以温度为函数的硝仿系炸药的爆发分解反应动力学参数

用爆发点试验装置测定了6种硝仿系炸药:2,2,2-三硝基乙基-N-硝基-甲胺(TNMA)、二(2,2,2-三硝基乙基-N-硝基)乙二胺(BTNEDA)、4,4,4-三硝基丁酸-2,2,2-三硝基乙酯(TNETB)、二(2,2,2-三硝基乙醇)缩甲醛(BTNF)、1,1,1,3-四硝基丙烷(TETNP)和二(2,2,2-三硝基乙基)硝胺(BTNNA)在不同温度下的爆发延滞期.依据谢苗诺夫方程lnt_(lag,i)=E_α/RT_i-lnA_α,由lnt_(lag,i)对1/T_i的关系,用作图法和最小二乘法计算了爆发分解反应的表观活化能(E_α)、指前因子(A_α)和5 s爆发点.用非线性等转化率积分法所得的表观活化能(E_α)校验了由lnt_(lag,i)～1/_Ti关系得到的Eα值.借助热力学关系式,计算了爆发分解反应的活化热力学参数活化自由能(ΔG≠),活化焓(ΔH≠)和活化熵(ΔS≠)].结果表明: (1) E_α和作图法所得E_α间的相对误差在±5%以内; (2) E_α与最小二乘法所得E_α相等的事实佐证了不同温度下爆发分解反应延滞期内的分解深度是相等的,所得E_α和A_α值是可接受的,谢苗诺夫方程推导过程中采用A_α>>G(α)的假设是合理的; (3) 以5 s爆发点和ΔG~#为判据,6种硝仿系炸药对热抵抗能力的次序为:TNETB＞BTNF＞BTNEDA＞TETNP＞TNMA＞BTNNA.

Kinetic Parameters of Explosive Decomposition Reaction of Trinitromethyl Explosives as a Function of Temperature

The time lag prior to explosion of six trinitromethyl explosives: 2,2,2-trinitroethyl-N-nitromethyl amine(TNMA), bis(2,2,2-trinitroethyl-N-nitro) ethylene diamine(BTNEDA), 2,2,2-trinitroethyl-4,4,4-trinitrobutyrate(TNETB), bis(2,2,2-trinitroethyl) formal(BNTF), 1,1,1,3-tetranitropropane(TETNP) and bis(2,2,2-trinitroethyl-nitramine(BTNNA) at different temperature was measured by an explosion temperature test apparatus. The apparent activation energy (E_α) and pre-exponential constant (A_α) of the explosive decomposition reaction and the value of T corresponding to t=5 s, T_(t=5s), in Semenov′s equation for the relationship governing the time lag t, prior to explosion after heating to a temperature, T(K): lnt_(lag,i)=(E_α)/(RT_i)-lnA_α were calculated. The values of E_α obtained by integral isoconversional non-linear method were used to check the values of E_α obtained by plotting lntlag,i against 1/T_i. With the help of thermodynamic formulae, the thermodynamic parameters of activation free energy of activation (ΔG≠), enthalpy of activation (ΔH≠) and entropy of activation (ΔS≠)] for the explosive decomposition reaction were calculated. The results show that:(1) the relative error between the values of E_α by plotting method and E_α is within ±5%; (2) the fact of E_α=E_α by the linear least-squares method indicates that:(a) the fraction of material reacted during the time lag prior to explosion at different temperature is equal;(b) the values of Eα and A_α obtained are acceptable and (c) assumption of adopting A_α>>G(α) in derivation of Semenov′s formula are tenable; (3) using T_(t=5s) and ΔG~≠ as criteria, the heat-resistance ability of six trinitromethyl explosives decreases in the order TNETB＞BTNF＞BTNEDA＞TETNP＞TNMA＞>BTNNA.