Alcohols in Hydrocarbons

Alcohols in Hydrocarbons. There is not much material available on the photolysis of the primary and secondary alcohols in hydrocarbon solvents with the exception of a study on isopropanol (129), in which it was found that (i(H2) remained unaltered or was slightly increased if isopropanol was diluted by n-hexane. The 

The t-butanol/hydrocarbon system has attracted more Interest (135,82,83). As has been shown above neat t-butanol in its photolysis differs markedly from the primary and secondary alcohols in that the formation of hydrogen is not the major process. Rather, it is the scission of the C-C bond. On dilution with a hydrocarbon solvent, however, (i(H2) increases and )(CH ) (which is an approximate measure for the C-C split) decreases strongly (82). More detailed studies have been undertaken in dilute solutions (0.04 to 1.15 mol/1) (83) in order to try and correlate the photolytic behavior of t-butanol, and the marked change in the absorption coefficient of t-butanol with dilution, and its state of aggregation in the hydrocarbon solvent. It is known that t-butanol forms various aggregates, but opinions as to their structure often differ for example, trimer (170) or tetramer (171) species are considered to predominate if concentrations are not too low. 

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The transitions between different oxoforms for hexavalent derivatives are scarcely studied. The derivatives of all the three known series (i.e., Cr02(0R% Cr205(0R )2, and Cr308(0R )2) are formed simultaneously on Cr03 interaction with alcohols in hydrocarbon media and can be separated by thin-layer chromatography on silica gel [131]. 

In contrast, the reactions of Ru3(CO)i2 with propargyl alcohols in CH3OH-KOH solutions lead to the hydrido-allenylidene eomplexes HRu3(CO)9(HCCCRR ) (Fig. 30) not previously observed in the direct synthetic route starting from Ru3(CO)i2 and propargyl alcohols in hydrocarbons these complexes are formed upon loss of OH with a reaetion mechanism still unknown. 

Among the analytical applications using near-infrared spectroscopy have been the following determinations water in hydrocarbons water in alcohols water in carboxylic acids alcohols in hydrocarbons alcohols in acids acids in hydrocarbons acids in anhydrides amines in hydrocarbons benzene in hydrocarbons and olefins in hydrocarbons. By differential techniques it is possible, for example, to lower the sensitivity limits (detectability) by another factor of 10 over the usual limits. The usual limit for water in alcohols ranges from 0.05 to 0.2 %. Examples of special interest to biochemists are the applications of Klotz and Frank (1965) of near-... 

At about 1951, both Wilbur Kaye at Tennessee Eastman and Harry Willis in the Plastics Division of ICI in the U.K. began exploring NIR. Wilbur Kaye modified a Beckman DU UV instrument and worked on the development of the Beckman DK for NIR. Kaye thoroughly discussed the spectra of several compounds, including hromoform, chloroform, methylene chloride, benzene, methanol, and m-toluidine. He cited potential application of the spectral region to the analysis of mixtures of organic compounds, including water in hydrocarbons and other solvents, alcohols in hydrocarbons, acids, amines, benzene, and olefins in hydrocarbons. 

Clemmensen reduction of aldehydes and ketones. Upon reducing aldehydes or ketones with amalgamated zinc and concentrated hydrochloric acid, the main products are the hydrocarbons (>C=0 —> >CHj), but variable quantities of the secondary alcohols (in the case of ketones) and unsaturated substances are also formed. Examples are ... 

The procedure is to pass purified hydrogen through a hot solution of the pure acid chloride in toluene or xylene in the presence of the catalyst the exit gases are bubbled through water to absorb the hydrogen chloride, and the solution is titrated with standard alkali from time to time so that the reduction may be stopped when the theoretical quantity of hydrogen chloride has been evolved. Further reduction would lead to the corresponding alcohol and hydrocarbon ... 

Typical nonsieve, polar adsorbents are siUca gel and activated alumina. Kquilihrium data have been pubUshed on many systems (11—16,46,47). The order of affinity for various chemical species is saturated hydrocarbons < aromatic hydrocarbons = halogenated hydrocarbons < ethers = esters = ketones < amines = alcohols < carboxylic acids. In general, the selectivities are parallel to those obtained by the use of selective polar solvents in hydrocarbon systems, even the magnitudes are similar. Consequendy, the commercial use of these adsorbents must compete with solvent-extraction techniques. 

The physical and chemical properties are less well known for transition metals than for the alkaU metal fluoroborates (Table 4). Most transition-metal fluoroborates are strongly hydrated coordination compounds and are difficult to dry without decomposition. Decomposition frequently occurs during the concentration of solutions for crysta11i2ation. The stabiUty of the metal fluorides accentuates this problem. Loss of HF because of hydrolysis makes the reaction proceed even more rapidly. Even with low temperature vacuum drying to partially solve the decomposition, the dry salt readily absorbs water. The crystalline soflds are generally soluble in water, alcohols, and ketones but only poorly soluble in hydrocarbons and halocarbons. 

The term gasohol has come into wide usage to identify, generally, a blend of gasoline and ethanol, with the latter derived from grain. The term may also be appHed to blends of methanol or other alcohols in gasolines or other hydrocarbons, without regard to sources of components. 

Physical properties of glycerol are shown in Table 1. Glycerol is completely soluble in water and alcohol, slightly soluble in diethyl ether, ethyl acetate, and dioxane, and insoluble in hydrocarbons (1). Glycerol is seldom seen in the crystallised state because of its tendency to supercool and its pronounced freesing point depression when mixed with water. A mixture of 66.7% glycerol, 33.3% water forms a eutectic mixture with a freesing point of —46.5°C. 

Cyclohexanedimethanol is miscible with water and low molecular weight alcohols and appreciably soluble in acetone. It has only negligible solubihty in hydrocarbons and diethyl ether (6). 

Natural Products. Various methods have been and continue to be employed to obtain useful materials from various parts of plants. Essences from plants are obtained by distillation (often with steam), direct expression (pressing), collection of exudates, enfleurage (extraction with fats or oils), and solvent extraction. Solvents used include typical chemical solvents such as alcohols and hydrocarbons. Liquid (supercritical) carbon dioxide has come into commercial use in the 1990s as an extractant to produce perfume materials. The principal forms of natural perfume ingredients are defined as follows the methods used to prepare them are described in somewhat general terms because they vary for each product and suppHer. This is a part of the industry that is governed as much by art as by science. 

Pa-s (45 P) flash point, 11°C crystallization temperature, 7°C miscible in alcohols inmiscible in hydrocarbons. 

Potassium Methylate. Potassium methoxide [865-33-8] KOCH, mol wt 70.13, is a fine, free-flowing, yellowish-white, caustic, hygroscopic powder purity 96.5—99% powder density after loose shaking, 0.75 g/mL apparent density (packing weight), 1.00 g/mL medium grain size, 0.05 —0.8 mm easily soluble in alcohols (33% in methanol at 20°C), insoluble in hydrocarbons. 

Aluminum alkoxides are easily soluble in hydrocarbons and in chlorinated hydrocarbons, but sparingly soluble in alcohols. They are sensitive to moisture and dry storage is essential. Aluminum alkoxides are used extensively as intermediates, for example, in the Meerwein-Poimdorf reaction (94). 

In the initial black Hquor concentration, saponified fatty and resin acid salts separate as tall oil soaps (see Tall oil). These soaps can be skimmed from the aqueous spent Hquor, acidified, and refined to give a cmde tall oil composed of resin acids, chiefly abietic and neoabietic fatty acids, chiefly oleic and Hnoleic and an unsaponifiable fraction made of phytosterols, alcohols, and hydrocarbons. Tall oil is fractionated primarily into fatty acids (see... 

IManila Copal. The Manilas are collected in Indonesia and the Philippines. They are soluble in alcohols and ketones, and insoluble in hydrocarbons and esters. The resins soften between 81—90°C and have acid numbers of 110—141. Principal uses are in coatings and varnishes. 

The physical properties of vinyl chloride are Hsted in Table 1 (12). Vinyl chloride and water [7732-18-5] are nearly immiscible. The equiUbrium concentration of vinyl chloride at 1 atm partial pressure in water is 0.276 wt % at 25°C, whereas the solubiUty of water in vinyl chloride is 0.0983 wt % at 25°C and saturated pressure (13). Vinyl chloride is soluble in hydrocarbons, oil, alcohol, chlorinated solvents, and most common organic Hquids. 

Solubility. One of PVP s more outstanding attributes is its solubility in both water and a variety of organic solvents. PVP is soluble in alcohols, acids, ethyl lactate, chlorinated hydrocarbons, amines, glycols, lactams, and nitroparaffins. SolubiUty means a minimum of 10 wt % PVP dissolves at room temperature (moisture content of PVP can influence solubiUty). PVP is insoluble in hydrocarbons, ethers, ethyl acetate, j -butyl-4-acetate, 2-butanone, acetone, cyclohexanone, and chlorobenzene. Both solvent polarity and H-bonding strongly influence solubiUty (77). 

The heavy metal salts, ia contrast to the alkah metal salts, have lower melting points and are more soluble ia organic solvents, eg, methylene chloride, chloroform, tetrahydrofiiran, and benzene. They are slightly soluble ia water, alcohol, ahphatic hydrocarbons, and ethyl ether (18). Their thermal decompositions have been extensively studied by dta and tga (thermal gravimetric analysis) methods. They decompose to the metal sulfides and gaseous products, which are primarily carbonyl sulfide and carbon disulfide ia varying ratios. In some cases, the dialkyl xanthate forms. Solvent extraction studies of a large number of elements as their xanthate salts have been reported (19). 

The physical and thermodynamic properties of benzene are shown in Table 1 (2). Azeotrope data for benzene with selected compounds are shown in Table 2 (3). Benzene forms minimum-boiling azeotropes with many alcohols and hydrocarbons. Benzene also forms ternary azeotropes. 

In automotive and aerospace end uses, the apphcations ate also often electrical. Polysulfones do not have as good solvent resistance as poly(phenylene sulfide). They perform well in hydrocarbons like gasoline and oil, or in antifreeze, but ate attacked by the alcohol-blend fuel mixtures. This may limit their under-the-hood apphcations. 

The solubility of many steroids in ammonia-tetrahydrofuran-/-butyl alcohol is about 0.06 A/, a higher concentration than has been reported in other solvent systems. Still higher concentrations may be possible in particular cases by suitable variation in the solvent ratios Procedure 3 (section V) describes such a reduction of estradiol 3-methyl ether at a 0.12 M concentration. A few steriods such as the dimethyl and diethyl ketals of estrone methyl ether are poorly soluble in ammonia-tetrahydrofuran-/-buty] alcohol and cannot be reduced successfully at a concentration of 0.06 even with a 6 hour reduction period. The diethyl ketal of estrone methyl ether is reduced successfully at 0.12 M concentration using a two-phase solvent system of ammonia-/-amyl alcohol-methylcyclohexane (Procedure 4, section V). This mixture probably would be useful for any nonpolar steroid that is poorly soluble in polar solvents but is readily soluble in hydrocarbons. 

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