Scribd Logo
Upload

Welcome to Scribd!

  • 27 views

    Shahjalal University of Science and Technology, Sylhet Dept. of Chemical Engineering and Polymer Science Assignment No: 01

    Uploaded by

    Sourav Sutradhar
    This document contains the answers to four questions about Pourbaix diagrams. It defines a Pourbaix diagram, describes the key features of the diagram including different corrosion zones, lists some common uses of Pourbaix diagrams in predicting corrosion states, and discusses some limitations in their application including neglecting kinetic factors and non-standard conditions.

    Copyright:

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

    Shahjalal University of Science and Technology, Sylhet Dept. of Chemical Engineering and Polymer Science Assignment No: 01

    Uploaded by

    Sourav Sutradhar
    27 views7 pages
    This document contains the answers to four questions about Pourbaix diagrams. It defines a Pourbaix diagram, describes the key features of the diagram including different corrosion zones, lists some common uses of Pourbaix diagrams in predicting corrosion states, and discusses some limitations in their application including neglecting kinetic factors and non-standard conditions.

    Original Description:

    hjll

    Original Title

    2016332005

    Copyright

    © © All Rights Reserved

    Available Formats

    PDF, TXT or read online from Scribd

    Did you find this document useful?

    Is this content inappropriate?

    This document contains the answers to four questions about Pourbaix diagrams. It defines a Pourbaix diagram, describes the key features of the diagram including different corrosion zones, lists some common uses of Pourbaix diagrams in predicting corrosion states, and discusses some limitations in their application including neglecting kinetic factors and non-standard conditions.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    27 views7 pages

    Shahjalal University of Science and Technology, Sylhet Dept. of Chemical Engineering and Polymer Science Assignment No: 01

    Uploaded by

    Sourav Sutradhar
    This document contains the answers to four questions about Pourbaix diagrams. It defines a Pourbaix diagram, describes the key features of the diagram including different corrosion zones, lists some common uses of Pourbaix diagrams in predicting corrosion states, and discusses some limitations in their application including neglecting kinetic factors and non-standard conditions.

    Copyright:

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

    Shahjalal University of Science and Technology, Sylhet

    Dept. of Chemical Engineering and Polymer Science


    Assignment No: 01
    Course name: Corrosion Engineering
    Course Code: CEP-451

    Submitted To:
    Md. Mohibul Alam
    Associate Professor
    Dept. of CEP, SUST

    Submitted By:
    Sourav Sutradhar
    Reg. No: 2016332005
    Session: 2016-17
    Dept. Of CEP, SUST.

    Date of submission: 12-12-2020


    Ans To The Q.No.01
    Pourbaix Diagram: Pourbaix diagram (Electrode potential / PH diagram) is
    a graphical presentation of the thermodynamic equilibrium states of a metal-
    electrolyte system.
    An example of a Pourbaix diagram for the system iron-water is
    presented in the picture:

    Figure: Simplified Pourbaix diagram for 1M iron-water system at 770F (250C)


    The diagram defines the following zones of the equilibrium states:
    ▪ below the line a-b-j: Solid iron (immunity zone). The electrochemical
    reactions in this zone proceed in the direction of reduction of iron ions. No
    corrosion occurs in this zone.
    ▪ a-b-n-c-d-e: Aqueous solution of ion Fe2+ (corrosion zone). Metallic iron
    oxidizes in this zone.
    ▪ e-d-f-g-k: Aqueous solution of ion Fe3+ (corrosion zone). Metallic iron
    oxidizes (corrodes) in this zone.
    ▪ h-f-g-m: Aqueous solution of ion FeO42- (corrosion zone).
    ▪ c-d-f-h-i: Solid ferrous oxide Fe2O3 (passivation zone). Iron oxidizes
    (corrodes) in this zone however the resulted oxide film depresses the
    oxidation process causing passivation (corrosion protection of the metal
    due to formation of a film of a solid product of the oxidation reaction).
    ▪ n-c-i-p: Solid oxide Fe3O4 (Fe2O3*FeO) (passivation zone). The oxide
    film causes passivation.
    ▪ b-n-p-j: Solid hydroxide (II) Fe(OH)2 / FeO*nH2O / green rust
    (passivation zone).
    Ans To The Q.No.02
    Key to features on the diagram:

    • Solid lines separate species related by acid-base equilibria (line 1)

    • line a shows the pH at which half of the 1 M iron is Fe3+ and half is
    precipitated as Fe(OH)2
    • Pourbaix diagrams incorporate Z1/r calculations and acid-base
    equilibria
    • the position of an acid-base equilibrium is dependent on the total
    concentration of iron
    ➢ reducing the total concentration of Fe3+ will reduce the driving
    force of the precipitation
    ➢ reducing the total iron concentration from 1 M to 10-6 M (more
    realistic concentrations for geochemists and corrosion
    engineers) shifts the boundary from pH 1.7 to pH 4.2
    ➢ In general, in more dilute solutions, the soluble species have
    larger predominance areas.

    • Longer dashed lines enclose the theoretical region of stability of the water to
    oxidation or reduction ((lines 4 & 6) while shorter dashed lines enclose the
    practical region of stability of the water (5 & 7)
    o Dashed line 4 represents the potential of water saturated with
    dissolved O2 at 1 atm (very well aerated water).
    o above this potential water is oxidized to oxygen:

    2 H2O + 4 H+ (aq) O2 + 4 e- Eo = +1.229 V

    ➢ theoretically water should be oxidized by any dissolved


    oxidizing agent Eo > 1.229
    ➢ in practice, about 0.5 V of additional potential is required to
    overcome the overvoltage of oxygen formation (dashed line 5)

    • Dashed line 6 represents the potential of water saturated with dissolved H 2 at


    1 atm pressure (high level or reducing agents in solution).
    • Below this potential water is reduced to hydrogen:

    2 H+ + 2 e- Eo = +1.229 V

    o in practice, an overvoltage effect prevents significant release of


    hydrogen until the lower dashed line 7 is reached
    Ans To The Q.No.03
    Uses of Pourbaix Diagrams:

    • Any point on the diagram will give the termodynamically most stable
    (theoretically the most abundant) form of the element for that E and pH.

    o E=+0.8 V and pH = 14
    predominant form is FeO42-.

    • The diagram gives a visual representation of the oxidizing and reducing


    abilities of the major stable compounds of an element

    o Strong oxidizing agents and oxidizing conditions are found only at the
    top of the diagram.
    The lower boundaries of strong oxidizing agents are high on the
    diagram.
    o Reducing agents and reducing conditions are found at the bottom of a
    diagram and nowhere else.
    Strong reducing agents have boundaries that are low on the diagram.
    o A species that prevails from top to bottom at the pH in question has no
    oxidizing or reducing properties at all within that range.

    • Pourbaix diagrams allow for more accurate predictions of the forms in which
    the different elements will exist in natural waters.
    • Pourbaix diagrams are useful in predicting the spontaneous direction of
    electrochemical reactions, identifying the corrosion products and predicting
    the changes in environment in terms of potential and pH that result in high
    or low corrosive attack
    Ans To The Q.No.04
    Limitations of Pourbaix diagrams:

    ▪ The diagrams provide no information about the kinetic parameters of the


    corrosion reactions.
    ▪ The diagrams consider pure metals and aqueous solutions at standard
    conditions (temperature 298K, pressure 1 bar, ion concentration 10 -6M).
    Thermodynamic conditions of corrosion for alloys and for non-standard
    conditions differ from those described by Pourbaix diagrams.
    ▪ The diagram do not take into account non-ideal behavior of aqueous
    solutions.
    ▪ Some thermodynamic data used for building diagrams are not precise
    enough.
    ▪ This method is limited to wet corrosion where varying pH is involved.
    ▪ These diagrams are purely based on thermodynamic data and do not
    provide any information on the reactions.
    ▪ Consideration is given only to equilibrium conditions in specified
    environment and factors, such as temperature and velocity are not
    considered which may seriously affect the corrosion rate.
    ▪ The activity of species is arbitrarily selected as 10-6 gmol which is not
    realistic.
    ▪ Pourbaix diagrams deal with pure metals which are not of much interest to
    the engineers.
    ▪ All insoluble products are assumed to be protective which is not true, as
    porosity, thickness, and adherence to substrate are important factors.

    Although the above disadvantages appear to be substantial, the advantages


    offered by the Pourbaix diagrams far outweigh their limitations.

    Reference:
    https://people.wou.edu/~courtna/ch412/pourbaix.htm
    https://www.substech.com/dokuwiki/doku.php?id=pourbaix_diagrams
    http://www.uobabylon.edu.iq/eprints/publication_12_18276_228.pdf

    You might also like