Scaling of Operations

If it is assumed that in an extraction test 10-20 g of plastics is contacted with 700 ml of extraction liqnid which is subsequently extracted with a low boiling solvent to remove additives and this extract is concentrated to 2 ml, i.e., all the additives which migrate from the original polymer are concentrated into 2 ml of solvent, then if each additive is originally present in the polymer at 0.1%, then if complete additive migration occurs, the extract will contain 10-20 mg of each additive per 2 ml. If however, only 10% additive migration occurs, then the extract will contain 1-2 mg of each additive per 2 ml. 

Knowing the extinction coefficients of BHT and 2-hydroxy-4-n-octoxybenzophenone it is possible to calculate the weight of each of these substances that must be present in the volume of test solution applied to the plate (Table 12.2). 

Thus a suitable volume of the 2 ml extracts for application to the plate is 0.1 ml (which contains 500-1000 pg of each additive if complete additive migration from the polymer has occurred and 50-100 pg of each if only 10% additive migration has occurred). 

The TLC procedure described next for separating the additives and recovering each component for UV spectroscopy is based on the assumption that only 10% additive migration occurs from the polymer. Quantities should be adjusted if additive migration differs appreciably from 10%. 

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The requirements of the analysis determine the best method. In choosing a method, consideration is given to some or all the following design criteria accuracy, precision, sensitivity, selectivity, robustness, ruggedness, scale of operation, analysis time, availability of equipment, and cost. Each of these criteria is considered in more detail in the following sections. 

Another way to narrow the choice of methods is to consider the scale on which the analysis must be conducted. Three limitations of particular importance are the amount of sample available for the analysis, the concentration of analyte in the sample, and the absolute amount of analyte needed to obtain a measurable signal. The first and second limitations define the scale of operations shown in Figure 3.6 the last limitation positions a method within the scale of operations. ... 

Scale of operation for analytical methods. Adapted from references 7a and 7b. 

Scale of Operation The scale of operation for precipitation gravimetry is governed by the sensitivity of the balance and the availability of sample. To achieve an accuracy of 0.1% using an analytical balance with a sensitivity of 0.1 mg, the precipitate must weigh at least 100 mg. As a consequence, precipitation gravimetry is usually limited to major or minor analytes, and macro or meso samples (see Figure 3.6 in Chapter 3). The analysis of trace level analytes or micro samples usually requires a microanalytical balance. 

Scale of Operation In an acid-base titration the volume of titrant needed to reach the equivalence point is proportional to the absolute amount of analyte present in the analytical solution. Nevertheless, the change in pH at the equivalence point, and thus the utility of an acid-base titration, is a function of the analyte s concentration in the solution being titrated. 

The scale of operations, accuracy, precision, sensitivity, time, and cost of methods involving redox titrations are similar to those described earlier in the chapter for acid-base and complexometric titrimetric methods. As with acid-base titrations, redox titrations can be extended to the analysis of mixtures if there is a significant difference in the ease with which the analytes can be oxidized or reduced. Figure 9.40 shows an example of the titration curve for a mixture of Fe + and Sn +, using Ce + as the titrant. The titration of a mixture of analytes whose standard-state potentials or formal potentials differ by at least 200 mV will result in a separate equivalence point for each analyte. 

Where in the scale of operations do the microtitration techniques discussed in Section 9B.8 belong ... 

Scale of Operation Molecular UV/Vis absorption is routinely used for the analysis of trace analytes in macro and meso samples. Major and minor analytes can be determined by diluting samples before analysis, and concentrating a sample may allow for the analysis of ultratrace analytes. The scale of operations for infrared absorption is generally poorer than that for UV/Vis absorption. 

Scale of Operation Atomic absorption spectroscopy is ideally suited for the analysis of trace and ultratrace analytes, particularly when using electrothermal atomization. By diluting samples, atomic absorption also can be applied to minor and major analytes. Most analyses use macro or meso samples. The small volume requirement for electrothermal atomization or flame microsampling, however, allows the use of micro, or even ultramicro samples. 

Scale of Operation The scale of operations for atomic emission is ideal for the direct analysis of trace and ultratrace analytes in macro and meso samples. With appropriate dilutions, atomic emission also can be applied to major and minor analytes. 

Scale of Operation Coulometric methods of analysis can be used to analyze small absolute amounts of analyte. In controlled-current coulometry, for example, the moles of analyte consumed during an exhaustive electrolysis is given by equation 11.32. An electrolysis carried out with a constant current of 100 pA for 100 s, therefore, consumes only 1 X 10 mol of analyte if = 1. For an analyte with a molecular weight of 100 g/mol, 1 X 10 mol corresponds to only 10 pg. The concentration of analyte in the electrochemical cell, however, must be sufficient to allow an accurate determination of the end point. When using visual end points, coulometric titrations require solution concentrations greater than 10 M and, as with conventional titrations, are limited to major and minor analytes. A coulometric titration to a preset potentiometric end point is feasible even with solution concentrations of 10 M, making possible the analysis of trace analytes. 

Scale of Operation Voltammetry is routinely used to analyze samples at the parts-per-million level and, in some cases, can be used to detect analytes at the parts-per-billion or parts-per-trillion level. Most analyses are carried out in conventional electrochemical cells using macro samples however, microcells are available that require as little as 50 pL of sample. Microelectrodes, with diameters as small as 2 pm, allow voltammetric measurements to be made on even smaller samples. For example, the concentration of glucose in 200-pm pond snail neurons has been successfully monitored using a 2-pm amperometric glucose electrode. ... 

The second factor influencing detection limits is the instrumental method used to monitor the reaction s progress. Most reactions are monitored spectrophotometrically or electro-chemically. The scale of operation for these methods was discussed in Chapters 10 and 11 and, therefore, is not discussed here. 

The majority of FI A applications are modifications of conventional titrimetric, spectrophotometric, and electrochemical methods of analysis. For this reason it is appropriate to evaluate FIA in relation to these conventional methods. The scale of operations for FIA allows for the routine analysis of minor and trace analytes and for macro-, meso-, and microsamples. The ability to work with microliter injection volumes is useful when the sample is scarce. Conventional methods of analysis, however, may allow the determination of smaller concentrations of analyte. 

Control technology requirements vary according to the scale of operation and type of emission problem. For instance, electrostatic precipitator design requirements for fly-ash control from 1000-MW coal-fired power boilers differ from those for a chemical process operation. In the discussion that follows, priority is given to control technology for the CPI as opposed to the somewhat special needs of other industries. 

A most useful feature of the agglomeration technique is its ability to work with extreme fines. Even particles of less than nanometer size (ca 10 ° m) can be treated, if appropriate, so that ultrafine grinding can be appHed to materials with extreme impurity dissernination to allow recovery of agglomerates of higher purity. A number of appHcations of Hquid-phase agglomeration have reached either the commercial or semicommercial pilot scale of operation. 

Year Various Dimensionless (PSR) d Profit-sales ratio defined by Eq. (9-235) Quantity defining tbe scale of operation Dimensionless Various... 

The recycle requirements of products in different apphcations can vaiy substantially depending upon the scale of operation, the ease of diying, and the finished-product specification. The location of reintroduction of undried material back into the diying medium has a significant impact upon the dryer performance and final-product characteristics. 

Direct Scale-Up of Laboratory Distillation Ljficiency Measurements It has been found by Fair, Null, and Bolles [Ind. Eng. Chem. Process Des. Dev., 22, 53 (1983)] that efficiency measurements in 25- and 50-mm (1- and 2-in-) diameter laboratory Oldersbaw columns closely approach tbe point efficiencies [Eq. (14-129)] measured in large sieve-plate columns. A representative comparison of scales of operation is shown in Fig. 14-37. Note that in order to achieve agreement between efficiencies it is necessaiy to ensure that (1) tbe systems being distilled are tbe same, (2) comparison is made at tbe same relative approach to tbe flood point, (3) operation is at total reflux, and (4) a standard Oldersbaw device (a small perforated-plate column with downcomers) is used in tbe laboratoiy experimentation. Fair et al. made careful comparisons for several systems, utibzing as large-scale information tbe published efficiency studies of Fractionation Research, Inc. 

Method Product size (mm) Granule density Scale of operation Additional comments Tyj)ical applications... 

Eirst-aid measures for people exposed to nitrogen dioxide are mentioned in Chapter 9. In any event, containment, ventilation and/or appropriate respiratory protection should be considered depending upon scale of operation and level of exposure. 

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