Water butyl alcohol mixture

Mw = 2 380 000 g mol in a water/r-butyl alcohol mixture to determine the temperature dependence of excluded volume, assuming the Kuhn length of PMMA is 17 A ... 

A typical example [84] involves the preparation of an alkyd resin from phthalic anhydride (712 gm), trimethylolpropane (399 gm), isodecyl alcohol (277 gm), and xylene (22 gm) and heating (190°-280°C) to remove water azeotropically and give a resin of acid value 23. The product is diluted with a 4 1 xylene butyl alcohol mixture to 75% solids. A lacquer is prepared by mixing 16 gm of the above alkyd resin solution with 3 gm of a methylated melamine-formaldehyde condensate along with 7.5 gm of titanium oxide and 0.225 gm of /7-toluenesulfonic acid monohydrate. Sufficient xylene butanol (4 1) is added to give a 55% solids solution. A film of this solution is dried for 30 min at 120°C. The film is hard and stable to 10% sodium hydroxide. 

J. Julliard, J. P. Morel, and L. Avedikian, J. Chem. Phys., 69, 787 (1972). Conductivities of potassium formate, acetate, isobutyrate, cyclo-hexanecarboxylate and benzoate in water-tert butyl alcohol mixtures. 

Figure Activation parameters for the reaction of nickeHji) with 2,2 -bipyridine in water-ethanol and water-t-butyl alcohol mixtures, normalized with respect to those in pure water (298 K),...

Photochemical replacement of a substituent by a nucleophile occurs ortho and para to electron-donating substituents. These reactions are successful for hahdes as nucleofuges. An example is the conversion of p-chloroanisole to p-methoxybenzonitrile upon irradiation with cyanide ion. In the case of the isomeric chlorophenols and chloroanisoles, irradiation with alcohols involves a mixture of substitution (replacement by -Cl or -OR) and dehalogenation. The outcomes of these reactions maybe highly solvent dependent, as shown by studies on the replacement of fluoride by CN and OH, when o- and p-fluoroanisoles are photolyzed with KCN in water/t-butyl alcohol mixtures. ... 

The tendency to separate is expressed most often by the cloud point, the temperature at which the fuei-alcohol mixture loses its clarity, the first symptom of insolubility. Figure 5.17 gives an example of how the cloud-point temperature changes with the water content for different mixtures of gasoline and methanol. It appears that for a total water content of 500 ppm, that which can be easily observed considering the hydroscopic character of methanol, instability arrives when the temperature approaches 0°C. This situation is unacceptable and is the reason that incorporating methanol in a fuel implies that it be accompanied by a cosolvent. One of the most effective in this domain is tertiary butyl alcohol, TBA. Thus a mixture of 3% methanol and 2% TBA has been used for several years in Germany without noticeable incident. 

Reflux a mixture of 68 g. of anhydrous zinc chloride (e.g., sticks), 40 ml. (47 -5 g.) of concentrated hydrochloric acid and 18-5 g. (23 ml.) of sec.-butyl alcohol (b.p. 99-100°) in the apparatus of Fig. 777, 25, 1 for 2 hours. Distil oflF the crude chloride untU the temperature rises to 100°. Separate the upper layer of the distillate, wash it successively with water, 5 per cent, sodium hydroxide solution and water dry with anhydrous calcium chloride. Distil through a short column or from a Claisen flask with fractionating side arm, and collect the fraction of b.p. 67-70° some high boiling point material remains in the flask. Redistil and collect the pure cc. butyl chloride at 67-69°. The yield is 15 g. 

In a 250 ml. separatory funnel place 25 g. of anhydrous feri.-butyl alcohol (b.p. 82-83°, m.p. 25°) (1) and 85 ml. of concentrated hydrochloric acid (2) and shake the mixture from time to time during 20 minutes. After each shaking, loosen the stopper to relieve any internal pressure. Allow the mixture to stand for a few minutes until the layers have separated sharply draw off and discard the lower acid layer. Wash the halide with 20 ml. of 5 per cent, sodium bicarbonate solution and then with 20 ml. of water. Dry the preparation with 5 g. of anhydrous calcium chloride or anhydrous calcium, sulphate. Decant the dried liquid through a funnel supporting a fluted Alter paper or a small plug of cotton wool into a 100 ml. distilling flask, add 2-3 chips of porous porcelain, and distil. Collect the fraction boiling at 49-51°. The yield of feri.-butyl chloride is 28 g. 

An alternative method for isolating the n-butyl ether utilises the fact that n-butyl alcohol is soluble in saturated calcium chloride solution whilst n-butyl ether is slightly soluble. Cool the reaction mixture in ice and transfer to a separatory fimnel. Wash cautiously with 100 ml. of 2-5-3N sodium hydroxide solution the washings should be alkaline to litmus. Then wash with 30 ml. of water, followed by 30 ml. of saturated calcium chloride solution. Dry with 2-3 g. of anhydrous calcium chloride, filter and distil. Collect the di-n-butyl ether at 139-142°. The yield is 20 g. 

Methyl ethyl ketone. Use the apparatus of Fig. Ill, 61, 1 but with a 500 ml. round-bottomed flask. Place 40 g. (50 ml.) of see. butyl alcohol, 100 ml. of water and a few fragments of porous porcelain in the flask. Dissolve 100 g. of sodium dichromate dihydrate in 125 ml. of water in a beaker and add very slowly and with constant sturing 80 ml. of concentrated sulphuric acid allow to cool, and transfer the resulting solution to the dropping funnel. Heat the flask on a wire gauze or in an air bath until the alcohol mixture commences to boil. Remove the flame and run in the dichromate solution slowly and at such a rate that the temperature... 

Equip a 1 Utre three-necked flask or a 1 litre bolt- head flask with a reflux condenser and a mercury-sealed stirrer. Dissolve 50-5 g. of commercial 2 4-dinitro-l-chlorobenzene in 250 ml. of rectified spirit in the flask, add the hydrazine solution, and reflux the mixture with stirring for an hour. Most of the condensation product separates during the first 10 minutes. Cool, filter with suction, and wash with 50 ml. of warm (60°) rectified spirit to remove unchanged dinitrochlorobenzene, and then with 50 ml. of hot water. The resulting 2 4-dinitrophenylhydrazine (30 g.) melts at 191-192° (decomp.), and is pure enough for most purposes. Distil oflF half the alcohol from the filtrate and thus obtain a less pure second crop (about 12 g.) recrystallise this from n-butyl alcohol (30 ml. per gram). If pure 2 4-dinitrophenylhydrazine is required, recrystallise the total yield from n-butyl alcohol or from dioxan (10 ml. per gram) this melts at 200° (decomp.). 

The purified commercial di-n-butyl d-tartrate, m.p. 22°, may be used. It may be prepared by using the procedure described under i o-propyl lactate (Section 111,102). Place a mixture of 75 g. of d-tartaric acid, 10 g. of Zeo-Karb 225/H, 110 g. (136 ml.) of redistilled n-butyl alcohol and 150 ml. of sodium-dried benzene in a 1-litre three-necked flask equipped with a mercury-sealed stirrer, a double surface condenser and an automatic water separator (see Fig. Ill, 126,1). Reflux the mixture with stirring for 10 hours about 21 ml. of water collect in the water separator. FUter off the ion-exchange resin at the pump and wash it with two 30-40 ml. portions of hot benzene. Wash the combined filtrate and washings with two 75 ml. portions of saturated sodium bicarbonate solution, followed by lOu ml. of water, and dry over anhydrous magnesium sulphate. Remove the benzene by distillation under reduced pressure (water pump) and finally distil the residue. Collect the di-n-butyl d-tartrate at 150°/1 5 mm. The yield is 90 g. 

The mixture was then cooled to 30-40°C and the dissolved acetylene was sucked Over" in a water-pump vacuum (10-20 mmHg) and condensed in a receiver cooled at -78°C. The contents of the receiver were shaken three times with 20-ml portions of ice-water in a small separating funnel or dropping funnel in order to remove small amounts of tert.-butyl alcohol. After drying over a very small amount of... 

Step 3 in Figure 5 6 shows water as the base which ab stracts a proton from the car bocation Other Bronsted bases present in the reaction mixture that can function in the same way include tert butyl alcohol and hydrogen sulfate ion... 

A typical feed to a commercial process is a refinery stream or a steam cracker B—B stream (a stream from which butadiene has been removed by extraction and isobutylene by chemical reaction). The B—B stream is a mixture of 1-butene, 2-butene, butane, and isobutane. This feed is extracted with 75—85% sulfuric acid at 35—50°C to yield butyl hydrogen sulfate. This ester is diluted with water and stripped with steam to yield the alcohol. Both 1-butene and 2-butene give j -butyl alcohol. The sulfuric acid is generally concentrated and recycled (109) (see Butyl alcohols). 

More Complex Mixtures. AH the sequences discussed are type I Hquid systems, ie, mixtures in which only one of the binary pairs shows Hquid—Hquid behavior. Many mixtures of commercial interest display Hquid—Hquid behavior in two of the binary pairs (type II systems), eg, secondary butyl alcohol—water—di-secondary butyl ether (SBA—water—DSBE), and water—formic acid—xylene (92). Sequences for these separations can be devised on the basis of residue curve maps. The SBA—water—DSBE separation is practiced by ARGO and is considered in detail in the Hterature (4,5,105,126). 

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