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METAL COMPLEX EQUILIBRIA

Many metal ions, especially transition metals,
form coordinate covalent bonds with
molecules or anions having a lone pair of e-s.

This type of bond formation is essentially a

Lewis acid-base reaction
For example, the silver ion, Ag+, can react with
ammonia to form the Ag(NH3)2+ ion.
TDCVillar
Ag+ + 2 :NH3 Ag(NH3)+2
Chem 32

METAL COMPLEX EQUILIBRIA METAL COMPLEX EQUILIBRIA

M + L ML
M + L ML
Ag+ + 2 :NH3 Ag(NH3)+2
Coordination number maximum number of
A metal (Lewis acid) - is an electron deficient species, thus coordinating ligands.
accept electrons from a ligand
N = 4 tetrahedral or square planar
Ligand (Lewis base) is a complexing agent N = 5 trigonal bipyramidal
an e- rich, and thus, e- donating species N = 6 octahedral

e.g. H2O, :NH3

Coordination Compound - compounds formed from
combination of metal ions with a complexing agents
Coordination number The actual number of point of
attachment (pair of es) accepted by the metal.

Metal when dissolved in water react with It is common practice to omit the water and
water to form hydrated compound. write the reaction in simplified form.

CuSO4 + 6 H2O Cu(H2O)62+ + SO42-

Cu2+ + 4 NH3 Cu(NH3)42+ + 4 H2O
Cu(H2O)62+ + 4 NH3 Cu(NH3)42+ + 4 H2O

Fe(H2O)63+ + SCN- FeSCN2+ + 6H2O Fe3+ + SCN- FeSCN2+ + 6H2O

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Ligand Ligand
monodentate - if it donates a single pair of monodentate - if it donates a single pair of
electrons electrons
e.g. X-, CN- , OH-, pyridine, H2O, :NH3

Ag+ + 2 :NH3 Ag(NH3)+2 Co2+ + 6 :NH3

Ligand Ligand
bidentate ligand - donates two pairs of electrons. bidentate ligand - donates two pairs of electrons.
e.g. ethylenediamine, :NH2CH2CH2H2N:
[Co(en)3]3+ [Pt(en)2]2+

Ni2+ + 2
Co2+ +3

Dimethylglyoxime (DMG)

Ligand
Polydentate ligand/multidentate ligand The aqueous silver ion forms a complex ion
also called a chelating agent with ammonia in steps.
e.g. EDTA, Ag+ + :NH3 Ag(NH3)+
trien (triethylenetetraamine)
Ag(NH3)+ + :NH3 Ag(NH3)+2
When you add these equations, you get the
overall equation for the formation of Ag(NH3)2+.

Cu2+ + trien Ag+ + 2 :NH3 Ag(NH3)+2

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The formation constant for Ag(NH3)2+ is: M X MX K f1

MX

M X
[ Ag ( NH 3 ) 2 ]
Kf
[ Ag ][ NH 3 ]2 MX X MX 2 K f2
MX
M X
The formation constant, Kf , is the equilibrium constant for
the formation of a complex ion from the aqueous metal ion
and the ligands.
Net reaction:
M 2 X MX Kf Kf
MX 2
Ag+ + 2 :NH3 Ag(NH3)+2 2
1 2
MX X 2
The value of Kf for Ag(NH3)2+ is 1.7 x 107.

The overall, or cumulative formation constants MX n 1 X MX n

are denoted n.
For the reaction: [ ]
M 2 X MX Kf Kf
MX 2 =
1 ][]
MX X 2
2
1 2

Cumulative formation constant

2 K f K f n K f K f K n
1 2
1 2

Dissociation constant, Kd Sample Problem:

Reciprocal, or inverse value of Kf.
Also called instability constant (Kinst)
The equation for the dissociation of Ag(NH3)2+ is
Ag ( NH 3 ) 2 (aq ) Ag (aq ) 2 NH 3 (aq)
A divalent metal ion reacts with a ligand to form a
1:1 complex. Find the concentration of the metal ion
in a solution prepared by mixing 1L 0.20 M M 2+ and
1L of 0.20 M ligand (L). kf = 1.0x108

The equilibrium constant equation or Kd is

1 [ Ag ][ NH 3 ]2
Kd
K f [ Ag ( NH 3 ) 2 ]

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Distribution of Metal among Several Complexes

Calculation of Alpha Values for Metal Complexes
Silver ion forms a stable 1:1 complex with trien.
Calculate the [Ag+] when 25.00 mL of 0.0100M AgNO3 Consider stepwise formation of Ag(NH3)2+
is added to 50.00 mL of 0.015 M trien Kf = 5.0 x 107
1. Ag+ + :NH3 Ag(NH3)+

K f1
Ag ( NH ) 2.1 x 10

Ag NH
3 3

3

2. Ag(NH3)+ + :NH3 Ag(NH3)+2

Kf
Ag( NH ) 8.2 x 10 3 2

Ag( NH NH
3
2
3 3

Distribution of Metal among Several Complexes Distribution of Metal among Several Complexes
Calculation of Alpha Values for Metal Complexes Calculation of Alpha Values for Metal Complexes
MBE: C Ag Ag Ag ( NH ) Ag ( NH )

3

3 2

Overall reaction:

Ag+ + 2 :NH3 Ag(NH3)+2 1.) 0 Ag

Ag

C Ag

Overall formation constant:

2.) 1 AgNH
Ag ( NH )
3

C Ag
2 K f K f 1.7 x 107
3

1 2

2 Ag ( NH
Ag( NH ) 3 2

3 )2
3.
C Ag

Then,

Ag ( NH ) AgNH
4.) from Kf

0 Ag
1

Ag NH Ag Ag ( NH ) Ag ( NH )
3
K f1
3 3 3 2

5.) from K f 2

Ag ( NH ) 0



K f2
Ag ( NH NH Ag(NH )
3 2
3 2
3 3

6.) substitute 4.) to 5.)

Ag(NH ) 3 2

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General equation for the alpha metal and alpha

complexes
ASSIGN: Derive
1
=
1 + 1 [] + 2 []2 + 3 []3 + + []
1.) 1 [or (3 )+ ] and

1 []
2.) 2 [or (3 )2 + ] =
1 + 1 [] + 2 []2 + 3 []3 + + []

[]
=
1 + 1 [] + 2 []2 + 3 []3 + + []

Complexes of EDTA and metal ions Complexes of EDTA and metal ions
Ethylenediaminetetraacetic acid (EDTA) Has six potential sites for bonding with metal

-
O O
-
O
O N
N O
O
-O O-
ethylenediaminetetracetate (EDTA)

EDTA metal complex EDTA metal complex

Kf
MY n4

M Y
n 4

Ag+ + y4- AgY3-

Al3+ + y4-
General reaction of EDTA

Zn2+ + y4-
Mn+ + Y4- MY (n-4)+

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Acid/Base Properties of EDTA Fractional compositional diagram of EDTA

EDTA is a hexaprotic system (H6Y2+) with 4 carboxylic
acids and 2 ammoniums:

We usually express the equilibrium for the formation of

complex ion in terms of the Y4- form (all six protons
dissociated). You should not take this to mean that
only the Y4- form reacts

Fractional compositional diagram

Concentration of EDTA
of EDTA and all Effect of pH on the composition of EDTA
its forms will depend on pH
As in acid base equilibria, we can define for each
species as the fraction of EDTA e.g. Y 4

Y 4
Y 4

C EDTA
At acidic pH H4Y will
Y
Y
4-

predominate and at basic pH

Y4- will predominate.
4
H Y H Y
6
2
5

H Y H Y H Y HY Y
4 3
-
2
2- 3- 4-

At moderately acidic pH H2Y2-

(pH 3-6) predominates

Effect of pH on the composition of EDTA Conditional Formation Constants

Following our previous derivation in acid base equilibria

Also called effective formation
Ka1 Ka2 Ka3 Ka4 constants
Y 4 pH dependent equilibrium constant
D that apply at a single pH only

D= [H+]4 + ka1 [H+]3 + ka1ka2[H+]2 +

ka1ka2ka3[H+] + ka1ka2ka3ka4

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Conditional Formation Constants

Recall

A divalent metal ion reacts with a ligand to form a Ca2+ + Y4- CaY2- kf = 5.0x1010
1:1 complex. Find the concentration of the metal ion
in a solution prepared by mixing 1L 0.20 M M 2+ and
Kf = [CaY2-]
1L of 0.20 M ligand (L). kf = 1.0x108 [Ca2+][Y4-]

Since there are some other

forms of EDTA
[Ca2+] [Y4-]

Then, [Ca2+] = CEDTA

Conditional Formation Constants Conditional Formation Constants

Then, Y 4
Y
4
[ 2 ]
CT =
2+ 4
Y
4
Y 4
CEDTA
Rearranging
Substitution in the [ 2 ]
formation constant =
2+ [ 4 ] Conditional
expression [ 2 ]
4 = = Formation
2+ Constants
[ 2 ]
=
2+ 4

Conditional Formation Constants

Sample problem:
Calculate the fraction of EDTA present

Kf
MY n4
as Y4- in a solution at pH 8.00 and pH
11.0 and its mole percent.
M Y
n 4

Ka1=1.02 x 10-2 Ka2=2.14 x 10-3

Ka3=6.92 x 10-7 Ka4=5.50 x 10-11

K'f
MY K
n4

M C n
T
4 f

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Assign:
Ca2+ + y4- CaY2- Factors affecting the titration curve
EDTA Titration Discuss the effect of the ff:
Derive a curve (pM as a function of volume of 1. The value of the formation constant.
EDTA) for the titration of 50.0 mL of 0.0050 M 2. The concentrations of EDTA and metal ion.
Ca2+ (buffered at pH=10) with 0.0100 M EDTA. 3. The pH of the solution
Ve=25.0 mL

Effect of Auxilliary complexing agents on metal ion Effect of Auxilliary complexing agents on metal ion
concentrations concentrations

Metals reacts most completely with EDTA at basic Complexing agent

solutions This is a ligand that binds strongly enough to the
Zn2+ + y4- ZnY2- metal to prevent hydroxide precipitation, but
But the problem is that many of them also form weak enough to be displaced by EDTA
insoluble hydroxides or basic oxides which makes
the reaction slow making the titration impossible. NH3 is especially useful for this purpose because
Zn2+ + OH- Zn(OH)2 it forms soluble complexes with many transition
metals and when mixed with its conjugate acid
To avoid this problem we often have to use an auxiliary
complexing agent e.g., NH3, tartrate, citrate, or
ammonium ion, it form a basic pH buffer.
triethanolamine to react with the metal ion and prevent its
precipitation when the solution is made basic

Effect of Auxilliary complexing agents on metal ion Effect of Auxilliary complexing agents on metal ion
concentrations concentrations

Complexing agent Complexing agent

Zn2+ + NH3 Zn(NH3)2+ Zn(NH3)22+ + NH3 Zn(NH3)32+

Zn( NH ) 2
Kf3
Zn( NH ) 2

Kf
Zn( NH ) NH
3 3

Zn NH
3
2 2 = 2.29 x 102
1
3
= 1.62 x 102 3 2 3

Zn(NH3)2+ + NH3 Zn(NH3)22+ Zn(NH3)32+ + NH3 Zn(NH3)42+

Zn( NH ) 2
K f4
Zn( NH ) 2

K f2
Zn( NH ) NH
3 4
Zn( NH ) NH
3 2
2 = 1.95 x 102 2 = 1.07 x 102
3 3 3 3 3

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Effect of Auxilliary complexing agents on metal ion Effect of Auxilliary complexing agents on metal ion
concentrations concentrations

Complexing agent Sample problem:

Calculate the concentration of Zn2+ in a 0.0100 M zinc
CZn Zn 2
+ Zn(NH 3 ) 2
+ Zn(NH ) 3 2
2
+ nitrate solution buffered at pH 9.15 with NH 3/NH4Cl. The
free ammonia concentration in the buffer is 0.0800 M.
Zn(NH ) 3 3
2
+ Zn(NH )
3 4
2

Zn 2
Zn Zn
2 2

Zn' CZn

1
Zn
1 K f NH 3 K f K f NH 3 K f K f K f NH 3 K f K f K f K f NH 3
2 2 3 4
1 1 2 1 2 3 1 2 3 4

EDTA Titration in the presence of complexing

agent
Sample problem: Titrations involving Unidentate Ligand
Calculate the pZn2+ for solutions prepared by adding
1. Liebig method for cyanide
20.00, 25.00 and 30.00 mL of 0.0100 M EDTA to 50.00
Analyte: CN-
mL of 0.00500 M Zn2+. Assume that both the Zn2+ and
Titrant: AgNO3
EDTA are 0.0100 M in NH3 to provide a constant pH of
Indicator: self-indicating
9.0
2 = 3.0 x 1016 4 = 5.0 102 Titration reaction: Ag+ + 2CN- Ag(CN)2-

2+ = 1.17 105 Indicator reaction: Ag+ + Ag(CN)2- Ag(CN)2-

Sample problem:

How many grams of NaCN are present in a solution that is

Titrations involving Unidentate Ligand
titrated just to a permanent turbidity with 26.05 ml of AgNO 3
2. Nickel determination by titration with CN- solution containing 8.125 g of AgNO3 per liter.
Analyte: Ni2+ AgNO3 = 169.9 g/mole NaCN = 49.01
Titrant: KCN Ag+ + 2CN- Ag(CN)2-
Indicator: suspended AgI(s)
Condition: Analysis is done in ammoniacal
solution
Titration reaction:
Ni(NH3)42+ +4CN- Ni(CN)4 2- + 4NH3
Indicator reaction:
AgI + 2CN- Ag(CN)2- + I-

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Titrations involving Polydentate Ligand Titrations involving Polydentate Ligand

(Chelometry) (Chelometry)

EDTA-most popular chelon

Preparation of EDTA
Most commonly available are the free acid H4Y and the
disodium salt, Na2H2Y

Standardization of EDTA
Unit of concentration: M or Titer
1o standard: CaCO3

Sample Problem:
Indicators for EDTA titrations
A CaCO3 solution that will be used to standardize EDTA was
prepared by dissolving 2.8000 g of solid CaCO3 in 100 mL dilute The indicator is usually a weaker chelate forming ligand.
HCl. A 20.00 mL aliquot was taken for titration with EDTA
consuming 29.00 mL of the titrant to reach the endpoint. Express MgIn- (Color 1) + Y4- MgY2- + In3- (Color 2)
the concentration of EDTA in molarity and in CaCO3 titer.
Na2H2Y22H2O = 372.24 g/mole
CaCO3 = 100.09 g/mole EBT(Eriochrome Black T)

Common metal ion indicator

1. Direct titration EDTA is used to titrate the metal

directly
- Mg2+ and other divalent ions can be determined

Sample Problem:
A 100.0 mL aliquot of a city drinking water was treated with a small
amount of an NH3-NH4Cl buffer to bring the pH to 10. After the
addition of Calmagite indicator, the solution required 21.46 mL of
5.140 x 10-3 M EDTA. Calculate the water hardness in terms of ppm
CaCO3.

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2. Back-titrations used for analysis of metallic ions
that form very stable complexes with EDTA but for which a
satisfactory indicator is not available.
M2+ + Y4- MY2- + unr Y4-
unr Y4- + Mg2+ MgY2-
3. Replacement (displacement) reactions replacing the
analyte with an acceptable substitute
Hg2+ does not have a satisfactory indicator, but a
displacement titration is feasible. Hg2+ is treated
with excess Mg(EDTA)2- to displace Mg2+, which is
titrated with standard EDTA.
Hg2+ + MgY2- Mg2+ + HgY2-
Widely used technique for controlling interferences
and titrating mixtures of ions
Ex CN- F-, thiourea (NH2)2CS
Masking agent an auxiliary ligand that preferentially
forms highly stable complexes with the potential
interference
- used to prevent one element from interfering
the analysis of another element
e.g. Al3+ in a mixture of Mg2+
- Al3+ can be measured by first masking the Al3+ with
F-, thereby leaving only the Mg2+ to react with EDTA.
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Sample Problem:
A 25.00 mL aliquot of a solution containing Hg2+ in dilute
HNO3 was treated with 10.00 mL of 0.04882 M EDTA and the
pH was adjusted to 10.00 mL with an NH3 buffer. Two drops
of EBT were added and the unreacted EDTA was back-
titrated with 0.01137 M Mg2+, requiring 24.66 mL to reach
the endpoint. What is the molarity of Hg2+ in the sample?
Widely used technique for controlling interferences
and titrating mixtures of ions
Ex CN- F-, thiourea, (NH2)2CS
Masking agent an auxiliary ligand that preferentially
forms highly stable complexes with the potential
interference
- used to prevent one element from interfering
the analysis of another element
CN- masks Cd2+, Zn2+, Hg2+, Co2+, Cu+, Ag+, Ni2+, Pd2+, Pt2+,
Fe2+, and Fe3+, but not Mg2+, Ca2+, Mn2+, or Pb2+.
e.g. when CN- is added to a solution containing Cd2+ and
Pb2+, only Pb2+ reacts with EDTA.
Demasking agent causes the release of a metal
from masking complex
CN- complexes can be demasked with formaldehyde:
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Sample Problem:

A 25.00 mL sample of unknown containing Fe3+ and Cu2+ required

16.06 mL of 0.05083 M EDTA for complete titration. A 50.00 sample
of the unknown was treated with NH4F to protect the Fe3+. The Cu3+
was reduced and masked by addition of thiourea. Upon addition of
25.00 mL of 0.05083 M EDTA, the Fe3+ was liberated from its
fluoride complex and formed an EDTA complex. The excess EDTA
required 19.77 mL of 0.01883 M Pb2+ to reach an endpoint using
xylenol orange. Find the concentration of Cu2+ and Fe3+ in M.

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