V O L U M E 28, N O .

4, A P R I L 1 9 5 6 459

acteristic lines to be counted, and absorption effects in three
regions to consider. The three counts should, however, contain
enough information in many cases to permit the drawing of valid
conclusions.
ACKNOWLEDGMENT
The authors wish to thank G. E. Pellissier, Physics and An-
alytical Chemistry Division, Applied Research Laboratory,
United States. Steel Corp., for the set of tin-plate standards;
and Virginia Thomas and Gloria Kowaleski for help with the
investigation.
, LITERATURE CITED
(1) Beeghly, H. F., J . Electrochem. SOC.97, 152 (1950).
(2) Brissey, R. &I., Liebhafsky, H. d.,Pfeiffer, H. G., 56th Annual
iMeeting, BSTM, Atlantic City, N. J., June 1953, ASTM
Spec. Tech. Publ. 157.
(3) Compton, A. H., Allison, S. K., "X-Rays in Theory and Experi-
ment," 2nd ed., Van Nostrand. ivew York, 1935.
(4) Glocker, R., Schreiber, H., Ann. P h ~ s i k85, 1089 (1928).
(5) Koh, P. K., Caugherty, B., J . A p p l . Phgs. 23, No. 4 , 4 2 7 (1952).
(6) Liebhafsky, H. A., Pfeiffer, H. G., Zemany, P. D., ANAL.
CHEW27, 1257 (1955).
W.,Elec. M j g . 49, 124 ( M a y 1952).
(7) Pellissier, G. E., Wicker, E.
(8) Pfeiffer, H. G., Zemany, P. D., dVczture 174, 397 (1954).
(9) Rhodin, T. N., ANAL.CHEM.27, 1857 (1!355).
(10) Rhodin, T. N., Pittsburgh Conference on Analytical Chemistry
and Applied Spectroscopy, Pittsburgh, Pa., March 1955.
(11) Zemany, P. D., Liebhafsky, H. A., J . Electrochem. SOC.103,
No. 3 (1956).
RECEIVED for review October 3,1955. Accepted January 17, 1956. Division
of Analytical Chemistry, 128th Meeting, ACS, Ninneapolis, Rlinn., Sep-
tember 1955.

Determination of Iron by Ultraviolet Spectrophotometry

ROBERT BASTIAN, RICHARD WEBERLING, and FRANK PALILLA
Sylvania EIecMc Products Co. he., Kew Gardens, N. Y.

A n ultraviolet spectrophotometric method for the 0.7

determination of iron utilizes the absorption of the
ferric ion in perchloric acid solution. The system shows 0.6
excellent stability, good sensitivity, and adherence to
the usual absorption laws. The method has been ap- 0.5
plied to a wide variety of industrial alloys and glass
0.40
samples containing 0.03 to 0.9% iron. Because no 0
special reagents are needed, iron can often be deter- 4
0.30
mined in conjunction with the determination of other
elements, and, if desired, the entire sample can be =:
9 0.20
recovered and used for subsequent determinations.
Owing to the simplicity and rapidity of the method,
0.10
it is well suited for routine analyses. The interference
of a variety of elements is considered.
'200 210 220 230 240 250 260 270 2W 290
WAVE LENGTH (rnp)

T HE ultraviolet absorption spectra of ferric perchlorate

and ferric sulfate solutions have been examined previously
for analytical applications (5). The ferric sulfate system was
Figure 1. Absorption spectrum of iron(II1) in
perchloric acid solution
0.93 mg. of iron(II1) a n d 10 ml. of 70% perchloric acid per 100 ml.
felt to be better because of less interferences encountered from
other metals. Further investigation has shown, however, that
the ferric perchlorate system can be used to advantage in the
analysis of a large number of industrial materials. The precipi-
tation of insoluble sulfates is avoided, and the perchloric acid
medium is often more desirable when other elements are to be
determined on the same solution. I n addition, the sensitivity
is somewhat greater than the ferric sulfate system.

APPARATUS AND REAGEKTS '

The following were used: Beckman Model DU spectro-

photometer with ultraviolet accessories and 1.00-em. silica cells;
primary standard iron metal (Hach Chemical Co., Ames, Iowa);
70 to 72% perchloric acid; methanol; 0.03% hydrogen peroxide
(freshly prepared I to 1000 dilution of 30% hydrogen peroxide).
The above, and other unspecified reagents, were of C.P. quality.

CHARACTERISTICS O F FERRIC PERCHLORATE SYSTEM ml. OF 70% PERCHURIC A C I D PER 100 ml.

The absorption spectrum of ferric perchlorate in excess per-
chloric acid is shown in Figure 1. Although the absorption peak
is a t 240 mp, 260 mu is preferred as the wave length for analysis
because many other metals interfere less a t that point.
The dependence of the absorption on acidity is shown in Figure
2. The absorption rises until about 1 or 2 ml. of perchloric acid
are present per 100 ml., then remains nearly constant up t o high
Figure 2. Effect of acidity
Solutions contain 0.94 mg. of iron(I[I) per 100 ml.
concentrations of the acid. At high acidity, the iron is presum-
ably present as free ferric ion.
A concentration of 10 ml. of perchloric acid per 100 ml. was
460
selected for the analyses. Variations of &5 ml. from this point
gave results within the error in photometric reading (&0.2%
transmittance), so that a graduate can be used to measure the
amount of acid needed.
Adherence of the system to the normal absorption laws is
excellent a t both 240 and 260 mp, up to an absorbance of a t least
0.8. A typical run over this range a t 24" C. gave a molar ab-
sorptivity a t 240 mp of 4.16 X l o 3 f 0.03, and a t 260 mp of
2.88 X 103 zk 0.02 liter per mole cni. These data compare
favorably with those of Buck, Singhadeja, and Rogers (-$), who
found the peak in l d l perchloric acid a t 239 mp and a molar
absorptivity of 4.1 X IO3 liters per mole cm.
The absorbing species is extremely stable. Several solutioiis
allowed to stand for 24 hours showed no significant change in
reading a t 240 or 260 mp. A single solution read a t several times
over a period of 1 month at 260 mp showed no significant change.
An increase in temperature decreases the absorbance a t both
240 and 260 mp. The effect is of the order of a few tenths of
1% per degree (22" to 32' C.) a t 240 mp and considerably less
a t 260 mp. Temperature is, therefore, unimportant for low per-
centage work.
ABSORBANCE OF OTHER METALS
Table I shom the absorbance of other metals which, unless
otherwise specified, are in the valence state normally attained
by fuming with perchloric acid.
Table I. Absorbance of Other Elenieiitse
7" Element Having Absorbance
Equal t o 0.001% Fe
Element 240 m p 260 nw
S i . .41, Mg, Zn, Cd,
Ba, Ca, Na, hIn(I1)" > 100 >IO0
Pn c,n
A number of base metals, including nickel, have an absorption
such that, if the material consisted of 100% of the element,
an error of less than 0.001% iron would result. Of the two m v e
lengths, 260 mp is much more favorable with respect to copper,
lead, and bismuth. If large amounts of copper are present, how-
ever, a separation is indicated. Vanadium and molybdenuni
interfere seriously a t both wave lengths. The interference of
titanium is serious if the ratio of titanium to iron is high, but
often this is not the case.
The high absorption of oxidized chromium makes it desii able
to reduce this element to the trivalent state. This can be ac-
complished by boiling the diluted solution n i t h methanol or
hydrogen peroxide, neither of which affects the absorption of the
iron. The absorption of methanol is so low that i t need not be
removed; however, hydrogen peroxide does have some absorp-
tion and, if a large excess is added, it must be destroyed by boiling.
If chromium is present in large amounts, it can be evolved as
chromium oxychloride by dropping hydrochloric acid into the
fuming perchloric acid solution, taking to fumes again, and le-
peating several times. The residual chromium is then treated
as described above.
Manganese has a very lorn absorption in the divalent state.
When samples containing large amounts of manganese are evap-
orated to perchloric acid fumes, manganese dioxide may separate.
ANALYTICAL CHEMISTRY
This is readily redissolved by the addition of a little hydrogen
peioside. When samples containing 1 to 5 mg. of manganese
per 100 ml. of final dilution were carried through the unmodified
procedure, manganese dioxide did not visibly separate. Results
for iron were high by not more than 0.01 to 0.06 mg., apparently
because of partial oxidation of the manganese to a higher va-
lence. The effect was not reproducible and not always obtained;
it was never obtained on solutions containing less than 1 mg. of
manganese, Boiling the diluted solution with 1 ml. of methanol
or 1 ml. of 0.03% hydrogen peroxide was found to eliminate this
effect. No loner amounts of reducing agents were tried because
the absorption of these amounts is negligible.
ANALYTICAL PROCEDURES
Absence of Significant Amounts of Manganese and Chromium.
The solution should contain about 0.9 mg. (0.3 to 1.5 mg.) of iron
and 10 ml. of excess perchloric acid per 100 ml. of final dilution.
Unless hydrofluoric acid is present, the solution is taken to per-
chloric acid fumes in an uncovered 250-ml. Erlenmeyer flask
provided with a lip. After cooling, the sides are washed down
and the solution is fumed again to expel all volatile acids. The
sides are washed down again, and about 40 ml. of water and a few
glass beads are added. The contents of the flask are boiled for 1
minute to espel chlorine, and silica is filtered off if necessaiy.
After cooling, the solution is diluted t o volume and the absoib-
ance is read a t 260 mp.
Hydrogen Peroxide Reduction. The same procedure is fol-
lon-ed, except that after the final addition of water, the solution
is heated t o boiling and enough hydrogen peroxide is added to
dissolve precipitated nianganese dioxide in high manganese
materials and to reduce chromium present; 1 ml. of 0.03%
hydrogen peroxide will eliminate the manganese effect in the
range of 1 to 5 nig. Four milliliters of 0.03% hydrogen peroxide
have an absorption a t 260 mp equal to 0.01 mg. of iron (about
0.02 mg. of iron a t 240 mp). I t was confirmed experimentally
that this quantity of peroxide is sufficient to reduce slightly
more than 1 mg. of chromium.
The strong color of oxidized chromium often permits limiting
the amount of peroxide added. In an otherwise colorless material,
after taking to perchloric acid fumes and adding a little watei,
0.1 or 0.2 mg. of chromium can be seen. Even in the presence
of 1 gram of nickel, comparison of the cooled solution v i t h a nickel
sample containing no chromium ieveals 0.5 to 1 mg. of chromium.
If a large excess of peroxide is added, it can be destroyed by
boiling in the presence of a catalyst. Several metals, includiiig
iron, act in this manner.
Tests were conducted on solutions containing 0.3 mg. of iron,
10 ml. of perchloric acid, and 30 ml. of 0.03% peroxide. These
were diluted to about 100 ml. in 250-ml. Erlenmeyer flasks and
glass beads v-ere added. The solutions were boiled vigorously for
35 minutes, adding boiling water as needed to prevent evapora-
tion to perchloric acid fumes. Readings a t 240 and 260 mp
checked with those to which no peroxide was added. In the
presence of additional metals, it is likely that this boiling time
could be reduced.
Application of this procedure in the absence of any metals
indicated that appreciable amounts of peroxide mere still un-
destroyed. Therefore, no peroxide should be added to a blal!k;
or, if desired, a standard can be carried through the entlre
procedure.
The hydrogen peroxide reduction method is the one most
\\idely employed in this laboratory. Even if chromium and
manganese are presumed absent, a little 0.03% peroxide is usually
added as a precautionary measure.
Methanol Reduction. The original rocedure is followed, ex-
cept that after the addition of 40 ml. o!n;qter, I ml. of methanol
is added. The solution is heated to boiliyg, then boiled for 2
minutes. This procedure reduces several milligrams of chromium
and eliminates the manganese effect in the range of 1 t o 5 mg.
Methanol, in the amount of 3.7 ml., has an absorption a t 260 mp
equal to 0.01 mg. of iron (4.2 ml. a t 240 mp).
Concentrated perchloric acid or its fumes should not come in
contact with alcohol or its vapor. Standard practice in this
laboratory is to conduct the methanol reduction in a separate
hood reserved for organic materials, and on an electric hot late.
As a further precaution, a dilute solution of methanol mig\t be
added, although this was not done in this work.
EFFECT OF REDUCTANTS
The figures given in Table I can be used as correction factors
(if the correction introduced is not too large) in cases where
interfering elements are piesented in approximately known
V O L U M E 28, NO. 4, A P R I L 1 9 5 6 461

The preferred procedure is the hydrogen peroxide reduction

Table 11. Analysis of Cathode Nickel method using 1 ml. of 0.03% hydrogen peroxide. Results on
% F e Found Av. several ASTM round robin samples using this method are
Heat % Fe Corr. Dev., given in Table 11, along with some results by the alcohol reduc-
N0.G PrescntC Uncorr. for Ti *%
€11400 0.036 0.030 0.035 <0.001
tion procedure.
O.ORFt 0.035 <0.001 A synthetic nickel oxide sample for use as a spectrographic
84 0.000 0.003 0.002 <0.001 standard was also analyzed by this technique. This sample
202 0.063 O.OG4 0.063 <0.001 contains more iron than cathode nickel and about 0.02 to 0.03%
0 OG5b 0.004 0.001
chromium.
1025 0.033 0.033 0.033 <0.001
0.0316 0 031 <o. 001 Metallic samples were dissolved in nitric acid and the oxide
:3153 O.llG 0.113 0.113 <0.001 sample in aqua regia; final dilutions mere 100 ml. Blanks
0.1156 0.115 <o, 001 averaged 0.001% iron and were deducted. The correction for
NiO Lot 1 0.39 0.40 0.40 <o. 01 titanium is not more than 0.001% iron and is probably within
One-gram samples of all except NiO, Lot 1, which was 0.25 gram. the error of either this or the ASTM thiocyanate method ( 1 ) .
b Methanol reduction.
C Average of results from several different laboratories, chiefly b y thio- The perchlorate method is simpler; no correction is needed for
cyanate method.
the nickel background, and the same solution can be used for
the determination of several other elements.
Silica Base Materials. These samples were treated by the
amounts. If methanol is used as a reducing agent, these factors ASTRl Cl69-43 routine method for the determination of RzO,
should remain unchanged. This mas found t o be true in the case alkalies, and alkaline earths in soda lime glass ( 2 ) , with the ex-
of molybdenum and vanadium. ceptions noted. Two-gram samples were dissolved in hydro-
If excess hydrogen peroxide is added and boiled out, the factors fluoric and nitric acids in a platinum dish and fumed trice with
should remain unchanged except for the titanium, molybdenum, perchloric acid; 0.5 gram of boric acid n-as added during the
and vanadium group. Here, only vanadium is partially reduced, second fuming to help expel fluorides. In preparing the final
so that about 4 parts of vanadium equal I part of iron a t both solution, no hydrochloric acid mas added; instead, the required
wave lengths. amount of perchloric acid was used. In eome cases, the samples
I n order to determine the effect upon titanium, vanadium, vere diluted to 100 ml. instead of 200 ml. In the case of sample
and molybdenum of not removing peroxide, from 1.5to 2.0 mg. per 102, an aliquot was taken and diluted further.
100 ml. of these elements were treated with 10 ml. of 0.03% The samples contained very little manganese, and no chro-
hydrogen peroxide in the cold. The readings on vanadium and mium was reported. Nevertheless, except in the cases noted,
molybdenum were lo\\-ered by about 50% because of formation 1 to 2 ml. of 0.03% hydrogen peroxide were added to guard
of peroxy complexes. Although the reading on the titanium against traces of chromium. This n as not boiled out. In some
solution increased, if the reading due to the hydrogen peroxide cases, the solutions .sere very slightly turbid and were filtered
alone mas deducted, it, too, v a s decreased by about the same before reading.
amount. In the presence of 1 ml. of 0.03% peroxide, the ti- Blanks run on the platinum dishes, averaged about 0.004%
t,anium correction factor was essentially the same as in its absence. ferric oxide and were deducted. No corrections were made for
This suggests a possible method for decreasing the interference titanium, because this was negligible in all cases. The valucs
of this group by adding, in the cold, the same amount of peroxide in Table I11 seem to be in satisfactory agreement with those
to samples and standards. Higher concentrations of peroxide obtained by the Bureau of Standards.
could profitably be tried. Because the interference of the above NBS silicon metal sample 57 was analyzed by the same pro-
elements in the samples of interest was small, this subject was
not investigated further.
Table 111. Analysis of Silica Biasc RIaterials
EFFECT OF A N I O N S
Ax-.
h'BS Type of FezOa, % Dev.,
All volatile anions should be expelled by fuming. Nitrates No. hf aterial Present Found i 7c
have a strong absoiption in the ultraviolet region. Chlorides 12s Soda-lime glass 0,039 0.040a 0.001
and fluorides coniples with iron; 10 mg. of fluoride per 100 nil. 0.043 0.002
depressed the absorption of 1 mg. of iron b y 32% a t 260 mp, and 80 Soda-lime glass 0.065 0.059 <0.001
(0.057-0.07)
17% a t 240 nip. The addition of 0.2 gram of aluminum (as 89 Lead barium glass 0.049 0.050a <0.001
perchlorate) reduced this eiror to about 1% a t 260 nip, and to 17.5% PbO, 1.4% BaO 0.052 <0.001
less than 1% a t 240 m p , because of the formation of an aluminum 93 Borosilicate glass 0.076 0.078 0 003
12.76% Bz0a
fluoride complex (6). Boric acid in amounts up to 0.25 gram
102 Silica brick 0.66 0.67 <0.01
per 100 ml. had no effect upon the absorption of iron. O.lG% TiOz
Of the nonvolatile anions, 50 mg. of sulfate ion had no effect No peroxide used.
on 1 mg. of iron a t either wave length. Fifty milligrams of
phosphate increased the reading on 1 mg. of iron by 3% a t 260
nip and decreased it by about 2% a t 240 mp. Table IV. Analysis of Alurniiiiuni Alloys
AXALYSIS O F SAMPLES
% of Other 7cF e Found AV.
NBS Elements of 7F e Dev.,
No. Interest Present Uncorr. Corr. i
Most of the analyses have been done without separating inter- 85.4 cu2.5
fering elements, unless the interference is appreciable. Each Cr 0.23 0.208 0.21 0.21 1 0 01
T i 0.016
value reported in the following tables represents an average of
86C Cu7 9 0.00 0.91 0.90" <0.01
two or three determinations run simultaneously. Ti 0.035
Cathode Nickel. By cathode nickel is meant types 220, 225, a7 Si G 2
and 330 (6). These samples contain 99% minimum nickel Cr 0.17 0 46 0.47 0.46b 0.01
Ti 0.16
(plus cobalt) and not mole than a few tenths of 1% of copper,
Corrected for C u and Ti.
iron, manganese, carbon, silicon, magnesium, and aluminum. b Corrected for Ti.
Titanium occurs in amounts from O . O O ~ ot o about 0.04%.
462 A N A L Y T I C A L CHEMISTRY
The errors introduced by copper and titanium in the samplcs
Table 17. Analysis of nliscellaneous Alloys are, for most purposes, negligible.
% of Other % Fe -4I,. Miscellaneous Alloys. Table V shows results on materials in
NBS Elements of Separation Der., which separations were made as indicated. The residual chro-
No. Interest Procedure Present Found & %,
157 Cu72 Cu plated out 0.053 0.054 <0.0)1 mium in No. 169 was reduced by excess hydrogen peroxide, which
Ni 18 was boiled out. Hydrogen peroxide reduction was also used on
Zn 9 . 7
No. 162. The values given are uncorrected; the results would be
169 Ni 77 Cr volatilized as CrOZClz 0 . 5 4 0.54 <0.01
Cr 20 with HC1 the same if the corrections were applied for vanadium and tita-
v 0.01s nium. I n the case of Nos. 169 and 162, 1-gram samples were car-
I62 Ni 66 Ge isolated by single 0.31 0.34 <0.01 ried through the reduction procedure, and suitable aliquot3
c u 29 precipitation with
Mn 2 . 3 ammonia taken.
Cr 0 . 2 4
Ti 0 . 2 0 Sample 169 was also analyzed without separating chromium;
this element instead was reduced with methanol. Uncorrected,
a value of 0.b6Y0 iron mas obtained; corrected for chroniiuni
and vanadium, this result was 0.53%.
cedure; a value of 0.66% iron was obtained against a certified
value of 0.650/,.
Aluminum Alloys. Table IV shows results on sonic aluminun? LITERATURE CITED
alloys. Samples 858 and 86C mere dissolved in aqua regia. (1) Am. SOC.Testing Materials, Philadelphia, Pa., Committee B-4,
Hydrogen peroxide was the reducing agent; the vioual end point Tentative Photometric Methods for the Chemical Analysis of
w ~ used
s with a slight excess added. Sample 87 was dissolved Electronic Nickel, E-54T, 1954.
in Eodium hydroxide in a nickel crucible. The reaction mixture ( 2 ) Am. SOC.Testing Materials, Standards, P t . I I , 1944.
was transferred t o an Erlenmeyer flask with dilute hydrochloric (3) Bastian, R., Weberling, R., Palilla, F., AXAL.CHEM.25, 284
acid. Nitric and perchloric acids mere added, the solution was (1953).
(4) Buck, R. P., Singhadeja, S., Rogers, L. B., Ibid., 26, 1240 (1954).
taken to fumes, silica filtered off, and chromium reduced with
hydrogen peroxide. An identical result mas obtained on inother (6) International Nickel Co., Inc., New York, "Inco Nickel Alloys for
Electronic Uses," 1951.
sample which mas dissolved in sodium hydroxide in a nickel (6) T'anossi, R., Anales amc. gulm. aroentina 29, 48 (1941).
crucible and taken up in dilute perchloric acid. The iron was
oxidized dropwise with permanganate, and the excess per- RECEIVEDfor review November 3, 1955. Accepted January 28, 1956,
manganate reduced with methanol. In this case only a very Pittsburgh Conference on Analytical Chemistry and Applied Speotroscopy.
small amount of silica separated. Pittsburgh, Pa., March 1955.

Reaction of Hydrogen Peroxide with Complexes of (Ethylenedinitril0)-

Tetraacetic Acid and Nitrilotriacetic Acid
KUANG LU CHENG' and PETER F. LOTT
Department of Chemistry, University of Connecticut, Storrs, Conn.

New color reactions of iron and cobalt with (ethylene-

dinitri1o)tctraaeetic acid (EDTA) and iiitrilotriacetic
acid (NTA) in the presencc of hydrogen peroxide at pI1
above 10 are reported. Iron-EDTA gives a purple color
and iron-NTA gives an unstable brown color upon addi-
tion of hydrogen peroxide. Under similar conditions,
cobalt-EDTA gives a bluc color and cobalt-NTA gives
a purple color. It is believed that these colored coni-
pounds are peroxy coniplexcs. The results of the tests
for all coninioxi iuetals arc reportcd, and the possibilitics
of applying these color reactions to analysis of iron,
cobalt, NTA, and EDTA are discussed. A simple and
selective procedure has bcen dcvelopcd for the spcctro-
photometric dcterniinntion of uranium in the presence
of other iiictals 13y using a mixture of NTA, hydrogen
peroxide, and aninioniuni hydroxidc. NTA co~nplexes
most interrering metals and prevcnts thein from form-
ing interfcring colors or precipitates. At a ~ v i l v elength
of 4'8.5 m p , the use of NTA pcrinits the nieasurcnieiit of
uranium in the prcsence of iron, inolylxlciiunii, and
vanadium.
I Present address, Westinghouse Electric Corp., East Pittsburgh, Pa.
T HE use of chelating compounds for masking interfering
metals has been a subject of continuing interest. (Etliylene-
dinitri1o)tetraacetic acid and nitrilotriacetic acid have relatively
weak power to chelate uranyl, molybdate, vanadate, tungstate,
and chromate ions which exist in solution as charged groups in-
stead of free metal cations. Determination of molybdenum,
tungsten, and uranium based 011 this principle has been reported
( 4 , 6, 7 ) .
Results are given here which show the masking effect of nitrilo-
triacetic acid on the hydrogen peroxide method for uranium and
the interesting color reactions of peroxide with the iron and cobalt
complexes of (ethylenedinitri1o)tetraacetic acid and nitrilotri-
acetic acid.
COMPLEXING INTERFERING METALS WITH
NITRILOTRIACETIC ACID IN HYDROGEN PEROXIDE
METHOD FOR URASIUM
Several methods for the determination OF uranium, based 011
the yellow color of the uranium peroxide compound, have been
reported (1, 5,8). None is satisfactory without the separation
of interfering substances, except that iron may be complexed with
tartaric acid. No previous reference has been found on the use
of nitrilotriacetic acid or (ethylenedinitri1o)tetraacetic acid for
complexing interfering metals in the determination of uranium
with peroxide. A procedure for the elimination of interfering