3.

RATE LAWS & STOICHIOMETRY

3.1 Basic Definitions

Homogeneous/Heterogeneous
Catalytic/Noncatalytic
Reversible/Irreversible
 
XA <1 XA = 1 for t = 

3.1.1 The Reaction Rate Constant

Kinetic Expression or Rate Law

-rA = k(T) fn (CA, CB, …)


reaction rate constant

Arrhenius Equation: k T   A  e  E / RT

A  preexponential factor
E  activation energy, J/mol
R  gas constant, = 8.314 J/mol K
T  absolute temperature, K

Activation energy is determined experimentally from experiments at

different temperatures

E1
ln k  ln A    (3-3)
R T 
   
y = a – b x

3-1
Example 3 – 1

AB+C

first-order
E=?

k(s-1) 0.00043 0.00103 0.00180 0.00355

T(K) 313 319 323 333
1000/T(K-1) 3.2 3.14 3.10 3.05

Convert equation (3-3) to log base 10

E 1
log k  log A   
2.3  R  T 

Plot k vs.
1
T
 
 10 3 K 1 on semilog paper

0.01
3.04 3.06 3.08 3.1 3.12 3.14 3.16 3.18 3.2 3.22
k (s -1)

0.001

0.0001
3 -1
1/T x 10 (K )

3-2
For two different points

E 1
log k1  log A   
2.3  R  T1 

E  1 
log k 2  log A   
2.3  R  T2 

Substracting yields

k2 E  1 1
log    
k1 2.3  R  T2 T1 

2.3  R  logk 2 / k1 
E 
1 / T2  1 / T1

Use the decade method (i.e. k1/k2 = 10)

k1 = 0.005  1/T1 = 0.00303

k2 = 0.0005  1/T2 = 0.00319
log (k2/k1) = -1

J
2.3  8.314
2.3  R mol.K
E  
1 / T2  1 / T1
0.00319  0.00303 1
K
kJ
E  120
mol

The larger the E, the more temperature-sensitive is the reaction rate.

3-3
3.1.2 The Reaction Order

fn(cj)  determined from experiments

 rA  k  C A  CB
: order with respect to A
: order with respect to B
 + : overall order

,, +  do not have to be integers.

CO + Cl2  COCl2

 rCO  k C CO C Cl3 /22

2N 2 O 
Pt
2N 2  O 2

k C N 2O
 rN 2O 
1  k C O 2

C O 2 : small  “apparent” 1st order (N2O)

C O 2 : large  “apparent” 1st order (N2O)
-1st order (O2)

Units of k

zero order: -rA = k

[k] = mol/dm3s

First order: -rA = kCA

[k] = s-1

Second order: -rA = kCA2

[k] = dm3/mols

3-4
3.1.3 Elementary Reactions and Molecularity

Elementary reaction is one in which the reaction order of each species is

identical with the stoichiometric coefficient of that species for the reaction
as written.

H2 + I2  2HI
-rH2 = kCH2·CI2 elementary

CO + Cl2  COCl2 non elementary

-rCO = kCCO·CCl23/2

Molecularity is the number of atoms, ions or molecules involved

(colliding) in the rate-limiting step of the reaction.

NaOH + CH3Br  CH3OH + NaBr

elementary reaction 

-rMB = kCNaOHCCH3Br

Example 3 – 2

NaOH + C(CH3)3Br  C(CH3)3OH + NaBr

reaction order = ?

rate law determined from experiments

-rTBB = kCTBB

3.1.4 Reversible Reactions

k1
2C6H6 C12H10 + H2
k2

reversible and elementary

-rB = k1CB2 – k2CD·CH2

 C D  C H2 
 rB  k1  C B2  

 KC 
k1
KC  = concentration equilibrium constant
k2
(true only for elementary reactions)

3-5
Thermodynamic Relationships

b c d
A B C  D (gas-phase)
a a a

Pressure equilibrium constant

PCc / a  PDd / a
KP 
PA  PBb / a

Pi = partial pressure of species i, in atm

Concentration equilibrium constant

CCc / a  C Dd / a
KC 
C A  C Bb / a

For ideal gases

KP = KC (RT)
c d b
    1
a a a

KP is a function only of temperature, Van’t Hoff’s equation:

d ln K P H rn T 

dT RT 2

d ln K P H rn TR   C P T  TR 

dT RT 2
If CP = 0, we can integrate to obtain

K p2 H rn TR   1 1
ln    
K p1 R  T1 T2 

3-6
From Van’t Hoff’s equation

Hrn – ve (exoth.) T KP 
Hrn + ve (endoth.) T KP 

Kp Kp

T T

Exothermic reaction Endothermic reaction

Equilibrium constant (in terms of activities)

 Cc / a   Dd / a
K 
 A   Bb / a

 RT  lnK T   Grn T 

c  d  b
Grn  Gc  G D  G B  G A
a a a
Example C – 1
H2O + CO CO2 + H2

T = 1000K
P = 10atm
yH2O = yCO = 0.5 initially
Xe = ?
Grn = – 730 cal/mol at 1000K & 10 atm
 RT  ln K  Grn T 

cal cal
 1.987  1000 K  ln K   730 
mol  K mol
K  1.44

3-7
  CO 2   H 2
K 
 CO   H2O

fi fugacity
i 
fi standard state

Ideal gases: fi= Pi fi0 = 1 atm

PCO 2  PH 2
K 
PCO  PH 2O

Using ideal gas law: Pi = Ci RT

CCO 2  C H 2
K 
CCO  C H 2O

Since volume of reaction mixture doesn’t change as reaction proceeds.

C CO,e  C CO,O  1  X e 
C H2O,e  C H2O,O  1  X e   C CO,O  1  X e 
C CO2 ,e  C CO,O  X e from stoichiometry:
C H 2 ,e  C CO,O  X e CO2 produced = CO reacted
2
Xe
K   1.44 
1  X e 2
X e  0.55

3-8
3.1.5 Nonelementary Reactions

H2 + Br2 2HBr

Proceeds by a free-radical mechanism

1
Br2 2Br 
2
3
Br   H 2 HBr  H 
4

H   Br2 

5
HBr  Br 

2Br  Br2


k1  C H 2  C Br
1/ 2

rHBr 

k 2  C HBr /C Br2

There is no correspondence between stoichiometry and rate law.

CH3CHO CH4 + CO

 rCH 3CHO  k  C 3/2

CH 3CHO

3.2 Present Status of Our Approach to Reactor Sizing and Design

Reactor Design Equation

+
– rA = f(Cj)
+  -rA = g(X)
Cj = hj(X)

3-9
3.3 Stoichiometric Table

Use the stoichiometric table to relate the concentrations of different

species to each other.

The stoichiometric table presents the relationships between reacting

molecules for a single reaction.

aA + bB cC + dD

Divide by the stoichiometric coefficient of A

b c d
A B C  D
a a a
rate of formation of C =

c
rate of disappeara nce of A
a

rC 
c
 rA    c rA
a a
Similarly

c
rC  rD
d
Generally

 rA  rB r r
  C D
a b c d

3-10
 3.3.1 Batch Systems

b c d
A + B  C + D
a a a

Initially: NAO NBO NCO NDO

b c d
Change: -NAOX  N AO X N AO X N AO X
a a a

Remain: NA NB NC ND

NA = NAO - NAO ·X
b
NB = NBO  N AO X
a
c
NC = NCO + N AO X
a
d
ND = NDO + N AO X
a

d c b 
NT = NTO +     1  ·NAO · X
a a a 

NT = NTO +  ·NAO · X

d c b
    1
a a a

 represents the change in the total number of moles per mole of A

reacted.

3-11
 STOICHIOMETRIC TABLE

Species Initially (mol) Change (mol) Remaining (mol)

A NAO -NAO X N A  N AO  N AO  X

b b
B NBO  N AO X N B  N BO  N AO  X
a a

c c
C NCO N AO X N C  N CO  N AO  X
a a

d d
D NDO N AO X N D  N DO  N AO X
a a

I
NIO NI = NIO
(inerts)

 d c b 
NTO N T  N TO      1 N AO X
 a a a 

Calculate concentrations by

Ni
Ci 
V

3-12
 NA N AO 1  X 
CA  
V V

NB N BO  b / a  N AO  X
CB  
V V

Define:

N io C io y
i    io
N AO C AO y AO
N BO N CO N DO
B  , C  ,D 
N AO N AO N AO

N AO  B  b / a   X 
CB 
V

NC N  c / a N AO  X
CC   CO
V V

N AO  c  c / a X 
CC 
V

N D N DO  d / a  N AO  X
CD 
V V

N AO  D  d / a   X 
CD 
V

We need now V(X) to obtain Cj = hj(X)

3-13
3.3.2 Constant-Volume Reaction Systems

In constant-volume or constant-density systems the reacting system

undergoes no change in volume as the reaction progresses.

Gas-phase

 When the reactor is a sealed vessel

 When  = 0 (and P,T constant)
e.g. CO + H2O CO2 + H2

Liquid-phase

 Most reactions taking place in solution (except polymerizations)

For a constant-volume system:

V = VO

Therefore

N AO 1  X 
CA   C AO 1  X 
VO

N AO  B  b / a  X   b 
CB   C AO  B  X 
VO  a 

 c 
C C  C AO  C  X 
 a 

 d 
C D  C AO  D  X 
 a 

3-14
 Example 3 – 3

3A + B  3C + D

is a liquid-phase reaction.
Set up a stoichiometric table.

1 1
A B  C  D
3 3

C BO C CO C DO
V  V0 ,  B  , C  , D 
C AO C AO C AO

N A N A N AO 1  X 
CA     C AO 1  X 
V VO VO

Species Initially Change Remaining Conentration

A NAO -NAOX NAO(1-X) CAO(1-X)

1  X  X
B NBO  N AO X N AO  B   C AO  B  
3  3  3

C NCO NAOX NAO(C+X) CAO(C+X)

1  X  X
D NDO N AO X N AO  D   C AO  D  
3  3  3

Inert NIO  NIO CIO

NTO 0 NT=NTo

3-15
Example 3 – 4

For previous example and

CAO = 10 mol/liter CCO = CDO = 0

CBO = 2 mol/liter
CD = ?
CB = ?
XA = 20%, 90%

CCO C DO
C  0 D  0
C AO C AO

a) XA = 20%

X mol  0.2  mol

C D  C AO    10    0.67
3 lt  3  lt

 X mol  2 0.2  mol

C B  C AO  B    10     1.33
 3 lt  10 3  lt

b) XA = 90%

X mol  0.9  mol

C D  C AO    10  3
3 lt  3  lt

 2 0.9  mol
C B  10      1
 10 3  lt

Negative concentration!
XA = 90% impossible
B is the limiting reactant

3-16
3.3.3 Flow Systems

Batch system: Nj, Njo

Flow system: Fj, Fjo

FA
Recall: CA =


FA F Ao
CA   1  X 
 
F F  b / a  F AO  X
CB  B  BO
 
F F  c / a  F AO  X
CC  C  CO
 
F F  d / a  F AO  X
CD  D  DO
 

For liquids  no volume change

 = o

F AO
CA  1  X   C AO 1  X 
O

 b 
C B  C AO   B  X  etc.
 a 

F BO C  C y
B   BO O  BO  BO
F AO C AO   o C AO y AO

3-17
 STOICHIOMETRIC TABLE

Feed rate to Change in

Effluent Rate from Reactor
Species Reactor Reactor
(mol/time)
(mol/time) (mol/time)

A FAO -FAO X F A  F AO 1  X 

b  b 
B FBO = BFAO  F AO X F B  F AO   B  X 
a  a 

c  c 
C FCO = CFAO F AO X F C  F AO   C  X 
a  a 

d  d 
D FDO = DFAO F AO X F D  F AO   D  X 
a  a 

I FIO = IFAO – F I  F AO   I

 d c b 
F T  F TO      1  F AO  X
FTO  a a a 

F T  F TO   F AO X

3-18
3.3.4 Volume Change with Reaction

N2 + 3H2 2NH3

Batch System (const P): V changes

Flow System :  changes

Relate V (or ) to X through an equation of state:

PV  ZN T RT (3-30)
atm
2 K
1.1 mol
atm.lt
mol.K
Z = compressibility factor

For t = 0: POVO=ZO  NTO  R  TO (3-31)

(3-30)  (3-31) 
 P  T  Z  N T 
V  V O  O        (3-32)
 P   O   O   N TO
T Z 

For a Batch system:

From stoichiometric table:

NT = NTO + NAO  X

NT N AO
1    X  1    y AO X
N TO N TO
yAO: mole fraction of A at t=0

If all of the species in stoichiometric equation are in the gas phase, then

d c b
    1
a a a

3-19
 when reaction is
Define  completed

change in total number of moles

 
total number of moles fed to reactor

d c b  N 
     1   AO   y AO  
a a a   N TO 
  y AO  

Equation (3-32) becomes

 P   T   Z 
V  V O  O     Z  1   X 
 P  O  O 
T

We will only consider cases where Z=ZO

 P   T 
V  V O  O    1   X 
 P  O 
T

b c d
So for a variable-volume BR and A  B  C  D
a a a
NA N AO 1  X  T O P
CA    
V V O 1   X  T PO
 1  X  TO P
C A  C AO   
 1   X  T PO
NB N AO  B  b / a   X  T O P
CB    
V V O 1   X  T PO
   b / a   X  T O P
C B  C AO  B  
 1  X  T PO

3-20
For a Flow system:

FT P
CT   (3 – 40)
 ZRT
At reactor entrance

F TO PO
C TO   (3 – 41)
O Z O RT O

(3 – 40)  (3 – 41) and assuming Z = ZO 

 F   PO   T 
   o  T     
 F TO  P  O 
T

From stoichiometric table

FT  FTO  F AO  X

F TO  F AO  X  PO   T 
  O    
F TO  P  TO 

 P  T 
   O 1  y AO    X  O   
 P  TO 

 P  T 
   O 1   X  O   
 P  TO 

3-21
 b c d
So for a flow system and A  B  C  D
a a a
FA F 1  X  TO P
CA   AO  
  O 1   X  T PO

 1  X  TO P
C A  C AO   
 1  X  T PO

FB F   b / a   X   TO P
CB   AO B 
  O 1   X  T PO

   b / a   X  T O P
C B  C AO  B 
 T 
 1  X  PO

FC F   c / a   X   TO P
CC   AO C 
  O 1   X  T PO

   c / a   X  T O P
C C  C AO  C 
 T 
 1  X  PO

FD F   d / a   X   TO P
CD   AO D 
  O 1   X  T PO

   d / a   X  T O P
C D  C AO  D 
 T 
 1  X  PO

Note that the Cj = hj(X) expressions are identical to the

ones of a variable-density Batch system.

3-22
 Example 3-6

2SO2 + O2  2SO3
A B C

Flow reactor
Feed: 28% SO2, 72% air
PO = 1485 K Pa const.
TO = 227C
Assume: -rA = kCA  CB (k = 200lt/mol.s)
Develop the –rA = g(X) relationship
A + ½B  C

STOICHIOMETRIC TABLE

Species Initially Change Remaining

A FAO FAO X F A  F AO 1  X 

F AO X  X 
B FBO = B  FAO  F B  F AO   B  
2  2 

C 0 +FAO X FC  F AO X

I FIO = IFAO – F I  F IO   I  F AO

F AO X
FTO F T  F TO 
2

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 F BO
B 
F AO
FAO = 0.28  FTO
FBO = 0.72  0.21  FTO

0 . 72  0 . 21
B   0 . 54
0 . 28
F 0 . 72  0 . 79
 I  IO   2 . 03
F AO 0 . 28
FA F 1  X 
CA   AO
 
   O 1   X  O 
P T
P TO
P  PO , T  TO
   O 1   X 
F AO 1  X   1 X 
CA   C AO  
 O 1   X   1  X 
P
C AO  y AO  C TO  y AO  O
RT O
1485 K Pa
 0 . 28
K Pa  dm 3
8 . 314  500 K
mol  K
mol
 0 .1
dm 3

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  1
  y AO    0.28   1 - 1 -    0 . 14
 2

 1 X  mol
C A  0 .1   
 1  0 . 14  X  dm
3

 1   1 
F AO   B  X   B  X 
CB
F
 B   2 
 C AO 
2 
  O 1   X  1   X 
 0 . 54  0 . 5  X  mol
 0 .1   
 1  0 . 14  X  dm
3

 r A  kC A CB

dm 3  1 X  mol  0 . 54  0 . 5 X  mol
 200  0 .1     0 . 1   
mol  s  1  0 . 14  X  dm
3
 1  0 . 14 X  dm
3

2 1  X 0 . 54  0 . 5 X 
 rA 
1  0 . 14  X 2
0 . 5 1  0 . 14  X 
2
1

 rA 1  X 0 . 54  0 . 5  X 

1
 rA

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