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    Temperature Dependence

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    kim
    The rates of most chemical reactions increase exponentially with temperature according to the Arrhenius equation. This equation describes the temperature dependence of the rate constant k, where the activation energy Ea is the minimum energy that reactant molecules must possess for a reaction to occur. Collision theory holds that molecules must collide with sufficient kinetic energy to exceed Ea, while transition state theory views the reactive intermediate as a stable complex lasting only a few vibrations, and relates the temperature dependence of k to the standard free energy of the transition state.

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    Temperature Dependence

    Uploaded by

    kim
    92 views13 pages
    The rates of most chemical reactions increase exponentially with temperature according to the Arrhenius equation. This equation describes the temperature dependence of the rate constant k, where the activation energy Ea is the minimum energy that reactant molecules must possess for a reaction to occur. Collision theory holds that molecules must collide with sufficient kinetic energy to exceed Ea, while transition state theory views the reactive intermediate as a stable complex lasting only a few vibrations, and relates the temperature dependence of k to the standard free energy of the transition state.

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    4. Temperature Dependence

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    The rates of most chemical reactions increase exponentially with temperature according to the Arrhenius equation. This equation describes the temperature dependence of the rate constant k, where the activation energy Ea is the minimum energy that reactant molecules must possess for a reaction to occur. Collision theory holds that molecules must collide with sufficient kinetic energy to exceed Ea, while transition state theory views the reactive intermediate as a stable complex lasting only a few vibrations, and relates the temperature dependence of k to the standard free energy of the transition state.

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    Download as pptx, pdf, or txt
    92 views13 pages

    Temperature Dependence

    Uploaded by

    kim
    The rates of most chemical reactions increase exponentially with temperature according to the Arrhenius equation. This equation describes the temperature dependence of the rate constant k, where the activation energy Ea is the minimum energy that reactant molecules must possess for a reaction to occur. Collision theory holds that molecules must collide with sufficient kinetic energy to exceed Ea, while transition state theory views the reactive intermediate as a stable complex lasting only a few vibrations, and relates the temperature dependence of k to the standard free energy of the transition state.

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    TEMPERATURE DEPENDENCE

    ARRHENIUS EQUATION

    The rates of most reactions are very sensitive to


    temperature.
    For the majority of the cases, the rate increases
    rapidly with increasing temperature.
    The dependence of rate on temperature
    manifests in the temperature dependence of the
    rate constant, k.
    Svante Arrhenius (1887) suggested that, for
    many reactions, the rate constant varies
    exponentially with the reciprocal of temperature.
    ARRHENIUS EQUATION
    - Ea / RT
    k = Ae
     The parameter A, is called the Pre-exponential
    Factor or the Frequency Factor.
     Ea is the Activation Energy
     R and T are the Universal Gas Constant and Absolute
    Temperature, respectively.
     The equation can be expressed in logarithmic terms:

    ln k = ln A - Ea / RT
     A plot of ln k versus 1/T is linear, with slope –Ea /R.
    ACTIVATION ENERGY
    ACTIVATION ENERGY
     The reaction coordinate is a convenient way to
    represent the change of the reactants into products
    as the reaction takes place.
     The reactant particles must together have sufficient
    energy to react.
     As the temperature is increased, the fraction of
    particles having energy greater than Ea increases,
    and the rate of reaction correspondingly increases.
     Because the process must be reversible at
    microscopic level, the same barrier will be present
    for the reverse reaction.
    COLLISION THEORY

    The basic assumption of the collision theory is


    that molecules must collide (including collisions
    at the walls of the vessel, in many cases).
    The rate of a reaction whose mechanism is

    M + N P
    is given by
    v = k [M][N] = A [M][N] exp (-Ea /RT)
    At high temperatures, the exponential term
    approaches unity, hence the maximum rate is
    vmax = A [M][N]
    COLLISION THEORY

    At high temperatures the rate of reaction is


    dependent on the collision frequency for M and N;
    i.e. A[M][N].
    The exponential factor (e–Ea/RT) resembles a
    Boltzmann probability distribution (e-E/kT). It can
    be considered to represent the fraction of
    molecules that have sufficient energy to react.
    The major limitation of the Collision Theory is its
    assumption that only molecular kinetic energy is
    involved in the activation process, ignoring
    configurational or entropic contributions.
    TRANSITION STATE THEORY

    • Introduced in 1935 by Eyring et al. and later


    developed by Zewail in 1988.
    • The theory considers the reactive intermediate
    or transition state to be just a stable molecule
    lasting only a few molecular vibrations.
    • In the transition state theory, every elementary
    reaction
    k
    d[P]
    M + N P = k[M][N]
    dt

    is written as
    TRANSITION STATE THEORY
    ‡ ‡
    K ‡ k
    M + N MN P

    where K‡ is the equilibrium constant between the


    transition state and the reactants;
    and k‡ is the universal rate constant
     But
    ‡ [MN‡] d[P]
    K = and = k‡ [MN‡]
    [M][N] dt

     Neither K‡ nor k‡ are experimentally measurable.


    TRANSITION STATE THEORY
     Combining the two above equations:
    d[P]
    = k‡ K‡ [M][N ] = k[M][N]
    dt
     Therefore

    k = k‡K‡
     The transition-state theory shows that the universal rate
    constant
    k‡ = kBT/h
    where kB is the Boltzmann constant
    h is the Plank’s constant
    TRANSITION STATE THEORY
     But the equilibrium constant is related to the standard
    free energy of the reaction by
    DG‡ = -RTlnK‡
     Therefore
    ‡
    k BT k BT -G /RT
    k = K
    ‡
    = e
    h h
     The temperature dependence of reactions is frequently
    expressed in terms of the Arrhenius equation

    k = Ae-Ea/RT or lnk = -Ea/RT + lnA


    TRANSITION STATE THEORY
     Ea can be determined experimentally by measuring the reaction
    rate at several temperatures over a wide range.
     A plot of lnk versus 1/T then gives a straight line of slope equal
    to –Ea/R.
     The value of Ea incorporates the term DH and the value of A
    reflects the entropy term.
     At constant pressure, Ea and DH are related by

    DH‡ = Ea - RT
     And DS‡ is related to A by

    DS‡ = R[ln(h/kBT) + lnA - 1]


     The enthalpy and entropy of activation reflect the response of the
    reacting system as a whole to formation of the transition state.
    THANK YOU

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