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Theories of acid base indicators

  • Acid-base indicators are substances that change color depending on the pH of the solution they are in.

  • They are typically weak organic acids or bases that exhibit different colors in their protonated and deprotonated forms.

  • These indicators are crucial in titrations as they help signal the endpoint of the reaction by undergoing a visible color change.

There are two main theories that explain the behavior of acid-base indicators:

 illustrating acid-base titration, with clear color changes of the solution as the reaction progresses
illustrating acid-base titration, with clear color changes of the solution as the reaction progresses

1) Ostwald Theory (Ionization Theory)

  • The Ostwald theory explains the behavior of acid-base indicators based on the ionization equilibrium of weak acids or bases.

  • According to this theory:

    • Ionization Equilibrium: In the presence of a base, a weak acidic indicator (HIn) can lose a proton (H⁺) to form its conjugate base (In⁻).

HIn ↔ H+ + In-

  • Color Change: Both the protonated form (HIn) and the deprotonated form (In⁻) have different colors due to differences in their electronic structures.

  • pH Dependence: The equilibrium shifts based on the pH of the solution, causing a color change as the concentration of H⁺ ions changes.

Example:

Phenolphthalein:

  • Ionization Equilibrium:

HIn (colorless) ↔ H+ + In- (pink)

  • Behavior:

    • In acidic solutions, the equilibrium favors the colorless protonated form (HIn).

    • In basic solutions, the equilibrium shifts towards the pink deprotonated form (In⁻).

Methyl Orange:

  • Ionization Equilibrium:

HIn (red) ↔ H+ + In- (yellow)

  • Behavior:

  • In acidic solutions, the equilibrium favors the red protonated form (HIn).

  • In basic solutions, the equilibrium shifts towards the yellow deprotonated form (In⁻).

2) Quinonoid Theory (Resonance or Quasi-Valence Theory)

  • The quinonoid theory, also known as the resonance (quasi-valence) theory, explains the color change of indicators based on the resonance structures and electron distribution in the molecules.

  • According to this theory:

    • Resonance Structures: Indicators can exist in two tautomeric forms—benzenoid and quinonoid structures—which have different colors.

    • Electron Distribution: Gaining or losing a proton changes the electron distribution, altering the absorption of light in the visible spectrum and thus the color.

    • Color Dependence: The color of the indicator is determined by the predominant resonance structure at a given pH.

Example:

Phenolphthalein:

  • Structural Change:

    • In acidic solutions, phenolphthalein exists in its colorless lactone (benzenoid) form.

    • In basic solutions, it loses a proton to form a pink-colored quinonoid structure.

  • Color Change Mechanism: The shift from the lactone form to the quinonoid form changes the electron delocalization, resulting in a color change.

Methyl Orange:

  • Structural Change:

    • In acidic conditions, methyl orange exists in a red-colored benzenoid form.

    • In alkaline conditions, it shifts to a yellow-colored quinonoid form.

  • Color Change Mechanism: The change in resonance structures alters the wavelengths of light absorbed, leading to a visible color change.


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