Volatile species

A gravimetric method in which the loss of a volatile species gives rise to the signal. 

When thermal or chemical energy is used to remove a volatile species, we call the method volatilization gravimetry. In determining the moisture content of food, thermal energy vaporizes the H2O. The amount of carbon in an organic compound may be determined by using the chemical energy of combustion to convert C to CO2. 

Thermogravimetry The products of a thermal decomposition can be deduced by monitoring the sample s mass as a function of applied temperature. (Figure 8.9). The loss of a volatile gas on thermal decomposition is indicated by a step in the thermogram. As shown in Example 8.4, the change in mass at each step in a thermogram can be used to identify both the volatilized species and the solid residue. 

The principle of headspace sampling is introduced in this experiment using a mixture of methanol, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, benzene, toluene, and p-xylene. Directions are given for evaluating the distribution coefficient for the partitioning of a volatile species between the liquid and vapor phase and for its quantitative analysis in the liquid phase. Both packed (OV-101) and capillary (5% phenyl silicone) columns were used. The GG is equipped with a flame ionization detector. 

During the vulcanization, the volatile species formed are by-products of the peroxide. Typical cure cycles are 3—8 min at 115—170°C, depending on the choice of peroxide. With most fluorosihcones (as well as other fluoroelastomers), a postcure of 4—24 h at 150—200°C is recommended to maximize long-term aging properties. This post-cure completes reactions of the side groups and results in an increased tensile strength, a higher cross-link density, and much lower compression set. 

Pa (10 10 ° Torr)) condition such that the volatile species travels at a relatively high velocity to the substrate wafer. The growth rate is 0.01-0.3 ///min which starts to be competitive with CVD deposition rates. 

Rhenium Halides and Halide Complexes. Rhenium reacts with chlorine at ca 600°C to produce rheniumpentachloride [39368-69-9], Re2Cl2Q, a volatile species that is dimeric via bridging hahde groups. Rhenium reacts with elemental bromine in a similar fashion, but the metal is unreactive toward iodine. The compounds ReCl, ReBr [36753-03-4], and Rel [59301-47-2] can be prepared by careful evaporation of a solution of HReO and HX. Substantiation in a modem laboratory would be desirable. Lower oxidation state hahdes (Re X ) are also prepared from the pentavalent or tetravalent compounds by thermal decomposition or chemical reduction. 

Under equiUbrium or near-equiUbrium conditions, the distribution of volatile species between gas and water phases can be described in terms of Henry s law. The rate of transfer of a compound across the water-gas phase boundary can be characterized by a mass-transfer coefficient and the activity gradient at the air—water interface. In addition, these substance-specific coefficients depend on the turbulence, interfacial area, and other conditions of the aquatic systems. They may be related to the exchange constant of oxygen as a reference substance for a system-independent parameter reaeration coefficients are often known for individual rivers and lakes. 

One of the components, A (not necessarily the most volatile species of the original mixture), is withdrawn as an essentially pure distillate stream. Because the solvent is nonvolatile, at most a few stages above the solvent-feed stage are sufficient to rectify the solvent from the distillate. The bottoms product, consisting of B and the solvent, is sent to the recoveiy column. The distillate from the recoveiy column is pure B, and the solvent-bottoms product is recycled back to the extractive column. 

The key features of soot are its chemical inertness, its physical and chemical adsorption properties, and its light absorption. The large surface area coupled with the presence of various organic functional groups allow the adsorption of many different materials onto the surfaces of the particles. This type of sorption occurs both in the aerosol phase and in the aqueous phase once particles are captured by cloud droplets. As a result, complex chemical processes occur on the surface of soot particles, and otherwise volatile species may be scavenged by the soot particles. 

Analysis of substances migrating from food contact plastics is possible at very low levels in real foods. Volatile species are the easiest to determine. 

Contamination of metal with other distillates is largely overcome when reducing selected compounds with Zr since the alkali metal is then the only volatile species. Mixtures of CSHSO4 and Cs2Cr04 react explosively, however, carrying particulates over, unless slow heating rates and a large excess of Zr are employed. 

Multicycle vacuum distillations have been assessed ". The distillations were effected at 700°C. Data on the effect of distillation rate and of fraction distilled on the purity of the sample are collected in Table 1. These data show that the technique is effective in removing the less volatile impurities As, Co, Cu, Cr, Fe, Ga, Mn and Sb from Mg but has little effect on more volatile species, Ba, Zn and Zr. Increase of the distillation rate or the fraction distilled leads to a decrease in the effective purification. Double (99% fraction) distillation gives a product of similar purity to that of a single (72% fraction) distillation . Single (78% fraction) distillation of a Mg sample (assay 99.9%) unusually rich in Mn (300 fig g" ) at 3.5 g h gave a decrease (Xl0 ) in Mn content (to 0.025 fig g ) a similar value (0.04 fig g" ) was obtained from a doubly (99% fraction) distilled sample. This technique gives Mg with assays of 99.9995%... 

The increasing sophistication and detection capabihties of instruments (tike GC-MS, LC-MS, etc.) used in the analysis of contaminants in a factory atmosphere are enabhng the identification of chemical compounds hitherto not suspected of being present. The range of volatile species so far identified during vulcanization is shown in Eigure 37.6 [49]. 

FIGURE 37.6 The volatile species liberated during vulcanization reactions and which have been identified so far. (From Lawson, G., in C.W. Evans (ed.). Developments in Rubber and Rubber Composites-2, Applied Science, Essex, 75-94, 1983.)... 

Typical characterization of the thermal conversion process for a given molecular precursor involves the use of thermogravimetric analysis (TGA) to obtain ceramic yields, and solution NMR spectroscopy to identify soluble decomposition products. Analyses of the volatile species given off during solid phase decompositions have also been employed. The thermal conversions of complexes containing M - 0Si(0 Bu)3 and M - 02P(0 Bu)2 moieties invariably proceed via ehmination of isobutylene and the formation of M - O - Si - OH and M - O - P - OH linkages that immediately imdergo condensation processes (via ehmination of H2O), with subsequent formation of insoluble multi-component oxide materials. For example, thermolysis of Zr[OSi(O Bu)3]4 in toluene at 413 K results in ehmination of 12 equiv of isobutylene and formation of a transparent gel [67,68]. 

Plasticiser/oil in rubber is usually determined by solvent extraction (ISO 1407) and FTIR identification [57] TGA can usually provide good quantifications of plasticiser contents. Antidegradants in rubber compounds may be determined by HS-GC-MS for volatile species (e.g. BHT, IPPD), but usually solvent extraction is required, followed by GC-MS, HPLC, UV or DP-MS analysis. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out. The determination of antioxidants in rubbers by means of HPLC and TLC has been reviewed [58], The TLC technique for antidegradants in rubbers is described in ASTM D 3156 and ISO 4645.2 (1984). Direct probe EIMS was also used to analyse antioxidants (hindered phenols and aromatic amines) in rubber extracts [59]. ISO 11089 (1997) deals with the determination of /V-phenyl-/9-naphthylamine and poly-2,2,4-trimethyl-1,2-dihydroquinoline (TMDQ) as well as other generic types of antiozonants such as IV-alkyl-AL-phenyl-p-phenylenediamines (e.g. IPPD and 6PPD) and A-aryl-AL-aryl-p-phenylenediamines (e.g. DPPD), by means of HPLC. 

In-fibre derivatisation/SPME has been reported for the analysis of polar analytes. Derivatisation allows target analytes to be converted to less polar and more volatile species prior to GC analysis. In-fibre derivatisation with diazomethane was applied to long-chain (Ci6, Cig) fatty acids in aqueous solutions. Initially, the polyacrylate fibre was placed in an aqueous sample containing the fatty acids. After sufficient extraction time,... 

The most frequently used methods for elemental analysis in plastics (certainly in the past) deal with digestions of some kind. Also, some derivatisation methods (e.g. hydride generation for element analysis, or the equivalent TMAH treatment for molecular analysis) may be used to generate volatile species which are more easily separated from each other by chromatography. Derivatisation reactions are often far from being well controlled. 

Water (TAL) Purging of sample with gas followed by cryogenically trapping volatile species onto solid sorbent GC column GC/AAS 0.5 ng/g No data Chau et al. 1980... 

Examination of volatile and semi-volatile species such as solvents, monomers, plasticisers, etc. 

For identification of other organic rubber compounding ingredients such as waxes, and most antioxidants/antiozonants, sample extraction with diethyl ether, followed by GC-MS of the resulting extract is commonly employed. Examination of volatile species can also provide information on the nature of curatives employed. 

Figure 9. The quadrupole mass spectrometer signal for volatile species released from 0.90 nm palladium acetate film as a function of 2 MeV He+ ion dose. Mass 15 is shown for both CH3 and CH4 because of overlap at m/e 16 with oxygen. Mass 31 is shown for C2H6 (13C isotope) because of overlap at m/e 30 with major fragments of other parent ions.

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