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Lect 23 - Conductometric Titrations

Conductometric titration is a technique that uses a conductometer to monitor the changes in conductivity of a solution during a chemical reaction, such as a titration. There are several types of conductometric titrations depending on whether the acid and base are strong or weak. For a strong acid-strong base titration, conductivity decreases sharply at the equivalence point as H+ is replaced by Na+. For a weak acid-strong base titration, conductivity increases slightly throughout as CH3COO- and Na+ ions form. Conductivity also remains nearly constant or increases slightly for titrations involving one or more weak reactants. The shape of the conductivity curve provides information about the equivalence point.

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139 views

Lect 23 - Conductometric Titrations

Conductometric titration is a technique that uses a conductometer to monitor the changes in conductivity of a solution during a chemical reaction, such as a titration. There are several types of conductometric titrations depending on whether the acid and base are strong or weak. For a strong acid-strong base titration, conductivity decreases sharply at the equivalence point as H+ is replaced by Na+. For a weak acid-strong base titration, conductivity increases slightly throughout as CH3COO- and Na+ ions form. Conductivity also remains nearly constant or increases slightly for titrations involving one or more weak reactants. The shape of the conductivity curve provides information about the equivalence point.

Uploaded by

Harsh Kumar Jha
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© © All Rights Reserved
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lect 23:Conductometric Titrations

Conductometry is a measurement of electrolytic conductivity to monitor a progress of


chemical reaction. Conductometry has notable application in analytical chemistry, where
conductometric titration is a standard technique.

conductometric titration: In this method we determine the point where reaction is


completed w i t h t h e h e l p o f a c o n d u c t o m e t e r t h a t m e a s u r e s t h e changes in
conductance of solution produced by the ions in the solution.This point at which this transition
occurs is called Equivalence point.

At Equivalence point we measure the volume of base used to neutralize the acid ions completely
in the solution. Putting these values in formula we can get the strength of acid

The principle of conductometric titration is based on the fact that during the titration,one of the
ions is replaced by the other and invariably these two ions differ in the ionic conductivity with the
result that conductivity of the solution varies during the course of titration. The equivalence point
may be located graphically by plotting the change in conductance as a function of the volume of
titrant added.
1-Strong Acid with a Strong Base, e.g. HCl with NaOH:
HCl + NaOH → NaCl + H2O
H+ + Cl- + Na+ + OH- → Na+ + Cl- + H2O
Before titration the conductance is high which is due to HCl  H+ + Cl- mobility of H+ is 350
and that of Cl- ion is 73. Upon addition of NaOH the H+ ion reacts with OH- ion to form the
very weakly ionized water molecule. This means that the H+ ion is removed from the medium
and replaced by Na+ ion which has a mobility of 43; thus a continuous abrupt decrease in
conductance occurs during the titration till the end point. Beyond the end point there is excess
Na+ and OH- ions with 43 and 198 mobility due to continuous addition of NaOH So there is
continuous increase in conductance and the curve will have a V shape , the end point is the
minimum of the curve.
Conductometric titration of a strong acid (HCl) vs. a strong base(NaOH) .

2. Weak Acid with a Strong Base, e.g. acetic acid with NaOH:

CH3COOH + Na+ + OH- → CH3COO- + Na+ + H2O

Before titration low initial conductance is observed due to low H+ obtained during
dissociation of weak CH3COOH.During titration we can observe slight decrease of
conductance due to consumption of H+ . During progress of titration we can observe slight
increase in conductancedue to the presence of CH3COO- &Na+ and nearly constant H+ due
to the buffer action of the produced CH3COONa and the remaining CH3COOH. After end
point excess NaOH will lead to increase in conductance due to increasingof Na+ and OH- .

Conductometric titration of a weak acid (acetic acid) vs. a strong base (NaOH).

3. Strong Acid with a Weak Base, e.g. sulphuric acid with dilute ammonia:
Initially the conductance is high and then it decreases due to the replacement ofH+. But after the
endpoint has been reached the graph becomes almosthorizontal, since the excess aqueous
ammonia is not appreciably ionised in the presence of ammonium sulphate.

Conductometric titration of a strong acid (H2SO4) vs. a weak base(NH4OH).

4. Weak Acid with a Weak Base: The nature of curve before the equivalence point is similar to
the curve obtained by titrating weak acid against strong base.After the equivalence point,
conductance virtually remains same as the weak base which is being added is feebly ionized and,
therefore, is not much conducting.

Conductometric titration of a weak acid (acetic acid) vs. a weak base (NH4OH).

 5. Mixture of a Strong Acid and a Weak Acid vs. a Strong Base or a Weak Base: The
initial conductivity is high it is due to HCl which by common ion effect suppress the ionization
of H3COOH. Upon titration; decrease in conductivity occurs due to replacement of H+ ion
with mobility 350
by Na+ ion with mobility 43 , till all the H+ ions from HCl are neutralized.CH3COOH will thus
ionize and react with NaOH.The change in conductivity will take place in similar way as
described above.
Conductometric titration of a mixture of a strong acid (HCl) and a weak acid (CH3COOH) vs. a
strong base (NaOH) or a weak base (NH4OH).

Aggregated ions

M+A- ↔MA↔M+ +A-


θC C αC αC
MAM+ ↔ MA+M+
άC αC C
AMA- ↔ MA+A-
άC αC C
Where MA 1:1 elwctrolyte,A- and M+ are anion and cation respectively, M+A- is nonconducting
ion pair, MAM+ and AMA- are conducting triple ions.
Let us consider the equilibrated reaction:
MA↔M+ +A-
k1=[ M+][ A-]/[ MA+]
k1=( αC)( αC)/(C)
α=(k1/C )1/2 ……1
Where k1 is the equilibrium constant.
For equilibrated reaction
MAM+↔ MA+M+
k2=[ MA][ M+]/[ MAM+]
k2=( C)( αC)/( άC )
k2= αC/ ά……….2
substitution eqn 1 into eqn 2
k2= =(k1/C )1/2 C/ ά
k2= =(k1C )1/2 / ά
ά==(k1/C )1/2C/k2
ά==(k1C )1/2 / k2
Equivalent conductance can be represented as
Λ=αΛ0+ ά Λ0,
Λ=(k1/C )1/2Λ0+ (k1C )1/2 / k2Λ0
Λ= k11/2 Λ0/C1/2+ (k11/2/ k2) Λ0C/ C1/2
Λ C1/2= k11/2 Λ0+ (k11/2/ k2) Λ0C
Plotting of Λ C1/2 versus C gives a straight line with a slope equal of (k11/2/ k2) Λ0 and intercept
equal of k11/2 Λ0.The later equation can be rewritten as following:
Λ = A/C1/2 +BC1/2
Where A equal of k11/2 Λ0 and B is equal of (k11/2/ k2) Λ0.The relationship between equivalent
conductance Λ and C1/2 is indirect as a result of formation of an ion pairs that restricted the
conduction by free ions M+ and A-when the concentration is increases until the equivalent
conductance reaches the minimum value. Above that, any excess increasing of concentration
leads to increasing of Λ as a result of formation of conducting triple ions MAM+ and AMA-.

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