The measurement of composition

There are numerous properties of materials which can be used as measures of composition, e.g. preferential adsorption of components (as in chromatography), absorption of electromagnetic waves (infra-red, ultra-violet, etc.), refractive index, pH, density, etc. In many cases, however, the property will not give a unique result if there are more than two components, e.g. there may be a number of different compositions of a particular ternary liquid mixture which will have the same refractive index or will exhibit the same infra-red radiation absorption characteristics. Other difficulties can make a particular physical property unsuitable as a measure of composition for a particular system, e.g. the dielectric constant cannot be used if water is present as the dielectric constant of water is very much greater than that of most other liquids. Instruments containing optical systems (e.g. refractometers) and/or electromechanical feedback systems (e.g. some infra-red analysers) can be sensitive to mechanical vibration. In cases where it is not practicable to measure composition directly, then indirect or inferential means of obtaining a measurement which itself is a function of composition may be employed (e.g. the use of boiling temperature in a distillation column as a measure of the liquid composition—see Section 7.3.1). 

In the following account, the more common means of composition analysis are presented. The descriptions are not intended to be exhaustive as many methods of analysis are specific to particular processes. Reference should be made to manufacturers literature for further information. 

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While the mole fraction is a natural measure of composition for solutions of metallic elements or alloys, the mole fraction of each molecule is chosen as the measure of composition in the case of solid or liquid mixtures of molecules.1 In ionic solutions cations and anions are not randomly mixed but occupy different sub-lattices. The mole fractions of the atoms are thus an inconvenient measure of composition for ionic substances. Since cations are mixed with cations and anions are mixed with anions, it is convenient for such materials to define composition in terms of ionic fractions rather than mole fractions. In a mixture of the salts AB and AC, where A is a cation and B and C are anions, the ionic fractions of B and C are defined through... 

Most of these methods are rapid in their response to the particular property which is the measure of composition, but frequently their overall behavior is sluggish because of the time delays in leading the stream samples to the test cells. 

Infrared spectroscopy is a recognized standard method of analysis for characterization and identification, and for the measurement of composition of a wide range of materials. The infrared spectrum is a unique physical property of a molecular species, and the spectral information obtained can be correlated directly to the chemical structure of the material, and the underlying composition in the case of admixtures. Infrared spectroscopy is also one of the most widely utilized analytical methods for the identification and characterization of plastics and polymers. The first sections of this chapter have focused on the specific attributes of the technique as they relate to the analysis of polymeric materials. In this final section, the focus is on the more general and fundamental aspects of infrared measurements, and the methods used for the handling of plastics and polymers. 

When a solid or a gas is added to a liquid solvent at a given temperature, the dissolving process gradually slows down as the solution becomes more concentrated. When dissolving stops —in spite of the presence of some undissolved solute—the solution is said to be saturated. The maximum quantity of solute (relative to the quantity of solvent) that will dissolve is the SOLUBILITY. It may be expressed in any of the measures of composition described in Section 10.3 weight percent, mole fraction, molarity, etc. 

Any meaningful discussion of current capabilities in the measurement of composition must focus on the real world of practical materials. 

Ellipsometry measurements can provide infomiation about the thickness, microroughness and dielectric ftinction of thin films. It can also provide infomiation on the depth profile of multilayer stmctiires non-destmctively, including the thickness, the composition and the degree of crystallinity of each layer [39]. The measurement of the various components of a complex multilayered film is illustrated m figure Bl.26.17 [40]. 

The atomic force microscope (ATM) provides one approach to the measurement of friction in well defined systems. The ATM allows measurement of friction between a surface and a tip with a radius of the order of 5-10 nm figure C2.9.3 a)). It is the tme realization of a single asperity contact with a flat surface which, in its ultimate fonn, would measure friction between a single atom and a surface. The ATM allows friction measurements on surfaces that are well defined in tenns of both composition and stmcture. It is limited by the fact that the characteristics of the tip itself are often poorly understood. It is very difficult to detennine the radius, stmcture and composition of the tip however, these limitations are being resolved. The AFM has already allowed the spatial resolution of friction forces that exlribit atomic periodicity and chemical specificity [3, K), 13]. 

Hospital sterilizer loads vary in composition, thus the challenge presented to the test organism can vary considerably, depending on the type and contents of packages in which they are placed. The benefits of a standardized test-pack constmction and test protocol are obvious, and such recommendation is made by AAMI for steam and ethylene oxide sterilizers (11). More recentiy in European (CEN) and International (ISO) standards, biological indicators are considered as additional information supplemental to the measurement of physical parameters. Indeed, for sterilization using moist heat (steam), the biological indicator information is not considered to be relevant. 

X-ray fluorescence spectrometry consists of the measurement of the incoherent scattering of x-rays (phenomenon 3 above). It is used primarily to determine the elemental composition of a sample. 

A convenient method for assessing the extent of surface oxidation is the measurement of volatile content. This standard method measures the weight loss of the evolved gases on heating up to 950°C in an inert atmosphere. The composition of these gases consists of three principal components hydrogen, carbon monoxide, and carbon dioxide. The volatile content of normal furnace blacks is under 1.5%, and the volatile content of oxidized special grades is 2.0 to 9.5%. 

Flash Point. As fuel oil is heated, vapors are produced which at a certain temperature "flash" when ignited by an external ignition source. The flash point is the lowest temperature at which vapor, given off from a Hquid, is in sufficient quantity to enable ignition to take place. The flash point is in effect a measure of the volatiHty of the fuel. The measurement of flash point for pure Hquids is relatively straightforward. However, the measured value may depend slightly on the method used, especially for Hquid mixtures, since the composition of the vapor evolved can vary with the heating rate. Special... 

Composition The law of mass aclion is expressed as a rate in terms of chemical compositions of the participants, so ultimately the variation of composition with time must be found. The composition is determined in terms of a property that is measured by some instrument and cahbrated in terms of composition. Among the measures that have been used are titration, pressure, refractive index, density, chromatography, spectrometry, polarimetry, conduclimetry, absorbance, and magnetic resonance. In some cases the composition may vary linearly with the observed property, but in every case a calibration is needed. Before kinetic analysis is undertaken, the data are converted to composition as a function of time (C, t), or to composition and temperature as functions of time (C, T, t). In a steady CSTR the rate is observed as a function of residence time. 

Physical-property measurements are sometimes equivalent to composition an yzers, because the composition can frequently be inferred from the measurement of a selected physical property. 

Specific-Ion Electrodes In addition to the pH glass electrode specific for hydrogen ions, a number of electrodes that are selective for the measurement of other ions have been developed. This selectivity is obtained through the composition of the electrode membrane (glass, polymer, or liquid-liquid) and the composition of the elec trode. Tbese electrodes are subject to interference from other ions, and the response is a function of the total ionic strength of the solution. However, electrodes have been designed to be highly selective for specific ions, and when properly used, these provide valuable process measurements. 

The Kellogg and DePriester charts and their subsequent extensions and generahzations use the molar average boiling points of the liquid and vapor phases to represent the composition effect. An alternative measure of composition is the convergence pressure of the system, which is defined as that pressure at which the Kvalues for aU the components in an isothermal mixture converge to unity. It is analogous to the critical point for a pure component in the sense that the two... 

Temperature is the hardest parameter to control in a fractionation system. It exhibits high process and measurement lag. Temperature can also be ambivalent as a measure of composition. Pressure changes are reflected quickly up and down the column. Temperature changes are not. It is typical to provide three-mode controllers for all temperature applications. 

The atom flux sputtered from a solid surface under energetic ion bombardment provides a representative sampling of the solid. Sputtered neutral mass spectrometry has been developed as method to quantitatively measure the composition of this atom flux and thus the composition of the sputtered material. The measurement of ionized sputtered neutrals has been a significant improvement over the use of sputtered ions as a measure of flux composition (the process called SIMS), since sputtered ion yields are seriously affected by matrix composition. Neutral panicles are ionized by a separate process after sputter atomization, and SNMS quantitation is thus independent of the matrix. Also, since the sputtering and ionization processes are separate, an ionization process can be selected that provides relatively uniform yields for essentially all elements. 

In summary, the forte of SNMS is the measurement of accurate compositional depth profiles with high depth resolution through chemically complex thin-film structures. Current examples of systems amenable to SNMS are complex III-IV laser diode structures, semiconductor device metallizations, and magnetic read-write devices, as well as storage media. 

Mangipudi et al. [63,88] reported some initial measurements of adhesion strength between semicrystalline PE surfaces. These measurements were done using the SFA as a function of contact time. Interestingly, these data (see Fig. 22) show that the normalized pull-off energy, a measure of intrinsic adhesion strength is increased with time of contact. They suggested the amorphous domains in PE could interdiffuse across the interface and thereby increase the adhesion of the interface. Falsafi et al. [37] also used the JKR technique to study the effect of composition on the adhesion of elastomeric acrylic pressure-sensitive adhesives. The model PSA they used was a crosslinked network of random copolymers of acrylates and acrylic acid, with an acrylic acid content between 2 and 10%. 

Four different material probes were used to characterize the shock-treated and shock-synthesized products. Of these, magnetization provided the most sensitive measure of yield, while x-ray diffraction provided the most explicit structural data. Mossbauer spectroscopy provided direct critical atomic level data, whereas transmission electron microscopy provided key information on shock-modified, but unreacted reactant mixtures. The results of determinations of product yield and identification of product are summarized in Fig. 8.2. What is shown in the figure is the location of pressure, mean-bulk temperature locations at which synthesis experiments were carried out. Beside each point are the measures of product yield as determined from the three probes. The yields vary from 1% to 75 % depending on the shock conditions. From a structural point of view a surprising result is that the product composition is apparently not changed with various shock conditions. The same product is apparently obtained under all conditions only the yield is changed. 

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