Titrasi Presipitasi

Outline
1. Essence and classification of methods
precipitation titration
2. Titration Curves
3. Argentometry
4. Thiocyanatometry
5. Mercurometry
6. Sulphatometry
7. Hexacianoferratometry
 Precipitation Titratons
Precipitation titrimetry, which is based on
reactions that yield ionic compounds of limited
solubility, is one of the oldest analytical
techniques. The slow rate of formation of most
precipitates, however, limits the number of
precipitating agents that can be used in titrations
to a handful. The most widely used and important
precipitating reagent, silver nitrate, which is used
for the determination of the halogens, the
halogen-like anions. Titrations with silver nitrate
are sometimes called argentometric titrations.
 Requirements
• The analyte should be dissolved in water and
give an ion which would be active in
precipitation reaction.
• The precipitate should be practically insoluble
(Ksp<10-8 to 10-10, S<10-5 mol/L).
• There is no coprecipitation.
• Precipitate should form quickly enough.
• There should be a way for determining the
equivalence point.
Classification of precipitation titration
methods (based on titrant):
1. Argentometry
2. Thiocyanatometry
3. Mercurometry
4. Sulphatometry
5. Hexacianoferratometry
 2. Titration Curves

Curve plotting of titration is based on a rule

of solubility product.

A B  mA  nB
m n

And accordingly

Ksp  [ A ]  [B]
m n
 The Shapes of Titration Curves
Titration curves for precipitation reactions are
derived in a completely analogous way to the
methods described for titrations involving strong
acids and strong bases. P-functions are derived for
the preequivalence-point region, the post-
equivalence point region, and the equivalence
point for a typical precipitation titraton.
Most indicators for argentometric titrations
respond to changes in the concentration of silver
ions. As a consequence, titraton curves for
precipitation reactions usually consist of a plot of
pAg versus volume of AgNO3.
Precipitation titration curve for 50.0 mL of
0.0500 M Cl– with 0.100 M Ag+. (a) pCl
versus volume of titrant; (b) pAg versus
volume of titrant.
 The factors which define value of
inflection points of titration on curves of
precipitation titration

• Concentration of titrant solutions and the

analyte (the higher the concentration, the
sharper the slope of the inflection point.)

• Solubility of a precipitate (The smaller the

solubility, the sharper the slope of the
inflection point)
Influence of precipitate solubility on
titration inflection point
 Influence of other factors on inflection
point of the precipitation titration

• Temperature (the higher the temperature,

the higher the solubility of a precipitate
and the less sharp slope inflection point)

• Ionic strength of the solution (the higher

the ionic strength of a solution, the higher
the solubility of a precipitate and the less
sharp slope inflection point)
 Titration of 50 mL of 0.05 M NaCl by
0.1000M AgNO3 continued

pAg = –log 10[Ag+].

Precipitation AgCl

Sharp increase in
Free Ag+

Volume AgNO3
 Successful titrations of ions by Siver
Nitrate

pAg = –log 10[Ag+].

Precipitation AgI

Precipitation AgBr

Precipitation AgCl

Volume AgNO3

A Sharp increase in
Free Ag+ signals the endpoint in each case
 Successful titrations of Mixtures by Siver
Nitrate

pAg = –log 10[Ag+].

Precipitation AgI first

Precipitation AgCl second

Volume AgNO3

A Sharp increase in
Free Ag+ signals the endpoint in each case
Sigmoidal titration curve Linear segment titration curve.
Spectrophotometric titration
curve of transferrin with ferric
nitriloacetate.
Titration curve for the titration of 50.00 ml of 0.1000M AgNO3 with
0.1000M KSCN.
Factors influencing the sharpness of end points

1) Reagent concentration
[T], [A]   eT 

2) Completeness of reaction
Solubility  e.p. change jump
I– Ksp=8.3 ×10–17
Br– Ksp=5.0 ×10–13
Cl– Ksp=1.8 ×10–10
IO3– Ksp=3.0×10–8
BrO3– Ksp=5.7×10–5
Titration of a mixture by potentiometric detection
Titrant (ex. Ag+)

Two precipitable ions

(ex. Cl–, I–)

Ex. 0.0502M KI + 0.0500M KCl

0.0845 M AgNO3
Ksp AgI << Ksp AgCl
8.3×10 –17 1.8 ×10–10
Coprecipitation
[Ag+][Cl–] / [Ag+][I–]
= [Cl–] / [I–] = 8.3×10 –10/1.8×10–17
= 1/ 4.6 ×10–7
Titration curves for 50.0 ml of a solution 0.0800 M in Cl and 0.0500 M in
I or Br.
 End Point for Argentometric Titrations
Three types of end points are: (1) chemical, (2)
potentiometric, (3) amperometric. Potentiometric
end points are obtained by measuring the potential.
To obtain an amperometric end point, the current
generated between a pair of silver microelectrodes is
measured and plotted as a function of reagent
volume. The chemical end point consists of a color
change or the appearance or disappearance of
turbidity. The requirements are (1) the color change
should occur over a limited range in the p-function,
and (2) the color change should take place within the
steep portion of the titration curve.
 3. Argentometry
This is a precipitation titration in which Ag+ is the titrant.
X- + Ag+ = AgX
where: X- = Cl-, Br-, I-, CN-, SCN-, etc..
• Titrant: AgNO3 – secondary standard solution
• Standardization оn primary standard solution of
Sodium chloride
AgNO3 + NaCl = AgCl  + NaNO3
• Indicator for standardization - 5 % Potassium chromate
K2CrO4 (to appearance reddish-brown precipitate of
Silver chromate):
2AgNO3 + K2CrO4 = Ag2CrO4+ 2KNO3.
 Argentometry:

• without indicator:
 Gay-Lussac method (method of even
turbidity)
 method to point enlightenment
• with indicator:
 Mohr method
 Fajans – Fisher – Khodacov method
 Volhard method
 Gay-Lussac method (method of
even turbidity)
If solution NaBr titrate by solution AgNO3 (or on the
contrary) there is a reaction:
Br- + Ag+ = AgBr↓
• For determination of equivalence point it is
necessary to select two identical portions of a
solution before the titration end. To one of them
add a drop of AgNO3 solution, on another - a drop
of NaBr solution at the same concentration.
Titration will finish when there will be identical
intensity of turbidity in both portions of solution.
 Method to enlightenment point
 The method of titration to an enlightenment point can
be applicable when insoluble compounds is in colloidal
state. For example, determination of І- ions by silver
nitrate, AgІ forms, it is adsorbing І- and receive
negative charges (colloidal solution of AgІ forms).

 As more and more І- ions react with Ag+ ions, particles

AgІ gradually lose adsorbed by them І- ions, and their
charge decreases. In the end of titration occur
coagulation of particles and their sedimentation. The
solution thus is absolutely clarified.
 Formation of a Colored Precipitate
The Mohr Method
Sodium chromate can serve as an indicator for the
argentometric determination of chloride, bromide,
and cyanide ions by reacting with silver ion to form a
brick-red silver chromate (Ag2CrO4) precipitate in the
equivalence-point region. The reactions involved in
the determination of chloride and bromide (X-) are

titration reaction: Ag+ + X- AgX(s) [white]

indicator reaction: 2Ag+ + CrO42- Ag2CrO4(s)
[red]

The solubility of silver chromate is several times

grater than that of silver chloride or silver bromide.
 Mohr method
• Titrant: AgNO3 – secondary standard solution
• Stanardization on primary standard solution of
sodium chloride NaCl (by a measured volume
of primary standard solution):
AgNO3 + NaCl = AgCl  + NaNO3
• Indicator - 5 % potassium chromate K2CrO4 (to
formation precipitate of reddish-brown
Ag2CrO4):
2AgNO3 + K2CrO4 = Ag2CrO4+ 2KNO3
• Determinate substance: chloride Cl-, bromide
Br-.
• Medium: рН~ 6,5-10,3.
• Usage: quantitative definition of sodium
chloride, potassium chloride, sodium bromide,
potassium bromide, etc.
 Restrictions of usage of Mohr method:
• It is impossible to use titation in acidic solutions:
2CrO42- + 2H+ = Cr2O72- + H2O
• It is impossible to use titration in the presence of
ammonia, etc. ions, molecules which can be
ligands on relation to Silver ions
• It is impossible to use titration in the presence of
many cations (Ba2+, Pb2+, etc.) which form the
painted precipitates with chromate ions CrO42-
• It is impossible to use titration in the presence of
reducers which reduce chromate ions CrO42- to
Cr3+ ions
• It is impossible to use titration in the presence of
many anions (PO43-, AsO43-, AsO33-, S2- etc.)
which with Silver ions give the painted precipitates
Adsorption Indicators: The Fajans Method
An adsorption indicator is an organic compound that
tends to be adsorbed onto the surface of the solid in
a precipitation titration. Ideally, the adsorption occurs
near the equivalence point and results not only in a
color change but also in a transfer of color from the
solution to the solid (or the reverse).
Fluorescein is a typical adsorption indicator useful for
the titration of chloride ion with silver nitrate. In
aqueous solution, fluorescein partially dissociates
into hydronium ions and negatively charged
fluoresceinate ion that are yellow-green. The
fluoresceinate ion forms an intensely red silver salt.
Titrations involving adsorption indicators are rapid,
accurate, and reliable.
Fajans – Fisher – Khodacov method
• Titrant: AgNO3 – secondary standard
solution
• Standardization on primary standard
solution of sodium chloride NaCl (by a
measured volume of primary standard
solution):
• Medium: рН~ 6,5-10,3 (for determination of
clorides) and рН~ 2,0-10,3 (for
determination of bromides and iodides).
• Indicators of method:
– dichlorofluoroscein (for determination of clorides)
– eosine (for determination bromides and iodides)
 The mechanism of indicators action

AgNO3 + NaCl = AgCl + NaNO3

HInd  H+ + Ind-

Adsorption indicator whose color when adsorbed

to the precipitate is different from that when it is in
solution
 Colour
Indicator Solution Surface of
precipitate
Dichloro- greenish yellow pink
fluoroscein

eosine yellowish-
yellowish-red redish - violet

• A number adsorption abilities of anion at рН~7

on a precipitate surface of Silver chloride
• I- > CN- > SCN- > Br- > eosine > Сl- >
dichlorofluoroscein > NO3- > ClO4-
 Conditions of titration:
• Acidity of solutions
• Concentration of reacting solutions
• The account adsorption abilities of indicators
and ions which present in a solution
• Titration near equivalence point is necessary
to spend slowly
• Titration with adsorption indicators spend in a
diffused light
Use:
• Quantitative definition of chlorides, bromides,
iodides, thiocyanides, cyanides.
 The Volhard Method (Colored Complex)

In the Volhard method, silver ions are titrated with a

standard solution of thiocyanate ion:
Ag+ + SCN- AgSCN(s)
Iron (III) serves as the indicator. The solution turns
red with the first slight excess of thiocyanate ion:

Fe3+ + SCN- Fe(SCN)2+

Kf 
 Fe( SCN ) 
2+
-  105
.  10
3
red 3+
 Fe  SCN 
The titration must be carried out in acidic solution to
prevent precipitation of iron(III) as the hydrated
oxide.
…continued…

The most important application of the

Volhard method is for the indirect
determination of halide ions. A measured
excess of standard silver nitrate solution is
added to the sample, and the excess silver
ion is determined by back-titration with a
standard thiocyanate solution.
 Volhard method
• Titrant: AgNO3, ammonium or potassium
thiocyanide NH4SCN, KSCN - secondary
standard solution
• Stardadization AgNO3 on primary standard
solution NaCl, NH4SCN, KSCN on
standardization solution AgNO3:
AgNO3 + NH4SCN = AgSCN + NH4NO3
• Indicator by standardization of ammonium
or potassium thiocyanide with iron (ІІІ) salts
(NH4Fe(SO4)212H2O in presence of nitric
acid) to the formation of the reddish colored
Fe(SCN)2+ complex:
Fe3+ + SCN- = [Fe(SCN)]2+
• Medium: in presence of nitric acid
• Indicators of method: iron (ІІІ) salts
NH4Fe(SO4)212H2O in presence of nitric
acid
• Determinate substance: halogenides,
thiocyanides, cyanides, sulphides,
carbonates, chromates, oxalates, arsenates
etc.
Until equivalence point (e.p.)
Hal- + Ag+ (excess) = AgHal
Ag+(rest) + SCN- = AgSCN
After e. p.
Fe3+ + SCN- = [Fe(SCN)]2+
(reddish)
!!! At determination of iodides the indicator is added in the
end of titration to avoid parallel:
2Fe3+ + 2I- = 2Fe2+ + I2
Advantages of Volhard method
Titration possibility:
• In very acidic solutions
• In the presence of many cations which interfere by
definition in Mohr method
End point detection in argentometric titration 

Detection techniques in precipitation titrations :

 Indicator  Potentiometry  Light scattering / turbidimetry of nephelometry

Titration Mohr Volhard Fajans

Titration Ag+ + Cl–  AgCl Ag+ + Cl–  AgCl Ag+ + Cl–  AgCl
reaction white Back titration :
Ag+ + SCN–  AgSCN
white
End point 2Ag + CrO4  Ag2CrO4 SCN + Fe  FeSCN2+
+ 2– – 3+ Electric double
layer
reaction red soluble red with adsorption
Ind.
pH 7~10.5 Kf= 1.05×103
Dichlorofluorescein

Use Cl –, Br –, CN – Cl –, Br –, I – Cl –, Br –, I –, SCN –

No use I –, SCN –
Table 13-3, p.362
 4. Thiocyanatometry
• This is a precipitation titration in which SCN- is the
titrant.
• Titrant: ammonium or potassium thiocyanide
NH4SCN, KSCN - secondary standard solution
• Stardadization: on primary standard
solution of AgNO3:
AgNO3 + NH4SCN = AgSCN + NH4NO3
• Indicator by standardization of ammonium
or potassium thiocyanide with iron (ІІІ) salts:
Fe3+ + SCN- = [Fe(SCN)]2+
• Medium: in presence of nitric acid
• Indicator: iron (ІІІ) salts NH4Fe(SO4)212H2O in
presence of nitric acid
Determine substance: drugs, which contain Silver
(Albumosesilber, colloid silver - Kollargol, silver
nitrate).

!!! At the analysis of drugs which contain

nonionic silver, preliminary it is heated with
sulphuric and nitric acids (receive ionic
compound).

!!! At determination of iodides the indicator is added

in the end of titration to avoid parallel:
2Fe3+ + 2I- = 2Fe2+ + I2
 Advantages of Thiocyanatometry
Titration possibility:
• In very acidic solutions
• In the presence of many cations which
interfere by determination in Mohr
method
 5. Mercurometry
• Mercurometry – this is a precipitation
titration in which Hg22+ is the titrant
2Cl- + Hg22+ = Hg2Cl2 Ksp = 1,310-18
2I- + Hg22+ = Hg2I2 Ksp = 4,5 10-29

• Titrant: Hg2(NO3)2 - secondary standard

solution
• Stardadization: on primary standard
solution of NaCl:
Hg2(NO3)2 + 2NaCl = Hg2Cl2 + 2NaNO3
• Indicators: 1) solution of iron (ІІІ) thiocyanide (from
reddish to colourless)
2Fe(SCN)2+ + Hg22+ = Hg2(SCN)2 + 2Fe3+
!!! For the account of titrant volume which is used on
indicator titration, do “blind test”

2) 1-2 % spirit diphenylcarbazone (to blue

color)
!!! Indicator is added before end of titration

• Determinate substance: chlorides and iodides.

• Medium: very acidic (may be to 5 mol/L H+ ions).
 Advantages of mercurometry:
• Possibility usage titration in very acidic solutions
• Titrant is cheaper
• Mercury (I) Salts are less soluble, therefore
accuracy and sensitivity of titration more, and
inflection point on a curve is much more
• Possibility of titration with the diphenylcarbazone
indicator in the muddy and painted solutions
• Probably reversive titration of Mercury (І) salts
Lack:
• Mercury (І) salts are very toxic.
 6. Sulphatometry
• Sulphatometry – this is a precipitation titration in which
SO42- is the titrant
Sometimes bariummetry – this is a precipitation titration in
which Ba2+ is the titrant
Reaction of method:
Ba2+ + SO42- = BaSO4↓
determinate titrant
substance
• Titrant: secondary standard solution of H2SO4, Ba(NO3)2,
BaCl2.
• Stardadization: solution of H2SO4 on primary standard
solution of Na2B4O7 or Na2CO3 (crystal.) with methyl
orange; Ba(NO3)2 or BaCl2 on secondary standard solution
of H2SO4 with nitrchromazo or orthanilic А.
• Indicators: use metallochrome indicator - nitrchromazo
or (orthanilic С), orthanilic А.
BaInd + H2SO4 = BaSO4 + H2Ind
violet white roze
precipitate solution
Determinate substance:
• Direct titration:
- by sulphatic acid – content of Barium
- by barium chloride or barium nitrate – content of sulphates

!!! For completeness of sedimentation of barium ions use as

solvent of 50 % ethanol
!!! Sometimes, as the indicator use sodium rodizonate
Sulphatometry
Ex. Ba2+ + SO42–  BaSO4
(white)
T
End point
Turbidimetry : The intensity
of light scattered by
particles of precipitate is V(titrant, ml)
measured
Detection of end point:
1) Turbidimetry :
stabilizer(glycerol-alcohol mixture)
2) Indicator :
rhodizonate + Ba2+  Red ppt
 7. Hexacyanoferratometry
Hexacyanoferratometry - this is a precipitation
titration in which K4[Fe(CN)6] is the titrant
• Titrant: secondary standard solution
K4[Fe(CN)6]
• Stardadization: on standard solution of
KMnO4 in sulphatic acid
5K4[Fe(CN)6] + KMnO4 + H2SO4 = 5K3[Fe(CN)6] + MnSO4 +
3K2SO4 + 4H2O

• Indicator by standardization - Methyl

violet (from yellow-dreen to red-brown).
Indicators:
diphenylamine at the presence of a small
amount of potassium hexacyanoferrate (ІІІ)
for definition Zn2+, Mn2+
3,3-dimetilnaftizin for definition Cu2+, Zn2+,
Cd2+, Pb2+, Fe2+, Ni2+ etc.
alizarin red S for definition Zn2+, Pb2+,
Th(IV)
diphenylcarbazone for definition Cd2+

Determinate substance: metal cations

(direct titration), displacement titration –
phosphate ions.
sample KCl + K2SO4 mass= 2,44g
vol= 250mL
Aliquot 1 vol= 50mL

Mohr titration 41,4mL 0,05818M AgNO3

Aliquot 2 vol= 50mL

add NaB(Ph)4 Vol= 40mL 0,1082M

ppt redissolve --> Mohr titration 50mL

Aliquot 1 --> mmol Cl=(V*M)AgNO3 titration 1=
2,40632mmol (1)
Aliquot 2 --> mmol K+ = (mmol Cl + 2*mmol SO4)
= (V*M)AgNO3 titr2 = 2,90784mmol (2)
mmol SO4= 0,5*(mmol(2)-mmol(1))=
0,25076mmol
%KCl= 36,71%
=D17/D18*F24*(39+35,5)/1000*1/D16*100

%K2SO4= 8,94%
13-28
sample= 1,998g Cl- + CLO4-
vol= 250mL
Aliquot 1 50mL
titration AgNO3 13,97mL 0,08551M
Aliquot 2 50mL
reduction of Cl)4---> Cl-
titration AgNO3= 40,12mL
from Aliquot 1 mol Cl-=mol AgNO3= (V*M)AgNO3 titration 1= 1,194575mmol (1)
from aliquot 2= mol Cl- + mol ClO4-= (V*M)AgNO3 titration 2= 3,430661mmol (2)
mmol ClO4-= (2) -(1) 2,236087mmol
%Cl= 10,61%
=B19/B20*G26*35,5/1000*1/B18*100
%ClO4= 55,68%
=B19/B22*G28*(35,5+4*16)/1000*1/B18*100