UNIT IV.

Precipitation titrations
1. Introduction.
2. Titration curves.
3. End point detection.
4. Practical aspects and applications: Mohr method,
Volhard method, Fajans method.
1. Introduction

Precipitation reactions are based on reactions that yield ionic compounds of

limited solubility.
Phases involved: a precipitate or solid phase, an aqueous phase saturated with the
dissolution ions of the precipitate.
1. Introduction

Basic concepts:
Solubility, concentration of a chemical species in saturated solution. It is the
maximum concentration of that species in solution before it begins to precipitate.
It varies according to parameters such as temperature and concentration of other
ions in solution (ionic strength and common ion effects).

Solubility product constant. It is the constant that regulates the balance of

precipitation. It determines the solution concentrations of the ions of a certain
salt.

CmAn ↔ mCn+ + nAm- Kps = [Cn+]m [Am-]n

[Cn+] = m . S [Am-]= n . S Kps = (m . S)m (n . S)n = mm . nn . Sm+n

𝑚𝑚+𝑛𝑛
m+n 𝐾𝐾𝑝𝑝𝑝𝑝
𝐾𝐾𝑝𝑝𝑝𝑝 = mm . nn . 𝑆𝑆𝑀𝑀𝑚𝑚 𝑁𝑁𝑛𝑛
𝑆𝑆𝑀𝑀𝑚𝑚 𝑁𝑁𝑛𝑛 =
mm . nn
 1. Introduction

Characteristics of Kps
1. Kps is function of temperature.
2. Common ion effect. The presence of a strong electrolyte that contributes a
common ion to the solution of a precipitate decreases the solubility of the
precipitate. If the concentration of one of the ions of the precipitate in solution
increases, the other decreases, to keep the value of Kps constant.

Ej. Hg2Cl2 saturated with NaCl 0.030M. Solubility? Kps=1.2. 10-18

Hg2Cl2 ↔ Hg22+ + 2Cl- 𝐾𝐾𝐾𝐾𝐾𝐾 = 𝑥𝑥. (2𝑥𝑥 + 0.030)2 = 0.0302 𝑥𝑥

x 2x+0.030M
S 𝑥𝑥 = 1.3. 10−15 𝑀𝑀

𝐻𝐻𝐻𝐻22+ = 𝑥𝑥 = 1.3. 10−15 𝑀𝑀

[Cl-]
 1. Introduction

Characteristics of Kps

3. Saline effect. The presence of electrolytes cause an increase in the ionic

strength (f) of the medium and therefore in the solubility of the precipitate. It
is an important process because when a precipitate is generated there are
other ions in solution, apart from the species (ions) that form it.

Generally: MmNn(sol) ↔ m Mac + n Nac

KpsT = Kps fMm fNn

Eq. Debye-Hückel 𝑙𝑙𝑙𝑙𝑙𝑙𝑓𝑓 = −0,509𝑧𝑧𝑖𝑖2 𝐼𝐼

1 𝑛𝑛 2
𝐼𝐼 = � 𝐶𝐶𝑖𝑖 𝑧𝑧𝑖𝑖
2 𝑖𝑖
1. Introduction

4. Side reactions affect precipitation equilibria. Its influence is evaluated through

the conditional solubility product constants (Kps') and the side reaction
coefficients. They cause an increase in the solubility of the precipitates. The
solubilization equilibrium shifts to the right.

MmNn(sol) ↔ m Mac + n Nac Kps´= [M´]m[N´]n=[M]mαMm[N]nαNn= KpsαMmαNn

αM= [M´]/[M]; αN=[N´]/[N] α>1 ⇒ Kps´> Kps

The more important these reactions and the m and n coefficients are, the greater
the increase in solubility. Most important side reactions: Complex formation and
Acid-base
1. Introduction

5. If the product of the concentration of ions in solution is greater than or equal

to Kps, a precipitate will form.

Precipitation is quantitative when at least 99.9% of the species has precipitated (its
concentration in solution has decreased at least 1000 times). From the value of
the Kps, the solubility of any species can be calculated.
1. Introduction

Precipitation of mixtures
It consists of separating 2 or more ions, present in the same solution, precipitating
them consecutively, controlling the concentration of precipitating reagent.

The least soluble compound (lowest solubility) is the one that precipitates first.

Basic requirement: that their solubilities be different. (≠ Kps)

Precipitation is quantitative when at least 99.9% of the substance has been

precipitated (its concentration is 1000 times lower).

If the reactions have the same stoichiometry, Kps must differ by a factor of 103
times
1. Introduction

Eg. A mixture of 0.1M Cl- and I-.

AgCls 𝐾𝐾𝑝𝑝𝑝𝑝 = 1.56. 10−10 AgIs 𝐾𝐾𝑝𝑝𝑝𝑝 = 8.3. 10−17
Which ion precipitates first with Ag+?
Can these two ions be separated by precipitation with Ag+?

Eg. When AgNO3 solution is added to a 0.1 M solution of CrO42- and 0.1 M Cl-.
a) Which ion precipitates first and what concentration of Ag + is need?
b) When does the second ion start precipitating? which concentration of Ag + does it
need?

Kps AgCl: 1.56 x 10-10 Kps Ag2CrO4 : 6.15 x 10-12

2. Titration curves

Titration curves are the representation of the concentration of the species to be

analyzed against the titrant volume or the %titration.

Requirements of the precipitation reaction

1- Rapid precipitation. Quantitative (> 99.9%).
2- Defined stoichiometry, no coprecipitation
3- Provide adequate method to detect the equivalent point.
However, few precipitation reactions meet these requirements. The most
important are the reactions of Ag+ and Hg+.

pX
pX=- log [X]

mL of titrant
2. Titration curves

E.g. Titration of 25 mL solution of 0.1000 M KI with 0.0500M silver nitrate.

KI + AgNO3 ↔ AgI s + KNO3 AgI ↔ I- + Ag+ Kps = [I-] [Ag+] = 8.3x10-17

 Equivalence volume?

 Before starting: 15
13
In solution only l- is present 11
9

p[I-]
7
 Before the equivalence point: 5
There is free in solution.
I- 3
1
-1
0 20 40 60 80 100
 At the equivalence point Vollumen de AgNO3
[I-] = [Ag+]

 After the equivalence point.

[I-] comes from the dissociation of the precipitate.
2. Titration curves

E.g. Titration of 25 mL solution of 0.1000 M KI with 0.0500M silver nitrate.

KI + AgNO3 ↔ AgI s + KNO3 AgI ↔ I- + Ag+ Kps = [I-] [Ag+] = 8.3x10-17

pAg
pI
2. Titration curves

E.g. Titration of 25 mL solution of 0.0500 M Na2C2O4 with 0.0250M La3+. Kps = 1,0. 10-25

3C3O42-+ 2La3+ ↔ La2(C2O4)3 (s)

La2(C2O4)3 ↔ 2La3+ + 3C2O42- Kps = [La3+ ]2 [C2O42-]3 = 1,0. 10-25

pLa

pC2O4
2. Titration curves

Factors that affects the titration curve

• The higher the concentration, the greater the variation in the curve

Titration of NaI solutions. In each case,

a solution of AgNO3 of equal
concentration is used.

• The more insoluble the salt (lower Kps), the greater the jump in the titration
curve

Titration of 0.1 M solutions of

various anions with 0.1 M solution
of AgNO3
3. End point detection

a) Indicators that react with the titrant agent.

They compete against the analyte for the titrant, or against the titrant for the
analyte. In general, when the end point is reached, they cause the appearance or
disappearance of a precipitate or, they give rise to a change of color in the solution
that is titrated.
The most used are:
Ion CrO42-. Mohr method . CrO42- + 2 Ag+ ↔ Ag2CrO4 (red)
Ion Fe3+ . Volhard method Ag+ + SCN- ↔ AgSCN (white)
Fe+3 + SCN- ↔ Fe(SCN)2+ (red)

b) Adsorption indicators.
They are organic dyes, which are generally in an anionic form, and can be
adsorbed on the surface of a colloidal precipitate, immediately after the
equivalence point.
4. Practical aspects and applications

1. Mohr method
Determination of Cl- and Br-. Titration with AgNO3. Indicator: Cromate (CrO4-2)
Titration reaction:
Cl- + Ag+ ↔ AgCl (↓) White Kps AgCl = 1.78 x 10-10
Indicator reaction:
CrO4= + 2 Ag+ ↔ Ag2CrO4 (↓) Red brick Kps Ag2CrO4= 2.45 x 10-12

Requirement: Solubility of Ag2CrO4 > Solubility of AgX which ensures that the silver halide
always precipitates first
Precaution: [CrO4=] must be kept low so that the yellow color of the chromate does not mask
the precipitate. Usually ≤ 0.005 M.
Under these conditions, a titration error is committed that must be compensated with a
blank test.
pH range in which it can be applied: 6.5 < pH < 10.
4. Practical aspects and applications

1. Mohr method
Ex. The chloride ion content of a water sample is determined by the Mohr method. An
aliquot of 100 mL is titrated and 1.68 mL of 0.0976 mol / L AgNO3 solution is spent. What is
the concentration, in mg / L and in ppm of the chloride ion?
Titration reaction: Indicator reaction:
Cl- + Ag+ ↔ AgCl (↓) White CrO4= + 2 Ag+ ↔ Ag2CrO4 (↓) Red

1.68 mL solution
Cl- AgNO3 0.0976 mol/L
Ag+

Cl- Ion ??

100 mL de Muestra
4. Practical aspects and applications

2. Volhard method
Direct determination of Ag+ by using a standard solution of SCN-. It can also be applied to the
determination of any ion capable of forming an insoluble salt with Ag+, such as Cl-, Br-, I- by
back-titration.
Titrant : SCN-
Tritration reaction:
Ag+ + Cl- ↔ AgCl
Tritration reaction:
SCN- + Ag+ ↔ AgSCN Kps AgSCN = 1.16 . 10-12
The stability constant of the complex
Indicator reaction: that is formed is so great that it
competes with the precipitation
SCN- + Fe+3 ↔ FeSCN+2 Kestability =138 reaction.

While there is silver in solution the iron does not react.

The titration must be carried out in an acid medium, otherwise the iron (III) precipitates as
hydroxide.
4. Practical aspects and applications

2. Volhard method
Ex. To 25 mL of a solution containing NaBr and the Fe3+ indicator, 25 mL of 0.1 M solution of
AgNO3 is added. Calculate the g/L of NaBr in the problem solution, knowing that, to assess
the excess of Ag+, 20.72 mL of 0.0540 M solution of KSCN are required.

Br- + Ag+ ↔ AgBr (↓) Br- 20.72 mL solution

0.0540 M KSCN
SCN- + Ag+ ↔ AgSCN Ag+
SCN-
SCN- + Fe+3 ↔ FeSCN+2
25 mL NaBr
Indicator Fe3+
+
25 mL solution
0.1 M AgNO3
4. Practical aspects and applications

3. Fajans method
Background: use of adsorption indicators. They are organic compounds that are adsorbed on
the surface of the precipitate formed in the titration.
Determination of Cl-, Br-, I-, SCN-, SeO32-,..
The phenomenon of adsorption must occur at the equivalence point of the valuation.

Precipitate

Primary ionic layer

Fluorescein Dichlorofluorescein Tetrabromofluorescein
(eosine).
Secondary ionic layer

Fajans titration of Cl- with AgNO3 using dichlorofluorescein.

a) Indicator before the beginning of the titration.
b) Precipitated AgCl before the end point
c) Indicator adsorbed on the precipitate after the end point
4. Practical aspects and applications

3. Fajans method
Eg Titration of Cl- with AgNO3 solution, using fluorescein
M+ M+
Before the equivalence point. The anion Fluorescinate (Fl-) is M+
Cl -
Cl - M+

M+ Cl - Cl - M+

unable to adsorb remains in the solution that has a yellow color. M+

Cl -
AgCl
Cl -
M+

Cl - Cl -
Cl -
There are excess chlorides. The surface of the precipitate has a
M+
M+
M+ M+

negative charge, repels the indicator ions.

After the equivalence point. The anion Fl- is capable of forming
part of the secondary ionic layer and the precipitate becomes a
A- Fl-
Fl-
Ag+ Fl-
A-
Ag+ A-

bright pink color. Fl-

Ag+
AgCl
Ag+ Fl-
Fl- Ag+
There is excess Ag +, the surface of the precipitate acquires A-
Ag+
A-
Fl-

Fl-

positive charge.
The formation of fluoresceinate of Ag on the primary precipitate
(white) causes the appearance of a red color on its surface.