Acids and Bases

Chapter 12 • Definitions: Lewis – Electrons (acid: electron pair acceptor);

BrØnsted-Lowry (acid: proton donor)

EDTA Titrations
Lewis acid-base concept in Metal-Chelate Complexes

Metal ions (electron pair acceptor) Lewis acid

Ligand (electron pair donor) Lewis base

Coordination Number Complex Formation

Formation of coordinate bonds between Lewis Acids/Bases
K1
Ag ( aq ) + NH (aq)
+
Ag ( NH ) ( aq ) +

• The atom of the ligand 3

K2
3

Ag ( NH ) ( aq ) + NH (aq)
+
+
Ag ( NH ) ( aq )
that supplies the 3 3 3 2

+
nonbonding electrons [ Ag ( NH ) ] [ Ag ( NH ) ]
+

K = 3
K = 3 2

for the metal-ligand 1

[ Ag ][ NH ]
+ 2
[ Ag ( NH ) ][ NH ]
3
+

3
3
bond is the donor atom.
Formation constants (Kf) are the equilibrium constants for complex ion
• The number of these formation. The overall, or cumulative, formation constants are
atoms is the denoted i
coordination number. Ag (aq) + 2 NH (aq)
+
3
Kf
Ag ( NH ) (aq)
3 2
+

+
[ Ag ( NH ) ]
K = 3
= β = K ⋅K
2

[ Ag ][ NH ]
f + 2 2 1 2
3

Geometries Ligands
There are two common • Monodentate ligand: binds to
geometries for metals with a metal ion through only one
a coordination number of atom, e.g., CN-
four: • Multidentate ligand or
Tetrahedral & Square planar chelating ligand: has more
than one ligand donor atoms.
By far the most- • In ethylenediamine,
encountered geometry, NH2CH2CH2NH2 (i.e., en),
when the coordination each N is a donor atom.
number is six, is octahedral. en is bidentate.

1
 Chelating Effect
A multidentate ligand to form more stable metal complexes
than those formed by similar monodentate ligand

Chelating Agents EDTA

Ethylenediaminetetraacetic acid (H4EDTA or H4Y)
• Porphyrins (tetradentate ligands, in Ethylenediaminetetraacetate anion (EDTA-4 or Y-4)
heme and chlorophyll)
Ethylenediaminetetraacetate, mercifully abbreviated
EDTA, has six donor atoms.
• Adenosine triphosphate (ATP)
EDTA is a primary standard material.

Some Metals Form 7 or 8 EDTA Complexes

Coordinate Complexes
• EDTA forms 1:1 complexes with most metals (Not with
Group 1A metals)

• EDTA complexes are usually stable water soluble

complexes with high formation constants

• Formation constant, Kf, (or stability constant):

M n + + Y 4− ↔ MY n −4 Kf =
[MY ] n−4

[M ][Y ]
n+ 4−

• Kf could have been defined for any form of EDTA

2
 pH affects EDTA titration
Acid-Base Properties of EDTA:
CH2CO2H
HO2CH2C
EDTA is a hexaprotic
HNCH2CH2NH system (H6Y2+) with
HO2CH2C CH2CO2H
4 carboxylic acids
and 2 ammoniums
H6Y2+

pK1 = 0.0 pK 2 = 1.5 pK 3 = 2.0 pK 4 = 2.66

pK 5 = 6.16 pK 6 = 10.24

Mn+ + Y4− ↔ MYn−4

pH:

Hn Yn−4

Fraction of EDTA in the form Y4- pH Dependence of Y4-

αY =
[Y ] 4−

4−
[H Y ]+ [H Y
6
2+
5
+
] + [H Y ] + [H Y ] + [H Y ]+ [HY ]+ [Y ]
4 3
−
2
2− 3− 4−

[Y 4− ] [Y 4− ]
αY = 4− =
[ EDTA] C EDTA

K1K2K3K4 K5K6
ααY ==
44−Y −
{[H ] +[H ] K +[H ] K K +[H ] K K K +[H ] K K K K +[H ]K K K K K + K K K K K K }
+ 6 + 5
1
+ 4
1 2
+ 3
1 2 3
+ 2
1 2 3 4
+
1 2 3 4 5 1 2 3 4 5 6

Fractional Composition Diagram for EDTA Conditional Formation Constant

[ MY n − 4 ]
M n + + Y 4− ⇔ MY n− 4 Kf =
[ M n + ][Y 4 − ]

[Y ]
4-
[Y ] = α [EDTA] Kf =
[MY ] n−4
[MY ] n−4
αY =
[M ][Y ] = [M ]α [EDTA]
4-
4−
[EDTA] Y 4− n+ 4− n+
Y 4-

Conditional formation
K f' = α Y 4- K f =
[MY ] n−4

constant: [M ][EDTA ]
n+

Fixing the pH by buffering, then α Y 4− is a constant.

At any fixed pH, find α Y 4− and evaluate Kf’

3
 Example: Calculate the concentration of free Ca2+ in a EDTA Titration Curve
solution of 0.10 M CaY2- at pH 10 and pH 6. Kf for
CaY2- is 1010.65 (Table 12-2) 1. Excess Mn+ left after each
addition of EDTA. Conc. of free
Ca 2+
+ EDTA ↔ CaY 2−
K = α Y 4− K f
'
f metal equal to conc. of unreacted
at pH = 10.00, K = α K = (0.30)(10 ) = 1.3 × 10
'
f Y 4− f
10.65 10
Mn+.

at pH = 6.00, K = α K = (1.8 ×10 )(10 ) = 8.0 × 10

'
f Y 4− f
−5 10.65 5

2. Equivalence point: [Mn+] =

Ca 2+ + EDTA ↔ CaY2−
[EDTA] Some free Mn+ generated
by MYn-4 ⇔ Mn+ + EDTA
Conci 0 0 0.1
Concf x x 0.1 - x
3. Excess EDTA. Virtually all
K f' =
[CaY ] 0.1 − x
2−
[ ]
x = Ca 2+ = 2.7 ×10−6 M at pH = 10 metal in MYn-4 form.
[Ca ][EDTA ] = x
2+ 2
= 3.5 ×10-4 M at pH = 6

EDTA Titration Curve EDTA Titration Curve

EXAMPLE: Derive a titration curve for the titration of 50.0
1. Titration reaction: mL of 0.040 M Ca2+ (buffered at pH=10) with 5.00, 25.00, and
M n+ + EDTA⇔ MYn−4 Kf =αY4− Kf 26.00 mL of 0.080 M EDTA.
'

Ca 2+ + EDTA → CaY 2 −
K f' = α Y 4− K f = 0.30 *1010.65 = 1.3 × 1010
2. Reaction completes at each
point in the titration if Kf’ is large.
At equivalence point, Vol. of EDTA = 25.0 mL

5.00 ml, Before the equivalence point

3. Plot pM (= -log[Mn+]) vs. 25.00 ml, At the equivalence point
volume of EDTA added 26.00 ml, After the equivalence point

EDTA Titration Curve EDTA Titration Curve

EXAMPLE: Derive a titration curve for the titration of 50.0
EXAMPLE: Derive a titration curve for the titration of 50.0
mL of 0.040 M Ca2+ (buffered at pH=10) with 5.00, 25.00, and
mL of 0.040 M Ca2+ (buffered at pH=10) with 5.00, 25.00, and
26.00 mL of 0.080 M EDTA. 26.00 mL of 0.080 M EDTA.

At equivalence point, Vol. of EDTA = 25.0 mL

At equivalence point, Vol. of EDTA = 25.0 mL almost all the metal is in the form, CaY2-
5mL before the equivalence point
[CaY ] = (0.040)
2- 50.0
25.00 + 50.0
= 0.0267 M
[Ca ]2+
=
25.0 - 5.0
25.0
(0.040)
50.0
5.00 + 50.0
= 0.0291 M
Ca 2+ + EDTA ↔ CaY 2−
Conci 0 0 0.0267 K f' =
[CaY ] 0.0267 − x
2−

[Ca ][EDTA] = x = 1.8 ×10

10
2+ 2
Concf x x 0.0267 - x
Fraction
Remaining
x = 1.2 ×10 −6 M
2+
pCa = − log(0.0291) = 1.54 pCa 2+ = − log(1.2 × 10−6 ) = 5.91

4
 EDTA Titration Curve
EXAMPLE: Derive a titration curve for the titration of 50.0
mL of 0.040 M Ca2+ (buffered at pH=10) with 5.00, 25.00, and
26.00 mL of 0.080 M EDTA.

At equivalence point, Vol. of EDTA = 25.0 mL

26.00 mL 1.0 mL excess EDTA, after the equivalence point

1.00
[EDTA ] = (0.080) = 1.05 × 10 −3 M
50.0 + 26.00

[CaY ] = (0.040)
2- 50.0
50.0 + 26.00
= 2.63 ×10 −2 M

K f' =
[CaY ]
2−
2.63 ×10 −2

Ca 2+ = 1.4 ×10 −9 M
[Ca ][EDTA] = [Ca ](1.05 ×10
2+ 2+ −3
)
= 1.8 ×1010
pCa 2+ = 8.86

pH affects the titration of Ca2+ with EDTA

Auxiliary Complexing Agents

• A ligand that binds strongly enough to the metal to

prevent hydroxide precipitation, but weak enough to
be displaced by EDTA (e.g., ammonia, tartrate,
citrate, or trithanolamine)
Ammonia is a common auxiliary complex for transition metals
like zinc (p. 239)
K 'f' = α Zn 2+ α Y 4− K f
Kf’’ is the effective formation constant at a fixed concentration of
auxiliary complexing agent.

5
 Metal Ion Indicators Metal Ion Indicators
• To detect the end point of EDTA titrations, we usually
use a metal ion indicator or an ion-selective electrode
(Ch. 15)

• Metal ion indicators change color when the metal ion is

bound to EDTA:
MgEbT + EDTA ↔ MgEDTA + EbT
(Red) (Colorless ) (Blue)

– Eriochrome black T is an organic ion

• The indicator must bind less strongly than EDTA

EDTA Titration Techniques Example: 25.0 mL of an unknown Ni2+ solution was

• Direct titration: analyte is titrated with standard EDTA
with solution buffered at a pH where Kf’ is large
• Back titration: known excess of EDTA is added to
analyte. Excess EDTA is titrated with 2nd metal ion.
treated with 25.00 mL of 0.05283 M Na2EDTA. The pH
of the solution was buffered to 5.5 and than back-titrated
with 17.61 mL of 0.02299 M Zn2+. What was the
unknown Ni2+ in M?
mol EDTA = (25.00 mL)(0.05283 M) = 1.32 mmol EDTA

Zn 2+ + Y 4- ↔ ZnY 2-

mol Zn 2+ = (17.61 mL)(0.02299 M) = 0.4049 mmol Zn 2+

Ni 2+ + Y 4- ↔ NiY 2-
2+
mol Ni = 1.321 mmol EDTA - 0.4049 mmol Zn 2+ = 0.916 mmol

M Ni 2+ = (0.916 mmol)/(25.00 mL) = 0.0366 M

EDTA Titration Techniques

• Direct titration: analyte is titrated with standard EDTA with
solution buffered at a pH where Kf’ is large

• Back titration: known excess of EDTA is added to analyte.

Excess EDTA is titrated with 2nd metal ion.

• Displacement titration: For metals without a good indicator ion,

the analyte can be treated with excess Mg(EDTA)2-. The analyte
displaces Mg, and than Mg can be titrated with standard EDTA

• Indirect titration: Anions can be analyzed by precipitation with

excess metal ion and then titration of the metal in the dissolved
precipitate with EDTA.

• Masking agent: protects some componet of the analyte from

reaction with EDTA (render metal ions inactive without actually
removing them from solution). Demasking: releasing metal ion
from a masking agent.