[miller] idea in chemical MECHANICS 2SI 



acids of the halogens, had been studied by Burchard - in the laboratory 

 of Lothar Meyer, by Ostwald," by Meyerhoffer,* by Dr. Schlundt ^ in 

 AVisconsin, by Warder,® of Washington, by Magnanini '' in Italy, and by 

 Pendlebnry and Seward,^ and Judson and Walker ^ in England. Most 

 light had been thrown on the reaction by Prof. ISToyes;^*' but in the 

 opinion of the last chemists to work on this subject, Messrs. Judson and 

 Walker, expressed in 1898 after a review of the earlier papers : " The 

 action of hydriodic acid on the oxyacids of the halogens is of too intri- 

 cate a nature to give any satisfactory numerical results.'^ 



Attacked by the method of systematic exploration, however, this 

 problem proved easy of solution ; Messrs. Bray,^^ Duslmian ^^ and Clark^^ 

 expressed the relations between concentrations and rate in mathematical 

 form, traced out the influence of the iodine liberated during the reaction, 

 and recalculated most of the experimental work of their predecessors. 

 The remarkable catalytic action of chromic acid on one of these reactions, 

 discovered by Ostwald, has al.?o been studied in detail.^* 



In this connection, it became apparent that reactions of the fourth 

 order are plentiful as blackberries in August; and in the oxidjation of 

 ferrous salts b}' chromic acid. Miss Benson^^ found one of the fifth. The 

 opinion held between 1884 and 1895, that reactions of a higher order 

 than the second are curios, must, therefore, be given up. It probably 

 arose from the circmnstance that the mctliod of investigation employed 

 was unable to cope with the complicated cases. 



Some of these results might conceivably have been attained by a 

 judicious use of method number three. It is otherwise with the reactions 

 to which I will now refer. 



Schwieker,^*' who studied the formation of iodate by the action of 

 iodine on caustic potash in 1895, thought that he had discovered a re- 



»Zeit. phys. Chem., 2, 796 (1888). 

 •Zeit. phys. Chem., 2, 127 (1888). 

 *Zeit. phys. Chem., 2, ^85 (1888). 

 "Am. Chem. Jour. 17, 754 (1895). 

 •Am. Chem. Jour. 18, 23 (1896). 

 'Gazz. Chim. Ital., 21, 476 (1891). 

 "Proc. Roy. Soc, 45, 396 (1889). 

 •Jour Chem. Soc, 73, 411 (1S9S). 

 "Zeit. phys. Chem., 10. 599 (1896). 

 "Jour. Phys. Chem., 7, 92 (1903). 

 "Jour. Phys. Chem., 8, 453 (1904). 

 "Jour. Phys. Chem., 10, 679 (1906). 

 "Jour. Phys. Chem., //, .353 (1907 j. 

 "Jour. Phys. Chem., 7, 1 (1903). 

 "Zeit. phys. Chem., 16. 303 (1895). 



