Chemical Kinetics

Rates of reaction and analysis of

experimental data
 General mole balance

FA,out (mole/t)
GA,in (mole/t)
FA,in (mole/t)
generation outlet
inlet

G A   rAdV
V
dN A
FA,in  FA,out  G A 
dt
dN A
FA,in  FA,out   rAdV 
dt
V
 Batch Reactor
dN A
FA,in  FA,out  G A 
dt
FA,in  FA,out  0
G A   rAdV
V
dN A
 A
r dV 
dt
V
If we assume well mixed
model, conditions are the
GA (mole/t) same in every spot inside
the reacting volume

 rAdV  rAV
V
dN A
rAV 
dt
NAt  dN 
t   A
N A0  A 
r V
 CSTR dN A
FA,in  FA,out  G A 
dt
dN A
FA,in  FA,out   rAdV 
FA,in (mole/t) dt
V

If we assume well mixed model,

conditions are the same in every
spot inside the reacting volume.
Those conditions are the same
than in the outlet stream. Also
system is in steady state
GA (mole/t)
dN A
 0,  rAdV  rAV
dt
V
FA,in  FA,out  rAV  0
FA,out (mole/t)
FA,in  FA,out
V
rA
 PFR
dV

FA,in (mole/t) FA,i dGA FA,i+ dFA FA,out (mole/t)

dN A
FA,in  FA,out  G A 
dt
Differentiating with respect to
dN A
FA,in  FA,out   rAdV  volume
dt
V
dFA
Assuming steady state  rA
dV
dN A FA
0 dFA
dt V 
r
FA,in  FA,out   rAdV  0 FA0 A
V
 Reactor molar balance
Reactor Differential Algebraic Integral

NAt  dN 
dN A t   A
 rAV
N A0  A 
r V
GA
(mole/t)
dt

FA,in
(mole/t)

FA0  FA
V
GA
rA
(mole/t)

FA,out
(mole/t)

dV FA
dFA dFA
FA,out (mole/t)  rA V 
FA,in (mole/t) FA,i dG FA,i+

dV r
FA0 A
dFA
A
 Conversion
aA  bB  cC  dD
A is limiting reactant
b c d
A  B  C  D
a a a

moles A reacted
XA 
moles A fed

If NA0 are the initial moles of A loaded in the reactor,

and NA are moles of A remaining in reactor (NA) after
a certain time, then:

N A0  N A
XA   N A  N A0 1  X A 
N A0
 Stoichiometric Table
Mole balance for a batch reactor:
Species Initial Change Remaining
A N A0  N A0  X A  N A  N A0 1  X A 
b b
B N B0   N A0 X A  N B  N B0   N A0 X A 
a a
c
C NC 0 c
 N A0 X A  NC  NC 0   N A0 X A 
a a
d
D N D0 d
 N A0 X A  N D  N D0   N A0 X A 
a a
I NI 0  NI  NI 0
d c b 
Total NT 0 NT  NT 0      1 N A0 X A
a a a 


 Conversion
For a continuous reactor:
F  FA
X A  A0  FA  FA0 1  X A 
FA0

Or in terms of molar concentrations

FA   C A
FA0  0C A0
FA  FA0 1  X A 
0
CA  C A0 1  X A 

At constant volumetric flow   0
C A  C A0 1  X A 
 Stoichiometric Table
Mole balance for a continuous reactor:
Species Initial Change Remaining
A FA0  FA0  X A  FA  FA0 1  X A 
b b
B FB0   FA0 X A  FB  FB0   FA0 X A 
a a
c
C FC 0 c
 FA0 X A  FC  FC 0   FA0 X A 
a a
d d
D FD0  FA0 X A  FD  FD0   FA0 X A 
a a
I FI 0  FI  FI 0
d c b 
Total FT 0 FT  FT 0      1 FA0 X A
a a a 
 Balances in terms of conversion
For ideal gases P y P
CA  A = A
RT RT
y AP
 C A0 1  X A 
RT
RT
yA  C A0 1  X A 
P

Now we can derive mole balances for all ideal reactors

in terms of conversion. For batch reactor in differential
form:
dN A d  N A0 1  X A  
rAV   rAV 
dt dt
dX A
rAV   N A0
dt
 Balances in terms of conversion
For batch reactor in the integral form:
dX A
rAV   N A0
dt
XA
dX A
t   N A0 
r V
X A0 A
For CSTR reactor:

FA0  FA FA0  FA0 1  X A 

V V 
rA rA
F X
V  A0 A
rA
 Balances in terms of conversion
For PFR in differential form:
dFA
 rA
dV
d  FA0 1  X A  
 rA
dV
dX A rA

dV FA0
For PFR in the integral form
dX A rA

dV FA0
XA
dX A
V   FA0 
rA
X A0
 Reactor molar balance in terms of
Reactor
conversion
Differential Algebraic Integral

dX A XA
rAV   N A0 dX A
t   N A0 
dt r V
X A0 A
GA
(mole/t)

FA,in
(mole/t)

F X
V  A0 A
GA
rA
(mole/t)

FA,out
(mole/t)

dV
FA
dX A rA dX A
FA,in (mole/t) FA,i dG FA,i+ FA,out (mole/t)  V   FA0 
dFA
dV FA0 r
FA0 A
A
 Kinetic models from batch reactors
Integral method Puts a particular rate equation to
test, integrate C vs. t and compare with experimental
data. If fit is not satisfactory another model has to be
guessed and tested. Useful for reactions with
elementary kinetic models.

• Irreversible – unimolecular – first order kinetics

A → Products
dN A
 rAV
dt
dC A
 rA
dt
 Irreversible – unimolecular – first order kinetics
In terms of concentration Or in terms of conversion

dC A dX A
  kC A rAV   N A0
dt dt
dC A dX A
  kdt rA  C A0
CA dt
 CA  dX A
ln    kt kC A0 (1  X A )  C A0
 C A0  dt
dX A
kdt 
(1  X A )
ln 1  X A    kt
Irreversible – unimolecular – first order kinetics
• Irreversible – bimolecular – second order kinetics
A + B → Products
dN A
 rAV
dt
dC A
 rA
dt
dC A
 kC ACB
dt
C A  C A0 1  X A 
CB  CB 0  C A0 X A
dC A
 kC A0 1  X A   CB0  C A0 X A 
dt
 • Irreversible – bimolecular – second order kinetics
dC A
 kC A0 1  X A   CB0  C A0 X A 
dt
dX A
C A0  kC A0 1  X A   CB 0  C A0 X A 
dt
CB0
  B0
C A0
dX A
 kC A0 1  X A    B 0  X A 
dt
dX A
 C A0 kdt
1  X A    B0  X A 
  B0  X A   CB 
ln 
  1  X  
 ln     CB0  C A0  kt ,  B0  1
 B0 A    B0C A 
• Irreversible – bimolecular – second order kinetics
• Irreversible – order zero

dX A k
dC A 
 k dt C A0
dt
dC A0 1  X A  XA 
k
t
 k C A0
dt
• kinetic equations of order n
When mechanism of reaction is not known kinetics
can be of any order
dC A
rA   kC An
dt
After integration n≠1.
C A1n  C A01n   n  1 kt

For every experimental point we compute k for a given

n. The value that provides the minimum variation of k
under different conditions is the order of reaction.
n  1, C A  0  t  
n  1, C A  0  t  t End
Fractional orders (n<1) tend to increase with time
• Irreversible – bimolecular – second order kinetics

A + B → Products
dC A
 kC ACB
dt
CB0
  B0
C A0
Solve for ƟB0 =1
dC A
What if this reaction follows a second order  kC ACB
dt
A + 2B → Products
Solve for ƟB0 ≠ 2, ƟB0 = 2
X dX

1 a  X  , a 1
 ln
0
1  X  a  X   a  1 a 1  X 