Condensation of mixtures

The correlations given in the previous sections apply to the condensation of a single component such as an essentially pure overhead product from a distillation column. The design of a condenser for a mixture of vapours is a more difficult task. 

The term mixture of vapours covers three related situations of practical interest  

Total condensation of a multicomponent mixture such as the overheads from a multicomponent distillation. 

Condensation of only part of a multicomponent vapour mixture, all components of which are theoretically condensable. This situation will occur where the dew point of some of the lighter components is above the coolant temperature. The uncondensed component may be soluble in the condensed liquid such as in the condensation of some hydrocarbons mixtures containing light gaseous components. 

Condensation from a non-condensable gas, where the gas is not soluble to any extent in the liquid condensed. These exchangers are often called cooler-condensers. 

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Condensation of mixtures. It is easy to show with the help of a material balance that the composition of the first drop of condensate is determined by the relative rates of condensation. In practice, the condensate composition throughout a horizontal condenser often is assumed to be given by the relative rates of condensation (more on this in Chapter 15). 

In the case of R = Ph further derivatizations have been performed [94] yielding polycarbosilanes with unsaturated side chains [95] as well as a polysilaeAene (Scheme 7). The ceramic yield of the latter could be increased up to 91% if some of the phenyl groups remained [96]. Branched polycarbosilanes were obtained by a Wurtz condensation of mixtures of PhSiCls and Ph2SiCl2 with CH2Br2 [97]. 

Separation of mixtures of condensable and non-condensable components. If a fluid mixture contains both condensable and noncondensable components, then a partial condensation followed by a simple phase separator often can give a food separation. This is essentially a single-stage distillation operation. It is a special case that deserves attention in some detail later. 

In the first class, azeotropic distillation, the extraneous mass-separating agent is relatively volatile and is known as an entrainer. This entrainer forms either a low-boiling binary azeotrope with one of the keys or, more often, a ternary azeotrope containing both keys. The latter kind of operation is feasible only if condensation of the overhead vapor results in two liquid phases, one of which contains the bulk of one of the key components and the other contains the bulk of the entrainer. A t3q)ical scheme is shown in Fig. 3.10. The mixture (A -I- B) is fed to the column, and relatively pure A is taken from the column bottoms. A ternary azeotrope distilled overhead is condensed and separated into two liquid layers in the decanter. One layer contains a mixture of A -I- entrainer which is returned as reflux. The other layer contains relatively pure B. If the B layer contains a significant amount of entrainer, then this layer may need to be fed to an additional column to separate and recycle the entrainer and produce pure B. 

GattermaDD synthesis A method for the synthesis of aromatic hydroxyaldehydes. E.g. AICI3 is used to bring about the condensation of phenol with a mixture of gaseous hydrochloric acid and hydrocyanic acid an aldimine hydrochloride is formed and on hydrolysis gives p-hydroxybenzaldehyde... 

CH2 CH CH0. a colourless, volatile liquid, with characteristic odour. The vapour is poisonous, and intensely irritating to eyes and nose b.p. 53"C. It is prepared by the distillation of a mixture of glycerin, potassium sulphate and potassium hydrogen sulphate. It is manufactured by direct oxidation of propene or cross-condensation of ethanal with meth-anal. 

A separator is fed with a condensate/gas mixture. The condensate leaves the bottom of the separator, passes a flowmeter and is followed by a choke valve, after which the condensate is boiling. The flow can not be measured using the transit time method, due to the combination of short piping, the absence of a suitable injection point and the flow properties of the condensate, which is non-newtonian due to a high contents of wax particles The condensate can not be representatively sampled, as it boils upon depressuratioh... 

The material to be steam-distilled (mixed with some water if a solid compound, but not otherwise) is placed in C, and a vigorous current of steam blown in from D. The mixture in C is thus rapidly heated, and the vapour of the organic compound mixed with steam passes over and is condensed in E. For distillations on a small scale it is not necessary to heat C if, however, the flask C contains a large volume of material or material which requires prolonged distillation, it should be heated by a Bunsen burner, otherwise the steady condensation of steam in C will produce too great a volume of liquid. 

The set-up of Fig. 11, 41, 3 ensures the complete condensation of the steam when a rapid flow of steam is necessary for satisfactory results, and is useful in the distillation of large volumes of liquids of low vapour pressure, such as nitrobenzene. Thus the flask A containing the mixture may be of 3-litre capacity and B may be a 1-litre flask the latter is cooled by a stream of water, which is collected in a funnel and conducted to the sink. The receiver C must be of proportionate size all stoppers... 

In a 250 ml. conical flask, fitted with an air condenser of wide bore, place 50 g. (51 -5 ml.) of acetonylacetone (see Section V,9, Note 2) and 100 g. of ammonium carbonate (lump form). Heat the mixture in an oil bath at 100° until effervescence stops (60-90 minutes) some ammonium carbonate (or carbamate) sublimes into the condenser and this must be pushed back into the reaction mixture by means of a stout glass rod. Replace the air condenser by a Liebig s condenser with wide bore inner tube and reflux the mixture gently (bath temperature, 115°) for a further 30 minutes dissolve the solid which has sublimed into the condenser in about 5 ml. of hot water and return the solution to the reaction mixture. 

A mixture of an acid anhydride and a ketone is saturated with boron trifluoride this is followed by treatment with aqueous sodium acetate. The quantity of boron trifluoride absorbed usually amounts to 100 mol per cent, (based on total mola of ketone and anhydride). Catalytic amounts of the reagent do not give satisfactory results. This is in line with the observation that the p diketone is produced in the reaction mixture as the boron difluoride complex, some of which have been isolated. A reasonable mechanism of the reaction postulates the conversion of the anhydride into a carbonium ion, such as (I) the ketone into an enol type of complex, such as (II) followed by condensation of (I) and (II) to yield the boron difluoride complex of the p diketone (III) ... 

Furfural reacts with ketones to form strong, crosslinked resins of technical interest in the former Soviet Union the U.S. Air Force has also shown some interest (42,43). The so-called furfurylidene acetone monomer, a mixture of 2-furfurylidene methyl ketone [623-15-4] (1 )> bis-(2-furfurylidene) ketone [886-77-1] (14), mesityl oxide, and other oligomers, is obtained by condensation of furfural and acetone under basic conditions (44,45). Treatment of the "monomer" with an acidic catalyst leads initially to polymer of low molecular weight and ultimately to cross-linked, black, insoluble, heat-resistant resin (46). 

Fig. 11. Synthesis of DNQ photosensitizers found in commercial resists, (a) Condensation of l,2-diazonaphthoquinone-5-sulfonyl chloride with 1,2,3-trihydroxybenzophenone. Often the reaction is not carried to completion so the product is a mixture of monodi- and trisubstituted products, (b)...

Ethyl acetate [141-78-6] is produced commercially by the Tischenko condensation of acetaldehyde using an aluminum ethoxide catalyst (60). The Tischenko reaction of acetaldehyde with isobutyraldehyde [78-84-2] yields a mixture of ethyl acetate, isobutyl acetate [110-19-0] and isobutyl isobutyrate [97-85-8] (61). 

Resorcinol carboxylation with carbon dioxide leads to a mixture of 2,4-dihydroxyben2oic acid [89-86-1] (26) and 2,6-dihydroxyben2oic acid [303-07-1] (27) (116). The condensation of resorcinol with chloroform under basic conditions, in the presence of cyclodextrins, leads exclusively to 2,4-dihydroxyben2aldehyde [95-01-2] (28) (117). Finally, the synthesis of l,3-bis(2-hydroxyethoxy)ben2ene [102-40-9] (29) has been described with ethylene glycol carbonate in basic medium (118), in the presence of phosphines (119). Ethylene oxide, instead of ethyl glycol carbonate, can also be used (120). 

For methylene diphenyl diisocyanate (MDI), the initial reaction involves the condensation of aniline [62-53-3] (21) with formaldehyde [50-00-0] to yield a mixture of oligomeric amines (22, where n = 1, 2, 3...). For toluene diisocyanate, amine monomers are prepared by the nitration (qv) of toluene [108-88-3] and subsequent hydrogenation (see Amines byreduction). These materials are converted to the isocyanate, in the majority of the commercial aromatic isocyanate phosgenation processes, using a two-step approach. 

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