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    5 60 Lecture30

    Uploaded by

    Fahad Alasmi

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    5 60 Lecture30

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    Fahad Alasmi
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    6 views9 pages

    5 60 Lecture30

    Uploaded by

    Fahad Alasmi

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 9

    MIT OpenCourseWare

    http://ocw.mit.edu

    5.60 Thermodynamics & Kinetics


    Spring 2008

    For information about citing these materials or our Terms of Use, visit: http://ocw.mit.edu/terms.
    5.60 Spring 2008 Lecture #30 page 1

    Kinetics: Reaction Rates, Orders, Half Lives

    aA + bB → cC + dD

    Rate of Reaction:

    1 d[A] 1 d[B] 1 d[C ] 1 d[D]


    Rate = − =− = =
    a dt b dt c dt d dt

    N
    Experimentally ⇒ Rate = k∏ Ciγi
    i=1

    Where k = rate constant


    Ci = Concentration of Reactant “i”
    γi = Order of reaction with respect to
    reactant “i”

    ∑ γi = Overall rate of reaction


    i
    5.60 Spring 2008 Lecture #30 page 2

    I) Zero Order Reactions (rare)

    A → products

    d[A]
    − =k {k is in [moles/(liter sec)]}
    dt

    [A] = -kt + [A]o

    [A]

    t1/2 = [A]o/(2k)

    [A]o

    [A]o/2

    t1/2 t
    5.60 Spring 2008 Lecture #30 page 3

    II) First Order Reactions

    A → products

    d[A]
    − = k[A] {k is in [1/sec]}
    dt

    [A] = [A]o e-kt ln[A] = -kt + ln[A]o

    ln[A]

    ln[A]o

    Slope = -k

    t1/2 = (ln 2) / k = 0.693/k k = (0.693)/(t1/2)


    5.60 Spring 2008 Lecture #30 page 4

    III) Second Order Reactions

    a) Second order in one component

    A → products

    d[A]
    − = k[A] 2
    dt

    1 1
    = + kt
    [A] [A]o

    1/[A]

    Slope = k

    1/[A]o

    t1/2 = 1/(k[A]o)
    5.60 Spring 2008 Lecture #30 page 5

    b) First order in each of two components

    A +B → products

    d[A]
    − = k[A][B]
    dt

    1 [A][B]o
    kt = ln [A]o ≠ [B]o
    [A]o − [B]o [A]o [B]

    Special cases:

    1 1
    = + kt
    [A] [A]o
    i) [A]o = [B]o ⇒
    [A] = [B]

    This is like 2nd order in one component

    ii) [B]o <<[A]o ⇒ [B] = [B]oe-k’t

    where k’ = [A]ok

    This is pseudo 1st order


    5.60 Spring 2008 Lecture #30 page 6

    Determining Orders of Reactions

    I) Getting the data

    a) Quench the reaction, measure concentrations

    b) For gas phase, measure pressure vs. time

    c) Spectroscopically follow reactants/products

    Etc…

    II) Analyzing the data

    A) Reactions with one reactant:

    A → products

    a) Plot or analyze [A] vs. t

    ln[A] vs. t

    1/[A] vs. t

    and find which gives a straight line.

    b) Half-life method: measure t1/2 vs. [A]o

    1st order → t1/2 ∝ [A]o0

    2nd order → t1/2 ∝ [A]o-1

    etc….
    5.60 Spring 2008 Lecture #30 page 7

    c) Multiple lifetimes (t3/4 and t1/2) (at t3/4, [A]=[A]o/4 )

    t3/ 4
    1st order → t3/4 = (2ln2)/k ⇒ =2
    t1 / 2
    t
    2nd order → t3/4 = 3/([A]ok) ⇒ 3/ 4 = 3
    t1 / 2

    B) Reactions with more than one reactant:

    e.g. A + B + C → products

    a) Initial Rate Method

    Δ[A]
    For [A]o = Ro ≈ k[A]oα [B]oβ [C]oγ
    Δt t=0

    Δ[A] /
    For [A]o/ = Ro/ ≈ k[A]o/ α [B]oβ [C]oγ
    Δt t=0

    α
    R ⎛ [A]o ⎞

    Experimentally determine o/ = ⎜ ⎟
    Ro ⎜⎝ [A]o/ ⎟
    ⎠

    Ro
    If 2 [A]o/ = [A]o then, if =1 ⇒ α = 1
    Ro/
    Ro
    if = 2 ⇒ α=½
    Ro/
    Ro
    if =2 ⇒ α=1
    Ro/
    Ro
    if =4 ⇒ α=2
    Ro/
    etc…
    5.60 Spring 2008 Lecture #30 page 8

    b) Flooding or Isolation (goal is to try to make


    problem look like a one-
    reactant system)

    take [A]o << [B]o , [C]o

    e.g. flood system with B and C

    Then [B] ~ [B]o and [C] ~ [C]o

    d[A]
    So that − ≈ k'[A] α
    dt

    Where k' = k[B]oβ [C]oγ

    The reaction then becomes pseudo α-order with one


    reactant.

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