Toluene distributions

Figure 5.14 shows the toluene distribution of the solvent-diffused sample (5 min cured). The image contrast is based on the difference in swelling capability throughout the sample. More toluene is imbibed into the PBD-rich matrix and less solvent is imbibed into the ZDA-rich domains. Therefore, the ZDA-rich domain is shown as low intensity (blue) and PBD-rich region is shown as high intensity (red, yellow or green). The difference in toluene distribution results from the differences in solubility and crosslink density. 

Figure 5.14 Toluene distribution of the solvent-diffused sample (5 min cured). Reproduced from figure 2 of Ref. 28, with permission.

Toluene is readily absorbed from the lung and gastrointestinal tract, although studies in animals suggest absorption occurs more slowly in the gastrointestinal tract. Slow absorption also occurs through skin. Studies of humans and animals indicate that inhaled toluene distributes to tissues that are high in fat content (e.g., body fat, bone marrow, and brain) or well supplied with blood (e.g., liver). It seems reasonable to assume that similar distribution would occur for other routes of exposure. 

Pilar, S., and W.F. Graydon. 1973. Benzene and toluene distribution in Toronto atmosphere. Environmental Science and Technology 7 628-631. 

Partial rate factors may be used to estimate product distributions in disubstituted benzene derivatives The reactivity of a particular position in o bromotoluene for example is given by the product of the partial rate factors for the corresponding position in toluene and bromobenzene On the basis of the partial rate factor data given here for Fnedel-Crafts acylation predict the major product of the reaction of o bromotoluene with acetyl chlonde and aluminum chloride... 

The principle of headspace sampling is introduced in this experiment using a mixture of methanol, chloroform, 1,2-dichloroethane, 1,1,1-trichloroethane, benzene, toluene, and p-xylene. Directions are given for evaluating the distribution coefficient for the partitioning of a volatile species between the liquid and vapor phase and for its quantitative analysis in the liquid phase. Both packed (OV-101) and capillary (5% phenyl silicone) columns were used. The GG is equipped with a flame ionization detector. 

The Tatoray process was originally developed by Toray and is currendy Hcensed by UOP (53—57). A schematic of the process is shown in Figure 4. In this process, toluene or a mixture of toluene and Cg aromatics are reacted to form primarily xylenes and benzene. An equiUbrium distribution of xylenes is produced. As shown in Table 4, the ratio of xylenes to benzene can be adjusted by altering the feed ratio to toluene to aromatics. Trimethylbenzenes are the preferred aromatic compound. 

The first quantitative model, which appeared in 1971, also accounted for possible charge-transfer complex formation (45). Deviation from the terminal model for bulk polymerization was shown to be due to antepenultimate effects (46). Mote recent work with numerical computation and C-nmr spectroscopy data on SAN sequence distributions indicates that the penultimate model is the most appropriate for bulk SAN copolymerization (47,48). A kinetic model for azeotropic SAN copolymerization in toluene has been developed that successfully predicts conversion, rate, and average molecular weight for conversions up to 50% (49). 

Attempts have been made to develop methods for the production of aromatic isocyanates without the use of phosgene. None of these processes is currently in commercial use. Processes based on the reaction of carbon monoxide with aromatic nitro compounds have been examined extensively (23,27,76). The reductive carbonylation of 2,4-dinitrotoluene [121 -14-2] to toluene 2,4-diaLkylcarbamates is reported to occur in high yield at reaction temperatures of 140—180°C under 6900 kPa (1000 psi) of carbon monoxide. The resultant carbamate product distribution is noted to be a strong function of the alcohol used. Mitsui-Toatsu and Arco have disclosed a two-step reductive carbonylation process based on a cost effective selenium catalyst (22,23). 

The thermodynamic equilibria are illustrated in Figures 1 and 2. Figure 1 shows the resulting composition after pure pseudocumene or a recycle mixture of C PMBs is disproportionated with a strong Friedel-Crafts catalyst. At 127°C (400 K), the reactor effluent contains approximately 3% toluene, 21% xylenes, 44% C PMBs, 29% C q PMBs, and 3% pentamethylbenzene. The equihbrium composition of the 44% C PMB isomers is shown in Figure 2. Based on the values at 127°C, the distribution is 29.5% mesitylene, 66.0% pseudocumene, and 4.5% hemimellitene (Fig. 2). After separating mesitylene and hemimellitene by fractionation, toluene, xylenes, pseudocumene (recycle plus fresh), C q PMBs, and pentamethylbenzene are recycled to extinction. 

Processes. Toluene is nitrated ia two stages. Mononitration occurs ia mixed acid, 30% HNO and 55% H2SO4, at 30—70°C ia a series of continuous stirred-tank reactors. Heat is Hberated and must be removed. The isomer distribution is approximately 58% o-nitrotoluene 38% -nitrotoluene, and 4% y -nitrotoluene (Fig. 1). 

Acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, ethyl acetate, and tetrahydrofuran are solvents for vinyhdene chloride polymers used in lacquer coatings methyl ethyl ketone and tetrahydrofuran are most extensively employed. Toluene is used as a diluent for either. Lacquers prepared at 10—20 wt % polymer sohds in a solvent blend of two parts ketone and one part toluene have a viscosity of 20—1000 mPa-s (=cP). Lacquers can be prepared from polymers of very high vinyhdene chloride content in tetrahydrofuran—toluene mixtures and stored at room temperature. Methyl ethyl ketone lacquers must be prepared and maintained at 60—70°C or the lacquer forms a sohd gel. It is critical in the manufacture of polymers for a lacquer apphcation to maintain a fairly narrow compositional distribution in the polymer to achieve good dissolution properties. 

The molecular weight distribution of the feed affects the distribution of the product. If the naphtha is concentrated in the C -Cg range, more benzene and toluene are found in the product. If the feed is weighted to Cg—C q, more xylenes and higher aromatics are found. Some carbon number "shppage" occurs by dealkylation some C s form benzene by losing a methyl group, some CgS form toluene, etc. 

Noncatalytic ring chlorination of toluene in a variety of solvents has been reported. Isomer distributions vary from approximately 60% ortho in hydroxyhc solvents, eg, acetic acid, to 60% para in solvents, eg, nitromethane, acetonittile, and ethylene dichloride (49,50). Reaction rates are relatively slow and these systems are particularly appropriate for kinetic studies. 

Experimental data taken from the chlorination of toluene in a continuous stirred tank flow reactor at 111°C and irradiated with light of 500 nm wavelength yield a product distribution shown in Table 1 (1). 

Table 1. Distributions of Reactor Products from Batch Chlorination of Toluene...

Aromatic solvents or polycyclic aromatic hydrocarbons (PAFI) in water, e.g. can be detected by QCM coated with bulk-imprinted polymer layers. Flere, the interaction sites are not confined to the surface of the sensitive material but are distributed within the entire bulk leading to very appreciable sensor responses. Additionally, these materials show high selectivity aromatic solvents e.g. can be distinguished both by the number of methyl groups on the ring (toluene vs. xylene, etc.) and by their respective position. Selectivity factors in this case reach values of up to 100. 

They measured the distribution coefficient of n-pentanol between water and mixtures of -heptane and chloroheptane, -heptane and toluene, and n-heptane and heptyl acetate. The two phase system was thermostatted at 25°C and, after equilibrium had... 

Katz et al. tested the theory further and measured the distribution coefficient of n-pentanol between mixtures of carbon tetrachloride and toluene and pure water and mixtures of n-heptane and n-chloroheptane and pure water. The results they obtained are shown in Figure 17. The linear relationship between the distribution coefficient and the volume fraction of the respective solvent was again confirmed. It is seen that the distribution coefficient of -pentanol between water and pure carbon tetrachloride is about 2.2 and that an equivalent value for the distribution coefficient of n-pentanol was obtained between water and a mixture containing 82%v/v chloroheptane and 18%v/v of n-heptane. The experiment with toluene was repeated using a mixture of 82 %v/v chloroheptane and 18% n-heptane mixture in place of carbon tetrachloride which was, in fact, a ternary mixture comprising of toluene, chloroheptane and n-heptane. The chloroheptane and n-heptane was always in the ratio of 82/18 by volume to simulate the interactive character of carbon tetrachloride. 

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