PRECIPITATOMETRIC

(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.
Solubility = a saturated concentration of analyte
(crysstaline or solid form) dissolved in solvent at a
defined temperature.
BaSO4(p)
4( ) Ba2+ + SO42-
Solubility Product Constant : Ksp = [Ba2+] [SO42-]
(at equilibrium state)
Solubility product
Saturated solution is occured when a
continuous addition of a substance is
performed into its solvent until dissolution
precess is terminated
terminated, or it can be
achieved by increasing ionic concentration
until
ntil the precipitate formation
formation.

Solubility is influenced by temperature,

solvent properties
properties, and other ions
existed in a solution.
Solubility
y
s

Saturated

X (concentration
( t ti off ion)
i )
 Factors influencing the solubility

1. Temperature
2. Solvent properties
3. Common ions
4
4. Ionic activity
5. pH
6. Hydrolysis
7. eta hydroxyde
Metal yd o yde
8. 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 EException
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,HH3O+, free
energy released by ion–solvent 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 dSSr(NO
(NO3)2 can beb separatedt d iin solvent
l t
mixture containing alcohol and eter, which yields a soluble
Ca(NO3)2 and an insoluble Sr(NO3)2.
 3 Common ion effect
3.
Precipitate dissolves more easily in water than in solution
containing
t i i common iions. F For example,
l iin A
AgCl,
Cl solubility
l bilit
product of [Ag+][Cl-] < its constant of solubility product (Ksp
AgCl = 1x10-10) in pure water,
water where [Ag+]=[Cl-] = 1x10-5 M;
when AgNO3 is added upon [Ag+] = 1x10-4 M, the [Cl-]
decreases into 1x10-6 M,M and reaction shifts to the right side
as : Ag+ + Cl- AgCl
There is salt addition to the pprecipitate
p while concentration
of Cl- decreases.
This technique of common ion addition is oftenly used for :
1) completion of precipitation process
2) precipitate washing with a solution containing
common ion effect
If there is exessed common ions in a solution, the
precipitate solubility will be greater than estimated Ksp,
then common ion addition must be limited up to 10%.
Example : Calculate molar concentration of CaF2 dissolved
in a) water; b) CaCl2 0,01 M; c) NaF 0,01 M. Ksp CaF2 =
4 10-11
4x10 11. Hydrolysis
H d l i iis neglected.
l t d
CaF2(p) Ca2+ + 2 F-
a)) Solubility
S C 2+
s = [Ca 2 ], then [F-] = 2s

[Ca2+][F-] = Ksp
s . (2s)2 = 4x10-11, then s = 2,1 x 10-4 M
b) [Ca2+] = (0,01+s) ; [F-] = 2s; then s = 3,2 x 10-5 M
c) [Ca2+] = s ; [F-] = (0,01+s); then s = 4 x 10-7 M
Common ions decrease precipitate solubility, [F-] effect is
greater than [Ca2+] effect.
 Solubility of Ag-halide in Na-halide at 18 oC
Solubility of AgX, M
1

10-2

AgCl
10-4
AgBr
g
10-6
AgI
10-88

10-10

10-8 10-6 10-4 10-2 1

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
Δ=12% Δ=70%
0,005 1,08 1,48
0 010
0,010 1 12
1,12 1 70
1,70
Molarity is an ionic activity occured in a high diluted solution,
more concentrated solution decreases faster the activity
coefficient (f), caused by greater different charge of
attractive ionic force. The ionic effectivity (in equlibrium state)
decreases as well, and addition of precipitate is required to
recover ionic activity.
aAg+ . aCl- = Kosp (Ksp at a defined state of ionic activity)
fAg+[Ag+] . fCl- [Cl-] = Kosp
[Ag+][Cl-] = Kosp / fAg+ . fCl- = Ksp
The lower activity coefficient of both ion yields the greater
molar concentration of product. Increased BaSO4 solubility is
greater than solubility of AgCl, or ionic activity coefficient of
divalent ion is smaller than those of univalent ion.
In highly diluted solution the f = 1 and the Ksp = Kosp.
 Relative augmentation of the solubility
of AgCl and BaSO4 in KNO3 solution
s/so

1,7

16
1,6
BaSO4
1,5

1,4

13
1,3

1,2 AgCl

1,1

10
1,0
0,001 0,005 0,01 KNO3, M
Example : Calculate molar solubility of BaSO4 in KNO3
0,01 M solution using activity coefficient calculated by Debye-
Huckel equation. Solution of KNO3 (1:1) has ionic strength
equal to its molarity of 0,01M. Read from the table : fBa2+ =
0,667 ; fSO42- = 0,659.

Ksp = 1,00 x 10-10 / 0,667 x 0,659 = 2,27 x 10-10 = s2

then s = 1,51 x 10-5 M.

For it’s performed in neglected very low ionic solubility, the

activity effect is not a serious problem in the chemical analysis.
Precipitation process in high ionic concentration is quiet rare.
Hence, ionic activity influence gives no significant error.
 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+ + A-
HA + H2O H3O+ + A-
Analytical concentration Ca = [A-] + [HA] = [A-]{[H3O+]+Ka}/Ka
{[ 3O+]]+Ka = α1
Fraction of A- : [[A-]]/Ca = Ka / {[H
[A-] = α1 .Ca
Substituted to the Ksp p = [[M+][ [ +]]. α1.Ca
][A-] = [M
Ksp/α1 = Keff = [M+].Ca
Keff = Effective equilibrium constant, varied on the pH
for pH depends to α1.
b) Divalent salt :
MA2 M2+ + 2 A2-
H2A + 2 H2O 2 H3O+ + A2-

Kef = Ksp/α12 = [M2+] Ca2

[A2-] = α2 . Ca

α2 = Ka1.Ka2 / { [H3O+]+[H3O+]Ka1+Ka1Ka2 }

Kef = Ksp/α2 = [M2+] . Ca

Molar concentration of iron species in a ferric hydroxyde
solution as function of pH in room temperature

log C
Fe3+ [Fe3+][OH-]3 = Ksp = 2 x 10-39
-1
[FeOH2+][H+]/[Fe3+] = 9 x 10-4
FeOH2+ [Fe(OH)2+][H+]2/[Fe3+] = 5 x 10-7
-2 [Fe2(OH)24+][H+]2/[Fe3+]2 = 1,1 x 10-3
-3

-4
Fe(OH)2+
-5

-6

Fe2(OH)24+
-7

0 1 2 3 4 5
pH
 Solubility of HgS at 20 oC as function of pH in a
solution containing total sulfide H2S + HS-
log [Hg]total, log [Hg(HS)2], dst log [H2S],log [HS-]

H2S HS-
-2
-6

Hg total -3
-7

-4
4

-8

Hg(HS)2 -5
Hg.HS2- HgS22-
-9
9
4 5 6 7 8 9 10
pH
 6. Hydrolysis
6 yd o ys s e
effect
ect
A weak acid salt dissolved in water changes pH of the solution.
MA M+ + A-
A- + H2O HA + OH-

A 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.
 7. Metal hydroxyde effect
As occured by hydrolysis effect, when a metal hydroxyde
dissolved in water
water, the pH will be not changed
changed.
M(OH)2 M2+ + 2 OH-
OH- + H2O H3O+ + OH-
[M2+][OH-]2 = Ksp
[H3O+][OH-] = KwK
Charge balance : 2 [M2+] + [H3O+] = [OH-]
M l solubility
Molar l bilit can bbe calculatd
l l td ffrom th
these 3 equations.
ti
When M(OH)2 dissolved then [OH-] increases, this anion will
shift
hif water di
dissociation
i i reactioni to theh lleft
f (H2O is
i formed)
f d) :
M(OH)2 (p) M2+ + 2 OH-
2H2O H3O+ + OH-
Depend to solubility of OH- it should show two extreeme
conditions :
a) A very low solubility of precipitate where pH is not
changed by the reaction.
[H3O+] = [OH-] = 1,0
1 0 x 10-7
Ksp = [M2+][OH-]2
(1 0 x 10-7)2
s = Ksp / (1,0
b) A high solubility of precipitate increases [OH-], but
[H3O+] is very low (neglected).
Charge balance of these equation is either 2[M2+] =
[[OH-] or [OH
[ -] = 2s
Ksp = [M2+][OH-]2 = s (2s)2
3
s= Ksp/4
 8. Complex compound formation effect
Slightly soluble salt solubility is influenced by a compound
forming complex to the metal cation
cation. Complexing ion could be
an anion or a neutral molecule which is common or diverse to
e g hydrolysis effect of complexing ion of OH-.
the precipitate; e.g.
Example : NH3 is used for separing Ag from Hg.
Ag+ + NH3 Ag(NH3)+ 2 3 x 103
K1 = 2,3
Ag(NH3)+ + NH3 Ag(NH3) 2 + K2 = 6,0 x 103

Non-complexed silver fraction (β2) can be calculated as follow:

β2 = 1 / { 1 + K1[NH3] + K1K2[NH3]2 } = [Ag+] / CAg
Ksp = [Ag+][Cl-] = β2 CAg [Cl-]
Ksp/β2 = Kef = CAg [Cl-]
Example : Calculate molar solubility of AgCl in the solution
of NH3 0,01
0 01 M (as a final concentration of free ammonia
solution). Ksp AgCl = 1,0 x 10-10. Stability constant K1 =
2,3 x 103 and K2 = 6,0 x 103.

β2 = 1 / {{1 + 2,3
, + 103((10-2) + 1,4
, x 107 ((10-2)2 = 7,1
, x 10-4
Keff = 1,0 x 10-10 / 7,1 x 10-4 = 1,4 x 10-7
s = CAg = [[Cl-]
s2 = 1,4 x 10-7 , and s = 3,4 x 10-4 M

In existed precipitating ions, most of precipitate could form

soluble complex compound.
compound In the first step
step, the solubility
decreases into the minimum caused by common ion effect,
but then it increases after formating complex compound in
enough quantity.
AgCl forms soluble complex with Ag+ and Cl- :
AgCl + Cl- AgCl2-
AgCl2- + Cl- AgCl32-
A Cl + Ag
AgCl A + A 2Cl+
Ag

Curve
C r e of AgCl solubility
sol bilit in sol
solution
tion of NaCl and AgNO3
(AgCl is more soluble in AgNO3 0,1 M and NaCl 1 M than in water)

-1 -2 -3 -4 -4 -3 -2 -1

log[Cl-] -3 log[Ag+]

-4

-5
5

-6

log[Ag+] -7 log[Cl-]
 Titration Curve
In a titration of 50 ml of NaCl 0.10 M solution with a solution
of AgNO3 0.100 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+ + Cl- AgCl (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
After addition of 49.9 ml AgNO3 :
Ag+ + Cl- AgCl (p)
initial 4.99 mmol 5.00 mmol
change
h - 4.99
4 99 mmoll - 4.99
4 99 mmoll
equilibrium - 0.01 mmol
[Cl ] = 0.01
[Cl-] 0 01 mmoll / 99
99.9
9 mll = 1 0 x 10-44 M or pCl
1.0 Cl = 4.00
4 00

A the
At h EEquivalent
i l P
Point
i :
Ag+ + Cl- AgCl (p)
initial 5.00 mmol 5.00 mmol
change - 5.00 mmol - 5.00 mmol
equilibrium - -
[Ag+] = [Cl-] then [Ag+][Cl-] = Ksp = 1.0 x 10-10
[Cl-] = 1.0 x 10-5 or pCl = 5.00
After addition of 60.0
60 0 ml AgNO3 :
Ag+ + Cl- AgCl (p)
initial 6 00 mmol 5.00
6.00 5 00 mmol
change - 5.00 mmol - 5.00 mmol
equilibrium 1 00 mmol
1.00 -
[Ag+] = 1.00 mmol / 110 ml = 9.1 x 10-3 M
pAg = 2 2.04
04 or pCl = 10
10.00
00 – 2.04
2 04 = 7
7.96
96

Generally for halide salts :

A + + X-
Ag A X ((p))
AgX
Equilibrium constant : K = 1 / [Ag+][X-] = 1 / Ksp
S ll the
Smaller th Ksp,
K hi h the
higher th K off a titration
tit ti reaction.
ti
 ARGENTOMETRIC
TITRATION CURVES
AgI

13 AgBr

11
Ksp AgCl = 1 x 10-10 AgCl
X 10
pX KspAgBr = 2 x 10-12
12

KspAgI = 1 x 10-16
8

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 AgXA 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+ + X- AgX (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.
[X-] = 0.005 mmol / 99.95 ml = 5 x 10-5 M or pX = 4,30
a) If ΔpX = 2 2,00
00 then pX = 6 30 or [X-] = 5 x 10-77 M
6.30
The titration consumed 50.00 ml of titrant means one drop
excess off silver
il iion :
[Ag+] = 0.05 x 0.10 mmol / 100.05 ml = 5 x 10-5 M.
K = 1 / {(5 x 10-55)(5 x 10-77)} = 4 x 1010
Ksp = 1 / (4 x 1010) = 2,5 x 10-11 M

b) If we consider ΔpX = 1.00 the K = 4 x 109 will be obtained.

In the titration of X- with Ag+ ions, the ΔpX value at the equivalent
point depends on the analyte and titrant concentrations
concentrations.
These phenomena are equal to those in acid-base titration.
Before equivalent point : smaller the [X-], higher the pX.
At the equivelent point : smaller the [X-], smaller the ΔpX.
At a smaller titrant concentation,, the lower
curve branchement after the equivelent
point as well as the lower of ΔpX at the
point,
equivalent point.

To obtain a good feasible titration of Cl-

(analyte) with Ag+ (titrant) solutions, it is
required both concentrations of analyte
and titrant smaller than 0.10 M.
 Methods in
precipitatometric
p p titration
ƒ Argentometric method
ƒ Mercurimetric method
ƒ Kolthoff titration
Argentometric titration
Argentometry is the most usefull method of
precipitatometric titration, as it caused of very low
solubility product of halide (or pseudohalide) salts
salts,i.e.
ie

Ksp AgCl = 1,82 . 10-10 Ksp AgCN = 2,2 . 10-16

Ksp AgCNS = 1,1 . 10-12 Ksp AgI = 8,3 . 10-17
Ksp AgBr = 5,0 . 10-13

There are 3 techniques

Th h i off end
d point
i ddetermination
i i
• method of Mohr (indicator : chromic potassium)
• method of Volhard (indicator : ferric salt)
• method of Fajans (indicator : fluorosceince)
 ARGENTOMETRY – MOHR
Mohr titration is used for determination of halide or
solution. Chromate ion (CrO42-) is
pseudohalide in a solution
added to serve as indicator. At the end point the
chromate ion is combined with silver ion to form the
sparingly soluble, red, silver chromate, Ag2CrO4.
Ksp Ag2CrO4 = 1,21 2 . 10-12 mol3.LL-3
Ksp AgCl = 1,82 . 10-10 mol2.L-2
[ Please consider the stoichiometric unit of these ionic reactions ]

Although the solubility product constant (Ksp) of

AgCrO
g 4 is close to the Ksp of silver (
(pseudo)halida,
)
these silver salts have different solubility.
Mohr titration has to be performed at a neutral or
weak basic solution of pH 7-9 (or pH 6-10).

In a lower pH (acid) solution the chromate-

dichromate equilibrium decreases the sensitivity of
[CrO42-],
] then inhibits formation of Ag2CrO4
precipitate.
2 CrO42- + 2 H+ Cr2O72- + H2O
Chromate Dichromate

In a higher pH (basic) solution, Ag2O will be formed

as a black precipitate.
 Ag+ + Cl- AgCl (p)
Ag+ + CrO42- Ag2CrO4 (p) red

Solubility of Ag2CrO4 > Solubility of AgCl

(8 4 x 10-5 M)
(8.4 (1 35 x 10-5 M)
(1.35

If Ag+ solution is added to a Cl- solution

containing of small quantity of CrO42-, then AgCl
will firstly precipitated, while Ag2CrO4 has not
yet, and [Ag+] increases progressively until
solubility product of the ions reach the value of
Ksp Ag2CrO4 (2,0 x 10-12) to form red precipitate.
At the
th equivalent
i l t point
i t : pAg
A = pCl
Cl = 5.00
5 00

[Ag+][CrO
[A ][C O42-
2 ] = 2.00
2 00 x 10-12
12

Then [CrO42-] = 2.00x10-12 / (1.0x10-5)2 = 0.02 M

This chromate concentration is too high as

yellow
ll colour
l C O42-
off CrO 2 disturb
di t b visual
i l
observation of Ag2CrO4 (red). In laboratory work
we use usuallyll att 0.005
0 005 s/d
/d 0
0.01
01 M ffor
minimizing titration error. And it could be
corrected
t d by
b an indicator
i di t blank
bl k titration,
tit ti or by
b
AgNO3 solution standized to a pure chloride salt
(
(equall condition
diti to
t the
th sample l titration)
tit ti ) .
Mohr titration is limited at pH 6-10 (or pH 7-9).
I i reaction
Ionic ti ini basic
b i solution
l ti willill be
b :
Ag+ + OH- 2AgOH Ag2O + H2O
In acid sol tion [CrO42-
solution, 2 ] will
ill decrease until
ntil onl
only a
few of ionized HCrO4-, as the reaction will be
followed with the dichromate formation :
2H+ + CrO42- 2HCrO4- Cr2O72- + H2O
(chromate) (dichromate)
Ifthe [CrO42-]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.
Mohr method can be used for determining g Br-
and CN- in a weak basic solution, but it is not
feasible for I- and CNS- as of the salt
precipitate adsorption.

Ag+ can not be titrated with Cl- solution using

indicator of CrO42-, because Agg2CrO4 will be
early obtained and slowly dissolves near the
equivalent
q point.
p This shlould be overcome by y
performing a back titration technique : to the
solution of Agg+ we add standardized excessive
Cl- solution, then the excess of Cl- is titrated
with standardized Ag g+ using
g indicator of CrO42-
.
 ARGENTOMETRY - VOLHARD
Volhard titration is an indirect (back titration)
technique which is used if reaction is too slow or if
there is no appropriate indicator selected for
determining the equivalent point.
Titration principle :
Silver solution is added excessively to a (pseudo)halide
Br- + Ag+ AgBr (precipitate)
excess
After reaction has completed, the precipitate is filtered, then
the filtrate is titrated with a standardized thiocyanate solution.
Ag+ + SCN- AgSCN (solution)
Fe(III) indicator reacts with thiocyanate ion to form a
red colour solution :
Fe3+ + SCN- [Fe(SCN)]2+
Th reaction
The ti requiresi acid
id condition,
diti as iin b
basic
i
solution the ferric ions form Fe(OH)3 precipitate.
Ksp Fe(OH)3 = 2.10-39 39 mol3L-3
3

( [[Fe3+] = 10-2 M is usuallyy used))

Example
p : A solution of KBr is titrated with Volhard p
procedure requires
q
addition of 100 ml of excessed AgNO3 0,095 M, then titrated with 18,3
ml of KSCN 0,100 M using a Fe3+ indicator. Calculate Br- concentration in
the initial solution
solution.
Volhard method is very common for ion
determination based on Ag+ and Cl- reactions, as of
very low precipitate salt solubility
solubility. Acid condition is
required to avoid hydrolysis of Fe3+ indicator. In a
neutrall solution,
l i some off colour
l cations
i (Hg2+
(H 2 ,

Co2+, Ni2+, Cu2+) will precipitate and disturb the

stoichiometric reaction.
Volhard method can be used as a direct titration of
Ag+ with CNS- as well as back titration of Cl-, Br- and
I- determination.
d t i ti Th Br- and
These B d I- can nott be
b disturb
di t b
by the CNS- as solubility of AgBr is equal to those of
AgCNS, while solubility of AgI < solbility of AgCNS.
Titration error of Cl- determination would happen if
AgCl reacts with CNS- :
AgCl(s) + CNS- AgCNS + Cl-
Solubility of AgCNS < solubility of AgCl, then the
reaction in above will shift to the left side of the
reaction, and the result of Cl- analysis will be
lower But this could be prevented by filtering AgCl
lower.
precipitate or nitrobenzen (poison !) addition
before titration with CNS-. Nitrobenzen becomes a
lipid layer between precipitate and CNS- solution.
 ARGENTOMETRY – FAJANS
Fajans titration use adsorption indicators, i.e. organic
compounds which is adsorbed into colloidal
precipitate surface during the titration processes.
Example : Fluoresence in form of its fluorescenate (yellowish
green) anion react with Ag+ to form an intensive red
precipitate which is adsorbed to AgCl precipitate surface
caused by ionic pair interaction.
Fi t step
First t off titration
tit ti titrasi
tit i Fi l step
Final t off titration A +Ind
tit ti : Ag I d-

Cl-
Cl Ag+ Ind-
Cl- Cl-
Ag+ Ag+ Ind-
Cl- Cl- Ag+
Cl-
Cl
Cl- Ag+ Ind-
AgCl Ag+
AgCl Cl-
Cl- Ag+ Ind-
Adsorption of colour organic compound on a
precipitate surface could induce intramolecular
electronic shift
shift, then change solution colour
colour.
This phenomenon is usually used for end titration
d
detection
i off silver
il salt
l precipitation.
i i i
Before Eq.Pt. :
(AgCl).Cl- M+
Primary layer Secondary layer Excess of Cl-

After Eq.Pt.
q :
(AgCl).Ag+ X-
Primary
y layer
y Secondary
y layer
y g+
Excess of Ag
A precipitate tends to adsorp easily ions formating
slighty soluble salts with ions of the precipitate lattice.
Then, Ag+ or Cl- could be more easily adsorb by AgCl
precipitate
p p than byy Na+ or NO3-. These anions in the
solution will be attracted by the precipitate to form an
ionic secondary layer
layer.

Fluorescein
Fl i is
i a weakk organic i acid,
id fforms a flfluoresceinate
i t iion
which is not adsorbed by colloidal AgCl precipitate during
excess off Cl-. But
B t in
i the
th solution
l ti withith more excess off Ag A + the
th
fluoresceinate anion will be adsorbed to form a Ag+ shielding
l
layer, ffollowed
ll db by change
h th
the solution
l ti colour
l tto pink.
i k
The factors that must be consider in choosing
an adsorption indicator :
1) At the equivalent point
point, don’t
don t let the AgCl
precipitate grow too fast to form a big coagulant,
for this could sharply decrease adsorptivity of
the precipitate surface to indicator molecules.
But if it was happened,
happened we can overcome by
addition of dextrin molecules (as a protective
colloid) into the solution
solution, so that increase
particles dispersion, the colour change will be
reversible and after equivalent point we can
perform back titration using a standardized
chloride (Cl-)
(Cl ) solution
solution.
2) Adsorption of indicator should be happen near
and more fastly at the equivalent point. A bad
indicator performance will result a too strong
adsorption process resulting which can
substitute ion adsorbed before the equivalent
point.
3) The pH must be weel controlled for maintaining
indication ionic concentration asam, in basic or
acidic solution. For example, fluorescein (Ka =
10-7) in a solution having pH > 7 will release
small quantity of fluoreseinate ion, hence we
can not observe colour change of the indicator.
Fluorescein is used feasibly in a solution of pH
7-10, difluorescein (Ka=10-4) is at pH 4-10.
4) It is recommended to choose ionic form of
indicator with ionic charge in opposite of titrant
ion Adsorption of indicator can not happen
ion.
before an excess of titrant ion.
I a titration
In A + solution
tit ti off Ag ith Cl- methyl
l ti with th l violet
i l t
(as chloride salt of an organic base) could be
used d as an iindicator
di t off choice.
h i
Before an excess of Cl- in the solution that
resulting a negative charge on colloid layer,
cation should not be adsorbed. For this
condition, we can use dichlorofluorescein, but it
must be added just close to the equivalent point.
 Adsorption Indicators

INDICATOR ANALYTE TITRANT REACTION

CONDITION

Diklorofluorescein Cl- Ag+ pH = 4

Fluorescein Cl- Ag+ pH = 7 – 8
Eosin Br-, I-, SCN- Ag+ pH = 2
Thorin SO42- Ba2+ pH = 1,5 – 3,5
Bromcresol green SCN- Ag+ pH = 4 – 5
Methyl violet Ag+ Cl- acid solution
Rhodamin 6G Ag+ Br- HNO3 upto 0,3 M
O th h
Orthochrome T Pb2+ C O42-
CrO 2 neutral
t l 0,02
0 02 M soln
l
Bromphenol blue Hg22+ Cl- solution of 0,1 M
 List of Precipitation Titrations

ANALYTE 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) Volhard

(not filtered)
Cl-,CN-,CO32-,S2- AgNO3 + KSCN Fe(III) Volhard
C2O42-,CrO42- (filtered)

F- Th(IV) Alizarin Fajans

SO42- BaCl2 Tetrahydroxyquinoline Fajans
PO43- PbAc2 Dibromofluorescein Fajans
C O42-
CrO 2 PbA 2
PbAc Fl
Fluorescein
i F j
Fajans
Ag+ KSCN Fe(III) Volhard
Zn2+ K4Fe(CN)6 Diphenylamine Fajans
Hg22+ NaCl Bromphenol blue Fajans
 MERCURIMETRIC TITRATION
Hg2+ + 2 Cl- HgCl2 (as for other halides)

When halide ions is titrated with mercuric nitrate solution,

[Hg2+] is not found at the equivalent point caused of
precipitation of HgCl2 during the titration process.
After equivalent point, [Hg2+] increases, react with indicator
to form a Hg-indicator complex, e.g. Nitropruside form
white precipitate, acid solution of diphenylcarbazide or
diphenylcarbazon in forms intensive violet colour solution.
Mercurimetric titration requires a blanc titration:
0 17 ml of Hg(NO3)2 0,1
0,17 0 1 N for 50 ml of HgCl2 0,05
0 05 N
N.
This blanc titration volume varies as [HgCl2]EquivalentPoint
For the excess of [Hg2+] reacts with HgCl2 :
HgCl2 + Hg2+ 2 HgCl+
 KOLTHOFF TITRATION
Determination of Zn2+ (as titrant) which is precipitated with standard solution of
K-Ferrocyanide
( )6 + 3 Zn2+
2 K4Fe(CN) ( )6]2 + 6 K+
K2Zn3[[Fe(CN)
potassium ferro (II) cyanide potassium zink ferro (II) cyanide

Titration end point is detected by using external indicator such as uranylnitrate

uranylnitrate,
ammonium molybdate, FeCl3, etc, which needs a special technical skill. So it is
better to use internal indicators such as diphenylamine, diphenylbenzidine,
diphenylamine sulfonate,
sulfonate etc.
etc
A redox reaction of Fe2+ Fe3+ has rduction potential (at 30 oC) as follow :
E = Eo + 0,060 log [Fe(CN)63-] / [Fe(CN)64-]

Acidic solution of ferro-ferric cyanide has much lower reduction potential

compared to those required to oxydize the indicator, forms intensive coloured of
oxidized form. When Zn2+ is added to this solution then a Zn-ferrocyanide will be
formed, followed with increasing reduction potential for Fe(CN)64- removed from
( )64- completely
the solution. After Fe(CN) p y reacted,, a sharp
p increase of reduction
potential which is followed by appearing blue colour of oxidized form of indicator,
caused by excess of Zn2+.in the solution.
The END