pH INDICATOR

The compounds (mostly organic) which

change their color when pH of the solution
changes
Indicators are used to;
1) Check the pH of the solution.
2) Indicate the end-point i.e. completion of
the reaction.
At 25 C, considered the standard temperature, the pH
value of a neutral solution is 7.0. Solutions with a pH value
below 7.0 are considered acidic, whereas solutions with pH
value above 7.0 are basic (alkaline). As most naturally
occurring organic compounds are weak carboxylic acids and
amines, pH indicators find many applications in biology and
analytical chemistry.
Types of indicators
The choice of the indicator depends upon the nature of
the reaction. There are three basic types of indicators.
1) Acid- base indicator
2) Redox indicators
3) Precipitation indicators
For the quantitative analysis of metal cations, the use of
complexometric indicators is preferred.
Acid Base indicators:
These are the organic compounds which are used in acid
base titrations. Acid - base indicators, respond to a change
in the hydrogen ion concentration. Most of the indicators
are themselves weak acids other are weak bases which
responded to change hydroxyl ion concentration.

Color Blue Litmus Red Litmus
Acid turns red stays same
Base stays same turns blue
The most common indicator is found on "litmus" paper. It is red below pH 4.5 and blue above pH 8.2.

An indicator is usually some weak organic acid or base dye that
changes colors at definite pH values. The weak acid form (HIn) will
have one color and the weak acid negative ion (In
-
) will have a
different color. The weak acid equilibrium is:
HIn --> H+ + In
-


For phenolphthalein: pH 8.2 = colorless; pH 10 = red
For bromophenol blue: pH 3 = yellow; pH 4.6 = blue

Magic Pitcher Demonstration:
Phenolphthalein is an indicator of acids (colorless) and bases (pink).
Sodium hydroxide is a base, and it was in the pitcher at the
beginning, so when added to the phenolphthalein in beakers 2 and
4, it turned pink (top half of the graphic).
Explanation:
Equilibrium: HIn --> H
+
+ In
-

colorless pink
The equilibrium shifts right, HIn decreases, and In
-
increases. As the
pH increase between 8.2 to 10.0 the color becomes red because of
the equilibrium shifts to form mostly In
-
ions.

The third beaker has only the NaOH but no phenolphthalein, so it
remained colorless. The first beaker contain acetic acid and is skipped
over at first.
After pouring beakers 2, 3, 4 back into the pitcher it give a pink solution.
Bottom half of the graphic: When the pitcher is then poured back into
beakers 2, 3, 4 it is a pink solution.
In the first beaker, a strange thing happens in that the pink solution
coming out of the pitcher now changes to colorless. This happens
because the first beaker contains some vinegar or acetic acid which
neutralizes the NaOH, and changes the solution from basic to acidic.
Under acidic conditions, the phenolphthalein indicator is colorless.
Neutralization: HC
2
H
3
O
2
+ NaOH --> Na(C
2
H
3
O
2
) + HOH

The simplified reaction is:
H
+
+ OH
-
--> HOH
As OH
-
ions are added, they are consumed by the excess of acid
already in the beaker as expressed in the above equation. The
hydroxide ions keep decreasing and the hydrogen ions increase, pH
decreases.
See lower equation: The indicator equilibrium shifts left, In
-
ions
decrease. Below pH 8.2 the indicator is colorless. As H
+
ions are
further increased and pH decreases to pH 4-5, the indicator
equilibrium is effected and changes to the colorless HIn form.
Equilibrium: HIn --> H
+
+ In
-

colorless red

pH range of indicator
INDICATOR COLOR CHANGE pH RANGE
PHENOLPHTHALEIN COLORLESS to PINK 8.3 10.0
METHYL ORANGE RED to ORANGE 3.1- 4.4
METHYL RED RED to YELLOW 4.4 6.0
BROMOTHYMOL BLUE YELLOW to BLUE 6.0 7.6
LITMUS RED to BLUE 5.0 8.0
What is End Point?
In an acid- base titration, the base solution is gradually
added from a burette into an acidic solution in a titration
flask. When the amount of base added neutralize to the
amount of base added in the flask equivalence point or
End point will reached. The end point of the titration is
shown by color changes of an indicator , previously added
to the acidic solution in the titration flask.
pH CURVE
During an acid base titration, the pH of the solution in the
titration flask changes with the addition of titrant (i.e. base)
from the burette. A plot of pH against the volume of the
solution being added is known as pH curve.
e.g As NaoH is added to Hcl solution the pH of the solution
increases slowly at first, then rapidly in the vicinity of the end
point and again become slow. The end point lies at some place
on this vertical portion.
The colour change would happen when you mix the two
solutions together in exactly equation proportions. That end
point is known as the equivalence point.
Titration curves for strong acid v
strong base
When a strong acid (Hcl) is titrated against a strong base (NaoH),
when NaoH is added the pH increases slowly and gradually upto pH
4. At this pH 4, just 1-2 drops of NaoH from the burrette cause a
sharp change in pH from 4-10, and we get vertical portion of pH
curve which may extend from pH 4 to pH 10. at this vertical portion
there lies the end point. So any indicator which has pH range in this
vertical portion range will be suitable indicator for this type of
titration.
e.g. Phenolphthalein ( 8.3- 10.0)
Methyl red ( 4.4- 6.0)
Titration curves for strong acid v
weak base
When a strong acid (Hcl) is titrated against a weak base (NH4oH), its
pH increases slowly and gradually upto pH 3. At this pH 3, just 1-2
drops of NaoH from the burrette cause a sharp change in pH from 3-
8, and we get vertical portion of pH curve which may extend from pH
3 to pH 8 at this vertical portion there lies the end point. So any
indicator which has pH range in this vertical portion range will be
suitable indicator for this type of titration.
e.g. Methyl orange ( 3.1- 4.4)
Methyl red ( 4.4- 6.0)


It is only after the equivalence point that things become different.
A buffer solution is formed containing excess ammonium chloride.
This resists any large increase in pH - not that you would expect a
very large increase anyway, because ammonia is only a weak base.

Titration curves for weak acid v
Strong base
When a weak acid (CH3COOH) is titrated against a strong base
(NaoH), its pH increases very rapidly and gradually upto pH 6. At this
pH 6, just 1-2 drops of NaoH from the burrette cause a sharp change
in pH from 6-11, and we get vertical portion of pH curve which may
extend from pH 6 to pH 11 at this vertical portion there lies the end
point. So any indicator which has pH range in this vertical portion
range will be suitable indicator for this type of titration.
e.g. phenolphthalein (8.3- 10.00)
The start of the graph shows a relatively rapid rise in pH but this slows down as a
buffer solution is produced. Beyond the equivalence point (when the sodium
hydroxide is in excess) the curve is just the same as that end of the HCl - NaOH
graph.
Titration curves for weak acid v
weakbase
When a weak acid (CH3COOH) is titrated against a weak base
(NH4oH), its pH increases very slowly and there in no sharp change
in pH around end point, so missed a vertical portion of pH curve. So
no suitable indicator for this type of titration.
It so happens that these two are both about equally weak - in that
case, the equivalence point is approximately pH 7.
Notice that there isn't any steep bit on this graph.
Instead, there is just what is known as a "point of
inflexion". That lack of a steep bit means that it is difficult
to do a titration of a weak acid against a weak base
UNIVERSAL INDICATOR
A Universal indicator is a pH indicator composed of a solution of several
compounds that exhibits several smooth colour changes over a pH value range
from 1-14 to indicate the acidity or alkalinity of solutions. universal indicator is
typically composed of water, propan-1-ol, 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
3-6 Acid Orange/Yellow
7 Neutral Green
8-11 alkali Blue
> 11 Strong alkali Violet/Purple