Photochlorination studies. Part 9.—1, 1-dichloroethylene
Photochlorination studies. Part 9.—1, 1-dichloroethylene
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光氯化研究。第 9 部分。—1, 1-二氯乙烯
DOI：
10.1039/tf9666201838
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发表时间：
1966
影响因子：
--
通讯作者：
B. Fleischfresser
中科院分区：
文献类型：
--
作者：
P. Ayscough;F. Dainton;B. Fleischfresser
在25 - 48 ° C的静态体系中，采用连续或间歇光照，研究了1，1-二氯乙烯（偏二氯乙烯）的光氯化反应。该反应遵循链机理，类似于对其它氯代烯烃建立的机理，其中链终止是通过在烯烃压力大于2mm时三氯乙基自由基的双分子缔合。C_2H_2Cl自由基的复合速率常数（k_4）和与氯分子的反应速率常数（k_3）由log_（10）k_4（l）给出。mole-1 sec-1）=（10.02 ± 0.06）-（1.2 ± 0.7 kcal mole-1）/RT，log10k3（1.2 ± 0.7 kcal mole-1）mol-1 sec-1）=（8.84 ± 0.4）-（4.1 ± 0.7 kcal mol-1）/RT.总结并讨论了所有氯代烯烃（C_2H_4Cl_（4-n），0 <$n <$4）光氯化反应的Arrhenius参数.
The photochlorination of 1,1-dichloroethylene (vinylidene chloride) has been studied in a static system between 25 and 48°C using either continuous or intermittent illumination. The reaction follows a chain mechanism, similar to that established for other chloroalkenes, in which chain termination is by bimolecular association of trichloroethyl radicals at olefin pressures greater than 2 mm. The rate constants for recombination of C2H2Cl radicals (k4) and for reaction with chlorine molecules (k3) are given by log10k4(l. mole–1 sec–1)=(10.02±0.06)–(1.2±0.7 kcal mole–1)/RT, log10k3(l. mole–1 sec–1)=(8.84±0.4)–(4.1±0.7 kcal mole–1)/RT. The Arrhenius parameters for reactions in the photochlorination of all the chloroalkenes (C2H4Cl4–n, 0⩽n⩽4) are summarized and discussed.