Dehydrochlorination of 1,1,2-trichloroethane (112TCE) is a widely used method for preparing vinylidene chloride (VDC), which is an important polymeric monomer and intermediate of refrigerant. However, there are few reports on kinetics of this reaction system. In this work, density functional theory (DFT) calculation analyses and experiments were conducted to investigate the reaction mechanism and kinetics of 112TCE dehydrochlorination with sodium hydroxide (NaOH). DFT simulation results unveiled there were three parallel reactions which produce VDC, cis-1,2-dichloroethylene (C12DE) and trans-1,2-dichloroethylene (T12DE) respectively in the reaction process of 112TCE and NaOH. The activation energy of the reaction to produce VDC was lower than those of the other two reactions. Moreover, the kinetic parameters of the three parallel reactions, such as reaction orders, rate constants, pre-exponential factors and activation energies, were experimentally obtained by decoupling the overall reaction kinetics. All the parallel reactions are bimolecular elimination reactions and the rate expression of the intrinsic kinetics for generating VDC is$\frac{d{C}_{\text{t}}}{\mathit{dt}}=1.668\times {10}^{11}{e}^{\frac{-75662}{\mathit{RT}}}{C}_{\text{A}}{C}_{\text{B}}$. The reaction rate is three orders of magnitude higher than those of producing C12DE and T12DE, which is consistent with the DFT simulation results. These kinetics results are useful for the process optimization and reactor design in VDC production process.

1,1,2-三氯乙烷（112TCE）脱氯化氢是制备偏二氯乙烯（VDC）的一种广泛应用的方法，偏二氯乙烯是一种重要的聚合单体和制冷剂的中间体。然而，关于该反应体系的动力学的报道很少。本工作通过密度泛函理论 (DFT) 计算分析和实验研究 112TCE 与氢氧化钠 (NaOH) 脱氯化氢的反应机理和动力学。DFT 模拟结果揭示了三个平行反应，分别产生 VDC、顺式-1,2-二氯乙烯 (C12DE) 和反式-1,2-二氯乙烯（T12DE）分别在112TCE和NaOH的反应过程中。产生VDC的反应的活化能低于其他两个反应的活化能。此外，三个平行反应的动力学参数，如反应级数、速率常数、指前因子和活化能，通过对整体反应动力学的解耦实验获得。所有平行反应均为双分子消除反应，产生 VDC 的本征动力学速率表达式为$\frac{d{C}_{\text{吨}}}{\mathit{dt}}=1.668\times {10}^{11}{e}^{\frac{-75662}{\mathit{逆转录}}}{C}_{\text{一个}}{C}_{\text{乙}}$. 反应速率比生产 C12DE 和 T12DE 高三个数量级，这与 DFT 模拟结果一致。这些动力学结果有助于VDC生产过程中的工艺优化和反应器设计。