Unit 3 Volumetric Titrimetric Methods of
Unit 3 Volumetric Titrimetric Methods of
(TITRIMETRIC) METHODS OF
ANALYSIS
• Autoionization/protolysis of water
• pH calculations
• Equilibrium constants
2
• Buffers
UNIT CONTENT
Uses of titrimetry in chemical analyses
Basic calculations
Neutralisation titrations
– Acid-base indicators
– Titration curve for strong acid-strong base titrations
– Weak acid-strong base titration curves
– Strong acid – weak base titration curves
3
TITRIMETRIC METHODS OF ANALYSIS
• Classified based on the type of reaction involved
Acid-base titration – acidic or basic titrant reacts
with an analyte that is a base or an acid.
Complexometric titrations – involving a metal-
ligand complexation reaction
Redox titrations- the titrant is an oxidizing or
reducing agent
Precipitation titrations – analyte and titrant react
to form a precipitate
4
Conducting a
titration
experiment
A buret:
most essential piece
of equipment for an
acid base titration
and is a means of
delivering the
titrant to the
solution containing
the analyte
5
GENERAL TERMS IN TITRIMETRY
Titration:
Addition of a solution from a burette
(titrant) to a solution in a flask (titrand)
until there is an indication that the titrant
has reacted stoichiometrically with the
titrand.
Standards:
reagents of exactly known concentration
{(x ± y) units} used in volumetric analysis.
6
GENERAL TERMS IN TITRIMETRY
Primary (1°) standard:
substance of sufficient purity such that a
standard solution can be prepared from it by
directly weighing a quantity of it, dissolving it
and then diluting to a defined volume of
solution.
Secondary (2°) standard:
solution whose concentration has been
determined by comparison against a 1°
standard.
7
THE CRITERIA USED IN SELECTING PRIMARY STANDARDS
A primary standard
Can be weighed accurately either for the purpose of preparing a standard
solution (which then does not have to be standardized) or for the
comparison to a solution with which it reacts for the purpose of
standardizing that solution.
• Most titrations give no obvious indication that the equivalence point has
been reached. We stop adding titrant when we reach an END POINT
indicated by a colour change of an indicator added to the solution
containing the analyte.
SO , WHAT DO WE DO?
TITRATION STRATEGIES CONT’D
• If we add a known amount of I3-, such that it is in
excess, we can allow the reaction to go to completion.
• The I3- remaining can be titrated with thiosulfate, S2O32-
.
• I3- + 2S2O32- (aq) S4O62- (aq) + 3I-(aq)
• BACK TITRATION
– A titration in which a reagent is added to a solution
containing the analyte, and the excess reagent
remaining after its reaction with the analyte is
determined by a titration.
13
TITRATION STRATEGIES CONT’D
• When a suitable reaction involving the analyte does not exist it
may be possible to generate a species that is easily titrated. For
example, the sulphur content of coal can be determined by using a
combustion reaction to convert sulphur to sulphur dioxide.
15
Review of Solution concentration
•MOLARITY (M)
•The number of moles of solute dissolved per liter of solution and may
be calculated by dividing the number of moles dissolved by the number
of liters of solution:
16
•What is the molarity of a solution that has 4.5 mol of solute
dissolved in 300.0 mL of solution?
•Convert mL to liters
• 300.0 mL = 0.3000L
4.5mol
molarity 15M
0.3000L
17
WHAT IS THE MOLARITY OF A SOLUTION OF NAOH THAT HAS
0.491 G DISSOLVED IN 400 ML OF SOLUTION?
Convert from grams of solute to moles by dividing the grams by
the molar mass.
Convert from mL to L
18
•SELF TASK
–The
grams of solute calculated is weighed and placed in the
container. Water is added to dissolve the solute and to dilute the
solution to volume. The solution is then shaken to make it
homogeneous.
19
SOLUTION PREPARATION BY DILUTION- THE
MOLES OF SOLUTE IN A SOLUTION IS UNCHANGED BY DILUTION ONLY THE
AMOUNT OF SOLVENT IS CHANGED
CB×VB = CA×VA
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TITRATION CURVES
Finding the end point
13
12
11
10
9
8
7 Equivalence point
pH
6
5
4
3
2
1
0
0 10 20 30 40 50 60 70
23
Volume Base
TITRATION CURVES
• We can measure the titration curve experimentally by
suspending a pH electrode in the solution containing
the analyte monitoring the pH as titrant is added.
24
NEUTRALIZATION TITRATIONS
Acid-base indicators
Titration curves
Examples of methods
25
ACID-BASE INDICATORS
Weak organic acid or base.
[ In ][ H 3O ] [ HIn]
Ka [ H 3O ] K a
[ HIn] [ In ] 26
ACID-BASE INDICATORS
[ In ][ H 3O ] [ HIn]
Ka [ H 3O ] K a
[ HIn] [ In ]
pKa = -logKa
27
ACID-BASE INDICATORS
pH and the magnitude of the change in pH at
the equivalence point must be known.
Not necessary for indicator to change colour at
the equivalence point.
Usually, pH change around equivalence point is
rapid.
Therefore, an indicator beginning and ending its
colour change anywhere on the portion of the pH
curve where there is a sharp rise (or decline) in
pH, will be suitable.
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ACID-BASE INDICATORS
pH = -log[H3O+]
End points
Possible
indicators
29
Equivalence volume
NEUTRALIZATION TITRATIONS
To select the indicator for a neutralization titration
(acid-base) we must know:
13
12
11
10
9
8
7
pH
6
5
4
3
2
1
0
0 10 20 30 40 50 60 70
Volume Base
32
TITRATION CURVE FOR STRONG ACID-STRONG BASE
TITRATIONS
33
TITRATION CURVE FOR STRONG ACID-STRONG BASE
TITRATIONS
50 cm3 of 0.100 M HCl with 0.100 M NaOH
SELF TASK
Calculate pH for Vt < Ve
Vt = 1 50.00 mL
35
TITRATION CURVE FOR STRONG ACID-
STRONG BASE TITRATIONS
50 cm3 of 0.100 M HCl with 0.100 M NaOH
pH at equivalence volume:
HCl + NaOH H2O + Na+ + Cl-
[H3O+] = 1 x 10-7 pH = 7
36
TITRATION CURVE FOR STRONG ACID-STRONG BASE
TITRATIONS
50 cm3 of 0.100 M HCl with 0.100 M NaOH
13
12
11
10
9
8
7
pH
6
5
4
3
2
1
0
0 10 20 30 40 50 60 70
Volume Base
38
TITRATION CURVE FOR STRONG ACID-STRONG BASE
TITRATIONS
Summary
pH before equivalence point:
Strong Acid - Strong Base
pH = -log[H3O+] 13
pH
pH 4-10 C 6
pH 5-9 4
B
A: [HCl] = [NaOH] = 0.01 mol dm-3 3
pH 6-8 A 2
0
40 45 50 55 60
39
Bromothymol Blue (BB): 6.2 – 7.6
Methyl Orange (MO): 3.1 – 4.4
TITRATION CURVE FOR STRONG ACID-
STRONG BASE TITRATIONS
40
TITRATION CURVE FOR STRONG ACID-
STRONG BASE TITRATIONS
Issues of Concern:
end point vs. equivalence point !!!
Ka (H3BO3) Kb (H2BO3-)
5.81 x 10-10 1.75 x 10-5
pKa = 9.24 pKb = 4.76
Ka (AcOH) Kb (AcO-)
1.75 x 10-5 Kb = ?
pKa = 4.76 pKb = ?
50 mL of 0.10 mol L-1 acetic acid with 0.10 mol L-1 NaOH, Ka =
1.75 x 10-5, pKa = 4.76
a) Before titration starts (we have a solution of only HOAc):
The weak acid will partially dissociate establishing the
equilibrium:
CH3COOH + H2O CH3COO- + H3O+
I 0.10 0 0
C -x x x
E 0.10-x x x
Ka = [H3O+][CH3COO-]/[CH3COOH]
44
TITRATION CURVE FOR WEAK ACID-STRONG
BASE TITRATIONS
50 mL of 0.10 mol L-1 acetic acid
45
with 0.10 mol L-1 NaOH, Ka
= 1.75 x 10-5, pKa = 4.76
= (Vt)(0.10M)/1000 moles 49
TITRATION CURVE FOR WEAK ACID-STRONG
BASE TITRATIONS
50 mL of 0.10 mol L-1 acetic acid with 0.10 mol L-1 NaOH, Ka =
1.75 x 10-5, pKa = 4.76
The solution will contain both acetic acid and its conjugate base
acetate – a buffer is created.
= [(50.0)(0.10) - (Vt)(0.10M)]/50.0 + Vt
= (Vt)(0.10M)/50.0 + Vt 50
TITRATION CURVE FOR WEAK ACID-STRONG BASE TITRATIONS
[H3O+] = Ka[CH3COOH]/[CH3COO-]
& pH.
51
50 mL of 0.10 mol L-1 acetic acid with 0.10 mol L-1 NaOH, Ka = 1.75 x 10-5,
pKa = 4.76
Ka = [CH3COO-][H3O+]/[CH3COOH]
[H3O+] = Ka[CH3COOH]/[CH3COO-]
Hence, at Vt = 5 mL
[H3O+] =
1.75 x 10-5(0.10 x 50.0 – 0.10 x 5.00)/(0.10 x 5.00)
= 1.58 x 10-4 mol L-1 pH = 3.80
c) At Ve:
All the acetic acid has been neutralized to leave the
conjugate base and the equilibrium:
Ka x Kb = Kw
Kb= Kw/Ka
= 5.71 x 10-10 54
TITRATION CURVE FOR WEAK ACID-
STRONG BASE TITRATIONS
14
12
10
pH =
pKa at
8 Acetic acid titrated with NaOH
pH at Ve
pH
6
0.5Ve 14
4 12
2 10
0 8
0.1 M
pH
0 10 20 30 40 50 60 70 80
6
ml base
Ve 0.01 M
4
0.001 M
2
0
0 10 20 30 40 50 60 70 80
mL base
56
TITRATION CURVE FOR WEAK ACID-
STRONG BASE TITRATIONS
Acetic acid titrated with NaOH
14
Choice of indicators:
8
pH
6
as for strong acid –
4 strong base
2 titrations
0 The buffering region
0 10 20 30 40 50 60 70 80
mL base Ka = [CH3COO-][H3O+]/[CH3COOH]
= [H3O+] x {[CH3COO-]/[CH3COOH]}
The maximum buffering capacity when
[base] = [acid] 57
TITRATION CURVE FOR WEAK ACID-
STRONG BASE TITRATIONS
The effect of acid strength -
Ka
58
STRONG ACID – WEAK BASE TITRATION
CURVES
59
SUMMARY
61
REFERENCES
Lecture notes were prepared by Dr. K. Wilson and Dr.
D. Gordon-Smith and modified by Dr. Deon Bennett
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