Reaction Engineering

Chemical Kinetics /
Analysis of rate equations

1
Chemical Kinetics - outcomes

 Understand the significance of kinetics

 Aware of concentration dependencies

 Understand the difference elementary / non-elementary reactions
 Calculate the order of reaction
 Aware of temperature dependencies – Arrhenius, activation energy

2
The Rate Equation / Stoichiometry

aA  bB  cC  dD
1 dN A
 rA  rate of disappearance of A
V dt

r
1 dN C
C  rate of appearance of C
V dt

 rA  rB rC rD Relationship
   between rates of
a b c d reaction

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Concentration / Temp. dependency terms

r  f (conc., temp.)

 rA  [k (T )][ f (C A , CB ,...)]
Reaction rate Concentration
(constant) dependent terms

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 Concentration-dependent term

 rA  k[ f (C A , CB ,...)]
Almost without exception determined by experimental observation!!!

Most common expression:

  
 rA  kCA C B ....CD

Order of reaction:  order in A

 order in B
n      ...  overall order
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 rA  kCA C B

Elementary / Non-elementary Reactions

A B C  D stoichiometric coeff: a  b  c  d 1

 Elementary reactions – iff stoichiometric coefficients are the same as the

individual reaction order of each species
  a 1
 rA  kCACB   b 1
 Non-elementary reactions – stoichiometry does not match the kinetics

 rA  kC CB 2
A
 2
 1
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A sequence of elementary reactions
 Elementary reactions / Molecularity
 = the number of molecules involved in a reaction
 refers ONLY to elementary reaction!!! order  molecularity

Elementary reactions Rate Law Molecularity Comments

X P kCX unimolecular X decomposes

2X  P kCX2 bimolecular X collides with X

X collides with Y
X Y  P kCX CY bimolecular

3X  P kCX3 termolecular X+X+X collide

X  2Y  P kCX CY2 termolecular X+Y+Y collide

X Y  Z  P kCX CY CZ termolecular X+Y+Z collide 7

Non-elementary reactions
Overall reaction:
kexp
4 HBr ( g )  O2 ( g )  2 H 2O( g )  2 Br2 ( g )

Sequence of reactions – proposed mechanism: kexp=func(k1,k2,k3,k4)

k1
(1) HBr ( g )  O2 ( g )  HOOBr ( g ) (slow)

k2
(2) HOOBr( g )  HBr( g )  2HOBr( g ) (fast) elementary
k3 reactions
(3) HOBr ( g )  HBr ( g )  H 2O( g )  Br2 ( g ) (fast) (bimolecular)
k4
(4) HOBr ( g )  HBr ( g )  H 2O( g )  Br2 ( g ) (fast)
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kexp=k1
Concentration / Temp. dependency terms

r  f (conc., temp.)

 rA  [k (T )][ f (C A , CB ,...)]
Reaction rate Concentration
(constant) dependent terms

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Rate constant (k)

 rA  k[ f (C A , CB ,...)]
Dimensions vary with order of reaction (n) :

(time) 1 (concentration)1 n

CA -rA Reaction order Rate law k

(mol/m3) (mol/m3.s) zero  rA  k (mol/m3)/s

(mol/m3) (mol/m3.s) 1st  rA  kCA 1/s

(mol/m3) (mol/m3.s) 2nd  rA  kCA2 (m3/mol)/s
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Temperature dependency –
Arrhenius Law
 Arrhenius – suggested the following relationship:

k  k 0 e  E / RT
 k0 = frequency / pre-exponential factor
 E = activation energy [J/mol] or [cal/mol]
 R = gas constant = 8.314 J/mol.K=1.987 cal/mol.K
 T = absolute temperature [K]

Activation energy (E) definitions:

• Min energy that must be possessed by molecules to react
• Nothing more than an empirical parameter (some suggestions!)
• Average energy of (reacting molecules – all molecules)
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Temperature dependency –
Activation energy
 Activation energy (E) calculation:
• data for same concentration – different temperatures

k  k 0 e  E / RT
ln, log

E1 E 1
ln k  ln k 0    or
log k  log k0   
R T  2 .3 R  T 

T1,T2

k2 E  1 1  E 1 1
ln     log
k2
   
k1 R  T1 T2  k1 2.3R  T1 T2  12
 Activation energy calculation
example 1
 First order reaction: A BC
k (1/s) 0.00043 0.00103 0.0018 0.00355 0.00717
Data:
T(K) 313 319 323 328 333

k2 E 1 1 1/T Vs log k
log     4
k1 2.3R  T1 T2 
3.5

3
Log k
2.5
(2.3) R log( k 2 / k1 )
E 2
1 / T1  1 / T2 1.5

k1  0.005  1 / T1  0.00303 0.5

0
k2  0.0005  1 / T2  0.00319 0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325

1/T
13

E  120 kJ / mol Hint: for k2  0.1k1  log( k1 / k2 )  1

 Activation energy calculation
example 2
 To obtain pasteurised milk:
Reaction rate is inversely
 heating at 63°C for 30 min proportional with reaction time
 heating at 74°C for 15 s

Find the activation energy of the process

k2 t E 1 1 
ln  ln 1    
k1 t 2 R  T1 T2 
30 E  1 1 
ln    
t1  30 min  T1  336 K 0.25 8.314  336 347 

t2  15 sec  0.25 min  T2  347 K

E  422000 J / mol
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Activation energy calculation
example 3

Data on the tenebrionid beetle whose body mass is 3.3 g show that it can
push a 35-g ball of dung at 6.5 cm/s at 27 C, 13 cm/s at 37 C, and 18 cm/s
at 40 C. How fast can it push dung at 41.5 C? [B. Heinrich. The Hot-
Blooded Insects (Cambridge, Mass.: 1993).]

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Activation energy calculation
example 3

• The behavior of the beetle can be modeled by the Arrhenius equation.

• The beetle's speed (k) increases exponentially with temperature.

Arrhenius equation:

k  k 0 e  E / RT

To calculate how fast the beetle can push the ball determine:
 the activation energy (E)
 the Arrhenius coefficient (k0) of the beetle

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 Activation energy calculation
example 3

Rate (cm/s) Temp (K)

k1 = 6.5 T1 = 300 K

k2 = 13 T2 = 310 K

k3 = 18 T3 = 313 K

k4 = ? T4 = 314.5 K

• Plot ln(k) vs. 1/T

• Predict ln(k) for T=314.5 K

ln(k) for T=314.5 is equal to ~2.95 How would you solve the
This corresponds to a k4 value of 19.1 cm/s. problem analytically? 17
Analysis of rate equations - outcomes

 Be able to use experimental data to get empirical rate equations

 Necessity of a rate equation for design purposes

 Able to analyse different types of reactions
 Expand the analysis to multiple reactions
 Chain reactions and their interpretation & analysis

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Analysis of rate equations – general
issues
1 dNi
The rate equation: ri 
V dt

The form might be suggested by:

 Theoretical considerations
 Empirical curve-fitting procedure
The value of equation constants – experimental only!
 2 step-procedure:
 Find concentration dependency at Temp=const.
 Find temperature dependency of the rate constants

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Analysis of rate equations – general
issues (contd.)
1 dNi
The rate equation: ri 
V dt
Equipment used for getting the empirical data
 batch reactor – container that holds the reactants – usually for
homogeneous reactions
 flow reactor – continuous flow in / flow out - usually for
heterogeneous reactions
Measurements:
 concentration of a component
 change in physical properties (conductivity, refractive index)
 change in total pressure when V=constant.
 change in volume when P=constant. 20
Analysis of rate equations – general
issues (contd.)
1 dNi
The rate equation: ri 
V dt
Procedures for analysing the kinetic data:
 integral method:
 guess a form of rate equation
 integration & mathematical manipulation
 predict the plot of C=f (time) as a straight line
 plot the data and if good fit – accept the equation
 differential method:
 find (1/V)(dN/dt) from the data
 test the fit directly (no integration) 21
Constant volume batch reactor –
conversion

The volume of reaction mixture = constant dCA

 = constant density reaction system
 rA  
dt

N A0  N A
Conversion of A: XA  = the fraction of A
N A0 reacted away

N A0  N A NA N A /V CA
XA   1  1  1
N A0 N A0 N A0 / V C A0

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Constant volume batch reactor –
stoichiometric table
b c d
A B C D
a a a

Species Initially Change Remaining

(mol) (mol) (mol)

A N A0  ( N A0 X ) N A  N A0  ( N A0 X )
b
N B0 b
 ( N A0 X ) N B  N B 0  ( N A0 X )
B a a
c c
C NC0 ( N A0 X ) N C  N C 0  ( N A0 X )
a a
d d
D N D0 ( N A0 X ) N D  N A0  ( N A0 X )
a a
I (inert ) NI0  NI  NI0

d c b 
NT 0 N T  NT 0      1( N A0 X )23
a a a 
A. Integral method
- irreversible, unimolecular, first order rxs. -

A  Products
Test the first-order rate equation form:

dC A
 using concentration  rA    kCA
dt

dC A C A0 dX A
 using conversion  rA     kCA dX A C
k A
dt dt dt C A0
CA
X A  1
C A0

dC A
dX A   dX A
C A0  rA   k (1  X A )
dt
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A. Integral method
- irreversible, unimolecular, first order rxs. -

Separate & integrate:

dCA
 using concentration   kCA
dt

CA dC A t CA
  k  dt  ln  kt
C A0 CA 0 C A0

dX A
 using conversion  k (1  X A )
dt

XA dX A t
 ln(1  X A )  kt
0 1 X A
 k  dt
0 25
A. Integral method
- irreversible, unimolecular, first order rxs. -

Plot the experimental data & the proposed equation line:

-ln(CA/CA0) or –ln(1-XA)

slope  k

If the data fit Accept first-order rate equation

26
B1. Integral method
- irreversible, bimolecular, second order rxs. -

A  B  Products
Test the second-order rate equation form:

dCA dCB
 using concentration rA     kCA CB
dt dt

 using conversion  r   dC A  C A0 dX A  k C  C X C  C X 

A A0 A0 A B0 A0 A
dt dt

dC A
dX A  
C A0 M  C B 0 C A0
C A  C A0  C A0 X A
dX A
C B  C B 0  C A0 X A  rA  C A0  kCA2 0 (1  X A )(M  X A )
dt
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B1. Integral method
- irreversible, bimolecular, second order rxs. -

Separate & integrate:

XA dX A t
0 1  X A M  X A 
 C A0 k  dt
0

1 X B M  XA C B C A0 CB
ln  ln  ln  ln
1 X A M (1  X A ) C B 0C A MC A

 C A0 ( M  1)kt  (CB 0  C A0 )kt

Condition: M 1 or C A0  C B 0 28
B1. Integral method
- irreversible, bimolecular, second order rxs. -

Plot the experimental data & the proposed equation line:

M  XA C C
ln or ln B A0
M (1  X A ) C B 0C A

CB
ln
CA slope  (CB 0  C A0 )k

slope  (CB 0  C A0 )k t
CB 0
intercept  ln  ln M
C A0
C A0  C B 0 29

t
B2. Integral method
- irreversible, bimolecular, second order rxs. -

2 A  Products
The second-order rate equation form:
dC  1 1 1 XA
 rA   A  kCA2  kCA2 0 (1  X A ) 2    kt
dt C A C A0 C A0 1  X A

1 XA
CA 1 X A

slope  k

1 slope  C A0 k
intercept 
C A0
30

t t
B3. Integral method
- irreversible, bimolecular, second order rxs. -

A  2B  Products
The second-order rate equation form:

dCA
 rA    kCACB  kCA2 0 (1  X A )(M  2 X A )
dt

C B C A0 M  2X A M 2
ln  ln  C A0 ( M  2)kt
C B 0C A M (1  X A )

1 1 1 XA
 
C A C A0 C A0 1  X A
 2kt M 2 31