Feb.
, 1941 SPKCTROPHOTOMETKIC IDENTIFICATION OF COMPLEX
[CONTRIBUTION FROM THE DEPARTMENT
OF CHEMISTRY
Complex Ions. I. The Identification of Complex Ions in Solution by Spectrophoto-
metric Measurements'
BY WARRENC. VOSBURGHAND GERALDR. COOPER
A method for the identification of compounds
formed in solutions by reaction of two components
has been described by Job.? The method is ap-
plicable to complex ions. The formation of many
complex ions can be represented by the equation
A + nB J_ AB,, iIi
in which A is a metallic ion and B may be either a
moiecule like ammonia or an anion. T o deter-
mine n, solutions of A and B of the same molar
concentration are mixed in varying proportions,
and a suitable property of the resulting solutions
is measured. The difference (Y)between each
value found and the corresponding value of the
property calculated for no reaction is plotted
against the coniposition. The resulting curve
(Yagainst composition) should have a maximum
if the property measured has a larger value for the
complex ion than for A or B, or a minimum if
smaller. Job has shown that the composition a t
which the difference Y is a maximum bears a
simple relation to n of Equation I and is independ-
ent of the equilibrium constant. This method has
been called the method of continuous variations.
If the rxolar concentrations of the solutions of
4 and B are not the same, the position of the maxi-
mum in the curve is a function of the equilibrium
constant as well as of n. If n is known and the
stability of the complex ion not too great, the
equilibrium constant can be determined.
The absorption of monochromatic light is a
suitable property for this method, because com-
plex ions are often differently colored from their
components. Also, the absorption of light is pro-
portional to the coiicentration of the absorbing
species, which is one of the necessary conditions.
Spacu and Popper3 have used the refractive index
also.
While Job's results for several complex ions
seemed satisfactory, a series of mixtures contain-
ing cupric and bromide ions and another contain-
ing nickel ion and ammonia gave inconclusive re-
(1) Part of a thesis submitted in partial fulfillment of the require-
ments for the degree of Doctor of Philosophy in the Graduate School
o f Arts and Sciences of Duke University, June, 1989.
(2) Job, A n n . chim., [IO] 9, 113 (1928).
(3) Spacu and Popper, But. soc. sfiinfe Cluj 7 , 400 (1934); 8,
(1934)
.i
IONSIN SOLUTION 437
OF DUKEUNIVERSITY]
sults. Job noted that de Wijs4 had found i t nec-
essary to assume the formation of three different
complex ions from nickel ion and ammonia. In
a later paper5 he has shown that cupric and bro-
mide ions form two different compounds and has
pointed out that the method of continuous varia-
tions is not generally applicable when more than
one compound is formed.
I t seemed to the present authors that the
method of continuous variations would be more
useful if it could be readily ascertained in any
particular case whether or not more than one
compound is formed from a pair of components.
It was also of interest to see what use, if any,
could be made of the method when more than one
complex ion is formed from the same components.
Theoretical
Let us assume, with Job, that substances A and
B react according to Equation 1, and that solu-
tions of A and B, both of concentration M moles
per liter, are mixed in varying proportions. Let
the mixtures be made by the addition of x liter of
B to (1 - x ) liter of A ( x < l),with no appreciable
volume change on mixing, Let cl, c2 and CS be the
concentrations of A, B and AB,, respectively.
For any mixture the following equations apply
GI =M(1 - x j - cy (1)
c2 = Mx - ncg (2)
CIC2" = RCJ (8 )
Activity coefficients are not needed in Equation 3
if A and AB, are ions of the same valence type,
and B is a non-electrolyte. The condition for a
maximum in the curve of cB plotted against x is
that
dcsldx = 0 (4)
Differentiation of Equations 1, 2 and 3 and com-
bination of the three resulting differential equa-
tions with Equations l to 4 gives
n = x/(l - x) (5)
Determination of the value of x for which cs is a
maximum allows the calculation of n by Equation
5.
It remains to be shown that a maximum (or
(4) De Wijs, Hcc. frau. chim.,44, 669 (1'125)
( 5 ) lob, I n n c h i m . [111 6, 97 (1936)
438 WARRENC. VOSBURGH
AND GERALD
minimum) in the absorption of monochromatic coefficient of compound B is assumed t o be zero
light when x is varied coincides with the maximum which is often true in complex ion formation, the
of c3. If €1, ~2 and €8 are the extinction coefficients optical density of any of the solutions is given by
of A, B and AB, at a given wave length, the
optical density, d, is
d = I(e1c1 + +
EZCZ eac3)
where I is the length of path of the light through
the solution.
Let Y be the difference between d of Equation 6
and the optical density that the solution would
have had if there had been no reaction on mixing
the solutions of A and B.
+ +
Y = 1 [el61 62C2 €363 - ElM(1 - x) - EZMXI (7)
By differentiation of Equation 7 with respect t o x
it can be shown that Y is a maximum when c3 is a
maximum if e3 > €1, or a minimum when c8 is a
maximum if €3 < €1.
It has been assumed so far that only one com-
plex ion is formed. Let us now suppose that a
second complex ion is formed according to the
equation
AB, + qB AB(,+,) (11)
Let the concentration of the second complex ion be
c4. A c4 term must be added t o Equation 1, an-
other t o Equation 2 , and another equation added,
namely
C~C+ K'c4
The condition for a maximum in c3 can be shown
to be
If the stability of the two complex ions is such
that when c3 is a maximum c4 is small, n can be
determined, provided that the maximum in c3 can
be found experimentally. Similarly, it can be
shown that (n + q) can be determined from the
composition corresponding to a maximum in 64,
provided that a t the maximum c3 is small.
If three complex ions can be formed from the
same two components, and if they are rather
stable, the situation should not be much different
than when only two are formed. When an ap-
preciable amount of the third ion is present, the
amount of the first should be small, and i t is
necessary t o consider only two complex ions
a t a time.
The use of the optical density for the deter-
mination of the composition values corresponding
to the concentration maxima is not as simple when
two or more compounds are possible as when only
a single compound is formed. If the extinction
R. COOPER Vol. 63
d = Z(eici e3~a + +
€464) (10)
The difference Y , defined as for Equation 7, is
(6)
Y = Z[EICI + e3c3 + e4c4 - aM(1 - x)l (11)
Differentiation of Equation 11 and combination
with
d"l= dc
dx dx dx
(see Equation 1) gives
dx
(e3 - dc3
€I)% + (e4 - el)%]
dx (13)
I n general, the maximum (or minimum) value of
Y will not coincide with the maximum in either
c3 or c4, since i t is not necessary for either dcg/dx
or da/dx to be zero when dY/dx is zero. Fur-
thermore, the value of x a t which dY/dx is zero
should vary with the values of the extinction co-
efficients and so with the wave length used.
However, there are some useful special cases in
the application of Equation 13. If the wave
length can be chosen so that cl = el and €3 = =\ €1,
the maximum in Y corresponds t o the maximum
in c3. Also, if the wave length is such that €3 = 4
the same is approximately true, provided that the
(8) complex ions are highly stable. The condition
for maximum Y is then
&+dcr=o (14)
dx dx
When c4 and dc4/dx are small, as they must be
when c3 is a maximum (if compound AB, is highly
stable), the maximum in Y corresponds approxi-
mately t o the maximum in c3.
It can be shown similarly that a slightly differ-
ent Y-function is a maximum when c4 is a maxi-
mum, provided that e4 is considerably larger than
€3. Beyond the point of maximum AB, concen-
tration, as more B is added, AB,, + q) is formed
from AB,. If € 4 = €3, this reaction causes no
change in light absorption, but if €4 is enough larger
than €3, the optical density of the solution will con-
tinue t o increase after c3 is a maximum in spite of
the continuous dilution of the solution as B is
added. Let us define Y' as the difference be-
tween the actual optical density and the density
calculated on the assumption that all of the A has
been converted t o AB,%,but that the latter does
not react further with B. Let us assume further
that the complex ions are so stable that when con-
siderable AB,, + q ) is present, there is no appre-
Feb., 1941 SPECTROPHOTOMETRIC OF COMPLEX
IDENTIFICATION IN SOLUTION
IONS
ciable A left uncombined. The condition for
maximum Y' can then be shown to be
(E4 - =0
and since e4 - Q is finite, dc4/dx must be zero and
c4 is either a maximum or a minimum.
Experimental
Formation of Dichromate Ion.-The above theory indi-
cates that if two or more compounds can be formed from
components A and B, the value of x a t which Y is a maxi-
mum should vary with the wave length of the light used
for the measurement. If only a single compound is
formed, Y should be a maximum a t a fixed value of x
regardless of the wave length, provided that the extinction
coefficient of the compound differs from that of the colored
reactant. It should then be possible to determine
whether or not more than one compound is formed, by use
of several different wave lengths.
Before testing this conclusion with a pair of components
that may be presumed to form more than one compound,
it seemed desirable to try a pair that form only one. For
this purpose potassium chromate and hydrochloric acid
were chosen. The acid chromate ion HCrOa- is a weak
acid, but the first ionization constant of chromic acid is
so large that a negligible amount of undissociated chromic
acid would be present in a solution of acid chromate (and
dichromate) containing only a small excess of hydrochloric
acid.' It can be considered that practically the only re-
actions are
CrO4- + HaO+ HCr04-
2HCr04- CrZOr- +HzO
The formation of the dichromate ion will not interfere
with the method; the maximum concentration of dichro-
mate ion must come a t the same value of x as the maximum
concentration of acid chromate ion. The maximum in
both ions should come a t the point a t which equal volumes
of the equimolar solutions of acid and chromate have
been mixed. The maximum in Y should coincide with
the composition maximum. These conclusions are strictly
correct only if the ionic strength remains constant as the
composition is changed, since activity coefficients should
be included in the equilibrium equations. The activity
coefficients, if constant, have no more effect on the position
of the maximum than the equilibrium constant. How-
ever, constant ionic strength was not considered necessary
in the present case, because the object was to test the ef-
fect of varying wave length.
A 0.1 M potassium chromate solution was prepared by
weighing the required quantity of the recrystallized salt.
Mixtures of this solution with 0.1 M hydrochloric acid
solution were made in the proportions shown in Fig. 1,
x ml. of acid solution being added to (1 - x ) ml. of chro-
mate solution. The optical densities were measured a t
wave lengths 555, 545, 535, 525 and 505 m p by means
of a Bausch and Lomb spectrophotometer. Some addi-
tional measurements were made using 0.001 M solutions a t
wave lengths 470 and 410 mp by the use of a Coleman
Double Monochromator spectrophotometer with a 30
(6) News and Rieman, THISJOURNAL, 56, 2242 (1934).
439
mp slit.' Figure 1 shows the values of the difference, Y ,
between the measured density and that calculated from
the density a t the same wave length of the pure chromate
solution assuming no reaction on mixing the two solutions.
For most of the curves the Y-values have been multiplied
by a factor (constant for a particular curve) to save space.
All wave lengths gave a definite maximum or minimum a t
x = 0.5. This is what would be expected on the basis of
the above theory for a pair of substances that react (ap-
preciably) only in the molar ratio of one to one. The
curve for 410 mp has a minimum instead of a maximum
because the extinction coefficient for the chromate ion is
larger than that for the dichromate ion a t this wave length
1.o I I
Fig. 1.-Difference Yfor mixtures of equimolar solutions
of potassium chromate and hydrochloric acid. The ordi-
nates of most of the curves have been either increased or
decreased for economy of space.
Nickel Ion and o-Phenanthro1ine.-Nickel ion may be
expected to form more than one complex ion with o-
phenanthroline in solution, since solid complex salts
containing two and three molecules of the base to one
atom of nickel have been prepared.* Also, copper complex
salts containing one and two molecules of o-phenanthroline
to one atom of copper have been prepared by Blausb
(page 683). I t seemed possible that nickel ion might form
complex ions with o-phenanthroline having coordination
numbers (neglecting hydration) of two, four and six, as
it does with ammonia according to de W i j ~ . ~
Since o-phenanthroline is little soluble in water, it was
not possible to prepare a solution of suitable concentra-
tion. To make a series of mixtures, 40(1 - x ) ml. of 0.1
M nickel sulfate solution was diluted with 40x ml. of
water and the amount of solid o-phenanthroline required
for 40x ml. of 0.1 Msolution was dissolved in the solution.
The nickel sulfate had been treated for the removal of
cobaltQand recrystallized. The o-phenanthroline was re-
crystallized.
The optical density of the solutions was measured a t
wave lengths 500, 525, 540, 550, 585, 611, 635 and 650 mp
by means of the Bausch and Lomb spectrophotometer
(7) For these measurements the authors are indebted to Mr.
Robert K. Gould.
(8) (a) Pfeiffer and Tapperman, 2. anorg. allgem. chem.. 216, 273
(1933); (b) Blau, Monatsh., 19, 679 (1898).
(9) Deakin, Scott and Steele, 2. 9hysik. Chcm., 69, 126 (1909).
440 AND GERALD
WARRENC. VOSBURGH R. COOPER
and a curve was drawn for each solution in order that
interpolations could be made.
It will be apparent later, in agreement with theory,
that a random selection of a single wave length for the de-
termination of a curve similar to one of the curves of Fig. l
would lead to unsatisfactory conclusions. In order to be
able to select wave lengths in accordance with the theory,
the absorption spectra were determined of solutions con-
taining nickel ion and o-phenanthroline in the molar ratios
1: 1, 1:2 and 1:3. They are shown in Fig. 2. If it is tenta-
tively assumed that relatively stable compounds are formed
in these ratios, wave lengths may be selected that should
be suitable for testing the assumption. For the first
compound, the wave length 620 mp should be suitable,
since a t this wave length the 1:1 and 1 :2 mixtures have the
same extinction coefficient, and it may be presumed that
the corresponding compounds have nearly the same ex-
tinction coefficient. The small absorption of the third
compound a t 620 mp is favorable, also. Similarly for the
second compound, the wave length 580 mp should be
suitable and for the third 528 mp, since for the third it is
only necessary that the extinction coefficient exceed that
of the second as much as possible.Io
500 560 620 680
Wave length, mp.
Fig. 2 --Absorption spectra of solutions containing 0.02
mole of nickel sulfate per liter and 0.02, 0.04 and 0.06
mole, respectively, of o-phenanthroline. The tube length
was 4 cm.
At the appropriate wave lengths, density values were
read from the above-mentioned curves for the mixtures
of the 0.1 M nickel sulfate solution with water and phenan-
throline. These densities were plotted against the com-
position x , giving the three curves of Fig. 3 that are labelled
with wave lengths. The straight line in the lowest part
of Fig. 3 represents the calculated densities for no reaction.
The differences in ordinates between the density curve and
(lo) This is true if no compound exists with a higher ratio of o-
phenanthroline to nickel ion than one to three. Some more recent
experiments have shown that a solution containing nickel ion and o-
phenanthroline in one-to-four ratio gives a curve little different from
the one-to-three curve of Fig 2.
VOl. 63
the Straight line were plotted against s giving the curve
labelled Y. The difference Y has its maximum value when
x = 0.175 which is as close to 0.50 as could be expected.
This indicates the existence of an ion of the composition
Ni(phen)+f.
1= 620mp
0.8
0.3 0.5 0.7
X.
Fig. 3.-Absorption of mixtures of (1 - x ) liter of 0.1 &I
nickel sulfate solution with x liter of water and 0.1 x mole
of o-phenanthroline for wave lengths 528, 580 and 620 mp.
The straight lines are calculated density curves for no re-
action, and the curves Y,Y’ and Y” show the differences
between the density curves and the straight lines. Thq
measurements were made in 10-cm. tubes and the measured
densities were multiplied by 0.75 in plotting.
In the middle part of Fig. 3 the straight line gives den-
sities calculated on the assumption that the ion Ni(phen)++
is formed, but does not react with excess phenanthroline.
The density of the hypothetical pure Ni(phen)++ solution
a t x = 0.3 was calculated from the point on the density
curve for wave length 580 mp a t which x = 0.25, together
with the data for nickel ion from Fig. 2. Errors in this
calculated density would have only a small effect on the
conclusions. The difference curve for 580 mp, labelled Y’,
gives the difference between the other two curves as a
function of x. The maximum comes a t 0.685 as compared
with the expected 0.667 for the ion Ni(phen)z++.
The upper part of Fig. 3 is enough like the middle part to
need no special description. The maximum in the curve
Y ” comes a t x = 0.754 indicating the ion Ni(phen)s++.
Curves similar to the Y” curve were constructed directly
from the experimental densities for wave lengths of 500,
540 and 550 mp and they were very similar to the Y”curve
and had maximum values close to x = 0.75.
Nickel Ion and Ethylenediamine.-A similar series of
experiments was carried out with nickel sulfate and ethyl-
enediamine solutions. Three different ions may be ex-
Feb., 1941 SPECTROPHOTOMETRIC
IDENTIFICATION IONS
OF COMPLEX
pected here also. Grossman and Schiickll prepared thio-
cyanates with one, two and three moles of ethylenedi-
amine per mole of nickel thiocyanate and Inoue12 found
evidence from absorption spectra of the existence of the
three corresponding ions in solution.
I I
500 560 620 680
Wave length, mp.
Fig. 4.-Absorption spectra of solutions containing 0.02
mole of nickel sulfate and 0.02, 0.04 and 0.06 mole of
ethylenediamine per liter; tube length 4 cm.
The ethylenediamine was purified by fractional distilla-
tion. A solution was prepared and standardized by
titration with standard acid, with methyl orange as the
indicator. Solutions were prepared 0.02 M in nickel sul-
fate and in addition 0.02, 0.04 and 0.06 M in ethylenedi-
amine, respectively. Figure 4 shows the absorption spec-
tra of these solutions. Mixtures were then prepared of 0.1
iM nickel sulfate and 0.1 M ethylenediamine solutions and
the optical densities measured a t several wave lengths.
The Y-curves are given in Fig. 5. These were constructed
in the same manner as the corresponding curves of Fig. 3,
except that the density values were directly determined
instead of being found by interpolation. The Y-curve for
622 mp has a maximum a t x = 0.483 indicating the ion
Ni(en)++. The Y' curve for 578 mp has a maximum a t
x = 0.67 indicating Ni(en)*+", and two Y"-curves, for 545
and 530 mg, have maxima a little beyond x = 0.75, indicat-
ing Ni(en)a++.
I ' I
I
0.3 0.5 0.7
X.
Fig. 5.-Differences Y, Y' and Y"formixturesof (1 x )
liter of 0.1 M nickel sulfate and x liter of 0.1 M ethylene-
diamine. The dotted curve is for 600 mp. The ordinates
of the curve for 530 mp have been increased by 0.60.
..~
( I 1) Grossman and Schiick, 2. anorg. Chem., 60, 4 (1906).
(12) Inoue, J . Chem. SOC.J O ~ Q 64,
X . 65 (1'933); Chem. Abstracts,
a7, 2382 (1933).
IN SOLUTION 441
The dotted curve starting a t x = 0.5 is the Y'-curve for
wave length 600 mfi. Reference to Fig. 4 shows that this
is an incorrect choice, since the one-to-three mixture
has a n appreciably smaller density at this wave length
than the one-to-two mixture. The resulting Y-curve has
a broad maximum between x = 0 A0 and x = 0.65, and
this does not correspond to any simple ratio of ethylene-
diamine to nickel ion.
The curve for 530 mp was determined with 0.199 iM
solutions. I t s ordinates were increased by 0.60 in plotting
to avoid confusion. That the curves for both 545 and
530 mp have maxima near x = 0.75 emphasizes again
the fact that for the identification of the compound of
highest B content any wave length that is absorbed con-
siderably more strongly by this compound than by the
others will be satisfactory.
Copper Ion and Ammonia.-Job2 (p. 186) measured the
absorption of a series of mixtures of a copper nitrate solu-
tion and an ammonia solution. His Y-curve had a maxi-
mum a t x = 0.8 indicating the ion Cu(NHs)4++. Since
his measurements were made a t only one wave length,
615 mp, there was no evidence that this ion is the only one
formed.
In addition to the ion Cu(NHa),++there is reason to look
for the ion Cu(NH&++ because of the existence of com-
plex salts containing one mole of dipyridyl or o-phenanthro-
line per gram-atom of coppersb and because of the evidence
for the analogous nickel compound.
The absorption spectra of a series of solutions containing
0.02 mole of copper sulfate, about 2.5 moles of ammonium
sulfate, and from 0.02 to 0.12 mole per liter of ammonia are
given in Fig. 6. The absorption spectra do not suggest
the existence of more than two compounds, although more
definite conclusions might be possible if the region of wave
lengths longer than 710 mp were available.
500 560 620 680
Wave length, m p .
Fig. 6.-Absorption spectra of solutions containing 0.02
mole of copper sulfate, 0.02 to 0.12 mole of ammonia and
2.5 moles of ammonium sulfate per liter. The tube
length was 1 cm.
If only the ions Cu(NH&++ and Cu(NH3)4++ exist, a
- variety of wave lengths should be available for confirma-
tion of the tetrammine ion by the method of continuous
variations, among them the 615 mp used by Job. The
diammine ion could only be found with a wave length in
the vicinity of 710 m p , where the absorption is nearly
the same for several of the mixtures, particularly the one-
to-two and one-to-six mixtures. Figure 7 shows the Y
442 AND GERALDR. COOPER
WARRENC. VOSBURGH
and I" curves resulting from measurements of a series of
mixtures of 0.104 M copper sulfate solution and 0.103 M
ammonia solutions, with enough ammonium sulfate to
prevent precipitation. Wave lengths 710 and 720 mp led
t o maxima a t x-values of 0.65 and 0.68, respectively, in-
dicating the ion Cu(NH&++. The curve for wave length
575 mp has a maximum a t 0.795, indicating the ion Cu-
("a),++. Wave length 545 mp gave practically the
same results as 575.
0.3 0.5 0.7
X.
-
Fig. 7.-Differences Y and Y' for mixtures of (1 x )
liter of 0.104 M copper sulfate and x liter of 0.103 M arn-
monia, and enough ammonium sulfate in both solutions
t o prevent precipitation. The ordinates of the curve for
720 mp have been decreased by 0.10 in plotting.
Some measurements were made on solutions containing
nickel ion and ammonia, but the results were less satis-
factory than for copper. The complicated nature of the
equilibria, combined with too low stability of the ions
formed, was probably the reason. The results, as far as
they went, were in agreement with the conclusions of
de Wijs4 concerning this system.
Discussion
As Job has pointed the method of continu-
ous variations is a simple and rapid method for
determining the formula and also the stability of
a compound provided there is assurance that only
a single compound is formed from the compo-
nents in question. The above observations give a
method of determining whether or not more than
one compound is formed, provided that the ab-
sorption of light is the property employed. It is
only necessary to make measurements with a
variety of wave lengths, covering the region of the
spectrum absorbed. If all wave lengths lead to
the same result. as in Fig. 1, i t may be concluded
that only a single compound is formed. One ex-
ception t o this should be mentioned; a colorless
compound might be overlooked if formed in addi-
tion to a colored one.
If more than one compound is formed, the
method of continuous variations can still help in
gaining information as t o the formulas for the
compounds, if the compounds are sufficiently
stable. Caution is necessary in such cases, and
Vol. 63
the conclusions might well be held as provisional
until checked by a quantitative method.
Indications are sometimes given by the shape
of the curves in the method of continuous varia-
tions as t o the existence of more than one com-
pound. For example, Fig. 1 may be compared
with the topmost curve in Fig. 3. The latter is
convex toward the x-axis because the first com-
pound formed when o-phenanthroline is added to
nickel ion does not absorb much light of wave
length 528 mp. As x increases more and more of
the strongly absorbing compound is formed a t the
expense of the first. Job's curve for copper sul-
fate and ammonia is similar in shape, as were also
the corresponding copper-ammonia curves for
wave lengths 575 and 545 m p of this investigation.
This is additional evidence for a compound of
copper ion and ammonia with less than four moles
of ammonia per gram-atom of copper.
Summary
The theory of the method of continuous varia-
tions as given by Job is reviewed and extended to
cases in which more than one compound is formed
from a given pair of components.
The method has been applied t o the formation
of acid chromate and dichromate ions as a n ex-
ample of the case where the components react in
only a single ratio. It has been applied to the
complex ions formed by nickel ion with o-phen-
anthroline and with ethylenediamine, and also to
the complex ions of copper ion and ammonia, as
examples of cases in which the components react
in more than a single ratio. The absorption of
monochromatic light was the property measured
in each case. When only a single compound is
formed, the results are independent of the wave
length of the light used. When more than one
compound is formed, the results obtained depend
on the wave length of the light, and for useful con-
clusions the wave lengths used must be carefully
selected.
Both o-phenanthroline and ethylenediamine
unite with nickel ion in the proportions of one,
two and three moles to one mole of nickel ion.
Copper ion and ammonia form a complex ion with
two moles of ammonia per gram atom of copper as
well as the one with four.
DURHAM, N. C. RECEIVED SEPTEMBER7 , 1940
March, 1948 SULFOSALICYLATE
OF FERRIC
SPECTROPHOTOMETRY COMPLEXES 1195

[(;ONTRIBUTION FROM THE DEPARTMENT

OF CHEMISTRY OF THE UNIVERSrTY OF TEXAS]

Spectrophotometric Studies on Complex Formation with Sulfosalicylic Acid. I.

With Iron I11
BY ROBERTT. FOLEY C. ANDERSON'
AND ROBBIN

Sulfosalicylic acid has long been known as an ied with the total molarity of the two kept con-
analytical reagent for iron,2 giving characteristic stant. Several typical transmittance curves for
colors with iron(II1) solutions, apparently be- solutions a t a pH of 2.38 are shown in Fig. 1.
cause of complex formation. The color variations,
100
shading from violet through deep red or rose in
acid solutions to yellow in alkaline, suggest that
more than one complex may be involved. The
present investigations were undertaken to obtain 80
information concerning the nature of the complex
or complexes responsible for these effects.
Experimental
Materials.-Stsndard iron( 111) perchlorate solution 60
was prepared by dissolving primary standard iron wire in &
hydrochloric and nitric acids. Perchloric acid was then
added and the solution boiled slowly to drive off the more e
volatile acids. 40
C. P. sulfosalicylic acid (Eastman Kodak Co.) was
dissolved in water, with sufficient perchloric acid to
adjust to the same PH as that of the iron(II1) perchlorate
solution. The solution was standardized by titration with
sodium hydroxide, 20
Sodium hydroxi.de solution for use in adjusting the PH
was prepared from Merck Reagent grade sodium hy-
droxide. I t was standardized with potassium acid phthal-
ate. All solutions were prepared in calibrated apparatus
a t 25'. 0
Apparatus.-$" measurements were made with a Beck- 400 500 600 700
mann PH meter, Model G, with an accuracy of t 0 . 0 2
PH unit. A.
Light absorption measurements were made with an Fig. 1.-Method of continuous variations-absorption
Automatic Recording General Electric Spectrophotom-
eter of the Hardy type' over a range of 400 t o 700 mp
curves. The [ Fe"'] /[ Fe"'] +
[sulfosalicylic acid] ratio
with slit adjustment t o measure a 10 mp band. Per varied as I, 0.1; 11, 0.2; I11 0.3; IV, 0.4; TT, 0.5; VI,
cent. transmission values for solutions of equal concentra- 0.6; VII, 0.7; VIII, 0.8; IX, 0.9; X, 1.0.
tion prepared independently varied not more than 0.3 per
cent. From these curves values of the optical density
Procedure.-Calculated volumes of iron( 111) per- (D = loglo 1/T where T =.transmittance) for a
chlorate and sulFosalicylic acid were mixed. Sodium particular wave length were calculated for each
hydroxide was then added if needed t o adjust the PH and
the whole diluted t o the proper volume and allowed to solution. Sulfosalicylic acid and perchloric acid
stand one hour. The transmittance curve was then show no absorption a t the wave lengths used.
recorded, the absorption cells being rinsed very carefully The absorption for a system with no reaction is
before filling with each sample. determined therefore by subtracting the optical
Preliminary experiments showed that the solutions
reached equilibrium within one hour and showed no density of iron(II1) perchlorate determined from
measurable variation thereafter for periods of less than curve X of Fig. 1. Subtraction of this absorption
twenty-four hours, for a particular wave length, from the optical den-
The absorption cell was not thermostated, but all solu-
tions were brought to constant temperature before meas- sity of the solution gives D,a quantity which is
urements were made. proportional to the concentration of the complex
and which passes through a maximum when the
Results ratio of iron(II1) to total sulfosalicylic acid in the
The composition of the complex was studied solution is the same as that in which they react to
using Job's method of continuous variation^,^ the form the complex.*J was plotted against the
ratio of iron(II1) to sulfosalicylic acid being var- ratio
.
. ~

(1) Presented in piirt at Southwest Regional Meeting, American concn. Fe(II1) (moles/l.)
Chemical Society, Dallas, Texas, Dec. 12, 1946.
(2) Alten, Wielandi and Hille, Z . anorg. allgem. Chcm., 216, 81
concn. Fe(II1) +
concn.H0&3CBHS(OH)COOH
(1933); Thiel and Peter, 2. anal. Chcm., 109, 161 (1935); Kennard The results for wave lengths of 440, 500 and 540
and Johnson, Texas #cad. Sci. Proc. and Trans., 27, 45 (1943). mp are shown in Fig. 2.
(3) Hardy, J . Ogf. SOC.Am.,811,305 (1935); 88,360 (1938); U.S. The occurrence of the maximum of in the
Patent 1,987,441(1985).
(4) Job, A a n . chin;!., [lo] 9, 113 (1928); Voshurgh and Cooper, curves of Fig, 2 a t a ratio of 0.5 indicates that un-
'rHIS JOURNAL, 63, 437 (1941). (6) Moore and Anderson, i b i d . , 67, 167 (1945).
1196 ROBERTT. FOLEY c. ANDERSON
AND ROBBIN
0 0.2 0.4 0.6 0.8 1.0
[FelAFeI f R.
Fig. 2.--bIethod of continuous variations, pH 2.38.
der these conditions the iron and sulfosalicylic acid
react in a 1: 1 ratio to form the complex.
It may be noted also that the absorption is es-
sentially the same a t the two extremes where the
ratio of iron(II1) to R (sulfosalicylate) is 9 :1 and
1:9. Reasonable approximations for the extinc-
tion coefficients may be calculated by assuming
that under such conditions essentially all of the
reagent present in smaller proportion will react to
form the complex. Correction can be made for
absorption by excess iron(II1). For the solution
with ratio iron(II1) : R = 9: 1, the value so ob-
tained for the molar extinction coefficient of the
complex was 753 a t a wave length of 508 mp. For
solutions of ratios 1:9, 8 :2, and 2 :S, respectively,
the corresponding values were 756, 761, 752.
Thus there is no indication that in this pH range
complex formation occurs with more than one iron
(111) ion or R group. Similar agreement is ob-
tained for absorption a t other wave lengths.
With a change in pH, the results vary markedly.
In more strongly acid solutions (e. g., pH 0.9)
curves similar to those in Fig. 2 are obtained, ex-
cept that the maximum tends to shift slightly to a
concentration ratio of 0.46. Some variation is also
apparent in solutions with excess sulfosalicylic
acid as contrasted to excess iron; but, in general,
solutions a t pH values less than 2.5 show closely
similar behavior.
From the curves of Fig. 1, values of the extinc-
tion coefficient may be calculated as indicated
above. These can then be used to calculate the
Concentration of the complex in other solutions,
e. g., where equal concentrations of iron and sulfo-
salicylic acid are present. A better value for the
extinction coefficient may then be calculated. By
a series of successive approximations reasonably
good values for the apparent dissociation constant
(where R = sulfosalicylic acid concentration) K =
[F~(III)][R]/ [FeR] may be determined. At PH
2.38 and ionic strength of 0.061 a value of 1.3
(*0.2‘1 X 10-6 is obtained. A t pH 0.9 and ionic
strength 0.153 the value is 2.1 ( ~ 0 . 4 X
) (6) Rabinowitch and Stockmayet, THISJOURNAL, 64, 335 (1942);
Earlier workers2 have referred to red or orange
or yellow “complexes” in less acid solutions, but
Vol. 70
experiments a t higher PH values in the present
work indicate that information on such complexes
based on ordinary color measurements alone is of
doubtful significance. Typical results are shown
in the curves of Fig. 3, for solutions of different PH
and constant iron(II1) and sulfosalicylic acid con-
centrations. The position of maximum absorption
and thus the color of the solutions changes as well
as the extent of absorption.
I
400 500 600 700
A.
Effect of PH.
Fig. 3.-[Fe]”1 = 1.791 X lo-* mole/l. [sulfosalicylic
acid] = 2.292 X lo-* mole/l.: I, PH, 1.95; 11, PH, 3.03;
111, PH, 4.05; IV, pH 5.72; V, pH 9.38.
Graphs of D against concentration ratios show
maxima shifted toward values less than 0.5. For
pH 4.58, for example, the maximum 5 occurs a t a
concentration ratio of 0.25-0.30 and for pH 6.2
the maximum is between 0.1 and 0.2. These
maxima might be taken as evidence of complexes
with more R groups, but in some cases more than
five sulfosalicylic acid molecules reacting per iron
(111) ion would be indicated. It seems evident
that other factors than complex formation are
involved and that such maxima do not represent
the compositions of real complexes.
It has been shown6 that, even a t pH 2.38,
FeOH++ is of major importance in iron(II1) solu-
tions; and, although dissociation constants for sul-
fosalicylic acid are not known exactly, experi-
ments on buffers’ have shown that the sulfonic
acid group is highly ionized and that between pH 1
and pH 4 conversion in large measure to - 0 8 -
SCH3(OH)COO- should occur. These changes in
ionic species might account in part for the effect
of the hydrogen ion.
However, blank determinations show that in
solutions of high pH, iron(II1) perchlorate solu-
tions absorb more strongly in the same regions as
the iron(II1)-sulfosalicylic acid mixtures, prob-
ably as a result of formation of hydrous iron(II1)
oxide sols, Where excess iron is present many of
Bray and Hershey, ibid., 66, 1889 (1934).
(7) Private communication. U.S. Bur. Stds., Dr. R. 0.Bates.
March, 1948 OF TRISODIWM
REACTIONS MONOBISMUTHIDE
IN LIQUIDAMMONIA 1197

the mixtures form precipitates of hydrous iron
(111)oxide on standing. The Job method may be
applied successfully where other equilibria in solu-
tion are involved but any such sol formation
makes uncertain the comparison and interpreta-
tion of absorption data for mixtures of varying
concentrations.
Just recently, Babko's experiments on iron-sal-
icylic acid systems, which might be expected to be
closely analogous to the sulfosalicylic acid system,
have been reported.* He found FeR+ (violet) in
acid solution, then FeR2- (red), and finally F e R p
(yellow) a t about pH 10, but abstracts available
do not indicate what corrections were made for
hydrolysis or dissociation.
Experiments are now under way to extend trans-
mittance measurements on the ironsulfosalicylate
systems to the ultraviolet region in an attempt to
determine concentrations of the various species,
especially Fe013++, so that their effects may be
measured.
Effect of Temperature.-The instrument used
is such that accurate control of temperature
is not possible, but approximate measurement
of the temperature effect showed that increased
(8) Babko J. Gen. Chem. (U.S.S. It.), 16, 745 (194.33; C.A . , 40,
7042 (1947).
temperatures increase the extent of complex
formation. The per cent. transmittance decreased
about 7% on heating from 20 to 40'. A thermo-
stated absorption cell has now been built so that
the temperature effect may be measured more ac-
curately in an attempt to determine the extent of
dissociation of the complex.
The authors wish to express their appreciation
to Mr. Leland L. Antes, Microscopy Specialist,
Bureau Engineering Research, University of
Texas, for his assistance in connection with use of
the spectrophotometer.
Summary
1. Spectrophotometric studies of complex
formation between iron(II1) and sulfosalicylic
acid were made over a $H range of 1to 9.
2. I n strongly acid solutions (to $H 2.4) iron
(111) and sulfosalicylic acid react in a 1: 1 ratio to
form a violet complex. Stability of the complex is
a function of the acidity.
3. Measurements a t higher PH values indicate
complexes of other mole ratios, but accurate for-
mulas could not be determined from ordinary
concentration measurements.
AUSTIN, TEXAS RECEIVED JUSE 30, 1947

[C!ONTRIBUTION FROM THE DEPARTMENT

OF CHEMISTRY OF THEUNIVERSITY OF TEXAS]

Some Reactions of Trisodium Monobismuthide in Liquid

BY GEORGEW. WATTAND THOMAS
E. MOORE*
Although numerous intermetallic compounds of but rather to an insoluble mixture of bismuth(I1)
the alkali and alkaline earth metals have been oxide, sodium hydroxide and sodium peroxide
prepared in liquid ammonia, the literature pro- 4NasBi + 502 +
vides very little information concerning their re- 4Bi0 + 6NaOH + 6NaNH2 (2a)
actions in this m e d i ~ m . ~
The present paper is
concerned with the preparation Of trisodium
4NaaBi + 8% +4Bi0 + 6NatO2 (2b)
I n addition, the following reactions of trisodium
monobismuthide and the study of its properties as monobismuthide have been observed,
a reducing agent in liquid ammonia. Since there
is no known method for the production of pure so- NasBi + 2Bi +NarBi (3)
dium bismuthate, it was of interest (particularly in 2NarBi + 6NH4Br 2Bi + ONaBr + 6NHa i-

-
+

3Hz (4)
view of the work of McCleary and Fernelid) to
determine whether trisodium monobismuthide NarBi +
3AgI +Bi 3Ag +
3NaI + (5j
NasBi f BiIa +2Bi -I- 3NaI (6;
could be oxidized to sodium bismuthate by treat- 2NalBi + BirOs + 3NHs
ment with molecular oxygen. 4Bi 3NaOH+ 3NaNHr + (7)
Trisodium monobismuthide was prepared by In the course of this work the conventional type
the reaction
of apparatus for the study of reactions in liquid
BiIa -I- 6Na +NaaBi + 3NaI (1) ammonia at its boiling temperature has been
Treatment of the purified monobismuthide with modified extensively. The major improvements
molecular oxygen leads not to sodium bismuthate are concerned with technique for filtration in a
(1) This work was supported, in part, by grants from The Uni-
closed system.
versity Research Institute, Project No. 25. Experimental
(2) Presented at the Second Southwestern Regional Meeting of Appmatug.-with the exceptions noted below, the
the American Chemical Society, Dallas, Texas, Dec. 13, 1946. over-all details of construction and mode of operation of
(3) Present addr-: Department of Chemistry, The Oklahoma A. the equipment shown in ~ i 1 are ~ similar
. to those de-
nnd M. College, Stillwater, Oklahoma. scribed by Johnson and Fernelius.6 Both reactors A
(4) Johnson and Fernelius, J . Cirem. Educafiolc, 7,981-999 (1930).
( 5 ) McClenry and Fernelius, THISJOURNAL, 66, 803 (1934). (6) Johnson and Fernelius, J . Chem Education, 6,445 (1929)