement system. The best examples of this are in physical metrology where traceability is often based on direct measurements of the SI units. There is also general agreement that a similar SI fink is highly desirable in the case of chemical measurements, but, for a variety of reasons, direct chemical traceability is difficult to achieve in most of the analytical chemistry applications. Only a very few analytical chemistry procedures exhibit a direct measurement capability that allows the set-up of a traceable measurement pathway such as in physical metrology measurements most of these procedures have been accepted as primary methods if carried out under certain constraints (CCQM 1998). 

Taylor JK (1985) Principles of Quality Assurance of Chemical Measurements. NBS (now NIST)... 

CZIM Chemical Measurement Department, Slovak Institute of Metrology, Kar-... 

EURACHEM is a network of organizations in Europe, having the objective of establishing a system for the international traceability of chemical measurements and the promotion of good quality practices. It provides a forum for the discussion of common problems and for developing an informed and considered approach to both technical and policy issues. 

Within Europe there are thousands of organizations concerned with analytical measurement. However, within the broad field of testing, chemical measurement has generally been poorly represented. EURACHEM was established to address this concern by enabling analytical laboratories to work together, across international boundaries, on analytical measurement issues. EURACHEM s uniqueness as an organization comes from its primary concern, which is the analytical quality of chemical measurement. 

BERM-6 brought to the forefront the concern for traceability of chemical measurements to internationally recognized standards. 

Notwithstanding the above-mentioned difficulties, there are efforts in progress in numerous global regions to address the issue of reliability in chemical measurements through development and utilization of RM (Iyengar and Wolf 1998). Examples include ... 

In addition to the direct analysis of a sample for its quantitative and/or qualitative composition, HS-GC can be used for physico-chemical measurements, such as the determination of vapour pressures. 

---