Chlorination of n-decane

Model vs. Experimental Results. The model described by the preceding equations was used to simulate the behavior of an experimental gas-liquid CSTR (chlorination of n-decane ( 9)), and its predictions were compared to those of a model in which the liquid volatility is neglected. The physicochemical parameters used in the simulation are given elsewhere (10, 16), and the computational procedure adopted to solve for 0 is also reported elsewhere (16). 

Van de Vusse [16, 17] also performed experiments on the chlorination of n-decane, a reaction system of the type considered here, in a semibatch reactor. In such a reactor the chlorine gas is bubbled continuously through a batch of n-decane. In some experiments the n-decane was pure, in others it was diluted with dichlorobenzene. In some experiments the batch was stirred, in others not. The experimental results could be explained in terms of the above considerations. In all experiments y > 1 (from 150 to 500), hence the rate of the process was limited by diffusion, but the selectivity was only affected when Cgo/C i < y. This condition was only fulfilled for the experiments in which n-decane (B) was diluted. For only these experiments were the selectivities in nonstirred conditions found to differ from those with stirring. 

The same is true of chlorinated hydrocarbons and the chlorination of n-decane can be summarised as (8)... 

An analysis equivalent to that proposed above has been carried out by Hoffman et al (18). They used data relevant to the chlorination of n-decane with m = n = 1 i.e. the reaction is first order with respect to each component. For a single backmixed gas-liquid reactor (equivalent to the element of Fig. 2), it was demonstrated that the interaction of mass transfer and chemical reaction gave rise to the possibility of up to 5 steady states for a single overall second order reaction. In their quantitative treatment, they made use of a reaction factor E., which is related to the normal enhancement factor by... 

Use of the boundary condition with C. constant is somewhat artificial and neglects the material baiance on the gas stream, and therefore avoids a consideration of the yield of liquid phase product R with respect to the utilisation of gas phase reagent A. Van de Vusse (24) solved the diffusion reaction equations numerically, and showed how the theory could be used to explain the experimentally dissolved influence of stirring on the chlorination of n-decane. Fig. 14 shows yield of R with respect to B as a function of the conversion of B, as determined experimentally. A serious loss of yield occurs in the absence of stirring, due to the reduction in the mass transfer coefficient. Van de Vuuse (22) concluded that selectivity limitations would occur if /m(1) > 2 and moreover if <... 

Van de Vusse [1966 a, b] also performed experiments on the chlorination of. n-decane, with a reaction scheme of the type considered here, in a semibatch reactor. In such a reactor the chlorine gas is bubbled continuously through a batch of /2-decane. In some experiments the /2-decane was pure, in others it was diluted with dichlorobenzene. In some experiments the batch was stirred, in others not. 

For complex reactions, the product distribution can be affected by mixing in direct analogy to the homogeneous case discussed earlier. Some of the first experiments in this area were conducted on chlorination of n-decane by van de... 

At the end of the reactions no trace of PEG was detected in n-decane (experiments of Table 1) or in mineral oils treated in the same way (IR and NMR analysis). In the reactions of Table 1 as in the following ones here reported, the residual PCB were usually the low-chlorinated polychlorobiphenyls these ones have been reported to be the less toxic. 

Consequently, it appears likely fliat flie alcohols, ketones, o-cresol, ethyl acetate, and pyridine will degrade rapidly in soil if rapidly is defined as having a half-life of 10 days or less. Most ofthe benzene derivatives, F-11, and the chlorinated aliphatic hydrocarbons may be relatively persistent in soil. Analogous information was not located for diethyl ether, hexane, decane, or tetrahydrofuran. ATSDR for example, found that there was little information available for the degradation of n-hexane in soil. It was suggested that n-hexane can degrade to alcohols, aldehydes, and fatty acids under aerobic conditions. 

Following on the work of Teramoto, Hoffman, Sharma and Luss (28) have performed an analysis of the adiabatic gas-liquid reactor operating in continuous backmixed flow of the liquid phase for this consecutive (1,1) - (1,1) reaction. They used data relative to the system chlorine/n-decane with a selectivity ratio of k /kp = 1. 1 The boundary conditions were formulated in terms of overall material balances on the gas and liquid phases, so that for component A, the boundary condition at the film-bulk junction is given by... 

The solubility of the solvents in T able 17.1.1 ranges from those that are miscible with water to those with solubilities that are less than 0.1 mg/L (Table 17.1.2). Acetone, methanol, pyridine and tetrahydrofuran will readily mix with water in any proportion. The solvents that have an aqueous solubility of greater than 10,000 mg/L are considered relatively hydrophillic as well. Most of the benzene derivatives and chlorinated fluorocarbons are relatively hydrophobic. Hexane and decane are the least soluble of the 31 solvents in Table 17.1.1. Most material safety data sheets for decane indicate that the n-aUcane is insoluble and that the solubility of hexane is negligible. How the solubility of each solvent affects its fate in sod, water, and air is illustrated in the following sections. 

---