Distillation 8 INDEX

Cetane index ASTM D 4737 ISO 4264 Correlation between density and distillation... 

Determination of the physical constants and the establishment of the purity of the compound. For a solid, the melting point is of great importance if recrystalhsation does not alter it, the compound may be regarded as pure. For a hquid, the boiling point is first determined if most of it distils over a narrow range (say, 1-2°), it is reasonably pure. (Constant boUing point mixtures, compare Section 1,4, are, however known.) The refractive index and the density, from which the molecular refractivity may be calculated, are also valuable constants for liquids. 

The concentration of distilled glycerol is easily determined from its specific gravity (15) by the pycnometer method (16) with a precision of 0.02%. Deterrnination of the refractive index also is employed (but not as widely) to measure glycerol concentration to 0.1% (17). 

Phenol quahty tests and analyses can be divided into two categories wet lab and Hquid and gas chromatography. In the wet lab, phenol is tested for pH, sohdification point, solubiUty in water, bromine index, color, and distillation ranges. Phenol concentration, impurities, and CHP contents are analy2ed using highly automated Hquid and gas chromatography. 

Hplc techniques are used to routinely separate and quantify less volatile compounds. The hplc columns used to affect this separation are selected based on the constituents of interest. They are typically reverse phase or anion exchange in nature. The constituents routinely assayed in this type of analysis are those high in molecular weight or low in volatility. Specific compounds of interest include wood sugars, vanillin, and tannin complexes. The most common types of hplc detectors employed in the analysis of distilled spirits are the refractive index detector and the ultraviolet detector. Additionally, the recent introduction of the photodiode array detector is making a significant impact in the analysis of distilled spirits. 

Free-swelling tests are commonly used to measure a coal s caking characteristics. A sample of coal is packed in a cmcible or tube, without compaction, and heated at a fixed rate to about 800°C. Infusible coals distill without changing appearance or state of agglomeration. The fusible coals soften, fuse, and usually sweU. The profile of the resultant coke is compared to a series of reference profiles so that a swelling index can be assigned. The profiles represent indexes between 0 and 9. The best cokes come from coals having indexes between 4 and 9. 

As an example, the battery-limits capital cost can be estimated for the production of 10,000 t/yr of ethylene (qv) from ethanol (11). Seven processing blocks, ie, vaporizer, reactor, water quench, compressor, dryer, distillation, and energy recovery, can be identified. The highest temperature is 350°C (reactor), and the highest pressure is about 1.7 MPa (17 atm) (compressor, two towers). If a materials-pressure factor, + of 1.03 is assumed, then for N = 7 0 = 0.87 1/0 = 1 64 and f =0 K = 6.3. This gives the 1981 cost as 4.4 X 10 . The 1991 battery-Hmits investment can be obtained, by updating with the CE Plant Cost Index, as 5.3 x 10 . ... 

When simple Hquids like naphtha are cracked, it may be possible to determine the feed components by gas chromatography combined with mass spectrometry (gc/ms) (30). However, when gas oil is cracked, complete analysis of the feed may not be possible. Therefore, some simple definitions are used to characterize the feed. When available, paraffins, olefins, naphthenes, and aromatics (PONA) content serves as a key property. When PONA is not available, the Bureau of Mines Correlation Index (BMCI) is used. Other properties like specific gravity, ASTM distillation, viscosity, refractive index. Conradson Carbon, and Bromine Number are also used to characterize the feed. In recent years even nuclear magnetic resonance spectroscopy has been... 

BP Method for Distillation The bubble-point method for distillation, particularly when the components involved cover a relatively narrow range of volatihty, proceeds iteratively by the following steps, where k is the iteration index for the entire distillation column. 

Titles of periodicals are defined as in the Chemical Abstracts Service Source Index (CASSI), except that full stops have been omitted after each abbreviated word. Abbreviations of words in the texts of Chapters 4, 5 and 6 are those in common use and are self evident, e.g. distn, filtd, cone and vac are used for distillation, filtered, concentrated and vacuum. 

The wide range of refractive index is related to the time interval between distillation and measurement. The longer one waits, the higher is the refractive index. This is apparently due to rapid formation of dimer. 

Figure 12.21. (c) Elongation at break, (d) Macklow-Smith flow index. (The Distillers Company... 

The reaction mixture is heated and allowed to reflux, under atmospheric pressure at about 100°C. At this stage valve A is open and valve B is closed. Because the reaction is strongly exothermic initially it may be necessary to use cooling water in the jacket at this stage. The condensation reaction will take a number of hours, e.g. 2-4 hours, since under the acidic conditions the formation of phenol-alcohols is rather slow. When the resin separates from the aqueous phase and the resin reaches the requisite degree of condensation, as indicated by refractive index measurements, the valves are changed over (i.e. valve A is closed and valve B opened) and water present is distilled off. 

The undistilled />-methoxyphenylacetonitrile weighs 125-139 g. (85-95%) and has a refractive index close to that of the distilled product. It can be used for many purposes, such as... 

Bromine (128 g., 0.80 mole) is added dropwise to the well-stirred mixture over a period of 40 minutes (Note 4). After all the bromine has been added, the molten mixture is stirred at 80-85° on a steam bath for 1 hour, or until it solidifies if that happens first (Note 5). The complex is added in portions to a well-stirred mixture of 1.3 1. of cracked ice and 100 ml. of concentrated hydrochloric acid in a 2-1. beaker (Note 6). Part of the cold aqueous layer is added to the reaction flask to decompose whatever part of the reaction mixture remains there, and the resulting mixture is added to the beaker. The dark oil that settles out is extracted from the mixture with four 150-ml. portions of ether. The extracts are combined, washed consecutively with 100 ml. of water and 100 ml. of 5% aqueous sodium bicarbonate solution, dried with anhydrous sodium sulfate, and transferred to a short-necked distillation flask. The ether is removed by distillation at atmospheric pressure, and crude 3-bromo-acetophenone is stripped from a few grams of heavy dark residue by distillation at reduced pressure. The colorless distillate is carefully fractionated in a column 20 cm. long and 1.5 cm. in diameter that is filled with Carborundum or Heli-Pak filling. 4 hc combined middle fractions of constant refractive index are taken as 3-l)romoaccto])lu iu)nc weight, 94 -100 g. (70-75%) l).p. 75 76°/0.5 mm. tif 1.57,38 1.5742 m.]). 7 8° (Notes 7 and 8). 

Alcohol can be detected h,v dislilJicig a few c.c. of Ihc sample with water, aud testing the distillate by the usual iodoform reaction. It the sample bo wHshed with warm waler in a separator, and the retractivu index of the washed otto l>c examined, it will be found to he higher than that ol the original otto. II this exoes.s be more (ban fl-Ofll i is almost certainly due to alcohol. 

---