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    Problem-set-3

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    Hà Nguyễn Thị Việt

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    Problem-set-3

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    Hà Nguyễn Thị Việt
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    Problem-set-3

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    General Chemistry II

    Problem set #3

    1. For the reaction: 4A(g) + 3B(g) 🡪 2C(g) the following data were obtained at constant temperature.

    a. What is the order with respect to each


    reactant?
    b. Write the rate law.
    c. Calculate k (using the data from Expt. 1).

    Rate = k[A]a[B]b; Look at experiment 2 and 4


    a = order with respect to A, - same [A] but double [B]
    b = order with respect to B, -> we can neglect [A] as it doesn’t change
    k = rate const
    - initial rate also double
    -> rate constant is positive k>0
    The rate law of this reaction
    Rate = k[A]2 [B]1 => Rate = k[B]b
    => Rate2 / Rate4 = ([B]2 / [B]4)b
    We calculate k by => 45/90 = (½)b
    substituting the data from
    => ½ = (½)b
    experiment
    => b = 1 = order of reaction with respect to B
    k = Rate / ([A]2 [B]1)
    = 5 / (0.12 *0.1) = 5000
    L/mol*min Look at experiment 1 and 2
    - same [B] but triple [A]
    -> we can neglect [B] as it doesn’t change

    - initial rate increase by a factor of 9


    ->rate constant is positive k>0
    => Rate = k[A]a
    => Rate2 / Rate1 = ([B]2 / [B]1)a
    => 45/5 = (1/3)a
    => 1/9 = (1/3)a
    => a = 2 = order of reaction with respect to A
    2. The rate law for the reaction 2NOBr(g) 🡪 2 NO(g) + Br2(g) at some temperature is

    a. If the half-life for this reaction is 2.00 s when [NOBr]0 = 0.900 M, calculate the value of k for this
    reaction.
    b. How much time is required for the concentration of NOBr to decrease to 0.100 M?

    Look that rate law of the reaction -> this is a 2nd order reaction
    The integrated rate law for 2nd order reactions: 1/[A] = kt + 1/[A]0
    [A]0 = initial concentration
    [A] = concentration at the time (t)

    With the half life: t1/2 = 1/(k[A]0)


    => k = 1/(t1/2[A]0)
    k = 1/(2*0.9) = 5/9 L/mol*s

    We have: 1/[A] = kt + 1/[A]0


    Time required for NOBr to reach 0.1M
    t = (1/[A] - 1/[A]0)/k = (1/0.1 - 1/0.9)/(1/(2*0.9)) = 16s

    3. The reaction
    (CH3)3CBr + OH- 🡪 (CH3)3COH + Br
    in a certain solvent is first order with respect to (CH 3)3CBr and zero order with respect to OH-. In
    several experiments, the rate constant k was determined at different temperatures. A plot of ln(k)
    versus 1/T was constructed resulting in a straight line with a slope value of -1.10 × 10 4 K and a y-
    intercept of 33.5. Assume k has units of s-1.
    a. Determine the activation energy for this reaction.
    b. Determine the value of the frequency factor A.
    c. Calculate the value of k at 25 oC.
    General Chemistry II

    We know some stuff about k (rate const) Use log to get things down on the ground
    We need to know Ea (activation energy) ln(k) = ln(A * e^(-Ea/RT))
    -> Arrhenius equation: k = A * e^(-Ea/RT) ln(k) = lnA + (-Ea/RT)
    A - frequency factor (same unit as k) A plot of ln(k) versus 1/T = a straight line with a slope
    R - gas const = 8.314 J/mol*K value of -1.10 × 104 K and y-intercept of 33.5.
    T - temperature in Kelvin ln(k) = (-Ea/R)*(1/T) + lnA
    => lnA = 33.5 => A = 3.54*10^14 s-1
    25oC = 298 K => Ea/R = 1.10*10^4
    => Ea = 1.10*10^4 * 8.314 = 91454 J/mol

    At 25oC.
    k = 3.54*10^14 * e^(-91454/(8.314*298)) = 0.0329 s-1
    4. For the reaction ABC + D ⇌ AB + CD, ΔHorxn = -55 kJ/mol and Ea(fwd) = 215 kJ/mol.
    Assuming a one-step reaction,
    a. draw a reaction energy diagram;
    b. calculate Ea(rev); rev = reverse reaction
    c. sketch a possible transition state if ABC is V-shaped.

    We have: ΔHorxn = Ea(fwd) - Ea(rev)

    => Ea(rev) = Ea(fwd) - ΔHorxn = 215 + 55 = 270 kJ/mol

    A possible transition state could be A-B-C-D


    ABC + D -> ABCD -> AB + CD

    And if ABC is V shape

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