Boiling point analysis

Fully automatic equipment for standardized boiling point analysis... 

Boiling point, boiling point analysis (true boiling point)... 

Example 4-7. ASTM End Point and T.B.P. Cut Point It is desired to determine the cut point on a true-boiling-point analysis curve that will give a product having an ASTM end point of 437 F. At an end point of 437 (curve A, Fig. 4-25) the true-boiling-point cut point is 21 F higher than the ASTM end point. The cut point is 437 plus 21, or 458°F. The following tabulation indicates approximate end points as well as cut points for other distillates ... 

True-boiling-point Analysis of Crude Oil. The property curves that have been discussed heretofore are of general usefulness. In the following pages the necessary laboratory procedure, the construction of the curves, and the evaluations of several stocks will be discussed. 

The reduced crude is then flashed under vacuum, distilling a clear lubricating oil stock and leaving solid tar. The lubricating oil stock can then be evaluated in the true-boiling apparatus. A true-boiling-point analysis of the crude oil is also necessary if the light stocks are to be evaluated. 

One has seen that the number of individual components in a hydrocarbon cut increases rapidly with its boiling point. It is thereby out of the question to resolve such a cut to its individual components instead of the analysis by family given by mass spectrometry, one may prefer a distribution by type of carbon. This can be done by infrared absorption spectrometry which also has other applications in the petroleum industry. Another distribution is possible which describes a cut in tei ns of a set of structural patterns using nuclear magnetic resonance of hydrogen (or carbon) this can thus describe the average molecule in the fraction under study. 

This analysis, abbreviated as FIA for Fluorescent Indicator Adsorption, is standardized as ASTM D 1319 and AFNOR M 07-024. It is limited to fractions whose final boiling points are lower than 315°C, i.e., applicable to gasolines and kerosenes. We mention it here because it is still the generally accepted method for the determination of olefins. 

Evidence of the appHcation of computers and expert systems to instmmental data interpretation is found in the new discipline of chemometrics (qv) where the relationship between data and information sought is explored as a problem of mathematics and statistics (7—10). One of the most useful insights provided by chemometrics is the realization that a cluster of measurements of quantities only remotely related to the actual information sought can be used in combination to determine the information desired by inference. Thus, for example, a combination of viscosity, boiling point, and specific gravity data can be used to a characterize the chemical composition of a mixture of solvents (11). The complexity of such a procedure is accommodated by performing a multivariate data analysis. 

Cool on-column injection is used for trace analysis. Ah. of the sample is introduced without vaporization by inserting the needle of the syringe at a place where the column has been previously stripped of hquid phase. The injection temperature must be at or below the boiling point of the solvent carrying the sample. Injection must be rapid and no more than a very few, usuahy no more than two, microliters may be injected. Cool on-column injection is the most accurate and reproducible injection technique for capihary chromatography, but it is the most difficult to automate. 

Applications. Transesterifications via alcoholysis play a significant role in industry as well as in laboratory and in analytical chemistry. The reaction can be used to reduce the boiling point of esters by exchanging a long-chain alcohol group with a short one, eg, methanol, in the analysis of fats, oils, and waxes. For more details see References 7 and 68. A few examples are given below. 

The retention gap method (1, 2) represents the best approach in the case of qualitative and quantitative analysis of samples containing highly volatile compounds. The key feature of this technique is the introduction of the sample into the GC unit at a temperature below the boiling point of the LC eluent (corrected for the current inlet pressure), (see Eigure 2.2). This causes the sample vapour pressure to be below the carrier gas inlet pressure, and has two consequences, as follows ... 

The retention gap techniques, essential for the analysis of very volatile components, are often replaced by concurrent eluent evaporation techniques, due to their simplicity and the possibility of transfering very large amount of solvent. In this case, the solvents are introduced into an uncoated inlet at temperatures at or above the solvent boiling point. 

The complexity of oil fractions is not so much the number of different classes of compounds, but the total number of components that can be present. Even more challenging is the fact that, unlike the situation with other complex samples, in which only a few specific compounds have to be separated from the matrix, in oil fractions the components of the matrix itself are the analytes. Figure 14.1 presents an estimation (by extrapolation) of the total number of possible hydrocarbon isomers with up to twenty carbon atoms present in oil fractions. Although probably not all of these isomers are always present, these numbers are nevertheless somewhat overwhelming. This makes a complete compositional analysis using a single column separation of unsaturated fractions with boiling points above 100 °C utterly impossible. 

Analysis shows that this oil consists of several ketones of the groups CuH qO of higher boiling-points and greater density than those of ionone. These ketones are optically active, and both their existence and their artificial production have been hitherto unknown. 

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