January 15, 1931 INDUSTRIAL A N D ENGINEERING CHEMISTRY 85

merely dipping it into the fused salt. In this manner the first point of inflection from the standpoint of time consumed
time of preparation of the reference electrode is greatly and of agreement of duplicate experiments. Obviously,
reduced (6). The silver-silver chloride electrode was dibasic acids and a mixture of acids of widely different
placed in the solution to be titrated together with the agar- strengths as well as the relative quantities of the acids present
agar electrode. The connections were changed after each in the mixture have a bearing on the problem.
addition of the alkali and the resulting points of inflection It is interesting to compare the order of the acids as deter-
agreed very well. Apparently there is no diffusion of the mined by the potential of the cell a t the halfway point of
benzoic acid from the reference electrode into the unknown titration. The well-known relation between the ionization
acid sample when the agar-agar plug is correctly made constant and the hydrogen-ion concentration in water a t the
(Figure 4). An off-balance of roughly 2 millivolts on the halfway point of titration should enable one to arrange the
potentiometer can be observed when employing the agar-agar acids in order of their strength. The solvent in our experi-
electrode whereas with the silver-silver chloride electrode, ments was butyl alcohol, the single potential of the silver-
an off-balance of 0.5 millivolt is perceptible. silver chloride electrode in butyl alcohol is unknown, and the
All the calculations in this paper are based on the first point effect of the acid or acids in the solvent is unknown. How-
of inflection which experimentally may be distinguished ever, the relative position of one acid to another should
from the second by the color of the solution, In the former remain unchanged. The e. m. f. a t the halfway point of
the solution is amber, whereas in the latter the solution is titration when graphically obtained is approximate, since
dark brown to black. If the first point of inflection is not few points are ordinarily taken in that region of the curve.
obtained, the result is in error due to over-titration. Table I11 contains these data.
Additional electrometric titrations (Figures 5, 6, 7), em-
ploying the silver-silver chloride electrode as the reference Table 111-Order of Acids a s Determined by E. M. F. a t Halfway
Filtration Point
electrode, were carried out in which known acid oil sam- E. M. F. at
ples were added in equivalent amounts to the unknown acid HALFWAY Ko IN
in the solvent as calculated by the first point of inflection. ACID POINT WATER
Hydrochloric 340
In this manner two points of inflection were obtained in the Salicylic 120 1 x 10-
experiment in which abietic acid was employed (Figure 51, Benzoic 65 6 X 10-6
whereas in Figure 1, employing five times as much abietic Cyclohexane carboxylic acid 40
acid, only one point of inflection was obtained. Apparently, Technical naphthenic 40
8 preliminary titration is necessary in order to carry out Stearic 25
Abietic 20
satisfactorily an electrometric titration of an unknown oil
sample. Three points of inflection were obtained when Literature Cited
titrating hydrochloric acid. It is quite probable that the
unknown acid in the solvent is not hydrochloric. Benzoic (1) Clarke and Wooten, J . Phys. Chem., 33, 1468 (1929).
and salicylic acids behaved as a single acid. The question (2) Furman, IND. ENG.CHEM.,Anal. Ed., 2, 213 (1930).
(3) MacInnes and Jones, J . A m . Chem. Soc., 48, 2831 (1929).
arises as to the use of the second point of inflection in the (4) Rabinowitsch and Kargin, 2. Elektrochem., 34, 311 (1928).
calculation of neutralization numbers. As applied to the (5) Seltz and McKinney, IND. ENG.CHEM.,20, 642 (1928).
acids used in these experiments, the authors prefer the (6)Seltz and Silverman, I b z d . , Anal. Ed., 2, 1 (1930).

Oxidation of Ferrous Iron bs Iodine in Presence of

Phosphate and Non-Existence of a Ferriphosphate
Complex'
Walter D. Bonner and Hendrick Romeyn, Jr.
UNIVERSITY OR UTAH, SALT LAKECITY, UTAH

N 1926 Bonner and Yost +

The reaction F e + + '/zIZ aq. +Fe+++ I- goes + ion (7). Any iodate pres-

I ( I ) published a method
for the determination of
ferrous iron using sodium hy-
to completion in the Presence of Phosphate and of a
moderate concentration of acid. This reaction, even
in solutions almost neutral, is too Slow to be O f analyti-
ent is a t the same time re-
duced to iodine by the iodide.
The liberated iodine is then
pochlorite as the oxidizing cal significance. titrated with t h i o s u l f a t e ,
agent. This method in brief The reason for the completion of the reaction is The r e a c t i o n s i n v o l v e d
isasfollows: Jj'errousiron,on probably the decrease in the ratio F e + + + to Fe++ are:
being added to a solution brought about by the addition of the phosphate.
c o n t a i n i n g disodium phos- Probably no complex ion is formed between ferric 2Fe++ C10- + +2H++
p h a t e and s o d i u m h y p o -
chlorite, is immediately oxi-
iron and phosphate, but only a weak electrolyte whose
composition probably ranges from FeP04 in solutions
2Fef++ c1-
31-
10s-
4C10-
4C1-
+ + + ++
+ Hzo (1)
2H++
HzO (2)
&zed to ferric iron and pre- containing little phosphate, to Fe(HzPO&in solutions
cipitated as a p h o s p h a t e . containing an excess of phosphate. The fundamental idea on
Addition of iodide to this mix- which this method is based is
ture results in the liberation of iodine and in the formation of that the ferric iron, converted by the phosphate into a fairly
a certain amount of iodate. Addition of acid dissolves the stable complex, is thus removed from the scene of the re-
ferric phosphate, presumably with the formation of a complex adion. There will therefore be no reverse reaction of ferric
1 Received June 9, 1930. iron with iodide, which ordinarily prevents the titration of
86 ANALYTICAL EDITION Vol. 3, No. 1

BO I I I I I I I approximately neutral are almost immediately oxidized by

iodine. Therefore we also determined the rate of the re-
action at various other acid concentrations. Using aurine
ro indicator to obtain neutral solution, as suggested by Willard
and Hall, we made rate measurements at 25" C. on solutions

60 4 of pH approximately 6.5, 2.5, and 1.5. At pH 6.5, and using

solutions about 0.03 N in ferrous iron, the reaction is complete
in about 6.5 hours. At pH 2.5 about 75 per cent of the iron
has been oxidized in 18 hours. At pH 1.5, the rate is about
the same as at pH 1.0, where most of our measurements were
made.

25' C . ; THIOSULFATE 40° C.; THIOSULFATE60' C.; THIOSULFATE

EQUIVALENT, 23 70 cc. EQUIVALENT, 24.1 cc. EQUIVALENT,
24 1 cr.

I
Thio- Oxi- Thio- Oxi- Thio- Oxi-
Time sulfate dized Time sulfate
Hours Cc. - -9% Hours Cc. %
0 . 0 0 3 7 . 4 5 0:OO 0 . 0 0 33.65 0.0 0.0 33.65 0.0
0 . 7 5 36.81 2 . 7 4 1 . 0 0 2 9 . 3 * 0 . 3 1 7 . 8 1 . 0 2 5 . 1 t0.1 35.5
1 . 0 0 36.80 2 . 7 4 3 . 0 0 2 6 . 0 . L O . 2 3 1 . 5 2 . 5 2 0 . 3 = t 0 . 3 65.0
1 . 5 0 36.47 4 . 1 3 5 . 0 0 2 0 . 8 . t O . 2 5 3 . 1 5 . 0 1 5 . 1 * 0 . 3 77.0
2.00 35.89 6.60
lo 2.50 35.95 6.34
3 . 0 0 35.76 7 . 1 1
4.00 25.28 9 . 1 4
5.00 34.90 10.78
20.50 30.01 31.40
2 4 . 0 0 29.12 3 5 . 1 8
1.0 20 3.0 410 5.0 6.0
Time in hours
Figure 1-Rate of Oxidation of Iron by Iodine
Using only 5 mg of ferrous iron, we were able to corroborate
the statement of Willard and Hall, referred to above. It is
ferrous iron with iodine. The idea of the complex was based interesting to note that we were able to carry out this oxida-
upon the work of Wineland and Ensgraber (7) already referred tion in the absence of phosphate, the ferric iron in this case
60.
being precipitated as the hydroxide instead of as a phosphate.
H. W. Foote (3) has suggested that the above method be
I n the absence of phosphate, however, the results were erratic
further simplified, either by direct titration of the ferrous and usually low. These neutral solutions either with or with-
iron by iodine in the presence of phosphate, or by adding out phosphate are very sensitive to atmospheric oxidation, and
an excess of iodine solution also in the presence of phosphate, air must be rigorously excluded.
and ititrating back with thiosulfate. That these proposed
modifications were not practicable was known to Bonner and
Theoretical Considerations
Yost at the time they wrote their paper. Nevertheless, acting
on Foote's suggestion, we have made a more careful examina- Since this reaction goes actually though slowly to com-
tion of the reactions involved.
pletion, and if the formation of a ferriphosphate complex
Rate of Oxidation of Iron by Iodine might be assumed, the explanation seems almost obvious,
The two reactions whose rates are involved are evidently:
We first determined the rate of the oxidation of ferrous iron
Fefff + H2P04-+ complex (3)
by iodine in the presence of phosphate, the solutions being
0.1 N in sulfuric acid. I n this way we were able to show
Fe++ +t 1 2 aq.+ Fe+++ I- + (4)
that the reaction actually goes to completion. The procedure Reaction 3 must be rapid, as is evidenced by the work of
adopted was to mix together, in glass-stoppered flasks, 15 cc. Bonner and Yost ( I ) , Reaction 4 is probably rather slow
of 0.1 N ferrous sulfate solution; 15 cc. of 0.3 N disodium and the equilibrium is known to be established quite slowly.
phosphate solution; 25 cc: of 0.1 N iodine solution; 50 cc. of
water. The mixed solutions were always 0.1 N in sulfuric
-acid which was added with the ferrous sulfate solution.
These flasks were kept in a thermostat at the desired tem-
perature, At definite intervals a flask was removed and the
excess iodine titrated with thiosulfate. A large number of
these determinations was made, and the results are readily
reprod'ucible. Figure 1 shows that the reaction is very slow
at 25" C., being in fact less than 50 per cent complete in 24
hours. At 40" C. the reaction is complete in about 15 hours, Figure 2-Potentiometric Titration of Ferric-Ferrous Solution
and at 60" C. in about 9 hours. We have no explanation for w i t h Phosphoric Acid
the curious hump in the 25" C. curve.
The data on which the curves of Figure 1are based are given At equilibrium and in the absence of phosphate, only a small
in detail in Table I. Each titration given is the mean of at part of the iron has been oxidized. The reason that Reaction
least two determinations. The precision of the experiments 4 goes to completion as written must be that the concentration
at 40" and 60" C. is of course much less than that of experi- ratio Fe+++to Fe++ in the presence of phosphate and a low
ments at 25" C. due to the higher vapor pressure of the iodine H + concentration is smaller than the equilibrium ratio of
causing some loss from the solutions. Fe+++to Fe++ in the same reaction, phosphate being absent.
Willard and Hall (6) have shown that small amounts of This latter equilibrium ratio is readily determined, and is
ferrous iron in the presence of phosphate and in solutions known to be approximately 10-3 (2). I n order to show what
January 15, 1931 INDUSTRIAL AND ENGINEERING CHEMHTRY 87
the ratio Fe+++to Fe++is in a solution containing phosphate, part of the color disappeared with the addition of the first
the following experiments were performed: cubic centimeter of phosphoric acid. Ten cubic centimeters
A solution was made up containing 25 cc. of 0.05 M ferrous of 0.1 N ferric chloride solution are almost completely de-
sulfate solution, 0.5 cc. of 0.05 M ferric sulfate solution, colorized by 0.5 cc. of 85 per cent phosphoric acid. These
Q.5 cc. of 0.1 N sulfuric acid solution, and 25 cc. of water. observations suggest that some compound richer in iron than
The ratio Fe+++ t o Fe++ in this solution was 0.02 or lo-1.70. is the primary phosphate is present in the solutions which
The measured e. m. f. of this solution a t 25 O C. against a normal contain little phosphoric acid. I n the second case cited,
calomel electrode was 0.359 volt. An entirely similar solu- the ratio of phosphate to iron is 1, suggesting the formula
tion was then made up, excepting only that the 25 cc. of FePOd.
water were replaced by 25 cc. of a 0.3 molal solution of di-
sodium phosphate. This solution gave an e. m. f. against
the same calomel electrode a t 25” C. of 0.255 volt. From
these measurements, by means of the relationship
E = E, 4-0.059 log Fe+++/Fe++
we calculate that the ratio Fe+++ to Fe’+ is now 10+a46.
The addition of the phosphate has therefore greatly decreased
the concentration of Fe+++ in the solution, and has de-
creased the ratio Fe+++ to Fe++ to a value markedly less
than the equilibrium ratio of Reaction 4. This seems to
substantiate our previous statement that the reason this
reaction goes to completion must be the decreased ratio
F e + + + to Fe++. This may be brought about by the for-
mation of a ferriphosphate complex. This conclusion is
made the more plausible by the fact that while the reaction
is completed in solutions 0.1 N in sulfuric acid, the reaction
is not completed in solutions approximately 3 N in acid.
I n other words, a t acid concentrations such that this hypo-
thetical complex cannot form, equilibrium is established with
but little Fef++ present. If one carries out this oxidation in
solutions nearly neutral, the progress of the reaction is ac-
companied by the formation of a white precipitate, pre-
sumably a ferric phosphate. This precipitate, filtered out
and washed, dissolves slowly in 3 N sulfuric acid to a colorless
solution. Addition of iodide to this solution liberates, a t
once, an abundance of iodine, showing that a t such an acid
concentration, the reaction cannot go to completion.

Non-Existence of Ferriphosphate Complex

The fact that the oxidation of ferrous iron by iodine fails to
proceed in the presence of 3 N acid seems to indicate that any
complex which may be formed is not a very stable one.
The evidence for the existence of such a complex seems to be
furnished entirely by the work of Wineland and Ensgraber
(7) who assign to it the formula Fe (PO&---. If any com-
plex is formed, even of moderate stability, it should be pos-
sible to determine both its presence and its composition by
means of a potentiometric titration of a ferric-ferrous solution
with phosphoric acid (e). Such a titration has been carried
out and its graph is given in Figure 2. For purposes of
comparison, the graphs obtained by titrating (a) silver nitrate
with potassium cyanide and (b) silver nitrate with ammonia,
Figure 3, are inserted. As is readily seen, the iron-phosphate
graph shows no indication of any complex as stable as the
silver ammonia complex. From coordination considerations,
the most likely complexes should be Fe(HPO&--- or
Pe(H2P04)6---. No indication is given of either of these.
The existence of any ferriphosphate complex must, therefore,
be called in question and the behavior of ferric solutions con-
taining phosphate attributed to the formation of a weak
electrolyte. Since, as the graph shows, the rapid change in
the Fe+++ t o Fe+’ ratio has ceased when the ratio of phos-
phate to ferric iron has become about 3, we may conclude
that the ultimate composition of the weak electrolyte ap-
proximates Fe(H2P04)3. However, the addition of a small
amount of phosphoric acid removes most of the color from a
ferric solution. Thus, in the titrations just cited, the greater
Figure 3-Titration of Silver Nitrate
The white precipitate referred to above, which forms during
the oxidation of ferrous iron by iodine in nearly neutral
solutions containing phosphate, contains as an average of 4
analyses, 26.8 per cent iron. These analyses were made by
the method of permanganate titration, following reduction
with stannous chloride ( 5 ) . Similar analyses made of the
product called by Wineland and Ensgraber “alkali free
ferriphosphoric acid” gave 26.6 per cent iron. As the com-
pound Fe2(HP0& contains 28.0 per cent iron, it is probable
that each of these substances is the secondary ferric phos-
phate.
Acknowledgment
A part of this work has been done by the senior author in the
Gates Chemical Laboratory of the California Institute of
Technology. He wishes here to express his appreciation of
all the many courtesies shown him.
Literature Cited
(1) Bonner and Yost, IND. END. CHEM.,18, 55 (1926).
(2) Fales, “Inorganic Quantitative Analysis,” p. 291, Century, 1925.
(3) Foote, “Annual Survey of American Chemistry,” Vol. 2, p. 134 (1927).
(4) Kolthoff and Furman, “Potentiometric Titrations,” p. 99. Wiley, 1925.
(A) Treadwrll-Hall. “Analytical Chemistry,” pp. 11 and 609, Wiley, 1919.
(6) Willard and Hall, J . A m . Chew. Soc., 44, 2244 (1922).
(7) Wineland and Ensgraber, 2. anorg. Chern., 84, 340 (1913).