TITRIMETRIC ANALYSIS

CHAPTER 4

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4.0 TITRIMETRIC ANALYSIS
 4.1 Standards
 4.2 Dilution & Standardization
 4.3 Indicator and choice of indicator
 4.4 End point and equivalent point
 4.5 Titration
 Acid base titrations
 Back titration

 Complexometric titrations

 Precipitation titrations

 Redox titration

 4.6 Calculations 2
STANDARDS
 A reagent solution of ACCURATELY KNOWN
CONCENTRATION is called a STANDARD SOLUTION

Definitions
1. Primary standard reagent is highly purified compound
that serves as a reference material in all volumetric/
titrimetric method

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 Stock solution- A Stock Solution is a concentrated
solution that will be diluted to some lower concentrated
for actual use. Stock solutions are used to save
preparation time, conserve materials, reduce storage
space, and improve the accuracy with which working
solutions are prepared.
 Working Solution is a name given to a chemical
solution made for actual use in the lab, usually made
from diluting or combining stock or standard solutions.

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Properties of Primary Standard Material/Reagent.

1. must exhibit HIGH PURITY, typically 100±0.05 %.

2. must exhibit HIGH STABILITY, preferably for years under

proper storage conditions. It must be stable with respect to both
spontaneous decomposition and reaction with moisture or air.

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3. preferably should not contain water of
hydration (hygroscopic).
4. High equivalent weight (more stable) is
preferable when used for standardization
solutions.
5. must not be costly.
6. should be easily available.

7. must be readily soluble.

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PREPARATION OF STANDARD SOLUTION.

 A PRIMARY standard solution can be prepared by dissolving

an accurately WEIGHED amount of the solid reagent .
 Usually a PRIMARY STANDARD in a SOLVENT and
diluted to an accurately KNOWN VOLUME of solution using
volumetric flask.
 Solution prepared using the primary standard will give
primary standard solution.

 EXAMPLE: Preparation of Na2CO3 (Lab 1b)

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 DILUTION
Dilution
Dilution -whenever you add solvent to a solution.
Adding solvent results in a solution of lower concentration.
You can calculate the concentration of a solution following a dilution by
applying this equation:
McVc = MdVd
 where M is molarity, V is volume, and the subscripts c and d refer to the
concentrated and diluted values.

 Example: How many millilieters of 5.5 M NaOH are needed to prepare 300 mL of 1.2 M
NaOH?
 Solution:
5.5 M x V1 = 1.2 M x 0.3 L
V1 = 1.2 M x 0.3 L / 5.5 M, V1 = 0.065 L, V1 = 65 mL
 So, to prepare the 1.2 M NaOH solution, you pour 65 mL of 5.5 M NaOH into your container8
and add water to get 300 mL final volume
 STANDARDIZATION
 Standardization is a process to determine the concentration of a
solution by titrating with a primary standard or with a solution of
known concentration

 For example, you could accurately weigh out 1.325 g of Na 2CO3 and
dissolve it in a little water, then add enough water to fill a 250 mL
volumetric flask. This solution would then be used to standardized the HCl
acid. This will give you a very accurate determination of the concentration
of the HCl solution.
 This is how the HCI solution has been standardized, and can
subsequently be used to accurately determine the concentration of an base
solution. Example NaOH (Lab 2b)

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 INDICATOR AND CHOICE OF INDICATOR

Acid –Base Indicators

The acid-base indicator function by changing colour

just after the equivalence point of a titration; this
colour change is called the end point.

The end point is most often detected VISUALLY.

Most acid-base indicators are organic dye molecules
which are either acids or bases.

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ACID –BASE INDICATORS
 Indicators can be monoprotic (HIn) or diprotic (H2In) acids.
 The acid form of an indicator is usually coloured; when it loses a proton
resulting in anion (In-) , or base form of the indicator, exhibiting different
colour.
HIn H+ + In-
(colour A) (colour B)

A diprotic acid indicator, H2In, ionizes in TWO steps as follows:

H2In HIn- + H+ H+ + In-

(colour A) (colour B) (colour C)

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SELECTING AND USING
INDICATORS
 Choose an indicator that undergoes a distinct colour
change at the equivalence point (true end point) of an
acid-base titration .
 Choose an indicator whose middle half of the pH
transition range (greatest colour change)
encompasses/overlap the pH at the equivalence point
or the pH at the steepest part of the titration curve.
 For indicator color change to be detectable by normal
eyesight, a rough tenfold excess of one or the other
form of the indicator must be present.

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 ACID-BASE INDICATORS
Common Name Transition range Colour Change
ACID BASE
Crystal violet 0.1 – 1.5 Yellow Blue
Thymol blue 1.2 – 2.8 Red Yellow
Mrthyl yellow 2.4 – 4.0 Red Yellow
Methyl orange 3.1 – 4.4 Red Yellow
Bromocresol green 3.8 – 5.4 Yellow Blue
Methyl red 4.2 – 6.3 Red Yellow
Chlorophenyl red 4.5 – 6.4 Yellow Red
Bromothymol blue 6.0 – 7.6 Yellow Blue
Phenol red 6.4 – 8.0 Yellow Red
Thymol blue 8.0 – 9.6 Yellow Blue
Phenolpthalein 8.0 – 9.7 Colourless Red
Alizarin yellow 10.0 – 12.0 colourless Violet
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 END POINT
DEFINATION : THE POINT AT WHICH THE
REACTION IS OBSERVED TO BE
COMPLETED.

The end point in volumetric method of analysis is the

signal that tells the analyst to stop adding reagent and
make the final reading on the burette.

Therefore the END POINT SIGNAL tells the analyst to

stop adding TITRANT and record the volume.

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End point is observed with the help of a suitable indicator :

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 EQUIVALENCE POINT
DEFINATION : THE POINT AT WHICH AN
EQUIVALENT OR STOICHIOMETRIC
AMOUNT OF TITRANT IS ADDED TO THE
ANALYTE

Theoritically at the equivalence point we can calculate the

amount of titrant that is required to react EXACTLY with
the amount of analyte present and

The volume of titrant required to just completely

react with the analyte is the TITER.
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 TITRIMETRIC ANALYSIS.
What is a titration :
A procedure of carefully controlled addition of reagent
(titrant) to an analyte.

Usually in
buret

Known Usually in a
concentration – conical flask
called standard 17
THE REQUIREMENTS FOR A
SUCCESSFUL TITRIMETRIC
PROCEDURE .
1. Reaction must be stoichiometric, well defined reaction between titrant
and analyte.

2. Sufficiently stable so that it is necessary to determine its concentration

only once

3. Reaction should be rapid with the analyte so that the time required
between the additions of reagent is minimized.

4. React completely with the analyte so that satisfactory end points can be
achieved

5. Reaction should have no side reaction, no interference from other

foreign substances.

6. Must have some indication of end of reaction, such as color change,

sudden increase in pH, zero conductivity etc 18
 1. ACID - BASE TITRATION
Definition: Arhenius

 Acid are species that can DONATE PROTON (H+ )

HA H+ + A-

 Base are species that can DONATE HYDROXIDE ions, (OH- )

BOH B+ + OH-
Definition: Bronsted
Acid  it can donate proton, H+
Base  it can accept proton, H+

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 TYPES OF ACID-BASE TITRATION
1. Titration of strong acid with strong base.
2. Titration of strong acid with weak base.
3. Titration of weak acid with strong base.
4. Titration of weak acid with weak base.

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 CHOOSING A TITRANT
 In theory, any strong acid or strong base can be used as titrant.
 The reason for this is that most reaction involving a strong acid or a
strong base is QUANTITATIVE.

Examples of strong acid titrants :

1. Hydrochloric acid (HCl),
2. Nitric acid (HNO3),

3. Perchloric acid (HClO4),

4. Phosphoric acid (H3PO4)

5. Sulphuric acid (H2SO4)

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WEAK ACID TITRANT
1. Acetic acid ,(CH3COOH)
2. Ammonium ion, (NH4-)
3. Hydrogen flouride, (HF)
4. Carbonic acid, (H2CO3)
5. Nitrous acid, (HNO2)
6. Hydrogen sulphide, (H2S)
7. Hydrogen cynide, (HCN)

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Strong base titrant Weak base titrant
Sodium hydroxide, NaOH Ammonium hydroxide,
Potassium hydroxide, NH4OH
KOH Amine acetate.
Magnesium hydroxide, Carbonate, CO32-
Mg(OH)2
Flouride ion, F-
Barium hydroxide , Sodium carbonate,
Ba(OH)2 NaCO3

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24
25
                                                                                                 

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 WEAK ACID / STRONG BES

1 5
3

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2 4 6
STRONG ACID V STRONG BASE

 You can see that neither indicator changes colour at the

equivalence point

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 However, the graph is so steep at that point that there will be
virtually no difference in the volume of acid added whichever
indicator you choose. However, it would make sense to titrate
to the best possible colour with each indicator.
 If you use phenolphthalein, you would titrate until it just
becomes colourless (at pH 8.3) because that is as close as you
can get to the equivalence point.
 On the other hand, using methyl orange, you would titrate
until there is the very first trace of orange in the solution. If
the solution becomes red, you are getting further from the
equivalence point.

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 STRONG ACID V WEAK BASE

This time it is obvious that phenolphthalein would be

completely useless. However, methyl orange starts to change from
yellow towards orange very close to the equivalence point.
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You have to choose an indicator which changes
colour on the steep bit of the curve.
WEAK ACID V STRONG BASE

This time, the methyl orange is hopeless! However,

the phenolphthalein changes colour exactly where you 31

want it to.
WEAK ACID V WEAK BASE

 The curve is for a case where the acid and base are both
equally weak - for example, ethanoic acid and ammonia
solution. In other cases, the equivalence point will be at
some other pH.

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 You can see that neither indicator is any use.
Phenolphthalein will have finished changing well before
the equivalence point, and methyl orange falls off the
graph altogether.
 It may be possible to find an indicator which starts to
change or finishes changing at the equivalence point, but
because the pH of the equivalence point will be
different from case to case, you can't
generalise.
 On the whole, you would never titrate a weak acid and
a weak base in the presence of an indicator.

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 CALCULATION
 Mol = mass (g)
molar mass (g/mol)

 Molarity (M) = Mol

Volume (L)

Mass (g ) = Liter (L) x Molarity mol x Molar Mass g

L mol
aA + bB cC + dD

MAVA = a
MBVB b

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 CALCULATION ACID-BASE
Example 1
A sample weighing 0.8365 g is a diprotic acid was dissolved
in 75.0 mL distilled water. Indicator was added and the
solution was titrated with sodium hydroxide solution. 35.35
mL was needed to reach the end point. Molar mass of acid is
150 gmol-1.
1. State whether the equivalence point is greater or less than 7.
2. Name a suitable indicator that can be used in the above
titration.
3. Calculate the molarity of the base.

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First write the reaction equation:
Equation: H2A + 2OH- = 2H2O + A2-

Mole acid = 0.835= 5.5767 x 10-3 mole

150

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Molarity of acid =
5.5767 x 10 -3 mol
0.075 L
= 0.0744 M

M a V=a 1
Mb Vb 2
2 x 0.0744 x 75
Molarity base Mb35.35
= 0.3157 M

= 0.3157 M # 37
Example 2
Calculate the concentration of vinegar in %w/v for a
titration of 25 ml of vinegar which was primarily diluted
10 times (25mL into 250mL), reacted with 22.4 ml of
0.1 M NaOH standard solution.
Mass of vinegar = (Litersvinegar)(Mvinegar)(Fwgtvinegar)
22.4 x 0.1
= (0.25)( )(60)
25

= 1.34g
In %w/v, concentration of vinegar is 1.34/25 = 5.4% 38

In g/mL
1) Write and balance the equation
CH3COOH + NaOH CH3COONa + H2O

MaVa =a = Ma x 25 = 1 all the values are from titration

MbVb b 0.1 x 22.4 1

Ma = 0.0896 M of acid

3) Calculate mole of acid , n = Molarity (M) x Volume (Liter)

= 0.0896 (mol/L) x 0.250 L
= 0.0224 mol @
4) Mass of acid (g) = molar mass x mol
= 60 g/mol x 0.0224 mol
= 1.344g
5) % w/v = (g/mL) x 100 = (1.344g / 25 mL ) x 100 = 5.4% 39