Scribd Logo
Upload

Welcome to Scribd!

  • 7 views

    (CHEM ENG 3029 - 7055) Lecture 7.3 - Slides (2024)

    Uploaded by

    sheen19970626

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    (CHEM ENG 3029 - 7055) Lecture 7.3 - Slides (2024)

    Uploaded by

    sheen19970626
    7 views14 pages

    Original Title

    [CHEM ENG 3029_7055] Lecture 7.3_Slides (2024)

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    7 views14 pages

    (CHEM ENG 3029 - 7055) Lecture 7.3 - Slides (2024)

    Uploaded by

    sheen19970626

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 14

    CHEM ENG 3029_7055

    Materials Science and Engineering


    Lecture 7

    Kinetics, Polarisation and Diffusion of Corrosion


    Lecture Structure
    Lecture 7 (Kinetics, Polarisation and Diffusion of Corrosion) is
    divided into the following sections:
    • L7.1 – Kinetics of Corrosion
    – Understanding Kinetics of Corrosion
    – Free Energy and Corrosion Current
    – Electrical Double Layer
    – Faraday's Law of Electrolysis
    – Corrosion Rate
    • L7.2 – Polarisation
    – Non-equilibrium Conditions
    – Equilibrium Conditions
    – Activation Energy for Anodic and Cathodic Reactions
    – Butler-Volmer Equation
    – Tafel Equation
    • L7.3 – Diffusion and Double Layer
    – Kinetics vs Diffusion
    – Diffusion as Controlling Factor of Corrosion

    Reference Book: W. D. Callister and D. G. Rethwisch, Materials Science and Engineering: An Introduction, John
    Willey & Sons ISBN: 9781119321590

    Complementary Reference Book: P. A. Schweitzer, Fundamentals Of Corrosion: Mechanisms, Causes, and


    Preventative Methods, CRC Press ISBN: 9781420067705
    Lecture Structure
    • L7.3 – Diffusion and Double Layer
    – Kinetics vs Diffusion
    – Diffusion as Controlling Factor of Corrosion
    L7.3 – Diffusion and Double Layer
    o Learning Objectives

    ✓ How diffusion can determine the kinetics of corrosion

    ✓ Formalisation of diffusion as controlling factor of


    corrosion

    University of Adelaide 5
    L7.3 – Diffusion and Double Layer
    • Kinetics vs Diffusion
    – Polarisation concerns kinetics at solid/liquid interface
    – Now need to look at transport of species in solution
    – Passage of electrons is very fast
    • Virtually instantaneous
    – Movement of ions is much slower
    • Ions are very much larger than electrons
    – For all reactions
    Rate of reaction is determined by the slowest step

    University of Adelaide 6
    L7.3 – Diffusion and Double Layer
    • Kinetics vs Diffusion
    We need to find the rate-determining step
    In corrosion cells the slowest process can differ:
    – With small currents
    • Transport of cathode reactant (e.g., dissolved O2 is easy)
    – Activation process is a rate-determining step

    – With large currents


    • Larger charge transfer required
    – Electrolyte cannot transfer sufficient ions
    – Speed of dissolved oxygen movement is the slowest step
    – Transport of dissolved oxygen is rate-determining
    • Process is diffusion-controlled

    University of Adelaide 7
    L7.3 – Diffusion and Double Layer
    • Diffusion as Controlling Factor of Corrosion
    No Current Uniform c
    0
    For a cathode
    Flowing Cathode Reactant Species
    c0 > c
    Current co
    Flowing
    c Decreases

    Slope of line is concentration gradient dc/dx

    University of Adelaide 8
    L7.3 – Diffusion and Double Layer
    • Diffusion as Controlling Factor of Corrosion
    – Fick’s First Law of Diffusion
    where J = flux of substance and D = diffusion coefficient

    – Faraday’s First Law of Electrolysis

    i = zFJ substituting for J in Fick’s Law

    Then

    – Simplifying by assuming a linear concentration gradient,


    as in the graph: can be replaced by (c0 – c)/x

    University of Adelaide 9
    L7.3 – Diffusion and Double Layer

    • Interested only in magnitude of current density


    – Concentration can never be negative
    • Minimum is therefore 0
    – Current density is greatest when the distant concentration c = 0
    – Therefore the limiting current or maximum current is:

    – If c > c0 then the concentration in the region of the electrode


    must be increasing
    • Sign change from - to + shows that the current is reversed

    University of Adelaide 10
    L7.3 – Diffusion and Double Layer
    • Using Nernst Equation
    – For condition 1 (no current):

    – For condition 2

    – However polarisation, η = change of potential from equilibrium


    so η = E2 – E1 and:

    University of Adelaide 11
    L7.3 – Diffusion and Double Layer
    • Using the expressions for i and iL
    – The expression below can be derived

    – Substituting into

    – We get

    • As i → iL then η → ∞

    Let’s discuss the Tafel plot more


    University of Adelaide 12
    L7.3 – Diffusion and Double Layer
    • As i → iL then η → ∞
    • Shown as non-linear effect on the cathodic part of the plot

    • For small currents


    – imeas → 0 Experimental Results
    • because ic → ia

    • For intermediate currents


    – imeas → ic – Tafel Equation holds

    • For higher currents


    – Deviates to more negative values
    • imeas approaches iL asyomptotically

    University of Adelaide 13

    You might also like