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Complexometric Titrations
EDTA
DTA forms stable complexes with most metal ions the exceptions being the
group 1 cations. The stability of the complexes can be attributed to the chelate
effect; when complexing a metal ion EDTA surrounds the metal cation, forming a
number of five-membered rings. Although ethylenediaminetetraacetic acid is already
shortened to EDTA, analytical chemist, shorten it even further to "Y".
Metal cation
Structure of EDTA
In a complexometric titration the analyte and titrant form a complex ion, and the
equilibrium constant is called the formation constant, Kf. Chelating (multidentate)
ligands form more stable complexes than do monodentate ligands, because the
entropy of complex formation favours the binding of one large ligand rather than
small ligands. Synthetic aminocarboyxlic acids such as EDTA have large
metal binding constants and are widely used in analytical chemistry.
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APCH231: EDTA
Here are some stability constants for the formation of metal-EDTA complexes:
Metal ion
KMY
Metal ion
KMY
Mg2+
4.9x108
Ni2+
4.2x1018
Ba2+
5.8x107
Cu2+
6.3x1018
Ca2+
5.0x1010
Zn2+
3.2x1016
Mn2+
6.2x1013
Pb2+
1.1x1018
Questions
1.
2.
EDTA is the most widely used complexing agent for routine analysis of water
hardness and other applications. EDTA is a multidentate ligand that is represented
by the formula H4Y.
conditions under which EDTA will be present in different forms including H4Y,
H3Y-, H2Y2-, HY3-, and Y4- . Therefore, controlling the pH is one major factor that
affects complexation.
For EDTA to react with a metal ion, the hydrogens attached to the carboxylate
groups must be removed. In strongly basic solution, these hydrogens are removed
by reaction with hydroxide ion. In more acidic solutions, metal ions must be able
to displace the hydrogens if a complex is to be formed. Since metal ions differ
significantly in their ability to displace the hydrogens, the solution acidity can be
used to regulate the reactivity of EDTA toward metal ions. For example, most
metal ions react quantitatively with a stoichiometric amount of EDTA at pH 10,
but only a few, such as Fe3+ and Hg2+, also react quantitatively at pH 2.
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APCH231: EDTA
The total concentration of EDTA will be the sum of all equilibrium species
CT = [H4Y] + [H3Y-] + [H2Y2-] + [HY3-] + [Y4-]
where CT is the total molar concentration of uncomplexed EDTA.
The fraction of any species can be found if desired where:
o = [H4Y]/CT
1 = [H3Y-]/CT
2 = [H2Y2-]/CT
3 = [HY3-]/CT
4 = [Y4-]/CT
Kf =
[M2+] [Y4-]
Y4- concentration is dependent on pH and, therefore, should be calculated as
follows:
4 =
K1K2K3K4
[H3O+]4+K1[H3O+]3+K1K2[H3O+]2+k1K2K3[H3O+]+K1K2K3K4
[Y4-] = 4CT
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APCH231: EDTA
eing a weak acid, EDTA dissociates in solution and it is the unprotonated form
abbreviated as Y4- that is the species found in the complex. The fraction (Y)
of the total EDTA that is present as Y4- depends on the pH of the solution; as shown
in the table below.
pH
pH
1.9x10-18
5.0x10-4
3.3x10-14
5.6x10-3
2.6x10-11
5.4x10-2
3.8x10-9
10
0.36
3.7x10
-7
11
0.85
2.3x10-5
12
0.98
Note that Y4- is present at very low concentrations in acidic solution and does not
become the predominant species until the pH exceeds a value of 10.
We can make use of these -values in calculating conditional stability constants for
metal-EDTA complexes, which take into account the pH of the solution in which the
complex is formed. The stability constant, KMY, for the formation of the metal-EDTA
complex:
Mn+ + Y4- MY(n-4)+
is given by:
K MY =
[ MY ( n 4)+ ]
[ M n+ ][Y 4 ]
[ MY ( n 4) + ]
[ M n + ] 4 CT
or:
4 K MY =
[ MY ( n 4) + ]
= K MY
[ M n + ]CT
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APCH231: EDTA
Question
3.
Calculate the fraction of EDTA present as Y4- in solution at the following pH:
a) pH 8. 0
b) pH 11.0.
Preferably,
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APCH231: EDTA
Question
4.
A 100.0 mL aliquot of city drinking water was treated with a small amount of
an ammonia ammonium chloride buffer to bring the pH to 10.
After the addition of Calmagite indicator the solution required 21.46 mL of
5.140 10-3 M EDTA for titration. Calculate the hardness in terms of parts per
million calcium carbonate.
uring a titration with EDTA, the metal ion solution is in the flask and EDTA is
added from the burette. At any point in the titration we can calculate the value
Y4-
Start
2.50x10-4 mol
1.00x10-4 mol
React
1.00x10-4 mol
1.00x10-4 mol
1.00x10-4 mol
Form
Final
CaY2-
1.50x10-4 mol
1.00x10-4 mol
The new volume is 50.0 + 10.0 = 60.0 ml and so [Ca2+] = 0.0025 M and pCa = 2.6.
Y4-
Start
2.50x10-4 mol
2.50x10-4 mol
React
2.50x10-4 mol
2.50x10-4 mol
CaY2-
2.50x10-4 mol
Form
Final
2.50x10-4 mol
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APCH231: EDTA
How can we calculate the [Ca2+]? All the Ca2+ has gone We have to remember
that the reaction is actually an equilibrium and some (very small amount) of the CaY2will dissociate to give some Ca2+ and we can find [Ca2+] by using:
=
K CaY
[CaY 2 ]
[Ca 2+ ]CT
The only Ca2+ in the solution will have come from the dissociation of the CaY2- and
this will also be the only source of uncomplexed EDTA; therefore:
[Ca2+] = CT
At pH 10, Y = 0.36 and K CaY = 0.36 x 5.0x1010 = 1.8x1010, so very little of the CaY2will actually have dissociated and we have:
[CaY2_]
and
1.8 x1010 =
3.3 x10 3
3.3 x10 3
=
[Ca 2+ ]CT
[Ca 2+ ] 2
solution:
Ca2+
Y4-
Start
2.50x10-4 mol
5.00x10-4 mol
React
2.50x10-4 mol
2.50x10-4 mol
2.50x10-4 mol
Form
Final
CaY2-
2.50x10-4 mol
2.50x10-4 mol
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APCH231: EDTA
[CaY 2 ] =
[CaY 2 ]
[Ca 2 + ]C EDTA
to find:
[Ca2+] = 5.6x10-11 mol dm-3 and pCa = 10.26
Questions
5.
0 ml of EDTA solution.
b)
c)
d)
6. For your answer to Q 5c) you assumed that [Zn2+] = CEDTA. Why are you justified in
making that assumption?
Questions
7. Look at the two titration curves (0.050 M Ca2+ titrated with 0.050 M EDTA).
a)
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APCH231: EDTA
b)
Titration Curve A
Titration Curve B
12.00
10.00
8.00
6.00
4.00
2.00
0.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0
10
15
20 25 30 35 40 45 50
V o l E D T A a dde d ( m l)
10
15
20 25 30 35 40 45 50
V o l E D T A a dde d ( m l)
8. Look at the following two curves, for the titration of 25.00 ml of Pb2+ solution
with EDTA at pH 6. One of the curves is for the titration of 0.050 M Pb2+ with
0.050 M EDTA, the other is for 0.0005 M Pb2+ with 0.0005 EDTA. Which is
which? Explain briefly.
Titration Curve D
15.00
15.00
10.00
10.00
pZn
pZn
Titration Curve C
5.00
0.00
5.00
0.00
10
15
20 25 30 35 40 45 50
V o l E D T A a dde d ( m l)
10
15
20 25 30 35 40 45 50
V o l E D T A a dde d ( m l)
Would you expect the presence of NH3 to have any effect on the value
of pZn? Briefly explain.
b)
Would you expect the presence of NH3 to affect the shape of the
titration curve? Briefly explain.
indicator this is a dye that can act as a complexing agent to complex the metal
being titrated. The colour of the indicator depends on whether it is attached to the
metal ion or free. At the beginning of a titration, some of the analyte metal ion is
complexed by the indicator.
Notes complied by Dr. C. Southway
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APCH231: EDTA
Mn+ + Inn-
M-In
As EDTA is added, the free metal ion concentration decreases but some metal ion
remains complexed by the indicator.
chosen, at the equivalence point the EDTA has complexed all of the free metal ion
and then removes the metal from the indicator complex (charges are removed for
simplicity):
MIn + EDTA MEDTA + In
Where MIn and In have different colours.
Among the very important indicators that are routinely used, you will encounter
two indicators namely Muroxide and Eriochrome Black T (solochrome Black).
However, there are many other indicators some of them are very important
because of their high selectivity towards specific metal ions.
Question
10.
What would happen if the metal-indicator complex was so stable that the EDTA
could not remove the metal from the complex?
here are several strategies for successful titrations using EDTA. In a direct
titration the analyte is titrated with a standard solution of EDTA, using a suitable
indicator. EDTA forms stable complexes with all metal cations except those in Group
1 of the Periodic Table. If a mixture of metal ions is to be titrated, it may be possible
to determine each one individually by selecting the titration conditions carefully. For
Notes complied by Dr. C. Southway
39
APCH231: EDTA
example, by adjusting the pH or by adding a masking agent which protects one of the
metal ions from reacting with EDTA.
Questions
11. You need to determine the concentrations of Mg2+ and Zn2+ in a mixture.
a)
Calculate the values of the conditional stability constants for MgY2and ZnY2- at pH 10.
b)
Calculate the values of the conditional stability constants for MgY2and ZnY2- at pH 4.
c)
12. A 25.00 ml aliquot of a solution containing Cu2+ and Fe3 was titrated with 16.06
ml of 0.05083 M EDTA. A second 25.00 ml aliquot of the Cu/Fe mixture was
treated with NaF to form a stable iron-fluoride complex. This mixture was then
titrated with 0.05083 M EDTA and the endpoint volume was found to be 5.43 ml.
Calculate the molar concentrations of Cu2+ and Fe3+.
13. A 50.00 ml aliquot of a solution containing Ca2+ and Mg2+ was buffered at pH 10
and titrated with 0.04865 M EDTA. The endpoint volume was 44.27 ml. A
second aliquot of the same mixture was made stongly basic by the addition of
NaOH this causes the Mg2 to precipitate as Mg(OH)2. The solution was then
titrated with the 0.04865 M EDTA and the endpoint volume was found to be
34.26 ml. Calculate the molar concentrations of Ca2+ and Mg2+.
quickly enough. In these cases, other strategies may be used. Sometimes a back
titration can be used if a suitable indicator is not available. A known quantity of
EDTA is added to the sample so that all of the analyte reacts with the EDTA and
some EDTA is left over. The amount of EDTA left over is then determined by
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APCH231: EDTA
titration with (for example) a standard solution of Mg2+. It is important that the metal
used to back-titrate the EDTA does not form a more stable EDTA complex than the
analyte does.
Question
14. A 25.00 ml sample containing Pb2+ was treated with 10.00 ml of 0.0367 M EDTA.
The excess EDTA was then back-titrated with 0.0461 M Mg2+ solution; 2.37 ml
was required.
a)
b)
Would the procedure have worked if Cu2+ had been used to back-titrate
the excess EDTA?
15. A 25.00 mL aliquot of a solution containing Hg2+ in dilute nitric acid was treated
with 10.00 mL of 0.04882 MEDTA and the pH was adjusted to 10.0 with an
ammonia buffer. Two drops of a freshly prepared EBT indicator solution were
added and the excess EDTA back titrated with 0.01137 M Mg2+, requiring
24.66 mL to reach the endpoint. What is the molarity of Hg2+ in the sample?
EDTA can also be used in indirect titrations the EDTA does not directly react with
the analyte, but reacts with some metal that can be related stoichiometrically to the
analyte.
Question
16. Sulfide ion was determined indirectly by titration with EDTA.
A 25.00 ml
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APCH231: EDTA
For example, cyanide ion can be used to mask certain metals that interfere in the
titration of Ca2+ or Mg2+ with EDTA. In the absence of cyanide, transition metals such
as Zn2+, Cd2+ and Hg2+ interfere by reacting simultaneously with the EDTA. When
cyanide ion is added, these cations form stable complexes and are prevented from
reacting with the EDTA.
The titration is performed then, if desired, a demasking agent can be added to free
the previously masked metal ions so that they can be determined.
If desired, Cd and Zn ions can be demasked by addition of chloral hydrate or a
3:1 formaldehyde : acetic acid solution.
Metals react most completely with EDTA in basic solution where many of them also
form insoluble hydroxides or basic oxides. Once formed, these insoluble products will
react only slowly with EDTA, making a titration impossible. To avoid this problem,
an auxiliary complexing agent may be added to react with the metal ion and prevent
its precipitation when the solution is made basic. The complex must be intermediate
in stability between the metal hydroxide and the metal-EDTA complex. In this way it
will form in preference to the hydroxide, but will give up the metal ion to the EDTA
titrant as it is added. Ammonia is especially useful for this purpose because it forms
soluble complexes with many transition metals, and when mixed with its conjugate
acid, ammonium ion, it forms a basic pH buffer.
References
1. Analytical Chemistry, Principles and Techniques, Larry G. Hargis.
2. iugaza.edu/users/abdellatif/.../Complexometric_titrations.htm -
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