Louis Gordon and

Eugene D. Salesin Precipitation from Homogeneous Solution

Cose Institute of Technology
Cleveland, Ohio A lecture demonstration

The precipitation of nickel with dimeth-
ylglyoxime generated in situ from biacetyl and
hydroxylaminel affords an ideal lecture demonstration
of the advantages of precipitation from homog~neous
solution (PFHS).2 I t is a simple demonstration and
one which has worked successfully for the authors.
When this demonstration is made in conjunction with
the conventioual precipitation of uickel with alcoholic
dimethylglyoxime, the difference in the physical
characteristics of the two precipitates becomes strik-
ingly evident.
Although the exact mechanism3 involved in the
precipitation of nickel dimethylglyoximate from homo-
geneous solution is not known, the following equations
probably describe the process:
dimethylglyoxime (reaction 3). The solution becomes
increasingly more yellow and subsequently long red
needles of the nickel chelate begin to appear in about
five minutes. I n the couventional procedure, precipita-
tion occurs too rapidly to permit visual observation of
the yellow complex except under certain condition^.^
If, from the start, a light beam is passed through the
homogeneous solution, both the development of the
yellow color and the formation of the precipitate are
readily observed. The nickel dimethylglyoximate crys-
tals precipitated from homogeneous solution exhibit a
slightly different reddish hue than those obtained by
conventional precipitation.
The Experiment
Solution A: Five g of amrnonit~mchloride, 3.0 g of hydraxyl-
amino hydrochloride, and 80 mg of Nit? are dissolved in enough
distilled water to hring the volume to about 200 ml. The pH
of the solution is adjusted to i . 5 with ammonium hydroxide and
the final volume is brought to 400 ml with distilled water.
Solution B: Exactly 0.60 g purified biacetpl (Burdick and

2
CH3-C=NOH
I
CHs-C=NOH
+ Ni+. -[ Soluble
Yellow
Complex
] - Jackson Laboratories, Muskegon, Michigan) is disnolved in
enough distilled water to hring the total volume to 400 ml.
Solution C: Five g of nmmonium chloride, 5 ml of eoncen-
trated ammonium hydroxide, and 80 mg of Nit' are dissolved
OH,.'OR
, in distilled water to a 400 ml volume.
Solution D: Forty ml. of a one per cent solution of dimethyl-
glyaxime in ethyl slcohol are nddod to sufficient1:1 ethyl nlcohol-
distilled water solution to bring the total volume to 400 ml.
Conuentional Precipitation: Pour Solution C into a one liter
beaker. Add Solution D to Solution C with stirring to produce
the voluminous nickel dimethylglyoximate.
Pwn'pitation from Homogeneom Solution: Pour Solution A
When the appropriate reagent solutions are first into a one liter beaker. Add Solution R with stirring. In a felr
mixed, the resulting solution is virtually colorless. minutes crystals of nickel din~eth,vIglyoximstehegin to precipitate
which will slowly grow several millimeters in length.
The solution begins to turn yellow apparently as the It is possible to adjust the pH of Solution A so that the pre-
result of complex formation between nickel and cipitation from homogeneous solution will begin in almost any
desired amount of time. An approximate guide is:

T h e cover
~p

Time of Start of
vH Precioitat~on.Min

The difference in the physical characteristics of the two pre-

cipitates will become even more apparent upon filtration.

The authors wish to acknowledge the partial assistance of the

Atomic Energy Commission under Contract AT(l1-1)-582.
SALESIN,E. D., AND GORDON, L., Talanta, 5, 81 (1960).
GORDON. , I,..
- , SALUTSKY.M. L.. AND WILLARD.H. H.. "Pre-
eipitntion from Homogeneom Solution," John Wiley and Sons,
T h e couttmting a p p u w m r i of nii:lir,l ~ l i m c t l ~ y l ~ l y ~ , r ipre-
mate Inc., New York, 1959.
cipitates is shown hy n pair of p l i r ~ t o r n i c r o ~ m l ~ Tho
h . sample "ALEESIN. E. D., A N D GORDON, L., research in progress.
pictured a t t h e left was prcripitatrtl from hamogrncoos solution ' D I E E L , H., "The Applications of the Diaximes to Analytical
as described in t h e text. T h e one shown a t t h e right was ob- Chemistry," The G. Frederick Smith Chemical Co., Columbus,
tained by conventional methods. Ohio, 1940, p. 13.

16 / Journal o f Chemical Education