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    D D D D : 114 4. Ad-Atoms and Underpotential Deposition

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    Rosario Pilar De La Cruz Castellanos
    1) Capacitance measurements have become an important method for investigating the electrochemical double layer at electrode surfaces. Equivalent circuit models that combine resistance and capacitance elements can describe the properties of the double layer. 2) Impedance spectroscopy measures the impedance of electrode surfaces over a range of frequencies. The impedance data is often represented graphically using Nyquist or Bode plots. 3) Common equivalent circuit models include a simple RC circuit for an ideal electrode and an RCtC circuit that also includes a charge transfer resistance for non-ideal electrodes. Parameter values can be extracted by fitting impedance data to these models.

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    D D D D : 114 4. Ad-Atoms and Underpotential Deposition

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    Rosario Pilar De La Cruz Castellanos
    27 views4 pages
    1) Capacitance measurements have become an important method for investigating the electrochemical double layer at electrode surfaces. Equivalent circuit models that combine resistance and capacitance elements can describe the properties of the double layer. 2) Impedance spectroscopy measures the impedance of electrode surfaces over a range of frequencies. The impedance data is often represented graphically using Nyquist or Bode plots. 3) Common equivalent circuit models include a simple RC circuit for an ideal electrode and an RCtC circuit that also includes a charge transfer resistance for non-ideal electrodes. Parameter values can be extracted by fitting impedance data to these models.

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    Impedancia_2

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    1) Capacitance measurements have become an important method for investigating the electrochemical double layer at electrode surfaces. Equivalent circuit models that combine resistance and capacitance elements can describe the properties of the double layer. 2) Impedance spectroscopy measures the impedance of electrode surfaces over a range of frequencies. The impedance data is often represented graphically using Nyquist or Bode plots. 3) Common equivalent circuit models include a simple RC circuit for an ideal electrode and an RCtC circuit that also includes a charge transfer resistance for non-ideal electrodes. Parameter values can be extracted by fitting impedance data to these models.

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    © All Rights Reserved
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    27 views4 pages

    D D D D : 114 4. Ad-Atoms and Underpotential Deposition

    Uploaded by

    Rosario Pilar De La Cruz Castellanos
    1) Capacitance measurements have become an important method for investigating the electrochemical double layer at electrode surfaces. Equivalent circuit models that combine resistance and capacitance elements can describe the properties of the double layer. 2) Impedance spectroscopy measures the impedance of electrode surfaces over a range of frequencies. The impedance data is often represented graphically using Nyquist or Bode plots. 3) Common equivalent circuit models include a simple RC circuit for an ideal electrode and an RCtC circuit that also includes a charge transfer resistance for non-ideal electrodes. Parameter values can be extracted by fitting impedance data to these models.

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    114 4.

    Ad-Atoms and Underpotential Deposition

    The classical Gibbs–Duhem equation must be modified to describe thermodynamic


    properties of solids. If temperature and pressure are kept constant, one obtains by the func-
    tion of Everett and Couchman31

    d
     qm dE  ∑ i di  (
      s ) d tot (4.30)
    i

    With Eq. (4.29) one gets

    d
    = qm dE  ∑ i di  (
     T) d e (4.31)
    i

    From Eq. (4.31) follows the Shuttleworth equation32

    ⎛ 
    ⎞
    ⎜ 
    T (4.32)
    ⎝  e ⎟⎠ E ,
    i

    Furthermore, a modified Lippmann equation is obtained

    ⎛ 
    ⎞ ⎛  ⎞
    ⎜ ⎟  qm  (
     T) ⎜ e ⎟ (4.33)
    ⎝ E ⎠  ⎝ E ⎠ 
    i i

    Gokhshtein derived a modified form of this equation.33


    The question of how to describe a solid surface is still being developed. To give some
    examples, Grafov recently derived a generalized Shuttleworth equation.34 The present
    concept was critically discussed by Lang and Heusler35 and Guidelli.36 Experimental
    efforts to verify the thermodynamic approach were published, e.g., by Haiss, Nichols,
    Sass, and Charlé.37

    4.2 PRINCIPAL METHODS FOR THE INVESTIGATION OF


    THE ELECTROCHEMICAL DOUBLE LAYER

    The first verification of the fundamental equations of Gibbs and Lippmann was based on
    surface tension (surface energy) measurements. The investigation of solid electrodes with
    this method is restricted. In the following paragraph a description is given of some of the
    modern methods, which are used for investigation of the electrochemical double layer.

    4.2.1 Measurement of capacitance

    Capacitance measurements have become an important method in electrochemistry.


    Combinations of resistance and capacitance elements, the so-called equivalent circuits,
    describe the electrochemical properties of the double layer. In the case of an ideally polar-
    izable electrode, the equivalent circuit is a linear combination of a double layer capaci-
    tance and an Ohmic electrolyte resistance (Figure 4.9a). The equivalent circuit of an
    4.2 Principal Methods for the Investigation of the Electrochemical Double Layer 115

    Figure 4.9 (a) Equivalent circuit of an ideally polarizable electrode, Rel electrolyte resistance and
    Cdl capacitance of the electrode. (b) Representation of the complex impedance as function of fre-
    quency,  in a Nyquist diagram.

    Figure 4.10 (a) Equivalent circuit of an electrode with charge transfer. Rel electrolyte resistance,
    Cdl capacitance of the electrode, and Rct charge transfer resistance. (b) Representation of the com-
    plex impedance as function of frequency,  in a Nyquist diagram.

    electrode with an additional charge transfer resistance across the double layer is shown in
    Figure 4.10a. More complex equivalent circuits are necessary if more elements must be
    taken into account. The Warburg impedance, for example, represents diffusion limitation.
    A detailed description is given in Chapter 5. In the most general approach a transfer func-
    tion can be defined. The determination of the elements of an equivalent circuit is of prime
    importance in electrochemical investigations.
    The result of the combination of a resistance and a capacitance is the complex impedance

    Z  Z re  iZ im (4.34)

    Any impedance point can be represented in the complex plane (Figure 4.11). For a
    capacitance, the imaginary part of the impedance has a negative sign.
    116 4. Ad-Atoms and Underpotential Deposition

    Figure 4.11 Representation of an impedance value Z() in the complex plane.

    The impedance can also be expressed in an exponential form

    Z  Z ei (4.35)

    with |Z| the modulus of the impedance and  the phase shift between output and input. The
    following equations relate the two representations:

    Z  Z re2  Z im
    2
    (4.36)
    Z re
    tan  (4.37)
    Z im

    The impedance of an Ohmic resistance is a real quantity

    ZR  R (4.38)

    The impedance of a capacitance is an imaginary quantity


    1
    ZC  i (4.39)
    C
    The serial combination of a resistance and a capacitance has the impedance
    1
    Zs = R − i (4.40)
    C
    The impedance of a parallel combination of a resistance and a capacitance is given by
    1 1
      i ⋅ C (4.41)
    Zp R
    4.2 Principal Methods for the Investigation of the Electrochemical Double Layer 117

    The impedance of the equivalent circuit in Figure 4.10a is obtained by the reciprocal com-
    bination of ZR and ZC. The result is linear (serial) combined with Zel  Rel. This leads to
    the following real and imaginary impedance terms, Z re and Z im, respectively

    Rct
    Z re  Rel  (4.42)
     Rct2 Cdl2
    2

    Rct2 Cdl
    Z im   (4.43)
    1  2 Rct2 Cdl2
    Two plots are used to represent the results of impedance measurements of electrochem-
    ical systems. In the Nyquist plot the negative imaginary part (y-axis) is plotted versus the
    real part (x-axis). The Nyquist plot of the equivalent circuits in Figures 4.9a and 4.10a is
    shown in Figures 4.9b and 4.10b.
    In the Bode plot log |Z| and || (y-axis) are plotted against the logarithm of frequency 
    (x-axis). Figure 4.12 shows the Bode plot of the equivalent circuit of the double layer with
    charge transfer (Figure 4.10a).
    The standard method to measure impedance values as a function of the potential is the
    Wheatstone bridge (Figure 4.13). The electrochemical cell is placed in one branch of the
    bridge. In the second branch a variable resistance and a variable capacitance are placed.
    An alternating current is applied to a potentiostat. In the reference circuit, capacitance
    and resistance are varied until the bridge current, measured with an AC instrument or an
    oscilloscope, is zero.
    For the measurement of the impedance, a modern “impedance spectrometer” provides
    automatic data registration over at least five decades of frequency. With this equipment it

    Figure 4.12 Bode plot representation of the impedance of the equivalent circuit in Figure 4.10a.

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