Boiling temperatures

Separation of high-molecular-weight heat-sensitive materials. High-molecular-weight materials are often heat sensitive and as such are usually distilled under vacuum to reduce their boiling temperature. 

Forward-feed operation is shown in Fig. 3.12a. The fresh feed is added to the first stage and fiows to the next stage in the same direction as the vapor flow. The boiling temperature decreases from stage to stage, and this arrangement is thus used when the... 

Sample size is 100 ml and distillation conditions are specified according to the type of sample. Temperature and volume of condensate are taken simultaneously and the test results are calculated and reported as boiling temperature as a function of the volume recovered as shown in Table 2.1. 

The results are presented as a distillation curve showing the boiling temperature (corrected to atmospheric pressure) as a function of the distilled volume. 

T being the boiling temperature (Kelvin) and S being tbe standard specific gravity (15.6°C/15.6°C). Refer to Chapter 4. 

Group the component in a petroleum fraction, which is possible if the normal boiling temperature and the standard specific gravity are known. This method gives correct results when the chemical structure is simple as in the case of a paraffin or naphthene. 

This is the average boiling temperature at atmospheric pressure (1.013 bar abs). This characteristic is obtained by direct laboratory measurement and is expressed in K or °C. 

If the boiling temperature is not known, it is somewhat risky to estimate it. One could, if the Watson characterization factor is known, use the following... 

For heavy fractions whose boiling temperatures exceed 600 K, it is better to use the method published by Lee and Kesler in 1975 ... 

Using the principle of corresponding states requires knowledge of pseudo-critical constants of petroleum fractions these should be estimated starting from characteristic properties which are the normal boiling temperature and the standard specific gravity. 

The concentrated mother Hquor contains a large amount of sulfuric acid in a free form, as titanium oxy-sulfate, and as some metal impurity sulfates. To yield the purest form of hydrated TiOg, the hydrolysis is carried out by a dding crystallizing seeds to the filtrate and heating the mixture close to its boiling temperature, - 109° C. The crystal stmcture of the seeds (anatase or mtile) and their physical properties affect the pigmentary characteristics of the final product. 

Commercial grades of sodium aluminate are obtained by digestion of aluminum tnhydroxide in aqueous caustic at atmospheric pressure and near the boiling temperature (7). Digestion of the aluminum hydroxy oxide in aqueous sodium hycboxide [1310-73-2] requbes pressures of up to 1.38 MPa (13.6 atm) and temperatures of about 200°C. Dry sodium aluminate is obtained by evaporation of water. Several processes for the production of sodium aluminate are known that do not reqube the addition of water. In one process, bauxite reacts with molten sodium hycboxide at approximately 400°C (8) in... 

Alkali metal sulfamates are stable in neutral or alkaline solutions even at boiling temperatures. Rates of hydrolysis for sulfamic acid in aqueous solutions have been measured at different conditions (Table 4) (8,10)-... 

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. 

The most important of these is the diboride, TiB2, which has a hexagonal stmeture and lattice parameters of a = 302.8 pm and c = 322.8 pm. Titanium diboride is a gray crystalline soUd. It is not attacked by cold concentrated hydrochloric or sulfuric acids, but dissolves slowly at boiling temperatures. It dissolves mote readily in nitric acid/hydrogen peroxide or nitric acid/sulfuric acid mixtures. It also decomposes upon fusion with alkaU hydroxides, carbonates, or bisulfates. 

Zirconium is not attacked by caustics up to boiling temperatures. It is resistant to molten sodium hydroxide to 1000°C, but is less resistant to potassium hydroxide. 

At higher temperatures the stable form is valentinite, which consists of infinite double chains. The orthorhombic modification is metastable below 570 °C however, it is sufficientiy stable to exist as a mineral. Antimony trioxide melts in the absence of oxygen at 656°C and partially sublimes before reaching the boiling temperature, 1425°C. The vapor at 1500°C consists largely of Sb O molecules, but these dissociate at higher temperatures to form Sb202 molecules. 

The boiling temperature of a permeant can be used to predict the solubihty coefficient only when the solubihty coefficients of other permeants of the same chemical family are known. 

Corrosivity. Corrosivity is an important factor in the economics of distillation. Corrosion rates increase rapidly with temperature, and in distillation the separation is made at boiling temperatures. The boiling temperatures may require distillation equipment of expensive materials of constmction however, some of these corrosion-resistant materials are difficult to fabricate. For some materials, eg, ceramics (qv), random packings may be specified, and this has been a classical appHcation of packings for highly corrosive services. On the other hand, the extensive surface areas of metal packings may make these more susceptible to corrosion than plates. Again, cost may be the final arbiter (see Corrosion and corrosion control). 

As an example, consider the residue curve map for the nonazeotropic mixture shown in Eigure 2. It has no distillation boundary so the mixture can be separated into pure components by either the dkect or indkect sequence (Eig. 4). In the dkect sequence the unstable node (light component, L) is taken overhead in the first column and the bottom stream is essentially a binary mixture of the intermediate, I, and heavy, H, components. In the binary I—H mixture, I has the lowest boiling temperature (an unstable node) so it is recovered as the distillate in the second column and the stable node, H, is the corresponding bottoms stream. The indkect sequence removes the stable node (heavy component) from the bottom of the first column and the overhead stream is an essentially binary L—I mixture. Then in the second column the unstable node, L, is taken overhead and I is recovered in the bottoms. 

A convenient way of representing the T—x y phase diagram (Eig. 14b) is by projection onto the composition triangle at the base of the figure. It is understood that the temperature varies from point to point on the projected vapor line and on the projected boiling envelope. The latter looks like an isothermal Hquid—Hquid binodal envelope, but is not. Each tie line across the boiling envelope is associated with a different boiling temperature (Eig. 15). 

Fig. 15. Isobaric vapor—liquid—liquid (VLLE) phase diagrams for the ethanol—water—benzene system at 101.3 kPa (D-D) representHquid—Hquid tie-lines (A—A), the vapor line I, homogeneous azeotropes , heterogeneous azeotropes Horsley s azeotropes, (a) Calculated, where A is the end poiat of the vapor line and the numbers correspond to boiling temperatures ia °C of 1, 70.50 2, 68.55 3, 67.46 4, 66.88 5, 66.59 6, 66.46 7, 66.47, and 8, the critical poiat, 66.48. (b) Experimental, where A is the critical poiat at 64.90°C and the numbers correspond to boiling temperatures ia °C of 1, 67 2, 65.5 3, 65.0 ...

The typical phase equiHbrium problem eacouatered ia distiHatioa is to calculate the boiling temperature and the vapor composition ia equiHbrium with a Hquid phase of specified composition at a givea pressure. If the Hquid phase separates, thea the problem is to calculate the boiling temperature and the compositions of the two equiHbrium Hquid phases plus the coexistiag vapor phase at the specified overall Hquid compositioa. Robust and practical numerical methods have been devised for solving this problem (95—97) and have become the recommended techniques (98,99). 

Normal Boiling Temperature The normal boiling temperature (point) is the temperature at which the vapor pressure equals exac tly 101,325 Pa (1 atmosphere). Caution shomd be taken in using values from older references, where the temperature may be reported for the prevaihng pressure (0.95-0.97 atm) rather than at 1 atmosphere. If at least two values of vapor pressure very close to 1 atmosphere are available, the normal boihng point can be interpolated or extrapolated on a plot of logP vs. l/T. Tme section on vapor pressure discusses this in more detail. 

Thr = reduced normal boiling temperature = Th/T,-Ty = normal boiling temperature, K Vr = critical pressure, kPa... 

Tbij = normal boiling temperature of pure component i or j, K... 

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