Chlorine atoms, distribution

Defieuw et al. [100] also investigated blends of the same PCL with CPE of different Cl contents with chlorine atoms distributed randomly on the polymer backbone molecular weight data are given in Table 7. Although lightly chlorinated polyethylenes are partially crystalUne, CPE-30.1 is amorphous and only amorphous CPEs were studied. Samples were prepared by co-precipitation of... 

These values assume chlorination in carbon tetrachloride solution under homogeneous conditions favoring random distribution of chlorine atoms along the chain. Viscous reaction conditions, faster chlorine addition rates, lower temperature conditions, etc, can lead to higher AH at equivalent chlorine levels because of more blocky chlorine distribution on the polymer chain. 

The distribution of chlorine atoms along the polymer chain has been studied in great detail. The distribution in various functional types is shown in Table 4 (18). High density polyethylene chlorosulfonated to 35% G1 and 1% S has been found to contain only 1.7% highly active chlorines, ie, reactive to weak bases. AH of these are attributed to the chlorine in the sulfonyl chloride group and those in beta position to SO2GI. No vicinal chlorides groups were found (19). 

The first patent on the chlorination of polyethylene was taken out by ICI in 1938. In the 1940s scientists of that company carried out extensive studies on the chlorination process. The introduction of chlorine atoms onto the polyethylene backbone reduces the ability of the polymer to crystallise and the material becomes rubbery at a chlorine level of about 20%, providing the distribution of the chlorine is random. An increase in the chlorine level beyond this point, and indeed from zero chlorination, causes an increase in the Tg so that at a chlorine level of about 45% the polymer becomes stiff at room temperature. With a further increase still, the polymer becomes brittle. 

If every collision of a chlorine atom with a butane molecule resulted in hydrogen abstraction, the n-butyl/5ec-butyl radical ratio and, therefore, the 1-chloro/2-chlorobutane ratio, would be given by the relative numbers of hydrogens in the two equivalent methyl groups of CH3CH2CH2CH3 (six) compared with those in the two equivalent methylene groups (four). The product distribution expected on a statistical basis would be 60% 1-chloro-butane and 40% 2-chlorobutane. The experimentally observed product distribution, however, is 28% 1-chlorobutane and 72% 2-chlorobutane. 5ec-Butyl radical is therefore formed in greater anounts, and n-butyl radical in lesser anounts, than expected statistically. 

CBS extrapolation 155, 278 CBS methods 10, 96, 155 cost vs. G2 methods 159 CBS-4 method 155 CBS-Q method 155 CCSD keywords 114 CH bond dissociation 186 charge xxxv, xlii, 15, 286 predicted atomic li charge distribution 20 Cheeseman 53 chlorine (atomic) 137, 159 chlorobenzene 165 chromium hexacarbonyl 52 Cioslowski 198 CIS keyword... 

The effect of the chlorine atom s partial appropriation of the electrons of the carbon-chlorine bond is to leave C, slightly electron-deficient this it seeks to rectify by, in turn, appropriating slightly more than its share of the electrons of the a bond joining it to C2, and so on down the chain. The effect of Ct on C2 is less than the effect of Cl on Cl5 however, and the transmission quickly dies away in a saturated chain, usually being too small to be noticeable beyond C2. These influences on the electron distribution in [Pg.22]

Next, we need to distribute the remaining electrons to achieve a noble gas electron configuration for each atom. Since four electrons were used to form the two covalent single bonds, fourteen electrons remain to be distributed. By convention, the valence shells for the terminal atoms are filled first. If we follow this convention, we can close the valence shells for both the nitrogen and the chlorine atoms with twelve electrons. 

Those remaining electrons are distributed around the chlorine atoms in a manner that would give each chlorine atom 8 electrons. So 6 more electrons are needed for each chlorine atom to complete its octet. 

Fig. 1.3 The influence of chlorine on the isotopic distribution. (A) No chlorine atom, (B) one chlorine atom, (C) two chlorine atoms.

These data were measured at or extrapolated to ambient temperature and pH values. The data are discussed in the text. NA = not available. b/ Kq = soil water distribution coefficient (K ) divided by the organic carbon content of the soil, cj Whenever possible, half-life for soil dissipation is derived from the field data half-lives described in the text rather than lab data. As such, it may not represent a true first-order process. Value has been estimated from the equation in ref. 20. e/ Hydrolysis of total residues (aldicarb + sulfoxide + sulfone). pK for p -phthalic acid is 3.5. The chlorine atoms of DCPA should lower the pK to about 2. Conditions optimized for soil metabolism. 

Interestingly, the interactions between zeolites and unsaturated chlorocarbons like trichloroethylene (TCE) are found to be strikingly different from those between zeolites and unsaturated hydrocarbons (i.e. ethylene and benzene). Both our simulations and our spectroscopic results on the adsorption of TCE in faujasites show that interactions between the n electrons and the cations, which dominate in the case of hydrocarbons, are replaced by interactions between the chlorine atoms and the cations [18]. Figure 3 shows typical positions of TCE in NaY zeolite as predicted by energy minimizations. This is a consequence of the different charge distribution in hydrocarbons and halocarbons. 

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