Ferenc Szabadvary
W0k0tt Gbbs and the
Technical University Budapest, Hungary Translated by Ralph E. Oesper University of Cincinnati Cincinnoti, Ohio
I
Centenary of Electrogravimetry
T h e first analytical determination by tneans of electrolysis was described in 1864. The inventor of this important method was Wolcott Gibbs. Actually it was surprisingly long before anyone came to the logical idea of applying the electric current arid the familiar phenomenon of electrolysis in the field of quantitative analysis. The first galvanic element, the famous "pile," bad been constructed as early as 1800 by Count Alessandro Volta (1745-1827) and in that same year William Cruikshank (1745-1800) observed that the metals deposit a t the negative pole if the current from a voltaic pile is passed through a metal salt solution (I). I n another paper (2) Cruiksha~ikremarked that "from these experiments it would appear that the gdvsnic influence might he employed with success in the andysis of minerals, more partieulsrly in separating lead, copper and silver from t,heir different solutions; s. very small quantity of a metal may likewise he detected in this way."
After this qualitative application of the electric current,, it was more than a half cent,ury before its quant,itative use came on t,he scene. I t is difficult to understand this long delay, because as early as 1835 Michael Faraday (1791-1867) had demonstrated that the amount of metal set frce is proportional to the quantity of elect,ricity passed through the solution. Ahout this time mamy different types of galvanic cells were being devised that not only were simpler and more convenient than t,he Voka cell but also they delivered a more steady current. Auiong them mas the carbon-zinc Bunsen battery (1841), which proved to he the best ( 3 ) . I n 1857 Gustav Maglms (1802-70) made an intensive study of the elect,rolyt.icdeposition of various metals and showed (,hat a t a particular cusrcnt density t,here was no cvolution of hydrogen, and also that a compact deposit result,ed. Thc deposilio~idepends also on "the ilegalive body with which the rnet,al is combined" (4). The paper published by Gibhs in 1864 (5) described t.he electrogravi~llet~ricdetermination of copper and nickel. I t appeared in t,he only journal the11 devoted exclusively to analytical chemist,ry, the Zeitschr
