Department of Chemical Engineering

CHE 321: Chemical Reaction Engineering

Week 3
Rate Laws and Stoichiometry
Summary: Reactor Mole Balances
The GMBE in terms of conversion, X for the reaction AB

Reactor Differential algebric integral

X
dX dX
Batch N A0  r AV t  N A0 
dt 0
 rAV
FA 0 X
CSTR V
rA
X
dX FA0 dX
PFR FA 0  rA V 
dV  rA
 0

X
dX FA0 dX
PBR FA 0  rA W 
 dW 0
 rA

CHE 321 3
Algorithm
How o find −𝒓𝑨 = 𝒇(𝑿) ra Kca
rat kCao I x

Step 1: Rate law −𝑟𝐴 = 𝑔(𝐶𝑖 )

Step 2: Stoichiometry 𝐶𝑖 = ℎ(𝑋)

Srep 3: Combine to get −𝑟𝐴 = 𝑓(𝑋)

CHE 321 4
 Basic Definitions
• Homogeneous reaction: one that involves only one phase.
• Heterogeneous reaction: involves more than one phase, and
reaction usually occurs at or very near the interface between
phases.
• Irreversible reaction: one that proceeds in only one direction
and continues in that direction until the reactants are exhausted
a A  b B 
 cC  dD
• Reversible reaction: one that can proceed in either directions,
depending on the concentrations of reactants and products
relative to the corresponding equilibrium concentrations

 cC  dD
a A  b B 


CHE 321 5
 Basic definitions
• In order to calculate the time required to achieve a given
conversion or to evaluate the reactor volume, it is necessary to
know the reaction rate.
• The reaction rate is commonly derived from experiments and
expressed in terms of the concentration, such that
−𝑟𝐴 = 𝑘𝑓(𝐶𝐴 , 𝐶𝐴 , … )
• The reaction rate constant “k” is usually expressed as function
of temperature using Arrhenius equation as follows:
𝑘 = 𝐴𝑇 𝑛 𝑒 −𝐸 Τ𝑅𝑇 (0 ≤ 𝑛 ≤ 1)
where E is the energy of activation (J/mol), R is the universal
gas constant (8.314 J/mol.K, T is the temperature (K) and A is
the frequency factor.
Note: k and A units depends on the overall reaction order
CHE 321 6
 Basic definitions
• The reaction order
Is the power to which the concentration is raised in the reaction
rate. For example, the reaction given by −𝑟𝐴 = 𝑘(𝐶𝐴 )𝑛 is of order n,
where n=1, 2, …

• Elementary reaction
Is the one which the reaction order of each species is identical to
the stoichiometric coefficient of that species. For example,
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷 ra Kca
If this is an elementary reaction it is of order a with respect to A
and of order b with respect to reactant B. The overall reaction order,
n, is: 𝑛 = 𝑎 + 𝑏.
ex 2A B
ra Kcal CHE 321 7
 Basic definitions
• The heat of reaction
Is the heat given off or consumed during a chemical in an
isothermal system and the reaction is aid to be exothermic for the
former and endothermic for the latter. For example:
𝐶𝐻4 + 2𝑂2 → 𝐶𝑂2 + 2𝐻2 𝑂 (-213 kcal per gmole CH4)
Is this exothermic or endothermic?
Burningcombustion
• Homogenous and heterogeneous reactions
A reaction is homogeneous if it takes place in one phase.
Example: The reaction above
While a reaction that takes place between different phases is
classified as heterogeneous.
Example: 𝐶(𝑠𝑜𝑙𝑖𝑑) + 𝑂2 (𝑔𝑎𝑠) → 𝐶𝑂2 (𝑔𝑎𝑠)

CHE 321 8
Stoichiometry
• Consider the following chemical reaction:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
A limiting so by a
• The capital letters represent chemical species and lower case
letters represent the stoichiometric coefficient.
• Dividing both side of the equation by “a” gives:
𝑏 𝑐 𝑑
𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
• For every mole of A, (b/a) moles of B are needed, (c/a) mole of
C and (d/a) moles of D are formed.

Make everything interms of limitingcomponent

CHE 321 9
 Relative Rates of Reaction
• The relative rates of reaction of the various species involved in a
reaction can be obtained from the ratio of stoichiometric
coefficients:
𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
𝑏 𝑐 𝑑
𝐴+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎

• Rate of disappearance of B is (b/a) the disappearance of A and

the rate of formation of C and D is (c/a) and (d/a) the
disappearance of A, respectively.
−𝑟𝐴 −𝑟𝐵 𝑟𝑐 𝑟𝐷 LA B
= = = rb
𝑎 𝑏 𝑐 𝑑 rg
rb Ikea
CHE 321 10
Relative Rates of Reaction
2A  B  3C

Given mol
 rA  10
dm3  s
Then what is rB and rC? rA rB rC
 
 2 1 3
E F
vb  rA mol
I  rB  5
2 dm3  s
vb 5
3 mol
rC  rA  15
7 5 2 dm3  s
u 12 3
re 15 CHE 321 11
 Step 1: Rate Laws
• Power Law Model:

 
rA  k ACA CB α order in A
β order in B
Overall Rection Order  α  β

• The units of –rA are always in terms concentration per unit

time while the units of the specific reaction rate, kA, will
vary with the overall order of the reaction (n):
 Concentration 
1n Va
Toffime
k A  
Time
CHE 321 12
Units of the reaction rate constant

Reaction Order Rate Law k unit

Zero -rA=kA mol/dm3.s

One -rA=kACA s-1

Two -rA=kACA2 dm3 mol-1 s-1

Three -rA=kACA3 (dm3)2 mol-2 s-1

o
mol =

volo Time

CHE 321 13
 Elementary rate law
2A  B  3C
A reactor follows an elementary rate law if the reaction orders
just happens to agree with the stoichiometric coefficients for the
reaction as written.
e.g. If the above reaction follows an elementary rate law
 rA  k AC CB2
A

2nd order in A, 1st order in B, overall third order

CHE 321 14
 Non-elementary law
 Rate Laws are found from Experiments
2A + 𝐵 → 3𝐶
 Rate Laws could be non-elementary. For example, reaction
could be:
› Second Order in A
› Zero Order in B
› Overall Second Order
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴2
−𝑟𝐵 = 𝑘𝐵 𝐶𝐴2
−𝑟𝐶 = 𝑘𝑐 𝐶𝐴2

CHE 321 15
 Examples of Rate Laws
In the example, i.e., 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷
The rate law can be written as:
−𝑟𝐴 = 𝑘𝐶𝐴𝑎 𝐶𝐵𝑏
Elementary Rate Law Non-elementary Rate Law
 If the stoichiometry  CO+CI2→COCI2
coefficients are the same as  rCO  kCCOCCI
3/ 2

the individual reaction 2

order of each species. This reaction is 1st order

H2 +I2  2HI with respect to CO, 3/2
order with respect to
rHI = k CH2 CI2
CI2 and 5/2 order overall.

CHE 321 16
Example 1-3: Rate Law
A+1/2 B  C 9 =
Ira rb =

If the reaction rate is  rA  kC ACB1 / 2 rb IkaCy"=

What is rB, rC and the units of the rate constant?

rA

rB 29 =
 1  1/ 2
rc ra
1 k
=

rB  rA   C ACB1 / 2 rc kCaCy"
=

2 2
rA rC

1 1
rC   rA  kC ACB1 / 2
CHE 321 17
 Example 1-3: continue
2) Calculate the rates of A, B, and C where the concentrations are CA
= 1.5 mol/dm3, CB = 9 mol/dm3 and kA = 2 (dm3/mol)(1/2)(1/s).
1.5 912 9
kCaCb" 2 x x
=

-ra
=

  dm 3 1/ 2 1   mol   mol 

1/ 2

 rA   2    1.5 9
  mol  s   dm   dm 3 
3
  I

mol
 rA  9
dm 3 .s
mol
rB  4.5
dm 3 .s
mol
rC  9
dm 3 .s

CHE 321 18
The Reaction Rate Constant
Arrhenius equation
• kA is the specific reaction rate (constant) and is given by
the Arrhenius Equation.
𝑘𝐴 = 𝐴𝑒 −𝐸 Τ𝑅𝑇
where:
E = Activation energy (cal/mol)
R = Gas constant (cal/mol.K)
T = Temperature (K)
A = Frequency factor (same units as rate constant k)

• Activation Energy: defined as the energy that must be

overcome in order for a chemical reaction to occur.

CHE 321 19
 912

Step 2: Stoichiometry
We shall set up Stoichiometry Tables using species A as our basis
of calculation in the following reaction. We will use the
stoichiometric tables to express the concentration as a function of
conversion. We will combine Ci = f(X) with the appropriate rate
law to obtain -rA = f(X).

A is the limiting reactant.

aA  bB cC  dD

b c d
or A  B C  D
a a a

CHE 321 20
 Useful Definitions
 Considering the reaction:
𝑏 𝑐 𝑑
A+ 𝐵 → 𝐶 + 𝐷
𝑎 𝑎 𝑎
 Parameters Θ𝑖
-

𝑁𝑖0 𝐶𝑖0 𝑦𝑖0

Θ𝑖 = = =
𝑁𝐴0 𝐶𝐴0 𝑦𝐴0
 Net mole change for the reaction
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠
𝛿=
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑
𝑑 𝐶 𝑏
𝛿= + − −1
𝑎 𝑎 𝑎

CHE 321 21
 Stoichiometry
𝑏 𝑐 𝑑
Na Nao(1 x)
=
- A+ 𝐵 → 𝐶+ 𝐷
𝑎 𝑎 𝑎
• Moles of A remaining (𝑁𝐴 ):
𝑁𝐴 = 𝑁𝐴0 − 𝑁𝐴0 𝑋
e⑲
converted d

• Moles of B reacted
𝑚𝑜𝑙 𝑜𝑓 𝐵 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑏
. 𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 = (𝑁𝐴0 𝑋)
𝑚𝑜𝑙 𝑜𝑓 𝐴 𝑟𝑒𝑎𝑐𝑡𝑒𝑑 𝑎

• Moles of B remaining (𝑁𝐵 ):

𝑁𝐵 = 𝑁𝐵0 − (𝑁𝐴0 𝑋) Relating tothe
𝑏
𝑎 limitingcomponent
• Let Θ𝐵 =𝑁𝐵0 /𝑁𝐴0 , then
𝑏
𝑁𝐵 =𝑁𝐴0 (Θ𝐵 − 𝑋) NB Nao (-X
=

𝑎
similarly,
𝑐 𝑐 Nb Nbo
=
-

Nas?X
𝑁𝐶 =𝑁𝐶0 + 𝑁𝐴0 𝑋 = 𝑁𝐴0 (Θ𝑐 −N 𝑋)
𝑎 𝑎 NC Nao (Oc
=
+ EX
Nc
CHE 321 Naot
=
Nao X 22
Batch System - Stoichiometry Table
ra KcaCB
call x d
Consider the reaction: 𝑎𝐴 + 𝑏𝐵 → 𝑐𝐶 + 𝑑𝐷 G inter
ofca
u
Fagot
Species Symbol Initial Change Remaining
A A NA0 -NA0X NA=NA0(1-X)
Nao
Mbo:

B B NB0=NA0ΘB -b/aNA0X NB=NA0(ΘB-b/aX)

C C NC0=NA0ΘC +c/aNA0X NC=NA0(ΘC+c/aX)

D D ND0=NA0ΘD +d/aNA0X ND=NA0(ΘD+d/aX)

Inert I NI0=NA0ΘI ---- NI=NA0ΘI
NT0 NT=NT0+δNA0X

CHE 321 23
Stoichiometry Constant Volume Batch
Note: If the reaction occurs in the liquid phase
or
if a gas phase reaction occurs in a rigid (e.g. steel) batch reactor, then
the volume is constant, i.e. V=V0 Ca -
CD
-

r k Caoli xi Cao OB box

NA N A 0 1  X 
CA    CA 0 1  X 
V V0
NB N  b   b 
CB   A0 
 B  X   C A0   B  X
V V0  a   a 
NC N A0  c   c 
CC    C  X   C A0  C  X 
V V0  a   a 
N N  d   d 
C D  D  A0   D  X   C A0   D  X 
V V0  a   a 

CHE 321 24
Stoichiometry Constant Volume Batch
Suppose rA  kA CA2 CB Cao O box
d
a
Batch: V  V0 Cao'll a

2  b 
 rA  k AC A0 1  X    B  X 
 3

 a 

Equimolar feed: B  1
b
Stoichiometric feed: B 
a
For Products Oc, Op 0
=

CHE 321 25
Example 2-3:
Consider the following elementary gas phase reaction in a rigid
batch reactor: a
-
k(aCb2
ra =

A + 2B → 𝐶 -ra kcao)
=
CalO-2x)
-x).

K(a03 (1 x)(OB-2x)2
= -

a/ Write the rate law in terms of the concentration

b/ Write the rate of reaction in terms of k, CA0 and X
Assume constant temperature and pressure.
−𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵2 ra KCaCb CaoOB 2x
𝑁𝐴 𝑁𝐵 2 ti x
Cao
−𝑟𝐴 = 𝑘 ra k Cao l X OB 2 x
𝑉 𝑉
𝑁𝐴 = 𝑁𝐴0 (1 − 𝑋) and 𝑁𝐵 = 𝑁𝐴0 (Θ𝐵0 − 2𝑋)
3
−𝑟𝐴 = 𝑘𝐶𝐴0 (1 − 𝑋) Θ𝐵0 −2𝑋 2

CHE 321 26
What is the Limiting Reactant?
Example:

3A + B  3C+ D 3 At FB C t t D

B t x 10 3 whiis 72
Moles A = 10; Moles B = 2 so B is limiting
2
- 0.2 mol
=

From the reaction stoichiometry:

18

1 0.333
=
but
only 0.2 available
3
so
limiting:B
moles B needed = 1/3  moles A = 1/3 10=3.33 > 2
 B is limiting reactant

CHE 321 27
Example 3-3:

A B

h and D initia
3A B 93C t D A Cao Cao i x
B 8 3 1 I I
Cb Cao OB tx
no change in n
At JB ga g C Cc Cao of x =Cao X

=Cao X
Since no (and D:

Oc 0
=

OD 0
⑲
to
=

CHE 321 28
Flow System – Stoichiometry Table

how would
we hunter this

of
interes
I C

Species Symbol Reactor Feed Change Reactor Effluent

A A FA0 -FA0X FA=FA0(1-X)
B B FB0=FA0ΘB -b/aFA0X FB=FA0(ΘB-b/aX)
C C FC0=FA0ΘC +c/aFA0X FC=FA0(ΘC+c/aX)
D D FD0=FA0ΘD +d/aFA0X FD=FA0(ΘD+d/aX)
Inert I FI0=A0ΘI ---------- FI=FA0ΘI
FT0 FT=FT0+δFA0X

Fi0 Ci0 0 Ci0 y i0 d c b

where: i     and     1
FA 0 CA 0 0 CA 0 y A 0 a a a
CHE 321 29
liquid
 Stoichiometry
Fi
Concentration Flow System: Ci 

Liquid Phase Flow System:   0
FA FA 0 1  X 
CA    CA 0 1  X  Flow, Liquid -Phase
 0
FBFA0  b   b 
CB     B  X   C A0   B  X 
 0  a   a 
I when no C in
FC FA0  c   c  reactants
CC    C  X   C A0  C  X 
 0  a   a 
FDFA0  d   d 
CD     D  X   C A0   D  X 
 0  a   a 
CHE 321 30
Volume change for gas phase system
• The Real gas law:
𝑃𝑉 = 𝑍𝑁𝑡 𝑅𝑇
• At initial condition the volume in the reactor is given by:
𝑃0 𝑉0 = 𝑍0 𝑁𝑡0 𝑅𝑇0 V VoPop
MT Mto
III to
tfNaox
• The reactor volume at any time is given by: MIG
𝑃0 𝑇𝑍𝑁𝑡
ng I t
SEE
𝑉= 𝑉0
𝑃 𝑇0 𝑍0 𝑁𝑡0 HI I t 8YaoX
• If the total number of moles converted per mole of reactant A is
, conversion is X, the total number of moles after reaction is:
𝑁𝑡
𝑁𝑡 = 𝑁𝑡0 + 𝛿𝑁𝐴0 𝑋 or = 1 + 𝛿𝑦𝐴0 𝑋 V Vo E Ix it8yaoX
𝑁𝑡0 P To
• The volume at anytime for an ideal gas (𝑍= 𝑍0 )is: It V Vol't
𝑃0 𝑇 𝑃0 𝑇 pepo Eaox
V = 𝑉0 (1 + 𝛿𝑦𝐴0 𝑋) or V = 𝑉0 (1 + 𝜀𝑋) V Vo it ex
𝑃 𝑇0 𝑃 𝑇0
CHE 321 31
Gas Phase Flow System I Yo Yi E
V
MI to Ep
Combining the compressibility factor
equation of state with Z = Z0 V
Niotytat
Stoichiometry: CT 
P v Vofl tfyaox I ⑱
Vo
Pop

ZRT
P0
CT 0 
Z 0 R0T0
FT  CT
FT 0  CT 0 0

FT P0 T
  0
FT 0 P T0
CHE 321 32
Gas Phase Flow System-continue

Fj Fj FT 0 Fj  P   T0 
Cj      
  FT P0 T  0 FT  P0   T 
0  
 FT 0 P T0 
F j  P   T0 
C j  CT 0   
FT  P0   T 
n
FT  FA  FB  FC  FD  FI  ...   Fj
j 1

CHE 321 33
 add?
to

Gas Phase Flow System-continue

when

↑
Recall:   0
FT P0 T FT  FT 0  FA0 X
·

FT 0 P T0

 FT 0  FA0 X  T P0  FA0  T P0
  0    0  1  X
 FT 0  T0 P  FT 0  T0 P


  T P0 T P0
 0 1   X 
A
 0  1  y A0 X 
  T0 P T P
  0

Where   yA0
CHE 321 34
 Gas Phase Flow System-continue
Fj T P0
Cj     0 1  X 
 T0 P

F j  F j 0  v j  FA0 X   FA0   j  v j X   j  Fj 0 / FA0

v j : the stoichiometric coefficient; -ve for reactants and +ve for products

b c d
A B C D vA  1, vB  b / a, vC  c / a, vD  d / a
a a a

FA0   j  v j X 
Fj C A0   j  v j X  T0 P
Cj   
  1   X  T P0
0
1  X  T P0
T0 P

CHE 321 35
Example 4-3: Gas reaction at constant temp and press
• The design equation requires knowledge of the relation between
the rate and conversion.
• Consider the following elementary gas phase reaction:
A+B→𝐶
The rate of reaction is given by:
−𝑟𝐴 = 𝑘𝐶𝐴 𝐶𝐵 = 𝑘
𝑁𝐴 𝑁𝐵
𝑉 𝑉
aagicos, -x).
-

O
v0(1+ 8490X(
oj
• For an ideal gas, if the reaction is carried out at constant
temperature and pressure, what would be the volume:
Answer: V = 𝑉 1
𝑃0 𝑇
(1 + 𝛿𝑦 𝑋)
e
0 𝑃 𝑇 𝐴0 -

V = 𝑉0 (1 + 𝛿𝑦𝐴0 𝑋)
(1−𝑋) 2
• The final rate of reaction is given by: −𝑟𝐴 = 𝑘(𝐶𝐴0 )2
(1+𝛿𝑦𝐴0 𝑋)2
CHE 321 36
 FA0 
d c b
  1
y A0  , CA0  y A0CT0 a a a
FT 0
change in total number of moles

mole of A reacted

      1 A0  y A0    y A0

d c b F
 a a a  FT 0

change in total number of moles for complete conversion


total number of moles fed to321
CHE the reactor 37
 Example 5-3
The gaseous reaction A  B is to be carried out at a constant
temperature and pressure in parallel tubes each of 3.0 m long
and 0.0254 m diameter. The required production rate of B is
17.21 mol/h. How many tubular reactors will be needed if the
required conversion is 90%? V 402x
10.0254)2(3)
=

I
OB=
=

Fb Fao10 +x)
=

Fas = 11 0.318mol/min
=

0.9
X40 min

Vis =0.00152m3
Fb0 0 Fb

-⑧
Fao(X) VT=
4XVs
=
=

n-tubes
v
DB 0
Information
=

3m
↳ 0.0254

Reaction rate constant = 53.6 min-1.

v 0.318
a(n(9)
Initial concentration of A, CA0=0.7 mol/m3
=

->

↑
53.4 X0.7

fodX Fao" -x)

E
Fb 17.21moi/h
=

v
=
v=

X 0.98
= 0.9 k2a0(1 20.095ms
k 53.4
=
V =

Fault a. v= (n(r-x) e
0.9

n =

0 =13
Ca0 0.7 mol/m3
=

0.00152

ya0=1
0
k(a 3
5ya0 ( 1)(1)
= =

ra
= -
-

e
ra k(a0)) X)
=
-

ra
= -
-

CHE 321 38
 Reversible Reactions
 Rate law for reversible reaction must
 Satisfy thermodynamic relationships at equilibrium and
 Reduce to the irreversible rate law when the concentration of
one or more of the reaction products is zero
↑
C,
• General reaction
Va =
-
+

forming
2,]
aA + bB  cC + dD
->
A
ra -=

a
kB k,c
0 =

Thermodynamic equilibrium relationship

=

At equilibrium ra o
=

c  d  a b
=
c d
C C  mol 
KC 
C C
Ce
a
De
b  KC    3 
Ae Be  dm 

39
Example:

kB
2C6 H 6  C12 H10  H 2 
kB
2 B  D  H 2
k B k B

Rate of deformation of benzene

-rB, forward = kBCB2 concentration equilibrium
I constant: Kc = kB/k-B

Rate of formation of benzene

rB, reverse = k-BCDCH2

The net rate of formation of benzene is the sum of the rates of formation
from the forward reaction and the reverse reaction
rB,net = rB, forward + rB, reverse Note: @ equilibrium: rnet = 0
rB, net = -kBCB2 + k-BCDCH2 rne + = -

4 2 k-CpCi
+
+

- rB, net = kB(CB2 – (k-B/kB)(CDCH2)) -

Ubnet =

k (B
+
-

k.(p[Hd

,0x]
=
+
-

Met SC2
- rB, net = kB(CB2 – (CDCH2)/KC)
-

rne+
kx(b(nz)
-

40
= k
+ [CB" -
 when use
to
(0-2x) or 71
-x)??
Example 6-3:
A mixture of 28% SO2 and 72% air is charged to a flow reactor
in which SO2 is oxidized

2𝑆𝑂2 + 𝑂2 → 2𝑆𝑂3
Yaziy
First, set up a stoichiometric table and write the rate of reaction
if it is first order with respect to SO2 and O2. Use constant
temperature and pressure of 227 °C and 1485 kPa, respectively.
ra kaCB
=
-

A C
B -
+

cas
-
=

ona
initial Remaining
change

tan
Eac Fao X Fr Fao(1 x)
-
=

Fb -

I FaoX *
b Fao(0r 2x)
=
-

I
co
FaoX Fc Fao(0c x)
= +

0.28 FI
Fra FM o

Fro
See P115 in Fogler 8 =1 - 1 -

2
3 ya08 (0.28770.5)
=
=

CHE 321 2 8.14

=
41
 Car
3a0
=

Example 7-3:

See P118 in Fogler

CHE 321 42