Analysis of Metal Ions by EDTA Titrations

EDTA titrations are carried out using a standard EDTA solution at a particular pH
(fixed with a buffer solution).

Important note: In practice, EDTA titrations are usually carried out at pH 10 or

higher - in order to minimize the variety of EDTA species in solution and,
specifically, to increase the fraction of Y4-.

EDTA titrations are used for:

• Finding unknown concentration of a metal ion in solution.
The task: to reach the equivalence point of titration, which is observed with
use of a metallochromic indicator.
• Construction of metal-EDTA titration curves.
Finding Unknown Concentration of a Metal Ion in Solution by EDTA Titration
Problem:
15.00 mL of an aqueous solution containing unknown concentration of Ni2+
were titrated with 0.1014 M EDTA solution at pH 10.0. What was the
concentration of Ni2+ in the unknown solution if 18.63 mL of the EDTA were
needed to reach the equivalence point of this titration?

Solution:
Ni2+ + EDTA NiY2- Note: Reaction stoichiometry is 1:1.
At the equivalence point, CNi2+VNi2+ = CEDTAVEDTA ;
CNi2+ = (CEDTAVEDTA )/VNi2+ = (0.1014 M × 18.63 mL)/(15.00 mL) = 0.1259 M
 Metal-EDTA Titration Curves
Mn+ + EDTA MYn-4 Kf' = Kf Y4-
The titration curve is a plot
pM vs. VEDTA
where pM = -log [Mn+] Region 3:
excess EDTA
The curve has 3 regions:
1) Before the equivalence point:
Concentration of free Mn+ is found as
Region 2:
excess of the metal over the added

pM
equivalence point
EDTA.
Region 1:
*Complex dissociation (reverse rxn) is excess Mn+
negligible due to a very large Kf.

2) At the equivalence point:

Moles of metal = Moles of added EDTA.
**Essentially all of the metal is bound in
the complex MYn-4; conc. of free Mn+ is
negligible.
Note: The larger the Kf, the greater
3) After the equivalence point: increase in pM is observed near the
equivalence point.
Excess EDTA; all metal is bound
in the complex MYn-4.
 EDTA Titration Calculations
Problem 1:
Construct the Mg-EDTA titration curve for the reaction of 50.0 mL of
0.0500 M Mg2+ (buffered at pH 10.0) with 0.0500 M EDTA:
Mg2+ + EDTA MgY2- ; Kf = 6.2×108
Solution:
Find the conditional complex formation constant: Kf ' = Kf Y4-
From the table: at pH = 10.0, Y4- = 0.30
Kf ' = (6.2×108)(0.30) = 1.9 ×108

Just a reminder: EDTA reacts with metal ions in mole ratio 1:1.
Q: How many mL of the EDTA solution will be needed to reach the equivalence
point of titration? A: 50.0 mL
Therefore,
-- with added VEDTA < 50.0 mL, free Mg2+ is in excess;
-- with VEDTA = 50.0 mL, Mg2+ and EDTA are mixed in equal molar amounts,
and both will be entirely bound in complex MgY2-;
-- after the equivalence point (VEDTA > 50.0 mL), free EDTA will be in excess.
 Important note: In the process of titration, total volume of the
solution is increasing, which leads to dilution of both of the reactants as
well as the product.
Due to this, to find the concentration of the compound of interest,
find its number of moles (or mmols) first, and then divide by the
current total volume of the solution.

1) Consider addition of 5.00 mL of EDTA (before the equivalence point)

[Mg2+] = (Initial moles of Mg2+ – Moles of added EDTA)/Vtotal

Note: Moles of added EDTA = Moles of complex MgY2- formed

[Mg2+] = [(0.0500 M × 50.0 mL) – (0.0500 M × 5.00 mL)]/(50.00 + 5.00) mL=

= 0.0409 M;
pMg = -log (0.0409) = 1.388 (following the rule of sig. figs)
pM ≈ 1.39
(In EDTA titrations, pM is usually reported with 2 digits after the decimal point).

pMg at any other point on the titration curve before the equivalence point
(i.e., VEDTA < 50.0 mL) is found analogously.
 2) Consider addition of 50.0 mL of EDTA (at the equivalence point)
All of the Mg2+ has been complexed by the equal molar amount of EDTA.
[MgY2-] = CEDTA added:
[MgY2-] = (0.0500 M × 50.0 mL)/(50.0 + 50.0) mL = 0.0250 M.

Note: Now, this is a problem about finding concentration of free Mg2+ in the
solution of 0.0250 M complex MgY2- at pH 10.0, at which Kf' = 1.9 ×108
(recall sample problem in Lecture 14).
The only source of free Mg2+ in solution is (weak) dissociation of complex MgY2-.
[MgY2-]
Mg2+ + EDTA MgY2- ; Kf' = = 2.2 1088
1.9 x×10
[Mg2+][EDTA]
Dissociation of X mol/L of MgY2- produces X mol/L of free Mg2+ and same
amount of free EDTA:
[Mg2+] = [EDTA] = X; [MgY2-] = 0.0250 – X  0.0250 M
(since Kf ’ is very large, complex hardly dissociates, so X << 0.0250 M).
Kf' = [MgY2-]/[Mg2+][EDTA] = (0.0250)/X2 = 1.9×108;
X = 1.15×10-5 M.
Therefore, [Mg2+] = 1.15×10-5 M; pMg = 4.939 ≈ 4.94
 3) Consider addition of 51.0 mL of EDTA (beyond the equivalence point)
EDTA is in excess; all of the Mg2+ is complexed.
Again, the only source of free Mg2+ is complex dissociation – now in the presence
of excess EDTA.
Find the concentration of free (excess) EDTA present in the solution:
CEDTA = (Moles of added EDTA - Initial moles of Mg2+)/Vtotal =
= [(0.0500 M × 51.0 mL) – (0.0500 M × 50.0 mL)]/(50.0 + 51.0) mL = 4.95×10-4 M.
Find the concentration of complex MgY2- in this solution:
CMgY2- = (0.0500 M × 50.0 mL)/(50.0 + 51.0) mL = 0.0248 M.
Let’s consider complex dissociation:
[MgY2-]
Mg2+ + EDTA MgY2- ; Kf' = = 2.2 1088
1.9 x×10
[Mg2+][EDTA]
Dissociation of X mol/L of MgY2- produces X mol/L of free Mg2+ and same amount of
additional free EDTA:
[Mg2+] = X; [EDTA] = 4.95×10-4 + X ≈ 4.95×10-4 M; [MgY2-] = 0.0248 – X  0.0248 M
(Kf ' is very large, complex hardly dissociates, so X is very small).
Kf' = [MgY2-]/[Mg2+][EDTA] = (0.0248)/(4.95×10-4 X) = 1.9 ×108; X = 2.6 × 10-7;
[Mg2+] = 2.6 × 10-7 M; pMg = 6.58
pMg at any other point on the titration curve after the equivalence point is found analogously.
Problem 2:
50.00 mL of 0.0500 M EDTA were added to 50.00 mL of 0.0300 M Ni2+ solution, and
the mixture was buffered at pH 3.0. What is the concentration of free Ni2+ in this
mixture? Kf (NiY2-) = 4.2×1018.
Solution:
Ni2+ + EDTA NiY2- ; Kf' = Kf Y4-
At pH = 3.0, Y4- = 2.1×10-11; therefore, Kf' = (4.2×1018)(2.1×10-11) = 8.8×107
Mmols of Ni2+ originally present = 0.0300 M × 50.00 mL = 1.50 mmol;
mmols of EDTA = 0.0500 M × 50.00 mL = 2.50 mmol.
Ni2+ and EDTA react in a molar ratio 1:1. Therefore, EDTA is added in excess, and
Ni2+is the limiting reactant which determines the formal concentration of the complex:
CNiY2- = (50.00 mL × 0.0300 M)/(50.00 + 50.00) mL = 0.0150 M.
Finding excess (free) EDTA:
CEDTA = [(50.00 mL × 0.0500 M) – (50.00 mL × 0.0300 M)]/100 mL = 0.0100 M.
Define [Ni2+] = X; [NiY2- ] = (CNiY2- − X); and [EDTA] = (CEDTA + X).
With large Kf', we may assume that almost all of the Ni2+ remains in the complex,
[NiY2- ] = (CNiY2- − X)  CNiY2- = 0.0150 M;
for the same reason, [EDTA] = (CEDTA + X)  CEDTA = 0.0100 M.
Kf' = [NiY2-]/[Ni2+][EDTA] = (0.0150) /(0.0100 X) = 8.8×107
X = 1.7×10-8; therefore, [Ni2+] = 1.7×10-8 M.
 Metal (or Metallochromic) Indicators Used in EDTA Titrations

Just a reminder: Acid-base indicators are weak organic acids HIn (or bases In),
whose undissociated form differs in color from its conjugate base/acid form
(In- or HIn+, respectively).
For an acid-base indicator, the pH range = pKa ± 1.

Metallochromic indicators are proton-ionizable organic chelating ligands that

form colored complexes with metal ions.

Typically, metallochromic indicators are weak acids that exchange protons for
metal ions, and during the proton dissociation, they change color.

Importantly, complexes of metal ions with metallochromic indicators are

less stable (have smaller Kf) than complexes of the same metal ions with
EDTA.
Due to this, EDTA displaces indicator from its colored complex with the
metal ion. This results in the indicator color change.
 Examples of metallochromic indicators used in EDTA-titrations:

CH3

Calmagite Eriochrome Black T

Contain 3 proton-ionizable groups, one of which, -SO3H, is
completely dissociated, while two others (-OH) dissociate partially.

H2In- + H2O HIn2- + H3O+

red blue
 Calmagite
Acidic behavior of Calmagite:
CH3 CH3
pKa1 = 8.1
O H2In- + H2O HIn2- + H3O+
red blue
Mg pKa2= 12.4
HIn2- + H2O In3- + H3O+
O blue orange

For EDTA-titration, the pH of the

Red form H2In- Complex MgIn- is red, solution is buffered at 10, so that
same as the acidic form H2In- in the absence of metal ion, ionized blue
form HIn2- dominates.

In presence of metal ion (for example, Mg2+), blue HIn2- is converted into
red complex complex MgIn-.

EDTA displaces indicator from its complex with metal ion (such as Mg2+):
MgIn- + EDTA HIn2- + MgY2-
red colorless blue colorless
At the equivalence point of titration, all of the metal is complexed with EDTA, and
free HIn2- is released. Hence, the solution changes color red → blue.
 Titration Methods Involving EDTA

This is the simplest and

the most convenient method
• Direct Titration
Concentration of analyte (metal ion) is determined via titration of this
metal’s aqueous solution (usually buffered at constant pH) with standard
aqueous solution of EDTA.
The end point of titration is determined with use of the appropriate
metal indicator.
 • Back Titration
Step 1: A known (accurately measured) excessive amount of a standard EDTA
solution is added to the analyte solution, so that all of the metal ion of interest is
bound in the EDTA-complex.

Step 2: The concentration of remaining free (excess) EDTA is found via back-
titration with a standard solution of other metal ion (usually Mg2+ or Zn2+) that
forms a weaker complex with EDTA than the analyte and therefore, it will not
displace the analyte from its own complex with EDTA.
The appropriate metal-indicator is used to observe the end point of this titration step.

Step 3: The concentration of the analyte metal is found as a difference of the

concentration of EDTA added in Step 1 and concentration of remaining free
EDTA found in Step 2.

When is back titration method applied?

If one of the following takes place:
-- No suitable metal-indicator for the analyte is available;
-- The reaction between the analyte and EDTA is slow;
-- The analyte forms precipitate at the pH required for the direct EDTA titration.
Example:
To 25.00 mL of a solution containing unknown concentration of Ca2+,
20.00 mL of 0.1150 M EDTA were added. Excess EDTA was back-titrated to
the equivalence point with 2.60 mL of 0.08622 M Zn2+ solution. What was the
concentration of Ca2+ in the unknown solution?

Solution:
Mmoles of EDTA added to Ca2+ solution:
Mmol EDTA = (0.1150 mmol/mL)(20.00 mL) = 2.300 mmol;
Mmoles of Zn2+ used for back-titration:
Mmol Zn2+ = (0.08622 mmol/mL)(2.60 mL) = 0.224 mmol;
Mmol Zn2+ = Mmol excess EDTA = 0.224 mmol;
Mmol EDTA complexed with Ca2+ = Mmol Ca2+ in the unknown sample
(25.00 mL):
Mmol Ca2+ = (2.300 – 0.224) mmol = 2.076 mmol;
Concentration of Ca2+ in the unknown solution:
[Ca2+] = (2.076 mmol)/(25.00 mL) = 0.08304 M.
 INTRODUCTION TO ANALYTICAL SEPARATIONS
Chapter 30
Separation is applied in order to isolate the analyte from the mixture with
potentially interfering constituents.
 Methods of Separation:
• Separations by Precipitation
• Distillation – separation of a more volatile constituent from
less volatile ones
• Solvent Extraction
• Sorption (“solid-phase extraction”) and Ion Exchange
• Chromatography
• Electrophoretic Methods
 Solvent Extraction (Chapter 30C)
Solvent extraction is based on distribution of the analyte between two immiscible
liquids, usually between aqueous solution and organic solvent. Commonly used
organic solvents: chlorohydrocarbons (CHCl3, CCl4, CH2Cl2), benzene, toluene,
n-octanol, hexanes, etc.

Distribution (partition) constant: Aq

A(aq)
(aA)org [A]org
K=  Org
(aA)aq [A]aq A(org)