Unit 5.

Metal complexation
What is a metal?

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Metal toxicity
• Drinking water standards
metal MCL Typical sources

iron 300 ppb steel, construction sites

mercury, Hg 1 ppb refineries, factories, landfills, cropland

cadmium, Cd 5 ppb galvanized pipe, metal refineries, batteries

antimony, Sb 6 ppb refineries, fire retardants, electronics

lead, Pb 10 ppb household plumbing

chromium, Cr 50 ppb steel mills, pulp mills

copper, Cu 1 ppm household plumbing, wiring

barium, Ba 1 ppm drilling wastes, metal refineries

selenium, Se 10 ppb petroleum refineries, mines

arsenic, As 25 ppb orchards, glass and electronics

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Metals in water
• Metals do not behave as free species in water
• Metals always have a coordination shell e.g., Cu(H2O) 42+ , Al(H2O) 63+

• To understand this behavior we need to adopt a more general theory than used for acids and
bases.
 Recap: Brønsted Lowry theory of acid and bases
• An acid is a substance from which a proton can be removed. Acids are proton
donors.
• A base is a substance that can remove a proton from an acid. Bases are
proton acceptors.
 Lewis theory of acid and bases
• An acid is a substance which can accept one or more electron pairs.
Acids are electron acceptors.

• A base is a substance that can donate one or more electron pairs to an acid.
Bases are electron donors.

• Acid-base reactions result in formation of a new compound called “Lewis

adduct”.
Lewis theory of acid and bases
A Lewis acid and base interact by sharing an electron pair.

Example: Formation of hydronium ion:

•• ••
O—H •• +
+ H O—H
H
H
H
ACID BASE
Lewis theory of acid and bases
Other examples involve metal ions.

•• ••
O—H
2+ Co
2+ •• ••
O—H
Co
H
H
ACID BASE

[Co(H2O)6]2+
 Metal complexation [Co(H2O)6]2+

Complex ion: Combination of metal ions (Lewis acids)

with Lewis bases such as H2O and NH3

[Cu(NH3)4]2+
Ligand
• Molecule that binds with metals at coordination site (complexing agent,
lewis base)
• Many ligands contain N, O and S as they have an unshared electron pair
(e.g., OH-, COOH, NH3)
• Monodentate vs. multidentate ligands

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Example of multidentate ligand

ethylenediaminetetraactetic acid (EDTA)

HOOC CH2 CH2 COOH
N CH2 CH2 N
HOOC C CH2 COOH
H2

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Metal complexation

Many complex ions are very stable:

Cu2+ + 4 NH3 = [Cu(NH3)4]2+

Keq for this reaction is called
“stability (or formation) constant”

[Cu(NH3)4]2+

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 Metal complexation
• Coordination chemistry
– Me(H2O)xn+
– typical is x = 4 to 6

Coordination number: is number of ligands with which a metal coordinates

– Metal complex
• a molecule (ligand) replaces a water
• e.g. hydroxide (OH-) sequentially replaces water
Me(H2O)6n
Me(H2O)5OHn-1
Me(H2O)4(OH)2n-2
Me(H2O)3(OH)3n-3
…etc. ...

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Metal complexation
• Complexation reactions with hydroxide ion replacing water
– complete reaction:
Me(H2O)xn+ + H2O = Me(H2O)x-1(OH)n-1 + H3O+

– simplified representation:
Men+ + OH- = MeOHn-1

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 Hydroxide stability
complexes
• Metal complexation by hydroxide

Ki constants
adding OH- sequentially

i constants
adding one or more OH- at a time

*Ki constants
adding H2O sequentially

*i constants
adding one or more H2O at a time

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Hydroxide stability complexes
• Sequential addition of one ligand to complex with i-1 ligands

– Ki constants for Fe3+ (up to 4 OH-)

Fe3+ + OH- = Fe(OH)2+ log K1 = 11.81

Fe(OH)2+ + OH- = Fe(OH)2+1 log K2 = 10.52

Fe(OH)2+1 + OH- = Fe(OH)30 log K3 = 6.07

Fe(OH)30 + OH- = Fe(OH)4-1 log K4 = 6.00

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Hydroxide stability complexes
– Sometimes can be simplier to assume formation of the complex at once, starting from
the free metal and i ligands to form MeLi

i constants for Fe3+ (up to 4 OH-)

Fe3+ + OH- = Fe(OH)2+ log 1 = 11.81

Fe3+ + 2OH- = Fe(OH)2+1 log 2 = 22.33

Fe3+ + 3OH- = Fe(OH)30 log 3 = 28.40

Fe3+ + 4OH- = Fe(OH)4-1 log 4 = 34.40

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Hydroxide stability complexes
• We can relate Ki and i :

i = K1 K2 K3 … Ki

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Hydroxide stability complexes: Example
What is the concentration of free Fe3+ in water at pH 6 containing a total ferric iron
concentration of 1M?

log 1 = 11.81
log 2 = 22.33
log 3 = 28.40
log 4 = 34.40

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Metal speciation
• In addition to water and OH- other ligands also form complexed metal ions:
– Monodentate ligands
• OH-, CO32-, SO42-, Cl-, F-, NH3, CN-, HS-

– Multidentate ligands (chelators)

• PO43-, EDTA4-

All complexation reactions have their own

Fe+3
formation/stability constants (Ki or i)
Metal speciation
• Values for logi
Metal speciation
• Values for logi
Metal speciation
• Table 8.3
– form of the i reactions:

Me n
Lm
 MeL  nm
1 
 MeL n m  
  
Me n
Lm

Me n
 2L m
 MeL2n2 m
2 
 MeL2n  2 m  
Me L  n m 2

Me n
 3L m n3m
 MeL3 2 
 MeL3n  3 m  
Me L  n m 3
Metal speciation
• Table 8.3
– form of the i reactions:

n
Me  H  L m
 MeHL  n  1 m 
1 
MeHL  n  1 m 

   
Me n
H 
Lm

n
Me  2 H  L  m
 MeH 2 L  n 2 m
2 
 MeH 2 L n 2 m  
Me H  L 
n  2 m
Metal speciation
• Which complex of Cd2+ is the most stable?

complex log 1
CdCO30 5.4
CdSO40 2.46
CdCl+ 1.98
CdF+ 1.1
CdPO4- 3.9
CdEDTA2- 16.28
CdCN+ 5.32
CdHS+ 10.17
Metal speciation
• Example: silver-chloride complexes. Which complex of is the most stable?

Ag+ + Cl- = AgCl0

log 
Ag+ + 2 Cl- = AgCl2-
AgL 3.27
Ag+ + 3 Cl- = AgCl32-
AgL2 5.27
Ag+ + 4 Cl- = AgCl43- AgL3 5.29
AgL4 5.51
 Equilibrium problems for complexation

1. Write all the reactions of interest

2. List all species present at equilibrium
3. Write equilibrium expressions using appropriate stability constants
4. Write mass balance equations for metals and ligands
5. If necessary make assumptions based on
• Relative magnitude of CT,metal and CT,ligand
• Magnitude of the stability constants
6. If necessary and appropriate, write the charge balance (depends on number of
equations and unknowns)
Metal speciation
What is the concentration of free Ag+ in a solution containing a total concentration of Ag(I)
= 10-8 M, a total concentration of Cl = 10-4 M at pH 12?

From Tables:

Ag+ + OH- = AgOH0 log 1 = 2.00

Ag+ + 2 OH- = Ag(OH)2- log 2 = 4.00

Ag+ + Cl- = AgCl0 log 1 = 3.27

Ag+ + 2 Cl- = AgCl2- log 2 = 5.27
Ag+ + 3 Cl- = AgCl32- log 3 = 5.29
Ag+ + 4 Cl- = AgCl43- log 4 = 5.51
Sources of stability constants
– Martell A.E. and Smith R.M., Critical Stability Constants. Plenum Press, New York
• Volume 1, Amino Acids, 1974
• Volume 2, Amines, 1977
• Volume 3, Other Organic Ligands, 1977
• Volume 4, Inorganic Complexes, 1976
• Volume 5, First Supplement, 1982
• Volume 6, Second Supplement, 1989

– NIST Critically Selected Stability Constants of Metal Complexes

http://nist.gov/srd/webguide/Critical/46_8.htm

– IUPAC Stability Constants Database (SC-Database)

http://www.acadsoft.co.uk/scdbase/scdbase.htm

– Chemical equilibrium model databases

• WATEQ, MINEQL, MINTEQ, PHREEQC etc.