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    Electrochem 2

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    kangirene9705
    [1] The Helmholtz double layer forms at the interface of a metal electrode and its salt solution when ions of opposite charge accumulate on either side, creating a separation of charge and an electrode potential. [2] The Nernst equation relates the voltage of an electrochemical cell to temperature, concentrations of reactants and products, and the standard electrode potential. It can be derived from thermodynamic equations relating free energy change and reaction quotient. [3] Applying the Nernst equation shows that cell voltage varies with temperature and concentration - increasing temperature and concentrations of oxidized species increases cell voltage.

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    Electrochem 2

    Uploaded by

    kangirene9705
    6 views16 pages
    [1] The Helmholtz double layer forms at the interface of a metal electrode and its salt solution when ions of opposite charge accumulate on either side, creating a separation of charge and an electrode potential. [2] The Nernst equation relates the voltage of an electrochemical cell to temperature, concentrations of reactants and products, and the standard electrode potential. It can be derived from thermodynamic equations relating free energy change and reaction quotient. [3] Applying the Nernst equation shows that cell voltage varies with temperature and concentration - increasing temperature and concentrations of oxidized species increases cell voltage.

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    electrochem 2

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    [1] The Helmholtz double layer forms at the interface of a metal electrode and its salt solution when ions of opposite charge accumulate on either side, creating a separation of charge and an electrode potential. [2] The Nernst equation relates the voltage of an electrochemical cell to temperature, concentrations of reactants and products, and the standard electrode potential. It can be derived from thermodynamic equations relating free energy change and reaction quotient. [3] Applying the Nernst equation shows that cell voltage varies with temperature and concentration - increasing temperature and concentrations of oxidized species increases cell voltage.

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    © All Rights Reserved
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    6 views16 pages

    Electrochem 2

    Uploaded by

    kangirene9705
    [1] The Helmholtz double layer forms at the interface of a metal electrode and its salt solution when ions of opposite charge accumulate on either side, creating a separation of charge and an electrode potential. [2] The Nernst equation relates the voltage of an electrochemical cell to temperature, concentrations of reactants and products, and the standard electrode potential. It can be derived from thermodynamic equations relating free energy change and reaction quotient. [3] Applying the Nernst equation shows that cell voltage varies with temperature and concentration - increasing temperature and concentrations of oxidized species increases cell voltage.

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    Electrochemistry Basics – III

    1
    Helmholtz double Layer
    • It is used to explain the origin of electrode
    potential
    • When a metal is immersed in its own salt
    solution, a charge separation will occur as
    shown in the figure (see next slide). And its
    reaction may represented as:

    M M n+ + ne-

    2
    3
    • In this case, +vely charged electrode surface
    attracts a layer of -vely charged electrons at
    the interface. Thus a double layer called
    Helmholtz electrical double layer is formed at
    the metal-solution interface.
    • And Across this double layer, a potential is
    developed (a separation of +ve and –ve layer
    means there is a work done and it is
    depending on the nature of the Metal and
    ions. This work done (by this cell system) is
    equivalent to Energy or Volt of this half cell.

    4
    Standard Electrode Potential
    • Standard electrode potential is the potential
    developed when the pure metal electrode is in
    contact with a solution of its own ions of unit
    concentration (1M) at 298K. It is denoted by
    E0 .

    5
    • Nernst Equation and its Applications

    6
    What is the significance of Nernst
    Equation?
    • Nernst equation relates the voltage of a cell as
    a function of its concentration and its
    temperature

    V = f ( [C], T )

    7
    Derivation
    Very Important
    • Consider an oxidation half cell:
    M → Mn+ + ne

    Here the voltage is produced at the expense of free


    energy change in the system.

    This Free energy change can be reprsented by vantHoff’s


    equation:

    8
    Where the T is the Temperature of the system,
    Q is the reaction Quotient, and it is defined as,

    Q = [Products] / [Reactants] =
    [Mn+] [e]n/[M]

    Here [M], i.e. Activity of solid is defined as 1; And


    activity of [e]n is also defined as 1.
    So that in this particular case (oxidation half cell)

    Q = [Mn+]

    9
    But there is another relation of change in free
    energy:

    n is the num. of electrons participated in the


    balanced cell reaction and F is Faraday; If we
    substitute this into the previous equation, we
    will get:

    10
    This equation can be divided by ( -nFEcell ) and
    this will lead:

    (A)

    And at standard conditions ( 298 Kelvin and substituting F, R, and converting natural
    logarithm to base 10 logarithm), we will get:

    (B)

    11
    Note that F is called Faraday and it is the charge
    of 1 mol of electrons,

    1 F = charge of 1 electron x Avogadro number


    = 1.60217662 × 10-19 coulombs x 6.023 x 10 23

    =
    96500 C

    12
    General Nernst Equation
    • For a reaction:

    aA +bB cC + d D ,

    the Nernst equation is written as

    13
    Nernst Equation of Daniell Cell
    First write the Overall Equation of Daniell Cell
    and identify n (ie. How many electrons are
    participating in the balanced eqn: Which is 2
    in this case)

    Here , E0cell = E0Zn - E0Cu

    14
    Effect of Temperature/Concentration on EMF of a Cell (Daniell Cell)

    By plotting the equation


    with respect to T, one can
    obtain the plot:

    Which means
    (1) Voltage varies with temperature and concentration and
    (2) to obtain more voltage from a Daniell Cell
    one has to increase the temperature and [Cu2+] ie. Concentration of Cu ions with
    15
    respect to that of Zn ions.
    Questions

    • Derive General Nernst Equation (Eqn (A) slide n:8)


    • Calculate the reaction quotient and then voltage
    of a cell, with a reaction:
    Cd(s) + Fe2+(aq) Cd2+(aq) + Fe(s), at 25 0C.
    Here, [Fe2+] = 0.6 M and [Cd2+(aq) ]=0.01M.
    E0cell = -0.04 V.

    16

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