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    CHEM. 204: Kinetic Properties of Chemical Reactions

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    myriam
    This document discusses the kinetics of chemical reactions. It covers: 1) Half-lives of reactions and how they depend on reaction order (zero, first, second, nth). 2) Molecularity refers to the number of reactant molecules involved in elementary reaction steps. Bimolecular reactions involve two reactants. 3) The Arrhenius equation describes how reaction rates increase with temperature due to molecules having higher average energies. The pre-exponential factor A relates to collision frequency, while the activation energy Ea is the minimum energy for reactions to occur.

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    CHEM. 204: Kinetic Properties of Chemical Reactions

    Uploaded by

    myriam
    32 views7 pages
    This document discusses the kinetics of chemical reactions. It covers: 1) Half-lives of reactions and how they depend on reaction order (zero, first, second, nth). 2) Molecularity refers to the number of reactant molecules involved in elementary reaction steps. Bimolecular reactions involve two reactants. 3) The Arrhenius equation describes how reaction rates increase with temperature due to molecules having higher average energies. The pre-exponential factor A relates to collision frequency, while the activation energy Ea is the minimum energy for reactions to occur.

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    204-KINETICS-3

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    This document discusses the kinetics of chemical reactions. It covers: 1) Half-lives of reactions and how they depend on reaction order (zero, first, second, nth). 2) Molecularity refers to the number of reactant molecules involved in elementary reaction steps. Bimolecular reactions involve two reactants. 3) The Arrhenius equation describes how reaction rates increase with temperature due to molecules having higher average energies. The pre-exponential factor A relates to collision frequency, while the activation energy Ea is the minimum energy for reactions to occur.

    Copyright:

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

    CHEM. 204: Kinetic Properties of Chemical Reactions

    Uploaded by

    myriam
    This document discusses the kinetics of chemical reactions. It covers: 1) Half-lives of reactions and how they depend on reaction order (zero, first, second, nth). 2) Molecularity refers to the number of reactant molecules involved in elementary reaction steps. Bimolecular reactions involve two reactants. 3) The Arrhenius equation describes how reaction rates increase with temperature due to molecules having higher average energies. The pre-exponential factor A relates to collision frequency, while the activation energy Ea is the minimum energy for reactions to occur.

    Copyright:

    © All Rights Reserved
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    of 7

    CHEM.

    204

    Kinetic Properties of
    Chemical Reactions

    References: Atkins Chapter 17


    Zumdahl Chapter 15

    A. Half-lives

    [ A]0
    • Zero order: t1 / 2 
    2k
    ln 2
    • First order: t1 / 2 
    k
    1
    • Second order: t1/ 2 
    k [ A]0

    • Generally: for nth order in [A]


    2n 1  1
    t1 / 2 
    (n  1) k [ A]0n 1

    1
    Illustrative example

    • For a second order reaction: Plot t1/2


    versus 1/[A]0 straight line of slope 1/k.

    [A]0 [A]1

    [A]1/2
    [A]0/2
    [A]0/4

    t1 t2 t

    B. Molecularity
    • Reaction mechanism  a sequence of
    elementary steps.
    H + Br2  HBr + Br bimolecular
    • Define: Molecularity of a given
    elementary step  number of reactant
    molecules coming together to react in
    that step.
    • The concepts of molecularity and
    elementary step are closely linked
    together.

    2
    Examples
    • ONE reactant: Unimolecular reaction
    CH2
    –  CH3 ─ CH ═ CH2
    CH2 Involves an elementary
    CH2 rate-determining step
    – SN1 reactions
    • TWO reactants: Bimolecular reaction
    – Dimerization of alkenes and dienes.
    – SN2 reactions:
    CH3I + CH3 ─ CH2O  CH3 ─ CH2O ─ CH3 + I

    Molecularity and elementary step

    • Rate law: v  k [CH3I] [CH3CH2O ]

    • Difference between order and molecularity:


    – Reaction order: empirical quantity, obtained
    from the experimental rate law.
    – Molecularity: refers to an elementary reaction
    step proposed as an individual step in an overall
    mechanism.
    • If the reaction is an elementary bimolecular
    process, then it has second order kinetics;
    but, if the kinetics are second order, then the
    reaction might be complex.

    3
    Rate law of an elementary step
    • ONLY for an elementary step: we can
    write the rate law from the chemical
    equation (stoichiometry):
    – A  Products d [ A]
    unimolecular
     k [ A]
    dt
    – A + B  Products d [ A]
    bimolecular  k [ A][ B ]
    dt
    – H2 + I2  2 HI : this is an overall
    chemical reaction, which is not
    bimolecular. It is a net result of a
    detailed, complex mechanism.

    C. Temperature dependence of
    reaction rates
    • For many reactions:
    Plot ln k versus 1/T
     straight line of
    negative slope.
    k  A e Ea / RT Arrhenius
    equation

    • A  Arrhenius, or
    pre-exponential, or
    frequency factor.
    • Ea  activation
    energy Van’t Hoff plot

    4
    Activation energy

    • High Ea: rate constant


    strongly depends on
    temperature.
    • Zero Ea: rate independent
    of T.
    • ve Ea: the rate decreases
    as T increases! Ea
    indicating a complex
    mechanism…
    • T-dependence of A may
    be very complicated 
    non-Arrhenius-like
    behavior.

    Activation energy
    • It is possible to define Activation
    Energy in a general manner:
    d ln k
    Ea  RT 2
    dT
    • Activation energies of successive
    elementary steps:

    5
    Significance of the Arrhenius parameters
    • A  collision frequency (Z)
    – Assume the reaction is gaseous and
    bimolecular:
    1
    •For like molecules: Z AA   crel N A2
    2
    •For unlike molecules: Z   c N N
    AB rel A B

    – Typically, in a gas at 1.00 atm, Z1028 cm3


    s 1.
    – The collision frequency  T1/2.

    Here (AB):

       d 2   (rA  rB )2
    1/ 2
     8kT 
    crel   
      
    mAmB
    
    mA  mB

    6
    Arrhenius parameters
    • Energetics of collisions:
    – Molecules must collide with energy
    at least equal to Ea, for the reaction
    to occur.
     E / RT
    – The fraction of molecules  e a

    Rate = collision frequency  energy factor


     steric factor
    Fraction of molecules
    = Z  e  Ea / RT
      with the right
    orientation

    T-dependence of the energy factor

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