Richard W.
Ramelte Formation of ~onothioc~anatoiron(lll)
Carleton College
Northfield, Minnesota
A photometric equilibrium study
N o approach to the analysis of a homo-
geneous equilibrium system is more illuminating than
the met,hod of simple spectrophotometry. Any
student can immediately and intuitively appreciate the
necessity of a relationship between color intensity and
concentration; the useful quantitative relationships
(Beer's law) are easy to teach; the apparatus (e.g.,
Leitz-Ituoy filter pholometer) can be beautifully simple
and yet have quite pleasing accuracy; and very impor-
tant at an early stage of instruction, the equilibrium
system can be thoroughly examined without disturbing
it or destroying a sample. For these reasons the author
feels that beginning equilibrium experiments using
photometry are especially instructive.
The "blood-red" complexes of thiocyanate with
iron(II1) are well known in qualitative analysis, quanti-
tative determination of iron, and considerable research
literature has accumulated on the formation and nature
of the series of species involved. At least one recent
general chemistry laboratory manual (1) shows a simple
visual colorimetric experiment designed to obtain an
approximate valne for the formation quot,ient of the
first complex ion, monothiocyanatoiron(111). It w2,s
felt that although this experiment was instructive as
published, it was inherently less accurate than desired,
suffered from an assumption that one can reliably pre-
pare a solution of known concentration of the ~ingle
complex, and could be strikingly improved if redesigned
with a procedure involving simple photometric measure-
ments. The discussion and directions given to the
students are an adaptation of the work by Frank and
Oswl~lt(S), and the reader is referred to their paper for
a fuller discussion.
Definition of the Chemical System. Thiocyanate ion
can react with ferric ion in acid solution to form a series
of thiocyanato- complexes:
I n the presence of high concentrations of thiocyanate
the higher complexes predominate, but if the molarity
of thiocyanate is very low the only complex formed in
appreciable amount is the monothiocyanatoiron(111)
ion, according to:
with the equilibrium quotient:
I n this experiment the concentration of thiocyanate
ion will always be less than 0.0002 M, and since the
Presented before the Division of Chemical Education at the
I42nd meeting of the ACS, Atlrtntie City, September, 1962.
equilibrium quotient for the formation of the dithiocya-
nato complex is approximately 13 (5),then the ratio:
Therefore, the higher complex v.ill never be more
than about a quarter of a per cent of the total.
Another possible chemical complication which must,
he avoided is the formation of hydroxyiron(II1) species.
The aquo-ferric ion is a moderately strong Br#nsted
acid, with a dissociation quotient (ionic strength =
0.5) of about G X (4). Therefore, if the
concentration of monohydroxyiron(111) ion is to be
reduced to negligible values, the hydronium ion con-
centration should he of the order of 0.5M. I n this ex-
periment this will be achieved by using such a concen-
tration of perchloric (or nitric) acid.
At this acidity, the uncomplexed iron(II1) ions do
not absorb visible light appreciably, and so the thio-
cyanate complex is the only colored species. It is
assumed that thiocyanate does not take on protons (i.e.,
that thiocyanic acid is strong), hut this is a point which
is not. clearly settled in the literature. Students might
be asked to discuss the quantitative implications of this
uncertainty.
The procedure will he to add small successive portions
of a solution containing 0.1 M iron(II1) ion and 0.5 M
hydroninm ion to a known volume of a solution con-
taining 0.0002 M thiocyanate ion and 0.5 M hydronium
ion. Thus, both the ionic strength and the acidity will
remain effectively constant during the experiment.
Either a nitrate or a perchlorate medium must be used
because other anions form iron complexes. If nitric
acid is used it would be wise to use fresh "white" con-
centrated acid to make the solutions and avoid the pos-
sibility of oxidation of thiocyanate by oxides of nitrogen.
Or better, the nitric acid can be cleaned effectively by
adding a few crystals of sulfamic acid ( 5 ) , which mill
not interfere with the experiment.
With each addition of the iron(II1) solution, the con-
centration of the monothiocyanate ion will increase,
and the transmission or absorbance, A , of the solution
can be measured. Since the complex is the only ab-
sorbing species,
A = eb[FeSCN++J (3)
where a is the absorptivity and b is the cell length.
However, the absorptivity cannot he determined in the
usual way because i t is not possible to prepare a solu-
tion with a known concentration of complex (unless one
knows the precise valne of the equilibrium quotient,
which would make this experiment pointless). It is
not feasible to add enough iron(II1) ion t,o force the
reaction quantitatively to the right, converting the
known total amount of thiocyanate completely to the
Volume 40, Number 2, February 1963 / 71
 colored complex. This is contrary to the assumption
involved in the simple visual experiment referred to
earlier. For accurate results it is necessary to intro-
duce a mathematical interpretation of the data which
does not require knowledge of the absorptivity. This
can be done as follows:
Algebraic Principles. For any of the equilibrium
mixtures involved in this experiment, the total molarity
of thiocyanate, C,, and of iron, C, can be represented
by:
Equations (2)-(5) may be combined to give:
Now, C! and C, a t any point can be calculated by or-
dinary molarity-volume relationships. The absorbance
can be measured in the usual way. But for a direct
solution of the equation to find Q it would be necessary
to know the product ab and this information is not
directly available. However, equation (6) is a. regular
quadratic expression in terms of the concentration of
complex, i.e., A/ab, and Frank and Oswalt showed that
it was convenient to use a series approximation formula
(6) for solution:
because at the low concentrations of iron and thiocya-
nate used in this experiment the first term alone on the
right side accounts for better than 99% of the value of
A/ab. Therefore, neglecting the higher terms of the
series, equation (7) can be rearranged to give:
which is the form used by Frank and Oswalt. When
values of CJJA are plotted versus corresponding
values of (Cf +
C,) a straight line should be obtained
with a slope/intercept ratio equal to the value of the
equilibrium quotient, Q.
An alternative arrangement of the equation is as
follows:
and a plot of A/C,C, versus A(Cf +
C,)/CJ, should
be linear with the slope equal to -Q. Thus, it turns
out to be unnecessary to know the absorptivity of the
complex ion, although this quantity can he calculated
as a byproduct in the determination of Q.
Labomlory Directions. Prepare the dilute thincyanate solution
as follows: into a 100-ml. vdumetric flask pipet 10 ml of the
provided 0.002 M (note the precise molarity given by the instrue-
tor) potassium thiocyanate, and alsv pipet 25 ml of 2.0 M per-
chloric (or nitric) acid. Dilute to the mark, mix well, and pour
"quantitatively" into a. 250-ml heaker. It will be assumed that
the f l a k delivered 100.0 ml.
Use a 1-ml pipet to add successive portions of the provided
0.1 M (note the precise molarity according to stmdardisatioo)
iron(II1) perchlorate (or nitrate) solution which also contains
0.50 M acid. After each addition, stir thoroughly, pour into a
photometer cell, measure the absorbance at the wavelcngt,h of
72 / Journal of Chemical Education
maximum absorption (445-450 mp), and return the sample to the
beaker, being careful to avoid loss of solution. The number of
points to he taken is arbitrary, from five to ten.
Calculations. The values of Cr and C, a t each point
are calculated simply by considering the dilutions which
the solutions have undergone. The values of absorb-
ance, which may have to be calculated from per cent
transmission readings, are not corrected for dilution.
Make the plot(s) as indicated, taking special care to
draw the best straight line. The method of least squares
is recommended but is not necessary. Calculate the
value of Q, and write a brief discussion of the errors
which are inherent in the experiment as it has been
carried out.
Results. The figure shows the experimental results
of one of the sophomore students. I t is typical that
the data fall on a good straight line, but because of
miscalculations, carelessness in plotting, graphs which
are too crude, etc., there will usually be a considerable
spread in values of Q. The accepted literature value
for Q is 138 at 25OC (2,7). We have obtained values
about 20% higher on the average, probably due to color
fading resulting from exposure to light. I t would be
best to dim the room and to work quickly.
Graphical determination of the formation quotient. Data
Andenon, Carleton College.
This experiment seems to be a very good one becausc
it brings out so many important principles of quantita-
tive work: the nse of volumetric ware, molarity-volume
relationships, spectrophotometry, the setting np of a
mathematical model for a proposed chemical system,
the problem of using extrapolation when there are too
many unknowns, t,he satisfaction of using one's own
data in the interpretation, the comparison with litera-
ture values, and the criticism of t,he experiment as a
whole.
Literature Cited
(1) SIENKO,M. J., ASD PLAXE,R. A,, "Experimentd Chrm-
istrv," 2nd ed., MeGraw-Hill, 1961.
(2) FRANK,H. S., AS,) OSWALT, R L., 3. Am. Chem. Soe., 69,
1321 (1947).
(3) YALMAN, R. G., J. Am. C h m . Soc., 83, 4142 (1961).
(4) BRAY,W. C., AND HERSHEY, A. V., . I . Cheis. Soc., 56,
Am.
1889 (1934).
(5) BRASTED, R., J . CHEM.EDUC., 28, 442 (1951).
( 6 ) Handbook of Chemistry and Physics, Chemical Rubber Co.,
41st ed., p. 322.
(7) LAGRENCE, (2. S., Trm9. Fnmday. SGC.,52,236 (1956).