Discussion on “the radiation theory of chemical action”
Discussion on “the radiation theory of chemical action”
复制标题
DOI：
10.1039/tf9221700598
复制
发表时间：
--
影响因子：
--
通讯作者：
F. A. Lindemann;S. Arrhenius;I. Langmuir;N. Dhar;J. Perrin;W. C. M. Lewis
中科院分区：
文献类型：
--
作者：
F. A. Lindemann;S. Arrhenius;I. Langmuir;N. Dhar;J. Perrin;W. C. M. Lewis
林德曼教授(译文)：由於我可支配的时间不多，我只会就我自己发表的有关化学反应速度的辐射理论的批评发表意见。如果佩林教授的前提是绝对正确的，那么他支持辐射理论的论点无疑是合理的。简而言之，他说，在一定的限度内，实验证明，如果浓度减少，反应速度不会改变，因此每秒的碰撞次数也会减少。他假设他可以外推到如此稀疏的浓度，以至于几乎不会发生碰撞，而且反应速度到那时仍然是恒定的。因此，他的结论是，反应速度不可能是由碰撞引起的，而只能是由某种外部因素造成的，显然，这一定是辐射。如果反应速度真的与碰撞的次数无关，这个论点是令人信服的；但我们的证据在低气压下肯定是不充分的。我的困难可以概括为：如果反应速度与给定波长的辐射密度成正比，那么蔗糖的反转(刘易斯教授研究的情况，10‘的温度系数为4-13)必须由波长1.05~的辐射密度确定。这个波长的辐射密度在阳光下比在黑暗中大5x1013倍，但反应以大致相同的速度进行。据我所知，佩林教授试图通过假设人们必须处理的不是频率v的辐射密度ur，而是一些吸收带v1+v2+…=a‘来满足这一点。但如果速度与uvl+uvs+成正比...我们将找不到
Professor FA Lindemann: In view of the short time at my disposal I will confine my remarks to the criticism of the radiation theory of chemical reaction velocity, which I myself have published. If Professor Perrin’s premises are absolutely correct his argument in favour of the radiation theory is no doubt sound. Briefly, he says it is expeiimentally established within certain limits that reaction velocity is not changed if the concentration, and therefore the number of collisions per second, is diminished. He assumes that he may extrapolate to such lorn concentrations that practically no collisions occur and that the reaction velocity will then still be constant. He concludes, therefore, that reaction velocity cannot be due to collisions but can only be due to some outside agency, which must obviously be radiation. The argument is convincing if it is true that reaction velocity is really independent of the number of collisions; but surely our evidence of this is quite inadequate at low pressures. My difficulty may be recapitulated as follows: If reaction velocity is proportional to radiation density of a given wave-length, then the inversion of sucrose (a case studied by Professor Lewis, which has a temperature coefficient of 4-13 for 10’) must be determined by the radiation density of wave-length 1.05~. Tho radiation density of this wave-length is 5 x 1013 times greater in sunlight than in the dark, yet the reaction proceeds at approximately the same rate.Professor Perrin attempts, as I understand, to meet this by assuming that one has to deal not with the density of radiation ur of frequency v, but with a number of absorption bands vl, v2 such that v1+ v2+...= a’. But if the velocity is’ proportional to uvl+ uvs+... we shall not find