How to determine the order of reaction?

Interpretation of Batch Reactor Data

const.- volume system

1 dN A
rA  
V dt

d (N A /V ) d (C A )
since constant vol. 
dt dt

A → Products

- rA = d [A] =
 k [A]n  
dt

- rA = dC A =
 k (C A )n  
dt

ⅰ)  case irreversible 1st-order Reaction.

A → Products
dC A
- rA =  = kCA  → ①
dt

separating variable
CA t
- dC A =

C A0
CA
k 
0
dt

CA
- ln C A0
= kt   CA = CA0 e-kt

Fractional Conversion XA
 N A0  N A
XA = N Ao
⇒ NA0XA = NA0 - NA

                   NA = NA0(1-XA) → ②

NA N A0 (1  X A )
CA= =   → ③
V V

     = CA0(1-XA)     → ④

From  ④,
-dCA = CA0 d XA     → ⑤
eqt ① becomes
C A0 dX A
-rA =   = kCA0(1-XA)
dt

dX A
∴ =k(1-XA)
dt

xA
  dX A =k t
   

0
1 X A 
0
dt

 -ln(1-XA)=kt

ⅱ) irreversible 2nd order reaction.

A + B  products
dC A dCB
- rA =  =  = k CA CB
dt dt
CA0 XA = CB0 XB
dC A C A0 dX A
- rA =  =
dt dt
{-dCA = CA0 dXA, CA = CA0 (1-XA) CB=CB0(1-XB)}
= k(CA0 - CA0 XA)(CB0 - CB0 XB)
Since CB0 XB = CA0 XA
= kCA0 (1 - XA)(CB0 - CA0 XA)
CB 0
= kCA0(1 - XA)( CA0 C A0
- CA0 XA)
CB 0
= k CA02 (1 - XA)(M - XA) where M = C A0
dX A
- rA = CA0 = k CA02(1 - XA)(M - XA) 
dt
xA
dX A = t


0
1  X A  M  X A 
kC A 0  dt
0

1 X B M  XA C BC A0 CB
= ln
1 X A
= ln
M (1  X A )
= ln
C B 0C A
= ln
MC A
= CA0(M-1)kt = (CBO - CA0)kt
CB C
ln
CA
= ln CBo + (CBO - CA0)kt
Ao

♣ special case
 2A ⇒ product
dC A
 - rA = - =2 k CA2 = k CA02 (1-XA)2
dt

1 1 1 XA
 = CA
- C A0
= C A0 1 X A
=2 kt

C Ao
CA = 1 2C Aokt
ⅲ) nth order reaction.
dC A
- rA = - = kCAn
dt
CA t
dC A =

C A0
C An
 k  dt
0

  1  1 1  = -kt  (*)
   n 1  n 1 
 n  1  CA C A0 

(CA1-n-CA01-n) = (n-1)kt

if n=2  eqt (*) becomes

1 1
CA
= C A0
+k

ⅳ) Zero order rxn.

dC A
-rA =  = k(CA)o= k
dt
i.e. CA = CA0 - kt

Pseudo first-order reaction.

A + B  products
dC A
- rA =  = k CA CB
dt
1. If reactant B is present in large excess over A
Then CB is almost consntant ko =kCB
dC A
 =ko CA CA = CA0 e-kot
dt

ko pseudo first order constant

2. Steady state reactants
OH + M →
dCM
 = k [OH] ss CM
dt
= k [OH]ss CM
= ko C M
where ko= k [OH]ss
ko pseudo first order constant
HW 2: Solve Problems No 10 (a)
Enzyme reaction.

C12H22O11 + H2O  C6H12O6 + C6H12O6

saccharase

(sucrose)                     (glucose) (fructose)

   at low[S]    d  S   k[S ]
dt
dS
   high[S]    const.
dt
Proposed Kinetic Mechanism
SE
 ES 
k3
PE

k1
k2
   1)  S & E react to form enzyme complex, ES, to become
product.
   2) Rate of reaction related to [ES]
   3) at steady state  d  ES  = 0
dt
 rate of ES formation = rate of ES removal
        k1[E][S] = k2[ES] + k3[ES]
 E k k
         ES  = k2  S  3     → ①
1

total amount of enzyme

[E]t = [E] +[ES]
 E  t  [ ES ] k2  k3
 ES  = k  S    
1

(k2+k3)[ES] = k1[S][E]t-k1[S][ES]
 k1  E  t [ S ]  E  t [S ]
[ES] = k1  S   (k 2  k3 )
= (k 2  k3 ) / k1   S 

reaction rate, rp is proportional to [ES]

-rs=rp=r
     r =-rs = - d[s]/dt =k1[S][E] -k2[ES] rp =k3[ES]
          r = rp = k3[ES] = k 3 E  t [S ]
K m  S 

maximum reaction rate, rmax, occurs when [ES] = [E]t

    rmax = k3[E] t
k 3 E  t S  rmax  S 
         r = =
K m  S  Km   S 

   where r is the rate of substrate removal by enzyme, and is

assumed to be proportional to [ES]

reaction rate, r in three regions

  ① [S]>>Km r = rmax (zero order)
  ② when Km = [ S ]  
            r = rm [ S ] = 1
rmax
Km   S  2

 ③ when Km>>S
            r = rm [ S ] = k [S ] (1st order)
Km

         km = half velocity constant

        I f km is low ==> greater affinity
of E and S
 Monod eqt. - based on the Michaelis-Menten eq
     Useful equation for the biomass growth rate

k = kmax [ S ]
Ks   S 

        where, k is biomass growth rate, kmax is the maximum

growth rate
  
           S is substrate (e.g. BOD, COD, TOC...etc)
 
BOD
dissolved oxygen(mg / l )consumed
BOD5 
dilution factor

Org  O2   CO2  H 2O  Pr oducts

Micro org

Organic matter degraded by microorganism under the

aerobic condition.

In excess of O2, first order approximation

Let 
     L= conc. of degradable org.(=BOD remaining)
      Lo= original conc. of biodegradable org. matter
         (ultimate BOD)
    

dL
  kL
dt
L  L0e  kt
question is k=?
     we don't know L0
Let y =L0-L (amount of material that has been degraded at
any time)
     y = DOin - DOt = BODt
     L0-L = y = L0-L0 e  kt

     y = L0 (1- e )  kt

x2
ex  1  x  
2!

1- =1 - (1 - kt + kt 2 + kt 3 )
e  kt
2! 3!

+  kt  -  kt  ]
2 3
kt
= kt [ 1 -
2! 3! 4!
also
+  kt  -  kt  ]
2 3
kt kt
kt( 1  )-3 = kt [ 1 -
6 2! 6 21.6
3
1-  kt 
e  kt  kt 1  
 6
  kt  
3

y  L0 (1  e  kt )  L0  kt 1   
 
 6   

1
y 
L0 kt
3 y
1
3
 L kt  3
 0
 kt  kt
1   1
 6 6

kt
1
1 6  1  kt
1
 1 1 1
y 3  L0 kt  3  L0 kt  3 6 L0 kt  3

1
 23 
t 3 1  k 
  L0 k 

1
3   1 t
y 3  6 L0 3 
 
1
 t 3

 y  a  bt
 
 1
1
=a
 L0 k  3

2
k 3
=b
1
6L0 3

k
1
=b
1
6 L0 k 3 3

6b
k 
a

6b 1
k  , L0 
a ka 3

Effect of Temperature on Reaction Rate.

Arrhenius' Law
      k  Ae
 Ea
RT

            ln k = ln A - Ea/RT

  
   A: pre-exponential factor, frequency factor
   Ea: activation energy
   R: ideal gas const.
   T: temp.(K)

Ea :activation energy ?
 For reaction, A + B →  product

1) postulate that the reaction proceeds through a activated

complex (high energy, unstable intermediate)

   A + B → activated complex

   activated complex → products

2) For the reaction proceed, energy required to form

activated complex : Ea
  
  Released amount of energy as a result of decomposition of
activated complex is △H (heat of reaction).

  For the reverse reaction.

  
  Activation energy of reverse reaction : (ΔH+Ea)
    Heat of reaction : Ea
How to determination Ea, k?
  k  Ae RTE
a

 Ea 1
ln k  ln A 
R T

plot  ln k   VS   1

T

     ◉ slope = - Ea
R

     ◉ intercept = ln A