KIMIA ANALITIK DASAR 2

SILABUS
Metode titrimetri; titrasi netralisasi; analisis
volumetri untuk reaksi pembentukan endapan
dan senyawa kompleks (argentometri); titrasi
pembentukan senyawa kompleks; analisis
volumetri secara oksidasi-reduksi
(redoksimetri); Analisis gravimetri

BUKU REFERENSI
David Harvey, Modern Analytical Chemistry, Mc Graw-
Hill
Skoog, D. A. and West, D.M., Fundamentals of
Analytical Chemsitry, Holt-Saunders International
edition.
Vogels Textbook of Quantitative Chemical Analysis,
Longman and Scientific, Essex
Christian, G.D., Analytical Chemsitry, 5
th
edition, John
Wiley and Sons, Inc., New York.

INTRODUCTION TO
TITRIMETRY
Most common types of titrations :
neutralization titrations
oxidation-reduction titrations
complex formation titration
precipitation reactions
In a titration, increments of titrant are added to the
analyte until their reaction is complete.
From the quantity of titrant required, the quantity of
analyte that was present can be calculated.
Figure 1
Titration Setup
TITRATIONS IN PRACTICE
Accurately add of specific
volume of sample solution to a
conical flask using a pipette
Known: volume of sample
Unknown: concentration of
analyte in sample
1
Pro Pipet
Slowly add standard
solution from a burette to
the sample solution
Known: concentration of
the titrant
2
Add until just enough titrant
is added to react with all the
analyte
The end point is signalled by
some physical change or
detected by an instrument
Known: volume of the titrant
Note the volume of titrant
used
3
If we have:
HA + BOH BA + H
2
O
Then from the balanced equation we know:
1 mol HA reacts with 1 mol BOH
analyte titrant
We also know:
C
BOH
, V
BOH
and V
HA
and
2
2 2
1
1 1
n
v c
n
v c

1
v c
1
v c
BOH BOH HA HA

HA
BOH BOH
HA
v
v c
c

STANDARD SOLUTIONS
Standard solution:
Reagent of known concentration
Primary standard:
highly purified compound that serves as a
reference material in a titration.
Determine concentration by dissolving an
accurately weighed amount in a suitable
solvent of known volume.
primary standard
1. High purity 100.0%
2. Stability toward air
3. Absence of hydrate water
4. Available at moderate cost
5. Soluble
6. Large F.W.
Secondary standard:
compound that does not have a high purity
Determine concentration by standardisation.
Titrate standard using
another standard.
Standard solutions should:
Be stable
React rapidly with the analyte
React completely with the analyte
React selectively with the analyte
EQUIVALENCE
POINT
The amount of added
titrant is the exact
amount necessary for
stoichiometric reaction
with the analyte in the
sample.
An estimate of the
equivalence point that
is observed by some
physical change
associated with
conditions of the
equivalence point.
Aim to get the difference between the equivalence
point and the end point as small as possible.
Titration error: E
t
= V
eq
V
ep

Estimated with a blank titration
END POINT VS
Indicators
used to observe the end point
(at/near the equivalence point)
Thymol blue indicator
Instruments can also be used to detect end points.
Respond to certain properties of the solution
that change in a characteristic way.
E.g.: voltmeters, ammeters, ohmmeters,
colorimeters, temperature recorders,
refractometers etc.
Add excess titrant and then determine the
excess amount by back titration with a second
titrant.
BACK TITRATION
Used when:
end point of back titration is clearer than end point
of direct titration
an excess of the first titrant is required to complete
reaction with the analyte
If we have:
HA + BOH BA + H
2
O
Then from the balanced equation we know:
1 mol HA reacts with 1 mol BOH
analyte titrant
If I add excess titrant and then react the excess with a
second titrant as follows:
HX + BOH BX + H
2
O
titrant 2 excess
Then from the balanced equation we know:
1 mol HX reacts with 1 mol BOH
We also know:
C
BOH
, C
HX
and V
HX
and
2
2 2
1
1 1
n
v c
n
v c

1
v c
1
v c
HX HX BOH BOH
(excess)

BOH
HX HX
BOH
c
v c
v (excess)

We also know v
BOH
(total)
v
BOH
(reacted) = v
BOH
(total) v
BOH
(excess)
1
v c
1
v c (reacted)
BOH BOH HA HA

HA
BOH BOH
HA
v
v c
c
(reacted)

From our initial titration:
HA + BOH BA + H
2
O
analyte titrant
we then know:
C
BOH
, V
BOH
(reacted) and V
HA

and we want to find C
HA
!

In summary:
HA + BOH BA + H
2
O
analyte titrant reacted
V
HA
C
BOH

HX + BOH BX + H
2
O
titrant 2 titrant excess
V
HX

C
HX
C
BOH

BOH
HX HX
BOH
c
v c
v (excess)
v
BOH
(reacted) = v
BOH
(total) v
BOH
(excess)
2
2 2
1
1 1
n
v c
n
v c

C
HA
?
HA
BOH BOH
HA
v
v c
c
(reacted)

Example:
50.00 ml of HCl was titrated with 0.02 M Ba(OH)
2
. The
end point was reached (using bromocresol green as
indicator after 20 ml Ba(OH)
2
was added.
What is the concentration of the HCl?
2
2 2
1
1 1
n
v c
n
v c

Example:
A 0.8 g sample of iron ore is dissolve in acid. The
iron is reduced to Fe
2+
and titrated with 0.02 M
KMnO
4
. 40 ml of titrant was added to reach the end
point. Calculate the % Fe in the sample.
MnO
4
-
+ 5Fe
2+
+ 8H
+
Mn
2+
+ 5Fe
3+
+ 4H
2
O
MnO
4
-
+ 5Fe
2+
..
100
sample of mass
analyte of mass
%Fe
Example:
The CO in a 20 L sample of gas was converted to CO
2
by passing the gas over iodine pentoxide heated to
150
o
C:
I
2
O
5
(s) + 5CO(g) 5CO
2
(g) + I
2
(g)
The iodine distilled at this temperature was collected
in an absorber containing 8 mL of 0.01 M Na
2
S
2
O
3
:
I
2
(aq) + 2S
2
O
3
2-
(aq) 2I
-
(aq) + S
4
O
6
2-
(aq)
The excess Na
2
S
2
O
3
was back titrated with 2 mL of
0.001 M I
2
solution.
Calculate the mg CO per liter of sample.

I
2
O
5
(s) + 5CO(g) 5CO
2
(g) + I
2
(g)
I
2
(aq) + 2S
2
O
3
2-
(aq) 2I
-
(aq) + S
4
O
6
2-
(aq)
I
2
(aq) + 2S
2
O
3
2-
(aq) 2I
-
(aq) + S
4
O
6
2-
(aq)
n
reacted
= REACTED
I
2
(aq) + 2S
2
O
3
2-
(aq) 2I
-
(aq) + S
4
O
6
2-
(aq)
I
2
O
5
(s) + 5CO(g) 5CO
2
(g) + I
2
(g)
I
2
(aq) + 2S
2
O
3
2-
(aq) 2I
-
(aq) + S
4
O
6
2-
(aq)
I
2
O
5
(s) + 5CO(g) 5CO
2
(g) + I
2
(g)
Calculate the mg CO per liter of sample.