山大物理化学英文下8.pptVIP

教育是给人戴一副有光的眼镜，能明白观察；不是给人穿一件锦绣的衣服，在人前夸耀。 教育是要让人戴能看从前看不见，并能看人家看不见的眼镜。 人受教育，求知识，原是为发现弊端。若是受了教育，仍处处觉得满意，那就是你的眼镜配错了。 胡适—学生与社会 1919.3.22 每日一句 For certain conclusion, the reaction should be studied in a wide time range. 9.8 The rate theory of unimolecular reaction Decomposition; isomerization Pseudo-unimolecular reaction It is obvious that a single molecule at ground state will not undergo any reaction except that it was activated by energy of some types. A ? A* ? P For unimolecular reaction, the puzzling question is that how do reactant molecules acquire necessary activation energy. At early 19th century, it was found that all unimolecluar reaction, such as gaseous decomposition and isomerization, is of first-order. For bimolecular reaction, before reaction takes place, reactants must collide with each other to acquire enough activation energy. This may lead to a conclusion that all gaseous reaction should be second-ordered. In 1919, Perrin proposed that, for unimolecular reaction, the reactant molecule was activated by absorption of infrared radiation from the container or other molecules – radiation activation theory. The result obtained from the radiation activation theory is in good accordance with the early observation of kinetic characteristics of the unimolecular reaction, i.e., unimolecular reaction is of first-order. Problems proposed by Langmuir : 1) the energy of the infrared radiation of the wall of container is very low and is not sufficient for activation. 2) some reactant molecules do not have an absorption band in the wave-length region of infrared radiation. 3) Latterly, it was observed that the unimolecular reaction is of second-order at low pressure and first-order at high pressure. [A] k∞ In 1921, Christiansen postulated that the activation of molecules in unimolecular reaction is also through intermolecular collision. For this theory, it is easy to explain the second-ordered feature of unimolecular rea