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    2 Kinetics

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    Latifah Fauziah
    1) Kinetics is the analysis of reaction mechanisms and rates at the molecular scale, including derivation of rate expressions, experimental testing, and theoretical prediction of rate constants. 2) Elementary reactions cannot be broken down further and proceed exactly as written. Reaction mechanisms are sequences of elementary steps. 3) The rate equation relates concentrations of reactants and products to the reaction rate through rate constants and reaction orders. Thermodynamic equilibrium is reached when the forward and reverse rates are equal. 4) Reaction rates depend on temperature according to the Arrhenius equation, with the pre-exponential factor and activation energy determining temperature dependence.

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    2 Kinetics

    Uploaded by

    Latifah Fauziah
    19 views18 pages
    1) Kinetics is the analysis of reaction mechanisms and rates at the molecular scale, including derivation of rate expressions, experimental testing, and theoretical prediction of rate constants. 2) Elementary reactions cannot be broken down further and proceed exactly as written. Reaction mechanisms are sequences of elementary steps. 3) The rate equation relates concentrations of reactants and products to the reaction rate through rate constants and reaction orders. Thermodynamic equilibrium is reached when the forward and reverse rates are equal. 4) Reaction rates depend on temperature according to the Arrhenius equation, with the pre-exponential factor and activation energy determining temperature dependence.

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    1) Kinetics is the analysis of reaction mechanisms and rates at the molecular scale, including derivation of rate expressions, experimental testing, and theoretical prediction of rate constants. 2) Elementary reactions cannot be broken down further and proceed exactly as written. Reaction mechanisms are sequences of elementary steps. 3) The rate equation relates concentrations of reactants and products to the reaction rate through rate constants and reaction orders. Thermodynamic equilibrium is reached when the forward and reverse rates are equal. 4) Reaction rates depend on temperature according to the Arrhenius equation, with the pre-exponential factor and activation energy determining temperature dependence.

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    Download as ppt, pdf, or txt
    19 views18 pages

    2 Kinetics

    Uploaded by

    Latifah Fauziah
    1) Kinetics is the analysis of reaction mechanisms and rates at the molecular scale, including derivation of rate expressions, experimental testing, and theoretical prediction of rate constants. 2) Elementary reactions cannot be broken down further and proceed exactly as written. Reaction mechanisms are sequences of elementary steps. 3) The rate equation relates concentrations of reactants and products to the reaction rate through rate constants and reaction orders. Thermodynamic equilibrium is reached when the forward and reverse rates are equal. 4) Reaction rates depend on temperature according to the Arrhenius equation, with the pre-exponential factor and activation energy determining temperature dependence.

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    Kinetics

    + P
    potential energy

    A B

    A
    B

    cataly st
    P
    A B

    cataly st P cataly st
    cataly st

    bonding reaction separation

    reaction coordinate

    IC-1/18 Lecture-2 02-09-2004


    What is Kinetics ?

    • Analysis of reaction mechanisms on the molecular scale


    • Derivation of rate expressions
    • Design and analysis of experiments to test rate equations
    and derive kinetic parameters
    • Theoretical prediction of rate constants
    • How can we improve it?

    IC-2/18 Lecture-2 02-09-2004


    Elementary steps

    A reaction is elementary if it cannot be split up in


    further steps. An elementary reaction proceeds exactly
    as expressed by the reaction equation.
    A reaction mechanism is a sequence of elementary steps.

    Discuss examples of elementary steps!

    IC-3/18 Lecture-2 02-09-2004


    The Rate Equation
    k
    
    a A b B cC d D
    

    k

    1 d [ A] 1 d [ B] 1 d [C ] 1 d [ D]
    r   
     a dt  b dt  c dt  d dt

     a b  c d
    r  k [ A] [ B]  k [C ] [ D]

    IC-4/18 Lecture-2 02-09-2004


    Free Energy and Entropy
    Equilibrium:
    • G = 0
    • Free energy:
    minimum
    • Entropy: maximum
     a b  c d
    r  k [ A] [ B ]  k [C ] [ D ]  0
     c d
    k [C ] [ D]
    K   a b
    k [ A] [ B]
    IC-5/18 Lecture-2 02-09-2004
    Free Energy and Entropy

    Reaction: G :  0
    • free energy: > minimum
    • entropy: < maximum

    c d
    1 [C ] [ D ]
    r  k  [ A] a [ B ] b (1  )  r 
     r 

    K [ A] a [ B ] b

    Kinetics Thermodynamics
    IC-6/18 Lecture-2 02-09-2004
    Chemical Equilibrium

    dG   A dn A   B dnB   C dnC   D dnD    i dni  0


    i
    dn A   A d , dnB   B d , dnC   C d , dnD   D d

    dG
       A  A   B  B  C C   D  D  i i  0
    d i

    The Chemical    0  RT ln(a )   0  RT ln( pi )


    i i i i 
    Potential p

    K (T )   (ci , eq )
    i
    G   i   0
    o
    i
    0

    i i
    IC-7/18 Lecture-2 02-09-2004
    Thermodynamics
    Table 2.2 Thermodynamic Data for Important Catalytic Reactions

    Reaction Ho (kJ/mol) Go 298(K)

    NH3  ½ N2 + 3/2 H2 + 45.9 + 16.4


    ½N2 + 3/2 H2  NH3 - 45.9 - 16.4
    N2 + 3 H2  2 NH3* - 91.9* - 32.8
    2 NO  N2 + O2* - 182.6 -175.2
    CH4 + H2O  CO + 3 H2 +205.9 +142.0
    CH4 + ½ O2  CO + 2 H2 - 35.9 - 86.8
    CH4 + 2 O2  CO2 + 2 H2O - 802.6 - 801.0
    CH4 + ½ O2  CH3OH - 275.6 - 111.77
    CO2 + 3H2  CH3OH + H2O - 49.3 + 3.5
    CO + 2H2  CH3OH - 90.5 - 25.1
    CO + H2O  CO2 + H2 - 41.2 - 28.6

    * this per two mole of NH3 or NO. Data taken from the JANAF Thermodynamic Tables.

    IC-8/18 Lecture-2 02-09-2004


    EX: Ammonia Synthesis
    N2 + 3 H2 = 2 NH3 1 P=100 bar
    with fugasity
    G° = -32.8 kJ/mol
    H° = -91.9 kJ/mol
    0.1 P=100 bar

    NH3 Fraction
    0.01 P=10 bar

    0.001 P=1 bar

     G / RT
    pNH 3 
    300 400 500 600 700 800
    K (T )  e  12 32
    p Temperature [K]
    p p
    N2 H2 IC-9/18 Lecture-2 02-09-2004
    The ammonia reactor
    inlet inlet

    N2+3 H2 = 2 NH3
    C
    G° = -32.8 kJ/mol
    A H° = -91.9 kJ/mol
    D
    B

    outlet
    IC-10/18 Lecture-2 02-09-2004
    Power Rate Laws

    Parametrization of the rate:


    nA nB nC nD
    r  k [ A] [ B ] [C ] [ D]
    or
    nA nB nC nD
    r  k p A p B pC p D

     ln r   ln r 
    nX   [X ] Reaction Order
     ln[ X ]  [X ]
    Example:  k K1K 2 p2
    r 
    1  K 2 p2 IC-11/18 Lecture-2 02-09-2004
    Equilibrium Constant and Free Energy

    - G° / RT - (H°-T S°) / RT


    K=e = e
    G° = standard Gibbs energy of reaction= H° - TS°

    Van 't Hoff equation:   ln( K (T ))


    2
    H  RT
    ` T
    H° = standard reaction enthalpy
    S° = Standard reaction entropy

     ln( K (T )) 1 K (T ) 1 K (T )   H
    H   RT 2  RT 2  RT 2
    T K (T ) T K (T ) 1 RT 2
    IC-12/18 Lecture-2 02-09-2004
    Temperature dependence of the rate constant

    - Eact / RT
    Arrhenius equation: k = ve

    E Eact = activation energy


    v = preexponential factor
    reactants
    Eact
    products

    reaction parameter

    IC-13/18 Lecture-2 02-09-2004


    Potential Energy Representation:
    dissociation - association

    A2 A#
    2 A A
    Energy (a.u.)

    Ea

    Ed
    H = Ed - Ea

    A2
    reaction coordinate or distance X-X
    IC-14/18 Lecture-2 02-09-2004
    Temperature Dependence of the Rate
    1000
    d [AB]
    R= 8.2 r = = k [A] [B]
    900
    dt
    800

    700
    Arrhenius: ln k = ln v Eact / RT
    600
    - Eact /RT
    k = ve

    ln k
    rate

    500

    400

    300

    200

    100

    0
    1 200 400 T (K) 600 800 1000 1000 / T

     ln( K (T )) 2  ln( K (T ))
    Eapp   RT  RT
    1 T
     
    T  IC-15/18 Lecture-2 02-09-2004
    Apparent Activation Energy

     ln r
    2
    Eapp  RT
    T
    Example:
     kK1 K 2 p2
    r 
    1  K 2 p2

    IC-16/18 Lecture-2 02-09-2004


    Heterogeneous Catalysis

    Adsorption
    O2  2   2 O 
    CO    CO 

    Reaction
    CO   O   CO2 *  2 
    Desorption
    CO 2   CO2  *
    IC-17/18 Lecture-2 02-09-2004
    Basic surface interactions

    • Reactions take place on the metal surface

    Molecular adsorption
    Dissociativ adsorption
    Diffusion
    Reaction
    Desorption

    CO CO2
    O

    IC-18/18 Lecture-2 02-09-2004

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