Acid Base Titrations PDF

Dr.
Puspendra Kumar
ACID BASE TITRATION

ACID – BASE CONCEPTS
• An acid-base titration (or neutralization titration) is based upon the chemical reaction
between an acid and a base.
• Several acid-base theories have been proposed to explain or classify acidity and basicity
properties of substances.
• Most familiar theory is the Arrhenius theory, but it’s applicable only to water.
• Other theories are more general and are applicable to other solvents.
1. ARRHENIUS THEORY (H+ & OH-)

• Arrhenius, as a graduate student, introduced a radical theory in 1894 (for which he
received the Nobel prize)
• An acid is any substance that ionizes (partially or completely) in water to give hydrogen
ions (which associates with the solvent to give hydronium ions, H3O+)
H3O+ +A-
HA + H2O
• A Base ionizes in water to give hydroxyl ions.
• Weak (partially ionized) bases generally ionize as follows:
BH+ + OH-
B + H2O
• While strong bases such as metal hydroxide (NaOH) dissociate as
M (OH)n Mn+ + nOH-
- This theory is obviously restricted to water as solvent.
2. BRONSTED-LOWRY THEORY (Taking and giving protons)

• In 1923, Bronsted and Lowry separately described what is known as the Bronsted-Lowry
theory.
• This theory states that an acid is any substance that can donate a proton, and a base is any
substance that can accept a proton.
• Thus we can write a “half reaction”
Acid = H+ +Base
• The acid and base of a half reaction are called conjugate pairs.
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Dr. Puspendra Kumar
• Free protons do not exist in solution and there must be a proton acceptor (base) before a
proton donor (acid) will release its proton.
3. LEWIS THEORY (Taking and giving electrons)
• In 1923, G. N. Lewis also introduced the electronic theory of acids and bases.
• In the Lewis theory, a base is a substance that can donate an electron pair and acid is a
substance that can accept an electron pair.
• Base, frequently contains oxygen or nitrogen as the electron donor.
• Thus, non hydrogen containing substances are introduced as acids.
AlCl3 + :O-R2 Cl3Al:OR2
Here, Aluminium Chloride is an acid and ether a base.
• This theory is useful to describe the indicator color change in non protonic systems
exhibiting acid-base reaction.
Summary of acid-base theories:
Name of theory Acid Base
1. Arrhenius theory Hydrogen ion donor Hydroxide ion donor
2. Bronsted-Lowry theory Proton donor Proton acceptor
3. Lewis theory Electron pair acceptor Electron pair donor
ROLE OF SOLVENT
• Water is amphiprotic in nature i.e. it can act either as an acid or as a base depending upon
experimental conditions.
• So aqueous titration methods are used.
• The solvent selected for acidimetry should be either neutral or acidic in nature.
e.g :- Neutral solvent – acetonitrile , alcohols, chloroform , benzene , dioxane ethyl
acetate.
• Neutral solvent do not enhance dissociation to a great degree.
Acidic solvent – Formic acid, acetic acid, propionic acid, acedic anhydrides, sulphonyl
chloride.
Acidic solvents are protogenic in nature and can be utilised for weak bases.
• The solvent should be non- toxic for its wide use in analysis.
• It should be liquid at the time of analysis.
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• The organic solvents are used but its mainly dependent on their properties such as –
1. Self dissociation
2. Dielectric constant
3. Acid base character of solvent
1. CAPABILITY OF SELF DISSOCIATION
• Solvent can be classified as dissociating and non dissociating solvents.
• Dissociating solvents such as ‘Ethanol’ dissociates to give ethoxide ion.
C2H5OH C2H5O- + H+
• Acetic acid gives acetate ion
CH3COOH CH3COO- + H+
• Hydrogen ion represents solvated protons and its range varies with the solvent. (Solvated
proton means proton bound with solvent)
• Some solvent dissociates without the production of solvated protons. eg. Acetic
anhydride
[CH3CO]2O CH3COO- + CH3CO+
Acetic anhydride Acetate ion Acetylium ion
• A non dissociating solvent includes ethers, hydrocarbons.
• These solvents may dissociate but it is not usually detectable.
• It is always possible to define ion product of dissociating solvent.
• Here, the solvent is represented by “A B”
AB A+ + B-
Ion- product (Ks) can be written
Ks = [A+] [B-]
The smaller is the value of Ks of a solvent, the greater is the range available for titration.
2. DIELECTRIC CONSTANT
• If we assume the solvents as a homogenous medium and the ions present as point
charges, these expressions can be applied for this system also.
• It can be concluded that higher the D value of the solvent, smaller amount of
energy will separate the ions. i.e It will be easy to dissolve the ionic solute.
• In a solvent of high dielectric constant, complete dissociation of polar ionic solute
occurs easily.
Dr. Puspendra Kumar
• Dielectric constant for some solvents.

o Cyclohexane 2.02
o Chloroform 4.81
o Methanol 32.6
o Water 78.5
3. ACID -BASE CHARACTER
• The non aqueous solvent can be classified based on its proton donor –acceptor
properties.
• The solvent exert an influence on the acid-base properties of the solute.
• They are of 4 types namely :-
a. Protogenic
b. Protophilic
c. Aprotic
d. Amphiprotic
• The dissociating solvent AB dissociates to give the cation A+ [Lyonium ion] and
the anions [Lyate ion].
• The lyonium ion is reponsible for acidic character of solvent and lyate ion is
responsible for basic character of solvent.
a) Protogenic solvent: They are acidic in properties. These solvents have relatively high
dielectric constant, they are ionized.
Eg. Acetic acid, formic acid and propionic acid.
b) Protophilic solvent: They are basic in nature and reacts with acid to form the solvated
proton. These solvents have high dielectric constant. They are ionized.
Eg. Pyridine, Dimethylformamide, ethylenediamine.
c) Aprotic solvent: These are the solvent cannot able to donate hydrogen. In this solvent
both acidic and basic properties are entirely absent.
Eg. Hexane and carbon tetra chloride.
d) Amphiprotic solvent: These solvent have both protogenic and protophilic properties.
Eg. Water, Ethanol.
Dr. Puspendra Kumar
RELATIVE STRENGTH OF ACID AND BASES

• As per Bronsted-Lowry theory at equilibrium.
• The free proton cannot exist in solution in measurable concentration.
• Reaction does not take place unless a base is added to accept the proton from the acid.
By contributing the equations –
A1 B1 + H+ ………………… (a)
B2 + H+ A2 ………………… (b)
We obtain,
A1 + B2 + H+ B1 + H+ + A2
A1 + B2 + H+ B1 + H+ + A2
A1 + B2 B1 + A2 ………………… (c)
According to the law of mass action
K = [B1][A2] / [A1][B2] ………………… (1)
Where; the constant ‘K’ depends on the temperature and the nature of the solvent.
• This expression is strictly valid for the extremely dilute solutions.

• To use the above expression for measuring the strength of an acid , a standard acid-base
pair, say A2 – B2 , must be chosen , and It is usually convenient to refer acid – base
strength of the solvent.
• In water the acid –base pair (H3O+-H2O) is taken as standard.
• The equilibrium defining acid is therefore.
A + H2O B + H3O+ ………………… (d)
So, the constant,
K’ = [B] [H3O+] / [A] [H2O] ………………… (2)
Equation (d) represent dissociation of the acid A in water and constant ‘K’ is closely
related to the dissociation constant A in water.
• When dealing with dilute solutions , the value of [H2O] may be regarded as constant and
equation (2) may be expressed as :-
Ka = [B] [H+] / [A] ………………… (3)
• This equation defines the strength of acid A
Dr. Puspendra Kumar
• For example ammonium ion, which interacts with water as shown by the equation
NH4+ + H2O NH3 +H3O+
The acid stregth is given by
Ka= [NH3][H+] / [NH4+]
So, [NH4+] = [NH3][H+] / Ka
• Since any protolytic reaction involving an acid must also involve its conjugate base
NH4 + OH-
NH3 + H2O
So, Kb= [NH4+][OH-] / [NH3]
Since [H+][OH-] = Kw (the ionic product of water)
We have Kb=Kw/Ka
• The value of Ka and Kb for different acids and bases vary through many powers of ten.
• It is often convenient to use the dissociation constant exponent pK defined by
pK = log10 (1/K)= -log10k.
The larger the pKa value is, the weaker is the acid and the stronger the base.
Dr. Puspendra Kumar
IONIZATION
• Strong acid or strong base is one in which solute acid or base reacts fully with solved
whereas,
• A weak acid or weak base solution is once in which only psrtisl or insignificant reaction
with solvent occurs.
• One can also relate the strength of acid or base with the extent of Ionization
• E.g:- HCL is a strong acid in water because it is completely ionized whereas acetic acid is
a weak acid in water because it is slightly ionized.
• So, the strength of an acid is related to the conc. of H+ ions that are produced on
ionization and at any given concentration will depend upon the value of degree of
dissociation.
H2O +HCl H3O+ + Cl-
H2O + CH3COOH ↔ H3O+ + CH3COO-
LAW OF MASS ACTION

• This law was first proposed by Goldberg and Wage in 1867 and can be expressed as:-
• “The rate of a chemical reaction is proportional to the active masses of the reacting
substances”
• In dilute solutions where conditions approach the ideal state ‘active masses may represent
by the concentration of the reacting substances.
• i.e. gm-molecules or gm-ions per litre.
The constant of proportionality is known as ‘velocity constant’
Now,
Let’s consider a homogeneous, reversible reaction
A + B C + D
According to the law of mass action
Vf = K1 [A][B]
Vb = K2 [C][D]
Where,
• Vf = Velocity of the forward reaction
• Vb = Velocity of backward reaction
Dr. Puspendra Kumar
• [A], [B], [C], [D] = Molar concentration of A, B, C and D respectively.

• K1 and K2 are constants.
At equilibrium,
Vf = Vb
K1 [A][B] = K2[C][D]
K1/K2 = [C] [D] / [A] [B]
Since, K1 and K2 are constants, K1 fraction must also be a constant.
• This result may be generalized as
• When equilibrium is reached in a reversible reaction, at constant temperature,
the product of the molecular conc. of the resultants RHS divided by the
product of the molecular conc. of reactants LHS
• Each conc. being raised to a power equal to the number of molecules of that
substances taking part in the reaction, is constant.
• Hence,
K = Equilibrium constant of the reaction
• In extension, the equilibrium constant for the general reversible reactions
aA + bB+ cC pP+ qQ +rR
K= [P]p[Q]q[R]r / [A]a[B]b[C]c
• Where a, b, c ……………….and p, q, r are number of molecules of reacting species.
It’s a mathematical model that explains & predicts behavior of solution in dynamic
equilibrium.
COMMON ION EFFECT

• A weak electrolyte AB, when dissolved in water will dissociate to a small extent into
A+& B- ions
• If, in this solution, we add a strong electrolyte CB, it will dissociate into C+ & B- ions.
• So both the electrolytes will give B- which is called the common ion effect.
A+ + B- (POORLY DISSOCIATED)
AB
C+ + B- (STRONGLY DISSOCIATED)
CB
• The effect of addition of CB to solution of AB will thus increase the conc. of B- ions.
Dr. Puspendra Kumar
• This will push equilibrium to backward direction as per the law of mass action
AB A+ + B-
• So, that the poor dissociation of AB will further decrease.
• Thus, when to a solution of a weak electrolyte a strong electrolyte with common ion is
added, the dissociation of the weak electrolyte is suppressed, this is known as the
common ion effect.
IONIC PRODUCT OF WATER

• Water is auto ionized into H3O+(aq) and OH-(aq) ions although to a very small extent.
• The Equilibrium constant for this reaction ‘Kw’ is called the ionic product for water
Kw= [H3O+]*[OH-]
At 250C Kw=1×104
For pure, neutral water
[H3O+] = [OH-]=1.0×10-7mol/litre.
• Anything added to water which raises [H3O+] above 1.0×10-7mol/ltr,causes [OH-] to
immediately drop below 1.0×10-7mol/ltr
• So keeping Kw constant at 1.0×10-14mol/litre.
Reaction with Strong Acid and Bases
Strong acid react completely with water to form [H3O+]
e.g.:- HCl + H2O H3O+ + Cl-
(ACID 1) (BASE 2) (ACID 2) (BASE 2)
Strong bases also completely react with watre and form [OH-].
e.g:- H2O + H- H2 + OH-
(ACID 1) (BASE 2) (ACID 2) (BASE 2)
Calculating conc. of H+ and OH- in solutions of strong acids & bases

i.e. 0.50 mol HCL dissolved in 1.0 litre H2O, then [H3O]=0.50 mol/litre
pH=-log10[H3O+]
In Neutral solution pH=7.0
In Acidic solution pH<7.0
In Basic solution pH>7.0
From Ionic product for water
Dr. Puspendra Kumar
pKw = pH + pOH
so, pH + pOH = 14.0
pH
pH is a numeric scale used to specify the acidity or alkalinity of an aqueous solution. It is the
negative of the logarithm to base 10 of the activity of the hydrogen ion. Solutions with a pH less
than 7 are acidic and solutions with a pH greater than 7 are alkaline or basic. Pure water has a pH
of 7 and is neutral being neither acid nor alkaline.
The pH scale is traceable to a set of standard solutions whose pH is established by international
agreement. Primary pH standard values are determined using a concentration
conce cell with
transference, by measuring the potential difference between a hydrogen electrode and a standard
electrode such as the silver chloride electrode. The pH of aqueous solutions can be measured
with a glass electrode and a pH meter, or indica
indicator.
pH is defined as the decimal logarithm of the reciprocal of the hydrogen ion activity, aH+, in a
solution
pH indicators
Indicators may be used to measure pH, by making use of the fact that their color changes with
pH. Visual comparison of the color of a test solution with a standard color chart provides a
means to measure pH accurate to the nearest whole number. More precise measurements are
possible if the color is measured spectrophotometrically, using a colorimeter of
spectrophotometer. Universal indicator consists of a mixture of indicators such that there is a
continuous color change from about pH 2 to pH 10. Universal indicator paper is made from
absorbent paper that has been impregnated with universal indicator.
pOH
pOH is sometimes used as a measure of the concentration of hydroxide ions, OH−, or alkalinity.
pOH values are derived from pH measurements. The concentration of hydroxide ions in water is
related to the concentration of hydrogen ions by
where KW is the self-ionisation

ionisation constant of water.
Taking logarithms
Dr. Puspendra Kumar
Relation between pOH and pH.
pH in living systems
S. No. Compartment pH
1. Gastric acid 1
2. Lysosomes 4.5
3. Granules of chromaffin cells 5.5
4. Human skin 5.5
5. Urine 6.0
6. Pure H2O at 37 °C 6.81
7. Human Eye 7.0-7.4
7.4
8. Cytosol 7.2
9. Cerebrospinal fluid (CSF) 7.5
10. Blood 7.34––7.45
11. Mitochondrial matrix 7.5
12. Pancreas secretions 8.1
HYDROLYSIS OF SALTS
A salt is formed between the reaction of an acid and a base. Usually, a neutral salt is formed
when a strong acid and a strong base is neutralized in the reaction:
H+ + OH- = H2O
Most neutral salts consist of cations and anions. These ions have little tendency to react with
water. Thus, salts consisting of these ions are neutral salts. For example: NaCl, KNO3, CaBr2,
CsClO4 are neutral salts.
Cations of the neutral salts: Na+, K+, Rb+, Cs+, Mg+, Ca+, Sr+, Ba+
Anions of the neutral salts: Cl-, Br-, I-, ClO4-, BrO4-, ClO3-, NO3-
When weak acids and bases react, the relative strength of the conjugated acid-base
acid pair in the salt
determines the pH of its solutions. The salt, or its solution, so formed can be acidic, neutral or
basic. A salt formed between a strong acid and a weak base is an acid salt,
salt for example NH4Cl.
A salt formed between a weak acid and a strong base is a basic salt,, for example NaCH3COO.
Dr. Puspendra Kumar
Hydrolysis of Acidic Salts

A salt formed between a strong acid and a weak base is an acid salt. Ammonia is a weak base,
and its salt with any strong acid gives a solution with a pH lower than 7. For example, let us
consider the reaction:
HCl + NH4OH = NH4+ + Cl- + H2O
In the solution, the NH4+ ion reacts with water (called hydrolysis) according to the equation:
NH4+ + H2O = NH3 + H3O+.
The acidity constant can be derived from Kw and Kb.
[H3O+] [NH3] [OH-]
Ka = ------------------------------
[NH4+][OH-]
= Kw / Kb
Hydrolysis of Basic Salts
A basic salt is formed between a weak acid and a strong base. The basicity is due to the
hydrolysis of the conjugate base of the (weak) acid used in the neutralization reaction. For
example, sodium acetate formed between the weak acetic acid and the strong base NaOH is a
basic salt. When the salt is dissolved, ionization takes place:
NaAc = Na+ + Ac-
In the presence of water, Ac- undergo hydrolysis:
H2O + Ac- = HAc + OH-
And the equilibrium constant for this reaction is Kb of the conjugate base Ac- of the acid
HAc. Note the following equilibrium constants:
[HAc] [OH-]
Kb = ------------------
[Ac-]
[HAc] [OH-] [H+]

Kb = -------------- ----
[Ac-] [H+]
[HAc] [OH-] [H+]

Kb = ------------------
[Ac-] [H+]
Kb = Kw / Ka
Dr. Puspendra Kumar
Thus,
Ka Kb = Kw
or
pKa + pKb = 14 for a conjugate acid-base pair.
HENDERSON HESSELBACH EQUATION

Consider the ionization of a weak acid HA which has some pKa. It is often convenient to be
able to relate the pH of a solution of a weak acid to the pKa of the acid and the extent of
ionization. The reaction would be
HA (reversible arrows) H+ + A-
The acid dissociation constant (Ka) for this reaction would be given by the equation
This equation can be rearranged to isolate the hydrogen ion concentration on the left,
because, remember, we want an equation relating the pH of the solution to the pKa and
the extent of ionization of the weak acid. The rearranged form of the equation is
By definition, log 1/ [H+] = pH , and log 1/Ka = pKa , so that by taking the log of the equation
above, we get the equation
This is the well-known Henderson-Hasselbalch equation that is often used to perform the
calculations required in preparation of buffers for use in the laboratory, or other
applications. Notice several interesting facts about this equation.
• First, if the pH = pKa, the log of the ratio of dissociate acid and associated acid will be
zero, so the concentrations of the two species will be the same. In other words, when the
pH equals the pKa, the acid will be half dissociated.
Dr. Puspendra Kumar
• Second, notice that as the pH increases or decreases by one unit relative to the pKa, the
ratio of the dissociate form to the associated form of the acid changes by factors of 10.
That is, if the pH of a solution is 6 and the pKa is 7, the ratio of [ A-]/[ HA] will be 0.1,
will if the pH were 5, the ratio would be 0.01 and if the pH were 7, the ratio would be 1.
• Also, note that if the pH is below the pKa, the ratio will be < 1, while if the pH is above
the pKa, the ratio will be >1. In short, there is a lot of information in the Henderson-
Hasselbalch equation. You would be wise to study this equation to understand its various
ramifications.
BUFFER SOLUTIONS
Buffers are solutions that by definition resist a change in pH when a small amount of acid, base
or water is added to it.
An acidic buffer solution can be made by mixing a weak acid with the salt of its conjugate base.
For example, acetic acid with sodium ethanoate.would make a buffer solution with a pH of less
than 7. The way this is usually done is to take a solution of acetic (ethanoic acid) and add sodium
hydroxide as a limiting reagent to it. Once all the sodium hydroxide has reacted with the acid,
some acid will be left along with the salt, sodium ethanoate.
NaOH + CH3COOH → NaCH3COO(aq) +H2O +CH3COOH
(excess) (left over)
The solution acts a buffer like this. The acid is weakly dissociated but the salt is fully dissociated
so there is a lot of ethanoate in solution.
NaCH3COO(aq) → Na+ + CH3COO-
CH3COOH → CH3COO- + H+
If a small amount of acid is added the extra H+ initially decreases the pH but then combines with
acetate shifting the second equilibrium to the left so the concentration of H+ remains unchanged.
If a small amount of base is added the pH initially increases but then the OH- ions react with the
H+ ions to make water and the acid dissociates more anion and once again the concentration of
H+ remains constant.
OH- + H+ → H2O, then
-
CH3COOH → CH3COO + H+
Dr. Puspendra Kumar
A basic buffer solution can be made by mixing a weak base with the salt of its conjugate acid.
For example, ammonia with ammonium chloride would make a buffer solution with a pH of
more than 7. You could also add HCl as a limiting reagent to a solution of ammonia so both
ammonia and ammonium ion are present in the solution.
NH4Cl → NH4+ + Cl-
NH3 + H2O → NH4+ + OH-
If a small amount of H+ ions are added the pH initially decreases and then the weak base,
ammonia, reacts with the H+ and causing the pH to increase to its original value.
NH3 + H+ → NH4+
If a small amount of base is added the pH initially increases and then
OH- + H+ → H2O,
Water is formed and then NH4+ dissociates to form more H+ ions restoring the solution to its
original pH.
Blood is an example of a buffered solution. The bicarbonate ion plays a very important role in
maintaining blood pH. The transport of oxygen in the blood is very pH dependent.
HHb+ + O2 → H+ + HbO2
This binding produces hydrogen ions making the process pH sensitive.
CO2(aq) + H2O(l) → H2CO3(aq) → H+(aq) + HCO3-(aq)
Carbon dioxide produced in cellular respiration produces carbonic acid in the blood stream.
Hemoglobin is a protein with basicity that can accept the protons being produced. The pH of the
blood must be maintained between 7.35 and 7.45 to allow proper cellular function.
Calculations
The H+ concentration and thus the pH can be calculated from the Ka expression of the weak acid.
Ka =
[H ][A ]
+ −
rearrange to [H ] = K[A[HA] ]
+ a
[HA] −
We can take the – log of this equation to get

pH = pKa-log [HA]/[A], the Henderson Hasselbach equation
In using this equation it is assumed that the acid is essentially undissociated and that all the base
(A-) comes from the dissolved salt.
Dr. Puspendra Kumar
The pH of the solution then depends the ratio of the concentrations not their actual amounts. A
diluted buffer will still have the same pH but not have the ability to absorb as much excess acid
or base as a buffer made with more concentrated solution.
The optimum situation for a buffer solution is one in which the concentrations of acid and
conjugate base are equal. In this situation pH = pKa. A buffer will work well however if there
are reasonable amounts of acid and base (within a 10:1) ratio so in a range pH = pKa +/- 1
A similar calculation can be done with basic solutions in which case the final result is:
pOH = pKb + log [salt]/[base]; Then(convert to pH in the usual manner)

Example
Solid sodium acetate (ethanoate) is added to 0.200 M acetic acid until its concentration reaches
0.050 M. Given that the Ka = 1.74x10-5 for acetic acid, calculate the pH of the buffer solution.
(Assume no volume change.)
Solution: [H ] = K[A[HA] ] .
+ a
−
= (1.74 x 10-5 x 0.200M)/0.0500M

= 6.96 x 10-5 M
So, pH = 4.157
Alternatively, using the logarithmic form of the equation the problem can be solved.
pH = pKa - log [HA]/[A-]
= -log(1.74 x 10-5 )–(log 0.200/0.0500)
= 4.760–0.602
= 4.158
Dr. Puspendra Kumar
NEUTRALIZATION CURVES
Definitions
1- Strong acid or Base.
A strong acid is completely dissociated into its component ions in dilute aqueous
solution. Strong base are also completely dissociated into it components ions.
Eg: HCL, NaOH, KOH etc.
2- Weak acid.
A weak acid is one which is incompletely dissociated. The extent to which it dissociates
is characterized by Ka.
3- Weak base.
Weak base does not ioni ed fully in an aqueous solution the extent of dissociation of
dissociates is characterized by Kb.
4- Buffer solution.
It is a solution of substance or a mixture of substances which helps in maintaining and
establishing pH
Neutralization curves
• If we study the changes in the hydrogen ion conc. during the course of titration we get a
clear idea about the mechanism of neutralization process.
• The pH value of greatest importance is the one near the equivalence point as it helps us in
selecting an indicator which will give the smallest titration error.
• The curve obtained by plotting pH as ordinate against the percentage of acid remaining
during titration is known as neutralization curve or more generally titration curve.
Dr. Puspendra Kumar
1 STRONG ACID- STRONG BASE TITRATION.

When a strong acid and a strong base are mixed together, as in titration one by other,
the reaction can be represented as
H+ + OH- H2O
Since,
• It is reverse of ionization of water.
• The calculation of titration curve is illustrated as consider titration of 100ml 1N HCL
with 1N NaOH The pH before titration commences is pH of 1N HCl.
Therefore,
(H+) = 1N or pH=0
After adding 1ml of titrant, the volume becomes 101 ml and it contains.
(100-1) = 99ml equivalent of acid in 101 ml or 99/101 eq/litre.
[H+]= 99/101
So,
pH = -log(99/101)
pH = log(101/99) = log 1.020
pH = 0.0086
After addition of 50 ml titrant
(H+)= 50/150
pH = log (150/50)
pH = 0.4771
(H+) = 25/175
pH= 0.8451.
(H+) = 10/190
pH= 1.2787
(H+) = 1/199
pH= 2.2788
Dr. Puspendra Kumar
After addition of 99.9 ml titrant

(H+) = 0.1/199.9
pH= 3.3008
After addition of 100 ml titrant, the pH will change sharply to 7 (equivalence point)
Then after addition of 101 ml of titrant
[OH-] = 1/201
pOH = log (201/1)
pOH = 2.3032
pH = 14 – pOH
pH= 14 – 2.3032
pH = 11.6968
As the titration proceeds the pH rises slowly, but near the equivalence point the change in pH is
very sharp 3.3 (or 2.2988) to 7.0.
So, with 1N Solution; any indicator which is effective in pH range 3 to 10.5 may be used.
Example: Phenolphthalein, Methyl orange, Methyl red, Bromothymol blue, Phenol red.
Dr. Puspendra Kumar
2. WEAK ACID WITH A STRONG BASE TITRATION.

This type of titration may be represented as
HA + OH = H2O + A
HA represents a weak acid that why it is written in the un-dissociated form.
There are 3 important differences between this titration and that between a strong acid
and a strong base.
(a) The (H+) is small at the start of the titration (but pH will be greater)
In 0.1 HCl (H+) = 0.1and pH=1.0.
In 0.1N CH3COOH (H+) = 1.34 x 10-3 and pH=3.127
Because CH3COOH is a week acid and is poorly dissociated, hence it gives smaller
concentration of H+ ions.
(b) As alkali solution is added to the weak acid the salt formed produces common ion effect,
so that the dissociation of the weak acid is suppressed.
Eg: When NaOH is added to CH3COOH there is a formation of salt and the following
equilibria exist.
CH3COOH H+ +CH3COO- (Poorly dissociated)
CH3COONa Na+ + CH3COO- (Strongly dissociated)
Common Ion
The dissociation of CH3COOH is thus suppressed so the (H+) ion concentration is further
decreased or pH of the solution is greater than that observed in the titration of HCl with
NaOH.
(c) In the titration of HCl with NaOH , pH at equivalence point is 7, but If a weak acid like
CH3COOH is taken pH at completion of titration is more than 7.
This is due to the hydrolysis of the salt formed.
CH3COONa + H20 CH3COOH + Na+ + OH-
Due to the hydrolysis, OH- is greater than H+ in the solution is alkaline (Basic)
i.e. its pH is greater than 7
The pH at the equivalence point can be calculated by:
pH= ½ pKw+ ½ pKa+ ½ logC -------------------------- (1)
Dr. Puspendra Kumar
If 50ml of 0.1N NaOH is added to 50ml 0.1N CH3COOH, the total volume will become
100ml and so the concentration of sodium acetate formed will be 0.05M thus,
Kw= 10-14 , So pKw=- log 10-14 pKw=14.00
-5
Ka= 1.8 X 10 , pka= 4.74
C=0.05, log C=log 0.05, So log C= 2‾.70
½ pKw=7.0,
½ pKa=2.37 and
logC= 2-.70 = 0.70-2.00 = -1.30
½ Log C = -0.65
Substituting this value in eq. (1)
pH= 7.0 + 2.37 + (-0.65)
pH=9.37-0.65
pH= 8.72
When 0.1N CH3COOH is titrated with 0.1N NaOH, at the ph at equivalence point 8.72
not 7.
The above discussion can be summarized by stating, that the.
-Initial pH is higher.
-The rate of increase of pH during the titration is greater.
-The pH at the point is equivalence higher.
Dr. Puspendra Kumar
3 WEAK BASE WITH STRONG ACID TITRATION

We can consider the titration of 0.1M & 0.1N aq. Ammonia solution with 0.1M &0.1N HCl
solution.
The reaction involved
NH4OH + HCl ----> NH4Cl + H2O
The salt NH4Cl is hydrolysis and NH4 + H2O ----> NH4OH + H+
Due to formation of H+ ion the ph at the equivalence point will be slightly on acid side as shown
by the following calculate
Suppose we titrate 50ml of 0.1M NH4OH with 0.1M HCl, the ph at the equilance point will be,
pH= ½ pKw – ½ pKb – ½ log C ------------------------- (2)
Now,
Kw= 10-14 , So pKw=- log 10-14 pKw=14.00
Kb= 1.8 X 10-5, pkb= 4.74
C=0.05, log C=log 0.05, So log C= 2‾.70
½ pKw=7.0,
½ pKb=2.37 and
Where Kb is the dissociation constant of NH4OH at the equivalence point the concentration C of
the salt will be 0.05M so,
logC= 2-.70 = 0.70-2.00 = -1.30
pH= 7.00-2.37-(-0.65)
pH = 5.28
Dr. Puspendra Kumar
(4) TITRATION OF WEAK ACID WITH WEAK BASE

Let us consider the titration of 0.1M CH3COOH with 0.1N NO4OH.
CH3COOH + NH4OH CH3COONH4 + H2O
The salt formed, CH3COONa, undergoes hydrolysis,
CH3COONH4 + H2O CH3COOH + NH4OH
The disadvantage in such titrations is that the inflection on the pH neutralization curve is very
small near the equivalence point:-
For example:
In the titration of 0.1N CH3COOH with 0.1N NH4OH the pH near the equivalence point slowly
raises to 6 to 8, with more dilute solutions the rises in pH is smaller.
It should be noted that, if the pH change at the equivalence point is smaller than 2 pH units, it is
very difficult to judge the colour change and accurate result cannot be achieved.
In this type of titration equivalence depends on the relative values of dissociation constant
If Ka=Kb then pH=7
If Ka>Kb then pH>7
If Ka<Kb then pH<7
Generally mixed indicator is used for these titrations.
Dr. Puspendra Kumar
Acid Base Indicators

“Indicators is a substance which exhibits color change at a particular stage of a chemical
reaction.”
• These are the substance which exhibits different colors at various values of pH.
• Indicators are weak acid or weak base which have different colors in their conjugate base &
acid forms.
• Most indicators are used in dilute solution form.
• For an acid base titration we select an indicator which will show a distinct color change at pH
close to the equivalence point.
Theories of Indicators
(a) Ostwald theory
(b) Resonance theory
(a) Ostwald Theory:-

- The first theory explain the behaviour of indicators was given by W. Ostwald
- According to his theory
“The undissociated indicator acid (HIn) or a base (InOH) has a color different than its ions”.
For an acid indicator equivallence can be written as
HIn H+ + In-
- In an acid solution, there is a deprression of ionization of indicator due to common ion effect.
- In alkali solution ionization increases & solution acquires of ionized form.
HIn H+ + In-
By applying law of mass action
KIna = [H+] [In-] / [HIn]
[H+] = KIna x [HIn] / [In-]
Taking log on both side
log [H+] = log KIna + log [HIn] / [In-]
Taking negative log
-log [H+] = -log KIna - log [HIn] / [In-]
Dr. Puspendra Kumar
pH = -log KIna + log [In-] / [HIn]
pH = pKIna + log [In-] / [HIn]
KIna is dissociation constant of indicator, the color of the indicator depends upon the ratio of
concentration of ionized & unionized form & hence directly proportional to pH.
The indicator should be such that the pH at equivalence pint false within the transition interval
of the indicator.
S. No. Titration Between pH at end point Commonly used indicator

1. Weak acid & strong base Alkaline Range Thymol blue,
Phenolphthein,
Thymolphthalein.
2. Strong acid & weak Base Acidic Range Methyl orange,
Methyl Red,
Bromocresol Green
Dr. Puspendra Kumar
(b)Resonance Theory:-
• All the acid base indicators, which are commonly used are organic compounds.
• The difference in color of some compound in acid & base medium is apparently due to difference
in structure of two forms.
• Color shown by the compound is associated with the capability of the compound to absorb the
visible light & this capability is related to the electronic structure.
• Change in the electronic features will result in the absorption of different color components of
light with a resultant color change.
HO OH
HO OH
OH-
OH
O
-
O COO
Colorless OH-
- -
O O O O
- -
COO COO
Pink/Red Color Pink/Red Color
The Pink/Red color in alkaline solution is due to increased possibility of resonance between various ionic
forms.
Dr. Puspendra Kumar
SOME INDICATORS WITH THEIR PH RANGE (SELECTION OF INDICATORS)

Indicators used in various titrations
1. Strong acid strong base titrations.
Eg: Methyl orange, Methyl red, Phenolphthalein Bromothymol Blue, Phenol Red.
2. Weak acid strong base titrations.
Eg: Phenolphthalein, Thymolphthalin, Thymol Blue.
3. Strong acid weak base titrations
Eg: Methyl orange, Methyl red, bromophenol, Bromocresol green.
4. Weak acid weak base titrations
Eg: Mixed Indicators.
S. No. Indicators name pH range Acid Alkaline
1. Methyl Orange 3.1 - 4.4 Red Orange
2. Thymol Blue 1.2 - 2.8 Blue Yellow
3. Bromophenol blue 3.0 - 4.6 Yellow Blue
4. Bromocresol Green 3.8 - 5.4 Yellow Blue
5. Methyl Red 4.2 - 6.3 Red Yellow
6. Phenol Red 6.8 - 8.4 Yellow Red
7. Phenolpthalein 8.3 - 11.0 Colorless Pink/Red
According to the type of titration, we choose the appropriate indicator which gives color change at defined pH
range.
Dr. Puspendra Kumar
MIXED INDICATORS
• In some cases, the pH range is very narrow and the color change over this range must be very
sharp.
• With ordinary acid base indicators, the color change is not sharp and abrupt, but it extends over 2
units of pH. However, sometimes, it is desirable to have sharp color change over a narrow and
selected range of pH. This can be achieved by the use of mixture of indicators whose pKind values
are close together and the overlapping colors are complementary at an intermediate pH value.
• This is not easily possible with ordinary acid base indicators.
• Result may be achieved by the use of the suitable mixture of indicators.
• These are generally selected, so that there pKIn values are closed together & overlapping colors
are complimentary at an intermediate pH value.
• Example:- A mixture of equal parts of neutral red(0.1% solution in alcohol) & methylene blue
(0.1% in alcohol) gives a sharp colour change from violet blue to green in passing from acid to
alkaline solution at pH 7.
• Color-change indicator for acid-base titration end points in which a mixture of two indicator
substances is used to give sharper end-point color changes.
POLYPROTIC SYSTEM
• Acid or bases that can donate or accept more than one proton.
• Proteins are the common example of a polyprotic system.
+NH3
-
O R
The name "polyprotic" literally means many protons. Therefore, observing some specific acids and
bases which either lose or accept more than one proton. Then, the equations used in finding the degree
of dissociation. Finally, with given examples, we will be able to approach problems dealing with
polyprotic acids and bases.
Polyprotic acids are specific acids that are capable of losing more than a single proton per molecule in
acid-base reactions. (In other words, acids that have more than one ionizable H+ atom per molecule).
Dr. Puspendra Kumar
Protons are lost through several stages (one at each stage), with the first proton being the fastest and
most easily lost. Contrast with monoprotic acids in section Monoprotic Versus Polyprotic Acids And
Bases.
POLYAMINE SYSTEM
A polyamine is an organic compound having two or more primary amino groups –NH2.
This class of compounds includes several synthetic substances that are important feedstocks for
the chemical industry, such as ethylene diamine H2N–CH2–CH2–NH2, 1,3-diaminopropane H2N–
(CH2)3–NH2, and hexamethylenediamine H2N–(CH2)6–NH2.
It also includes many substances that play important roles in both eukaryotic and prokaryotic
cells, such as putrescine H2N–(CH2)4–NH2, cadaverine H2N–(CH2)5–NH2, spermidine H2N–
(CH2)4–NH–(CH2)3–NH2, and spermine H2N–(CH2)3–NH–(CH2)4–NH–(CH2)3–NH2.
Piperazine is an example of a cyclic polyamine. Cyclen and cyclam are examples of macrocyclic
polyamines. Polyethylene amine is a polymer based on aziridine monomer.
AMINO ACID TITRATIONS

Amino acids playing an integral role in the structure and function of proteins, amino acids are
perhaps one of the most important biomolecules as proteins themselves participate in nearly
every physiological event within a cell. In order to understand the acid-base properties of
Dr. Puspendra Kumar
proteins and their resulting behavior as polyionic macromolecules, we will begin by

investigating the properties of their constituent amino acids. With each containing at least one
amino and carboxylic acid group, amino acids are classified as amphoteric substances and react
with both acids and bases as follows:
The ionic form of the amino acid present in an aqueous solution is dependent upon the solution’s
pH. In titration of amino acid; identification of an unknown amino acid via an acid-base titration.
Titration curves of amino acids are very useful for identification. i.e. Titration of glycine given
below.
Simple amino acids, like glycine, have two dissociation steps: (1) the loss of H+ from the acidic
carboxyl group at low pH; and (2) the loss of H+ from the more basic amino group at high pH.
The pKa value for each dissociable group of an amino acid can be determined from such a
titration curve by extrapolating the midpoint of each buffering region (the plateau) within the
curve. Also revealed from the diagram is a point on the curve where the amino acid behaves as a
Dr. Puspendra Kumar
neutral salt. Specifically, this point is known as the isoelectric point (pI), and is loosely defined
as the pH where the amino acid is predominantly a zwitterion. Furthermore, the pI can be
approximated as halfway between the two points of strongest buffering capacity and can be
estimated by:
Where K1 and K2 are the dissociation constants for the deprotonation of glycine’s carboxylic acid
and amino groups.

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ACID BASE TITRATION

1. ARRHENIUS THEORY (H+ & OH-)

2. BRONSTED-LOWRY THEORY (Taking and giving protons)

• Dielectric constant for some solvents.

RELATIVE STRENGTH OF ACID AND BASES

• This expression is strictly valid for the extremely dilute solutions.

LAW OF MASS ACTION

• [A], [B], [C], [D] = Molar concentration of A, B, C and D respectively.

COMMON ION EFFECT

IONIC PRODUCT OF WATER

Calculating conc. of H+ and OH- in solutions of strong acids & bases

where KW is the self-ionisation

Relation between pOH and pH.

Hydrolysis of Acidic Salts

[HAc] [OH-] [H+]

[HAc] [OH-] [H+]

HENDERSON HESSELBACH EQUATION

We can take the – log of this equation to get

pOH = pKb + log [salt]/[base]; Then(convert to pH in the usual manner)

= (1.74 x 10-5 x 0.200M)/0.0500M

1 STRONG ACID- STRONG BASE TITRATION.

After addition of 99.9 ml titrant

2. WEAK ACID WITH A STRONG BASE TITRATION.

3 WEAK BASE WITH STRONG ACID TITRATION

(4) TITRATION OF WEAK ACID WITH WEAK BASE

Acid Base Indicators

(a) Ostwald Theory:-

pH = -log KIna + log [In-] / [HIn]

pH = pKIna + log [In-] / [HIn]

S. No. Titration Between pH at end point Commonly used indicator

Pink/Red Color Pink/Red Color

SOME INDICATORS WITH THEIR PH RANGE (SELECTION OF INDICATORS)

S. No. Indicators name pH range Acid Alkaline

1. Methyl Orange 3.1 - 4.4 Red Orange

2. Thymol Blue 1.2 - 2.8 Blue Yellow

3. Bromophenol blue 3.0 - 4.6 Yellow Blue

4. Bromocresol Green 3.8 - 5.4 Yellow Blue

5. Methyl Red 4.2 - 6.3 Red Yellow

6. Phenol Red 6.8 - 8.4 Yellow Red

7. Phenolpthalein 8.3 - 11.0 Colorless Pink/Red

AMINO ACID TITRATIONS

proteins and their resulting behavior as polyionic macromolecules, we will begin by

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