ACID-BASE
TITRATION
7.4
LEARNING OUTCOMES
[Link] CHANGES IN pH DURING ACID-
BASE TITRATION IN TERMS OF STRENGTHS
OF ACIDS AND BASES
[Link] SUITABLE INDICATORS FOR
ACID-BASE TITRATIONS
ACID-BASE INDICATORS
-AN ACID-BASE INDICATORS OR pH INDICATORS IS A WATER
SOLUBLE DYE THAT CHANGES COLOUR ACCORDING TO THE
CONCENTRATION OF HYDROGEN IONS IN THE SOLUTION TO
WHICH THE INDICATOR IS ADDED
-THEY ARE ALSO WEAK ORGANIC ACIDS OR BASES THAT
DISSOCIATE SLIGHTLY IN AQUEOUS SOLUTION TO FORM IONS
-THE INDICATORS CHANGE COLOUR BECAUSE THEIR IONS HAVE
COLOURS THAT ARE DIFFERENT FROM THE UNDISSOCIATED
MOLECULE
a) in aqueous solution, the following equilibrium is established
between the indicator, HIn and its conjugate base, In-
b) at low pH values, the concentration of H3O+ is high and so
the equilibrium shifts to the left. The indicator thus has colour A.
c) at high pH values, the concentration of H3o+ is low. The
equilibrium shifts to the right. Thus the indicator has colour B.
d) If [HIn]=[In-], the colour has an intermediate colour
a) applying the law of mass action for reversible reaction in the
equation above, we have:
where K is called the indicator dissociation constant.
b) the indicator is about to change colour when [HIn]=[In-]
-at this point, KHin = [H3O+] and pH of the solution = [pKHIn+]
In general, a distinct colour change occurs if [HIn]/[In-] is more
than 10 or less than 1/10
-If [HIn]/[In-] is more or equal to 10, that is 90% or more in HIn
form, the colour of HIn will be seen
-If [HIn]/[In-] is less or equal to 1/10, that is 90% or more in In-
form, the colour In- will be seen
EQUIVALENCE POINT AND END POINT
OF A TITRATION
-EQUIVALENCE POINT= The point at which there are equal
amounts (in moles) of H3O+ and OH- in the titration flask
-At this point, the neutralisation is complete and neither the acid
nor the alkali is in excess. The solution is consists of salt and
water only.
-END POINT= The point at which the indicator changes colour
a) in acid-base titration, a suitable indicator must be chosen so
that the end point coincides with the equivalence point
b) if a suitable indicator is used, the indicator will change colour
sharply at the equivalence point
CHOOSING AN INDICATOR FOR AN
ACID-BASE TITRATION
-changes in pH that occur during the titration of an acid with an
alkali can be followed by using a pH meter.
-A standard solution of an alkali is
added slowly from a burette to a
solution of hydrochloric acid and the
pH of the solution is recorded.
-Then, a graph of pH against the
volume of alkali added is then plotted.
-This graph is known as the pH curve
or the titration curve.
In order for an acid-base titration to be carried out successfully,
a) pH must change sharply by several units at the equivalence
point so that the end point can be identified by a suitable indicator
b) pK, of the indicator chosen for the titration should be equal to or
close to the pH at the equivalence point of the titration
c) pH range for the indicator should lie on the vertical part of the
titration curve otherwise the indicator colour will change either
before or after the equivalence point
STRONG ACID-STRONG BASE TITRATION
The pH curve is obtained when 25.0 cm^3 of 0.1 mol dm^-3
hydrochloric acid is titrated with 0.1 mol dm^-3 sodium hydroxide
solution. The value of pH for 0.1 mol dm^-3 hydrochloric acid is 1.0
and the pH value for 0.1 mol dm^-3 sodium hydroxide is 13.
pH change before the equivalence point
as sodium hydroxide solution is added to hydrochloric acid, pH
of the solution increases slowly
pH change at the equivalence point
the equivalence point of this titration occurs when 25.0 cm^3
of 0.1 mol dm^-3 NaOH are added to 25.0 cm^3 of 0.1 mol
dm^-3 of HCl
when one drop (approximately 0.05 cm^3) of excess NaOH is
added from the burette, the pH changes very sharply from 3.5
to 10.5
the pH at the equivalence point is the pH of the salt solution
produced. Thus, the pH at equivalence point is 7.00, which is
the pH of the sodium chloride solution
pH change after the equivalence point
beyond the equivalence point, pH rises slowly until it
reaches the pH of excess sodium hydroxide added,
that is, pH 13
choice of indicator
any indicator that changes colour in the pH range
from 3.5 to 10.0 is suitable for this titration
therefore, indicators such as methyl orange,
phenolphthalein or bromothymol blue can be used for
strong acid-strong base titrations
STRONG ACID-WEAK BASE TITRATION
The pH curve shows how the pH changes when 0.1 mol dm^-3
ammonia solution (a weak base) is added to 25.0 cm^3 of 0.1 mol
dm^-3 hydrochloric acid.
pH change before the equivalence point
as the alkali is added, the pH changes slowly at first, but at the
equivalence point, the pH changes very rapidly from about 3 to
7
choice of indicator
thus, any indicator which changes colour between pH 3 to 7 will
identify the end point accurately
the indicator range of methyl orange lies on the vertical part of
the titration curve. This indicator will therefore change colour
sharply at the equivalence point. Hence, this indicator is
suitable for the titration.
Phenolphthalein is unsuitable because its pH range lies above
the vertical portion of the graph. It will not change colour until
the pH of the solution is 8, which is after the equivalence point.
pH change before the equivalence point
as the alkali is added, the pH changes slowly at first, but at the
equivalence point, the pH changes very rapidly from about 3 to
7
choice of indicator
thus, any indicator which changes colour between pH 3 to 7 will
identify the end point accurately
the indicator range of methyl orange lies on the vertical part of
the titration curve. This indicator will therefore change colour
sharply at the equivalence point. Hence, this indicator is
suitable for the titration.
Phenolphthalein is unsuitable because its pH range lies above
the vertical portion of the graph. It will not change colour until
the pH of the solution is 8, which is after the equivalence point.
pH value of solution at equivalence point
the salt formed for the titration between NH3 and HCl is NH4Cl.
NH4Cl is a salt of a strong acid-weak base.
the conjugate acid, NH4+ ion undergoes hydrolysis to produce
an acidic solution
Hence, the pH value of the solution at equivalence point is about
5.0
WEAK ACID-STRONG BASE TITRATION
The pH curve shows the pH changes during the titration of 25 cm^3
of 0.1 mol dm^-3 ethanoic acid (a weak acid) with 0.1 mol dm^-3
sodium hydroxide solution (a strong base)
pH change before the equivalence point
the pH change starts at 2.87 and not 1.0 because ethanoic acid
is a weak acid
there is a sharp increase in pH, from 6.5 to 10.5 at the
equivalence point. This sharp increase is smaller than in strong
acid-strong base titration.
the pH of the solution at equivalence point is about 8.5
because the salt formed, CH3COONa undergoes hydrolysis.
CH3COONa is a salt of weak acid-strong base.
the conjugate base, CH3COO- ion undergoes hydrolysis to
produce an alkaline solution
choice of indicator
Phenolphthalein (pH range of 8.2-10.0) is a suitable indicator
because it shows a sharp colour change at the equivalence
point.
the pH range of methyl orange (3.4-4.2) does not lie within the
vertical portion of the pH curve. Thus, the methyl orange is not
a suitable indicator because it will change colour before the
equivalence point is reached
WEAK ACID-WEAK BASE TITRATION
The pH curve shows the changes in pH when 0.1 mol dm^-3
ethanoic acid (weak acid) is titrated with 0.1 mol dm^-3 ammonia
solution (weak base).
for this type of titration, there is
no sharp increase of pH at the
equivalence point. The pH
changes gradually over a range of
pH values. Thus, no indicator is
suitable for this type of titration.
TITRATIONS OF WEAK POLYPROTIC ACIDS
phosphoric(V) acid is tribasic. It reacts with alkalis such as sodium
hydroxide in three stages:
figure below shows the changes in pH when 25.0 cm^3 of 0.1 mol
dm^-3 phosphoric(V) acid, H3PO4 is titrated with 0.1 mol dm^-3
aqueous sodium hydroxide
the first equivalence point at pH 4.6 corresponds to the first
stage of the reaction, that is, the formation of NaH2PO4.
when more sodium hydroxide solution is added, a second
equivalence point is reached at pH 9, corresponding to the
formation of Na2HPO4
although we expect a third equivalence point at 75 cm^3 , it is
not realised in this titration. This is because the pH of Na3PO4
solution is about 13, which is as basic as the NaOH used in the
titration.
choice of indicator
methyl orange is a suitable indicator for the first equivalence
point, while phenolphthalein is a suitable indicator for the
second equivalence point
the pH changes at the third equivalence point is not very
distinct and occurs in strongly alkaline solution. No indicator is
satisfactory in detecting the third end point.
STRONG ACID- STRONG ACID-
STRONG BASE WEAK BASE
suitable indicators: suitable indicators:
methyl orange or methyl orange
phenolphthalein (end (end point between pH
point between pH 3.5- PRO 3-7)
10.5)
WEAK ACID- WEAK ACID-
STRONG BASE WEAK BASE
suitable indicators: no indicator is suitable for
phenolphthalein (end this type of titration as
point between 6.5-10.5) there is no sharp increase
in pH at the equivalence
point
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