INTRODUCTION

❖ Precipitation Titrations
TO
❖ Complexometric Titrations
QUANTITATIVE
❖ Redox Titrations
CHEMICAL
ANALYSIS
 PRECIPITATION TITRATIONS
Precipitation titrations involve the formation of a slightly soluble precipitate.

For example, Argentometric titrations. In these titrations, silver nitrate is used as a

titrant. Ag+ reacts with X- to form a precipitate AgX.
Solubility product
Precipitation titration curves

Precipitation titration curves is the plot of pAg+ versus mL added of AgNO3.

Example:

For a titration of 100 mL 0.1 M NaCl with 0.1 M AgNO3, calculate the pAg+ at
the following additions: zero, 10, 50, 90, 99, 99.9, 100, 100.1, 101, 110 mL.
Sketch the titration curve.
At zero mL AgNO3 At 10.0 mL AgNO3 At 50.0 mL AgNO3
Cl− =0.1 M 90×0.1 50×0.1
Cl− = = 0.08181 Cl− = = 0.033
pCl- = 1 110 150
pAg+ = 9.92 – 1 = 8.92 pCl- = 1.087 pCl- = 1.477
pAg+ = 8.833 pAg+ = 8.44
At 90.0 mL AgNO3 At 99.0 mL AgNO3 At 90.9 mL AgNO3

10×0.1 1.0×0.1 0.1×0.1

Cl− = = 5.26×10 −3 −
Cl = =5.025×10−4 Cl− = =5×10−5
190 199 199.9
pCl- = 2.27 pCl- = 3.3 pCl- = 4.3
pAg+ = 7.64 pAg+ = 6.62 pAg+ = 5.62
At 100 mL AgNO3 At 100.1 mL AgNO3 At 101 mL AgNO3

9.92 0.1×0.1 1×0.1

pCl− + pAg+ = = 4.96 Ag+ = = 5×10−5 Ag+ = = 5×10−4
2 200.1 201
pAg+ = 4.3 pAg+ = 3.3
pCl- = 5.62 pCl- = 6.62
At 110 mL AgNO3 At 150 mL AgNO3

10×0.1 50×0.1
Ag+ = = 4.76×10−3 Ag+ = = 0.02
210 250
pAg+ = 2.3 pAg+ = 1.7
pCl- = 7.62 pCl- = 8.22
When plotting the titration
curve, the smaller the Ksp the
sharper is the end point.
DETECTION OF THE END POINT
(I) Mohr method (formation of a coloured precipitate)

This method is used for chloride and bromide determination in a neutral

solution (pH 6.5 – 9) with AgNO3 as a titrant.

Few drops of K2CrO4 solution is used as indicator. When the precipitation of

AgCl is completed the first excess of Ag+ react with the indicator to
precipitate red silver chromate.
The concentration of indicator is very important. The Ag2CrO4 should just start
precipitating at the equivalence point, where we have saturated solution of AgCl

[Ag+]= Ksp of AgCl

[Ag+]= 1.2 × 10−10 =1.1×10-5

Ksp of Ag2CrO4
[CrO42−]=
[Ag+]2

1.7×10 −12
[CrO42−]= −10
= 0.014 M
1.2×10
Limitation of Mohr method
1- Mohr method should be performed in neutral or faintly alkaline solution
(pH 6.5 – 9)
❑ In acidic solution (pH less than 6)

❑ In alkaline solution (pH more than 10)

2- In the titration of iodide, AgI adsorb the chromate ions strongly, so that a
false end point is obtained
(II) Volhard method (formation of a soluble coloured compound)

In this method silver ions in the presence of free nitric acid are titrated with
standard solution of KSCN or NH4SCN. Ferric ions (Ferric nitrate or ferric
ammonium sulphate) are used as indicator.

When the precipitation of AgSCN is completed, the first excess of SCN- react
with Fe3+ to form a reddish-brown colouration of the complex [Fe(SCN)]2+.

This method can be used for the determination of Cl-, Br- and I- .

A known excess of AgNO3 is added to precipitate AgX and the excess Ag+ is
back titrated with KSCN in the presence of nitric and Fe3+ indicator.
Limitations of Volhard method
Ksp AgCl = 1.2×10-10
1- In the titration of chloride
Ksp AgSCN = 7.1×10-13
Silver thiocyanate is less soluble than silver chloride so the thiocyanate
may react with AgCl

It is necessary to prevent this reaction by one of the following methods

❑ AgCl is filtered before the back titration.

❑ An immiscible liquid (nitrobenzene) is added to protect AgCl from SCN-
2- In iodide titration

Fe3+ indicator should not be added until excess Ag+ is present otherwise the
dissolved iodide react with Fe3+
(III) Fajans method (the use of adsorption indicator)

The theory of this method depends on two facts

1. A precipitate has a tendency to adsorb one of its ions presents in solution.

2. Adsorption indicator tends to be adsorbed by the precipitate at the
equivalence point, with a colour change.

Adsorption indicators are acid dyes e.g. Fluorescein (In-) or base dyes as
Rhodamine (R+)
For example

In the titration of Cl- with Ag+ we have the following forms of AgCl

❑ During precipitation: AgCl adsorb Cl- as a primary layer, then adsorb Na+
as a secondary layer

❑ At the end point: AgCl adsorb Ag+ then adsorb NO3-

❑ But in the presence of fluorescein indicator, we have In-

In the titration of Ag+ with Cl- we have the following forms of AgCl
(IV) Turbidity method (Liebig method)

Is used for CN- determination with AgNO3. The end point is determined by
the appearance of permanent turbidity.

❑ During precipitation: AgCN is precipitated which dissolve by shaking, in

the form of soluble potassium argento cyanide (K[Ag(CN)2]).

❑ At the end point: Silver argento cyanide (Ag[Ag(CN)2])is formed which

appear as a permanent turbidity.
Exercise

Chloride in a brine solution is determined by Volhard method. A 10.0 mL

aliquot of the solution is treated with 15 mL of standard 0.1182 M silver
nitrate solution. The excess silver is titrated with standard 0.101 M potassium
cyanide solution, requiring 2.38 ml to reach the red Fe(SCN)2+ end point.
Calculate the concentration of chloride in the brine solution, in g/L.
(At.wt. Cl = 35.5 g/mol).
Examples

❑What is the solubility of PbI2 in g/L if the solubility product is 7.1×10-9

❑ Calculate the molar solubility of PbSO4 and compare it with that of PbI2.
❑ What pH is required to precipitate Fe(OH)3 from 0.1 M FeCl3.
 COMPLEXOMETRIC TITRATIONS

❑ Complexometric titrations involve the formation of a complex.

❑ Complexometric titrations are very useful for metal ions determinations.

❑ Many metal ions form complexes with a variety of complexing agents,

called ligands. Most ligands contain O, S or N as a complexing (donor)
atoms.
e.g.
For such reactions the equilibrium constants are called formation constants Kf
or stability constants Ks.
Example

A divalent metal M2+ reacts with a ligand to form 1 : 1 complex ML2+. Calculate
the concentration of M2+ in a solution prepared by mixing equal volumes 0.2 M
metal and 0.2 M ligand. (Kf = 1.0×108)

0.1- x [M2+] = x = 3.2×10-5 M

1×108 =
x2
Chelates
❑ An organic agent that possesses two or more complexing groups is called a
chelating agent.

❑ The complex formed is called a chelate. The chelating agent is called

ligand.

❑ Titration with a chelating is called a chelatometric titration, a type of

complexometric titrations.

For example, EDTA titration

EDTA (EthylenDiamineTetraAcetic acid)
❑ Is the most widely used chelating agent for metal ions determination.
❑ EDTA is a polyprotic acid (H4Y) of the formula:

❑ EDTA in the form of H4Y is insoluble in water, so that its disodium salt is
used, which dissociates in water to give H2Y2-.
❑ EDTA forms 1 : 1 chelates with the most of metal ions in the periodic table.
Acid base equilibria of EDTA
❑ EDTA has four Ka values
Metal chelation
Metal chelation with EDTA is accompanying with the liberation of two
equivalents of hydrogen

The quilibrium constants are pH dependent.

The formation constants:
Consider the formation of Ca2+---EDTA chelate.

The equilibrium constant is called the formation constant Kf

[CaY2-]
Kf = 2+ 4-
Ca [Y ]
The Fractional Composition of EDTA

❑ EDTA exists in five species

H4Y, H3Y-, H2Y2-, HY3- and Y4-

❑ EDTA has four Ka values

Conditional formation constant:
Substitution Y4- by F4 CEDTA in the equation

[CaY2-]
Kf =
Ca2+ F4CEDTA

[CaY2-]
Kf F4 = Kf `=
Ca2+ CEDTA

Kf ` is the conditional formation constant.

Example

Calculate the fraction of EDTA that

exists as Y4- at pH 10.0, and from this
calculate the pCa in 100 ml solution of
0.1 M Ca2+ at pH 10.0 after adding 100
ml of 0.1 M EDTA (Kf = 5×1010)
Complexometric titration curve

❑ Is a plot of pM (- log[Mn+]) versus the

volume of added EDTA.

❑ The larger the formation constant the

sharper is the end point.
Detection of the end point “Metal ion sensitive indicators”

❑ The usual method is the using of metal ion sensitive indicators.

❑ Metal ion sensitive indicators are chelating agents that form a metal chelate
of a different colour from that of free indicator.

❑ The only requirement is that the metal-indicator chelate is less stable than
metal-EDTA chelate.

❑ E.g., Eriochrome black T which is suitable for Mg2+ and Zn2+ determination.
Types of EDTA Titrations
(I) Direct Titration

The metal ion to be determined is directly titrated with a standard solution of

EDTA in the presence of a buffer solution and a suitable metal ion indicator.
e.g. Mg2+ or Zn2+ titration with EDTA, using Erichrome black T as indicator
and NH4Cl-NH4OH (pH 10) as a buffer.
(II) Back Titration
Many metals cannot, for various reasons, be titrated directly
1. They may precipitate from the solution in the pH range necessary for the titration.
2. They may form inert complexes.
3. A suitable metal indicator is not available.
In such cases an excess of standard EDTA solution is added, the resulting solution is
buffered to the desired pH, and the excess of the EDTA is back-titrated with a standard
metal ion solution (Mg2+ or Zn2+ solution ). The end point is detected with Erio-T which
responds to the zinc or magnesium ions introduced in the back-titration.
(III) Substitution Titration

The metal cation to be determined may be treated with the magnesium

complex of EDTA, when the following reaction occurs:

The amount of magnesium ion set free is equivalent to the cation present and
can be titrated with a standard solution of EDTA and a suitable metal
indicator.
Example: Determination of Ca2+
(IV) Alkalimetric Titration
When a solution of disodium ethylenediaminetetraacetate, Na2H2Y, is added
to a solution containing metallic ions, complexes are formed with the
liberation of two equivalents of hydrogen ion:

The hydrogen ions thus set free can be titrated with a standard solution of
sodium hydroxide using an acid-base indicator such as phenolphthalein.
(V) Miscellaneous Methods
EDTA can be used for the determination of anions as indicated in the following examples
1. Sulphate may be determined by precipitation as barium sulphate or as lead sulphate. The
precipitate is dissolved in an excess of standard EDTA solution, and the excess of EDTA
is back-titrated with a standard magnesium or zinc solution using solochrome black as
indicator.
2. Phosphate may be determined by precipitating as Mg(NH4) PO4.6H2O, dissolving the
precipitate in dilute hydrochloric acid, adding an excess of standard EDTA solution,
buffering at pH = 10, and back-titrating with standard magnesium ion solution in the
presence of solochrome black.
 SOME SOLVED PROBLEMS
❑ How many milliliters of 0.1 N HCl solution will react with 10.0 mL of
0.25 N solution of NaOH?
(N × V)HCl = (N × V)NaOH
0.1 × V = 0.25 × 10 VHCl = 25 mL
❑ How many milliliters of 0.1 N HCl solution will react with 0.4 g NaOH?
(N × V)HCl = weight g × 1000/eq.wt NaOH
0.1 × V = 0.4×1000/40 VHCl = 100 mL
❑ How many milliliters of 0.25 M H2SO4 solution will react with 10.0 mL of 0.25 M
solution of NaOH?
H2SO4 + 2NaOH = Na2SO4 + 2H2O
2(M× V) H2SO4 = (M × V) NaOH
2 × 0.25 × V = 0.25 × 10 VH2SO4 = 5.0 mL

❑ How many milliliters of 0.25 M H2SO4 solution will react with 0.25 g NaOH?
H2SO4 + 2NaOH = Na2SO4 + 2H2O
2 (M × V)H2SO4 = weight g × 1000/eq.wt NaOH
2 × 0.25 × V = 0.25×1000/40 VHCl = 12.5 mL
❑ A 0.2638 g soda ash sample sample is analyzed by titrating the sodium carbonate
with standard 0.1288 M HCl solution, requiring 38.27 mL. Calculate the percent
sodium carbonate in the sample.

CO32- + 2H+ = CO2 + H2O CO32- + 2H+ = CO2 + H2O

(M × V)HCl = 2 × weight g × 1000/M.wt Na2CO3 (N× V)HCl = weight g × 1000/eq.wt Na2CO3
0.1288 × 38.27 = 2 × weight g × 1000/106 0.1288 × 38.27 = weight g × 1000/53
weight = 0.2612 g weight = 0.2612 g
Percent = 0.2612×100/0.2633 = 99.01% Percent = 0.2612×100/0.2633 = 99.01%
❑The Iron (II) in an acidified solution is titrated with 0.0206 M KMnO4
solution. If the titration required 40.2 mL, how many milligrams iron
are in solution?
5Fe2+ + MnO4- + 8H+ = 5Fe2+ + Mn2+ + 4H2O
weight mg of Fe2+/ At.wt = 5 × M × V
weight mg of Fe2+/ 55.84 = 5 × 0.0206 × 40.2
weight mg of Fe2+ = 231.21 mg
❑How many milliliters of HCl 38%(w/w), specific gravity 1.19 are
required to prepare 1.0 liter of 0.1 M solution?
1000 ml = 1190 g soln./L
= 1190 × 0.38 g HCl/L
= 1190 × 0.38/36.5 mol/L
= 12.389 M
(M× V) before= (M × V) after
12.389 × V = 0.1 × 1000
V = 8.072 mL
Titer: is the number of milligrams of analyte that react with 1.0 mL of
titrant.
❑ Express the titer of 0.05 M KMnO4 solution in mg Fe2O3/mL.
5Fe3+ ≡ MnO4-
5 Fe2O3 ≡ 2 MnO4-
weight mg of Fe2O3/ M.wt = (5 × M × V)/2
weight mg of Fe2O3/ 159.65 = (5 × 0.1 × 1)/2
weight mg of Fe2O3= 19.96 mg
Titer = 19.96 mg Fe2O3/mL.
 OXIDATION-REDUCTION TITRATIONS (REDOX TITRATIONS)
Oxidation: is a loss of electrons

Reduction: is a gain of electrons

Equivalent weights of oxidizing or reducing agents
Old definitions
Oxidation: combination with oxygen. Reduction: loss of oxygen.
Equivalent weight: the weight which react with or replace 8.0 grams of oxygen.
Electrode potential:
It is the measure of the tendency of a half reaction to loss or gain electrons.
Higher standard reduction potential E0 means high ability to be reduced
or act as oxidizing agent.
For example: for the following two half reaction cerium will be reduced
while iron will be oxidized
Examples: write the balance reactions

E0 of Fe3+/Fe2+ is higher than E0 of Sn4+/ Sn4+ so the iron will be reduced

while tin will be oxidized
 Nernest Equation

For a half reaction:

Problems: A solution is 10-3 M in Cr2O72- and 10-2 M in Cr3+. If the pH is 2.0, what is
the potential of the half reaction? Eo = 1.33 V
5.0 mL of 0.1Ce2+ solution is added to 5.0 mL of 0.3 M Fe2+ solution. Calculate the
potential of Pt electrode dipping in solution (relative to NHE)
Calculation of the equilibrium constant of a redox reaction:
For a redox reaction: a Ox1 + b Red11 = a Red1 + b Ox11
The equilibrium constant is given by:
Equilibrium constant for a half reaction can be calculated form standard
electrode potential
At equilibrium: E1 = E2
Exercise
Calculate the equilibrium constants for the following redox reactions:
Calculation of The Potential at The Equivalence Point for Redox Reaction
For the following redox reaction:

Drive a mathematical equation that express the potential at the equivalence

point.
At the equivalence point [Fe2+] = [Ce4+] and [Fe3+] = [Ce3+]

2Eeq = E0Fe + E0Ce Eeq = (E0Fe + E0Ce)/2

Example
Drive an expression for the equivalence point potential in the titration of U4+
with Ce4+. Assume both solutions are 1.0 M IN H2SO4.
Here we use the formal potential for Ce4+ in 1.0 M H2SO4
The potential of the system Eeq is given by both:

Multiply the first equation (A) by 2 and add it to the second equation (B) to
obtain equation (C)
At the equivalence point:
[U4+] = [Ce4+]/2 and [UO22+] = [Ce3+]/2
Equation (C) turns to equation (D)
In the previous example, find the potential at the equivalence point
 Redox Titration Curve
Redox titration curve is the plot of potential E (volts) versus the added
volumes of titrant.
Example
Calculate E (volts) during the titration of 100.0 mL 0.1 M Fe2+ with 0.1 M Ce4+
solution in acid medium, at the following additions 10, 50, 90, 99. 99.9, 100,
100.1, 101, 110, 150 and 200 mL Ce4+ solution. Sketch the titration curve.
 Detection of the End Point
(I) By potentiometric measurements
• Titration curve shows potential as a function of the volume of added titrant.
The equivalence point is marked by a steep rise in voltage.
• The voltage change near the equivalence point increases as the difference
between E0 of the two redox couples in the titration increases. The larger
the difference in E0, the greater the equilibrium constant for the titration.
• The equivalence point can be detected from normal or derivative titration
curve.
• we measure electrode potential, E, versus volume of titrant, V, during a
redox titration. The end point is the maximum of the first derivative,
∆E/∆V, or the zero crossing of the second derivative, ∆ (∆E/∆V)/ ∆V.
(II) Redox Indicators

• A redox indicator is a compound that changes color when it goes from its
oxidized to its reduced state. The indicator ferroin changes from pale blue
(almost colorless) to red.
(III) The Starch-Iodine Complex

• Numerous analytical procedures are based on redox titrations involving

iodine. Starch is the indicator of choice for these procedures because it
forms an intense blue complex with iodine.

• Starch is not a redox indicator; it responds specifically to the presence of I2,

not to a change in redox potential.
(IV) Self-indicating reagents.

• This is well illustrated by KMnO4, one drop of which will impart a visible
pink coloration to several hundred millilitres of solution, even in the
presence of slightly coloured ions, such as iron (III).
 Balancing the oxidation-reduction equations
Guidelines for Balancing Redox Equations:
1. Determine the oxidation states of each species.
2. Write each half reaction and for each:
a. Balance atoms that change oxidation state.
b.Determine number of electrons gained or lost
c. Balance charges by using H+ (in acidic solution) or OH- (in basic solution).
d.Balance the rest of the atoms (H's and O's) using H2O.
3. Balance the number of electrons transferred for each half reaction using the
appropriate factor so that the electrons cancel.
4. Add the two half-reactions together and simplify if necessary
Assigning Oxidation Numbers
The following rules for assignment of oxidation numbers are listed in
hierarchical order.

1. Pure elements (in their natural, standard state): O2, Cl2, F2,….. = 0.

2. Monatomic ions: = ionic charge: Mg2+ = +2.

3. F is always F (-1) in compounds.

4. Alkali metals (those in the 1st column of the periodic table): = +1.
5. Alkaline-earth metals (those in the 2nd column of the periodic table): = +2.
6. Hydrogen is almost always H (+1). The exception is in metal hydrides
(MHx).
7. Oxygen is almost always O (-2) in compounds. Exceptions are O-O , H2O2
and O-F.
The sum of all oxidation numbers in the species will equal the total charge
of that species.
Example: Find the oxidation number of Br in HBrO2
1 × (X) + 1 × (+1) + 2 × (-2) = 0
X = +3
Balance the following aqueous reactions: