Beruflich Dokumente
Kultur Dokumente
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
(After Martell)
CHrCOOR
CHrCOOH
Ethylenediaminetetraacetic acid
NaOOC.H&
CHrCOONa
[ HWC
CH&OOH
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
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.
- .
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.)
Experiment IV.
Stability of Complexes
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
~~~~~
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
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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.)
-,,
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no 707-19 11457)
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( 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).