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EDTA AND COMPLEX FORMATION

A Demonstration Lecture
M. B. JOHNSTON and A. J. BARNARD, Jr.
J. T. Baker Chemical Company, Phillipsburg,
New Jersey

H. A. FLASCHKA
Georgia Institute of Technology, Atlanta, Georgia

BYTHEIR nature general textbooks often lag by many


years in their inclusion of salient advances in analytical
reagents. Teachers are aware of this lag when confronted with the necessity of up-dating lectures and
courses. Often this requires tedious collection and
digestion of data scattered through the world literature.
Such is the case with EDTA. Only a few current
textbooks devote space to this versatile titrant, masking agent, and chromogenic agent. A few books
confine their remarks to the EDTA titration of water
hardness, but give only limited background information
even for this special application.
It is the purpose of this paper to aid in resolving this
problem by presenting some integrated experiments
designed to serve as a general introduction to watersoluble chelates, and especially to EDTA and its use
in analytical chemistry. These experiments also delineate some special aspects of metal complexes that are
sometimes a source of practical difficulty, and that, on
the other hand, can sometimes be applied to advantage
in chemical analysis. The experiments are scaled to
serve as lecture demonstrations; however, they can he
readily adapted to student use by employing the same
reagent solutions and reducing the volumes employed
appropriately (with the exception of Experiment I X
which can he performed as given).
All of the reagent solutions, with two exceptions, can
be readily prepared from reagent chemicals availahle

(After Martell)

VOLUME 35, NO. 12, DECEMBER, 1958

in most instructional laboratories. The two special


reagents, disodium ethylenediaminetetraacetate dihydrate and Eriochrome Black T (Erie T for short), are
readily available through laboratory supply houses.
The intention is not merely t o give 'Lcook-book"
recipes but also to provide some background information by discussion of the experimental phenomena.
This information can only he presented briefly and in
summary form. Hence, a selected bibliography is appended that cites some relevant monographs (1-4), reviews (5-11), trade literature (13-id), and a few papers
of historic interest (10,15-17).
EDTA is the alphabetic designation for ethylenediaminetetraacetic acid or its anion form ethylenediaminetetraacetate.
HOOC-H,C
)N.cH~cH,N<
HOOGHC

CHrCOOR
CHrCOOH

Ethylenediaminetetraacetic acid

NaOOC.H&

CHrCOONa

[ HWC
CH&OOH

Disodium ethylenediaminetetrrtacetilte dihydrate

Because of the very low water solubility of the free


acid, a solution of the disodium salt is usually employed
as the reagent. The usefulness of EDTA stems from
the presence of six ligand groups which permits honding with an equal number of coordination positions of a
metal ion. I n almost all cases a 1:l metal-EDTA
complex (chelate) is formed and in a single step. The
presence of carboxylic acid groups confers water solubility on such metal complexes. The steric configuration (18) of a metal-EDTA complex is shown in the
figure. A fuller treatment of the theoretical background for the use of EDTA will be found in works
cited in the bibliography (1-4, 10-11,16-18).
The following sections of this paper present the directions for the preparation of the required reagents,
followed by the experiments. The experiments are
arranged so that the principles or phenomena to be
studied are briefly summarized followed by working
directions into which are interpolated brief statements
concerning the observations.
The final experiment (IX) is an actual EDTA titration. Rather than a study of the simple titration of a

single metal ion in pure solution, a slightly more complicated example has been selected which familarizes the
student with such phenomena as indicator-blocking and
masking. This titration can be performed either as a
lecture experiment or as an actual student laboratory
determination (using, if desired, "unknown" solutio&
or mixtures of magnesium and iron(II1) salts).
REAGENTS

The following directions yield amounts sufficient to


conduct Experiments I through VIII twice, and Experiment IX about twenty times if it is to be conducted
quantitatively as a student exercise. All chemicals
employed should be of reagent grade.
EDTA, 0.1 M . Dissolve 18.6 g. of disodium ethylenediaminp
tetraacetate dihydrate; dilute to 500 ml. with H20.
Stock water. Use exclusively water free of metal ions, either
carefully redistilled or deionized via cation exchange. (Often
"distilled" water contains interfering amounts of metals.) For
demonstration purposes (is., except in Expt. IIID or in Expt.
IX, when conducted quantitrttively), ordinary distilled water
may be used if interferences are excluded by addition of 5 drops
of 0.1 M EDTA per liter.
Erio T solution. Dissolve 0.1 g. of Eriochrome Black T in 25
ml. of methanol (must be freshly prepared); alternatively, use
a 1: 100 ground mixture with NaCl (indefinitely stable).
Buffer, pH 10. Dissolve 35.0 g. of NHCI in 200 ml. aqueous
NH, (taken directly from supplier's battle); dilute to 500 ml.
with H20.
Buffer, pH 6. Dissolve 21.8 g. of sodium acetate trihydrate
and 5.2 ml. of glacial acetic acid in H20; dilute to 250 ml. with
HZO.
Buffer,pH 5. Dissolve 2.7 g. of sodium acetate trihydrate in
19.2 ml. of 1 M HC1; dilute to 100 ml. with H20.
Metal salt solutions. Prepare 100 ml. of 0.1 M aqueous salutions of the following salts: BaCL, Cr(NO,),, Ni(NO&, K2CreOi,
Zn(NO&, and 200 ml. of the following: Mg(NOa)., FeCl..
Bismuth nitrate, 0.1 M . Dissolve 4.9 g. of Bi(NOa)r5H?0in
3 ml. of coned. HNOs and 10 ml. of H20. When solution is complete, dilute to 100 ml. with H20. (Do not employ heat to effect
&lution.)
Other s~lutionsinclude methyl orange (0.1 g./lW ml. of H20),
100 ml. 15% KI, 10 ml. 10% (NHJaSO,, 100 ml. 1 M NaOH,
100 ml. 1 M HC1,3% H202.
Solid reagenk include KCN, tartaric acid, ascorbic acid (reagent ar U.S.P.).
Standard Solutions for Ezpt. I X . Use only deionized or redistilled water in the preparation and comparison of the following
standard solutions.
EDTA, 0.0100 M . Dry about 4 g. of reagent grade disodium
ethylenediaminetetraitcetate at 80C. for about 2 hours. Weigh
accuratelv 3.722 e. of this dried material, dissolve in and dilute
d o n e h e r in a volumetric flabk. Transfer the saluwith ~ . to
tion at once to a polyethylene bottle for storage.
Mapesium nit~afe
standardized soh. Dilute 50 ml. of the 0.1
M Mg(NOa)%
to 500 ml. with H.O. Compare this solution with
the 0.0100 M EDTA as follows: Pipet 25 ml. of this Mg(NO&
solution into a 100-ml. beaker, add 10 ml. of pH 10 buffer, and
dilute to 50 ml. with H?O. Add a few crystals of KCN (to avoid
any possible indicetor blocking by trace heavy metals), a few
drops of Erio T solution, and titrete with the 0.0100 M EDTA
until the last tint of red has just disappeared. Preferably warm
the solution slightly during the titration because the rate of
reaction between the megnesium-indicator complex and EDTA
is somewhat slow st room temperature. (One ml. of 0.0100 M
EDTA = 0.2432 mg, of magnesium.)
EXPERIMENTS

with various metals that differ markedly in color from


that of the free, "unmetallized" indicator. Metal
indicators in general also show more or less pronounced
color changes with changes in pH. The present experiment demonstrates the metal indicator activity of
Erio T as well as its pH-sensitivity. This dye shows a
wine red color in strongly acidic solution, which passes
to a dark blue color in the pH interval 6 to 7, and this
to a red a t 11 to 12. The metal complexes formed by
the dye in the pH range of about 6.5 to 11, are usually
red.
In each of five vessels place 90 ml. of stock H,O and 3 drops of
Erio T solution and stir. Use these solutions in the following
exoeriments.
Ezpl. IA. To the first vessel add 10 ml. of pH 10 buffer. Stir.
Note the blue solution oolor.
Ezpt. IB. To the second vessel add 10 ml. of 1M HCI. Stir.
Note the red color.
Ezpt. ZC. To the third vessel add 10 ml. of 1 M NaOH.
Stir. Note the red color and contrast the shade developed in
Expt. IB.
(If desired, a single solution of the dye may be carried through
the chanees in color: however. the ~roeressivedilution creates a

Before performing the following experiments, explain that the use of a buffered medium assures that no
change in hydrogen ion concentration occurs, and that
therefore color changes observed must be due to a reaction of the metal ion with the dye (metal indicator).
The sensitivity of the reaction of metal ions with Erio T
is amazingly high. Even
or 10-%M Mg(NO8)?
solutions give a faint red tint (see also Expt. IIID).
Ezpl. ID. To the fourth vessel, add 10 ml. of pH 10 buffer.
Stir. Note the color is the same as that in Expt. IA. Now add
one drop of 0.1 M Mg(NO&. Note the immediate color change
from blue to red.
Ezpt. IE. Repeat Expt. I D substituting one drop of 0.1 M
Zn(NO.)l. Note the color change from blue to a red differing
somewhat in shade from that obtained in Expt. ID.

Before performing the following experiment, it may


be explained that a metal and hydrogen ion (both
cations) compete for the metal indicator. Hence, a
pH range must be selected in which the metal can
compete successfully if the dye is to serve for the detection of a metal.
Ezpt. I F . Add one drop of 0.1 M Zn(N0a)s to the solution
from Expt. IB (i.e., the eecond vessel). Note that the solution
color is unchanged.
Experiment 11. Metal Complex Formation

EDTA reacts with many polyvalent metal ions to


form water-aoluble metal complexes. EDTA is a
tetrabasic acid. Two hydrogens have strongly acidic
properties: the other two are only weakly acidic. The
anion species predominating in about neutral solution
may therefore be written as HzY-$. If complexation
occurs, this anion is engaged completely and hydrogen
ion is liberated. This can be expressed for a divalent
metal ion, M+?,in the form of the following equation:

Experiment I. The Metal Indicator

Metal indicators are sensitive to changes in pM,


that is, the negative logarithm of the concentration of
the "free" metal ion. (The "free" metal ion, of course,
may be in the form of such solution complexes as acetato,
chloro, aquo, etc.) Metal indicators form complexes

I t may be explained that the further this reaction


proceeds to the right, the greater is the stability of the
metal complex, and the greater the acidity produced.
Under certain circumstances this increase in acidity
JOURNAL OF CHEMICAL EDUCATION

can serve as a basis of calculating the stability constant


of the metal-EDTA complex.
The phenomenon of complexation is demonstrated in
the followinn exneriments in two wavs: The increase in
acidity on the mixing of neutralized solutions of a metal
salt and of EDTA is visualized by use of an acid-base
indicator. Further, the formation of a colored metalEDTA complex is shown.

- .

Ezpt. IIA. Add 10 ml. of 0.1 M Zn(NO& and 3 drops of


methyl orange solution to 90 ml. of stoek H20. Prepare a. second
solution containing 10 ml. of 0.1 M EDTA, 3 drops of methyl
orange solution, and 90 ml. of H?O. Nate that both solutions
sre yellow (if not, add aqueous NH8 drapwise rts necessary).
Now pour bath solutions simultaneously into a large beaker or a
large cylinder. Note the color change from yellow to red. (If
desired, in a psrsllel experiment the Zn(NO& and EDTA solutions can he mixed without addition of methyl orange: thus ascertaining that the zinc-EDTA complex is colorless.)

The color of the EDTA complex of some metals is


different from that of the "free" metal ion. This can
serve to demonstrat,e complexation. (Reference to the
classical complexation of copper(I1) with ammonia may
he expedient.)
Ezpt. IIB. To each of two vessels, add 10 ml. of 0.1 M
Ni(NO&, 20 ml. of pH 5 buffer and 60 ml. of stock H.O. Nate
the green solution color of the "free" nickel ion. To one vessel
add 10 ml. of 0.1 M EDTA. Note the color change from green
to blue indicating formation of the nickel(I1)-EDTA complex.
To the second vessel add 10 ml. of stock H 2 0 so that the final
volumes are identical in both vessels. Save both salutians for
comparison purposes in Expt. IV.
Ezpt. IIC. To a third vessel add 10 ml. of 0.1 M EDTA, 20
ml. of pH 5 buffer, 60 ml. of H.0, and then 10 ml. of 0.1 M
NifNO.1,. Note the formation of the hlue color of the nickel(II1E d ~ ~ - & n p l e thus
x , indioating that the order of the a d d k i n
of reagents has no effect.
Complexation is also demonstrated hy formation of a colored
cbromium(I1I)-EDTA complex in Expt. V. If an additional
experiment is desired, the pink cohalt(I1)-EDTA complex may
be developed in stock HzO buffered to p H 10.

Experiment 111. Complexation and the Metal Indicator

The formation of a metal complex by the metal indicator Erio T as seen in Experiment I is an example of
compl?xation. The following experiments demonstrate
how EDTA, by forming a stronger complex, can abstract a metal from its complex with thie indicator. It
may be explained that. this is the basis of a visual detection of the end point in the EDTA titration. This
titration was introduced by G. Schwarzenbach (15-I?),
and Expt. I I I D was originally suggested by him (17).
Ezpt. IIIA. Add 5 ml. of 0.1 M Mg(NO& to 90 ml. of stock
H.0 and then 10 ml. of p H 10 buffer. Now add 10 ml. of 0.1 M
EDTA. Note the solution remains colorless; hence, the magnesium-EDTA complex is colorless.
Ezpt. IIIB. Add 3 drops of Erio T solution to 90 ml. of stock
water and then 10 ml. of pH buffer. Note the blue eolor of the
"free" dye (as already seen in Expt. IA). Now add 10 ml. of
0.1 M EDTA. Note the eolor is not changed; hence, there is
no "complication" due to a color reaction of the dye with EDTA.
Ezpt. IIIC. Add 3 drops of Erio T solution to 90 ml. of stack
H20and then 10 ml. of pH 10 buffer. Now add 5 ml. of 0.1 M
Mg(N0d1. Note the red color of the metal-dye complex (its
already seen in Expt. ID). Now add an amount of 0.1 M EDTA
greater than 5 ml. Note that the color reverts to that of the
"free" (unmetallized) dye. (If desired, the mobile character of
the system can he demonstrated by alternate additions of the
metal salt and EDTA solutions.)

The release of metal ions (mainly calcium) from soft


glass is an impressive demonstration of the sensitivity
VOLUME 35, NO. 12, DECEMBER, 1958

of a metal indicator and also emphasizes the principles


illustrated in Expt. IIIC. The following experiment
also delineates that soft glass vessels should be avoided
in analytical work with EDTA and metal indicators,
especially on the micro scale and with dilute solutions.
Ezpt. IUD. Take a soft glass container of capacity greater
than 100 ml., preferably s, new bottle not yet placed in use.
Rinse thoroughly with redistilled or deionized H*O( not with the
prepared stock 8 0 containing EDTA). Place 80 ml. of redistilled or deionized H 9 0 in the bottle, and add 10 ml. of buffer
pH 10 and 2 drops of Erio T solution. The solution should
develop a hlue color. If not, add a. very dilute EDTA solution
(obtained by 1:5 dilution of 0.1 M EDTA) dropwise until the
blue is just reached. Allow to stand for a. short time. Observe
the reappearance of the red color due to release of calcium ions
from the glass. Add a few more drops of diluted EDTA solution
and repeat the process. Take a soft glass rod and scratch the
inside wall of the container. Nate the rapid reappearance of the
red eolor because the scratched surface delivers large amounts of
ions.

Experiment IV.

Stability of Complexes

Experiment IIIC demonstrated the difference in the


stability of the complex of a single cation, namely
magnesium ion, mit,h two different complexing agents,
namely a mntnl indicator and EDTA. The following
experiment demonstrates the difference in the stability
of the complex formed by a single complexing agent,
namely EDTA, with two different metals. The experiment is based on the addition of nickel(I1) to a bismuthEDTA solution; the color of the nickel(I1)-EDTA
complex does not appear indicating the greater stability
of the bismuth-EDTA complex.
Ezpt. IVA. Add 10 ml. of 0.1 M EDTA to 10 ml. of 0.1 M
Bi(NO&. Dilute with 50 ml. of H 2 0 and add 20 ml. of pH
5 buffer. Note that the solution is colorless and hence that the
hismubh-EDTA eomnlex is colorless. Now add 10 ml. of 0.1 M

experiment use rertsanable care in measuring the volumes of bitmuth nitrate and EDTA solutions to assure that the bismuth
ion is not in excess; otherwise a turbidity may appear.)

The following experiments demonstrate how the relative stability of the complexes formed by nickel with
Erio T, EDTA and cyanide can he ranked on the basis
of simple color reactions. Attention may he called
to the fact that stability constants relate to equilibrium conditions and that false impressions may be
reached if reaction rates are not appreciated (see also
Expt. V). If desired, it may be explained that Expt.
IVB is an example of so-called indicator "blocking"
and that the nickel-Erio T complex dissociates only
very slowly.
Ezpt. IVB. Add 5 ml. of pH 10 buffer and 3 drops of Erio T
solution to 95 ml. of stock H 2 0 Add 2 drops of 0.1 M Ni(NO&.
Note the red color indicating the formation of the nickd(I1)-dye
complex. Add 0.1 M EDTA dropwise until an appreciable
excess (more than 15 drops) is present. Nate that the color of
the solution is unchanged. Allow to stand for 15 to 30 minutes,
note the blue color of the free dye is slowly attained. (A similar
solution, containing only 4 drops of 0.1 M EDTA will undergo
the color change in 3 to 4 minutes when warmed to about 70C.,
due to tho increase of reaction rate with temperature.)
Ezpt. IVC. Add 5 ml. of pH 10 buffer and 3 drops of 0.1 M
EDTA to 95 ml. of stack H20. Add 2 drops of 0.1 M Ni(N0s)s.
Now add 3 drops of Erio T solution. Note the blue color of the
"free" dye.
Ezpt. IVD. Add 5 ml. of pH 10 buffer and 3 drops of Eriochrome Black T indicator solution to 95 ml. of stock H.0. Add

Expt. VIIIB. Repeat Expt. VA or employ the violet solution


saved from that experiment. To that solution, add 20 drops of
1M NaOH. Note the color change from violet to blue.
Experiment IX. The EDTA Titration

An E D T A titration t o a visual end point is demonstrated in principle in Experiment 111. An applied


example t h a t may be performed either as a lecture
demonstration or as a student exercise is t h e titration of
magnesium in t h e presence of large amounts of iron.
T h e latter is masked by conversion t o t h e ferrocyanide
ion. This example is particularly instructive a s most
of the steps involve color changes.
I n t h e masking of iron(III), cyanide must be added
in alkaline solution so t h a t formation of hydrocyanic
acid is avoided; however, iron(II1) hydroxide would
then precipitate. This difficulty is avoided by first
adding tartrate ion t o form t h e soluble iron(II1)tartrate complex. This complex is then reacted with
cyanide ion in alkaline medium t o form ferricyanide
ion. However, this latter ion will oxidize Erio T and
thereby destroy its indicator action. Ferricyanide is
therefore reduced t o ferrocyanide b y the action of
ascorbic acid. This is a slow reaction; hence, warming
is necessary. (If applied materials are being analyzed,
ferrocyanide ion m a y form insoluble salts with some
cations; in t h a t case, dilute t h e solution sufficiently or
employ a back-titration, t h a t is,add a n excess of E D T A
and back-titrate with a metal salt solution such a s
magnesium nitrate.) As t h e rate of reaction of magnesium-indicator complex and E D T A is somewhat slow
a t room temperature, i t is preferable t o titrate the solution while i t is warm. Calcium, manganese(II), lead, or
zinc can be titrated in exactly t h e same way (and, if
present, vill be co-titrated with magnesium).
For a quantitative experiment, employ the standard
EDTA and magnesium nitrate solutions given under
"Reagents." For a semiquantitative demonstration,
merely dilute t h e 0.1 M E D T A and Mg(NO& solutions
tenfold.
To a me~wredamount (10
to 30 m1.l of standard Me(N0.I..
~
add some 0.1 M F~cI, (2 to 4 ml.) &d dilute to a v&m<&f
about 50 ml. (More iron can he tolerated without interference,
hut the amounts of reagents added in the masking step must
then be increased.) Neutralize the diluted sample solution by
dropwise addition of dilute NaOH (1 M NaOH diluted 1:5 with
H,O) until a slight turbidity of iron(II1) hydroxide persists.
Remove the turbidity with a few dmps of dilute HCI (1 M HC1
diluted 1:5 with HzO). Add about 0.3 g. of tartaric acid. Note
t.he brieht~*~
vt.llow solution color iimniII1)-tartrate comnlex).
Add 20~ml.of pH 10 buffer. ~ o t teh h the color fades: (if
a turbidity occurs, an insufficient amount of tartrate was added.)
~~~~

~~~~~

Some of t h e more direct implications of these experiments for analytical chemistry may be summarized.
Complexation of metals b y E D T A is delineated in Ex-,
periment 11, and in t h e nine experiments E D T A complexes are produced with eight cations. T h e use of
E D T A a s a titrant in t h e E D T A titration is demonstrated in principle in Experiment I11 and in detail in
Experiment I X . T h e behavior of a metal indicator and
its use in t h e detection of the end point are explored
in Experiments I through IV. T h e use of cyanide a s
a masking agent i n t h e E D T A titration is studied in
Experiments IX and IV. T h e use of E D T A as a
masking agent is demonstrated for a precipitation in
Experiment VIIA and for the reaction of a metal with
a chromogenic agent (Erio T ) in Experiment 111. T h e
use of E D T A a s a solubilizing agent is illustrated in
Experiment VIIB.
T h e ability of E D T A t o alter t h e redox equilibrium
of a metal system is demonstrated in Experiment VI.
This ability finds use in polarography, electroanalysis,
and in t h e E D T A titration in the detection of the end
point electrometrically or b y the use of redox indicators.
Colored metal-EDTA complexes obtained in Experiments 11, IV-VI, a n d V I I I suggest how E D T A can
serve as a chromogenic agent in photometric determinations, detection tests, and in photometric E D T A
titrations in which no auxiliary color-former is added.
LITERATURE CITED

(1) BAILAR,
J. C., JR., editor, "The Chemistry of Coordination
Compounds," Reinhold Publishing Corporation, New
York, 1956, 834 pp.
H., "EDTA Titrations. Introduction to Theory
(2) FLASCBKA,
and Practice," Pergamon Press, London and New York,
1958, in press.
G., "The Complexometric Titration,"
SCHWARZENBACA,
Methuen & Co., Limited, London, and Interscience Publishcrs, Inc., New York, 1957, 132 pp.
WELCHER,
F., "The Analytical Uses of Ethylenediaminetetrmcetic Acid," D. Van Nostrand Companv, Inc.,
Prinrdnn 10% 3fi5 nn

~~~

~~~

SOME IMPLICATIONS OF THE EXPERIMENTS

~~

~~

~~~~

~~

Add about 0.2 to 0.3 g. of KCN. Note that the color turns
bright yellow (ferricyanide formation). Add about 0.1 g. of
ascorbic acid. Note that the color turns to yellow-brown (mixed
ferri-femocyanide). Dilute the solution to a volume of about
150 ml. with H?O and heat almost to boiling. Note that the
color fades gradually to a faint yellow or to almost colorless
(ferrocyanideformation). (If performed as a lecture demonstration, the volume may be increased to 250 ml. or more and hot
water used for the dilution.)
Now add a few drops of Erio T solution. (If added before
reduction of the ferricyanide is complete, the indicator will he
oxidized.) Titrate while the solution is warm with 0.0100 M
EDTA untii the last tint of red has just disappeared and the
solution color is blue. (Oneml. of 0.0100 M EDTA is equivalent
to 0.0103 millimoles of the metal titrated or to 0.2432 mg. of
magnesium.)

VOLUME 35, NO. 12, DECEMBER, 1958

with added ihdexes in ref. l d ] :


(6) BARNARD,
A. J., JR., W. C. BROAD,
AND H. FLASCAKA,
"EDTA as a Microa~alvticalR e a n t . " Mierochemieal
J., 3, NO. l,to appear (is$..
(7) h s c a ~H.,
~ "Athylendiamin-tetraessigsaure
,
als Maskierungsmittel in der analytischen Chemie," Angew. Chem.,
e

-,,

,>"".,.

no 707-19 11457)
A-

(8) FLASCHM,H., A. J. BARNARD,


JR., AND W. C. BROAD,
"The EDTA Titration: Applications," Chemisl-Analyst,
46. 10612 (1957):
. . . ibid... 47.. 22-28. 52-56. 78-84. in
press (1958).
(9) PRIRIL,R., "Recent Advances in Chelatometry," Analyst,
83, 188-95 (1958).
(10) SCHWARZENBACH,
G., "Chelate Formation as a Basis for
Titration Processes," Anal. Chim. Acta, 7, 141-55

,-""-,.

( 1 45%

(11) SCHWARZENBACH,
G., 'The Complexones and Their
Analytical Application," Analyst, 80, 713-29 (1955).
(12) J. T. BAKERCEEMICALCO., "The EDTA Titration:
Nature and Methods of End Point Detection." Phiui~sburg, New Jersey, 1957,32 pp.
(13) THE Dow CEIEMICAL
Co., "Keys to Chelation," Midland,
Michiian, 1957.16 pp.
CEIEMIC~L
Co., "Sequestrene," Providence, Rhode
(14) ALROSE
Island, 1952, 54 pp. [available from Geigy Industrial
Chemicals, P. 0. Box 430, Yonkers, New York].

(15) SCKW~RZENBACE,
G., "Nouvelles mdthodes de dosage de
cehins cations mPtaIliques," Helv. Chim. Acfa, 29, 1338
(1946); U. S. patents 2,583,890 and 2,583,891 (1952).
(16) SCHWARZENBACH,
G., W. BIEDERMANN,
AND F. BANQERTER,
"Neue einfache Titriermethoden mr Beatimmung der
Wasserhiirte," Heb'. Chim. Acta, 29, 811418 (1946).

(17) BIEDERMANN,
W., AND G. S ~ A R Z E N B A C"Die
H , komplexometrisohe Titration der Erdalkelien und eiuiger
anderer Metalle mit Eriochromschwarz T," Chimia, 2 ,
5S59 (1948).
(18) MARTELL,
A. E., "The Behavior of Metal Complexes in
Aqueous Solutions,"J. CHEM.EDUC.,29, 270-80 (1952).

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