Precipitation Formation Titrations

I. General Principles
A. Involves formation of a precipitate
B. Must determine the volume of a
standardized titrant needed to just
precipitate all of the ion.
C. Need an indicator or electrode to
determine when the precipitation is
complete
II. For Method to Work
A. Must produce a very insoluble precipitate

B. Must have an indicator

III. Factors Affecting Solubility of A Precipitate

A. Temperature

B. Solvent

C. Common Ion Effect

D. Diverse (Neutral Salt, Activity) Effect

Molarity KNO3

0.000 M
0.001 M
0.005 M
0.010 M

Molar Solub. AgCl

1.00 x 10-5 M
1.04 x 10-5 M
1.08 x 10-5 M
1.12 x 10-5 M

Molar Solub. BaSO4

1.00 x 10-5 M
1.21 x 10-5 M
1.48 x 10-5 M
1.70 x 10-5 M

E. Effect of pH (high acidity)

1. Solubility of some salts (salts of weak
acids) depends on pH.

2. Example
CaC2O4 Ca +2 + C2O4-2
Ksp = [Ca+2] [ C2O4-2]
&2

C2O4-2 + H+ HC2O4-

Ka2 '

HC2O4- + H+ H2C2O4

CaC2O4 9

H+

&

[HC2O4 ]
&

Ka1 '

Ca+2

[H %][C2O4 ]

[H %][HC2O4 ]
[H2C2O4]

H+

C O HC O H C O
-2

F. Effect of Hydrolysis

1. Insoluble Salt MA 9
MA M+ + A2. Suppose A- is a salt of a very weak
Acid
A- + H2O HA + OH 3. Effect:

G. Effect of Complexation
1. Insoluble Salt e.g. AgCl
AgCl Ag+ + Cl 2. Suppose Ag+ forms a complex
Ag+ + 2 NH3 Ag (NH3)2+
3. Effect-

IV.

Regents Forming Organic Precipitates

A. Reagents Forming Chelate Compounds

1.

O
H
N

2.

Al+3

:N

B. Reagents Forming Salt-like Precipitate

1.
O O
O O
|| ||
||
||
C - C + Ca+2 >
C- C
/
\
/
\
O
O
O
O
\
/
Ca

2. B (C6H5)4- Tetraphenylboron
(-)

K+ + B(C6H5)4 - -----> KB (C6H5)4 9

3. Benzidine To Precipitate SO4-2
H

H
N:

:N

+ H2SO4

9
H

:N

N-H

+
H

SO4-2

V. Properties Desired of a Rxn For pptn

Titration
A. Very rapid rxn

B. Single stoichiometric rxn

C. Marked change in conc. of one of the

reactants or products at the endpoint

D. Indicator must exist to show the change

in concentration of the reactant or
product at the endpoint.

VI.

Titration Curve
A. For Ag+ + Cl- AgCl
B. Titrate Cl- unknown with
standardized Ag+
C. Monitor [Cl-]. Calculate pCl
pCl= -log [Cl-]
D. Plot pCl versus ml Ag+ added
Until EP [Cl-] relatively high
After EP [Cl-] relatively low
See large change in [Cl-] (pCl) at EP

PCl

ml Ag+

VII.

Theoretical Calculation of Titration

Curve
A. For known [Cl-] & known volume of
Cl- -titrate with standardized Ag+
soln.
Calculate pCl as a function of ml of
Ag+ added
B. Major Points
1. Start of Titration 0.00 ml
[Cl-] =
p Cl = - log [Cl-]

2. Prior To Equivalence Point

Calc. # moles Cl#
moles Ag+
That are mixed together
Calc. # moles Cl- remaining
number of moles Cl & remaining
[Cl ] '
number liters of solution
&

3. At Equivalence Point
Calc. solubility of AgCl in distilled
water
Solubility = [Cl-]

4. Beyond the equiv point

Calc. excess [Ag+]
[Cl -] = Ksp, AgCl
---------[Ag+] excess
pCl = -log [Cl-]

Calculation of Titration Curve for 50 ml of

0.100 M NaCl with 0.100 M of AgNO3.
Plot pCl vs ml of AgNO3 added at 1) start
of titration 2) after addition of 10.0 ml of
AgNO3 3) after addition of 49.9 ml AgNO3,
4) Equiv. pt; 5) After addition of 60 ml
AgNO3
1. At start of Titration

ie 0 ml AgNO3

[Cl-] = 0.100 M

-log [Cl-] = -(-1) = 1.0

2. After 10 ml AgNO3
Ag+ + Cl- AgCl
[Cl-]i = 0.100
m moles Cl & '

.100 mmoles
(50 ml)
ml

= 5.0 mmoles
mmoles Ag+ added = .100 mmoles/ml (10.0 ml)
= 1.0 mmoles
mmoles Cl- left = 5.0 mmoles -1.0 mmoles =
= 4.0 mmoles
Total Vol = 50 ml + 10 ml = 60 ml
[Cl-] = 4 mmoles ' 0.067 M
60 ml

pCl = 1.17

3. After Add of 49.9 ml

m moles of Cl- in solution = .
0.100 mmoles (50 ml) = 5.00 mmoles
ml

m moles of Ag+ added=

0.100 mmoles (49.9ml) = 4.99 mmoles
ml

_____________________________
mmoles Cl- left =
0.01 mmoles
Total Vol= 50 ml + 49.9 ml
[Cl-] = .01 mmoles ' 1.00x 10&4 M
99.9 ml

pCl = 4.00

4. After Add 50.0 ml-Equiv. pt

a) Neither an excess of Cl- or Ag+
b) Only source of Cl- is from
AgCl Ag+ + ClKsp = [ Ag + ] [ Cl - ]= 1.0 x 10-10
[ Ag + ] = [ Cl - ] = x
pCl = 5.00

5. After Addition of 60.0 ml AgNO3

Excess in Ag+
mmoles of Cl & i n solution ' .100

mmoles of Ag% in solution ' .100

mmoles
ml

50ml'5.0 mmoles

mmoles
60 ml ' 6.0 mmoles
ml

___________________
Excess Ag+ =1.0 mmoles

Total Vol = 50 ml + 60 ml = 110 ml

[Ag+] = 1.0 mmoles/ 110 ml = 9.1 x 10 -3 M
Ksp = 1 x 10-10 = [Ag+][Cl-]
[Cl &] '

1 x 10&10
[Ag %]

'

1.0 x 10&10
9.1 x 10&3

' 1.10 x 10&8

pCl = -log (1.10 x 10 -8) = 7.96

PCl

*
*
*
ml Ag+