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Titrimetric Methods of Analysis

Definition of Terms
• Tirtimetry: Any method in which volume is the signal

• Titrant: The reagent added to a solution containing the analyte and


whose volume is the signal.

• Equivalence point: The point in a titration where stoichiometrically


equivalent amounts of analyte and titrant react.

• End point: The point in a titration where we stop adding titrant.

• Indicator: A substance whose change in colour signals the end point of a


titration.

• Titration Error: The determinate error in a titration due to the difference


between the end point and the equivalence point.

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Definition…
• Back titration: A titration in which an excess
reagent is added to a solution containing the
analyte, and the excess remaining after its
reaction with the analyte is determined by a
titration.

• Displacement titration: A titration in which the


analyte displaces a species, usually from a
complex, and the amount of the displaced
species is derermined by a titration.
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Definition…
• A solution of which the titre is accurately
known is described as standard solution.
• The titre of solution is the number of grams of
substance per 1mL of solution.
• Standard solutions are solutions of accurately
known concentration.

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• Titrimetric methods are classified into four groups
based on the type of reaction involved:
– Acid–base titrations, in which an 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, where the titrant is an oxidizing or
reducing agent; and
– Precipitation titrations, in which the analyte and titrant
react to form a precipitate.
• Despite the difference in chemistry, all titrations share
several common features.

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Volumetric calculations
• In acid - base titrmetry the quantitative
relationship between the analyte and the
trtirant is determined by the stoichiometry of
the relevant reactions.
• For a titration to be accurate we must add a
stoichiometrically equivalent amount of
titrant to a solution containing the analyte.
• This stoichiometric mixture represents the
equivalence point.

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• The product of the equivalence point volume,
Veq, and the titrant’s concentration, CT, gives
the moles of titrant reacting with the analyte:
Moles titrant = Veq x CT
• Knowing the stoichiometry of the titration
reaction(s), we can calculate the moles of
analyte.

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• For a general reaction
aA + tT product
moles of A = a/t x moles of T

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• Any chemical reaction can serve as a
titrimetric method provided that the following
three conditions are met:
– All reactions involving the titrant and analyte must
be of known stoichiometry.
– The titration reaction must occur rapidly
– A suitable method must be available for
determining the end point with an acceptable
level of accuracy.

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• In an acid - base reaction the number of
protons transferred between the acid and
base is conserved:
moles of H+ donated x moles acid = moles H+ accepted x moles base
mole acid moles base

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Acid-Base Titration Curves
• The experimentally determined end point
should coincide with the titration’s equivalence
point
• For an acid–base titration, the equivalence
point is characterized by a pH level that is a
function of the acid–base strengths and
concentrations of the analyte and titrant.

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Titrating Strong Acids and Strong
Bases
• Let’s consider the titration of 50.0 mL of 0.100
M HCl with 0.200 M NaOH.
• For the reaction of a strong base with a strong
acid the only equilibrium reaction of
importance is

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• At the equivalence point

or

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Before the equivalence point
• Before the equivalence point, HCl is present in
excess and the pH is determined by the
concentration of excess HCl.
• Initially the solution is 0.100 M in HCl, which,
since HCl is a strong acid, means that the pH is
pH = –log[H3O+] = –log[HCl] = –log(0.100) = 1.00
• The equilibrium constant for the reaction is
(Kw)–1, or 1.00 x1014.

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• After adding 10.0 mL of NaOH the
concentration of excess HCl is

• Where the pH is given by


-log [H3O+] = -log [HCl] = -log 0.050 = 1.3

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At the equivalence point
• At the equivalence point the moles of HCl and
the moles of NaOH are equal.
• Since neither the acid nor the base is in excess,
the pH is determined by the dissociation of
water.

• Thus, the pH at the equivalence point is 7.00.


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After the equivalence point
• For volumes of NaOH greater than the
equivalence point volume, the pH is
determined by the concentration of excess
OH–.
• For example, after adding 30.0 mL of titrant
the concentration of OH– is given by

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• Giving a pH of 12.10.

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Titration curve
• Titration curve: A graph showing the progress
of a titration as a function of the volume of
titrant added.
• A titration curve provides us with a visual
picture of how a property, such as pH, changes
as we add titrant

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Acid–base titration curve for 25.0 mL
of 0.100 M HCl with 0.100 M NaOH.

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• The titration curve is not unique to an acid–
base titration.
• Any titration curve that follows the change in
concentration of a species in the titration
reaction (plotted logarithmically) as a function
of the volume of titrant has the same general
sigmoidal shape.

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Titration curve for a complexation titration Titration curve for a redox titration

Titration curve for a precipitation titration

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Titrating a Weak Acid with a Strong
Base
• Let’s consider the titration of 50.0 mL of 0.100
M acetic acid, CH3COOH, with 0.100 M NaOH.
• Start by calculating the volume of NaOH
needed to reach the equivalence point; thus
moles CH3COOH = moles NaOH
MaVa = MbVb

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Before the equivalence point
• Before adding any NaOH the pH is that for a
solution of 0.100 M acetic acid.

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• Adding NaOH converts a portion of the acetic
acid to its conjugate base

• Any solution containing comparable amounts


of a weak acid, HA, and its conjugate weak
base, A–, is a buffer.
• So, we can calculate the pH of a buffer using
the Henderson–Hasselbalch equation:

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• Before the equivalence point, the
concentration of unreacted acetic acid is

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At the equivalence point
• At the equivalence point, the moles of acetic
acid initially present and the moles of NaOH
added are identical.
• Since their reaction effectively proceeds to
completion, the predominate ion in solution is
CH3COO–, which is a weak base.
• To calculate the pH we first determine the
concentration of CH3COO–.

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After the equivalence point
• After the equivalence point NaOH is present in
excess, and the pH is determined in the same
manner as in the titration of a strong acid with
a strong base.
• For example, after adding 60.0 mL of NaOH,
the concentration of OH– is

• With a pH of 11.96
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To compute values for a weak acid (or
a weak base) titration curve:
• 1. At the beginning, the solution contains only a weak acid or a
weak base, and the pH is calculated from the concentration of that
solute and its dissociation constant.
• 2. After various increments of titrant have been added (up to, but
not including, the equivalence point), the solution consists of a
series of buffers. The pH of each buffer can be calculated from the
analytical concentrations of the conjugate base or acid and the
concentrations of the weak acid or base that remains.
• 3. At the equivalence point, the solution contains only the
conjugate of the weak acid or base being titrated (that is, a salt),
and the pH is calculated from the concentration of this product.
• 4. Beyond the equivalence point, the excess of strong acid or base
titrant suppresses the acidic or basic character of the reaction
product to such an extent that the pH is governed largely by the
concentration of the excess titrant.

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Assignment
A 50.00 mL aliquot of 0.2 M NaCN (Ka for HCN is
6.2 x 10-10) is titrated with 0.25 M HCl:
1. Calculate the pH after the addition of (a) 0.00
(b) 10.00 (c) 20.00 (d) 30.00 (e) 40.00 (f) 50.00
and (f) 60.00 mL of the acid
2. Draw the titration curve by showing the
equivalence point

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Hypothetical titration curves for a series of weak bases of different strengths. The curves
show that indicators with mostly acidic transition ranges must be used for weak bases.

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