V O L U M E 27, NO.
10, O C T O B E R 1 9 5 5
perchloric acid, but did not interfere with the discernment of the
equivalence point. The addition of acetonitrile to the titration
solutions prevented precipitate formation; however, as commer-
cial grade acetonitrile is slightly basic, it was necessary to apply
a blank correction when it was used. I n analyzing tobacco sam-
ples the indicator end point was found to be sufficiently sharp not
to warrant the continued use of acetonitrile. However, aceto-
nitrile addition to the titration solutions would be advant:igeous
in the assay of commercial nicotine solutions.
It is believed that this procedure offers several advantages as a
routine procedure for alkaloid analyses. All of the alkaloids
are removed from the tobacco in a 15-minute extraction period,
the hydrocarbon extract may be titrated directly, thus eliminat-
ing the acid extraction and indirect titration steps necessary in
other titration procedures, no distillation is required as in the
gravimetric and spectrophotometric procedures, ammonia may
be eliminated as an interfering rnaterial in the analysis, and a
means is provided for determining tertiary and secondary alka-
loids in the same solution.
ACKNOWLEDGMENT
The authors wish to express their appreciation to Abner Eisner,
Eastern Regional Research Laboratories, for a supply of nor-
nicotine picrate; to Forrest Houston, University of Kentucky, for
furnishing some of the samples and analyses used in this study;
to Frank B. Wilkinson, Tobacco Branch of the Agricultural
Marketing Service, U. S. Department of Agriculture, for per-
mission to use data obtained on tiamples submitted by his com-
mittee; to Joel P. Clingman and Herman H. hlusselwhite for the
silicotungstate analyses; and to Jacquelyn B. Conrad for her
asyistance in the precision studies.
Vol umetric Determination of Zi iconium
An Ethylenediamine Tetraacetate Method Involving Back-Titration with Bismuth
JAMES S. FRITZ and MARLENE JOHNSON
institute for A t o m i c Research and D e p a r t m e n t of Chemistry, /ora State C o l k g e , Amos, lowa
Zirconium can be determined in acid solution by addi-
tion of excess ethylenediamine tetraacetate, followed
by back titration with bismuth nitrate. Thiourea is
used as the indicator. Verj few metals form complexes
which are strong enough to interfere with the method.
Most complexing anions, including sulfate, phosphate,
oxalate, thiocyanate, and tartrate, do not interfere.
Fluoride (except in low concentrations) interferes but
can be removed easily by fuming w-ith perchloric or sul-
furic acid. Slight modification of the procedure per-
mits determination of zirconium in the presence of
moderate amounts of thorium, titanium, niobium, or
tantalum without separation.
F OR many years macro quantities of zirconium have been de-
termined by tedious, time-consuming gravimetric methods.
Recently, however a number of titrimetric procedures have been
proposed. Kolthoff and Johnson ( 4 ) reported an amperometric
titration of zirconium, thorium, tin, and uranium with m-nitro-
phenylarsonic acid. White (8) developed an alkalimetric method
for zirconium following the quantitative isolation of zirconium
mandelate. Dhar and Das Gupta ( 1 ) determined zirconium by
either colorinctric or volumetric means following precipitation
with oxalohydroxamic acid. Fritz and Fulda (3)developed a
1653
LITERATURE CITED
(1) Assoc. Offic. Agr. Chemists, Official 1Iethods of Analysis,
7th ed., p. 69, 1950.
(2) Avens, A. W., and Pearce, G . W., IND. ESG. CHEX,Axar.. ED.,
11, 505 (1939).
(3) Bertrand, G.. and Javillier, AI., B t d . soc. c h i m . F r u m e , 5 ,
241 (1909).
(4) Rowen, C. V.,and Barthel, W. F., ISD.EXG.CHEhf., ASAL.
ED.,15, 596 (1943).
(5) Ibid., p. 740.
(6) Chapin, R. 11.,C . S.Dept. Agr., Bur. Animal Ind., Bull. 133
(1911).
(7) Garner, W. W.,Bacon. C. W.,Bowling, J . D., and Brown,
D . E., U. S.D e p t . -4gr., Tech. Bull. 414, 35 (1934).
(8) Griffith, K. B., and Jeffrey, R. K.,~ ~ X A LCHEII., . 20, 307
(1948).
(9) Houston, F. G., Ibid.,24, 1831 (1952).
(IO) Jeffrey, R. K.,J . Assoc. Oflc.Agr. Chemists, 34, 843 (1951).
(11) Kissling, R., U. S. Dept. Agr., Bur. Chem.. BiiZZ. 107, rev. 32
(1912); 2. anal. Chem., 21, 64 (1882).
(12) Larson, P. S.,and Haag, H. R., IXD.ESG. CHEX.,.IN.AL. ED.,
16, 86 (1944).
(13) Narkwood, L. N., J . Assoc. Ofic. Agr. Chemists, 22, 427 (1939).
(14) Ibid., 26, 283 (1943).
(15) Ogg, C. L., Willits, C. O., and Ricciuti, C. R., ANAL.CHEM.,22,
336 (1950).
(16) Schloesing, >I., Compt. rend., 23, 1142 (1846).
(17) Seaman, W..and Allen, E., ANAL.CHEM.,23, 592 (1951).
(18) Siggia, S.,Hanna, J. G., and Kervenski, I. R., Ibid., 22, 1295
(1950).
(19) Toth. J.. Chem.-Zto.. 25. 610 (1901).
(205 Wagner, C. D., Brown, 11. H.;andPeters. E. D . , J . Am. Chem.
Soc., 69, 2609 (1947).
(21) Willits, C . O., Swain, 11. L., Connelly, J. A., and Brice, B. A.,
ASAL. CHEM.,22, 430 (1950).
(22) Wolff, W. A., Hawkins. 11..1.,and Giles, W.E., J . B i d . Chem.,
175, 825 (1948).
RECEIVEDfor review January 3, 1955. .4ccepted May 21, 1955.
selective method in which zirconium is titrated u ith disodium
ethylenediamine tetraacetate [disodium (ethylenedinitrilo) tet-
raacetate EDTA] using Eriochromecyanine indirator. Milner
and Phennah ( 5 ) isolated the zirconium in zirconium-uranium
alloys by means of mandelic acid, then added ewes5 E D T A
and back-titrated the excess with ferric chloride using salicylic
acid indicator. Very recently Olson and Elving ( 6 ) published a
procedure for the amperometric titration of zirconium with cup-
ferron.
In the new method, excess E D T A is added to the sample,
forming a stable complex with zirconium. The excess is then
titrated 1%ith bisumuth nitrate using thiourea indicantor. The
p H , indicator concentration, etc., are the same as described
recently for the titration of bismuth (2). Few metal rations in-
terfere because zirconium and bismuth form stronger complexes
with E D T A than most metals, and in the back-titration bismuth
does not react with the thiourea indicator until the metal-EDTA
complexes which are much weaker than bismuth have been bro-
ken. Another important advantage is that zirconium can be
determined in the preEence of such anions as phosphate, sulfate,
thiocyanate, tartrate, and small amounts of fluoride.
EFFECT O F AVIONS
Zirconium can be titrated in the presence of chloride, nitrate,
perchlorate, tartrate, and thiocyanate without an\- difficulty
1654 ANALYTICAL CHEMISTRY

plexes than does thorium [log K for thorium is 23.2 (7)l. I t is

Table I. Titration of Zirconium in Presence of possible to determine zirconium in the presence of limited
Various Anions amounts of thorium or titanium by adding a large amount of
! ! !&o i t aR Zr Taken, Zr Found, Difference, ammonium sulfate as a masking agent.
Added Zr AI& Mg. wig.
Niobium and tantalum cause difficulty in almost all analytical
CNS- 10:1 43 2 43.2 &O.O
methods for zirconium. Niobium and tantalum cannot be kept
20: 1 43.2 43.0 -0.2
F -a 2:s 23.1 23.1 *o.o in a true solution unless a complexing agent is present; precipi-
4:s 23.1 23.1 fO.0 tation of the acid earths brings down appreciable quantities of
2:l 9 0 9.0 10.0
Po,--- 1:l 23.1 23.0 -0.1 zirconium. A completely clear solution can be obtained by dis-
2:1 23.1 23.1 *o.o solving a zirconium sample containing niobium or tantalum in
SiOa ~- 1:l 43.2 43.1 -0.1 hydrofluoric acid plus nitric acid. Sulfuric acid is then added
2:l 23.1 23.1 +0.0
and the solution is evaporated to white fumes. The sulfuric
SOP - - 4:l 23.1 23.2 +o.1
4:l 23.1 23.1 +o.o acid solution is cooled, a strong tartrate solution is carefully
a I n each case fluoride concentrarion was 4 mg. per 100 nil. or less. Con- added, and the analysis is completed by the method used for
centration of thiourea used was douhle t h a t recommended i n general pro- titration of zirconium in the presence of sulfate.
cedure.
Small amounts of iron(II1) and tin(1V) are titrated quanti-
tatively along with zirconium. If the concentration of iron is
too high, the yellow color of the ferric-EDTA complex interferes
with detection of the end point. When more than about 20 mg.
If sulfate is present, a precipitate is formed when excess EDTA of tin are present, precipitation occurs and incorrect results are
is added and the p H is adjusted to 2.0 in preparation for the back- obtained.
titration with bismuth. Extensive boiling will not completely Data for individual titrations of zirconium in the presence of
dissolve this precipitate and the results for zirconium are low. various metal ions are given in Tables I1 and 111. The interfering
Formation of a precipitate can be avoided by adding tartrate be- metal ions are also noted in Table I1 and the formation constants
fore the EDTA. Results for zirconium are still low unless the for the metal-EDTA complexes are given where such information
solution is heated to boiling after the EDTA has been added and is availahle. In Table IT results are given for the analysis of
the p H adjusted to approximately 2.0. Apparently the sulfatr sonie zirconium alloys.
or mixed sulfate-tartrate complex with zirconium is only slon 1)
converted to the zirconium-EDTA complex a t room tempera-
REAGENTS AND SOLUTIONS
ture. If excess EDTA is added to a solution of zirconium chlo-
ride a t room temperature, a large amount of sulfate may then Ammonium Tartrate. Prepare a 10% aqueous Rolution of
be added mithout any interference. diammonium tartrate.
Another way to titrate zirconium successfully in samples con- Bismuth Sitrate, O.05M. Dissolve 10 grams of bismuth metal
in nitric acid. Carefully dilute with distilled water until a per-
taining sulfate is to add a measured excess of EDTA, adjust the manent turbidity appears. Immediately add nitric acid in small
p H to about 6, boil to convert quantitatively to the zirconium- portions until the solution clears. Repeat this alternate addi-
EDTA complex, cool, adjust the pH to 2.0, and titrate. This tion of water and nitric acid until the solution is diluted to 1
scheme may also be e,nployed for titration of zirconium in the liter. Standardize by titration against
- EDTA solution using
thiourea indicator.
presence of phosphate or owdate EDTA. 0.05M. Dissolve 17 grams of reagent m-ade disodium
Fluoride, in concentrations up to 1mg. per 100 ml., does not ethylenediamine tetraacetate [&sodium(etKylenidinitrilo)tetra-
interfere with the titrimetric determination of zirconium. Higher acetate] in 1 liter of water. Standardize against pure zinc metal
concentrations of fluoride cause indistinct end points and low using Eriochromeblack T indicator and pH 10 buffer (amnionia-
ammonium chloride).
results for zirconium. Apparently the total fluoride concentra- Zirconium Chloride, 0.05M. Dissolve 16 grams of zirconium
tion, rather than the ratio of fluoride to zirconium, is the critical chloride octahydrate (which contain less than 100 p.p.m. of
consideration n ith regard to interference. hafnium) in 1 liter of 5% hydrochloric acid. Standardiie gravi-
I n the method of Fritz and Fulda ( 3 ) substances such as col- metrically by ignition to the oxide.
Thiourea, practical grade.
loidal silica absorb the zirconium-indicator complex and make All other chemicals used were of reagent grade.
the end point difficult or impossible to detect. The presence of
moderate amounts of colloidal silica does not interfere in any
n a y with the present method. APPARATUS
Data for individual titrations of zirconium in the presence of All titrations were performed using a 10-ml. buret which could
various anions are presented in Table I. be read easilv to within 0.01 ml. Magnetic stirring ivas em-
ployed. A pH meter equipped with standard glass and calomel
electrodes was used for all pH measurements.
EFFECT OF METAL CATIONS

.Ilthough several of the divalent metals form extremely stable PROCEDURES

complexes with EDTA, none of these was found to interfere ap-
preciably. The slight error observed when cobalt is present
may be caused by partial oxidation to the very stable cobalt(II1)-
EDTA complex. Titration of zirconium in the presence of alu-
minum is very tedious because the aluminum-EDTA complex
is broken only very slowly during the back-titration with bis-
muth. T o avoid this enough cupric ion is added before the
EDTA so that the cupric-EDTA complex will be formed instead
of the slow-reacting aluminum complex.
When thorium or titanium is present, a very gradual end
point is obtained and the determination is not a success. How-
ever, a considerable amount of the thorium-EDTA complex is
replaced by the bismuth during the back titration. This indi-
cates that both zirconium and bismuth form more stable com-
General Procedure. Take a sample or an aliquot containing
13 to 36 mg. of zirconium, and adjust the volume to about 100
ml. Add 10.00 ml. of O.05M EDTA and adjust the p H to 2.0
with dilut,e ammonia or dilute perchloric acid. Add 1.3 grams
of thiourea, and titrate with 0.05M bismuth nitrate to the first
yellow color due to the bismuth-thiourea complex. If the bis-
muth nitrate solution contains much excess acid it may be
necessary to readjust the p H to 2.0 when most of the required
bismuth has been added.
Sulfate or Phosphate Present. iidd 10.00ml. of0.05M EDTA,
and 10 ml. of !O% ammonium tartrate, and adjust the p H to
about 2.0. Boil for about 5 minutes, then cool and dilute to
100 ml. Adjust the p H to 2.0, add 1.3 grams of thiourea, and
titrate with 0.05M bismuth nitrate.
Fluoride Present. Add 5 ml. of 72% perchloric acid, evapo-
rate to fumes, and fume for 5 minutes. Dilute to 100 ml., and
V O L U M E 2 7 , NO. 10, O C T O B E R 1 9 5 5 1655

titrate according t o the general procedure using 2.5 grams of

thiourea. Alternatively evaporate to fumes of sulfuric acid, Table 111. Titration of Zirconium-Tin Mixtures
then follow the procedure given above for sulfate. Zr +Sn, Alilliniole- ~ i f i ~ ~ ~ ~ ~
Niobium or Tantalum Present. Adjust the sample size so ~~-
Zr, RIg. Sn, Mg. Taken Found Millimole
that less than 20 mg. of niobium and tantalum are present. Dis-
solve the sample in hydrofluoric acid or in hydrofluoric-nitric 23 1 12.0 0 353 0.353 -0.002
23.1 12.0 0,355 0.352 - 0 003
arid, then add 5 ml. of sulfuric acid, and evaporate t o fumes. 23.1 21.3 0.434 0.428 -0 009
Thoroughly cool, then slowly add 10 ml. of 10% ammonium 23,l 22.0 0.440 0 438 -0.002
tartrate. Complete the determination as outlined in the pro- 23.1 22.5 0.444 0.437 -0.007
cedure given above for sulfate.
Thorium or Titanium Present. Follow the general procedure, Table IV. Determination of Zirconium in Alloys
but adjust the sample size so that less than 25 mg. of thorium
or 5 mg. of titanium are present. After adding the EDTA, add Stated, Results, % Zr
Composition, Standard EDTA
3 grams of solid ammonium sulfate, then adjust the p H to 2.0, Alloy % Zr lab. methods method
add 1.3 grams of thiourea, and titrate with 0.05M bismuth Zr-Zn 14-18 ...
nitrate. Zr-Zn 15 13.4"
Tin Present. Take a sample or aliquot which contains 13 t o Zr-Th 65
23 mg. of zirconium and not more than 20 mg. of tin. If the Zr-Zn-Rlg 60-80 7fi:ib
Zr-hfg ... 87.56
solution is strongly acidic, adjust the pH t o about 0.5 with am- Zr-s 88 ...
Zr-Zn ... 9,oy
ZrF4 54.9 54.4
Zr(SO4)z 4Hz0 25.9 26 O C
Zr-Nb 91 . .
Zr-Nb 71
" JIandelic acid method.
Table 11. Titration of Zirconium in Presence of Various b Remelting and weighing.
Metal Inns C Pyrohydrolysis.
pK of Metal-
Ratio EDTA Coniplex Zr Taken Zr Found, Difference,
Meta1:Zi (7) Mg. RIg. ME.
1:l 43.2 43 0 -0 2 monia. Add exactly 10.00 ml. of 0.05-11 EDTA and follow the
2:l 43.2 43 1 -0 1
general procedure. Calculate the results a,* millimoles of zir-
1:l 10.13 43.2 43 3 +o 1 conium plus tin.
1:l 43.2 In terf p r e s
1:l 7 76 43.2 42 8 -0.4 Dl SCUSSION
2:l 43.2 42 8 -0 4
1:l , . . 43.2 43 4 +o 2 Hafnium n-ill be titrated along with zirconium. The resulh
2:l 43.2 43 2 1 0 0
obtained will be millimoles of zirconiuni plus hafnium. When
1:l 10.90 43.2 43.1 -0 1
2:l 43.2 43 1 -0 1 millimoles are converted to weight per cent, the amount of haf-
1:l 1G.46 43.2 43 0 -0 2 nium present must be taken into account. If the zirconium-
2:l 43.2 43.0 -0 2
hafnium ratio is not known, it is usually nearly correct to assume
1:l 13.98 43.2 43 6 +o 4 that 2% of the combined metals titrated is hafnium. The
2:l 21.6 21 8 +o 2
1:l 16 31 43.2 43.5 C0.3 "average" atomic weight, is then (0.98 X 91.2) +
(0.02 X
2:l 43.2 43.6 +0.4 178.6) or 93.0.
1:l 18.80 43.2 43.0 -0 2 The new method compares i'avorahlj- with other titrimetric
1:l 25.1 43.2 Interferes procedures which have been proposed for zirconium. It is more
1:l ... 43.2 Interferes convenient and rapid than titrimetric methods which require pre-
1:l 21 8 43.2 43.0 -0.2 liminary isolation of a precipitate. It compares favorably Kith
2:l 43.2 43.1 -0.1
1:l ... 43.2 43.0 -0 2
the method of Fritz and Fulda (3)in accuracy and selectivity and
2:1 43.2 43.1 -0.1 has the additional advantage that sulfate, phosphate, thiocya-
1:l 15.50 23.1 22.8 -0.3 nate, and certain colloids such as hydrated silica do not interfere.
1:l 2.79 43.2 43.0 -0.2 .In advantage of the Fritz and Fulda method (3) is that zirco-
2:l 43.2 43.3 f0.1
nium can be titrated in the presence of large amounts of iron.
1:l 8.69 43.2 43.2 =to 0 Iron interferes in the new method, but the interference is quan-
2:l 43.2 43.0 -0.2
1:l 14.04 43.2 43.0 -0 2 titative if the amount of iron present is not' too great.
2:l -13 2 43 1 -0.1 The selectivity and accuracy of the new method is approxi-
1:l 43.2 Interferes mately comparable to the amperomet,ric titrimetric procedure
1:l 1.66 43.2 43 1 -0 1 of Olson and Elving (6). Their method does not require removal
2:l 43.2 43 1 -0 1
2:s ... 23.1 23 1 IO 0 of fluoride but has t'he disadvantage that the titrant, employed
4:s 23.1 23 0 -0 1 (cupferron) is unstable in solution.
1:l 18.62 43.2 I n t erf Pres
1:l 18 04 43 2 43.7 fO 5 LITERATURE CITED
2:l 43.2 43 4 C0.2
1:l ... 21.6 20.3 -1 1 (1) Dhar, S.K., and Das Gupta, .4.K., J . Sci. Iiid. Research ( I 7 ~ d i a ) ,
1:l 8.63 43.2 43.0 -0.2 I I B , 500 (1952).
2:l 43.2 43.3 +O.l (2) Fritz, J. S., ASAL. CHEY.,26, 1 9 i 8 (1954).
1:l ... Interferes (3) Fritz, J. S., and Fulda, 11.O., Ibid., 26, 1206 (1954).
1:l ... 21.6 21 9 t0.3 (4) Kolthoff, I. >I., and Johnson, 11. .I J,. Electrochem.
, Soc., 98,
1:l 21.6 21.9 to 3 138 (1951).
2:s 23.2 23.1 23 0 -0 1 (5) Milner, G. W. C . , and Phennah, P. J., Aiialyst, 79, 475 (1954).
1:l 23.1 23 6 f O 5 (6) Olson, E. C . , and Elving, P. J., - 4 i v . k ~ .C H E Y . ,26, 1747 (1954).
1:l ... 9,3 96 f0.3 (7) Schwarzenbach, G., Gut, R . , and Anderegg, G., Help. Chim.
2:3 14.6 14 5 -0 1 Acta, 37, 937 (1954).
1:2 18.8 18 7 -0 1 (8) White, J. C., Paper A-21, dnal. Information Meeting. Oak Ridge
2:5 23.1 23 2 T O 1 Kational Laboratory, May 1953.
1:l ... 43.2 43 2 r O 0
2:l 43.2 43 0 -0 2 RECEIVED for review February 17, 1955. Accepted July 5, 1955. Pre-
1:l 16.50 43.2 43 4 +o 2 sented before the Division of Analytical Chemistry at the 127th JIeeting of
2:1 43.2 43 2 =to 0 the AMERICAX CHEMICAL SOCIETY,Cincinnati, Ohio. Contribution No. 395,
- Work performed in the .4nles Lahoratury (if the Atomic Energy Conllnisaion.