Abstract The thermal analysis of molybdenum hexacarbonyl has been performed under helium stream (2 K min−1) between room temperature and (1100 ± 2) K. According to mass spectrometry results, the organometallic sublimates between (330.4 ± 0.1) K and (339.7 ± 0.1) K, and the sublimation enthalpy, determined at two particular temperatures (ΔsubH(298.15 K) = (73.66 ± 0.02) kJ mol−1), is similar to the activation energy. As a matter of fact, the sublimation of Mo(CO)6(cr) follows a perfect-zero order reaction kinetic (Ea = (73.49 ± 0.10) kJ mol−1 and the pre-exponential factor is (8.33 ± 0.33) × 108 s−1). Furthermore, using Langmuir equation and thermogravimetry data, we were able to determine the vaporization constant (α) (=8.95 × 10−5 ± 1.45 × 10−7), the constant k (=80735 J0.5 mol−0.5 K−0.5) as well as ΔsubH (298.15 K) (equal to (75.91 ± 0.37) kJ mol−1). In the presence of ZSM-5 zeolite, the temperatures of Mo(CO)6(cr) decarbonylation, Ea and ΔsubH values were succinctly determined. Interestingly, the loss of the first CO ligand in Mo(CO)6(cr) occurred between (480 ± 0.1) K and (532 ± 0.1) K.

中文翻译：

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六羰基钼的热性能：动力学和热力学研究

摘要 六羰基钼在氦气流（2 K min-1）下在室温和（1100±2）K之间进行了热分析。根据质谱结果，有机金属在（330.4±0.1）K和（339.7）之间升华± 0.1) K 和在两个特定温度下确定的升华焓 (ΔsubH(298.15 K) = (73.66 ± 0.02) kJ mol-1)，与活化能相似。事实上，Mo(CO)6(cr)的升华遵循完全零级反应动力学（Ea = (73.49 ± 0.10) kJ mol−1，指前因子为（8.33 ± 0.33） × 108 秒-1）。此外，使用朗缪尔方程和热重数据，我们能够确定蒸发常数 (α) (=8.95 × 10−5 ± 1.45 × 10−7)，常数 k (=80735 J0.5 mol−0.5 K−0.5 ) 以及 ΔsubH (298.15 K)（等于 (75.91 ± 0. 37) kJ mol−1)。在ZSM-5沸石的存在下，Mo(CO)6(cr)脱羰的温度、Ea和ΔsubH值被简洁地确定。有趣的是，Mo(CO)6(cr) 中第一个 CO 配体的丢失发生在 (480 ± 0.1) K 和 (532 ± 0.1) K 之间。