Absolute Methods

The general attributes of the capillary rise method may be summarized as follows. It is considered to be one of the best and most accurate absolute methods, good to a few hundredths of a percent in precision. On the other hand, for practical reasons, a zero contact angle is required, and fairly large volumes of solution are needed. With glass capillaries, there are limitations as to the alkalinity of the solution. For variations in the capillary rise method, see Refs. 11, 12, and 22-26. 

Harkins W D and Jura G 1944 An absolute method for the determination of the area of a finely divided orystalline solid J. Am. Chem. Soc. 66 1362-6... 

Sample preparation for the modified Fischer assay technique, a standard method to determine the Hquid yields from pyrolysis of oil shale, is necessary to achieve reproducible results. A 100-g sample of >230 fim (65 mesh) of oil shale is heated in a Fischer assay retort through a prescribed temperature range, eg, ca 25.5—500°C, for 50 min and then soaked for 20 min. The organic Hquid which is collected is the Fischer assay yield (7). The Fischer assay is not an absolute method, but a quaHtative assessment of the oil that may be produced from a given sample of oil shale (8). Retorting yields of greater than 100% of Fischer assay are possible. 

Moisture measurements are important in the process industries because moisture can foul products, poison reactions, damage equipment, or cause explosions. Moisture measurements include both absolute-moisture methods and relative-humidity methods. The absolute methods are those that provide a primaiy output that can be directly calibrated in terms of dew-point temperature, molar concentration, or weight concentration. Loss of weight on heating is the most familiar of these methods. The relative-humidity methods are those that provide a primaiy output that can be more direc tly calibrated in terms of percentage of saturation of moisture. 

For a particular primary ion and fixed experimental conditions, the scattering cross-section is a function only of the mass and atomic number of the scattering atom, and can be calculated. Thus in principle, all the terms in Eq. (3.31) except the required Na are known. RBS is, therefore, an absolute method that does not require the use of standards. 

The accuracy of a determination may be defined as the concordance between it and the true or most probable value. It follows, therefore, that systematic errors cause a constant error (either too high or too low) and thus affect the accuracy of a result. For analytical methods there are two possible ways of determining the accuracy the so-called absolute method and the comparative method. 

Absolute method. A synthetic sample containing known amounts of the constituents in question is used. Known amounts of a constituent can be obtained by weighing out pure elements or compounds of known stoichiometric composition. These substances, primary standards, may be available commercially... 

In principle all methods except viscosity measurement can be used to obtain absolute values of molar mass. Viscosity methods, by contrast, do not give absolute values, but rely on prior calibration using standards of known molar mass. The relationship between polymer solution viscosity and molar mass is merely empirical but the techniques are widely used because of their simplicity. All of the absolute methods are time-consuming and laborious and are not used on a routine basis. As well as the techniques already mentioned, there is the size-exclusion method of chromatography known as Gel-Permeation Chromatography (GPC). All of these methods are discussed in detail in the sections that follow. 

Gel permeation chromatography (GPC) is a widely used technique for determining molar mass and molar mass distrihution of polymers. In its usual form it is not an absolute method, though hy making the appropriate measurements it may be made to be so. 

The various physical methods in use at present involve measurements, respectively, of osmotic pressure, light scattering, sedimentation equilibrium, sedimentation velocity in conjunction with diffusion, or solution viscosity. All except the last mentioned are absolute methods. Each requires extrapolation to infinite dilution for rigorous fulfillment of the requirements of theory. These various physical methods depend basically on evaluation of the thermodynamic properties of the solution (i.e., the change in free energy due to the presence of polymer molecules) or of the kinetic behavior (i.e., frictional coefficient or viscosity increment), or of a combination of the two. Polymer solutions usually exhibit deviations from their limiting infinite dilution behavior at remarkably low concentrations. Hence one is obliged not only to conduct the experiments at low concentrations but also to extrapolate to infinite dilution from measurements made at the lowest experimentally feasible concentrations. 

Values obtained for and a for a number of polymer-solvent pairs are given in Table XXX. It will be observed that the exponent a varies with both the polymer and the solvent. It does not fall below 0.50 in any case and seldom exceeds about 0.80. Once K and a have been established for a given polymer series in a given solvent at a specified temperature, molecular weights may be computed from intrinsic viscosities of subsequent samples without recourse to a more laborious absolute method. 

Several collaborating laboratories (usually five participating laboratories) test the proposed substance using a variety of techniques. The relative reactivity or relative absorbance of the impurities present in a substance must be checked when a nonspecific assay method is employed, e.g. by colorimetry or ultraviolet spectrophotometry. It is particularly important to quantify the impurities when a selective assay is employed. In such a case, it is best to examine the proposed substance by as many methods as practicable, including, where possible, absolute methods. For acidic and basic substances, titration with alkali or acid is simple but other reactions which are known to be stoichiometric may be used. Phase solubility analysis and differential scanning calorimetry may also be employed in certain cases. 

The method of semiconductor sensors allows one to determine the flux of atoms, to which the sensor was exposed, from electric conductivity measurements (provided coefficients of ionization and reflection of oxygen atoms from zinc oxide films are known). In other words, the sensor technique can be used in this case as an absolute method [21]. Indeed, variation of electric conductivity of a semiconductor film Acrpi due to adsorption is known to be caused by variation of carrier concentration An in the film, rather than by variation of their mobility / [21] ... 

Experimental variables such as temperature, flow rate, sample concentration and mobile phase composition can cause changes in the elution volume of a polymer [439,457,460-464]. Chromatographic measurements made with modem equipment are limited more by the errors in the absolute methods used to characterize the molecular weight of the calibration standards than any errors Inherent in the measurements themselves, since the determination of molecular weights by SEC is not an absolute method and is dependent on calibration [462]. The Influence of temperature on retention in SEC is not very great, since no strong sorptive interactions are involved in the retention mechanism. Temperature differences between the column and solvent delivery... 

Mass spectrometry is the only universal multielement method which allows the determination of all elements and their isotopes in both solids and liquids. Detection limits for virtually all elements are low. Mass spectrometry can be more easily applied than other spectroscopic techniques as an absolute method, because the analyte atoms produce the analytical signal themselves, and their amount is not deduced from emitted or absorbed radiation the spectra are simple compared to the line-rich spectra often found in optical emission spectrometry. The resolving power of conventional mass spectrometers is sufficient to separate all isotope signals, although expensive instruments and skill are required to eliminate interferences from molecules and polyatomic cluster ions. 

Quantitative and standardless (absolute method no calibration curves)... 

This method is primarily concerned with the phenomena that occur at electrode surfaces (electrodics) in a solution from which, as an absolute method, through previous calibration a component concentration can be derived. If desirable the technique can be used to follow the progress of a chemical reaction, e.g., in kinetic analysis. Mostly, however, potentiometry is applied to reactions that go to completion (e.g. a titration) merely in order to indicate the end-point (a potentiometric titration in this instance) and so do not need calibration. The overwhelming importance of potentiometry in general and of potentiometric titration in particular is due to the selectivity of its indication, the simplicity of the technique and the ample choice of electrodes. 

In the above-described measurement, which we call the absolute method, all pumps have equal speeds (rpm) owing to interconnection to the same drive-shaft. In order to express, if required, a deviation registered for the analyte concentration, one must calibrate with a standard by varying its rpm (B) with respect to that of the titrant (A) a B/A rpm ratio greater than unity means a proportionally lower concentration and vice versa. In general, the absolute method serves to control a sample stream with nearly constant analyte concentration as a sensor one uses not only electroanalytical but often also optical detectors. However, with considerably varying analyte concentrations the differential method is more attractive its principle is that in the set-up in Fig. 5.15 and with the sensor adjusted to a fixed and most sensitive set-point, the rpm of the sample stream (C) is varied with respect to that of the titrant (A) by a feedback control (see Fig. 5.3a) from the sensor via a regulator towards the... 

The interpretation of sterility results is divided into two stages by the USP relative to the type of sterility failure if one occurs. If sterility failure of the test samples occurred because of improper aseptic technique or as a fault of the test itself, stage 1 may be repeated with the same sample size. Sample size is doubled in a stage 2 testing, which is performed if microbial growth is observed in stage 1 and there is no reason to believe that the test was invalid. The only absolute method to guarantee the sterility of a batch would be to test every vial or ampoule. 

Hulanicki A (1995) IUPAC, Analytical Chemistry Division, Commission on General Aspects of Analytical Chemistry Absolute methods in analytical chemistry. Pure Appl Chem 67 1905... 

In our particular application, we do not have an absolute method of calibration because the alkyl chain length affects the EO distribution retention. However, mass spectrometry would be an ideal third dimension. The automated combination of two-dimensional chromatography and mass spectrometry is the next step toward the future of simultaneous separation and identification of very complicated samples. 

SEC or gel permeation chromatography (GPC) is one of the widely used chromatographic techniques [56,57]. In contrast to the already discussed colligative and scattering methods it is not an absolute method and requires proper calibration with some known polymer standards. One obtains not only the average molar masses (M , Mw, Mz) but the complete molar mass distributions. 

Size-exclusion chromatography (SEC) has been used to characterize the unimer-micelle distribution. However, SEC is not an absolute method and thus requires calibration. Since it is practically impossible to calibrate a SEC apparatus for the unimers and micelles formed by a block copolymer, only indicative MW values can be obtained. Moreover, several authors have noted a strong perturbation of the unimer-micelle equilibrium during SEC experiments even when interaction of the material with the SEC column was minimized [4,61,62],... 

Moreover it requires only simple apparatus. However, this method of determining Molecular weights is not an absolute method. To find the Molecular weight from the viscosity data, it is essential to use empirical equations that give viscosity as a function of the Molecular weight. These equations are set up with the aid of any suitable absolute method for the determination of the Molecular weights. 

The presence of aromatic amino acid residues results in proteins showing an absorption maximum at 280 nm and comparison of the absorbance value of a test solution with that of a standard solution provides a sensitive method of quantitation. This cannot be considered to be an absolute method of quantitation... 

Ideally an absolute method, capable of measuring F accurately should be used since this is not possible, an alternative approach is to quantify in a reproducible way the potential of the liquid phase for... 

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