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    Lecture 38

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    Hagere Ethiopia
    The document discusses the relationship between cell potential (E), Gibbs free energy (ΔrG), and the equilibrium constant (K) in electrochemical cells. It states that at equilibrium, ΔrG is equal to 0 and E is equal to 0. It also introduces the Nernst equation, which relates E, ΔrG, temperature (T), and K. Standard cell potentials are measured relative to the standard hydrogen electrode. The electrochemical series is also discussed, stating that the reaction is spontaneous if the reduction potential of the cathode is more positive than the oxidation potential of the anode. Finally, it briefly discusses chemical kinetics and different methods for measuring reaction rates.

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    Lecture 38

    Uploaded by

    Hagere Ethiopia
    10 views5 pages
    The document discusses the relationship between cell potential (E), Gibbs free energy (ΔrG), and the equilibrium constant (K) in electrochemical cells. It states that at equilibrium, ΔrG is equal to 0 and E is equal to 0. It also introduces the Nernst equation, which relates E, ΔrG, temperature (T), and K. Standard cell potentials are measured relative to the standard hydrogen electrode. The electrochemical series is also discussed, stating that the reaction is spontaneous if the reduction potential of the cathode is more positive than the oxidation potential of the anode. Finally, it briefly discusses chemical kinetics and different methods for measuring reaction rates.

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    The document discusses the relationship between cell potential (E), Gibbs free energy (ΔrG), and the equilibrium constant (K) in electrochemical cells. It states that at equilibrium, ΔrG is equal to 0 and E is equal to 0. It also introduces the Nernst equation, which relates E, ΔrG, temperature (T), and K. Standard cell potentials are measured relative to the standard hydrogen electrode. The electrochemical series is also discussed, stating that the reaction is spontaneous if the reduction potential of the cathode is more positive than the oxidation potential of the anode. Finally, it briefly discusses chemical kinetics and different methods for measuring reaction rates.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    10 views5 pages

    Lecture 38

    Uploaded by

    Hagere Ethiopia
    The document discusses the relationship between cell potential (E), Gibbs free energy (ΔrG), and the equilibrium constant (K) in electrochemical cells. It states that at equilibrium, ΔrG is equal to 0 and E is equal to 0. It also introduces the Nernst equation, which relates E, ΔrG, temperature (T), and K. Standard cell potentials are measured relative to the standard hydrogen electrode. The electrochemical series is also discussed, stating that the reaction is spontaneous if the reduction potential of the cathode is more positive than the oxidation potential of the anode. Finally, it briefly discusses chemical kinetics and different methods for measuring reaction rates.

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    The cell potential and the Gibbs energy

    ∆rG
    - νFE = ∆rG Þ E = − @ equilibrium: ∆rG = 0 Þ E = 0
    νF
    if ∆rG < 0 Þ E > 0 for a spontaneous reaction
    if ∆rG > 0 Þ E < 0 for a non-spontaneous reaction
    O
    and ∆ r G = ∆ r G + RT ln Q
    @ 25oC: 25.7 mV
    O
    ∆rG RT RT
    ln Q @ equilibrium:
    O
    Þ E=− − ln Q = E −
    νF νF νF O
    νFE
    standard cell potential ln K =
    Nernst equation RT

    Standard cell potentials are measured relative to the


    O
    standard hydrogen electrode: Pt(s)|| H2(g)|| H (aq) with E = 0 V
    +

    Nils Walter: Chem 260


    The electrochemical series

    O O O
    reduced E =E −E R L

    Þ a cell reaction
    is spontaneous
    if ERO > ELO

    O
    Cathode (Right): Cu2+(aq) + 2e- → Cu(s); ER
    O
    Anode (Left): Zn2+(aq) + 2e- → Zn(s); EL
    Overall (R-L): Cu2+(aq) + Zn(s)
    oxidized Cu(s) + Zn2+(aq)

    Low reduces high;


    high oxidizes low
    Nils Walter: Chem 260
    The rates of reactions: Chemical kinetics
    Atkins, Chapter 10
    What can we learn?
    → predict how quickly a reaction mixture approaches equilibrium
    → study the reaction mechanism (understand the elementary steps)
    How do we do it?
    → determine the stoichiometry and identify any side reactions
    → determine how the reagent and/or product concentrations change
    with time (@ constant T)
    }
    A) Quenching the reaction at defined times
    B) Real-time analysis by spectroscopy

    Stopped-flow method
    Flow method Nils Walter: Chem 260
    Kinetics can be measured when relaxing!?
    Reaction A B Connection between
    kinetics and equilibrium!
    A
    ↑
    @ equilibrium:

    Manfred Eigen:
    A → B is as fast as B → A
    Chemistry Novel B [ B]
    prize 1967 K=
    [ A]
    van’t Hoff equation: K ' ∆r H O æ 1 1 ö
    ln K '− ln K = ln = ç − ÷
    T dependence of K K R èT T'ø

    From the relaxation time the reaction rate


    relaxation can be calculated Þ fast reactions that reach
    their equilibrium quickly can be studied!

    Nils Walter: Chem 260


    Reaction rates
    Raw kinetic data: [reactant](t)
    Þ faster Stoichiometry and rate:
    ∆[reactant] A + B → C
    Rate = ( M −1s −1 )
    ∆t
    E.g., I2 + C2H4 → C2H4I2
    ∆A = -5
    Þ slower
    ∆B = -5
    Þ Rate =
    d[reactant] ∆C = 5
    dt
    d[A] d[B] d[C]
    − =− =
    dt dt dt
    2A → C
    ∆A = -10 −
    d[A]
    =2
    d[C]
    Þ −
    1 d[A] d[C]
    =
    ∆C = 5 dt dt 2 dt dt
    Nils Walter: Chem 260

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