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    Mohammad Kanchwala
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    1. A physical organic chemist observed two parallel first-order reactions where a starting material A reacts to form products P1 and P2. When the rates of formation of P1 and P2 were monitored independently, both reactions showed the same kinetic isotope effect. 2. For parallel first-order reactions, the rates of formation of each product P1 and P2 follow the same mathematical form. However, the rate constants k1 and k2 can be extracted from the pre-exponential terms, not from analyzing each reaction individually. 3. Mechanistic branch points like parallel reactions can be deceptive, as an undetected parallel pathway could incorrectly be interpreted as a single first-order reaction and obscure the

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    Calculations of first order kinetics

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    Parallel first order reactions

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    1. A physical organic chemist observed two parallel first-order reactions where a starting material A reacts to form products P1 and P2. When the rates of formation of P1 and P2 were monitored independently, both reactions showed the same kinetic isotope effect. 2. For parallel first-order reactions, the rates of formation of each product P1 and P2 follow the same mathematical form. However, the rate constants k1 and k2 can be extracted from the pre-exponential terms, not from analyzing each reaction individually. 3. Mechanistic branch points like parallel reactions can be deceptive, as an undetected parallel pathway could incorrectly be interpreted as a single first-order reaction and obscure the

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    © All Rights Reserved
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    10 views7 pages

    Parallel First Order Reactions

    Uploaded by

    Mohammad Kanchwala
    1. A physical organic chemist observed two parallel first-order reactions where a starting material A reacts to form products P1 and P2. When the rates of formation of P1 and P2 were monitored independently, both reactions showed the same kinetic isotope effect. 2. For parallel first-order reactions, the rates of formation of each product P1 and P2 follow the same mathematical form. However, the rate constants k1 and k2 can be extracted from the pre-exponential terms, not from analyzing each reaction individually. 3. Mechanistic branch points like parallel reactions can be deceptive, as an undetected parallel pathway could incorrectly be interpreted as a single first-order reaction and obscure the

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    © All Rights Reserved
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    Flag for inappropriate content
    of 7

    XIII.

    Parallel 1st-Order Reactions:

    A. Observed:

    A famous physical organic chemist made the following observation...


    H(D)
    H-atom Ph
    abstraction
    Me
    (D)H H(D)
    Ph H(D)

    Me
    Me

    cyclization
    H(D)
    H(D)
    Ph

    When the rate of formation of the products were monitored independently,


    it was found that...

    kH/kD = 2.1 in both cases!!


    XIII. Parallel 1st-Order Reactions:

    B. Given:
    k1
    A P1
    !!!
    k2
    A P2
    !!!

    • This case is central to the control of selectivity, but it can be deceptive.

    C. Rate Equation:

    1. Species A:

    -d[A]/dt = k1[A] + k2[A] = (k1 + k2)[A]

    [A] = [A0] e ( 1
    " k + k2 ) t

    !
    XIII. Parallel 1st-Order Reactions:

    2. Species P1 and P2:

    d[P1]/dt = k1[A] = k1[A0] e"( k1 + k2 ) t

    Integrate... (CRC #12)


    !
    k [A ]
    [P1 ] = 1 o (1" e"( k1 + k2 )t ) (1)
    k1 + k2

    Similarly...

    ! k2 [Ao ]
    [P2 ] =
    k1 + k2
    (1" e"( k1 + k2 )t ) (2)

    !
    XIII. Parallel 1st-Order Reactions:

    D. Graphics:

    k1
    [P1] A P1
    [X] !!!
    [P2] k2
    A P2
    [A] !!!

    time
    1. Starting Material A:
    Let...
    f(x) = aebx
    such that...
    f(x) = [A] x=t a = [A0] b = -(k1 + k2)
    XIII. Parallel 1st-Order Reactions:

    2. Products P1 and P2:

    Let...

    f(x) = a(1 - ebx)

    such that...

    f(x) = [P1] or [P2]

    a = k1[A0]/(k1 + k2)

    (or k2[A0]/(k1 + k2))

    b = -(k1 + k2)

    • The values of k1 and k2 can be extracted from the values of


    adjustable parameters a and b. However...
    XIII. Parallel 1st-Order Reactions:

    E. Caveat:

    Recall, for a 1st-order reaction...

    [P] = [A0] - [A] = [A0] - [A0] e-kt = [P∞](1-e-kt)

    f(x) = a(1 - ebx)

    • Therefore, formation of the products in parallel 1st-order reactions follow the


    same mathematical form as a single 1st-order reaction. However, in a parallel
    reaction, b = -(k1 + k2). The difference appears in the pre-exponential term, a.

    • If you monitor the formation of either P1 or P2 and analyze the data as a simple
    first-order reaction, you will get the same rate constant!

    • If either k1 or k2 has a kinetic isotope effect, the rate of formation of both


    products will show a kinetic isotope effect. Moreover, formation of P1 and P2 will
    exhibit the same kinetic isotope effect if treated as a simple (rather than parallel)
    1st-order reaction! Mechanistic branch points can be deceptive, and an
    undetected parallel pathway could be very misleading.
    XIII. Parallel 1st-Order Reactions:

    k1
    A P1
    !!!
    F. Selectivity: k2
    A P2
    !!!
    By dividing through the integral
    forms of the rate equations (eq (1) and eq (2))...

    [P1]/[P2] = k1/k2

    Alternatively, the integration can be skipped...

    d[P1]/dt k1[A] k1
    [P1 ]/[P2 ] = = =
    d[P2]/dt k2 [A] k2

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