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Precipitatometric Titration
Precipitatometric Titration
(PRECIPITATION)
TITRATION
An application method of
Inorganic Pharmaceutical Analysis
Lecturer : Dr. Tutus Gusdinar
Pharmacochemistry Research Group
School of Pharmacy
INSTITUT TEKNOLOGI BANDUNG
Precipitatometric Titration
Compared to acid-base or reduction-oxidation
titrations the precipitatometric titration has no much
more methods
Difficult to select a suitable indicator
Difficult to obtain an accurate precipitate composition,
the coprecipitation
p
p
effect is oftenly
y occured.
BaSO4(p)
4( )
Ba2+ + SO42-
Solubility
y
s
Saturated
X (concentration
(
t ti off ion)
i )
Temperature
Solvent properties
Common ions
Ionic activity
pH
Hydrolysis
eta hydroxyde
yd o yde
Metal
Complex compound formation
1. Temperature effect
Most of inorganic salts increase its
solubility by increasing temperature
temperature. Its
better to use hot/warm solution for filtering
and
d washing
hi precipitate.
i it t E
Exception
ti :
precipitates which are slighty soluble in
hot/warm solution (e.g. Hg2Cl2,
g 4PO4) could be filtered after
MgNH
previously stored in refrigerator.
2. Solvent effect
Most of inorganic salts dissolve in water but not in organic
solvent. Water molecule has a higher dipole moment and
could be attracted by cations or anions to form hydrate
ions Like hydrogen ion forming a hydrated ion
ions.
ion,H
H3O+, free
energy released by ionsolvent interaction could increase
attractive ionic force to precipitate more solid lattice.
Crysstaline ions have no attractive force into organic
solvents, its solubilityy is smaller than those in water. In
chemical analysis, solubility difference could be used as
basic of separation of many compounds. Example : mixed
off Ca(NO
C (NO3)2 and
dS
Sr(NO
(NO3)2 can be
b separated
t d iin solvent
l
t
mixture containing alcohol and eter, which yields a soluble
Ca(NO3)2 and an insoluble Sr(NO3)2.
10-4
AgBr
g
10-6
AgI
10-88
10-10
10-8
10-6
10-4
10-2
Concentration of NaX, M
4 C
4.
Common iion effect
ff t
Most of precipitated compounds increase its solubility in a
solution containing substance not reacted to precipitate
ions. This phenomena is called as ionic activity effect or
diverse ion effect or neutral salt effect.
effect For example,
example solubility
of AgCl and BaSO4 in KNO3 solution.
[KNO3] (M)
[AgCl]x10-55 M
[BaSO4]x10-55 M
0,000 (water)
1,00
1,00
0 001
0,001
1 04
1,04
1 21
1,21
0,005
1,08
0 010
0,010
1 12
1,12
=12%
1,48
1 70
1,70
=70%
BaSO4
1,5
1,4
13
1,3
1,2
AgCl
1,1
10
1,0
0,001
0,005
0,01
KNO3, M
5. pH effect
Solubility of weak acid salt depends on pH of the solution.
For example : oxalic, sulfide, hydroxyde, carbonate,phosphate.
Proton reacts with the anion to form weak acid, and increases
salt solubility.
a) Monovalent salt :
MA(p)
M+ + AHA + H2O
H3O+ + AAnalytical concentration Ca = [A-] + [HA] = [A-]{[H3O+]+Ka}/Ka
Fraction of A- : [[A-]]/Ca = Ka / {[H
{[ 3O+]]+Ka = 1
[A-] = 1 .Ca
Substituted to the Ksp
p = [[M+][
][A-] = [M
[ +]]. 1.Ca
Ksp/1 = Keff = [M+].Ca
Keff = Effective equilibrium constant, varied on the pH
for pH depends to 1.
b) Divalent salt :
MA2
H2A + 2 H2O
Fe3+
-1
FeOH2+
-2
-3
-4
Fe(OH)2+
-5
-6
Fe2(OH)24+
-7
0
pH
HS-
-2
-6
-3
Hg total
-7
-4
4
-8
Hg.HS2-
-5
Hg(HS)2
HgS22-
-9
9
4
pH
10
6. Hydrolysis
6
yd o ys s e
effect
ect
A weak acid salt dissolved in water changes pH of the solution.
MA
M+ + AA- + H2O
HA + OHA veryy weak acid HA has lower Ka and an insoluble MA has
lower Ksp. At a lower [A-] hydrolysis reaction is completed.
Depend
p
to the Ksp
p it should show two extreeme conditions :
a) A very low solubility of precipitate where pH is not changed
by hydrolysis reaction.
b) A high solubility of precipitate where OH- ion produced from
water molecule is neglected.
s=
Ksp/4
-2
-3
-4
log[Cl-]
-4
-3
-4
-5
5
-6
-7
-1
log[Ag+]
-3
log[Ag+]
-2
log[Cl-]
Titration Curve
In a titration of 50 ml of NaCl 0.10 M solution with a solution
of AgNO3 0.10
0 10 M
M, calculate chloride ion concentrations
during the titration and plot a titration curve of pCl vs ml of
AgNO3. Ksp AgCl = 10 x 10-10.
Condition before titration : [[Cl-] = 0.10 M or p
pCl = 1.00
After addition of 10 ml AgNO
g 3:
Ag+
+
ClAgCl (p)
initial
1.00 mmol
5.00 mmol
change
-1.0 mmol
-1.0 mmol
equilibrium 4.0 mmol
[Cl-] = 4.00 mmol / 60.0 ml = 0.067 M or pCl = 1.17
ARGENTOMETRIC
TITRATION CURVES
AgI
AgBr
13
11
Ksp AgCl = 1 x 10-10
12
KspAgBr = 2 x 10-12
KspAgI = 1 x 10-16
pX
X 10
AgCl
8
6
4
2
10
20
30
40
50
60
70
80
ml of AgNO3
Titration Feasibility
As in an acid-base titration, the feasible K value of precipitation
reaction could be calculated from its ionic concentrations.
Example :
A solution of 50 ml of NaX 0.10 M is titrated with 50 ml of
A NO3 0.10
AgNO
0 10 M
M. Calculate
C l l
the
h K and
d Ksp
K off AgX
A X when
h
addition of 49.95 ml of the titrant could achieve a completed
stoichiometric ionic reaction
reaction, where the pX changed in 2.00
2 00
units at the addition of 2 drops (0,10 ml) of titrant solution.
Consider NaX as a complete dissolved salt
salt, the reaction is :
Ag+ + XAgX (p)
K = 1/Ksp.
1/Ksp An addition of one drop of titrant performed before
the equivalent point consumes 4.995 mmol of Ag+, and
dissolved Ag+ needed to reach the equivalent point is :
(50 x 0.10) 4.995 mmol = 0.005 mmol.
Methods in
precipitatometric
p
p
titration
Argentometric method
Mercurimetric method
Kolthoff titration
Argentometric titration
ARGENTOMETRY
MOHR
Dichromate
AgCl (p)
Ag2CrO4 (p) red
At the
th equivalent
i l t point
i t : pAg
A = pCl
Cl = 5.00
5 00
2 ] = 2.00
12
[Ag+][CrO
[A
][C O422 00 x 10-12
Then [CrO42-] = 2.00x10-12 / (1.0x10-5)2 = 0.02 M
(dichromate)
If
is too low ( < 0,005 M) then the
reaction needs excessive addition of [Ag+] to
precipitate Ag2CrO4; this might be a titration
error.
error
Dichromate ion, Cr2O72-, can not be used as
indicator as Ag2Cr2O7 precipitate is easily
dissolved in this ionic solution.
ARGENTOMETRY
- VOLHARD
Br- + Ag+
AgBr (precipitate)
excess
Ag+ +
SCN-
AgSCN (solution)
ARGENTOMETRY
FAJANS
Cl-
ClCl-
ClCl
Cl-
AgCl
Cl-
Cl-
Ag+ IndAg+
ClAgCl
Ag+ IndAg+
Ag+ IndAg+
Ag+ Ind-
M+
Secondary layer
Excess of Cl-
After Eq.Pt.
q
:
(AgCl).Ag+
X-
Primary
y layer
y
Secondary
y layer
y
Excess of Ag
g+
Adsorption Indicators
INDICATOR
ANALYTE
TITRANT
REACTION
CONDITION
Diklorofluorescein
Fluorescein
Eosin
Thorin
Bromcresol green
Methyl violet
Rhodamin 6G
O th h
Orthochrome
T
Bromphenol blue
Ag+
Ag+
Ag+
Ba2+
Ag+
ClBr2
C O42CrO
Cl-
pH = 4
pH = 7 8
pH = 2
pH = 1,5 3,5
pH = 4 5
acid solution
HNO3 upto 0,3 M
neutral
t l 0,02
0 02 M soln
l
solution of 0,1 M
TITRANT
INDICATOR
METHOD
Cl-, Br-
AgNO3
K2CrO4
Mohr
Cl-,Br
Br-,II-,SCN
SCN-
AgNO3
Adsorption
Fajans
Br-,I-,SCN-,AsO43-
AgNO3 + KSCN
Fe(III)
Cl-,CN-,CO32-,S2C2O42-,CrO42-
AgNO3 + KSCN
Fe(III)
FSO42PO432
C O42CrO
Ag+
Zn2+
Hg22+
Th(IV)
BaCl2
PbAc2
PbA 2
PbAc
KSCN
K4Fe(CN)6
NaCl
Alizarin
Tetrahydroxyquinoline
Dibromofluorescein
Fl
Fluorescein
i
Fe(III)
Diphenylamine
Bromphenol blue
Volhard
(not filtered)
Volhard
(filtered)
Fajans
Fajans
Fajans
F j
Fajans
Volhard
Fajans
Fajans
MERCURIMETRIC TITRATION
Hg2+ + 2 Cl-
KOLTHOFF TITRATION
Determination of Zn2+ (as titrant) which is precipitated with standard solution of
K-Ferrocyanide
2 K4Fe(CN)
( )6 + 3 Zn2+
potassium ferro (II) cyanide
K2Zn3[[Fe(CN)
( )6]2 + 6 K+
potassium zink ferro (II) cyanide
The END