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    ElectroChemistry SG BTechClass II

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    Sania Reang

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    © All Rights Reserved
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    ElectroChemistry SG BTechClass II

    Uploaded by

    Sania Reang
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    ElectroChemistry SG BTechClass II (1)

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    3 views17 pages

    ElectroChemistry SG BTechClass II

    Uploaded by

    Sania Reang

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    © All Rights Reserved
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    ELECTROCHEMISTRY:-

    Concept of pH and pOH, buffer solutions, solubility product, common ion effect

    conductance of solutions- specific, molar and equivalent conductance,

    variation of molar conductance with dilution for strong and weak electrolytes;

    Kohlrausch’s law of independent migration of ions, Ostwald’s dilution law;

    Nernst equation for single electrode.

    Numericals (on pH and pOH, buffer solutions, solubility product).

    Dr. Susanta Ghanta, Department of Chemistry, NIT


    Agartala, India
    pH and pOH denote the negative log of the concentration of hydrogen or
    hydroxide ions.

    High pH means that a solution is basic while high pOH means that a solution
    is acidic.

    So here the basic definition of pH is that it's equal to negative log


    base 10 of the concentration of protons in your solution.
    A buffer solution is an aqueous solution consisting of a mixture of a weak acid and its conjugate base, or vice versa.
    Its pH changes very little when a small amount of strong acid or base is added to it. Buffer solutions are used as a
    means of keeping pH at a nearly constant value in a wide variety of chemical applications.
    In nature, there are many systems that use buffering for pH regulation.
    For example, the bicarbonate buffering system is used to regulate the pH of blood.

    Buffer solutions achieve their resistance to pH change because of the presence of an


    equilibrium between the weak acid HA and its conjugate base A−:

    HA ⇌ H+ + A− H+ + A−
    When some strong acid is added to an equilibrium mixture of the weak acid and its conjugate base,
    hydrogen ions (H+) are added, and the equilibrium is shifted to the left, in accordance with Le
    Châtelier's principle. Because of this, the hydrogen ion concentration increases by less than the amount
    expected for the quantity of strong acid added.

    Similarly, if strong alkali is added to the mixture, the hydrogen ion concentration decreases by less
    than the amount expected for the quantity of alkali added.
    Dr. Susanta Ghanta, Department of Chemistry, NIT
    Equation of Henderson-Hasselbalch

    The Henderson-Hasselbalch equation can be written as:

    pH = pKa + log10 ([A–]/[HA])

    Where [A–] denotes the molar concentration of the conjugate base (of the acid) and [HA] denotes the molar
    concentration of the weak acid.

    Therefore, the Henderson-Hasselbalch equation can also be written as:

    pOH = pKb + log ([Conjugate acid or Salt]/[Base]).


    Derivation of the Henderson-Hasselbalch Equation

    The ionization constants of strong acids and strong bases can be easily calculated with the help of direct
    methods.

    However, the same methods cannot be used with weak acids and bases since the extent of ionization of
    these acids and bases is very low (weak acids and bases hardly ionize).

    Therefore, in order to approximate the pH of these types of solutions, the Henderson-Hasselbalch Equation
    is used.
    Let us take an example of ionization of weak acid HA: HA + H2O ‗ H+ + A-

    Acid dissociation constant, K a can be given as: Ka = [H +] [A-]/[HA]

    Taking, negative log of RHS and LHS: -logKa = -log([H +] [A-]/[HA]) or -logKa = -log([H+]) -log([A-]/[HA])

    As we know, -log([H+]) = pH and -logKa = pKa

    The equation above can also be written as, pKa = pH - log([A-]/[HA])

    Rearranging the equation, pH = pKa + log([A-]/[HA])

    The above equation is known as Henderson-Hasselbalch equation, popularly known as Henderson equation.

    It is very useful for estimating the pH of a buffer solution and finding the equilibrium pH in acid-base reactions. From the
    equation, we can infer when

    pH = pKa then log([A-]/[HA])=0 or [A-] = [HA]

    Thus pH = pKa when the concentration of both the species are same or in other words, acid will be half dissociated.

    Similarly, for a weak base B: B + H2O = OH- + HB+

    pOH = pKb + log([BH+]/[B])


    Dr. Susanta Ghanta, Department of Chemistry, NIT
    Dr. Susanta Ghanta, Department of Chemistry, NIT
    THANK YOU

    Dr. Susanta Ghanta, Department of Chemistry, NIT


    Agartala, India

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