2- Propanol water

The one-step route from 2-propanol coproduces diisobutyl ketone and acetone, and is practiced in the United States by Union Carbide (61). The details of a vapor-phase 2-propanol dehydrogenation and condensation process for the production of acetone, MIBK, and higher ketones have been described in recent patents (62,63). The process converts an a2eotropic 2-propanol—water feed over a copper-based catalyst at 220°C and produces a product mixture containing 2-propanol (11.4%), acetone (52.4%), MIBK (21.6%), diisobutyl ketone (6.5%), and 4-methyl-2-pentanol (2.2%). 

Density. Density of LLDPE is measured by flotation in density gradient columns according to ASTM D1505-85. The most often used Hquid system is 2-propanol—water, which provides a density range of 0.79—1.00 g/cm. This technique is simple but requires over 50 hours for a precise measurement. The correlation between density (d) and crystallinity (CR) is given hy Ijd = CRj + (1 — Ci ) / d, where the density of the crystalline phase, ify, is 1.00 g/cm and the density of the amorphous phase, is 0.852—0.862 g/cm. Ultrasonic methods (Tecrad Company) and soHd-state nmr methods (Auburn International, Rheometrics) have been developed for crystallinity and density measurements of LLDPE resins both in pelletized and granular forms. 

Example Separation of 2-Propanol—Water. Consider the separation of a binary mixture of 60 mol % water and 40 mol % 2-propanol (or isopropyl alcohol (IPA)) into two products consisting of 2-propanol of 99.5 mol % purity and water with <100 ppm 2-propanol impurity. 

Bina System. The first task is to examine the characteristics of the 2-propanol-water-phase equiUbria (VLE, LLE, SEE) to determine the compositions of interest and any critical features. 2-Propanol forms a minimum boiling a2eotrope with water (80.4°C at 101.3 kPa (760 tort), 68 mol % 2-propanol). The a2eotrope is between the feed and the IPA product and is a distillation boundary, thus it is impossible to obtain both desired products from any single-feed... 

Table 5. Strategic Separations for 2-Propanol-Water System...

The feed compositions and products of each of these strategic separations remain ill-defined. The unspecified 2-propanol—water mixture, the input to each strategic separation, could be but is not necessarily the original feed composition. The MSA composition (pure hexane in this case) is such that one of the products of the strategic separation is in region II, ie, the strategic separation crosses the distillation boundary. Two opportunistic distillations from... 

Fig. 5. The acetone—2-propanol—water system where I represents the 2-propanol—water azeotrope, (a) Residue curve map (34) (b) material balance lines...

Tnethanolamine propham, chloropropham, swep, linurone, maloron stabilization and enhancement spray solution, 20% in 2-propanol, water investigations [241]... 

Reactions with NaBH4 go smoothly in water, ethanol or 2-propanol water reacts with NaBH4 but the system can be stabilized by the addition of alkali ethanol also reacts slowly with the hydride and 2-propanol not at all ... 

Note TLC was performed on silica gel, and the solvents were (1) -bntanol/glacial acetic acid/water (2 1 1, v/v), (IV) isoamyl alcohol/ethy methyl ketone/glacial acetic acid/water (40 40 7 13, v/v), (VII) n-bntanol/2-propanol/water/glacial acetic acid (30 50 10 2, v/v), (VIII) ethyl methyl ketone/acetic acid/methanol (3 1 1, v/v), and (IX) n-bntanol/benzyl alcohol/glacial acetic acid (8 4 3, v/v). 

To determine whether the loss of vitamin Bjj in microwave-treated foods was dne to the conversion of vitamin Bjj to some inactive vitamin B,2 degradation prodncts, the hydroxocobalamin that predominates in food was treated by microwave heating for 6 min and then analyzed by TLC on sihca gel 60 with -bntanol/2-propanol/water (10 7 10, v/v) as a solvent. The treated hydroxocobalamin was separated into fonr red spots intact hydroxocobalamin remained at the origin (Fignre 10.5) [10]. These hydroxocobalamin degradation products were further purified to homogeneity by the nse of TLC and HPLC and characterized. 

General procedure for Suzuki coupling. 4-Bromoanisole (125 pL, 1 mmol), phenylboronic acid (186 mg, 1.5 mmol), K2CO3 (0.55 g, 4 mmol) and the BaCei.j,Pdj,03.j, catalyst were mixed in a 20 ruL scintillation vial. A preheated 2-propanol/water solution (IPA/H2O, 1 1 v/v, 12 ruL, 80°C) was added, the vial was immediately placed on a hot plate stirrer and its temperature was maintained at (80 1) °C. The reaction mixture was stirred at 1000 rpm for 3 min, then cooled to room temperature. The 4-methoxybiphenyl product was extracted with diethyl ether (3 x 15 ruL). The organic fractions were washed with deionized water and dried with MgS04. After filtration, volatiles were removed under reduced pressure to yield the isolated product. 

Example 4.5 2-Propanol (isopropanol) and water form an azeotropic mixture at a particular liquid composition that results in the vapor and liquid compositions being equal. Vapor-liquid equilibrium for 2-propanol-water mixtures can be predicted by the Wilson equation. Vapor pressure coefficients in bar with temperature in Kelvin for the Antoine equation are given in Table 4.113. Data for the Wilson equation are given in Table 4.126. Assume the gas constant R = 8.3145 kJ-kmol 1-K 1. Determine the azeotropic composition at 1 atm. 

Solution To determine the location of the azeotrope for a specified pressure, the liquid composition has to be varied and a bubble-point calculation performed at each liquid composition until a composition is identified, whereby X = y,-. Alternatively, the vapor composition could be varied and a dew-point calculation performed at each vapor composition. Either way, this requires iteration. Figure 4.5 shows the x—y diagram for the 2-propanol-water system. This was obtained by carrying out a bubble-point calculation at different values of the liquid composition. The point where the x—y plot crosses the diagonal line gives the azeotropic composition. A more direct search for the azeotropic composition can be carried out for such a binary system in a spreadsheet by varying T and x simultaneously and by solving the objective function (see Section 3.9) ... 

The first bracket in this equation ensures that the bubble-point criterion is satisfied. The second bracket ensures that the vapor and liquid compositions are equal. The solution of this is given when x = y = 0.69 and x2 = y2 = 0.31 for the system of 2-propanol-water at 1 atm. 

Thus, if the saturated vapor pressure is known at the azeotropic composition, the activity coefficient can be calculated. If the composition of the azeotrope is known, then the compositions and activity of the coefficients at the azeotrope can be substituted into the Wilson equation to determine the interaction parameters. For the 2-propanol-water system, the azeotropic composition of 2-propanol can be assumed to be at a mole fraction of 0.69 and temperature of 353.4 K at 1 atm. By combining Equation 4.93 with the Wilson equation for a binary system, set up two simultaneous equations and solve Au and A21. Vapor pressure data can be taken from Table 4.11 and the universal gas constant can be taken to be 8.3145 kJ-kmol 1-K 1. Then, using the values of molar volume in Table 4.12, calculate the interaction parameters for the Wilson equation and compare with the values in Table 4.12. 

Hydrolyses of p-nitrophenyl and 2,4-dinitrophenyl sulfate are accelerated fourfold and eightfold, respectively, by cycloheptaamylose at pH 9.98 and 50.3° (Congdon and Bender, 1972). These accelerations have been attributed to stabilization of the transition state by delocalization of charge in the activated complex and have been interpreted as evidence for the induction of strain into the substrates upon inclusion within the cycloheptaamylose cavity. Alternatively, accelerated rates of hydrolysis of aryl sulfates may be derived from a microsolvent effect. A comparison of the effect of cycloheptaamylose with the effect of mixed 2-propanol-water solvents may be of considerable value in distinguishing between these possibilities. 

Recently, an example of cycloamylose-induced catalysis has been presented which may be attributed, in part, to a favorable conformational effect. The rates of decarboxylation of several unionized /3-keto acids are accelerated approximately six-fold by cycloheptaamylose (Table XV) (Straub and Bender, 1972). Unlike anionic decarboxylations, the rates of acidic decarboxylations are not highly solvent dependent. Relative to water, for example, the rate of decarboxylation of benzoylacetic acid is accelerated by a maximum of 2.5-fold in mixed 2-propanol-water solutions.6 Thus, if it is assumed that 2-propanol-water solutions accurately simulate the properties of the cycloamylose cavity, the observed rate accelerations cannot be attributed solely to a microsolvent effect. Since decarboxylations of unionized /3-keto acids proceed through a cyclic transition state (Scheme X), Straub and Bender suggested that an additional rate acceleration may be derived from preferential inclusion of the cyclic ground state conformer. This process effectively freezes the substrate in a reactive conformation and, in this case, complements the microsolvent effect. 

Fig. 18 Solubilities at 20°C of the two polymorphs of cimetidine, form A (<9>-) and form B (0), as a function of the mole fraction of 2-propanol in the 2-propanol/water system. Also shown are the solubility ratios (form A/form B) calculated at each solvent composition. (The data are adapted from Ref. 128.)...

Transition-metal catalysts are, in general, more active than the MPVO catalysts in the reduction of ketones via hydrogen transfer. Especially, upon the introduction of a small amount of base into the reaction mixture, TOFs of transition-metal catalysts are typically five- to 10-fold higher than those of MPVO catalysts (see Table 20.7, MPVO catalysts entries 1-20, transition-metal catalysts entries 21-53). The transition-metal catalysts are less sensitive to moisture than MPVO catalysts. Transition metal-catalyzed reactions are frequently carried out in 2-propanol/water mixtures. Successful transition-metal catalysts for transfer hydrogenations are based not only on iridium, rhodium or ruthenium ions but also on nickel [93], rhenium [94] and osmium [95]. It has been reported that... 

Various nucleophiles other than methanol can be introduced onto the carbonyl carbon. Anodic oxidation of acylsilanes in the presence of allyl alcohol, 2-methyl-2-propanol, water, and methyl /V-methylcarbamate in dichlorometh-ane affords the corresponding esters, carboxylic acid, and amide derivatives (Scheme 24) [16]. Therefore, anodic oxidation provides a useful method for the synthesis of esters and amides under neutral conditions. 

Various liquid chromatographic techniques have been frequently employed for the purification of commercial dyes for theoretical studies or for the exact determination of their toxicity and environmental pollution capacity. Thus, several sulphonated azo dyes were purified by using reversed-phase preparative HPLC. The chemical strctures, colour index names and numbers, and molecular masses of the sulphonated azo dyes included in the experiments are listed in Fig. 3.114. In order to determine the non-sulphonated azo dyes impurities, commercial dye samples were extracted with hexane, chloroform and ethyl acetate. Colourization of the organic phase indicated impurities. TLC carried out on silica and ODS stationary phases was also applied to control impurities. Mobile phases were composed of methanol, chloroform, acetone, ACN, 2-propanol, water and 0.1 M sodium sulphate depending on the type of stationary phase. Two ODS columns were employed for the analytical separation of dyes. The parameters of the columns were 150 X 3.9 mm i.d. particle size 4 /jm and 250 X 4.6 mm i.d. particle size 5 //m. Mobile phases consisted of methanol and 0.05 M aqueous ammonium acetate in various volume ratios. The flow rate was 0.9 ml/min and dyes were detected at 254 nm. Preparative separations were carried out in an ODS column (250 X 21.2 mm i.d.) using a flow rate of 13.5 ml/min. The composition of the mobile phases employed for the analytical and preparative separation of dyes is compiled in Table 3.33. 

The efficiency of nitrobenzene photoreduction may be increased remarkably in 2-propanol/hydrochloric acid mixtures. In 50% 2-propanol/water containing 6 moles l i HCl, acetone and a complex mixture of chlorinated reduction products are formed i ). Both HCl and 2-propanol (as hydrogen source) are needed. When sulfuric acid is substituted for HCl, enhanced photoreduction does not occtu . When using mixtures of HCl and LiCl to maintain a constant chloride concentration (6 M) and vary [H+], a constant disappearance quantum yield 366 =0.15 is found within the [H+]-range 0.05—6 moles l i. This strongly suggests that chloride ions play an essential role, probably via electron transfer to 3(n, tt )-nitrobenzene i > [Eq. (1)], but it is also evident from the data presented that the presence of add is probably important in subsequent steps, [Eq. (3)]. 

Novozymes, a subtilisin produced by Bacillus licheniformis, was used by Chen et al ° to carry out a dynamic kinetic resolution of benzyl, butyl, or propyl esters of DL-phenylalanine, tyrosine, and leucine. The hydrolysis was performed at pH 8.5 in 2-methyl-2-propanol/water (19 1) and the freed L-amino acids precipitated. The key feature bringing about continual racemization of the remaining D-amino acid esters was the inclusion of 20 mmol 1 pyridoxal phosphate. 

In a related experimental study, Cirkel and Okada compared mechanical and electrical percolation that developed during the gelation of 3 1 (v/v) 2-propanol/ water solutions of Nafion 117 in the acid and Na+ forms.Attention should be paid to the particular manner in which these samples were prepared, as different conditions may yield different results. Also, caution should be applied in comparing these results with those of percolation studies using preformed films, such as that of Hsu et al. ... 

Only one polymorphic form of the substance has been observed. A study was undertaken to attempt to produce different forms by flash cooling and slow evaporation from various solvents (V, V-dimethylformamide, acetonitrile,ethanol, dichloromethane,2-propanol, water (neutral pH, pH 5, and pH 9), ethanol/watermixtures (1 1, neutral and at pH 5 and 9). No additional forms were observed upon examination of the resulting crystals by x-ray powder diffraction. 

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