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ALLOY GROUP F.

Electrodeposition of Alloys of Several


Metals More Noble Than Hydrogen

T h e following several chapters deal w i t h the electrodeposition of the alloys of several


metals having standard electrode potentials m o r e noble (more positive) than that of
hydrogen. T h e s e metals are gold, platinum and their congeners, and antimony, arsenic,
b i s m u t h , and rhenium. T h e deposition of alloys of t w o other metals, copper and silver,
w h i c h belong to this group were discussed in earlier chapters.
W i t h the exception of rhenium and s o m e of the platinum metals, the metals of group F
can be deposited readily from acid baths w i t h theoretical efficiency and readily from s o m e
alkaline baths. R h e n i u m can be deposited from either acid or alkaline solutions, but only
w i t h low cathode current efficiencies and the deposits cannot be built u p to a thickness
greater than about 10 (0.4 mil) w i t h o u t exfoliating.
Since the metals of group F are relatively noble, their deposition potentials m u s t be
made more negative by c o m p l e x i n g agents in order to bring about their codeposition w i t h
more active metals. T h e codeposition of the group F metals does not proceed as easily as
one m i g h t expect o n the basis of their electrode potentials. T h e s e metals are s o
m u c h nobler than other metals in acid solutions that (with the exception of rhenium)
they tend to deposit o n t h e m readily by chemical replacement in the form of m o s s y
deposits. T h i s reactivity may be checked by converting the simple ions to c o m p l e x ions,
but the latter may be difficult to reduce at the cathode. For example, p l a t i n u m is readily
deposited from acid solutions, but does not deposit from a cyanide solution.
G o l d posesses the m o s t noble (positive) standard electrode potential of all the metals.
In a solution of monovalent gold ions its potential is 1.68 volts and in a solution of trivalent
gold ions, it is 1.50 volts. In comparison, the standard electrode potentials of several other
noble metals are as follows: Pt (divalent salt), 1.2 v o l t s ; palladium, 0.99 volt; r h o d i u m ,
about 0.8 volt; silver, 0.799 volt; and copper (cupric salt) 0.377 volt.
Since the group F metals are at one end of the electromotive series, their electrode
potentials are usually rather far r e m o v e d from those of m o s t metals w i t h w h i c h they are
codeposited. Consequently, the alloy plating systems of the group F metals are frequently
of the regular type (see Section 5.1.B*); that is, under diffusion control.
A l t h o u g h a large n u m b e r of alloys containing the metals of group F are probably
capable of deposition, only a small n u m b e r have b e e n investigated, and of these only the
gold alloys are commercially important. Studies have b e e n made of the c o d e p o s i t i o n of
gold w i t h copper, silver, tin, nickel, and a few other metals. T h e deposition of alloys of the
platinum metals has received only cursory attention. A few alloys of b i s m u t h or a n t i m o n y
w i t h copper, silver, or lead have b e e n electrodeposited.

* See V o l u m e I of this treatise for Chapters 1 to 2 1 .


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