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Chelation in Biochemistry
EDTA forms 1:1 complexes with metal ions by with 6 ligands: 4 O &
2N. EDTA is the most used chelating agent in analytical chemistry,
e.g. water hardness.
Acid/Base Properties of EDTA
• EDTA is a hexaprotic system (H6Y2+) with 4
carboxylic acids and 2 ammoniums:
pK1 0.0
O OH
O pK 2 1.5
+
pK 3 2.0
O NH
NH
+
OH pK 4 2.66
pK 5 6.16
OH
O OH pK 6 10.24
Y 4-
EDTA
EDTA Complexes
• The equilibrium constant for a reaction of metal
with EDTA is called the formation constant, Kf, or
the stability constant:
M n Y 4 MY n4
MY n4
Kf
M Y
n 4
f
M Y M EDTA
n 4 n
Y 4-
K f' Y 4- K f
MY n4
Mn EDTA MY n4 Kf' Y4 Kf
M EDTA
n
Example
• Calculate the concentration of free Ca2+ in a
solution of 0.10 M CaY2- at pH 10 and pH 6.
Kf for CaY2- is 4.9x1010 (Table 13-2)
Ca 2 EDTA CaY2 Kf' Y4 Kf
at pH 10.00, K f' Y 4 K f (0.36)( 4.9 1010 ) 1.8 1010
at pH 6.00, K f' Y 4 K f (2.3 10 5 )( 4.9 1010 ) 1.1106
Ca 2 EDTA CaY 2
Conc i 0 0 0.1
Conc f x x 0.1 - x
CaY 2
0.1 x
x Ca 2 2.4 106 M @pH 10
K f'
Ca EDTA x
2 2
Ca
2 25.0 - 5.0
50.0
(0.040) 0.0291 M
25.0 55.0
CaY
2- 50.0
(0.040) 2
2.63 10 M
76.0
Initial Dilution
Concentration Factor
CaY 2.6310
2 2
1.8 1010 Ca 2 1.4 109 M
Ca EDTA Ca (1.05 10
'
K f 2 2 3
)
pCa 2 8.86
Auxiliary Complexing Agents
• In aqueous solution, metal-hydroxide complexes
or precipitates can form, especially at alkaline pH