Najam A.
Qureshi Acid-base Titration
ACID–BASE TITRATIONS
(Neutralization titrations)
Introduction and Historical Development
Acid–base titrations, also known as neutralization titrations, are among the most fundamental
techniques in analytical chemistry for determining the concentration of acidic or basic substances.
The development of acid–base theory has evolved over time through significant scientific
contributions. In 1887, Arrhenius established that acids produce hydrogen ions (H⁺) upon
ionization in aqueous solutions. This concept was experimentally supported by Ostwald, who
measured hydrogen ion concentration electrically. Later, in 1908, Henderson introduced an
equation based on the law of mass action to calculate hydrogen ion concentration. In 1909,
Sørensen proposed the concept of pH as a convenient way to express acidity, and in 1916,
Hasselbalch modified Henderson’s equation into its logarithmic form, now known as the
Henderson–Hasselbalch equation. Finally, in 1923, Brønsted and Lowry expanded the definition
of acids and bases by introducing the proton transfer concept, which remains highly relevant in
modern titrimetry.
Acid–Base Concepts
Arrhenius Concept
According to the Arrhenius theory, acids are substances that produce hydrogen ions (H⁺) in
aqueous solution, while bases produce hydroxide ions (OH⁻). For example, hydrochloric acid
dissociates into hydrogen and chloride ions, whereas sodium hydroxide dissociates into sodium
and hydroxide ions. This concept explains many observable properties of acids and bases, such as
sour taste and the ability of acids to turn blue litmus paper red, while bases taste bitter and turn red
litmus paper blue. However, this theory is limited to aqueous solutions and cannot explain acid–
base behavior in non-aqueous systems.
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Najam A. Qureshi Acid-base Titration
Brønsted–Lowry Concept
The Brønsted–Lowry theory broadened the concept by defining acids as proton donors and bases
as proton acceptors, regardless of the solvent. For instance, in the reaction between hydrochloric
acid and ammonia, HCl donates a proton to ammonia, forming ammonium ion. This concept
introduces the idea of conjugate acid–base pairs and explains the behavior of substances like water,
which can act as both an acid and a base (amphoteric nature). This theory is more versatile and
applicable in both aqueous and non-aqueous systems.
Lewis Concept
The Lewis concept further extends acid–base definitions by focusing on electron pairs. According
to this theory, a Lewis acid is an electron pair acceptor, while a Lewis base is an electron pair
donor. For example, boron trifluoride (BF₃) acts as a Lewis acid by accepting an electron pair from
ammonia (NH₃), which acts as a Lewis base. This concept is particularly useful in explaining
complex formation reactions and is widely applied in coordination chemistry.
Role of the Solvent
The Arrhenius concept is limited to aqueous systems, so the solvent system theory was introduced
to explain acid–base behavior in different solvents. According to this theory, solvents undergo
auto-ionization to produce positive ions (solvonium ions) and negative ions (solvate ions). For
example, water produces H₃O⁺ and OH⁻ ions. In this context, an acid is defined as a substance that
increases the concentration of solvonium ions, whereas a base increases the concentration of
solvate ions. This concept explains why a substance may behave differently in different solvents.
1. NH4NO3 is a strong acid because it increases the NH4+ ions.
2. KNH2 is a strong base because it increases the NH2- ions.
3. HClO4 is a strong acid in water.
Strength of Acids and Bases
The strength of acids and bases is determined by their degree of ionization and is expressed using
dissociation constants. The ionic product of water is given by pKw, which equals 14 at room
temperature. The strength of an acid is represented by pKa, while the strength of a base is
represented by pKb. A lower pKa value indicates a stronger acid, while a lower pKb indicates a
stronger base. Strong acids such as hydrochloric acid completely dissociate in water, whereas weak
acids like acetic acid only partially dissociate. Similarly, strong bases like sodium hydroxide fully
ionize, while weak bases like ammonia do not.
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Najam A. Qureshi Acid-base Titration
Type Category pKa / pKb Range Examples
Acids Very Strong Acids pKa < 0 HClO₄, HI, HCl
Strong Acids pKa < 4.5 HF, H₃PO₄, HSO₄⁻
Weak Acids pKa < 9.5 CH₃COOH, HCN
Very Weak Acids pKa > 9.5 Phenol, HPO₄²⁻
Bases Strong Bases pKb < 4.5 NaOH
Weak Bases pKb < 9.5 Ammonia (NH₃)
Very Weak Bases pKb > 9.5 Acetamide, Urea
Law of Mass Action
The law of mass action states that the rate of a chemical reaction is proportional to the product of
the concentrations of the reactants. At equilibrium, this leads to the formation of an equilibrium
constant expression. In acid–base titrations, this law is used to derive expressions for dissociation
constants such as Ka and Kb. These constants are essential for understanding the behavior of weak
acids and bases during titration and for calculating pH at different stages.
Solubility Product and Common Ion Effect
In reactions involving sparingly soluble salts, the solubility product constant (Ksp) plays an
important role. It represents the product of the concentrations of ions in a saturated solution. The
addition of a common ion shifts the equilibrium and reduces solubility, leading to precipitation.
This phenomenon, known as the common ion effect, is important in precipitation titrations and
also influences acid–base equilibria.
Hydrolysis of Salts
Hydrolysis refers to the reaction of a salt with water to produce an acidic or basic solution. Salts
formed from strong acids and strong bases are neutral, while salts from strong acids and weak
bases produce acidic solutions. Conversely, salts from weak acids and strong bases produce basic
solutions. This concept is important in predicting the pH of solutions at the equivalence point
during titration.
Buffer Solutions
Buffer solutions are systems that resist changes in pH upon the addition of small amounts of acid
or base. They consist of a weak acid and its conjugate base or a weak base and its conjugate acid.
Buffers are essential in maintaining constant pH in biological systems, such as blood, and in
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Najam A. Qureshi Acid-base Titration
pharmaceutical formulations. The effectiveness of a buffer is described by its buffer capacity,
which increases with concentration.
Henderson–Hasselbalch Equation
The Henderson–Hasselbalch equation provides a mathematical relationship between pH, pKa, and
the ratio of conjugate base to acid. It is widely used to calculate the pH of buffer solutions. This
equation is derived from the acid dissociation constant and allows for easy estimation of pH
without complex calculations, making it highly useful in titration analysis.
Types of Acid–Base Titrations and Titration Curves
Acid–base titrations can be classified into four main types based on the strength of acids and bases
involved. In strong acid–strong base titrations, the pH changes sharply at the equivalence point,
which occurs at pH 7. In weak base–strong acid titrations, the equivalence point occurs at a pH
less than 7 due to the formation of an acidic salt. In weak acid–strong base titrations, the
equivalence point lies above pH 7 due to the formation of a basic salt. In weak acid–weak base
titrations, the pH change is gradual and no sharp endpoint is observed, making indicator selection
difficult. These titration curves are essential for understanding the behavior of different systems.
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Najam A. Qureshi Acid-base Titration
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Najam A. Qureshi Acid-base Titration
Indicators in Acid–Base Titrations
Indicators are weak organic acids or bases that change color depending on the pH of the solution.
They are used to visually detect the endpoint of a titration. The color change occurs due to a shift
in equilibrium between different ionic forms of the indicator. Common indicators include
phenolphthalein, which is colorless in acidic medium and pink in basic medium, and methyl
orange, which changes from red to yellow. The choice of indicator depends on the pH range of the
equivalence point.
Indicator Colour in Acid Colour in Base
Thymol blue Red Yellow
Methyl orange Red Orange
Methyl yellow Red Yellow
Bromo phenol blue Yellow Blue
Bromo cresol green Yellow Blue
Methyl red Red Yellow
Phenol red Yellow Red
Applications in Pharmaceutical Analysis
Acid–base titrations are widely used in pharmaceutical analysis for the quantitative determination
of drugs and chemicals. They are employed in the assay of compounds such as barbiturates, aspirin,
benzoic acid, and nicotinic acid. These titrations are also used for amino acid analysis,
determination of iodates, and quality control of pharmaceutical formulations. Their simplicity,
accuracy, and cost-effectiveness make them indispensable in laboratory practice.
Acid–base titrations form the backbone of volumetric analysis and are essential tools in
pharmaceutical chemistry. Their theoretical foundation, based on multiple acid–base concepts and
equilibrium principles, allows for precise quantitative analysis. Understanding these principles,
along with proper selection of indicators and conditions, ensures accurate and reliable results in
both academic and industrial applications.