Precipitation

Titration
Precipitation Titrimetry
• Precipitation titrimetry is based on reactions that
yield ionic compounds of limited solubility.

Analyte + Titrant  Precipitate

• This approach assumes that under the
experimental conditions used, the precipitate is
virtually insoluble.
Precipitation Titrimetry
• One of the oldest techniques, dating back to mid-1800s
• Because of the slow rate of formation of most precipitates, however,
there are only a few precipitating agents that can be used in
titrimetry.
Precipitation Titrimetry
• By far, the most widely used and most important precipitating
reagent is silver nitrate, which is used for the determination of
halides, the halide-like anions (SCN-1, CN-1, CNO-1), mercaptans,
fatty acids, and several divalent and trivalent inorganic anions.

• Titrimetric methods based on silver nitrate are sometimes called

argentometric methods.
Titrants and standards
• Silver nitrate is available in primary standard-grade
purity, but it is expensive.
• Titrants prepared from less pure silver nitrate can be
standardized with primary-standard potassium
chloride.
• Certain precautions must be taken with the
preparation of silver nitrate. The stability of atomic
silver makes silver ion a good reducing agent. Certain
proteins in skin can reduce silver ion to atomic silver,
leaving a dark brown stain on the skin.
Precipitation titration curve

• Consider the titration of a halide ion with silver

nitrate. The reaction involved is
AgNO3 + NaX  AgX(s) + NaNO3
• A titration curve for this method usually consists of o
plot of pAg versus the volume of silver nitrate added.
Precipitation titration curve
Region Major Constituents Remarks

Preequivalence AgX(s) + NaNO3+ NaX Consider the effect of

point common ion on solubility of
AgX
Equivalence AgX(s) + NaNO3 The only source of Ag+ is AgX
point
Postequivalence AgX(s) + NaNO3+ AgNO3 The excess AgNO3 is the major
point supplier of Ag+
Precipitation titration curve

12
Pre equivalence point - precipitation AgCl
10

8
pAg

6
Sharp increase in Free Ag+
4

0
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00

Vol of AgNO3 added

Precipitation titration curve

• High concentrations
of analyte and titrant
produce larger and
sharper end point
breaks than do low
concentrations.
Precipitation titration curve

• A product that is very

insoluble (small Ksp)
will lead to a titration
reaction that is very
complete with the
largest change in pAg.
Indicators for argentometric
titrations
Three types of end points are encountered in titrations
with silver nitrate:
• Potentiometric – obtained by measuring the potential
between a silver electrode and a reference electrode.
• Amperometric – obtained by plotting the current
generated between a pair of silver microelectrodes in the
solution of the analyte as a function of reagent volume
• Chemical – the end point produced by a chemical
indicator consists of a color change or, occasionally, the
appearance or disappearance of turbidity in the solution
being titrated.
Precipitation chemical indicators
Three chemical indicators are commonly used for argentometric
methods:
• the chromate ion
• adsorption indicator
• iron(III) ion
Chromate ion: The Mohr
Method
• Sodium chromate can serve as an indicator for the
determination of halide and cyanide ions by reacting with
silver ion to form a brick-red silver chromate precipitate in the
equivalence region.

• This approach relies on Ksp differences for two insoluble silver

salts. AgCl is much less soluble than silver chromate so it will
precipitate first.

Ag+ + Cl-1  AgCl(s) Ksp = 1.820x 10-10

white

2Ag+ + CrO4-2  Ag2CrO4(s) Ksp = 1.20x 10-12

brick red
Chromate ion: The Mohr
Method
At equivalence point:

The [CrO42- ] required to precipitate Ag2CrO4 chromate can be

computed from the Ksp of silver chromate taking into
account the concentration of silver ion at equivalence point
Chromate ion: The Mohr
Method

A concentration of 6.6 x 10-3 M CrO42- however imparts an

intense yellow color to the solution that offsets the detection
of a brick red silver chromate. Lower concentration can be
used provided that a blank is run to determine the amount of
silver nitrate needed to produce a visible brick-red color for
silver chromate.

• Must not conduct at acidic condition. A pH of about 8 is best.

At lower pH, CrO42- is protonated and becomes unavailable.
Adsorption indicator: 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 (or desorption) 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 reverse).
Adsorption indicator: Fajans Method
• Fluorescein is a typical adsorption indicator that is
useful for the titration of chloride ion with silver
nitrate.

Ag+ + Cl-1  AgCl(s)

AgCl(s) + Indicator  AgCl—Ag+:Indicator

(yellow-green) (red )

• Indicator is dichlorofluoroscein.
Adsorption indicator: The Fajans
Method
• Indicator is dichlorofluoroscein.
 Adsorption indicator: The Fajans
Method

Prior to reaching the equivalence point,

the chloride ion is in excess, and is the
primary adsorbed ion. The outer surface
is negative which acts to repel the
indicator.

After the equivalence point, the silver

ion is in excess and becomes the
adsorbed counter ion. The outer
surface is positive. The indicator can
now be attracted to the surface.
Adsorption indicator: The Fajans
Method
Factors affecting the adsorption end point
• Intensity of color is determined by the number of indicator molecules
adsorbed which is dependent on indicator’s concentration and
precipitate/s surface area.
• The indicator ion must not be able to displace the primary adsorbed
ion. It must be adsorbed by the counter ion present at the end point.
Adsorption indicator: The Fajans
Method
Factors affecting the adsorption end point
• The pH must be high enough to prevent the
conversion of In to HIn.
• High ionic strength may increase the ionization of
Ag+:Indicator altering the end point.
• A large surface area may increase the
photodecomposition of AgCl , so one must work
with diffused lighting.
Iron (III) ion: The Volhard Method
Direct Method
• 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:
Fe+3 + SCN-1 < --- > FeSCN+2 Kf = 1.05 x 103
• The titration must be carried out in acidic solution to
prevent precipitation of Iron (III) as the hydrated oxide.
Iron (III) ion: The Volhard
Method
Indirect Method, back titration
• Excess silver nitrate is added to the solution, the
precipitated AgCl is filtered off, and the excess silver is
determined by back titration with a standard
thiocyanate solution.
Ag+ + Cl-1  AgCl(s) + Excess Ag+
• Excess Ag+ + SCN-1  AgSCN(s) (back titration)
• Fe+3 + SCN-1  FeSCN+2 (end point)
Iron (III) ion: The Volhard
Method
Indirect Method, back titration
• Silver chloride is filtered off before doing the back
titration because AgCl is more soluble than AgSCN
AgCl(s) + SCN-1 < --- > AgSCN(s) + Cl-1
• This reaction causes the end point to fade and results
in overconsumption of thiocyanate ion during back
titration if the AgCl is not removed.
• The strong acidic environment required for the
Volhard method represents a distinct advantage over
other titrimetric methods of halide analysis.
 Sample Problems
• Calculate pCl for the titration of 100.0 mL of 0.1000 M Cl− with 0.1000
M AgNO3 for the addition of

a. 0.00 mL AgNO3
b. 20.00 mL AgNO3
c. 100.00 mL AgNO3
d. 110.00 mL AgNO3
 Sample Problems
a.) at 0.00mL  no titrant delivered

b.) at 20.00mL  before equivalence point

 Sample Problems
c.) at 100.00mL  Equivalence point
All the Cl- is reacted with Ag+

d.) at 110.00mL  beyond equivalence point

 Sample Problems
• A 2.0-g sample of chloride containing salt was dissolved in enough
water to produce a 100-ml solution. A 20-ml aliquot was taken and
titrated with 0.1052 M AgNO3 and required 14.20 mL to produce a
brick red color with Na2CrO4. Titration of a blank required 0.85 mL.
Calculate the %Cl in the sample.
 Sample Problems
Net volume: (14.2 – 0.85) mL = 13.35 mL
 Sample Problems
• What is the molarity of a solution of KSCN, and how many grams of
KSCN are contained in each liter if 19.80 mL are required to titrate the
silver in a 0.100-g sample of an alloy which contains 90.20% Ag?
 Sample Problems

For 1 L of 0.04223 M KSCN:

 Sample Problems
• To a 0.5000-g sample of impure SrCl2 in a liter of solution are added
1.784 g of pure silver nitrate crystals. After dissolving and filtering out
the precipitated AgCl, the filtrate requires 25.50 mL of 0.28000 M
KSCN. What is the percentage of SrCl2 in the sample?
• Ans: 53.27%
Sample Problems
• The arsenic in a 1.010-g sample of pesticide was
converted to H3AsO4 by suitable treatment. The acid
was then neutralized, and exactly 40.00 mL of
0.06222 M AgNO3 was added to precipitate the
arsenic quantitatively as Ag3AsO4. The excess Ag+ in
the filtrate and in the washings from the precipitate
was titrated with 10.76 mL of 0.1000 M KSCN; the
reaction was
Ag+ + SCN-1  AgSCN(s)
Calculate the percent As2O3 in the sample.
Sample Problems
Net mole AgNO3 = (40.00 mL)(0.06222 M AgNO3)
– (10.76 mL)(0.1000 M KSCN)
= 1.4128 mmole AgNO3  1.4128 x 10-3 mole AgNO3
Sample Problems
• The phosphorus content in a 2.00-mL liquid fertilizer sample was
determined by converting the phosphorus to phosphate and
precipitating Ag3PO4 with the addition of 50.00 mL of 0.1163 M
AgNO3. The excess AgNO3 was titrated with 0.1245 M KSCN. If 10.63
mL was required for back titration, what is the percentage of P2O5
(%w/v) in the liquid fertilizer?
Sample Problems
Reactions present:

Net mole AgNO3 = (50.00 mL)(0.1163 M AgNO3) – (10.63 mL)(0.1245 M KSCN)

= 4.492 mmole Ag+  4.492 x 10-3 mole AgNO3
 Sample Problems
• A mixture of LiCl and BaBr2 weighing 0.6000 g is treated with 45.15
mL of 0.2017 M AgNO3, and the excess is found to require 25.00 mL of
0.100 M KSCN solution for titration, using ferric alum as indicator.
What is the percentage of BaBr2 in the sample?
• Ans: 74.6%
 Sample Problems
Reactions present:

Let x = LiCl, y = BaBr2

(eqn 1)
 Sample Problems
Stoich analysis, convert the mass precipitates to mass Br

For eqn(2)

(eqn 2)
 Sample Problems
From (eqn 1) and (eqn 2)
(eqn 1)
(eqn 2)
Solve for x and y
x = 0.1522 g LiCl
y = 0.4478 g BaBr2