HITTORF, JOHANN WILHELM. - INTRODUCING THE NOTION OF "TRANSPORT NUMBERS" OF IONS.

Ueber die Wanderungen der Ionen während der Elektrolyse. Erste-Zweite und Dritte Mittheilung (+) Rechtfertigung seiner Mittheilungen "Ueber Wanderungen der Ionen". Elektrolyse einer lösung zweier Salze. (4 papers).

Leipzig, Johann Ambrosius Barth, 1853, 1856, 1858, 1859. Without wrappers in "Annalen der Physik und Chemie. Hrsg. von J.C. Poggendorff", Dritte und Vierte Reihe, Bd. 89 No. 6 u. 7, Bd. 98 No 5, Bd. 103 No 1, Bd. 106 No. 3. The 5 entire issues offered. Hittorf's papers pp. 177-211 (Bd. 89), pp. 1-33 (Bd.98), pp. 1-56 (Bd.103), pp.337-411 a. 513-586 (Bd. 106). In all 7 engraved plates. All issues fine and clean.

First printing of all 4 fundamental papers on electrochemistry, where Hittorf states his concepts of ionic migration and transport numbers, concepts that should be the foundation stones of the later evolved theory of ionization, culminating in Svante Arrhenius's famous discovery of electrolytic dissociation.

"After Faraday's experimental investigations in 1834, it was accepted that the electricity passing through an electrolytic cell was carried by the movement of charged ions produced from the decomposition of the compounds making up the solution. Daniell had extended these ideas in 1839 and showed that salts were compounds not of acid anhydrides and metallic oxides as had been thought, but of metallic cations and elemental or compound acid anions. Believing that the conductivity of solutions was due to these ions, he began a study of their transference. In 1853 Hittorf took up the problem. He extended the ideas of Daneill by reasoning inthe following manner: Cations and anions exist in solutions and migrate under the influence of current through the solution. The migration of the cation toward the cathode and away from the anode, and the deposition of the anode on the positive electrode, together result in a decrease of teh salt in the neighborhood of the anode. A similar analysis shows that there is also a decrease in the concemtration of the salt in the neighborhood of the cathode. If the motion of the two dissimilar ions were the same, the decrease in the concentration of the salt would be the same at the two electrodes.....Hwe concluded that the speeds of migration...were different and he characterized this fact by defining "transport numbers", which specified the portion of the transport of electricity carried by each ion. (DSB VI, p. 439). - Leicester & Klickstein "A Source Book of Chemistry", p. 400-406.

In the 2 issues of 1853 are contained 2 papers by Helmholtz of fundamental cjharacter, both in physiology and on the theory on the conservation of energy.
HERMAN HELMHOLTZ: "Ueber einige Gesetze der Vertheilung elektrischer Ströme in körperlichen Leitern mit Anwendung auf die thierisch-elektrischen Versuche (+) Ueber einige Gesetze....(Schluss). 2 papers. 1853. (Bd. 89 No.6 a. 7). Pp. 211-233 a. pp. 353-377.
"In this work (the papers offered) Helmholtz for the first time enters the field of mathematical physics and physiology, with the full equipment of the higher mathematical analysis, of which he was the only master in its application to the latter science.....This very interesting and fundamental work on the distribution of electrical currents in material conductors is purely mathematical in character, owing to Helmholtz's method of proving the theorems, which are intelligible enough from the physical point of view, It is essentially connected with the treatise on the CONSERVATION OF ENERGY, since helmholtz merely substitutes for the expression 'free tension' there employed, the identical concept of Gauss's potentia, or Green's potential function."(Koenigsberger in "Hermann von helmholtz", p. 99-103.).

Order-nr.: 43082