Introduction:

Quantitative analysis: is the determination of the absolute or relative amount (often

expressed as a concentration) of one, several or all substance(s) present in a sample.
Quantitative Classical
Chemical Analysis
Gravimetry Titrations

Acid-base Precipitaiton Complexometric Redox

Titrations involving
Dichromatometric
KMnO4 iodine (I2)

Permangani
metric Iodimetry

Iodometry
Iodometric titration of copper

Titration: is the process, operation, or method of determining the

concentration of a substance (analyte) in solution by adding to it a standard reagent
(titrant) of known concentration in carefully measured amounts until a reaction of
definite and known proportion is completed, as shown by a color change or by
electrical measurement, and then calculating the unknown concentration.

Equivalence point:
The point in a titration where the amounts of titrant and material being titrated are
equivalent chemically.

The end point :

The physical change which results when the equivalence point has been reached.
In colorimetric titrations, this is a color change of the indicator
Titration set up:
The apparatus

Conical flask Burette

Funnel Pipette

Types of titration that will be encountered in 250 chem lab. :

1- Neutralization titration (Acid –base reaction)

2- Precipitation titration.
3- Complexometric titration.
4- Redox titration.
Acid –base reactions

These titrations are based on the neutralization reaction that occurs between an acid
and a base, when mixed in solution.

Acid + Base a Salt + water

Key Concepts:

• Acid-base reactions involve a proton transfer

• The acid donates a proton to the base
• Acid-base reactions are also known as neutralization reactions
• Equivalence point is the point at which the moles of H+ is equal to the moles of
OH-
• An indicator is used to show the equivalence point during a titration

Acid-base Titration curves:

.
General Typical
Example Features of Curve
Type Titration Curve

Curve begins at high pH typical of

strong base and ends at low pH
Strong Acid
typical of strong acid.
and Strong HCl added to NaOH
Base
There is a large rapid change in pH
near the equivalence point (pH =7).

Curve begins at low pH typical of

strong acid, and ends at high pH
Strong Base
typical of strong base.
and strong NaOH added to HCl
Acid
There is a large rapid change in pH
near the equivalence point (pH=7).
Curve begins at a higher acidic pH
Weak Acid and ends at high basic pH.
NaOH added to acetic
and Strong
acid (CH3COOH)
Base The pH change at the equivalence
point (pH > 7)is not so great.

Curve begins at low pH and ends at

a less high basic pH.
Strong Acid
Ammonia (NH3)
and Weak
added to HCl The pH change at the equivalence
Base
point (pH < 7) is similar to that for
Strong Base and Weak Acid.

Curve begins at higher acidic pH

and ends at low basic pH.
Weak Acid Ammonia (NH3)
and Weak added to Acetic acid There is not a great pH change at
Base (CH3COOH) the equivalence point (pH ~ 7)
making this a very difficult titration
to perform.

Volumetric analysis to prepare and standardize Hydrochloric

Acid

*prepare 0.1 M HCl.

*The reaction between sodium carbonate and hydrochloric acid takes place in two
stages:
Na2CO3 (aq) + HCl (aq) → NaHCO3 (aq) + NaCl (aq) (1)

NaHCO3 (aq) + HCl (aq) → NaCl (aq) + CO2 (g) + H2O (l) (2)
Two indicators are needed to cover both stages:
• In stage 1, phenolphthalein is most suitable, and will respond to the pH change
associated with the formation of sodium hydrogen carbonate, NaHCO3.
• In stage 2, methyl orange is most suitable, and will respond to the pH change
associated with the final formation of sodium chloride, NaCl.
Procrdure:

1. Transfer a 10 ml aliquot (portion) of sodium carbonate solution to a 250 cm3

capacity conical flask. Add a few drops of phenolphthalein indicator solution.

2. Titrate with the hydrochloric acid. The end-point of the titration is when the
solution just changes from pink to colorless. Equation (1)

3-repate the process by methyl orange indicator solution, the end-point of the
titration is when the solution just changes from yellow to orange equation (2)

4- Repeat steps 1 - 3 until concordance (i.e. until the readings are the same or within
0.2cm3).

5-Tabulate your titration results.

Results:

Burette reagent

Conical flask reagent

Indicator

Volume 1 Volume 2 Volume 3 Mean volumes

6- Do the calculations using the following equation:

V1 M1 = V2 M2

Where:

V1 = volume of titrant used for the known solution

V2 = volume of titrant used for the unknown solution
M1 = Molarity of the known solution
M2 =Molarity of the unknown solution

Titration of Sodium Hydroxide with Hydrochloric Acid.

The reaction:

HCl + NaOH NaCl +H2O

procedure :

1- Pipette 10 ml of Sodium hydroxide solution into 250 ml conical flask.

2- Add 1-2 drops of Phenolphthalein solution.
3- Titrate with hydrochloric acid solution till the first color change.
4- Calculate the concentration of Sodium Hydroxide .
Titration of Acetic acid By Soduim hydroxide

Acetic acid is a monoprotic acid, with one acidic hydrogen atom.

A weak acid is a compound that partially ionizes in aqueous solution producing

hydronium (H3O+) ions. The general equation for the dissociation of any weak acid
can be written as:

HA (aq) + H2O (l) A- (aq) + H3O+ (aq) (1)

The addition of a strong base results in a neutralization reaction in which hydroxide

ions (OH-) react with hydronium to produce water:

H3O+ (aq) + OH- (aq) 2 H2O (l) (2)

As hydronium is consumed in the neutralization reaction, the equilibrium in

equation 1 is shifted to the right according to Le Chatelier’s Principle.
Neu tralization process can be written as the sum of equations (1) and (2):

HA (aq) + OH- (aq) A- (aq) + H2O (l) (3)

The concentration of the unknown solution can be determined by measuring the

volume of titrant added to reach the equivalence point. The equivalence point occurs
when all of the acid has been neutralized by the base. And it will
be determined by using an indicator that changes color at the equivalence point

procedure:
1-Pipette aliquot(10 ml) of acetic acid solution into 250mL conical flask..
2-Add 2-3 drops of phenolphthalein solution.
3-Titrate with NaOH solution till the first color change.
4-Calculate the concentration of Acetic Acid solution.
Titration of phosphoric acid with sodium hydroxide

Phosphoric acid is relatively weak, with pKa1=2.15, pKa2=7.20 and pKa3=12.35.

That means titration curve contains only two inflection points and phosphoric acid
can be titrated either as a monoprotic acid or as a diprotic acid. In the first case acid
has to be titrated against indicator changing color around pH 4.7 (for example methyl
orange) in the second case - against indicator changing color around pH 9.6(for
example phenolphthalein).

reaction

Depending on the indicator used reaction taking place is either:

H3PO4 + NaOH → NaH2PO4 + H2O

Or

H3PO4 + 2NaOH → Na2HPO4 +2H2O

The procedure:

• Pipette aliquot of phosphoric acid solution(10ml) into 250 mL conical flask.

•
• Add 2 drops of methyl orange or 2 drops of phenollphthalein solution

• Titrate with NaOH solution till the first color change.

• Calculate the concentration of phosphoric acid solution.

Titration the Mixture of Sodium Hydroxide and Sodium Carbonate

The composition of the solution can be deduced from the relative volumes of acid
needed to titrate equal volumes of the sample.

Titration with hydrochloric acid to a phenolphthalein end point (Vph.ph):

NaOH + HCI →NaCl + H2O

Na2CO3 + HCI → NaHCO3 + NaCl

Titration with hydrochloric acid to a methyl orange end point (VM.O):

NaHCO3 + HCI →NaCl + H2O + CO2

Components in sample Relationship between (Vph.ph) and (VM.O ) in the titration of an

equal volume of sample

NaOH +½Na2CO3 = Vph.ph

Na2CO3 = ½ VM.O

Procedure:
1. Load a burette with 0.1 N hydrochloric acid solution.

2. To conical flask pour in 10 ml aliquot of sample (Vsample).

3. Introduce 2-3 drops of phenolphthalein solution, and titrate with 0.1 N hydrochloric
acid solution until the solution lost the color. Read the burette mark (Vph.ph).

4. To the same conical flask, introduce 2-3 drops of methyl orange solution, and
titrate with 0,1 N hydrochloric acid solution until the solution just begin to change
colour. Read the burette mark (VM.O).

6. Repeat titration also two times. Calculate the median volumes of used hydrochloric
acid solution.

7. Calculate the concentration of NaOH and Na2CO3

Precipitation titration:

Introduction
Titration is a process by which the concentration of an unknown substance in solution
is determined by adding measured amounts of a standard solution that reacts with the
unknown. Then the concentration of the unknown can be calculated using the
stoichiometry of the reaction and the number of moles of standard solution needed to
reach the so called end point.

Precipitation titrations: are based upon reactions that yield ionic compounds of
limited solubility.

General Principles:

The major precipitation reaction used is that of silver with a range of anions. These
anions include:
o Chloride
o Bromide
o Iodide
o Thiocyanate

Titrations involving silver are termed argentometric, from the old name for silver,
argentum.

The reaction ratio is 1:1 and silver salts formed are generally quite insoluble.

Silver nitrate solutions slowly decompose when exposed to light, so they should be
kept in dark bottles.

Chemical Indicators:
There are three common chemical indicators that are associated with argentometric
titrations:
1. The chromate ion, CrO4-2(the Mohr method);
2. The ferric ion, Fe3+ (the Volhard method);
3. Adsorption indicators such as fluorescein (the Fajans method)
Comparison of silver titration methods:

Method Advantages Disadvantages

Mohr Simple Alkaline solutions only
Not suitable for iodide

Volhard Capable of direct silver and Must be 1M nitric indirect

halide analyses acid solution

Mohr method:
The Mohr method uses chromate ions as an indicator in the titration of chloride
ions with a silver nitrate standard solution. After all the chloride has been precipitated
as white silver chloride, the first excess of titrant results in the formation of a silver
chromate precipitate, End point is signalled by the appearance of the red silver
chromate. (1). The reactions are:
Ag ++ Cl - AgCl(s)
2Ag+ + CrO4 -2 Ag2 CrO4 (s)

By knowing the stoichiometry and moles consumed at the end point, the amount of
chloride in an unknown sample can be determined.

Solution during titration should be close to neutral.6-9.

Above this pH, silver starts to react with hydroxide anions, precipitating in form of
AgOH and Ag2O.

Below this pH chromate converts to dichromate, a bright orange colour thereby

obscuring the endpoint
Mohr’s method is suitable only for titration of chloride, bromide and cyanide
Determination of unknown of Chloride sample.

Procedure:
1-Pipette aliquot of chlorides solution into 250 mL Erlenmeyer flask.
2-Add 1 mL of 5% potassium chromate solution.
3-Titrate with silver nitrate solution till the first color change.
4- calculate the Concentration of NaCl

Volhard method
The Theory:

The Volhard method is based on the precipitation of silver thiocyanate in nitric acid
solution with iron (III) ion employed to detect excess thiocyanate ion:
Ag+ + SCN- → AgSCN (s) (white) Volhard Titration Reaction

The solution turns red with first slight excess of thiocyanate ion:

Fe+ + SCN- → FeSCN2+ (red) Volhard End Point Reaction

The titration with thiocyanate is carried out in acidic solution. When the silver (I) has
been precipitated as white silver thiocyanate, the excessive titrant will react with the
iron (III) indicator and form a soluble red complex. The color change at the end point
is not extremely sharp, but it can be detected with a little practice

In the Volhard method for determination of chloride and other anions, a known
amount of standard silver nitrate solution is added to the sample solution; the amount
of silver nitrate is in excess to react with the halide:
Ag+ + X- → AgX(s) + excess Ag+ Titration Reaction

The excess silver (I) is then back-titrated with standard thiocyanate

:
SCN- + excess Ag+ → AgSCN(s) Back-Titration Reaction

SCN- + Fe3+ → Fe(SCN)2+ End Point Reaction

procedures:

Part1: Determination of unknown silver sample by Volhard method

1-Pipette 10 ml silver nitrate solutions to a 250 ml conical flask

2-Add 5 ml of 1:1 nitric acid and 1 ml of ferric indicator

3-. Titrate with thiocyanate solution, shaking the solution thoroughly between

additions of drops. The end point is marked by the permanent appearance of the

reddish orange color of the ferricthiocyanate complex.

Part II: Determination of unknown KBr sample by Volhard method

1-Pipette 10 ml of KBr solution to 250 ml conical flask.

2-add 20 ml of AgNO3 ,5 ml of 6N HNO3 and 1ml of ferric indicator

3- titrate the excess of AgNO3 by solution of KSCN from the burette ,shaking will till

reach the end point .

4- make the blank,and calculate the concentration of KBr

Complexometric titration:
Introduction:

These titrations are based on the formation of a complex between the analyte and the
titrant. The chelating agent EDTA is very commonly used to titrate metal ions in
solution. These titrations generally require specialized indicators that form weaker
complexes with the analyte.
A common example is Eriochrome Black T for the titration of calcium and
magnesium ions or Murexide for the titration of Calcium.

Chelating agent
Ligands having more than one electron donating groups are called chelating agents

Complexometric titration with EDTA

ethylenediaminetetraacetic acid, has four carboxyl groups and two amine groups that
can act as electron pair donors, or Lewis bases. The ability of EDTA to potentially
donate its six lone pairs of electrons for the formation of coordinate covalent bonds to
metal cations makes EDTA a hexadentate ligand.

EDTA forms an octahedral complex with most 2+ metal cations, M2+, in aqueous
solution.

M2+ + H2Y-2 → MY-2 + 2H+

EDTA has the widest general application in analyses because of the following
important properties:
▪ It has low price.
▪ The special structure of its anion which has 6 ligand atoms
▪ The formation constant for most metal cation-EDTA complexes is very high
Factors influencing EDTA reactions:
􀂑The nature and activity of metal ion.
􀂑The pH at which the titration is carried out.
􀂑The presence of interfering ions such as CN
Organic solvents also increase the stability of complex
EDTA Determination of Total Water
Hardness

Purpose:

Determine the hardness in tap water samples.

Water hardness is an expression for the sum of the calcium and magnesium cation
concentration in a water sample. These cations form insoluble salts with soap,
decreasing soaps cleaning effectiveness. They also form hard water deposits in hot
water heaters. The standard way to express water hardness is in ppm CaCO3 which
has the formula weight of 100.1 g/mole.

Procedure:

1-Transfer a100 ml of tap water by graduated cylinder to the conical flask.

2-Add 1ml of buffer solution (PH10) and little particles of EBT indicator.

3-Titrate by standard solution of EDTA (0.01M), till the first color change (wine red
to Blue).

4-Calculate the total water hardness as concentration of CaCo3 in ppm.

Copper Analysis by Complexometric Titration

The complexing agent will be ethylenediaminetetraacetic acid (EDTA) in the form of

its disodium salt, EDTA forms complexes with many metal
This particular method can only be used in the absence of such ions as Ca2+, Ni2+, etc.
The reaction of complexation is:
Cu2+ (aq) + (EDTA)2–(aq) → Cu(EDTA)2– (aq) + 2H+1(aq)

The stoichiometry is one metal cation to one EDTA anion.

The indicator used for the titration is called murexide. This indicator is highly colored
and will complex with the copper ion to give different colored species. During the
titration, the EDTA2– forms a more stable complex and frees the indicator, which then
displays its original color. The appearance of the free indicator means that all metal
ions have been complexed by EDTA, which signals the end point.

Procedure:

1-Pipette 10 ml of CuSO4.5H2O to the conical flask.

2- add 1 ml of NH3 , 10 ml of distilled water and the Murexide indicator.

3- Titrate by 0.01M of EDTA.till the first color change.

4- calculate the concentration of Cu.

Oxidation/Reduction Reactions
Introduction:
Oxidation/Reduction Reactions :is the Reactions in which electrons are transferred
from one reactant to another
Example

Cu2+ + Zn (s) <====> Cu (s) + Zn2+

Oxidizing reagent : A reagent which tends to remove electrons from

another reactant. its oxidation number becomes less positive after it
reacts.
.
In the above reactant Cu2+ is the oxidizing agent. It has been reduced.
Cu2+ + 2e <=> Cu (s)

Reducing agent: A reagent which tends to give up electrons to another reactant. Its
oxidation number becomes more positive after it reacts.

In the above reaction Zn is the reducing agent. It has been oxidized.

Zn (s) <=> Zn2++ 2e

Examples of Oxidizing agents:

1-. KMnO4 ,
Permanganate ion in the acidic medium is a very strong oxidizing agent
MnO4￣ + 8H+ + 5e- → Mn2+ + 4H2O

2-. K2Cr2O7 in dil. H2SO4 is moderately strong oxidizing agent;

oxidizing ability depends strongly on pH, decreasing rapidly as solution becomes
more neutral
Cr2O72– + 14H+ + 6e– → 2Cr3+ + 7 H2O

3-. Iodine solution

I2 + +2 e- 2I–

Type of Redox Indicators:

Self Indicators: the titrant itself may be so strongly coloured that after the
equivalence point, a single drop of the titrant produces an intense colour in the
reaction. e.g. potassium permanganate
Such Indicators are called self indicators.

starch indicator: this indicator is used for titration involving iodine.

Redox indicators: such as Diphenylamine

Titration of Oxalic acid (H2C2O4) by Potassium permanaganate
Oxalic acid and Potassium permanaganate react in an acid medium according to the
following half-cell reactions:

C2O42- → 2CO2 + 2e- (oxidation half-cell) (1)

8H+ + MnO4- + 5e- → Mn2+ + 4H2O (reduction half-cell) (2)
The two half-cell reactions are combined to obtain the complete redox reaction:
5C2O42- + 16 H + + 2MnO4- → 10CO2 + 2Mn2+ + 8H2O (3)

From this balanced equation, you can see that there is a 5:2 stoichiometric ratio
between the moles of oxalate and the moles of permanganate.
pH dependence of oxidizing behavior
It is important to note that for many oxidants the pH of the medium is of great
importance and hence their oxidizing strength may vary depending on the medium in
which its reaction is studied. For example potassium permanganate is oxidizing agent
in all three mediums, acid, alkaline and neutral. However it is strongest
in acidic medium.
a. Strongly alkaline medium
MnO4￣ + e- → MnO42-

Permanganate ion Manganate ion

b. Neutral medium
MnO4￣ + 2H2O + 3e-- → MnO2↓ + 4OH-
Manganese dioxide ppt.
c. Acidic medium
MnO4￣ + 8H+ + 5e- → Mn2+ + 4H2O

Procedure

1-pipette a 10 ml of H2C2O4 to the conical flask.

2- Add10 ml of H2SO4 acid

3- Heat the solution to 60-90оC to speed the reaction.

4- Titrate the hot solution till reach the end point (pink color of the KMnO4)

5- Calculate the concentration of the Oxalic acid.

Titration of FeSO4.(NH4)2SO4.6H2O. sample by Potassium
dichromate solution.

Potassium dichromate (K2Cr2O7)is a very strong oxidizing agent . However it is not

as strong oxidizing agent as permanganate is. Potassium dichromate acts as oxidizing
agent in acidic medium only.

it can’t be used as a self indicator like KMnO4. this is because its reduction product
(Cr3+) is green which hinders in the visual detection of end point by observing
dichromate colour. Thus an indicator is must in this titration.
Mohr’s Salt
The reducing agent used in this titration is Mohr’s salt which is a double salt. Its
composition is FeSO4.(NH4)2SO4.6H2O. the redox active species in this compound is
Fe2+ whose oxidation can be represented as:
Fe2+ → Fe3+ + e-

The reaction:
K2Cr2O7 + 6FeSO4 + 7H2SO4 → K2SO4 + Cr2(SO4)3 + 3Fe2(SO4)3+ 7H2O
In ionic form the reaction can be written as
Cr2O72- + 6Fe2+ + 14 H+ → 2 Cr3+ + 6Fe3++ 7H2O
Orange green

This redox reaction can be split apart in two parts- one showing the oxidation and the
other reduction
Cr2O72-+ 6e￣ + 14H+ = 2 Cr3+ + 7H2O reduction
+ VI +III (Oxidation number has decreased)
6 Fe2+ → 6 Fe3+ + 6 e- oxidation
+II +III (Oxidation number has increased)

The end point of the titration as indicated earlier has to be defined with the help of an
indicator.
Diphenylamine is use as redox indicator
The end point is marked with an intense blue violet color.

Procedure:
1-Pipette 10 ml of FeSO4.(NH4) 2SO4.6H2O to the conical flask.

2-Add 10 ml of H2SO4(2M) ,5 ml of Phosphoric acid and 1ml of Diphenyl Amine

indicator.
.
3- Titrate the solution by standard solution of K2Cr2O7 till reach the end point (dark
blue).
4- Calculate the concentration of the FeSO4.(NH4) 2SO4.6H2O sample.
REDOX TITRATIONS WITH IODINE
Introduction:

Titrations that create or consume I2 are widely used in quantitative analysis.

Iodine is a moderately weak oxidizing agent; it is reduced to form the iodide anion, as
follows:
I2(aq) + 2e. 2I- (aq)
The above redox reaction is completely reversible, and so the iodide anion is a
moderately weak reducing agent that will react with oxidizing analytes to produce
iodine.
In iodimetric titrations,(direct titration)
the analyte (a reducing agent) reacts with iodine to produce iodide:
iodimetry Aox + I2 Ared + 2I-
where Aox and Ared are the oxidized and reduced forms, respectively, of the analyte.

conditions:
neutral or mildly alkaline (pH = 8) to weakly acid solutions

.If the pH is too alkaline , I2 convert to Hypo iodate and Iodide

If the solution is too acid the starch used for the end point detection tend to
hydrolyze or decompose in this medium

iodometric (indirect titration)

When an analyte that is an oxidizing agent is added to excess iodide to produce
iodine, and the iodine produced is determined by titration with sodium thiosulfate, the
method is called "iodometry".

Example:
2 Cu 2+ + 4I- → 2CuI + I2
Then the iodine (I2) is usually titrated with standard thiosulfate
as follows:
2S2O3-2. + I2 S4O6-2. + 2I-

The iodine produced in this reaction is stoichiometrically related to the amount of

analyte originally present in the sample.
The end point is detect with starch.
The disappearance of the blue starch-I2 complex color indicates the end of the
titration.
,
The reason for such timing:
Starch is added just before the end point( the color become pale yellow)
because:
1. iodine-starch complex is slowly dissociated.

2. starch has a tendency to hydrolyze in acid solution.

Titration of Sodium thiosulfate (Na2S2O3) by Iodine( I2)

2S2O32- + I2 → S4O62- + 2I-

Procedure :

1-Pipette 10 ml of Na2S2O3 to the conical flask.

2-Add 1ml of Starch indicator.

3-Titrate the solution By I2 solution and shaking till reach the blue color of the I2 –
starch complex.

4-Calculate the concentration of the I2 solution

Iodometric titration of copper.

Iodometric determination of copper is based on the oxidation of iodides to iodine by

copper (II) ions, which get reduced to Cu+

For the best results reaction should take place in the slightly acidic solution (pH
around 4-5),
To detect titration end point we will use a standard indicator for iodine titrations -
starch. We start with a solution containing relatively high concentration of iodine, so
indicator has to be added close to the end point.

2 Cu 2+ + 4I- → 2CuI + I2
I2 + 2S2O32- → 2I- + S4O62-

Procedure:

1-Pipette aliquot containing copper (II)(10ml) of CuSO4.5H2O into 250 ml conical

flask with a glass stopper.

2-Add 20 ml of potassium Iodide10%.

3-Add 20ml of (2M) H2SO4 and dilute the solution by 20 ml distilled water.

4- Titrate the solution till reach the pale yellow color

5 -add 1ml of starch indicator.

6-Continue the titration until blue color disappears.

7 Calculate the Concentration of the CuSO4 .5H2O