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    Kinetics of Buffered Reaction

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    jaanabhenchod
    A short powerpoint presentation on two problems of Chemical Kinetics. The problem is a solution to an Olympiad question.

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    Kinetics of Buffered Reaction

    Uploaded by

    jaanabhenchod
    85 views17 pages
    A short powerpoint presentation on two problems of Chemical Kinetics. The problem is a solution to an Olympiad question.

    Original Title

    Chemical Kinetics

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    A short powerpoint presentation on two problems of Chemical Kinetics. The problem is a solution to an Olympiad question.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    85 views17 pages

    Kinetics of Buffered Reaction

    Uploaded by

    jaanabhenchod
    A short powerpoint presentation on two problems of Chemical Kinetics. The problem is a solution to an Olympiad question.

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    You are on page 1of 17

    KINETICS OF BUFFERED

    REACTION

    Nitramide NO2NH2 decomposes


    slowly in aqueous solution
    according to the reaction:
    NO2NH2 (aq)
    N2O (g) + H2O (l)
    The experimental kinetic law is as
    follows:
    +
    dt
    [H
    O
    ] 2]
    d[N2O] = k [NO
    3 2NH

    a) What

    is the apparent
    order of this reaction in a
    buffered solution?
    ANSWER :

    In a buffer solution
    [H3O+]
    is constant and the reaction is
    of the first order:
    v = kl [NO2NH2]
    3

    Which of the following


    mechanisms is the most
    appropriate for the
    interpretation of this kinetic
    law?
    b)

    Mechanism 1:
    k1
    NO2NH2
    N2O +H2O

    Mechanism 2:
    k
    NO2NH2 + H3O+ 2
    k-2
    equilibrium)

    NO2NH3+ + H2O

    (rapid

    k3
    NO2NH3+

    N2O + H3O+

    (rate limiting

    step)
    5

    Mechanism 3:
    k4

    NO2NH2 + H2O
    equilibrium) k-4

    NO2NH + H3O+ (rapid

    k
    NO2NH
    step)

    H3O+ + OH
    reaction)

    k6

    N2O + OH

    (rate limiting

    2 H2O your answer. (very fast


    Justify

    ANSWER :

    The rate laws of the three mechanisms


    proposed are:
    v1 = k1 [NO2NH2]
    v2 = k3 [NO2NH3 +] k
    =-2k3k2 [NO2NH2] [H3O+]
    + NH ]
    v3 = k5 [NO2NH ] =
    [NO
    k-4k5k4 [H
    O
    2]
    2
    3

    Thus, it is the third mechanism that is


    correct.

    c) Show

    the relationship between


    the experimentally observed
    rate constant and the rate
    constants
    of
    the
    selected
    mechanism.
    ANSWER:

    k =k-4k5k4

    d) Show

    that hydroxyl ions catalyze


    the decomposition of nitramide.
    The decomposition is studied in
    a buffered solution of a constant
    volume V at a constant
    temperature by measuring the
    partial pressure of the gas N2O,
    considered to be insoluble in
    water, in a constant volume of
    the same value V above the
    solution.
    9

    t(min)

    p(Pa)

    10

    15

    2
    0

    2
    5

    6800 12400172002080024000

    After a sufficiently long time, the


    pressure stabilises at 40000 Pa.

    ANSWER:
    Noting that [H3O+]= KW /[OH ]
    It follows v = k/ KW [NO2NH2] [OH
    ]
    which shows the catalytic role of
    OH

    e Express the pressure p as


    ) function of time and the

    constant kl such that


    kl =
    [H3Ok+ ]
    ANSWER:
    d[N2O] can be expressed by the
    change
    of pressure dp(N2O)/RT
    (according to pV = nRT). We obtain:
    dt
    RT dt
    RT dt
    v= d[N+2O] = 1 dp(N2O) = 1
    [H3O ]
    k[NO2NH2]

    dp =
    1

    We also know that ,


    V[NO2NH2]=n(NO2NH2 )-n(N2O)=n(N2O)
    -n(N2O)
    from which
    dp = k RT (n(N2O) )-n(N2O) and
    thus
    dt [H3O+] V
    dp = k

    (p-p)= kl (p-p)

    Integration gives p= p(1- ekIt)


    1

    f) Verify graphically that the kinetic

    law is confirmed by these


    experimental results.
    ANSWER:

    -0.2
    -0.4
    -0.6

    10

    15

    20

    t(mins)
    x
    x
    x

    -0.8

    ln(p-p)
    p

    g Calculate kl giving its units.


    )
    ANSWER:

    The graph of f(x) = ln(1p/p)=-klt


    Is a straight line with the slope kl
    as shown in previous graph
    kl was determined to be 3.7102
    min-1.
    1

    REFERENCES
    THE 22ND INTERNATIONAL
    CHEMISTRY OLYMPIAD, 1990
    (Problem -5).
    CHESMISTRY AND CHEMICAL
    REACTIVITY by John C. Kotz,
    Paul M. Treichel,
    John Raymond Townsend,Pg. 720
    1

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