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Introduction
Introduction
Fe-DTPA Complex
EDTA Titrations
Kf = 8x109 Kf = 4x109
Multidentate ligand: a chelating agent with more than one free electron pair
- Stoichiometry is 1:1 regardless of the ion charge
Monodentate ligand: a chelating agent with only one pair of free electrons
EDTA
EDTA has 6 nitrogens & oxygens in its structure giving it 6 free electron pairs
that it can donate to metal ions.
- High Kf values
- 6 acid-base sites in its structure
EDTA Titrations
EDTA
The most basic form (Y4-) is the one which primarily reacts with metal ions.
EDTA-Mn Complex
EDTA Titrations
EDTA
[Y 4 ]
Y 4
EDTA
where [EDTA] is the total concentration of all free EDTA species in solution
EDTA
[MY n- 4 ]
Kf
[M n ][Y 4 ]
Note: This reaction only involves Y4-, but not the other forms of EDTA
[Y 4 ] Y 4 EDTA
where Y4-is dependent on pH
EDTA Titrations
EDTA
EDTA
[Y 4
] Y 4 EDTA
[MY n- 4 ]
Kf
[M n ][Y 4 ]
[MY n- 4 ]
Conditional or effective formation constant: K 'f K K f Y 4-
(at a given pH) [M n ][EDTA ]
EDTA Titrations
EDTA
K 'f K f Y 4-
EDTA
4.) Example:
What is the concentration of free Fe3+ in a solution of 0.10 M Fe(EDTA)- at pH
8.00?
EDTA Titrations
EDTA
5.) pH Limitation
Note that the metal –EDTA complex becomes less stable as pH decreases
- Kf decreases
- [Fe3+] = 5.4x10-7 at pH 2.0 -> [Fe3+] = 1.4x10-12 at pH 8.0
5.) pH Limitation
By adjusting the pH of an EDTA
titration:
one type of metal ion (e.g. Fe3+) can
be titrated without interference from
others (e.g. Ca2+)
EDTA Titrations
K 'f K f Y 4-
pM log [M n ]
EDTA Titrations
2.) Example
What is the value of [Mn+] and pM for 50.0 ml of a 0.0500 M Mg2+ solution
buffered at pH 10.00 and titrated with 0.0500 m EDTA when (a) 5.0 mL, (b)
50.0 mL and (c) 51.0 mL EDTA is added?
Kf = 108.79 = 6.2x108
2.) Example
(a) Before Equivalence Point ( 5.0 mL of EDTA)
Before the equivalence point, the [Mn+] is equal to the concentration of excess
unreacted Mn+. Dissociation of MYn-4 is negligible.
moles of Mg2+
originally present moles of EDTA added
2.) Example
(b) At Equivalence Point ( 50.0 mL of EDTA)
Original volume of
Original [Mn+] Mn+ solution Moles Mg+ ≡ moles MgY2-
(0 .0500 L)
[MgY 2 ] (0 .0500 M )
(0.0500 L 0.0500 L)
[MgY 2 ] 0.0250 M
EDTA Titrations
2.) Example
(b) At Equivalence Point ( 50.0 mL of EDTA)
[Mg ( EDTA )- 2 ]
K 'f K f Y 4
[Mg 2 ][EDTA ]
8 ( 0.0250 x )
( 6.2 10 )( 0.30 )
( x )( x )
Solve for x using the quadratic equation:
2.) Example
(c) After the Equivalence Point ( 51.0 mL of EDTA)
Virtually all of the metal ion is now in the form MgY 2- and there is excess,
unreacted EDTA. A small amount of free M n+ exists in equilibrium with
MgY4- and EDTA.
[EDTA ] 4.95 10 4 M
EDTA Titrations
2.) Example
(c) After the Equivalence Point ( 51.0 mL of EDTA)
Calculate [MgY2-]:
Original volume of
Original [Mn+] Mn+ solution Moles Mg+ ≡ moles MgY2-
[MgY 2 ] 0.0248 M
EDTA Titrations
2.) Example
(c) After the Equivalence Point ( 51.0 mL of EDTA)
[Mg2+-] is given by the equilibrium expression using [EDTA] and [MgY 2-]:
( 0.0248 M )
( 6.2 10 8 )( 0.30 )
( x )( 4.95 10 4 M )
2.) Example
Final titration curve for 50.0 ml of 0.0500 M Mg 2+ with 0.0500 m EDTA at pH
10.00.
- Also shown is the titration of 50.0 mL of 0.0500 M Zn2+
1
Fraction of free metal ion (M) depends on the M
equilibrium constants () or cumulative formation 1 1 [ L ] 2 [ L ] 2 n [ L ] n
constants:
2.) Illustration:
Titration of Cu+2 (CuSO4) with EDTA
Addition of Ammonia Buffer results in a dark blue solution
- Cu(II)-ammonia complex is formed
Addition of EDTA displaces ammonia with corresponding color change
Metal Ion Indicator: a compound that changes color when it binds to a metal
ion
- Similar to pH indicator, which changes color with pH or as the compound
binds H+
For an EDTA titration, the indicator must bind the metal ion less strongly than
EDTA
- Similar in concept to Auxiliary Complexing Agents
- Needs to release metal ion to EDTA
2.) Illustration
Titration of Mg2+ by EDTA
- Eriochrome Black T Indicator
Addition of EDTA
Precipitate is then reacted with excess EDTA to bring the metal ion back into
solution