Erik Larsen

and J. Eriksen
Thiocyanato Chromium(lll) C O ~ P ~ ~ X ~ S
H. C. QIrsted Institute
University of Copenhogen Separation by paper electrophoresis
DK-2100 Copenhogen 0,
Denrnork and estimate of stability constants

In the classic papers b y N. Bjermrnl.2 he described the
formation in solution of all members in the series
[C~(NCS),(HZO)~-~]+'~-~' (n = 0-6). Further he mea-
sured the complexity constants for all the species. Since
the substitution reactions on chromium(III) are slow a t
room temperature (the complexes are said t o be robust),
Bjermm prepared solutions which were equilibrated by
pmlonged heating t o 50C. After cooling t o room tempera-
ture the robustness allowed for chemical analyses of the
species which were in m u t u a l equilibrium a t 50C. Very
tedious procedures for the separation of t h e complexes, or
alternatively conductivity measurements, lead t o com-
plexity constants for all the six stepwise equilibria
c~(Ncs)~_JHP)~_~+"-"' NCS- z=?+
comprise t h e first example of a set of data describing the
successive formation of all possible members i n a series.
The separation of the geometrical isomers of the same
compositions, for example facial and meridional
Cr(NCS)3(H20)3, has not yet been accomplished for this
system, however. Here we report a n experiment in which
the differently charged species from mixtures which have
been equilibrated a t 100C are separated by paper electro-
phoresis.
T h e experiment is designed a s a student exercise in a
general chemistry laboratory course and serves to
Preparation of the Equilibrium Solutions
Fmm stock solutions of 2 M KNCS and 1 M Cr(H20)dNOd~
kept in pipet bottles, 10 solutions are made up in small test tubes
by diluting 1 drop of the 1 M Cr3+ solution to 10 drops by water
and/or thioeyanate solution. The table shows the compositions.
After being shaken the solutions are kept in a boiling water bath
for 20 min. During this time the solutions come very nearly to
equilihrium and the test tuhes are then placed in an ice bath to
quench the reactions. All the solutions change colors during the
heating. Thus solution no. 1 becomes green due to the formation
of polynuclear (p-) hydroxy complexes of which (H2O)sCr-
(OH)Cr(H20)8+ is the simplest. The reverse reaction towards
the reformation of the aqua ion is slow so that such polynuclear
hydmxy complexes have been called latently basic compounds. In
the other solutions the formation of thiocyanato complexes causes
more intense violet colors.
Paper Electrophoresis
An electrophoresis chamber with water cooled support (Camag
HVE) is used in combination with a home-made power supply. In
this electrophoresis all the paper is efficiently pressed against the
cooled hattom by an inflated polyethylene bag. Whatmann 3 MM
chromatography paper (20 X 40 cm) is marked with a line divid-
ing the paper in two squares and the line further divided in 11
parts. After soaking the paper in 1 M NaN03 the solutions nos.
2-10 are applied to paper in amounts which will allow spots to be
visible after the separation (-50 pl). Cr(HzO)eZ+ directly fmm
the stock solution without previous heating is also applied to the
paper. Any dilution makes it difficult to see the more weakly col-
ored aqua ion and heating produces many species such that a
very broad band develops during the electrophoresis. In addition,
it is useful to apply a solutionJ of pure K3Cr(NCS)s which is only
found in small amounts in the equilibrium mixtures.

Demonstrate the existence of all the CI(NCS),(HZO)~-,+'~-"' 'Bjermm, N., D. Kgl. Danske Vidensk. Selsk. Skrifter I.
~.
snecies.
~~~~~~

l'em~testimate of rhe strpwise formation constants.

raekke, Noturuidensk. og Mathem. Afd., Xn, 4 (1915) 1-65 (in
Danish with an abstract in French (3 pages)).
Demonstrate I he robuatn~asofehwmium(llI)complexes. ZBjermm, N., Z.Anorg.Allg. Chem., 119, 179 (1921).
Show rhr principles of paper electrophures~s. 3Raeslar, J., Liebigs Ann., 141,185 (1867).

Stabilitv Constants for Various Chromium (Ill) Concentrations

Bjerrum's absorption
Solution no 1 2 3 4 5 6 7 8 9 10 vslues analyais

Dropa of water 9 8 7 6 5 4 3 2 1 0
Drons of 2 M N C S - 0 1 2 3 4 5 6 7 8 9
Total concn of N C S - (MI 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
era* 1 1 0 0 0 0 0 0 0 0
Relative CrL 0 10 1 1 0 0 0 0 0 0
cone of C~LP 0 10 5 10 1 1 0 0 0 0
spaciea CrLl 0 0 3 10 5 10 10 5 3 5
in each CrL 0 0 0 2 2 5 8 5 5 30
solution cib 0 0 0 0 0 0 1 1 2 20
CrLr 0 0 0 0 0 0 0 0 0 1
ri 0 1.5 2.2 2.6 3.1 3.3 3.5 3.6 3.9 4.4
Conc of bound N C S - (M) 0 0.15 0.22 0.26 0.31 0.33 0.35 0.36 0.39 0.44
Cone of free N C S (MI 0 0.05 0.18 0.34 0.49 0.67 0.85 1.04 1.21 1.36 225
KI 2W 3W
K. 20 28 30 20 27
Ka 3.3 3.0 10 1.5 4.5 4.5
XI 0.6 0.8 0.75 0.94 1 1.4 4 1.9 2.1
Kr 0.14 0.2 0.3 0.5 0.8 1.1
KG 0.04 0.4 0.7

122 / Journal of Chemical Education

 With a current of 160 mA a separation between Cr(H20)e3+
and Cr(NCS)& of some 10 em isobtained within 1.5 hr.
Formation Constants
From the electrophoresis paper it is possible to roughly
estimate visually the ratios between the different com-
plexes. This is justified since all these complexes have
rather similar spectra which vary gradually through the
series. When the relative concentrations of the various
~ ~
complexes in the equilibrium mixtures are known the
mean decree of c o m ~ l e xformation, ri, and the free thiocy-
anate cokentration are readily calculated. The relative
concentrations of complex species and the calculated
values of [NCS-] inserted in the equilibrium expression
yield the various constants. The table shows results from
an experiment performed by students. These are in good
agreement with those determined by Bjerrum. The change
of the temperature from 50-100C should cause the com-
plexity constants to become smaller.1 I t has been f ~ u n d l . ~ this set of constants is only to demonstrate that such a
that the variation with temperature is only small and a
factor of two between the constants for 50C and those
found here for 100C is the most we expect. Bjermm
reached this conclusion after analysis of a solution which
had been kept for equilibration a t room temperature for 3
yr.1 As noted by Bjermm the obtained K's are not ther-
modynamic equilibria constants. Neither are they directly
comparable with each other since the Ionic strength varies
a meat deal throueh the series of solutions for which the
d u e s are ohtainei. However, just as the original study of
this system contributed to the extension of our knowledge
of complex chemistry in solution this same chemical sys-
tem provides for students a simple, peadagogical intro-
duction to the field. A useful review of work done on the
thiocyanato chromium(III) system is given in Rossotti and
Rossotti's b k . 5
As a curiosity we include in the table constants ob-
tained hv analyzing
. . the various bands by means of atomic
absorption spectroscopy. The solutions were for thls pur.
pose made up with the ionic strength kept constant at 1.0
1KaCIO.I. The various bands were cut our and the rhro-
mium e&acted several times with a total of 50 rnl 0.1 M
HNOJ. The extraction was far from quantitative (85-95%
of the applied chromium was found) and thus the value of
procedure is in some cases possihle.
-~ ~p
4Poulsen, K. G., Bjerrurn, J., and Paulsen, I., Acto Chern.
Scand., 8,921 (1954).
5Rossotti, F. J. C., and Rossotti, H., "The Determination of
Stability Constants," McGraw-Hill Book Ca., New Yark, 1961.
Volume 52, Number 2, February 7975 / 123