Kyung Hee University · Department of Chemistry · Bioanalysis Laboratory

Chapter 11:
EDTA Titrations

Quantitative Chemical Analysis

Eighth Edition

Daniel C. Harris
* Some figures from Quantitative Chemical Analysis (7th Ed.) with the permission of W.H. Freeman & Company
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Metal-Chelate Complexes
EDTA (ethylenediaminetetraacetic acid, hexaprotic H6Y2+)
Complexometric metal titrations forming strong 1:1 complexes
Industrial processes, soaps, cleaners, food additives,
environmental processes,…

EDTA occupies 6 coordination sites, for example [CoEDTA]- is an

octahedral Co3+ complex.
Both N atoms (blue) and O atoms (red) coordinate to the metal.
EDTA is used in consumer products to complex the metal ions which
catalyze decomposition reactions.
HO2CH2C CH2CO2H

HNCH2CH2NH

HO2CH2C CH2CO2H

H6Y2+
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Metal-Chelate Complexes
Lewis acid; electron-pair acceptor Lewis base; electron-pair donor
Monodentate ligands bind through one donor atom only.
-Therefore they occupy only one coordination site.
Multidentate ligands (or chelating agents) bind through more than one donor
atom per ligand.
-Example, ethylenediamine (en), H2NCH2CH2NH2.
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Metal-Chelate Complexes
Fig 11-1 Mn-EDTA complex; hexadentate

Fig 11-2 ATP; tetradentate ligand ATP-Mg2+-2H2O

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Metal-Chelate Complexes
Fig 11-4 Aminocarboxylic chelating agents
1:1 complex with all metals (except Li+, Na+, K+)
Complexometric titration
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EDTA
Virtually every element can be analyzed with EDTA (directly or indirectly)
Forms stable water soluble complexes
High formation constants.
A primary standard material – a highly purified compound that serves as a
reference material.

Acid-Base Properties
EDTA: hexaprotic system (H6Y2+, H5Y+, H4Y, H3Y-, H2Y2-, HY3-, Y4-)
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EDTA
Fractional Composition of EDTA Solutions
Fig 11-7 ; Fractional composition of EDTA as a function of pH

Note that only the fully

ionised , -4 – charged
anion(Y4-) binds to metal
ions

Fraction of EDTA in the form Y 4-

[Y 4- ] [Y 4 - ]
a Y 4- = 2+ + - 2- 3- 4-
=
[H6 Y ] + [H5 Y ] + [H4 Y] + [H3 Y ] + [H2 Y ] + [HY ] + [Y ] [EDTA]
K1K 2 K 3 K 4 K5 K6
=
{ +
[H+ ]6 + [H ]5 K1 + [H+ ]4 K1K 2 + [H+ ]3 K1K 2 K 3 + [H+ ]2 K1K 2 K 3 K 4 [H+ ]K1K 2 K 3 K 4 K5 + K1K 2 K 3 K 4 K5 K6 }
[EDTA] : Total concentration of all “free” uncomplexed EDTA species in solution.
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EDTA
Formation Constant (Stability Constant)
4-
One mole of EDTA (in the form Y ) reacts with one mole of Metal ion.

n+
M +Y ↔ 4-
� MY n-4 [MY n-4 ]
K f = n+ 4-
[M ][Y ]
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EDTA

Conditional Formation Constant

Fixing the pH by buffering: Then a Y 4- is constant.

[Y 4 - ] = a Y 4- [EDTA]
Consider EDTA complex formation as if the uncomplexed EDTA is in one form.

Mn+ + EDTA �↔ MY n-4

' [MY n- 4 ]
K = a Y 4 - K f = n+
f
Conditional formation constant: at a given pH
[M ][EDTA]
At any fixed pH, find a Y 4- and evaluate Kf’
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EDTA

Ex Free (remaining uncomplexed) Fe3+ in 0.10 M FeY- at pH 4.00 and pH 1.00?

Fe3+ + EDTA �↔ FeY - K f' = a Y 4 - K f
At pH 4.00: Kf’ = (3.0 x 10-9)(1.3 x 1025) = 3.9 x 1016
At pH 1.00: Kf’ = (1.4 x 10-18)(1.3 x 1025) = 1.8 x 107

x2 1 3+
ìï1.6 x 10-9 M at pH 4.00
= ® x( = [Fe ]) = í -5
F - x Kf ' ïî7.4 x 10 M at pH 1.00

Metal-EDTA complex becomes less stable at lower pH

à A high pH is desirable. Fig 11-9
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EDTA
Effect of pH on EDTA Titration of Ca 2+

Less distinct
end point

At this range Y4- predominates, thus

titrations are routinely done in buffered
solutions near or above pH 10.
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EDTA Titration Curves

n+ n-4 ' [MY n- 4 ] At a given pH
M + EDTA �↔ MY K = a Y 4 - K f = n+
f
[M ][EDTA]

For large Kf’: Reaction complete at each point in the titration.

Titration curve: Plot pM (= -log[M]) vs. volume EDTA
Region 1
Excess Mn+ left after each addition of EDTA.
Conc. of free metal equal to conc. of unreacted Mn+.

Region 2
Equivalence point: [Mn+] = [EDTA]
Some free Mn+ generated by MYn-4 Û Mn+ + EDTA

Region 3
Excess EDTA. Virtually all metal in MYn-4 form.
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EDTA Titration Curves

Titration Calculations
Titration of 50.0 mL of 0.0500 M Mg2+ (pH 10.00) with 0.0500 M EDTA
Mg2+ + EDTA ↔
� MgY 2- K f' = a Y 4 - K f = (0.30)(6.2 x 108 ) = 1.9 x 108

Region 1: Before the equivalence point

Excess metal ion, dilution
VEDTA = 5.00 mL
45.00 50.00
[Mg2+ ] = 0.0500 M ( )( ) = 0.0409 M ® pMg2+ = 1.39
50.00 50.00+5.00
Original Fraction Dilution
concentration remaining factor

Region 2: At the equivalence point

2- 2+ x2 1
MgY �↔ Mg + EDTA = x = 1.15 x 10-5 M ® pMg2+ = 4.94
F' - x K f '
50.00
Dilution; [MgY 2- ] = 0.0500 M ( ) = 0.0250 M
50.00+50.00
Original Dilution
concentration factor
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EDTA Titration Curves

Region 3: After the equivalence point
Excess EDTA, dilution
VEDTA = 51.00 mL
1.00
[EDTA] = 0.0500 M ( ) = 0.000495 M
50.00+51.00
Original Dilution
concentration factor

50.00
[MgY 2- ] = 0.0500 M ( ) = 0.0248 M
50.00+51.00

' [MgY 2- ]
K = a Y4- K f =
f 2+
® [Mg2+ ] = 2.6 x 10-7 M ® pMg2+ = 6.58
[Mg ][EDTA]
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EDTA Titration Curves

The Titration Curve

EDTA Titration Curves for Ca 2+ and Sr 2+

(Buffered at pH 10)

*Ca2+ end point more distinct.

*Lower pH, Kf’ decreases, & End point less distinct.

*We cannot raised pH arbitrarily:

Metal hydroxides might precipitate.

Beware
Complications due to formation of MOH+, M(OH)2(aq), M(OH)2(s), M(OH)3-,…
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Auxiliary Complexing Agents

Auxiliary Complexing Agents
To permit many metals to be titrated in alkaline solutions with EDTA, we use an
auxiliary complexing agent, which is a ligand, such as ammonia, tartrate, citrate,
or triethanolamie, that binds the metal strongly enough to prevent metal
hydroxide from precipitating but weakly enough to give up the metal when EDTA
is added.
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Auxiliary Complexing Agents

EDTA Titration with an Auxiliary Complexing Agent Needs to Consider
Metal-Ligand Equlibria
Ex. Titration of Zn2+ by EDTA in the presence of NH3.
=> Requires a new conditional formation constant to account for the fact that
only some of the EDTA is in the form of Y4- and only some of the zinc not bound
to EDTA is in the form Zn2+.

Mn+ + Y4- ↔ MYn-4

Kf = [MYn-4]/[Mn+][Y4-] = [MYn-4]/αMn+ CMn+αY4- [EDTA]

CM = [M] + [ML] + [ML2]

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Metal Ion Indicators

Metal ion indicator; changes its color when bound to a metal ion
must bind metal less strongly than EDTA
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Metal Ion Indicators

Back titration when a metal blocks the indicator (M-In > M-EDTA or slow reaction)
Calmagite is “blocked by” Cu2+, Ni2+, Co2+, Cr3+, Fe3+, and Al3+ .
Cu2+ titration 1. Excess standard EDTA added to Cu2+ à Cu-EDTA + EDTA
2. Indicator added; In cannot take EDTA from already formed Cu-EDTA
3. Excess EDTA titrated with Mg2+
Kf(Mg2+-EDTA) < Kf(Cu2+-EDTA); Mg2+ can only take free EDTA.
Kf(Mg2+-In) < Kf(Mg2+-EDTA); In à Mg-In after the equivalence point
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Metal Ion Indicators

At low pH, H+ competes with the metal
ion for the EDTA è less binding
At too high pH, OH- competes with the
metal ions, precipitation (metal
hydroxide, M(OH)n) è less binding

Fig 12-14 Guide to EDTA titrations; pH

range, auxiliary complexing
agents, indicators
Pb-EDTA; pH 3 to pH 12
Auxiliary complexing agents
(weaker than EDTA) are
needed for pH 9-12.
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EDTA Titration Techniques

Direct Titration
Buffered to an appropriate pH; Kf’ large enough, distinct indicator color change
Auxiliary complexing agent; ammonia, tartrate, citrate, triethanolamine,…
Color Plate 7 ; Cu2+ using ammonia at pH 10 (vivid color change)
Preventing precipitaion; Pb2+ with tartrate at pH 10

Left: 0.02 M CuSO4 before titration. Center: Color of Cu(II)-ammonia complex after
addition of ammonia buffer, pH 10. Right: End point color when all ammonia ligands
have been displaced by EDTA. In this case, the auxiliary complexing agent
accentuates the color change at the end point
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EDTA Titration Techniques

Back Titration
Excess EDTA added à Back titration with a weaker-binding metal
If the analyte blocks the indicator; Cu2+, Ni2+, Co2+, Cr3+, Fe3+, Al3+
If the analyte precipitates in the absence of EDTA; Al3+ at pH 7
Ex Back titration of 25.00 mL of Ni2+ in dilute HCl with Zn2+ at pH 5.5
Add 25.00 mL of 0.05283 M Na2EDTA
Neutralized with NaOH à pH adjusted to 5.5 with acetate buffer; Ni-EDTA, EDTA
Indicator (xylenol orange) added à yellow; Ni-EDTA, EDTA, In
Titration with 17.61 mL of 0.02299 M Zn2+ à Red; Ni-EDTA, Zn-EDTA, Zn-In
(25.00 mL)(0.05283 M) = 1.3208 mmol of EDTA added
(17.61 mL)(0.02299 M) = 0.4049 mol of excess EDTA titrated with Zn2+
0.9159 mol of Ni2+ à [Ni2+] = 0.3664 M
Back titration of Al3+; EDTA prevents precipitation of Al(OH)3 at pH7.
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EDTA Titration Techniques

Displacement Titration
If no proper metal ion indicator is available,
Hg2+: Hg2+ + MgEDTA2- à HgEDTA2- + Mg2+ (Mg2+ is a very weak EDTA binder.)
Then, Mg2+ is titrated with EDTA.
Ag+ : 2 Ag+ + Ni(CN)42- à 2 Ag(CN)2- + Ni2+
Then, Ni2+ is titrated with EDTA.

Indirect Titration
Anions that form precipitates with certain metal ions (CO32-, CrO42-, S2-, SO42-…)
Ba2+ + SO42- à BaSO4(s) with excess Ba2+ at pH 1
Precipitation
Filtered, washed, and then boiled with excess EDTA at pH 10
à BaSO4(s) into Ba(EDTA)2-
Excess EDTA is back-titrated with Mg2+ BaSO4 precipitate
Filtration filter
Ba2+
The precipitate is filtered and washed. filtrate
à Excess metal ion in the filtrate is titrated with EDTA.
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EDTA Titration Techniques

Masking: A reagent that protects some component of the analyte from reaction
with EDTA.
F-; Be2+, Ti4+, Fe3+, Al3+
Caution: HF formed by F- in acidic solution.
CN- ;Cd2+,Cu+,Ag+, Ni2+, Pd2+, Fe3+, Fe2+
Caution: Cyanide forms toxic HCN gas below pH 11.
Triethanolamine; Al3+, Fe3+, Mn2+
2,3-Dimercaptopropanol; Bi3+, Cd2+, Cu2+, Hg2+, Pb2+

masking à Selectivity

Demasking: A reagent releases metal ion from a masking agent.

Formaldehyde; Cyanide complexes can be demasked with formaldehyde.