MEASUREMENT OF pH

INTRODUCTION
pH is universally express the intensity of the acid or alkaline
condition.
Expressing the hydrogen-ion concentration or the hydrogen-ion
activity.
In olden days acids and bases were originally distinguished by
their taste, Acids litmus paper red. Bases taste turn litmus paper
blue.
Concept of pH, initially proposed by the Danish chemist
Sørensen in 1909.

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DEFINITION OF pH
 pH is the negative logarithm of hydrogen ion concentration of an aqueous
solution.
 It is an important parameter to determine the quality of water.
 The pH value is expressed as:
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pH = −log10 [H+]

 pH scale is usually represented as ranging from 0 to 14.

 Solutions with pH less than 7 are acidic and solution with pH greater than
7 are basic.
 pH is temperature dependent.

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pH Scale:

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pH Contd.,
The pH of natural water usually lies in the range of 6.0 to 8.5.
Scientists often use logarithmic scales for quantities that vary
widely in magnitude. So, pH is measured in log scale.
Ex: pH 4 , [H+]= 0.0001, [H+]=10−4.
pOH is a measure of hydroxide ion OH− ion concentration.
pOH= 14- pH
pH has no direct adverse effect on health.
Higher value of pH results in scale formation in heating
apparatus.

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MEASUREMENT OF pH
The pH of any aqueous solution can be measured in different ways
such as.
 Indicators
 Glass electrode
 Hydrogen electrode

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 Indicators

 Indicators are substances whose solutions change colour due to

changes in pH.
 Colour changes in well-defined pH ranges.
 In general, these compounds are weak acids or weak bases.
 Figure shows pH scale with indicator.

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Properties of Indicators Acid colour pH range Base colour

various acid- Methyl violet Yellow 0-2 Violet

Malachite green (acidic) Yellow 0-1.8 Blue-green
base
Thymol blue (acidic) Red 1.2-2.8 Yellow
indicators.
Bromphenol blue Yellow 3-4.6 Blue
Methyl orange Red 3.1-4.6 yellow-orange
Bromcresol green Yellow 3.8-5.4 Blue
Methyl red Red 4.4-6.2 Yellow
Litmus Red 4.5-8.3 Blue
Bromthymol blue Yellow 6-7.6 Blue
Phenol red Yellow 6.8-8.4 Red
Metacresol purple Yellow 7.6-9.2 Purple
Thymol blue (alkaline) Yellow 8-9.6 Blue

Phenolphthalein Colourless 8.2-9.8 pink

Thymolphthalein Colourless 9.3-10.5 Blue
Alizarin yellow Yellow 10.1-11.1 Lilac

Malachite green Green 11.4-13 colourl 8

es
Indicator Contd.,

 Phenolphthalein changes from colourless to pink in the pH range 8.2

to 8.4 and has been the colour indicator commonly used in
environmental analysis.
 pH levels of 3.7 to 4.5. the indicator commonly used in the past for
such purpose was methyl orange.
 The colour of hydrangea a natural type of indicator.

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Picture shows various colours of hydrangea flowers.
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GLASS ELECTRODE

 Would develop a potential related to the hydrogen-ion activity with-

out interference from most other ions.
 Its use has become the standard method of measuring pH.
 Glass electrode is used most routine laboratory purpose, being
capable of measuring pH within a ±0.1 pH unit.
 Glass electrode which generates a potential varying linearly with the
pH of the solution in which it is immersed.

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Construction of Glass Electrode
Typical three-component composition of 72% SiO2 , 22%
Na2O, 6% CaO.
Contains an internal standard acidity solution typically 0.1
M HCl, sometimes.
with the addition of AgCl wire.

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Reference electrode
 Purpose of a reference electrode is to provide continuity to the
electrical circuit.
 since the potential across a single half-cell cannot be measured.
 A reference electrode should satisfy the following basic
requirements:
1) The potential developed should be independent of temperature.
2) The potential developed should be independent of H+ ion
concentration.
3) The potential developed should not change with time.

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Glass electrode connected with reference electrode
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Combination Electrode
Sometimes the reference and measuring electrodes are
housed together, This type of electrode is known as
Combination Electrode.
The combination is dipped in the solution whose pH is to
be measured.
The output voltage is the difference between the e.m.f.s
generated by the measuring glass electrode and the
reference electrode.

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Figure for Combination Electrode
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WORKING OF GLASS ELECTRODE
 A potential is developed across the two surfaces of this glass bulb, when dipped in
aqueous solution.
 This potential is sensitive to the H+ ion concentration, having a sensitivity of 59.2
mv/pH at 250C.
 The buffer solution inside the glass bulb has a constant H+ ion concentration and
provides electrical connection to the lead wire.
 When you place the bulb into a solution, the hydrogen ions in the solution will
move toward the glass electrode.
 This will cause a tiny voltage across the glass blub, voltage is picked up by the
silver wire and passed to the voltmeter
 The voltmeter will amplify and change the voltage value into a value we can use,
pH units
 The H+ ion activity difference between the solution inside the electrode and the
external one is measured as electric potential difference. Then, converted in pH
units (0-14) by the instrument.

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Hydrogen electrode
 A hydrogen electrode is made by platinum wire or a platinum plate.
 solution is saturated with hydrogen gas.
 The electrode potential is inversely proportional to pH of the
solution.
 The hydrogen electrode was found to be suitable device for
measuring hydrogen-ion activity.
 With its use, it was found that pure water dissociates to yield a
concentration of hydrogen ions equal to about 10−7 mol/L.
H2O ⇌ H+ + OH−

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Hydrogen electrode Contd.,
 Since water dissociates to produce one hydroxide ion for each hydrogen
ion, it is obvious that about 10−7 mol/L of hydroxide ion is produced
simultaneously. By substitution into the equilibrium equation, we obtain
H+ OH−
=K
H2O
 But, since the concentration of water is so extremely large and is
diminished so very little by the slight degree of ionization, it may be
considered as constant (its activity equal 1) and Eq. can be written as
H+ OH− = K w
 And for pure water at about 25°C,
H+ OH− = 10−7 × 10−7 = 10−14
This is known as the ion product or ionization constant for water

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Hydrogen electrode Contd.,
 However, this method is not appropriate for daily use because of the
effort and expense involved
 With the inconvenience of handling.

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Application of pH data

It is important in almost every phase of environmental

engineering and science.
In the field of water supplies, it is a factor that must be
considered in chemical coagulation, disinfection, water
softening and corrosion control.
Determination of pH is one of the important objective in
biological treatment of waste water.
pH value or range is of immense value for any chemical
reaction.
It is used in the calculation of carbonate, bicarbonate, CO2
corrosion, stability index and acid base equilibria.
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Reference
 Clair N. Sawyer and Perry L. McCarty “Chemistry for Environmental
Engineering and Science” Fifth Edition.

 A. E. Mirsky and M. L. Anson. “ A description of the glass electrode and its use
in measuring hydrogen ion concentration.”

 Bates, Roger G. “Determination of pH: theory and practice”.

 Butler J. N. “Ionic Equilibrium: A Mathematical Approach”.

 Scorpio, R. “Fundamentals of Acids, Bases, Buffers & Their Application to

Biochemical Systems”

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THANK YOU