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12/01/2011




   Course Title: General and Inorganic
                Chemistry

                   TOPIC 3: CHEMICAL KINETICS
                             Lecturer and contacts

                             Mr. Vincent Madadi
                 Department of Chemistry, University of Nairobi
                           P. O. Box 30197-00100,
                                 Nairobi, Kenya
                          Chemistry Dept. Rm 114
                            Tel: 4446138 ext 2185

            Email: vmadadi@uonbi.ac.ke, madadivin2002@yahoo.com

                Website: http://www.uonbi.ac.ke/staff/vmadadi


1/12/2011                             mov                         1




                            Introduction

• Kinetics is the study of rates of chemical reactions and
  the mechanisms by which they occur.

• The reaction rate is the increase in concentration of a
  product per unit time or decrease in concentration of a
  reactant per unit time.

• A reaction mechanism is the series of molecular steps
  by which a reaction occurs.


1/12/2011                             mov                         2




                                                                              1
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     Thermodynamic vs kinetics of reaction
• Thermodynamics determines if a reaction can occur.
  Kinetics determines how quickly a reaction occurs

• Some reactions that are thermodynamically feasible
  are kinetically so slow as to be imperceptible

• The Rate of a Reaction
     Cdiamond + O2(g)→ CO2(g) ΔG°= -396kJ
                    Very Slow

            H+(aq) + OH-(aq) → H2O(l) ΔG°= -79kJ
1/12/2011               Very Fastmov                   3




                 Rate of chemical reaction
• 2 N2O5 → 4 NO2 + O2

• 2 moles of N2O5 disappear for every 4 moles of NO2
  and 1 mole of O2 formed.

• Reaction rates are the rates at which reactants
  disappear or products appear.

• This movie is an illustration of a reaction rate.

1/12/2011                       mov                    4




                                                                   2
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                    Reaction rate

• Reaction rate is the change of concentration of a
  reactant or product per unit time
            aA + bB → cC + Dd
      Reaction rate = ΔConcentration
                           Δtime

• Rate is expressed either as rate of appearance of product
  or rate of disappearance of reactant

• E.g.
                   aA + bB → cC + dD
1/12/2011                    mov                          5




                    Reaction rate
             2 NO2(g) → 2 NO(g) + O2(g)




1/12/2011                    mov                          6




                                                                      3
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                           Reaction rate


• Mathematically, the rate of a reaction can be written as:




•     Square brackets [ ] are often used to express molarity
      (i.e.[HCl] means Molarity of HCl)

•      The relative rates of consumption of reactants and
       formation of products depend on the reaction stoichiometry

    1/12/2011                       mov                              7




                           Reaction rate
    • The relative rates of consumption of reactants and formation
      of products depend on the reaction stoichiometry

    • For the reaction
           2HBr (g) → H2 (g) + Br2 (g)

    • two moles of HBr are consumed for every one mole of H2
      which is formed




    1/12/2011                       mov                              8




                                                                                 4
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                     Reaction rate
• Experimental Rate Law: the rate of a reaction is
  proportional to the product of the concentrations of
  the reactants raised to some power.

• For a reaction
              aA + bB → products,
  the rate law is the equation
             rate = k[A]x[B]y

• Relationships Between Rate and Concentration
1/12/2011                    mov                          9




                    Reaction rate
• x and y are the orders of the reaction in [A] and [B]
  respectively

• The overall order of the reaction is x + y

• x and y are usually small integers, but may be zero,
  negative, or fractions

• k is the specific rate constant


1/12/2011                    mov                          10




                                                                       5
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                         Rate constant k
 • Units depend on overall reaction order

 • Value does not change with concentration

 • Value does not change with time

 • Valid for a specific temperature

 • Dependent on presence or absence of a catalyst

 • Value must be determined experimentally


 1/12/2011                        mov               11




             Factors that affect rate of reaction
• They are six key factors that affect rate of
  reaction:
   1)        Nature of reactants and products
   2)        Concentration
   3)        Temperature
   4)        Catalyst
   5)        Surface area
   6)        Light radiation


 1/12/2011                        mov               12




                                                                 6
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        Factors that affect rate of reaction
 1. Nature of reactants and products
 • Chemical reactions involve rearrangement of bonds: Bonds in
   reactants are broken and new bonds are formed in products

 • In organic or molecular reactions, large number of bonds are
   broken in reactants and formed in products-hence reactions are
   slow
 • E.g. Hydrolysis of cane sugar:

             C12H22O11 + H2O         C6H12O6 + C6H12O6
               Cane sugar             glucose   fructose

 1/12/2011                          mov                          13




         Factors that affect rate of reaction...
• Inorganic reactions involve ions, hence no bonds to be broken in
  reactants . The reactions are faster.
• E.g.
  Ag+(aq) + NO3-(aq) + Na+Cl-(aq)       AgCl(aq) + NaNO3(aq)

• Concentration
• Based on the rate law of mass action, the rate of reaction is
  directly proportional to the product of the concentration of the
  reactants at a particular temperature

• For reaction        aA + bB             cC + dC


 1/12/2011
                          Rate = K[A]a[B]b
                                    mov                          14




                                                                              7
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        Factors that affect rate of reaction ...
3) Temperature
• In most reactions, the rate of reaction doubles with 10 K increase
   in temperature

• But with 10 k increase in temperature, collision frequency (Z)
  increases by a factor of 1.016

  I.e. Z α T½
       Z2/Z1 = (T2/T1)1/2 = (310/300)1/2 = 1.016
• However, the rate increases by almost 100%

• This is because increasing temperature by 10 K increases the
    number of active molecules (molecules with E > Ea) which
    increases the rate drastically mov
 1/12/2011                                                         15




       Factors that affect rate of reaction ...
     Effect of increase in temperature by 10 K




 1/12/2011                       mov                               16




                                                                                8
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        Factors that affect rate of reaction...

• 4) Catalyst
• A catalyst is a substance that alters the rate of reaction without
  itself getting consumed

• There are two types of catalysts:
• Positive catalyst: It increases the rate of reaction e.g.
                 MnO2
       2KClO3                  2KCl + 3 O2
                   300 ⁰C
• MnO2 acts as a positive catalyst since uncatalysed reaction
  takes place at 700 ⁰C and is slower
1/12/2011                       mov                              17




        Factors that affect rate of reaction...

• Negative catalyst: This is the catalyst which retards
  the rate of reaction e.g. Oxidation of chloroform is
  retarded by ethanol
                 1% ethanol
  4CHCl3 + 3 O2              4COCl2 + 2Cl2 + H2O

Mechanism of catalysis
• A catalyst alters the rate of reaction by providing a
  path with lower or higher activation energy

1/12/2011                       mov                              18




                                                                               9
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        Factors that affect rate of reaction...

5) Surface area
• The rate of homogeneous reaction is influenced by
   the surface area of the reactants

• Particle size decreases, surface area increases for the
  same mass because of creation of new surfaces.
  Hence the rate of reaction increases

• E.g. Powdered zinc reacts faster with dilute HCl than a
  block of zinc
1/12/2011                  mov                          19




        Factors that affect rate of reaction...

6) Light radiation
• The rate of photochemical reaction is affected by light
   radiation

• Photons (E = hv) supply the necessary energy of
  activation to the reactant molecules to form products

             λ = 400 nm
• E.g. H2 + Cl2        2HCl
1/12/2011                  mov                          20




                                                                    10
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                 Order of reaction
• This is the sum of the powers of the concentration
  term in an experimentally established rate law
• Example
              aA + bB → cC + dD

• The theoretical rate law is:
           Rate = K[A]a[B]b

• But experimentally determined rate expression is:
            Rate = K[A]α[B]β
1/12/2011                   mov                          21




            Order of reaction cont.
• Where α and β are the actual moles of A and B and
  may not be necessarily be equal to “a” and “b”

• Overall order of reaction is given by the sum of the
  individual orders i.e.

• Overall order = α + β

• Order of reaction can be zero, +ve, -ve or fraction.
  But higher orders of reaction are rare
1/12/2011                   mov                          22




                                                                     11
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            Order of reaction cont.
• In complex reactions the order of reaction is
  determined by the slowest step of the reaction which
  is also called the rate determining step




1/12/2011                   mov                         23




             Molecularity of reaction
• This is the total number of molecules in the step
  leading to chemical reaction

• For any reaction, the least number of molecules is one

• Thus molecularity cannot be zero or fraction

• Types of molecularity:

1) Unimolecular reactions:
•1/12/2011
    Reactions involving one molecule of the reactants
                             mov                        24




                                                                    12
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                Molecularity of reaction
 • Example:
   PCl5           PCl3 + Cl2

 2) Bimolecular reactions
    CH3COOC2H5 + H2O           CH3COOH + C2H5OH

 3) Thermolecular reactions
    2NO + O2         2NO2



 1/12/2011                     mov                      25




             Pseudo uni-molecular reactions
• The reaction in which the order is one but molecularity
  is 2

• E.g.
  CH3COOC2H5 + H2O             CH3COOH + C2H5OH

• Order is one because water is in excess, hence
  concentration does not change during the reaction

• Thus, the rate is independent of the conc. Of water but
   only dependent on conc. of ester
 1/12/2011                  mov                         26




                                                                    13
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                        Rate law
• Exercise
1) The rate of reaction 2NO + O2              2NO2
  follows the rate law Rate = K[NO]2[O2]
  If K = 2x 10-6 mol-1L2, What is the rate of the reaction
  when [NO] = 0.04 molL-1 and [O2] = 0.2 molL-1

   [ Ans = 6.4 x 10-10 molL-1s-1]



1/12/2011                     mov                        27




                        Rate law
2. The rate of the reaction
   2NO + O2            2NO2
is doubled when the concentration of O2 is doubled,
   but increases by factor of 8 when the concentration
   of both reactants is doubled.
Determine the:
a) Order of reaction wrt NO and O2
b) Overall order of reaction


1/12/2011                     mov                        28




                                                                     14
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                         Activation energy
• This is the additional amount of energy that reactant
  molecules must acquire in order to react and form products

• It is defined as the amount of energy that the reactants must
  absorb to pass over the activation energy barrier to form
  products
• Activation energy diagram


                                Ea
                  Reactant
             ER
     E Th


                                                 Product

 1/12/2011                       mov                              29




                    Activation Energy cont.
• E = Eth –ER
        = Threshold Energy –Energy possessed by molecules
• The activation energy is related to the rate constant K and
  temperature T according to Arrhenius equation

 K = Ae-Ea/RT
Where A = Frequency factor
      K = rate constant
      T = temperature in Kelvin
      R = Gas constant
      E = Activation energy
      e = base of natural logarithm
 1/12/2011                       mov                              30




                                                                              15
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             Derivation of Arrhenius equation
 • Arrhenius equation is derived from the Vant’
   Hoffs reacton isochore
             dlnKc/dT = ΔE/RT2
   and the reaction dynamic equilibrium
             A+B=C+D
 • Kc for the reaction,
   Kc = Kf/Kb = [C][D]/[A][B]
   Kf[A][B] = Kb[C][D]

 • Hence, Kc = Kf/Kb
 1/12/2011                  mov                            31




      Derivation of Arrhenius equation cont.
• If ΔE is written as Ef –Eb, then from equation 1 and 2
  then,

• dlnKf/dT – dlnKb/dT = Ef/RT2 – Eb/RT2

• or dlnk/dT = E/RT2

  dlnk = EdT/RT2

• Integrating the equation gives,
      lnk = -E/RT + C
 1/12/2011                  mov                            32




                                                                       16
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     Derivation of Arrhenius equation cont.
• Provided E is a constant, the equation can be written
  as:
      k = Ae-E/RT
• This is the Arrhenius equation

• Application of activation energy
1) To determine activation energy




1/12/2011                   mov                           33




            Determination of activation Energy

• There are two methods for determining of activation
  energy Ea

    1) Graphical method
    2) Rate constant method

1) Graphical method
• From Arrhenius equation, K = Ae-E/RT

• Applying lo to both sides of the equation,
1/12/2011                 mov                             34




                                                                      17
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  Determination of activation Energy cont.
• lnK = lnA – Ea/RT
• >2.303logK = 2.303logA – Ea/RT

• >logK = logA – Ea/2.303RT

• >logK = -Ea/2.303RT + logA
 Ξ y = mx + C

• Plotting logK against 1/T give a straight line and Ea can
  be calculated
1/12/2011                    mov                              35




      Graphical Determination of activation
                     energy
• Graph                       Log A



                              Slope = -Ea/2.303RT


            Log K
                                      Ea = slope x -2.303 R




1/12/2011                    mov                              36




                                                                          18
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      Graphical Determination of activation
                    energy...
• Slope = -Ea/2.303xR

• Ea = -2.303 x R x Slope

• Log A = Intercept

            A = Antilog (Intercept)


1/12/2011                     mov                      37




      2. Determination of activation energy
           from rate constant method
• From K = Ae-Ea/RT

• lnK = lnA – Ea/RT

• Let at Temperature T1 and rate constant K1; and at T2
  and rate constant K2

• For small change in temperature, the change Ea and
  A do not significantly change

1/12/2011                     mov                      38




                                                                   19
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    Determination of activation energy from rate
                constant method ...
• Thus,
  lnK1 = lnA – Ea/RT1                              3
  lnK2 = lnA – Ea/RT2                              4

• Subtracting 3 from 4,
• LnK2 – lnk1 = Ea/RT1 – Ea/RT2                    5

• logK2/K1 = Ea [1/T1 – 1/T2]
            2.303
• logK2/K1 = Ea [(T2-T1)/T1T2]
               2.303R
 1/12/2011                  mov                            39




    Determination of activation energy from rate
                constant method...
 • Log K2/K1 = Ea [(T2-T1)/T1T2]                 Eq. 6
                   2.303R
 Since K1, K2, T1 and T2 are known, Ea can be calculated
    from the equation 6




 1/12/2011                  mov                            40




                                                                       20
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                          Rate Laws
• A rate law shows the relationship between the reaction rate and
  the concentrations of reactants. Exponents tell the order of the
  reaction with respect to each reactant.

• This reaction is
      First-order in [NH4+]
      First-order in [NO2−]
• The overall reaction order can be found by adding the
  exponents on the reactants in the rate law.

• This reaction is second-order overall.


• For gas-phase reactants use PA instead of [A]
    1/12/2011                     mov                            41




                    Integrated Rate Laws
• These are expressions which relate the concentration of
  the reactants with time

• Application:
1) Used to predict amount of reactant or product at a
   particular time
2) Predict how long the reaction will take
3) To predict when a toxic chemical can be disposed

•       Can be classified into Zero, first, second and third
        order reactions
    1/12/2011                     mov                            42




                                                                             21
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               Integrated Rate Laws cont.
1) Zero order reactions
• This is a reaction where the rate of reaction is
   independent of the concentration of the reactants


•     Derivation:
•     Let                                   A              Product
•     Initial conc. (mol/l) t = 0,          a                 0
•     At time t = t,                        a-x               x

•     Where x is the concentration of the reactant (A)
      undergoing decomposition
1/12/2011                             mov                                    43




            Zero order reactions cont.
• Rate expression for zero order reaction:
• dx/dt α (a-x)0 ........................................................Eq.1

• Or dx/dt = Ko(a-x)o = ko .......................................Eq. 2
• K0 is the rate constant for zero order reaction

• Integrating the equation,
• ∫dx = ∫Kodt = Ko ∫dt
  x = Kot + C, .............................................................Eq. 3
• Where C is the integration constant
1/12/2011                             mov                                    44




                                                                                           22
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             Zero order reactions cont.
 • But when t = 0 and x = 0
 • Thus,
       0 = Ko x 0 + C .............................................Eq. 4
 • Hence C = 0
 • Substituting the value of C into equation 3 gives,
     x = Kot
 • Therefore, Ko = x/t ...........................................Eq. 5

 • Eq.5 is the rate constant equation for zero order
   reaction
 1/12/2011                         mov                                 45




             Zero order reactions cont.
• Units for rate constant:
• Ko = x/t = conc/time = molL-1/s = molL-1s-1


• Half-life –This is the time duration in which half the
  concentration of reactants is transformed into products
• Thus at t = t½, x = a/2,

• Substituting these values into equation 5
  K0 = a/2t½        t ½ = a/2k0           t½ α a
• This shows that half-life of a zero order reaction is
  directly proportional to the initial concentration
 1/12/2011                         mov                                 46




                                                                                   23
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            Zero order reactions cont.
• Graph for zero order reaction

                      The rate of reaction is independent
                      of the concentration of reactants

      Rate




                   Concentration of reactants
1/12/2011                   mov                             47




              First Order Reactions
• First Order Reactions
• These are reactions where the sum of the powers of
  concentration of the exponential term in an
  experimentally established rate law is one

• Thus the rate of reaction is dependent on the single
  power of the concentration term of the reactants

• Example:
• For the reaction,    A              Product
1/12/2011                   mov                             48




                                                                        24
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             First Order Reactions cont.
 • Initial conc (molL-1) at t=0, a                       o ......Eq. 1
 • Conc (molL-1) at t=t           a-x                    x .......Eq. 2

 • Where x moles of A have decomposed into products in
   time “t”

 • Deferential, -d(a-x)/dt or dx/dt α(a-x) ...............EQ. 3
 • Or dx/dt = k1(a-x) ...............................................Eq. 4
 • Where, K1 is the rate constant for first order reaction.

 1/12/2011                           mov                                  49




             First Order Reactions cont.
• Rearrangement,
• dx/(a-x) = k1dt ....................................................Eq. 5

• Integrating,                        [identity ∫dx/x = ln x]
       ∫dx/(a-x) = k1 ∫dt
    -ln(a-x) = k1t + C ..............................................Eq. 6
• Where C = constant of integration
• But at t=0, x = o

• Substituting the values into equation 6,
 1/12/2011                           mov                                  50




                                                                                      25
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             First Order Reactions cont.
•   -lna = C .............................................................Eq. 7
•   Substitute the value of C into equation c,
•   -ln(a-x)= k1t –lna ................................................Eq. 8
•   Rearranging
•    k1t = lna – ln(a-x)
•   K1 = ln[a/(a-x)]x 1/t
•   Change ln to log10                        [lnx = 2.303logx]
•   K1 = (2.303/t)log(a/a-x) .......................................Eq.8
•   This is the expression for rate constant for first order
    reaction
 1/12/2011                                    mov                                              51




             First Order Reactions cont.
• Unit of the rate constant
• From Eq. 8
• K1 = (2.303/t)log(a/a-x) = conc/(time xconc)
  k1 = 1/time = s-1 ...................................................................Eq. 9

Graph for first order reaction
• From equation 8
• -ln(a-x)= k1t –lna

• Multiply though by -1
•1/12/2011
    ln(a-x)= -k1t + lna                       mov                                              52




                                                                                                           26
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               First Order Reactions cont.
 • Introduce log10
 • 2.303log(a-x) = -k1t + 2.303 x log(a)

 • Or log(a-x) =           -k1 x t + log(a) ...........................Eq. 10
                            2.303
              Ξ y =mx +c
                               Log(a)

                                 Slope = -k1/2.303
Log(a-x)


  1/12/2011                t            mov                                53




              Second order reactions cont.
 • From the graph,
 • K1 = -2.303 x slope

 • Half-life of first order reaction
 • From Eq. 8, K1 = 2.303 Log (a/a-x)
                            t
 • At t = t ½ , x = a/2

 • Substituting the values into the equation
 •   K1 = 2.303 Log (a/a - a/2) = 2.303 log 2
           t½                       t½

  1/12/2011                             mov                                54




                                                                                       27
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            First Order Reactions cont.
• Making t ½ the subject,
• t½ = 2.303 log 2 = 2.303 x 0.301 = 0.693
         k1              k1           k1

• Thus, t½ = 0.693/k1

• This means that for 1st order reactions, half-life is
  independent of the initial concentration of reactants



1/12/2011                  mov                         55




               3. Second order reaction
• These are reactions in which the sum of the powers of
  the of the concentration term in an experimentally
  established rate law is 2

• There are two cases of second order reaction
• Case 1:    2A              Product
• Thus, Rate law = dx/dt = K[A]2        Order = 2

• Case 2:     A+B                Product
• Rate law = dx/dt = k[A][B]               order = 2

1/12/2011                  mov                         56




                                                                   28
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             Second order reaction cont.
• Case 1: Occurs when the concentration of both reactants
  is the same

• Case 2: Occurs when the concentration of both reactants
  is NOT the same

• 1) Case 1: Concentration of both reactants is the same

• Let the reaction, A +                  A              Product
• Initial conc. t=0 a                      a              0 ..Eq. 1
• Conc. At t = t a-x                      a-x             x ...Eq. 2
 1/12/2011                         mov                                 57




             Second order reaction cont.
• Conc. is in mol L-1
• Thus, x molL-1 of the reactant A decomposes in time t

• Deferential,
• dx/dt α (a-x)(a-x) or dx/dt α (a-x)2             ..................Eq. 3

• Introduce rate constant k2

• dx/dt = k2 (a-x)2         ......................................Eq. 4
• Where k2 is the rateconstant for the second order
  reaction
 1/12/2011                         mov                                 58




                                                                                    29
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                Second order reaction cont.
• Rearranging,
• dx/ (a-x)2 = k2 dt .....................................................Eq. 5

•    Integrating,
•    ∫dx/(a-x)2 = k2∫dt          note [∫xndx = xn+1/n+1]
•    Hence,
•    1/(a-x) = k2t + C ...................................................Eq. 6

• Where C = constant of integration
• But when t= 0, x= 0
    1/12/2011                          mov                                   59




                Second order reaction cont.
• Substituting the values into the equation,
• 1/a = C
• Substitute the value of C into equation 6
•   1/(a-x) = k2t + 1/a        .............................Eq. 7

• Thus, K2t = 1/(a-x) - 1/a

• Hence, K2 = (1/at) x [x/(a-x)] ...................Eq. 8

• Eq.8 is the expression for rate constant for second order reaction
  where initial conc. of the reactants is the same
    1/12/2011                          mov                                   60




                                                                                         30
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            Second order reaction cont.
• Case 2: When concentration of both reactants is
  different

• Let the reaction, A +                  B              Product
• Initial conc. t=0 a                     b                0 ..Eq. 1
• Conc. At t = t a-x                     b-x               x ...Eq. 2

• Where x mol/L of A and B decomposed in time t to
  form product
1/12/2011                          mov                                 61




            Second order reaction cont.
•   Differential
•   dx/dt α (a-x)(b-x)
•   dx/dt = K2(a-x)(b-x)
•   Where K2 is the rate constant for second order
    reaction

• Separating the variables,
• dx/[(a-x)(b-x)] = K2 dt ..........................................Eq. 3


1/12/2011                          mov                                 62




                                                                                   31
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            Second order reaction cont.
• Integration by parts

•      ∫ dx        = ∫ A dx       +       ∫B dx         = ∫k2dt ...Eq.4
        (a-x)(b-x)     (a-x)               (b-x)

•         1        = A +                  B        ......................Eq.5
        (a-x)(b-x)   (a-x)               (b-x)

• Multiply through by (a-x)(b-x)

• 1 = A(b-x) + B(a-x) ..............................................Eq. 6
1/12/2011                          mov                                      63




            Second order reaction cont.
• When x = a, 1 = A(b-a)
   Thus, A = 1/(b-a)
• When x = b, 1 = B(a-b)
  Thus, B = 1/(a-b)
Or
• ∫ dx        = 1    ∫dx + 1 ∫dx       = k2 ∫ dt ..Eq. 7
    (a-x)(b-x) (b-a) (a-x) (a-b) (b-x)

• Factorise the middle term by 1/(a-b)

• = ∫ dx      = 1 [ ∫dx - ∫dx ] = k2 ∫ dt ...Eq. 8
   (a-x)(b-x) (a-b)  (b-x) (a-x)
1/12/2011                          mov                                      64




                                                                                        32
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            Second order reaction cont.
• ∫       dx     = 1 [ -ln(b-x) + ln(a-x)] = k2 ∫ dt ..Eq. 9
        (a-x)(b-x) (a-b)

Therefore,

• =           1 [ ln (a-x) ] = k2t + C ......................Eq. 10
            (a-b)    (b-x)

When t = 0, x = 0,
Substituting into the equation 14,

1/12/2011                             mov                                 65




            Second order reaction cont.
• =           1 [ ln (a ] = C .....................................Eq. 11
            (a-b)    (b)

• Substitute the value of C in eq. 15 into eq. 14

• =           1 [ ln (a-x) ] = k2t + 1 [ ln (a ]..........Eq. 12
            (a-b)    (b-x)           (a-b)   (b)

Thus
•    K2 =           1        [ ln b(a-x) ] ............................Eq. 13
                  (a-b)t          a(b-x)
1/12/2011                             mov                                 66




                                                                                       33
12/01/2011




                Second order reaction cont.
• Applying log10

• K2 = 2.303 log b(a-x) .............................................Eq. 14
      (a-b)t     a(b-x)

Characteristics:
Unit : K2 = 1 x x
            at (a-x)

                   = 1/(conc x time)

                K2 = [conc. X time]-1   .............................................................Eq. 15
    1/12/2011                           mov                                                            67




                Second order reaction cont.
• K2 = [mol-1s]-1 = mol-1Ls-1

•    When one of the reactants is in excess,
•    i.e. Let a>> b
•    a-b = a,          a-x =a
•    Thus b and x can be neglected in comparison to a

• Hence, K2 = 2.303 logb(a-x) ................................Eq. 16
               (a-b)t  a(b-x)

•       k2 = = 2.303 log(b/b-x)) .....................................Eq. 17
                 at
    1/12/2011                           mov                                                            68




                                                                                                                     34
12/01/2011




            Second order reaction cont.
• k2a = = 2.303 log(b/b-x)) ................................Eq. 18
            t

• k’ = = 2.303 log(b/b-x)) .................................Eq. 20
            t

Where K2a = k’ = rate constant for the first order
 reaction



1/12/2011                       mov                                  69




            Second order reaction cont.
• Graph for second order reactions



 1 lnb(a-x)
(a-b) a(b-x)



                                  t

1/12/2011                       mov                                  70




                                                                                 35
12/01/2011




            Second order reaction cont.
• Half life
• From equation 8, case 1
• K2 = 1 x x
        at (a-x)

• t = t 1/2 , x = a/2

• K2 = 1 x a/2
       at ½ (a – a/2)

• t ½ = 1/k2.a .....................................................Eq. 21
1/12/2011                           mov                                      71




            Second order reaction cont.
• Thus t ½ is directly proportional to 1/a




1/12/2011                           mov                                      72




                                                                                         36

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Chemical kinetics lecture

  • 1. 12/01/2011 Course Title: General and Inorganic Chemistry TOPIC 3: CHEMICAL KINETICS Lecturer and contacts Mr. Vincent Madadi Department of Chemistry, University of Nairobi P. O. Box 30197-00100, Nairobi, Kenya Chemistry Dept. Rm 114 Tel: 4446138 ext 2185 Email: vmadadi@uonbi.ac.ke, madadivin2002@yahoo.com Website: http://www.uonbi.ac.ke/staff/vmadadi 1/12/2011 mov 1 Introduction • Kinetics is the study of rates of chemical reactions and the mechanisms by which they occur. • The reaction rate is the increase in concentration of a product per unit time or decrease in concentration of a reactant per unit time. • A reaction mechanism is the series of molecular steps by which a reaction occurs. 1/12/2011 mov 2 1
  • 2. 12/01/2011 Thermodynamic vs kinetics of reaction • Thermodynamics determines if a reaction can occur. Kinetics determines how quickly a reaction occurs • Some reactions that are thermodynamically feasible are kinetically so slow as to be imperceptible • The Rate of a Reaction Cdiamond + O2(g)→ CO2(g) ΔG°= -396kJ Very Slow H+(aq) + OH-(aq) → H2O(l) ΔG°= -79kJ 1/12/2011 Very Fastmov 3 Rate of chemical reaction • 2 N2O5 → 4 NO2 + O2 • 2 moles of N2O5 disappear for every 4 moles of NO2 and 1 mole of O2 formed. • Reaction rates are the rates at which reactants disappear or products appear. • This movie is an illustration of a reaction rate. 1/12/2011 mov 4 2
  • 3. 12/01/2011 Reaction rate • Reaction rate is the change of concentration of a reactant or product per unit time aA + bB → cC + Dd Reaction rate = ΔConcentration Δtime • Rate is expressed either as rate of appearance of product or rate of disappearance of reactant • E.g. aA + bB → cC + dD 1/12/2011 mov 5 Reaction rate 2 NO2(g) → 2 NO(g) + O2(g) 1/12/2011 mov 6 3
  • 4. 12/01/2011 Reaction rate • Mathematically, the rate of a reaction can be written as: • Square brackets [ ] are often used to express molarity (i.e.[HCl] means Molarity of HCl) • The relative rates of consumption of reactants and formation of products depend on the reaction stoichiometry 1/12/2011 mov 7 Reaction rate • The relative rates of consumption of reactants and formation of products depend on the reaction stoichiometry • For the reaction 2HBr (g) → H2 (g) + Br2 (g) • two moles of HBr are consumed for every one mole of H2 which is formed 1/12/2011 mov 8 4
  • 5. 12/01/2011 Reaction rate • Experimental Rate Law: the rate of a reaction is proportional to the product of the concentrations of the reactants raised to some power. • For a reaction aA + bB → products, the rate law is the equation rate = k[A]x[B]y • Relationships Between Rate and Concentration 1/12/2011 mov 9 Reaction rate • x and y are the orders of the reaction in [A] and [B] respectively • The overall order of the reaction is x + y • x and y are usually small integers, but may be zero, negative, or fractions • k is the specific rate constant 1/12/2011 mov 10 5
  • 6. 12/01/2011 Rate constant k • Units depend on overall reaction order • Value does not change with concentration • Value does not change with time • Valid for a specific temperature • Dependent on presence or absence of a catalyst • Value must be determined experimentally 1/12/2011 mov 11 Factors that affect rate of reaction • They are six key factors that affect rate of reaction: 1) Nature of reactants and products 2) Concentration 3) Temperature 4) Catalyst 5) Surface area 6) Light radiation 1/12/2011 mov 12 6
  • 7. 12/01/2011 Factors that affect rate of reaction 1. Nature of reactants and products • Chemical reactions involve rearrangement of bonds: Bonds in reactants are broken and new bonds are formed in products • In organic or molecular reactions, large number of bonds are broken in reactants and formed in products-hence reactions are slow • E.g. Hydrolysis of cane sugar: C12H22O11 + H2O C6H12O6 + C6H12O6 Cane sugar glucose fructose 1/12/2011 mov 13 Factors that affect rate of reaction... • Inorganic reactions involve ions, hence no bonds to be broken in reactants . The reactions are faster. • E.g. Ag+(aq) + NO3-(aq) + Na+Cl-(aq) AgCl(aq) + NaNO3(aq) • Concentration • Based on the rate law of mass action, the rate of reaction is directly proportional to the product of the concentration of the reactants at a particular temperature • For reaction aA + bB cC + dC 1/12/2011 Rate = K[A]a[B]b mov 14 7
  • 8. 12/01/2011 Factors that affect rate of reaction ... 3) Temperature • In most reactions, the rate of reaction doubles with 10 K increase in temperature • But with 10 k increase in temperature, collision frequency (Z) increases by a factor of 1.016 I.e. Z α T½ Z2/Z1 = (T2/T1)1/2 = (310/300)1/2 = 1.016 • However, the rate increases by almost 100% • This is because increasing temperature by 10 K increases the number of active molecules (molecules with E > Ea) which increases the rate drastically mov 1/12/2011 15 Factors that affect rate of reaction ... Effect of increase in temperature by 10 K 1/12/2011 mov 16 8
  • 9. 12/01/2011 Factors that affect rate of reaction... • 4) Catalyst • A catalyst is a substance that alters the rate of reaction without itself getting consumed • There are two types of catalysts: • Positive catalyst: It increases the rate of reaction e.g. MnO2 2KClO3 2KCl + 3 O2 300 ⁰C • MnO2 acts as a positive catalyst since uncatalysed reaction takes place at 700 ⁰C and is slower 1/12/2011 mov 17 Factors that affect rate of reaction... • Negative catalyst: This is the catalyst which retards the rate of reaction e.g. Oxidation of chloroform is retarded by ethanol 1% ethanol 4CHCl3 + 3 O2 4COCl2 + 2Cl2 + H2O Mechanism of catalysis • A catalyst alters the rate of reaction by providing a path with lower or higher activation energy 1/12/2011 mov 18 9
  • 10. 12/01/2011 Factors that affect rate of reaction... 5) Surface area • The rate of homogeneous reaction is influenced by the surface area of the reactants • Particle size decreases, surface area increases for the same mass because of creation of new surfaces. Hence the rate of reaction increases • E.g. Powdered zinc reacts faster with dilute HCl than a block of zinc 1/12/2011 mov 19 Factors that affect rate of reaction... 6) Light radiation • The rate of photochemical reaction is affected by light radiation • Photons (E = hv) supply the necessary energy of activation to the reactant molecules to form products λ = 400 nm • E.g. H2 + Cl2 2HCl 1/12/2011 mov 20 10
  • 11. 12/01/2011 Order of reaction • This is the sum of the powers of the concentration term in an experimentally established rate law • Example aA + bB → cC + dD • The theoretical rate law is: Rate = K[A]a[B]b • But experimentally determined rate expression is: Rate = K[A]α[B]β 1/12/2011 mov 21 Order of reaction cont. • Where α and β are the actual moles of A and B and may not be necessarily be equal to “a” and “b” • Overall order of reaction is given by the sum of the individual orders i.e. • Overall order = α + β • Order of reaction can be zero, +ve, -ve or fraction. But higher orders of reaction are rare 1/12/2011 mov 22 11
  • 12. 12/01/2011 Order of reaction cont. • In complex reactions the order of reaction is determined by the slowest step of the reaction which is also called the rate determining step 1/12/2011 mov 23 Molecularity of reaction • This is the total number of molecules in the step leading to chemical reaction • For any reaction, the least number of molecules is one • Thus molecularity cannot be zero or fraction • Types of molecularity: 1) Unimolecular reactions: •1/12/2011 Reactions involving one molecule of the reactants mov 24 12
  • 13. 12/01/2011 Molecularity of reaction • Example: PCl5 PCl3 + Cl2 2) Bimolecular reactions CH3COOC2H5 + H2O CH3COOH + C2H5OH 3) Thermolecular reactions 2NO + O2 2NO2 1/12/2011 mov 25 Pseudo uni-molecular reactions • The reaction in which the order is one but molecularity is 2 • E.g. CH3COOC2H5 + H2O CH3COOH + C2H5OH • Order is one because water is in excess, hence concentration does not change during the reaction • Thus, the rate is independent of the conc. Of water but only dependent on conc. of ester 1/12/2011 mov 26 13
  • 14. 12/01/2011 Rate law • Exercise 1) The rate of reaction 2NO + O2 2NO2 follows the rate law Rate = K[NO]2[O2] If K = 2x 10-6 mol-1L2, What is the rate of the reaction when [NO] = 0.04 molL-1 and [O2] = 0.2 molL-1 [ Ans = 6.4 x 10-10 molL-1s-1] 1/12/2011 mov 27 Rate law 2. The rate of the reaction 2NO + O2 2NO2 is doubled when the concentration of O2 is doubled, but increases by factor of 8 when the concentration of both reactants is doubled. Determine the: a) Order of reaction wrt NO and O2 b) Overall order of reaction 1/12/2011 mov 28 14
  • 15. 12/01/2011 Activation energy • This is the additional amount of energy that reactant molecules must acquire in order to react and form products • It is defined as the amount of energy that the reactants must absorb to pass over the activation energy barrier to form products • Activation energy diagram Ea Reactant ER E Th Product 1/12/2011 mov 29 Activation Energy cont. • E = Eth –ER = Threshold Energy –Energy possessed by molecules • The activation energy is related to the rate constant K and temperature T according to Arrhenius equation K = Ae-Ea/RT Where A = Frequency factor K = rate constant T = temperature in Kelvin R = Gas constant E = Activation energy e = base of natural logarithm 1/12/2011 mov 30 15
  • 16. 12/01/2011 Derivation of Arrhenius equation • Arrhenius equation is derived from the Vant’ Hoffs reacton isochore dlnKc/dT = ΔE/RT2 and the reaction dynamic equilibrium A+B=C+D • Kc for the reaction, Kc = Kf/Kb = [C][D]/[A][B] Kf[A][B] = Kb[C][D] • Hence, Kc = Kf/Kb 1/12/2011 mov 31 Derivation of Arrhenius equation cont. • If ΔE is written as Ef –Eb, then from equation 1 and 2 then, • dlnKf/dT – dlnKb/dT = Ef/RT2 – Eb/RT2 • or dlnk/dT = E/RT2 dlnk = EdT/RT2 • Integrating the equation gives, lnk = -E/RT + C 1/12/2011 mov 32 16
  • 17. 12/01/2011 Derivation of Arrhenius equation cont. • Provided E is a constant, the equation can be written as: k = Ae-E/RT • This is the Arrhenius equation • Application of activation energy 1) To determine activation energy 1/12/2011 mov 33 Determination of activation Energy • There are two methods for determining of activation energy Ea 1) Graphical method 2) Rate constant method 1) Graphical method • From Arrhenius equation, K = Ae-E/RT • Applying lo to both sides of the equation, 1/12/2011 mov 34 17
  • 18. 12/01/2011 Determination of activation Energy cont. • lnK = lnA – Ea/RT • >2.303logK = 2.303logA – Ea/RT • >logK = logA – Ea/2.303RT • >logK = -Ea/2.303RT + logA Ξ y = mx + C • Plotting logK against 1/T give a straight line and Ea can be calculated 1/12/2011 mov 35 Graphical Determination of activation energy • Graph Log A Slope = -Ea/2.303RT Log K Ea = slope x -2.303 R 1/12/2011 mov 36 18
  • 19. 12/01/2011 Graphical Determination of activation energy... • Slope = -Ea/2.303xR • Ea = -2.303 x R x Slope • Log A = Intercept A = Antilog (Intercept) 1/12/2011 mov 37 2. Determination of activation energy from rate constant method • From K = Ae-Ea/RT • lnK = lnA – Ea/RT • Let at Temperature T1 and rate constant K1; and at T2 and rate constant K2 • For small change in temperature, the change Ea and A do not significantly change 1/12/2011 mov 38 19
  • 20. 12/01/2011 Determination of activation energy from rate constant method ... • Thus, lnK1 = lnA – Ea/RT1 3 lnK2 = lnA – Ea/RT2 4 • Subtracting 3 from 4, • LnK2 – lnk1 = Ea/RT1 – Ea/RT2 5 • logK2/K1 = Ea [1/T1 – 1/T2] 2.303 • logK2/K1 = Ea [(T2-T1)/T1T2] 2.303R 1/12/2011 mov 39 Determination of activation energy from rate constant method... • Log K2/K1 = Ea [(T2-T1)/T1T2] Eq. 6 2.303R Since K1, K2, T1 and T2 are known, Ea can be calculated from the equation 6 1/12/2011 mov 40 20
  • 21. 12/01/2011 Rate Laws • A rate law shows the relationship between the reaction rate and the concentrations of reactants. Exponents tell the order of the reaction with respect to each reactant. • This reaction is First-order in [NH4+] First-order in [NO2−] • The overall reaction order can be found by adding the exponents on the reactants in the rate law. • This reaction is second-order overall. • For gas-phase reactants use PA instead of [A] 1/12/2011 mov 41 Integrated Rate Laws • These are expressions which relate the concentration of the reactants with time • Application: 1) Used to predict amount of reactant or product at a particular time 2) Predict how long the reaction will take 3) To predict when a toxic chemical can be disposed • Can be classified into Zero, first, second and third order reactions 1/12/2011 mov 42 21
  • 22. 12/01/2011 Integrated Rate Laws cont. 1) Zero order reactions • This is a reaction where the rate of reaction is independent of the concentration of the reactants • Derivation: • Let A Product • Initial conc. (mol/l) t = 0, a 0 • At time t = t, a-x x • Where x is the concentration of the reactant (A) undergoing decomposition 1/12/2011 mov 43 Zero order reactions cont. • Rate expression for zero order reaction: • dx/dt α (a-x)0 ........................................................Eq.1 • Or dx/dt = Ko(a-x)o = ko .......................................Eq. 2 • K0 is the rate constant for zero order reaction • Integrating the equation, • ∫dx = ∫Kodt = Ko ∫dt x = Kot + C, .............................................................Eq. 3 • Where C is the integration constant 1/12/2011 mov 44 22
  • 23. 12/01/2011 Zero order reactions cont. • But when t = 0 and x = 0 • Thus, 0 = Ko x 0 + C .............................................Eq. 4 • Hence C = 0 • Substituting the value of C into equation 3 gives, x = Kot • Therefore, Ko = x/t ...........................................Eq. 5 • Eq.5 is the rate constant equation for zero order reaction 1/12/2011 mov 45 Zero order reactions cont. • Units for rate constant: • Ko = x/t = conc/time = molL-1/s = molL-1s-1 • Half-life –This is the time duration in which half the concentration of reactants is transformed into products • Thus at t = t½, x = a/2, • Substituting these values into equation 5 K0 = a/2t½ t ½ = a/2k0 t½ α a • This shows that half-life of a zero order reaction is directly proportional to the initial concentration 1/12/2011 mov 46 23
  • 24. 12/01/2011 Zero order reactions cont. • Graph for zero order reaction The rate of reaction is independent of the concentration of reactants Rate Concentration of reactants 1/12/2011 mov 47 First Order Reactions • First Order Reactions • These are reactions where the sum of the powers of concentration of the exponential term in an experimentally established rate law is one • Thus the rate of reaction is dependent on the single power of the concentration term of the reactants • Example: • For the reaction, A Product 1/12/2011 mov 48 24
  • 25. 12/01/2011 First Order Reactions cont. • Initial conc (molL-1) at t=0, a o ......Eq. 1 • Conc (molL-1) at t=t a-x x .......Eq. 2 • Where x moles of A have decomposed into products in time “t” • Deferential, -d(a-x)/dt or dx/dt α(a-x) ...............EQ. 3 • Or dx/dt = k1(a-x) ...............................................Eq. 4 • Where, K1 is the rate constant for first order reaction. 1/12/2011 mov 49 First Order Reactions cont. • Rearrangement, • dx/(a-x) = k1dt ....................................................Eq. 5 • Integrating, [identity ∫dx/x = ln x] ∫dx/(a-x) = k1 ∫dt -ln(a-x) = k1t + C ..............................................Eq. 6 • Where C = constant of integration • But at t=0, x = o • Substituting the values into equation 6, 1/12/2011 mov 50 25
  • 26. 12/01/2011 First Order Reactions cont. • -lna = C .............................................................Eq. 7 • Substitute the value of C into equation c, • -ln(a-x)= k1t –lna ................................................Eq. 8 • Rearranging • k1t = lna – ln(a-x) • K1 = ln[a/(a-x)]x 1/t • Change ln to log10 [lnx = 2.303logx] • K1 = (2.303/t)log(a/a-x) .......................................Eq.8 • This is the expression for rate constant for first order reaction 1/12/2011 mov 51 First Order Reactions cont. • Unit of the rate constant • From Eq. 8 • K1 = (2.303/t)log(a/a-x) = conc/(time xconc) k1 = 1/time = s-1 ...................................................................Eq. 9 Graph for first order reaction • From equation 8 • -ln(a-x)= k1t –lna • Multiply though by -1 •1/12/2011 ln(a-x)= -k1t + lna mov 52 26
  • 27. 12/01/2011 First Order Reactions cont. • Introduce log10 • 2.303log(a-x) = -k1t + 2.303 x log(a) • Or log(a-x) = -k1 x t + log(a) ...........................Eq. 10 2.303 Ξ y =mx +c Log(a) Slope = -k1/2.303 Log(a-x) 1/12/2011 t mov 53 Second order reactions cont. • From the graph, • K1 = -2.303 x slope • Half-life of first order reaction • From Eq. 8, K1 = 2.303 Log (a/a-x) t • At t = t ½ , x = a/2 • Substituting the values into the equation • K1 = 2.303 Log (a/a - a/2) = 2.303 log 2 t½ t½ 1/12/2011 mov 54 27
  • 28. 12/01/2011 First Order Reactions cont. • Making t ½ the subject, • t½ = 2.303 log 2 = 2.303 x 0.301 = 0.693 k1 k1 k1 • Thus, t½ = 0.693/k1 • This means that for 1st order reactions, half-life is independent of the initial concentration of reactants 1/12/2011 mov 55 3. Second order reaction • These are reactions in which the sum of the powers of the of the concentration term in an experimentally established rate law is 2 • There are two cases of second order reaction • Case 1: 2A Product • Thus, Rate law = dx/dt = K[A]2 Order = 2 • Case 2: A+B Product • Rate law = dx/dt = k[A][B] order = 2 1/12/2011 mov 56 28
  • 29. 12/01/2011 Second order reaction cont. • Case 1: Occurs when the concentration of both reactants is the same • Case 2: Occurs when the concentration of both reactants is NOT the same • 1) Case 1: Concentration of both reactants is the same • Let the reaction, A + A Product • Initial conc. t=0 a a 0 ..Eq. 1 • Conc. At t = t a-x a-x x ...Eq. 2 1/12/2011 mov 57 Second order reaction cont. • Conc. is in mol L-1 • Thus, x molL-1 of the reactant A decomposes in time t • Deferential, • dx/dt α (a-x)(a-x) or dx/dt α (a-x)2 ..................Eq. 3 • Introduce rate constant k2 • dx/dt = k2 (a-x)2 ......................................Eq. 4 • Where k2 is the rateconstant for the second order reaction 1/12/2011 mov 58 29
  • 30. 12/01/2011 Second order reaction cont. • Rearranging, • dx/ (a-x)2 = k2 dt .....................................................Eq. 5 • Integrating, • ∫dx/(a-x)2 = k2∫dt note [∫xndx = xn+1/n+1] • Hence, • 1/(a-x) = k2t + C ...................................................Eq. 6 • Where C = constant of integration • But when t= 0, x= 0 1/12/2011 mov 59 Second order reaction cont. • Substituting the values into the equation, • 1/a = C • Substitute the value of C into equation 6 • 1/(a-x) = k2t + 1/a .............................Eq. 7 • Thus, K2t = 1/(a-x) - 1/a • Hence, K2 = (1/at) x [x/(a-x)] ...................Eq. 8 • Eq.8 is the expression for rate constant for second order reaction where initial conc. of the reactants is the same 1/12/2011 mov 60 30
  • 31. 12/01/2011 Second order reaction cont. • Case 2: When concentration of both reactants is different • Let the reaction, A + B Product • Initial conc. t=0 a b 0 ..Eq. 1 • Conc. At t = t a-x b-x x ...Eq. 2 • Where x mol/L of A and B decomposed in time t to form product 1/12/2011 mov 61 Second order reaction cont. • Differential • dx/dt α (a-x)(b-x) • dx/dt = K2(a-x)(b-x) • Where K2 is the rate constant for second order reaction • Separating the variables, • dx/[(a-x)(b-x)] = K2 dt ..........................................Eq. 3 1/12/2011 mov 62 31
  • 32. 12/01/2011 Second order reaction cont. • Integration by parts • ∫ dx = ∫ A dx + ∫B dx = ∫k2dt ...Eq.4 (a-x)(b-x) (a-x) (b-x) • 1 = A + B ......................Eq.5 (a-x)(b-x) (a-x) (b-x) • Multiply through by (a-x)(b-x) • 1 = A(b-x) + B(a-x) ..............................................Eq. 6 1/12/2011 mov 63 Second order reaction cont. • When x = a, 1 = A(b-a) Thus, A = 1/(b-a) • When x = b, 1 = B(a-b) Thus, B = 1/(a-b) Or • ∫ dx = 1 ∫dx + 1 ∫dx = k2 ∫ dt ..Eq. 7 (a-x)(b-x) (b-a) (a-x) (a-b) (b-x) • Factorise the middle term by 1/(a-b) • = ∫ dx = 1 [ ∫dx - ∫dx ] = k2 ∫ dt ...Eq. 8 (a-x)(b-x) (a-b) (b-x) (a-x) 1/12/2011 mov 64 32
  • 33. 12/01/2011 Second order reaction cont. • ∫ dx = 1 [ -ln(b-x) + ln(a-x)] = k2 ∫ dt ..Eq. 9 (a-x)(b-x) (a-b) Therefore, • = 1 [ ln (a-x) ] = k2t + C ......................Eq. 10 (a-b) (b-x) When t = 0, x = 0, Substituting into the equation 14, 1/12/2011 mov 65 Second order reaction cont. • = 1 [ ln (a ] = C .....................................Eq. 11 (a-b) (b) • Substitute the value of C in eq. 15 into eq. 14 • = 1 [ ln (a-x) ] = k2t + 1 [ ln (a ]..........Eq. 12 (a-b) (b-x) (a-b) (b) Thus • K2 = 1 [ ln b(a-x) ] ............................Eq. 13 (a-b)t a(b-x) 1/12/2011 mov 66 33
  • 34. 12/01/2011 Second order reaction cont. • Applying log10 • K2 = 2.303 log b(a-x) .............................................Eq. 14 (a-b)t a(b-x) Characteristics: Unit : K2 = 1 x x at (a-x) = 1/(conc x time) K2 = [conc. X time]-1 .............................................................Eq. 15 1/12/2011 mov 67 Second order reaction cont. • K2 = [mol-1s]-1 = mol-1Ls-1 • When one of the reactants is in excess, • i.e. Let a>> b • a-b = a, a-x =a • Thus b and x can be neglected in comparison to a • Hence, K2 = 2.303 logb(a-x) ................................Eq. 16 (a-b)t a(b-x) • k2 = = 2.303 log(b/b-x)) .....................................Eq. 17 at 1/12/2011 mov 68 34
  • 35. 12/01/2011 Second order reaction cont. • k2a = = 2.303 log(b/b-x)) ................................Eq. 18 t • k’ = = 2.303 log(b/b-x)) .................................Eq. 20 t Where K2a = k’ = rate constant for the first order reaction 1/12/2011 mov 69 Second order reaction cont. • Graph for second order reactions 1 lnb(a-x) (a-b) a(b-x) t 1/12/2011 mov 70 35
  • 36. 12/01/2011 Second order reaction cont. • Half life • From equation 8, case 1 • K2 = 1 x x at (a-x) • t = t 1/2 , x = a/2 • K2 = 1 x a/2 at ½ (a – a/2) • t ½ = 1/k2.a .....................................................Eq. 21 1/12/2011 mov 71 Second order reaction cont. • Thus t ½ is directly proportional to 1/a 1/12/2011 mov 72 36