THIS MODULE CONSISTS OF SIX STUDY UNITS

 Basic concepts

 Volumetry

 Gravimetry

 Surface characterisation

 Atomic spectrometry

 Separation methods

Each of these study units is sub-divided into different study sections

 What is Analytical Chemistry????

Analytical chemistry is the study of the separation, identification, and quantification of

the chemical components of natural and artificial materials

Branches of analytical chemistry

Qualitative Quantitative
gives an indication of the identity of determines the amount of certain
the chemical species in the sample components in the substance

Qualitative: recognized by color, boiling point, solubility, taste

 Classification of Quantitative Methods of Analysis

Classical methods
Instrumental Method
Gravimetric Method: mass is use an instrumental technique to
measured. assay the amount of sample
Volumetric Method: volume is
measured

Electro analytical Spectrophotometric

Measurement of electrical property Interaction of light and matter
Overall Learning Outcomes

• State the requirements for a titration

• Classify various volumetric methods
• Describe a titration curve
• Determine the concentrations of various analytes using
volumetric analysis
 Volumetric analysis
• Procedures in which the volume of reagent needed to
react with an analyte is measured.

• Commonly used to determine the unknown

concentration of a known reactant.

• Volumetric analysis is often referred to as titration, a

laboratory technique in which one substance of
known concentration and volume is used to react
with another substance of unknown
concentration.
Common Types Of Titrations
Terms
• Titration : A procedure for determining the amount of some
unknown substance (the analyte ) by quantitative reaction with a
measured volume of a solution of precisely known concentration
(the titrant).
• Titrant : The substance that quantitatively reacts with the
analyte in a titration . The titrant is usually a standard solution
added carefully to the analyte until the reaction is complete.
• Indicators : organic chemicals that change colour as the pH of a
solution changes
• Direct titration : Titrant is added to the analyte until the
reaction is complete.
• Back titration : Adding a known excess of reagent to the analyte,
then, a second reagent is used to titrate the excess of the first
reagent.
Cont.
• Equivalence point : point in a titration at which equivalent
amounts of titrant is the exact amount necessary for
stoichiometric reaction with the analyte.
• End point : the point in a titration when a physical change
occurs that is associated with the condition of chemical
equivalence.
• Titration error : The difference in volume or mass between
the equivalence point and the end point.
titration error : eT = Vep – Veq
Vep = actual volume at end point,
Veq = theoretical volume of equivalence point
Cont.

• Titration Curve: The plot of pH vs. volume.

• Standard solution : A solution of precisely known
concentration.
• Primary standard : An ultra-pure (99.9% purity) compound
that serves as the reference material for a titrimetric
method of analysis.
• Secondary standard : A compound whose purity has been
established by chemical analysis and that serves as the
reference material for a titrimetric method of analysis
• Standardization : A process in which the concentration of a
solution is determined by using the solution to titrate a
known amount of another reagent.
 Requirement for Successful
Volumetric Titration

• Reaction must be stoichiometric, well defined

reaction between titrant and analyte.
• Reaction should be rapid.
• Reaction should have no side reaction, no
interference from other foreign substances.
• Must have some indication of end of reaction, such
as color change, sudden increase in pH, zero
conductivity, etc.
• Known relationship between endpoint and
equivalence point.
 Properties of The Primary
Standard
• Be commercially available in a high state of purity

• Stable over long periods of time

• Not decompose when dissolved in water

• Not be volatile (so losses due to evaporation do not

occur)

• Not absorb water or carbon dioxide from the

atmosphere

• Reasonably large formula weight

 Titration Curves
• Titration of acid/base reactions involve the process of
neutralization in order to determine an unknown
concentration.
• Acid-Base titrations can be made up of both strong
and weak acids or bases.
• However, in order to determine the unknown
concentration of an acid or base, you must add the
opposite so that neutralization can be reached.
• Therefore, an acid of unknown concentration will be
titrated using a basic standard solution and a base of
unknown concentration will be titrated using an acidic
standard solution.
Cont.
• Acid-Base titrations often require the use of some kind of
indicator depending on the strength of acid or base that is
being titrated.

• In some cases a weak base or weak acid is used or a pH

meter which reads the pH of the solution being titrated.

• Once the pH of the titrated solution equals seven, either

indicated by a change in colour or on a pH meter one can
determine that titrations is complete.
What happens during titration
Cont.

• Examples of acid-base titrations include :

 Titration of a Strong Acid with a Strong Base

 Titration of a Weak Acid with a Strong Base

 Titration of a Weak Base with a Strong Acid

 Titration of a Weak Polyprotic Acid

Cont.
Strong Acid/Strong Base Curve

• The standard solution is a strong acid and the

unknown concentration solution is a strong base.
• This can be acknowledged by the change in pH as
the standard solution is being added.
Cont.

• Since the graph begins at a high pH of 14 then the

original solution must be a strong base.

• The graph ends at pH close to 0 and it can be inferred

that the standard solution being added to reach
neutralization must be a strong acid.
Back Titration (Indirect Titration)
• Generally a two-stage analytical technique: Reactant A of
unknown concentration is reacted with excess reactant B
of known concentration.
• A titration is then performed to determine the amount of
reactant B in excess.
• Back titrations are used when:
 One of the reactants is volatile, for example ammonia.
 An acid or a base is an insoluble salt, for example
calcium carbonate
 A particular reaction is too slow
 Example
A student was asked to determine the concentration of ammonia, a volatile substance, in a
commercially available cloudy ammonia solution used for cleaning.
First the student pipetted 25.00 mL of the cloudy ammonia solution into a 250.0mL conical flask.
50.00 mL of 0.100 mol L-1 HCl(aq) was immediately added to the conical flask which reacted with
the ammonia in solution.
The excess (unreacted) HCl was then titrated with 0.050 mol L-1 Na2CO3(aq). 21.50 mL of
Na2CO3(aq) was required. Calculate the concentration of the ammonia in the cloudy ammonia
solution.
Cont.

Step 1: Determine the amount of HCl in excess from

the titration results
2HCl(aq)+ Na2CO3(aq)→ 2NaCl(aq) + CO2(g)+ H2O(l)

Calculate the moles, n, of Na2CO3(aq) that reacted in

the titration

The amount of HCl that was added to the cloudy

ammonia solution in excess was 2.150 x 10-3 mol
Cont.

Step 2: Determine the amount of ammonia in the

cloudy ammonia solution
Calculate the total moles of HCl originally added
to the diluted cloudy ammonia solution:
n(HCltotal added) = 0.100 x 50.00 x 10-3 = 5.00 x 10-3 mol
Calculate the moles of HCl that reacted with the
ammonia in the diluted cloudy ammonia solution
n(HCltitrated) + n(HClreacted with ammonia) = n(HCltotal added)
n(HCltotal added) = 5.00 x 10-3 mol
n(HCltitrated) = 2.150 x 10-3 mol
n(HClreacted with ammonia = 5.00 x 10-3 mol - 2.150 x 10-3 mol = 2.85 x 10-3 mol
Write the balanced chemical equation for the reaction
between ammonia in the cloudy ammonia solution and
the HCl(aq).
NH3(aq) + HCl(aq) → NH4Cl(aq)

c = concentration (molarity) = 2.85 x 10-3 ÷ 25.00 x 10-3

= 0.114 mol L-1
 Constructing the
titration curve
• Consider the titration of 50.0 mL of 0.100 M HCl
using a titrant of 0.200 M NaOH.
• When a strong base and a strong acid react the
only reaction of importance is

• The first task in constructing the titration curve is to

calculate the volume of NaOH needed to reach the
equivalence point, Veq.
• At the equivalence point, moles HCl = moles NaOH
Cont.

• The volume of NaOH needed to reach the

equivalence point is

• Before the equivalence point, HCl is present in

excess and the pH is determined by the
concentration of unreacted HCl.
Cont.

• At the start of the titration the solution is 0.100 M in

HCl, which, because HCl is a strong acid, means that
the pH is

Step 2:

• After adding 10.0 mL of NaOH the concentration of

excess HCl is
Cont.

Step 3: The pH at the equivalence point for the titration of a strong acid with a
strong base is 7.00.
Step 4: Calculate pH values after the equivalence point by determining the
concentration of excess titrant.

To find the concentration of H3O+ we use the Kw expression

 GROUP ASSIGNMENT
Construct a titration curve for the titration of
50.0 mL of 0.0500 M HCOOH with 0.100 M NaOH

Show all calculations, tables and curve

To be submitted 9th March 2020 in class

Complexation reactions and titrations
Formation of complexes
Ligand: Is an ion or a molecule that forms a covalent bond
(involves sharing of electron pairs between atoms) with a
cation or a neutral atom by donating a pair of electrons, which
are then shared.

Water, ammonia and halide ions are common inorganic

ligands.

Example: we refer to Cu(II) dissolved in water as Cu2+, but it is

actually complexed by water to form species such as
Cu(H2O)42+
Formation of complexes
Coordination number: Coordination number of a cation is the
number of covalent bonds that it tends to form with an
electron donor (ligand). Typical values of the coordination
number is 2, 4 and 6. The specie that forms can be positive,
neutral or negative.

Example: Cu(II) has a coordination number of 4. It can form

cationic Cu(NH3)42+, neutral Cu(NH2CH2COO)2 and anionic
CuCl42- species
Formation of complexes
Chelate: Is produced when a metal ion coordinates with two or
more donor groups of a single ligand to form a five- or six-
member heterocyclic ring.

Example: Cu(II) and glycine

This is an example of a bidentate (mono/uni-, tri-, tetra-,

penta-, etc. dentate also occurs)
Titrations with inorganic complexing agents
Most simple inorganic ligands are mono/unidentate (only one
atom in the ligand binds to the metal), which can lead to low
complex stability and indistinct end points during titration. As
titrants multidentate ligands, particularly those having four or six
donor groups, have two advantages over their unidentate
counterparts:

• Generally react more complete with cations and thus produce

sharper end points
• Usually react with metal ions in a single step process, whereas
complex formation with unidentate ligands usually involves
two or more intermediate species.
Aminocarboxylic acid titrations
17D-1 EDTA
EthyleneDiamineTetraacitic Acid is the most widely used complexometric titrant.
Structural formula:

EDTA has six potential sites for bonding a metal ion: the four carboxyl groups and
the two amino groups. Thus, EDTA is a hexavalent ligand.
EDTA
Acid properties of EDTA: Dissociation of EDTA leads to the
formation of five species: H4Y, H3Y-, H2Y2-, HY3- and Y4-.
 EDTA
Zwitterion: Is an ion that bears
both positive and negative
charge.
Complexes of EDTA and metal ions
EDTA is valuable as titrant, because:

• It combines with the metal ions in a ratio of 1:1 regardless of

the charge on the cation. Example
Ag+ + Y4- ↔ AgY3-
Al3+ + Y4- ↔ AlY-

• It forms chelates with all cations, except alkali metals

• Chelates are sufficiently stable for titrations
Titration methods employing EDTA – self study!

17D-7
Titration methods
involving EDTA

Direct titration Displacement

Back titration
(with 4 sub methods
headers)

Example
Titration methods employing EDTA
E.g. Back titration:
How: A measured excess of standard EDTA solution is added to the
analyte solution. After the reaction is complete, the excess EDTA is back-
titrated with cations for which a satisfactory indicator exists.

Why: i) Useful for the determination of cations that form stable

complexes with EDTA and for which a satisfactory indicator is not
available.
ii) It is also useful for cations that react slowly with EDTA.
Scope of EDTA titrations – self study!

Interference from a particular cation can sometimes

be eliminated by adding a suitable masking agent.

Masking agent: Is a complexing agent that reacts

selectively with a component in a solution to prevent
that component from interfering in a determination.
EDTA – something interesting

Chelation therapy is the use of chelating

agents, such as EDTA, to detoxify poisonous
metals such as mercury, arsenic and lead by
converting them to a chemically inert forms
that can be excreted without further
interaction with the body.
Determination of water hardness

What is hard water?

Is hard water a problem?
Practical examples of water hardness?
Example 1 of water hardness
Hard water contains calcium, magnesium and heavy metal ions that form
precipitates on taps and kettles.
Example 2 of water hardness
Water hardness is NB for industrial applications (e.g. cooling towers, pipes, etc.).
Example 3 of water hardness

Hard water contains calcium, magnesium and heavy metal ions

that form precipitates with soap. e.g. Mafikeng hard water that
forms scum in the bath.
How is water hardness expressed?

Hard water contains calcium, magnesium

and heavy metal ions that form
precipitates. [Ca] and [Mg] are usually
higher than other metal ions and the
hardness of water is therefore expressed as
equivalent of [CaCO3].
Determination of water hardness
Method:
i) Buffer sample to pH 10,
ii) followed by EDTA titration
iii) Mg forms least stable EDTA complex of all multivalent
cations and is therefore not titrated until other cations have
been complexed
iv) Therefore a Mg ion indicator is used (e.g. Calmagite,
Eriochrome Black T)
v) Often a small amount of Mg-EDTA chelate is added to ensure
satisfactory indicator action

Why Mg-EDTA in point v) and not un-complexed Mg?

Take home message
Know and apply:

• EDTA structure + dissociation

• Zwitterion definition + EDTA application
• Value of EDTA as a titrant
• Titration methods employing EDTA
• Masking / De-masking
• Chelation therapy
• Water hardness definition, implications thereof,
method for determination of water hardness