pH,

Indicators
Titration
 Need of pH measurement
• To produce products with defined properties
• To protect equipment
• For research and development
 Basics about pH
• pH is the abbreviation of pondus hydrogenii
• pH = -log [H+]
• [H+] is in molar concentration
Basics about pH
 Basics about pH
• In any aqueous solution
Kw = [H+] [OH-] = Dissociation constant
It depends on temperature
• Acids
[H+] increases and [OH-] decreases
• Bases
[OH-] increases and [H+] decreases
 Electrochemical method
• Depends on hydrogen
activity in the solution
• It consists of two
electrodes
1. Measuring electrode
2. Reference electrode
 Glass electrode
• Dependent on hydrogen activity
• Glass membrane sensitive to H+ ions
 Titration
• A titration is an important quantitative
analytical technique.
• It is a process of determining the amount of a
specific unknown substance by reacting it
completely with a measured volume of a
standard reagent.
• The standard reagent must react with the
unknown in a definite and known relationship.
 Measurement of pKa by titration.
• pKa values are measured experimentally by titration. In a titration experiment, a
weak acid in solution is converted to its conjugate base by the addition of a strong
base. The numbers of moles of weak acid in solution is the same as the number of
moles of strong base needed to convert all conjugate acid molecules to their
conjugate base form. A sample equation for titration of acetic acid is shown
below.
CH3COOH + Na+ + OH- → CH3COO- + Na+ + H2O
• During the titration, two equilibrium reactions are occurring simultaneously.
1) H+ + OH- H2O and
2) CH3COOH  H+ + CH3COO-
That is, as an OH- ion is added to the solution, it combines with an H+ ion
present in solution. When the H+ ion is removed, a molecule of the conjugate acid
form of acetic acid dissociates a proton to restore equilibrium. The end result of
the titration is that the base converts all of the CH3COOH present to CH3COO-.
• Likewise, a strong acid (e.g., HCl) will stoichiometrically
convert a weak base to its conjugate acid.
CH3COO- + H+ + Cl- → CH3COOH + Cl
• The pKa turns out to be the midpoint of the plot of a
titration curve.
• An example of a titration curve is shown using acetic acid .
Note, that the pH changes rapidly at the ends of the titration
curve, and modestly in the middle for a given amount of
base added. The change in pH is least at the midpoint of the
curve, i.e., when 0.5 equivalents of strong base have been
added. This middle region of the curve is the optimum
buffering region for the weak acid, i.e., the pH changes least
on addition of a strong base or strong acid. At the midpoint
[CH3COOH] = [CH3COO-].
 Choice of an indicator
• The choice of an indicator in an acid/base
titration actually depends on the strength of
acids and bases involved, ph of indicator, and
how well the colors can be distinguished by
the eyes.
• If the difference in volume is small between
the equivalence and end points, then the
indicator can be used.
• For a strong acid and a strong base titration (e.g. HCl and NaOH)
methyl orange is a suitable indicator for this titration. Methyl
orange changes color over a pH range of 3.2 - 4.4. At pH of 4.4,
methyl orange gives a full color change, indicating the equivalence
point. Methyl orange gives color change very close to the
equivalence point, with an error of less than 0.1%. Methyl red (ph
range of 4.8 - 6.0) is also suitable for strong acid and strong base
titrations.
• For a weak acid and a strong base (e.g. Acetic acid and NaOH) A
suitable indicator is phenolphthalein. The pH of the mixture at the
equivalence point is 8.73 – phenolphthalein gives color change
between the ph range of 8.2 to 10.0.
• For a weak acid and a weak base color indicators are not suitable
for use to indicate the end-point (equivalence point). Color
indicators are useful if small quantities of either titrant is needed to
produce sharp recognizable color change. However, for weak
acid/base titration, large quantities of titrants are needed if color
change is to from - this results in huge errors.
• Strong acid v strong base.
This diagram shows the pH curve for adding a
strong acid to a strong base.

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 Cont…
• Strong acid vs 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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 Cont…
• Weak acid v strong base:
This time, the methyl orange is hopeless!
However , the phenolphthalein changes color
exactly where you want it to.

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 Cont…
• 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.

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 pH testing
• There are several ways to test pH
– Blue litmus paper (red = acid)
– Red litmus paper (blue = basic)
– pH paper (multi-colored)
– pH meter (7 is neutral, <7 acid, >7 base)
– Universal indicator (multi-colored)
– Indicators like phenolphthalein
– Natural indicators like red cabbage,
radishes
 What is indicator?
• It is a substance which is used to indicate the end point or
completion of a reaction by it’s colour change.”
• TYPES: Indicators are of two types – 1. natural e.g. turmeric,
litmus, china rose and red cabbage 2. artificial. E.g. pH indicators,
redox indicators, adsorption indicator etc
• ACID BASE INDICATORS: “Indicators are substances that are
used to test whether a substance is weakly acidic or basic or
neutral in nature. They change their color when added to a
solution containing an acidic or a basic substance.” Or
“Substances whose solutions change color due to changes in
pH. These are called acid-base indicators. They are usually weak
acids or bases, but their conjugate base or acid forms have
different colors due to differences in their absorption spectra”.
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 Theory
• The pH value of a neutral solution is 7.0.
• Solutions with a pH value below 7.0 are
considered acidic.
• Solutions with a pH value above 7.0 are
considered basic.
• Kln is known as the indicator dissociation
constant.
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Cont…

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Molecular Basis for the Indicator Color Change:

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 Example: Typical Acid-Base Indicator
Phenol Red
HO
O-

OH

pKa= 7.9 OH

O
+ H2O + H 3O +
S O
O
O S
phenolsulfonphthalein O
O
phenolsulfonphthalein
 Indicators
Reaction with Indicators
Indicator Colour in acidic Colour in alkaline
solution solution
Blue litmus paper
Red Blue
Red litmus paper
Red Blue
Methyl orange
Red Yellow
Phenolphthalein
Colourless Pink
 Application
• pH indicators are frequently employed in titrations in
analytical chemistry and biology to determine the extent of
a chemical reaction.
• For applications requiring precise measurement of pH, a pH
meter is frequently used.

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