Inorganic Chemistry

Types of Indicators
Group members
Sneha Abraham
Sneha Mary Prince
Tulip Roy
Yirmayeiri Mashangva
Yogita
Indicator
• Any substance that gives a visible sign, usually by a colour change, of the
presence or absence of a threshold concentration of a chemical species, such
as an acid or an alkali in a solution, is called an indicator.

• Indicator is a substance which is used to indicate the end point or completion

of a reaction by its colour change.

• The colour of indicator alters when the acidity or oxidising strength of the
solution or concentration of certain chemical species reaches a critical range
of values.
m
 Types of indicators
Based on sources of production, indicators can be
divided into:

Natural Indicators Artificial Indicators

• Phenolphthalein
• Litmus • Methyl Orange
• Turmeric • Bromothymol
a
Blue
• Universal Indicator
• China Rose Petals
• Red Cabbage
Indicators can also be
divided into:
Internal indicators
• Indicators in which one of the reactants
behaves as an indicator is known as internal
indicators. Self indicator is an example of
internal indicator.
• These are those indicators which takes part in
the reaction(titration) and after completion of
titration it changes the color of the solution
indicating the sharp end point.
• Eg: Potassium permanganate(KMnO4)
External Indicators
• Indicators that are added externally and which
do not exist in reactants are known as external
indicators. These are not recommended as
they lead to loss of some volume of reaction
mixture.
• These Indicators never take part in the original
chemical reaction but after completion of
reaction it changes the color of solution to
indicate the endpoint.
• Eg: Potassium Ferricyanide (K3[Fe(CN)6])
Acid-Base Indicators
•Acid-base indicators are chemicals used to determine whether an aqueous solution is acidic,
neutral, or alkaline. Because acidity and alkalinity relate to pH, they may also be known as
pH indicators.
•An acid-base indicator is a weak acid or weak base that dissociates in water to yield the
weak acid and its conjugate base or else the weak base and its conjugate acid. The species
and its conjugate have different colors.
•The point at which an indicator changes colors is different for each chemical. There is a pH
range over which the indicator is useful. So, the indicator that might be good for one solution
might be a poor choice to test another solution.
•Some indicators can't actually identify acids or bases, but can only tell you the approximate
pH of an acid or a base. For example, methyl orange only works at an acidic pH. It would be
the same color above a certain pH (acidic) and also at neutral and alkaline values.
How an Acid-Base indicator works?
• If the indicator is a weak acid, the acid and its conjugate base are different colors. If the
indicator is a weak base, the base, and its conjugate acid display different colors.

• For a weak acid indicator with the general formula HIn, equilibrium is reached in the
solution according to the chemical equation:

HIn(aq) + H2O(l) In-(aq) + H3O+(aq) ------(1)

• HIn(aq) is the acid, which is a different color from the base In-(aq). When the pH is low,
the concentration of the hydronium ion H3O+ is high and equilibrium is toward the left,
producing the color A. At high pH, the concentration of H3O+ is low, so equilibrium
tends toward the right side of the equation and color B is displayed.
The equilibrium constant for the reaction may be determined using the equation:

(law of mass action) {from (1)}

where is the indicator dissociation constant. The color change occurs at the point where the concentration of the acid and
anion base are equal:

which is the point where half of the indicator is in acid form and the other half is its conjugate base.

An indicator’s color is the visible result of the ratio of the concentrations of the two species In− and HIn. If most of the
indicator (typically about 60−90% or more) is present as In−, then we see the color of the In− ion. If most is present as
HIn, then we see the color of the HIn molecule. we can rearrange the equation for Ka and write:

𝐼 𝑛
−
𝑘𝑎
=
𝐻𝐼𝑛 ¿ ¿
This shows us how the ratio of [In−][HIn] varies with the concentration of hydronium ion.
pH of acidic indicator pOH of basic indicator
HIn(aq) + H2O(l) In-(aq) + H3O+(aq) InOH(aq) + H2O(l) In-(aq) + OH-(aq)
(law of mass action)
=

𝑝𝑂𝐻=𝑝 𝑘𝑏 +log¿¿ ¿

Henderson-Hasselbalch equation
Theory of indicators
Two theories have been proposed to explain the change of colour of acid-base indicators
with change in pH:
1.Ostwald’s theory
This theory was proposed by Ostwald in 1891. It is based on Arrhenius theory.
According to this theory:
(a) The colour change is due to ionisation of the acid-base indicator. The unionised form has
different colour than the ionised form.
(b) The ionisation of the indicator is largely affected in acids and bases as it is either a weak
acid or a weak base. In case, the indicator is a weak acid, its ionisation is very much low in
acids due to common H+ ions while it is fairly ionised in alkalies. Similarly if the indicator
is a weak base, its ionisation is large in acids and low in alkalies due to common OH- ions.
2. Quinonoid Theory
According to this theory:
(a) The acid-base indicators exist in two tautomeric forms having different structures. Two forms
are in equilibrium. One form is termed benzenoid form and the other quinonoid form.

(b) The two forms have different colors. The color change in due to the interconversion of one
tautomeric form into other.

(c) One form mainly exists in acidic medium and the other in alkaline medium.

Thus, during titration the medium changes from acidic to alkaline or vice-versa. The change in
pH converts one tautomeric form into other and thus, the colour change occurs.
Phenolphthalein has benzenoid form in acidic medium and thus, it is colourless while it has
quinonoid form in alkaline medium which has pink colour.

Methyl orange has quinonoid form in acidic solution and benzenoid form in alkaline
solution. The color of benzenoid form is yellow while that of quinoniod form is red.
 Phenolphthalein (
• Phenolphthalein is a weak organic acid with value of 9.4. It is Often written as “HIn” or “phph”.
• The working pH range of phenolphthalein is 8.2--10.0.
• It is used in Weak acid-Strong base titration where the pH range of titration is 7--11.

• Its undissociated molecule (HPh) is colourless while its ion ( is pink in colour.
• Under acidic conditions, the equilibrium is to the left, and the concentration of anions is too low for the
pink colour to be observed. However, under alkaline conditions, the concentration of anion becomes
sufficient for the pink colour to be observed.
Methyl Orange
𝑪𝟏𝟒
( 𝑯 𝟏𝟒 𝑵 𝟑 𝑵𝒂 𝑶𝟑 𝑺 ¿
• Methyl orange is a weak organic acid with pKa value of 3.7. The working pH of methyl orange is 3.2-4.4.
• It is used for strong acid-weak base titrations where the pH range is 3-7.
• The equilibrium in a solution of methyl orange can be represented by an equation in which we use HIn as
a simple representation for the complex methyl orange molecule:

• The anion of methyl orange, In−, is yellow, and the nonionized form, HIn, is red. When we add acid to a
solution of methyl orange, the increased hydronium ion concentration shifts the equilibrium toward the
nonionized red form, in accordance with Le Chatelier’s principle. If we add base, we shift the equilibrium
towards the yellow form in the left.
• At some point during the movement of the position of equilibrium, the concentrations of the two colours
will become equal. The colour you see will be a mixture of the two. In the methyl orange case, the half-
way stage where the mixture of red and yellow produces an orange colour happens at pH 3.7
Bromothymol Blue (C27H28Br2O5S)
• Bromothymol blue (also known as bromothymol sulfone phthalein, and BTB) is weak
acid indicator with value of 7.0.
• Despite its name, bromothymol blue solution may sometimes appear yellow or reddish
depending on the pH of the stock water used to prepare this pH indicator solution.
• Bromthymol blue changes color over a pH range from 6.0 (yellow) -7.6 (Blue). It is
bluish green in neutral solution.
• It is mostly used in applications that require measuring substances that would have a
relatively neutral pH (near 7).
• A common use is for measuring the presence of carbonic acid in a liquid.
Universal Indicator
• A universal indicator is a pH indicator made of a solution of several compounds that exhibit
several smooth colour changes over a wide range pH values to indicate the acidity or
alkalinity of solutions.
• A universal indicator is usually composed of water, 1-Propanol, phenolphthalein sodium
salt, sodium hydroxide, methyl red, bromothymol blue monosodium salt, and thymol blue
monosodium salt. The colours that indicate the pH of a solution, after adding a universal
indicator, are

pH range Description Colour

<3 Strong acid Red
Orange or
3–6 Weak acid
yellow
7 Neutral Green
8–11 Weak alkali Blue
Violet or
> 11 Strong alkali
Indigo
 Universal indicator components
Indicator Low pH colour Transition pH range High pH colour
Thymol blue (first
Red 1.2 – 2.8 Yellow
transition)
Methyl orange Red 3.2 – 4.4 Yellow
Methyl red Red 4.8 – 6.0 Yellow
Bromothymol blue Yellow 6.0 – 7.6 Blue
Thymol blue (second
Yellow 8.0 – 9.6 Blue
transition)
Phenolphthalein Colourless 8.2 – 10.0 Pink

Types:
A universal indicator is collectively a mixture of indicators which show a colour change in a solution, which interprets
how acidic or basic a solution is. A universal indicator can be in paper form or present in a form of a solution.

1.Paper form: It is a strip of coloured paper which changes colour according to the pH of the solution. The strip can
be placed directly onto a surface of a wet substance or few drops of the solution can be dropped onto the universal
indicator using dropping equipment. Paper universal indicator is preferable for dark colored solutions.
2. Solution: The main components of a universal indicator, in the form of a solution, are thymol blue, methyl red,
bromothymol blue, and phenolphthalein. This mixture is important because each component loses or gains protons
depending upon the acidity or alkalinity of the solution being tested. It is beneficial to use this type of universal indicator
in a colorless solution. This will increase the accuracy level of indication.
Redox Indicators
• A redox indicator is an indicator compound that changes color at specific electrode
potential differences.

• A redox indicator compound must have a reduced and oxidized form with different colors
and the redox process must be reversible. Further, the oxidation-reduction equilibrium
needs to be reached quickly. Only a few classes of compounds are useful as redox
indicators:

1. Phenanthroline and bipyridine metal complexes: The metallorganic systems change

color as the metal changes its oxidation state.

2. Organic redox compounds: In these indicators, a proton participates in the redox

reaction. Therefore, sometimes redox indicators are also divided into two general groups:
independent or dependent on ph.
pH independent pH dependent
Choice of Indicators
• Neutralization reactions are of the following four types:

(i) A strong acid versus a strong base

(ii) A weak acid versus a strong base
(iii) A strong acid versus a weak base
(iv) A weak acid versus a weak base

• In order to choose a suitable indicator, it is necessary to understand the pH changes in the above
four types of titrations. The change in pH in the vicinity of the equivalence point is most important
for this purpose. The pH indicator should be selected in such a way that the pH range for the color
change of the indicator must coincide with the pH at the equivalent point of reaction.
• The curve obtained by plotting pH as ordinate against the volume of alkali added as abscissa is
known as neutralisation or titration curve.
Each titration curve becomes almost vertical for some distance (except curve for weak
acid vs weak base) and then bends away again. This region of abrupt change in pH
indicates the equivalence point. For a particular titration, the indicator should be so
selected that it changes its colour within vertical distance of the curve.
 Indicator Ranges
• Strong acid + Strong base titration: resulting solution has a pH = 7, so bromothymol
blue could be used (pH range is 6.0 - 7.6)

• Weak acid + Strong base titration: resulting solution has a pH > 7 so phenolphthalein
could be used (pH range is 8.2 – 10.0)

• Strong acid + weak base titration: resulting solution has a pH < 7 so methyl orange
could be used (pH range is 3.1 – 4.4)

• Weak acid + weak base titration: results in a buffer solution. There is no vertical part in
its titration curve, hence no suitable indicator can be used for such a titration.
Everyday uses of indicators
1. Testing the acidity or basicity of soils, as some plants grow best in slightly acidic
soils(such as azaleas and pineapples) while others grow best in slightly basic soils (such as
violets)
2. Pineapples and violets have very different soil requirements. Because soil is dark in
colour, a white inert solid such as barium sulfate is mixed with the soil before the indicator
is added.
3. If a soil is found to be too acidic, it can be partially neutralised by adding a weak base such
as powdered limestone (calcium carbonate).
4. If a soil is found to be too basic, it can be partially neutralised by adding a weak acid such
as ammonium sulfate.
5. Testing home swimming pools, as they need to be approximately neutral.
6. Some flowers like hydrangeas can determine the acidity or basicity of the soil. These
flowers become blue if the soil is acidic, purple if the soil is neutral and pink if the soil is
basic. The intensity of the color depends on the amount of acid or base present in the soil.
References
• http://www.brainkart.com/article/Ostwald-s-theory-and-Quinonoid-T
heory_2908/
• https://www.chemguide.co.uk/physical/acidbaseeqia/indicators.html
• https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3
A_General_Chemistry_(Petrucci_et_al.)/17%3A_Additional_Aspects_
of_Acid-Base_Equilibria/17.3%3A_Acid-Base_Indicators
• https://groups.chem.ubc.ca/courseware/pH/section15/index.html#:~:
text=Using%20the%20Henderson%2DHasselbalch%20equation,unit%
20of%20the%20indicator's%20pKa.&text=In%20general%2C%20the%
20pKa,over%20which%20it%20changes%20colour
.
• https://www.thoughtco.com/definition-of-acid-base-indicator-604738