Transition metal catalysis of the heterogeneous decomposition of hydrazine: adiabatic kinetics by accelerating rate calorimetry

活化能 阿累尼乌斯方程 化学 动力学 过渡金属 反应速率常数 分解 量热法 化学计量学 催化作用 化学动力学 反应级数 物理化学 金属 反应速率 阿伦尼乌斯图 分析化学(期刊) 无机化学 热力学 有机化学 物理 量子力学
作者
Dennis D. Davis,Richard C. Wedlich,Nathalie B. Martin
出处
期刊:Thermochimica Acta [Elsevier BV]
卷期号:175 (2): 175-188 被引量:5
标识
DOI:10.1016/0040-6031(91)80064-p
摘要

The thermochemical kinetics of the transition-metal-catalyzed decomposition reaction of hydrazine have been studied using accelerating rate calorimetry. The reaction stoichiometry was determined by both product analysis and thermochemical balance. In the range 350–515 K when both liquid and vapor hydrazine are present, the decomposition proceeds according to: N2H4(1)→13N2(g)+43NH3(g) with ΔHrxn = −123.3 kJ mol−1 (515 K). In the range 515–590 K when only vapor is present in the reaction system, ΔHrxn = −154.8 kJ mol−1 (515 K). The reaction shows apparent zero-order kinetics and the rates were found to be proportional to the surface area of added metals in the form of powders or foils. Rates and activation parameters are reported for ten transition metals and the Fe : Ni : Cr alloy, 304L stainless steel. The activation energies and relative specific activities at 353 K are: Co (43 kJ mol−1, 3900); Ni (93 kJ mol−1, 310); Mo (76 kJ mol−1, 94); V (85 kJ mol−1, 66); Fe (119 kJ mol−1, 33); W (68 kJ mol−1, 11); Au (74 kJ mol−1, 7.8); Ti (95 kJ mol−1, 1.0); 304L (100 kJ mol−1, 0.43); Cr (105 kJ mol−1, 0.099); Ta (106 kJ mol−1, 0.06). The Arrhenius activation parameters for the various metals (and different samples of the same metal) show a linear compensation effect: In A = (1/θ)Ea/R + 1n ko with a compensation temperature, θ, of 445 K. Different samples of molybdenum powders showed θ = 432 K and an isokinetic temperature of 430 K, at which the rates for all molybdenum samples were equal. The relative activities are explained in terms of the binding energies of N-adatoms to the metal surface and an empirical thermochemical relationship is proposed. Additionally it is noted that the least catalytically reactive metals are those whose ambient-atmosphere oxide films are not reduced by hydrazine.
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