Quantitation methods

Several different approaches exist as to what peaks are measured and how the mixture component of interest is actually quantitated. We now discuss three of the more popular methods. 

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This chapter presents quantitative methods for calculation of enthalpies of vapor-phase and liquid-phase mixtures. These methods rely primarily on pure-component data, in particular ideal-vapor heat capacities and vapor-pressure data, both as functions of temperature. Vapor-phase corrections for nonideality are usually relatively small. Liquid-phase excess enthalpies are also usually not important. As indicated in Chapter 4, for mixtures containing noncondensable components, we restrict attention to liquid solutions which are dilute with respect to all noncondensable components. 

You will come across numerous examples of qualitative and quantitative methods in this text, most of which are routine examples of chemical analysis. It is important to remember, however, that nonroutine problems prompted analytical chemists to develop these methods. Whenever possible, we will try to place these methods in their appropriate historical context. In addition, examples of current research problems in analytical chemistry are scattered throughout the text. 

In Section lA we indicated that analytical chemistry is more than a collection of qualitative and quantitative methods of analysis. Nevertheless, many problems on which analytical chemists work ultimately involve either a qualitative or quantitative measurement. Other problems may involve characterizing a sample s chemical or physical properties. Finally, many analytical chemists engage in fundamental studies of analytical methods. In this section we briefly discuss each of these four areas of analysis. 

A quantitative method for reporting the ionic composition of a solution that takes into account the greater effect of more highly charged ions (jr). 

Standardizing the Method Equations 10.32 and 10.33 show that the intensity of fluorescent or phosphorescent emission is proportional to the concentration of the photoluminescent species, provided that the absorbance of radiation from the excitation source (A = ebC) is less than approximately 0.01. Quantitative methods are usually standardized using a set of external standards. Calibration curves are linear over as much as four to six orders of magnitude for fluorescence and two to four orders of magnitude for phosphorescence. Calibration curves become nonlinear for high concentrations of the photoluminescent species at which the intensity of emission is given by equation 10.31. Nonlinearity also may be observed at low concentrations due to the presence of fluorescent or phosphorescent contaminants. As discussed earlier, the quantum efficiency for emission is sensitive to temperature and sample matrix, both of which must be controlled if external standards are to be used. In addition, emission intensity depends on the molar absorptivity of the photoluminescent species, which is sensitive to the sample matrix. 

Brown and Lin reported a quantitative method for methanol based on its effect on the visible spectrum of methylene blue. In the absence of methanol, the visible spectrum for methylene blue shows two prominent absorption bands centered at approximately 610 nm and 660 nm, corresponding to the monomer and dimer, respectively. In the presence of methanol, the intensity of the dimer s absorption band decreases, and that of the monomer increases. For concentrations of methanol between 0 and 30% v/v, the ratio of the absorbance at 663 nm, Asss, to that at 610 nm, Asio, is a linear function of the amount of methanol. Using the following standardization data, determine the %v/v methanol in a sample for which Agio is 0.75 and Ag63 is 1.07. 

In potentiometry the potential of an electrochemical cell is measured under static conditions. Because no current, or only a negligible current, flows while measuring a solution s potential, its composition remains unchanged. For this reason, potentiometry is a useful quantitative method. The first quantitative potentiometric applications appeared soon after the formulation, in 1889, of the Nernst equation relating an electrochemical cell s potential to the concentration of electroactive species in the cell. ... 

Most potentiometric electrodes are selective for only the free, uncomplexed analyte and do not respond to complexed forms of the analyte. Solution conditions, therefore, must be carefully controlled if the purpose of the analysis is to determine the analyte s total concentration. On the other hand, this selectivity provides a significant advantage over other quantitative methods of analysis when it is necessary to determine the concentration of free ions. For example, calcium is present in urine both as free Ca + ions and as protein-bound Ca + ions. If a urine sample is analyzed by atomic absorption spectroscopy, the signal is proportional to the total concentration of Ca +, since both free and bound calcium are atomized. Analysis with a Ca + ISE, however, gives a signal that is a function of only free Ca + ions since the protein-bound ions cannot interact with the electrode s membrane. 

In potentiometry, the potential of an electrochemical cell under static conditions is used to determine an analyte s concentration. As seen in the preceding section, potentiometry is an important and frequently used quantitative method of analysis. Dynamic electrochemical methods, such as coulometry, voltammetry, and amper-ometry, in which current passes through the electrochemical cell, also are important analytical techniques. In this section we consider coulometric methods of analysis. Voltammetry and amperometry are covered in Section 1 ID. 

Sandell and KolthofP developed a quantitative method for iodide based on its catalytic effect on the following redox reaction. 

Onc-Factor-at-a-Timc Optimization One approach to optimizing the quantitative method for vanadium described earlier is to select initial concentrations for ITiOz and 1T2S04 and measure the absorbance. We then increase or decrease the concentration of one reagent in steps, while the second reagent s concentration remains constant, until the absorbance decreases in value. The concentration of the second reagent is then adjusted until a decrease in absorbance is again observed. This process can be stopped after one cycle or repeated until the absorbance reaches a maximum value or exceeds an acceptable threshold value. 

The fermentation-derived food-grade product is sold in 50, 80, and 88% concentrations the other grades are available in 50 and 88% concentrations. The food-grade product meets the Vood Chemicals Codex III and the pharmaceutical grade meets the FCC and the United States Pharmacopoeia XK specifications (7). Other lactic acid derivatives such as salts and esters are also available in weU-estabhshed product specifications. Standard analytical methods such as titration and Hquid chromatography can be used to determine lactic acid, and other gravimetric and specific tests are used to detect impurities for the product specifications. A standard titration method neutralizes the acid with sodium hydroxide and then back-titrates the acid. An older standard quantitative method for determination of lactic acid was based on oxidation by potassium permanganate to acetaldehyde, which is absorbed in sodium bisulfite and titrated iodometricaHy. 

The nitroparaftins have been determined by procedures such as fractionation, titration, colorimetry, kifrared spectroscopy, mass spectrometry, and gas chromatography. The early analytical methods and uses of polynitroparaftins as analytical reagents have been reviewed (11). More recent quaHtative and quantitative methods have also been reviewed (83). 

Fiber Analysis. Paper may be composed of one or several types of fibers, eg, animal, vegetable, mineral, and synthetic (see Eibers). Paper is generally composed of woody vegetable fibers obtained from coniferous (softwood) and deciduous (hardwood) trees. QuaUtative and quantitative methods have been developed to determine the fibrous constituents in a sheet of paper (see TAPPI T401). However, the proliferation in the number and types of pulping processes used have made the analysis of paper a much more complex problem. Comprehensive reviews of the methods are given in References 20 and 23. 

SALI mapping is a sensitive and quantitative method to characterize the spatial distribution of elements in both insulating and conductive materials. 

NAA is a quantitative method. Quantification can be performed by comparison to standards or by computation from basic principles (parametric analysis). A certified reference material specifically for trace impurities in silicon is not currently available. Since neutron and y rays are penetrating radiations (free from absorption problems, such as those found in X-ray fluorescence), matrix matching between the sample and the comparator standard is not critical. Biological trace impurities standards (e.g., the National Institute of Standards and Technology Standard Rference Material, SRM 1572 Citrus Leaves) can be used as reference materials. For the parametric analysis many instrumental fiictors, such as the neutron flux density and the efficiency of the detector, must be well known. The activation equation can be used to determine concentrations ... 

AFM through force or displacement modulation techniques. Numerous methods have evolved that take advantage of the greater sensitivity modulation techniques provide, allowing dissipative processes to be examined. However, evaluation of the probe/sample response requires care with test protocols and instrument calibration, as well as application of appropriate contact mechanics models only a few of these techniques have evolved into quantitative methods. 

Hart, M. and Hart, R., 1989. Quantitative Methods for quality and productivity Improvements, Quality Press. 

Remember also to take advantage of the team s individual, anecdotal experience with your company s management systems. Defining your company s management systems approach will be greatly enhanced by drawing on expert judgment as well as quantitative methods. 

Although the main emphasis of this chapter will be on qualitative human reliability methods in risk assessment, this section will illustrate the importance of both qualitative and quantitative methods in CPQRA. An example of a typical assessment, described by Ozog (1985) will be considered. The stages of the risk assessment are as follows ... 

The present edition is much enlarged and contains new pie-parations, reactions and quantitative methods, all of which have been carefully revised. My object has been not to follow any particular syllabus, but to present a variety of processes from which a selection may be made to suit the special needs of different students. 

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