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    Quasi-Equilibrium Hypothesis

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    Bemboy Subosa
    The quasi-equilibrium hypothesis assumes that all reversible elementary steps reach equilibrium rapidly except for the rate-determining step (RDS). The RDS must be the slowest step and directly followed by faster steps. Guidelines for formulating reaction mechanisms include analyzing products, considering atomic/electronic structures, ensuring feasible bond energies and reaction paths, and requiring consumption of all intermediates. Mechanisms proposed for the oxidation of arsenious acid by iodine in water involve rapid equilibria forming reactive intermediates before the slow RDS.

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    Quasi-Equilibrium Hypothesis

    Uploaded by

    Bemboy Subosa
    34 views16 pages
    The quasi-equilibrium hypothesis assumes that all reversible elementary steps reach equilibrium rapidly except for the rate-determining step (RDS). The RDS must be the slowest step and directly followed by faster steps. Guidelines for formulating reaction mechanisms include analyzing products, considering atomic/electronic structures, ensuring feasible bond energies and reaction paths, and requiring consumption of all intermediates. Mechanisms proposed for the oxidation of arsenious acid by iodine in water involve rapid equilibria forming reactive intermediates before the slow RDS.

    Original Description:

    Reaction Mechanisms

    Original Title

    Lecture 6 January 9

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    The quasi-equilibrium hypothesis assumes that all reversible elementary steps reach equilibrium rapidly except for the rate-determining step (RDS). The RDS must be the slowest step and directly followed by faster steps. Guidelines for formulating reaction mechanisms include analyzing products, considering atomic/electronic structures, ensuring feasible bond energies and reaction paths, and requiring consumption of all intermediates. Mechanisms proposed for the oxidation of arsenious acid by iodine in water involve rapid equilibria forming reactive intermediates before the slow RDS.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    34 views16 pages

    Quasi-Equilibrium Hypothesis

    Uploaded by

    Bemboy Subosa
    The quasi-equilibrium hypothesis assumes that all reversible elementary steps reach equilibrium rapidly except for the rate-determining step (RDS). The RDS must be the slowest step and directly followed by faster steps. Guidelines for formulating reaction mechanisms include analyzing products, considering atomic/electronic structures, ensuring feasible bond energies and reaction paths, and requiring consumption of all intermediates. Mechanisms proposed for the oxidation of arsenious acid by iodine in water involve rapid equilibria forming reactive intermediates before the slow RDS.

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    of 16

    Quasi-Equilibrium Hypothesis

    ASSUMPTIONS:
    All reversible elementary steps are in equilibrium.
    All reversible steps must immediately be followed by
    a rate-determining step.
    The rates of all steps after the RDS are several
    times faster than the rate of the RDS.

    Mechanism:
    k1

    N 2O5 NO2 NO3


    k2

    k3

    NO2 NO3 NO O2 NO2


    k4

    NO NO3 2 NO2

    (slow)

    Guidelines to Formulating Reaction


    Mechanisms
    The most fundamental basis for mechanistic
    speculation is a complete analysis of reaction
    products.

    Guidelines to Formulating Reaction


    Mechanisms
    The atomic and electronic structure of the reactants
    and products may provide important clues as to the
    nature of possible intermediate species.

    Guidelines to Formulating Reaction


    Mechanisms
    All of the elementary reactions involved in a
    mechanistic sequence must be feasible with respect
    to bond energies.

    Guidelines to Formulating Reaction


    Mechanisms
    A number of elementary reactions sufficient to
    provide a complete path for the formation of all
    observed products must be employed.

    Guidelines to Formulating Reaction


    Mechanisms
    All of the intermediates produced by the elementary
    reactions must be consumed by other elementary
    reactions so that there will be no net production of
    intermediate species.

    Guidelines to Formulating Reaction


    Mechanisms
    The great majority of known elementary steps are
    bimolecular, the remainder being unimolecular or
    termolecular.

    Guidelines to Formulating Reaction


    Mechanisms
    A postulated mechanism for a reaction in the
    forward direction must also hold for the reverse
    reaction (principle of microscopic reversibility).

    Guidelines to Formulating Reaction


    Mechanisms
    Transitory intermediates do not react preferentially
    with one another to the exclusion of their reaction
    with stable species.

    Guidelines to Formulating Reaction


    Mechanisms
    When the overall order of a reaction is greater than
    three, the mechanism probably has one or more
    equilibria and intermediates prior to the rate
    determining step.

    Guidelines to Formulating Reaction


    Mechanisms
    Inverse orders arise from rapid equilibria prior to the
    rate determining step.

    Oxidation of Arsenious Acid in


    Aqueous solution

    H 3 AsO3 I H 2O H 3 AsO4 3I 2H
    Rate Expression:

    k[ H 3 AsO3 ][ I ]
    r
    2

    [I ] [H ]

    Oxidation of Arsenious Acid in


    Aqueous solution
    Mechanism I

    H 3 AsO3 H 2 AsO3 H

    (equil)

    I 3 H 2O 2 I H 2OI

    (equil)

    H 2OI H 2 AsO3 H 2 AsO3 I H 2O

    (slow)

    H 2 AsO3 I I H 2 AsO3

    H 2 AsO3 H 2O H 3 AsO4 H

    (fast)

    Oxidation of Arsenious Acid in


    Aqueous solution
    Mechanism II

    H 3 AsO3 H 2 AsO3 H

    (equil)

    I 3 H 2O 2 I H 2OI

    (equil)

    H 2OI H 2 AsO3 H 2 AsO3 I H 2O

    (equil)

    H 2 AsO3 I I H 2 AsO3

    H 2 AsO3 H 2O H 3 AsO4 H

    (slow)

    Guidelines to Formulating Reaction


    Mechanisms
    Whenever a rate law contains non-integer orders,
    there are intermediates present in the reaction
    sequence.

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