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Introduction
1.) Metal Chelate Complexes
Any reagent which reacts with an analyte in a known ratio and with a large
equilibrium constant can potentially be used in a titration.
Metal
Ligand
Metal-Ligand Complex
Note: multiple atoms from
EDTA are binding Mn2+
EDTA Titrations
Introduction
1.) Metal Chelate Complexes
Ligand that attaches to a metal ion through more than one ligand atom
Elements that contain free electron pairs that may be donated to a metal
Fe-DTPA Complex
EDTA Titrations
Metal Chelation in Nature
1.) Potassium Ion Channels in Cell Membranes
K+ is chelated by O
in channel
EDTA Titrations
Metal Chelate Complexes
1.) Formation Constant (Kf)
The equilibrium constant for the reaction between a metal ion (M+n) and a
chelating agent (L-P) is known as a formation constant or stability constant.
Kf = 8x109
Kf = 4x109
EDTA Titrations
Metal Chelate Complexes
2.) Chelate Effect
Usually chelating agents with more than one electron pair to donate will form
stronger complexes with metal ions than chelating agents with only one
electron pair.
-
Multidentate ligand: a chelating agent with more than one free electron pair
-
Monodentate ligand: a chelating agent with only one pair of free electrons
EDTA Titrations
EDTA
1.) EDTA (Ethylenediaminetetraacetic acid)
One of the most common chelating agents used for complexometric titrations
in analytical chemistry.
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
2.) Acid-Base Forms
The most basic form (Y4-) is the one which primarily reacts with metal ions.
EDTA-Mn Complex
EDTA Titrations
EDTA
2.) Acid-Base Forms
Y 4
K1 K 2 K 3 K 4 K 5 K 6
Y 4
[Y 4 ]
[H6Y 2 ] [H5Y ] [H 4Y ] [H 3Y ] [H 2Y 2 ] [HY 3 ] [Y 4 ]
[Y 4 ]
EDTA
where [EDTA] is the total concentration of all free EDTA species in solution
EDTA Titrations
EDTA
3.) EDTA Complexes
The basic form of EDTA (Y4-) reacts with most metal ions to form a 1:1
complex.
-
Kf
[MY n- 4 ]
[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
3.) EDTA Complexes
The basic form of EDTA (Y4-) reacts with most metal ions to form a 1:1
complex.
EDTA Titrations
EDTA
3.) EDTA Complexes
[Y
] Y 4 EDTA
Kf
Kf
[MY n- 4 ]
[M n ] Y 4- [EDTA ]
[MY n- 4 ]
[M n ][Y 4 ]
K 'f
K K f Y 4-
[MY n- 4 ]
[M n ][EDTA ]
EDTA Titrations
EDTA
3.) EDTA Complexes
EDTA Titrations
EDTA
4.) Example:
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
EDTA Titrations
Minimum pH for Effective
Titration of Metal Ions
EDTA
5.) pH Limitation
EDTA Titrations
EDTA Titration Curves
1.) Titration Curve
The titration of a metal ion with EDTA is similar to the titration of a strong acid
(M+) with a weak base (EDTA)
K 'f K f Y 4
pM log [M n ]
EDTA Titrations
EDTA Titration Curves
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
Y4- at pH 10.0 = 0.30
mmol of Mg2+
EDTA Titrations
EDTA Titration Curves
2.) Example
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
[Mg
Original volume
solution
Volume titrant
added
Dilution effect
EDTA Titrations
EDTA Titration Curves
2.) Example
Original volume of
Original [Mn+]
Mn+ solution
[MgY 2 ] (0 .0500 M )
(0 .0500 L )
(0.0500 L 0.0500 L )
Original volume
solution
[MgY 2 ] 0.0250 M
Volume titrant
added
Dilution effect
EDTA Titrations
EDTA Titration Curves
2.) Example
0.0250
0.0250 - x
K 'f K f Y 4
[Mg ( EDTA )- 2 ]
[Mg 2 ][EDTA ]
( 0.0250 x )
( 6.2 10 )( 0.30 )
( x )( x )
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EDTA Titrations
EDTA Titration Curves
2.) Example
Volume excess
Original [EDTA] titrant
[EDTA ]
Original volume
solution
[EDTA ] 4.95 10 4 M
Volume titrant
added
Dilution effect
EDTA Titrations
EDTA Titration Curves
2.) Example
Calculate [MgY2-]:
Original volume of
Original [Mn+]
Mn+ solution
[MgY 2 ] (0 .0500 M )
(0 .0500 L )
(0.0500 L 0.0510 L )
Original volume
solution
[MgY 2 ] 0.0248 M
Volume titrant
added
Only Difference
Dilution effect
EDTA Titrations
EDTA Titration Curves
2.) Example
'
K f K f Y 4
( 6.2 10 8 )( 0.30 )
[Mg ( EDTA )- 2 ]
[Mg 2 ][EDTA ]
( 0.0248 M )
( x )( 4.95 10 4 M )
EDTA Titrations
EDTA Titration Curves
2.) Example
Final titration curve for 50.0 ml of 0.0500 M Mg2+ with 0.0500 m EDTA at pH
10.00.
-
EDTA Titrations
Auxiliary Complexing Agents
1.) Metal Hydroxide
Auxiliary Complexing Agents: a ligand can be added that complexes with Mn+
strong enough to prevent hydroxide formation.
-
1
1 1 [ L ] 2 [ L ] 2 n [ L ] n
K'f' Y 4 Zn2 K f
EDTA Titrations
Auxiliary Complexing Agents
2.) Illustration:
CuSO4
Cu-ammonia Cu-EDTA
EDTA Titrations
Metal Ion Indicators
1.) Determination of EDTA Titration End Point
Four Methods:
1.
2.
3.
4.
Potential
Measurements
Metal Ion Indicator: a compound that changes color when it binds to a metal
ion
-
For an EDTA titration, the indicator must bind the metal ion less strongly than
EDTA
-
(red)
(colorless)
(colorless)
(blue)
EDTA Titrations
Metal Ion Indicators
2.) Illustration
Addition of EDTA
Before
Near
Equivalence point
After
EDTA Titrations
Metal Ion Indicators
3.) Common Metal Ion Indicators
Most are pH indicators and can only be used over a given pH range
EDTA Titrations
Metal Ion Indicators
3.) Common Metal Ion Indicators
Useful pH ranges
EDTA Titrations
EDTA Titration Techniques
1.) Almost all elements can be determined by EDTA titration
Direct Titrations
Back Titrations
Displacement Titrations
Indirect Titrations
Masking Agents
EDTA Titrations
EDTA Titration Techniques
2.) Direct Titrations
Free EDTA left over after all metal ion is bound with EDTA
EDTA Titrations
EDTA Titration Techniques
4.) Displacement Titration
Used for some analytes that dont have satisfactory metal ion indicators
K f ( M n )Y 4 K f ( Mg 2 )Y 4
EDTA Titrations
EDTA Titration Techniques
5.) Indirect Titration
Precipitate is then reacted with excess EDTA to bring the metal ion back into
solution
Known
determine
free
Titrate
EDTA Titrations
EDTA Titration Techniques
6.) Masking Agents
Requires:
K f ( AlF 3 ) K f ( Al ( EDTA ))
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