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9 April, 20:36

The reaction described by H2 (g) + I2 (g) ⟶2HI (g) has an experimentally determined rate law of rate=k[H2][I2] Some proposed mechanisms for this reaction are: Mechanism A (1) H2 (g) + I2 (g) - →k12HI (g) (one-step reaction) Mechanism B (1) I2 (g) ⥫⥬=k-1k12I (g) (fast, equilibrium) (2) H2 (g) + 2I (g) - →k22HI (g) (slow) Mechanism C (1) I2 (g) ⥫⥬=k-1k12I (g) (fast, equilibrium) (2) I (g) + H2 (g) - →k2HI (g) + H (g) (slow) (3) H (g) + I (g) - →k3HI (g) (fast) Which of these mechanisms are consistent with the observed rate law? mechanism A mechanism C mechanism B In 1967, J. H. Sullivan showed that this reaction was dramatically catalyzed by light when the energy of the light was sufficient to break the I-I bond in an I2 molecule. Which mechanism or mechanisms are consistent with both the rate law and this additional observation? mechanism A mechanism C mechanism B

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  1. 9 April, 23:52
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    Mechanism A and B are consistent with observed rate law

    Mechanism A is consistent with the observation of J. H. Sullivan

    Explanation:

    In a mechanism of a reaction, the rate is determinated by the slow step of the mechanism.

    In the proposed mechanisms:

    Mechanism A

    (1) H2 (g) + I2 (g) →2HI (g) (one-step reaction)

    Mechanism B

    (1) I2 (g) ⇄2I (g) (fast, equilibrium)

    (2) H2 (g) + 2I (g) →2HI (g) (slow)

    Mechanism C

    (1) I2 (g) ⇄ 2I (g) (fast, equilibrium)

    (2) I (g) + H2 (g) ⇄ HI (g) + H (g) (slow)

    (3) H (g) + I (g) →HI (g) (fast)

    The rate laws are:

    A: rate = k₁ [H2] [I2]

    B: rate = k₂ [H2] [I]²

    As:

    K-1 [I]² = K1 [I2]:

    rate = k' [H2] [I2]

    Where K' = K1 * K2

    C: rate = k₁ [H2] [I]

    As:

    K-1 [I]² = K1 [I2]:

    rate = k' [H2] [I2]^1/2

    Thus, just mechanism A and B are consistent with observed rate law

    In the equilibrium of B, you can see the I-I bond is broken in a fast equilibrium (That means the rupture of the bond is not a determinating step in the reaction), but in mechanism A, the fast rupture of I-I bond could increase in a big way the rate of the reaction. Thus, just mechanism A is consistent with the observation of J. H. Sullivan
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