Distillation boiling-point method

Reagents. Phenyl Azide (freshly distilled), boiling point 49-50° C., at 5 mm. The phenyl azide was prepared according to the method of Lindsay and Allen (4). 

Ballast bulb (5 L) pressure gauge three long pieces of heavy-wall rubber pressure tubing. If the boiling-point method is used distillation flask appropriate thermometer to cover the desired range, with one-hole rubber stopper to allow adjustment of thermometer... 

Vapour pressures of sohd and hquid thorinm tetrachloride were measured at 880-1024, 1055 -1126 K by the transpiration techniqne and from 923 -1043, 1045 -1161 K by the boiling point method. The ThCLt nsed was prepared from thorium hydride and chlorine gas at 500 K, and pnrified by vacnnm distillation at 1000 K. The analysed Th/Cl ratio was reported to be 1/4. The container for both techniques was sihca, which could perhaps have reacted with ThCLt to form ThOCp. However, the results from the two techniques are self-consistent and agree well with those by [1939FIS/GEW2] and [1989LAU/HIL]. The melting temperatnre and enthalpy of fusion of ThCp were evaln-ated from the vapom pressure curves to be 1043 K, and (62.1 + 3.7) kJ-moF, respectively. 

This is the ASTM D 2892 test method and corresponds to a laboratory technique defined for a distillation column having 15 to 18 theoretical plates and operating with a 5 1 reflux ratio. The test is commonly known as the TBP for True Boiling Point. 

The simulated distillation method uses gas phase chromatography in conjunction with an apolar column, that is, a column where the elution of components is a function of their boiling points. The column temperature is increased at reproducible rate (programed temperature) and the area of the chromatogram is recorded as a function of elution time. 

This factor is the intermediate parameter employed in numerous calculational methods. For petroleum cuts obtained by distillation from the same crude oil, the Watson factor is generally constant when the boiling points are above 200°C. 

The accuracy depends on the fraction distilled it deviates particularly when determining the initial and final boiling points the average error can exceed 10°C. When calculating the ASTM D 86 curve for gasoline, it is better to use the Edmister (1948) relations. The Riazi and Edmister methods lead to very close results when they are applied to ASTM D 86 calculations for products such as gas oils and kerosene. 

The breaking up of azeotropic mixtures. The behaviour of constant boiling point mixtures simulates that of a pure compound, because the composition of the liquid phase is identical with that of the vapour phase. The composition, however, depends upon the pressure at which the distillation is conducted and also rarely corresponds to stoichiometric proportions. The methods adopted in practice will of necessity depend upon the nature of the components of the binary azeotropic mixture, and include —... 

An elementary account of the subject has been given in the previous Section. For the fractional distillation under diminished pressure of liquids diflfering only slightly in boiling point, a firactionating column (see Sections 11,15 and 11,17) must be used. Provision must, of course, be made for the insertion of a capillary tube into the fiask containing the mixture. This can be done by any of the following methods —... 

Method 2 (from potassium bromide and sulphuric acid). Potassium bromide (240 g.) is dissolved in water (400 ml.) in a litre flask, and the latter is cooled in ice or in a bath of cold water. Concentrated sulphuric acid (180 ml.) is then slowly added. Care must be taken that the temperature does not rise above 75° otherwise a little bromine may be formed. The solution is cooled to room temperature and the potassium bisulphate, which has separated, is removed by flltration through a hardened Alter paper in a Buchner funnel or through a sintered glass funnel. The flltrate is distilled from a litre distilling flask, and the fraction b.p. 124 127° is collected this contains traces of sulphate. Pure constant boiling point hydrobromic acid is obtained by redistillation from a little barium bromide. The yield is about 285 g. or 85 per cent, of the theoretical. 

If time is limited, the boiling point determinations by the distilling flask method for these liquids may be omitted. 

Reflux 1 ml. of the ether with 5 ml. of freshly distilled, constant boiling point hydriodic acid (Section 11,49,2), b.p. 126-128°, for 2-3 hours. Add 10 ml. of water, distil and collect about 7 ml. of liquid. Decolourise the distillate by the addition of a httle sodium bisulphite, and separate the two layers by means of a dropper pipette (Fig. 11,27,1). Determine the b.p. of the resulting iodide by the Siwoloboff method (Section 11,12) and prepare a crystalline derivative (Section 111,42). 

Separations based upon differences in the physical properties of the components. When procedures (1) or (2) are unsatisfactory for the separation of a mixture of organic compounds, purely physical methods may be employed. Thus a mixture of volatile liquids may be fractionally distilled (compare Sections 11,15 and 11,17) the degree of separation may be determined by the range of boiling points and/or the refractive indices and densities of the different fractions that are collected. A mixture of non-volatile sohds may frequently be separated by making use of the differences in solubilities in inert solvents the separation is usually controlled by m.p. determinations. Sometimes one of the components of the mixture is volatile and can be separated by sublimation (see Section 11,45). 

Determination of boiling points. Distillation method (Fig. II, 12, 1) for carbon tetrachloride (25 nil. distillation flask and small water condenser), and SiwoloboflF s method (Fig. II, 12, 2) for carbon tetrachloride, aniline and nitrobenzene. Calibration curve for thermometer. Determination of b.p. of unknown liquid. 

Most derivatives of aniline are not obtained from aniline itself, but ate prepared by hydrogenation of their nitroaromatic precursors. The exceptions, for example, /V-a1ky1ani1ines, /V-ary1ani1ines, sulfonated anilines, or the A/-acyl derivatives, can be prepared from aniline and have been discussed. Nitroanilines are usually prepared by ammonolysis of the corresponding chloronitroben2ene. Special isolation methods may be requited for some derivatives if the boiling points are close and separation by distillation is not feasible. Table 6 Hsts some of the derivatives of aniline that are produced commercially. 

Other Separation Techniques. Under some circumstances, distillation is not the best method of separation. Among these instances are the following when relative volatiHty is <1.05 when <1% of a stream is removed, as in gas drying (adsorption or absorption) or C2H2 removal (reaction or absorption) when thermodynamic efficiency of distillation is <5% and when a high boiling point pushes thermal stabiHty limits. A variety of other... 

In the fire codes, the atmospheric boiling point is an important physical property used to classify the degree of hazardousness of a Hquid. If a mixture of Hquids is heated, it starts to bod at some temperature but continues to rise ia temperature over a boiling temperature range. Because the mixture does not have a definite boiling poiat, the NFPA fire codes define a comparable value of boiling poiat for the purposes of classifying Hquids. For petroleum mixture, it is based on the 10% poiat of a distillation performed ia accordance with ASTM D86, Standard Method of Test for Distillation of Petroleum Products. 

It is important to note that simulated distillation does not always separate hydrocarbons in the order of their boiling point. For example, high-boihng multiple-ring-type compounds may be eluted earher than normal paraffins (used as the calibration standard) of the same boiling point. Gas chromatography is also used in the ASTM D 2427 test method to determine quantitatively ethane through pentane hydrocarbons. 

One of the most widely applicable and most commonly used methods of purification of liquids or low melting solids (especially of organic chemicals) is fractional distillation at atmospheric, or some lower, pressure. Almost without exception, this method can be assumed to be suitable for all organic liquids and most of the low-melting organic solids. For this reason it has been possible in Chapter 4 to omit many procedures for purification of organic chemicals when only a simple fractional distillation is involved - the suitability of such a procedure is implied from the boiling point. 

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