Netsu Sokutei, 31 (4), p. 194, (2004)

講座

非定温速度論(2)複数素過程の場合

Non-isothermal Kinetics (2) Multiple Elementary Processes

複数の素過程が関与する様々な過程の非定温速度論ついて考察した。最初に,核が発生しそれが成長する過程の非定温速度論の基本式を導き,定温条件の速度式と比較した。定速の加熱あるいは冷却の場合速度論解析が可能である。並進反応や続発反応についても同様に考察した。並進反応については不充分ではあるが解析に利用できる簡単な関係が見出される。続発反応については,特定の場合に限り基本式が書けるが,有用ではない。温度振動の可逆的過程の速度論解析への応用についても解説し,合わせて非可逆反応への適用についても考察した。
The theme dealt with in this article is non-isothermal kinetics of various processes in which multiple elementary processes are involved. Firstly fundamental equation of non-isothermal nucleation and growth process is derived and it is compared with isothermal fundamental equation. From the fundamental equation, method of kinetic analysis of data by constant rate heating or cooling is derived. Theoretical considerations are also made for parallel competitive reactions and consecutive reactions. For the former some simple relations useful to elucidate the process can be derived, but for the latter such a simple useful relation cannot be found, but a fundamental equation is derived for specific cases. Finally usefulness of temperature oscillation for analyzing reversible processes is discussed together with its application to a reaction of a single elementary process.