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    26 The Kinetics of Complex Reactions: V K (CH

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    Lukman Hakim
    The document summarizes reaction kinetics for complex chain reactions involving acetaldehyde decomposition and hydrogen bromine reaction. It also discusses conditions for thermal explosions in reactions involving hydrogen and oxygen. 1) Acetaldehyde decomposition follows a three-halves order rate law due to radical chain reactions involving CH3 and CH3CO intermediates. Applying a steady state approximation derives the observed rate law. 2) The hydrogen-bromine reaction has a more complex rate law than second order due to radical chain reactions involving H and Br intermediates. Applying a steady state approximation derives the empirical rate law. 3) Thermal explosions can occur when the rate of chain branching reactions exceeds the rate of chain terminating reactions, as

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    26 The Kinetics of Complex Reactions: V K (CH

    Uploaded by

    Lukman Hakim
    421 views4 pages
    The document summarizes reaction kinetics for complex chain reactions involving acetaldehyde decomposition and hydrogen bromine reaction. It also discusses conditions for thermal explosions in reactions involving hydrogen and oxygen. 1) Acetaldehyde decomposition follows a three-halves order rate law due to radical chain reactions involving CH3 and CH3CO intermediates. Applying a steady state approximation derives the observed rate law. 2) The hydrogen-bromine reaction has a more complex rate law than second order due to radical chain reactions involving H and Br intermediates. Applying a steady state approximation derives the empirical rate law. 3) Thermal explosions can occur when the rate of chain branching reactions exceeds the rate of chain terminating reactions, as

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    Chemical

    Original Title

    Lecture 18

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    The document summarizes reaction kinetics for complex chain reactions involving acetaldehyde decomposition and hydrogen bromine reaction. It also discusses conditions for thermal explosions in reactions involving hydrogen and oxygen. 1) Acetaldehyde decomposition follows a three-halves order rate law due to radical chain reactions involving CH3 and CH3CO intermediates. Applying a steady state approximation derives the observed rate law. 2) The hydrogen-bromine reaction has a more complex rate law than second order due to radical chain reactions involving H and Br intermediates. Applying a steady state approximation derives the empirical rate law. 3) Thermal explosions can occur when the rate of chain branching reactions exceeds the rate of chain terminating reactions, as

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    421 views4 pages

    26 The Kinetics of Complex Reactions: V K (CH

    Uploaded by

    Lukman Hakim
    The document summarizes reaction kinetics for complex chain reactions involving acetaldehyde decomposition and hydrogen bromine reaction. It also discusses conditions for thermal explosions in reactions involving hydrogen and oxygen. 1) Acetaldehyde decomposition follows a three-halves order rate law due to radical chain reactions involving CH3 and CH3CO intermediates. Applying a steady state approximation derives the observed rate law. 2) The hydrogen-bromine reaction has a more complex rate law than second order due to radical chain reactions involving H and Br intermediates. Applying a steady state approximation derives the empirical rate law. 3) Thermal explosions can occur when the rate of chain branching reactions exceeds the rate of chain terminating reactions, as

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    26 The kinetics of complex reactions

    26.1 The rate laws of chain reactions

    The thermal decomposition of acetaldehyde


    CH3CHO(g) → CH4(g) + CO(g)

    v = k[CH3CHO]3/2 26.1.1

    Initiation: CH3CHO → . CH3+ .CHO


    v = ki[CH3CHO]
    Propagation: CH3CHO + . CH3 → CH4 + CH3CO. kp
    Propagation: CH3CO. → .CH3 + CO k’p
    Termination: .CH3 + .CH3 → CH3CH3 kt

    The net rates of change of the intermediates are:


    d [ .CH 3 ]
    = k i [CH 3CHO ] − k p [ .CH 3 ][CH 3CHO ] + k ,p [CH 3CO . ] − 2k t [ .CH 3 ]2
    dt
    d [CH 3 CO . ]
    = k p [ .CH 3 ][CH 3 CHO ] − k ,p [CH 3 CO . ]
    dt
    Applying the steady state approximation to the above two equations
    0 = k i [CH 3 CHO ] − k p [ .CH 3 ][CH 3 CHO ] + k ,p [CH 3 CO . ] − 2k t [ .CH 3 ]2
    0 = k p [ .CH 3 ][CH 3CHO ] − k ,p [CH 3 CO . ]

    The sum of the above two equations is:


    ki [CH 3CHO ] - 2kt [.CH 3 ]2 = 0

    thus the steady state concentration of [.CH3] is:


    1/ 2
     k 
    [ CH3] =  i
    .
     [CH 3 CHO ]1 / 2
     2k t 
    The rate of formation of CH4 is:
    1/ 2
    d [CH 4 ]  k 
    = k p [ .CH 3 ][CH 3 CHO ] = k p  i  [CH 3 CHO ]3 / 2 26.1.2
    dt  2k t 

    Equation 26.1.2 is in agreement with the three-halves order observed


    experimentally.
    We have discussed earlier that hydrogen-bromine reaction has
    complicated rate law rather than the second order reaction as anticipated.
    Now we examine why
    H2(g) + Br2(g) → 2HBr(g)

    Yield
    k[ H 2 ][ Br2 ] 3 / 2
    v= 26.1.3
    [ Br2 ] + k '[ HBr ]

    The following mechanism has been proposed to account for the above
    rate law.

    Initiation: Br2 + M → Br. + Br. + M ki


    Propagation: Br. + H2 → HBr + H. kp1
    H. + Br2 → HBr + Br. kp2
    Retardation: H. + HBr → H2 + Br. kr
    Termination: Br. + Br. + M → Br2 + M* kt

    The net rates of formation of the two intermediates are


    d[ H . ]
    = k p1 [ Br . ][ H 2] − k p 2 [ H . ][ Br2 ] − k r [ H . ][ HBr ]
    dt
    d [ Br . ]
    = 2k i [ Br2 ][ M ] − k p1 [ Br . ][ H 2 ] + k p 2 [ H . ][ Br2 ] + k r [ H . ][ HBr ] − 2k t [ Br . ]2 [ M ]
    dt

    The steady-state concentrations of the above two intermediates can be


    obtained by solving the following two equations:
    k p1 [ Br . ][ H 2] − k p 2 [ H . ][ Br2 ] − k r [ H . ][ HBr ] = 0
    2k i [ Br2 ][ M ] − k p1 [ Br . ][ H 2 ] + k p 2 [ H . ][ Br2 ] + k r [ H . ][ HBr ] − 2k t [ Br . ] 2 [ M ] = 0

    1/ 2
    k  .
    [Br ] =  i  [Br2 ]1 / 2
     kt 
    . k p1 (k i / k t )1 / 2 [ H 2 ][ Br2 ]1 / 2
    [H ] =
    k p 2 [ Br2 ] + k r [ HBr ]
    substitute the above results to the rate law of [HBr]
    d [ HBr ]
    = k p1 [ Br . ][ H 2 ] + k p 2 [ H . ][ Br2 ] − k r [ H . ][ HBr ]
    dt
    1/ 2 3/ 2
    d [ HBr ] 2k p1 (k i / k t ) [ H 2 ][ Br2 ]
    = 26.1.4
    dt [ Br2 ] + (k r / k p 2 )[ HBr ]
    Equation 26.1.4 has the same form as the empirical rate law 26.1.4, so
    the two empirical rate constants can be identified as
    1/ 2
    k 
    k = 2k p  i 
     kt 
    k
    k’ = r
    k p2
    analyzing the effects of HBr, H2, and Br2 on the reaction rate based on
    equation 26.1.4.

    26.2 Explosions
    A thermal explosion is a very rapid reaction arising from a rapid
    increase of reaction rate with increasing temperature.

    A chain-branching explosion occurs when the number of chain


    centres grows exponentially.

    An example of both types of explosion is the following reaction


    2H2(g) + O2(g) → 2H2O(g)

    Initiation: H2 → H. + H.
    Propagation H2 + .OH → H. + H2O kp
    Branching: O2 + .H → O + .OH kb1
    O + H2 → .OH + H. kb2
    Termination H. + Wall → ½ H2 kt1
    H. + O2 + M → HO2. + M* kt2
    Analyzing the above reaction and show that an explosion occurs when
    the rate of chain branching exceeds that of chain termination.

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