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# H83RED Reactor Design

Stoichiometry
and
Rate Laws

Outline

## Rate Law and Reaction Rate Constant

Arrhenius Law
Elementary reaction
Order of Reaction
Rate Law for reversible reactions

Stoichiometric Table
Batch systems:
Constant volume and
Constant pressure

Flow systems:
Liquid phase
Gas phase reactions that have a change in the total number of moles
Reactors with variable volumetric flowrates

Types of Reactions

## Chemical kinetics deals with reaction rates

Homogeneous reaction
involves substances of only one phase

Phase

Types of Reactions

Heterogeneous reaction
involves more than one phase, and the
reaction usually occurs at or very near the
interface between the phases
B
Irreversible reaction A
proceeds in only one direction and continues
until the reactants are exhausted

Equilibrium

Reversible reaction
proceeds in both forward and reverse
directions; continues until the equilibrium state
is reached
A
B

Rate Law
The Rate Law and the Reaction Rate Constant
General form of the rate law, which is an algebraic equation representing the
reaction rate as a function of the concentrations (activities) of various species:

rA k( T ) f ( C A ,C B ,...)

(1)

## k = reaction rate constant

~ independent of the species concentrations
The specific reaction rate
constant, kA, is always referred to
a particular species

Exception
NaOH + HCl NaCl + H2O

## Reaction rate constant is an intensive parameter concentration-independent

Liquid Phase: k=f(temperature, total pressure, ionic strength, choice of solvent )

Gas Phase:

## k=f(temperature, catalysts, total pressure )

Rate Law
Temperature Dependency from Arrhenius Law

k( T ) Ae E / RT

(2)

## A = pre-exponential factor or frequency 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 characterise energy state of molecules which could

result in their chemical interaction
Minimum energy that molecules must have to react

E1
ln k A ln A
R T

(3)

## E , k~ sensitive to the temperature

E , k~ less sensitive to the
temperature

ln k, sec-1

ln k, sec-1

slope= -E/R
Low E

High E
1/T, K-1

1/T, K-1

Arrhenius Law
Rules of thumb:

ln k, sec-1

## Rate of reaction doubles for every 10 oC

increase in temperature

## ~ Only true for a specific combination

of activation energy and temperature

Low E
High E
1/T, K-1

## Temperature rise needed to double the rate of reaction

Average
Temperature

Activation Energy, E
40 kJ/mol

160 kJ/mol

280 kJ/mol

400 kJ/mol

0 oC

11 oC

2.7 oC

1.5 oC

1.1 oC

400 oC

65 oC

16 oC

9.3 oC

6.5 oC

1000 oC

233 oC

58 oC

33 oC

23 oC

## Reactions with high activation energies are very temperature-sensitive

Any given reaction is more temperature-sensitive at lower temperatures than
at higher temperatures

Arrhenius Law
Consider the following elementary reactions :

Solution
1) Which reaction has the higher activation energy?

## 2) Which reactions have the same activation energy?

3) Which reaction is virtually temperature insensitive?

Arrhenius Law
Solution
4) Which reaction will dominate (i.e. take place the fastest) at high temperatures?

## 5) Which reaction will take place the fastest at low temperatures?

Arrhenius Law
Finding k(T) given k(T0)

k (T0 ) Ae E / RT0
k (T ) Ae E / RT

substitute A k T0 e E / RT0
k (T ) k (T0 )e

E
RT0

E
RT

E 1 1
k(T) k(T0 )exp
R T0 T
If we know:
The specific reaction rate k0(T0) at a temperature T0
The activation energy, E,

We can find the specific reaction rate constant k(T) at any other
temperature,
T, for that reaction

Arrhenius Law
Determine the activation energy, E and frequency factor, A from the following data:

k (min-1)

0.001

0.050

T (oC)

0.0

100.0

Solution

## Arrhenius equation in logarithm form:

E1
ln k A ln A
R T

k( T ) Ae E / RT

Elementary Reaction
Elementary and Non- elementary Reactions
Rate law can be derived from collision theory

rA k( T ) f ( C A ,C B ,...)

(1)

## Assumption from Collision theory:

Reactant particles must collide with each other.
Reaction is a result of the collision of a single molecule A with a single
molecule B

## E: Energy required to activate the molecules into a state from which

reactant bonds can change into product bonds.
Only those collisions with enough energy to exceed E can lead to
reaction.
Rate of reaction is proportional to the number of such collisions.

## The number of collisions is proportional to the concentration of

reactant.

Elementary Reaction

## The dependence of possible collisions on the reactant concentrations.

A

4 collisions

A
molecule of A

6 collisions

B
A
molecule of B

B
9 collisions

Elementary Reaction
Elementary Reactions
If kinetic experiments results in a rate law, which corresponds to
the stoichiometric equation, we call such reactions elementary.
A +

## rA kCAC B corresponds to the stoichiometric

equation

Molecularity

Elementary step

Rate law

1. Unimolecular

A -> products

rate = k CA

2. Bimolecular

2A -> products
A + B -> products

rate = k C2A
rate = k CACB

3. Termolecular

3 A -> products
A + 2 B -> products
A + B + C -> products

rate = k C3A
rate = k CAC2B
rate = k CACBCC

## The molecularity of an elementary reaction is the number of molecules

(atoms) involved (colliding) in the reaction.

Elementary Reaction
Elementary and Non-Elementary Reactions
Elementary Reaction

H2 + I2

2HI

rH 2 kCH 2 C I 2
Non-Elementary
Reaction

H2 + Br2

rHBr

2HBr

1/ 2
k1C H 2 C Br
2

k 2 C HBr / C Br2

## Non-elementary reactions involve more complex, multi-step reactions

Rate law reflects a limiting step or combination of limiting steps
The rate limiting step is the slowest step in the sequence of steps
The overall rate of reaction depends on this slowest step

Elementary Reaction

## The Reaction Order and Rate Law

rA
General form of the rate law:

k AC A C B ...

Temperature-dependent
term

(4)

Concentration-dependent
terms

The order of a reaction refers to the power to which the concentrations are raise
The overall order of the reaction: n = + +
2 NO

+ O2

2 NO2

2N2O

2
rNO k NO C NO
CO 2

CO

+ Cl2

rCO kCCOC
H2 + Br2

rHBr

COCl2

3/ 2
Cl

k1C H 2 C

2HBr
1/ 2
Br2

k 2 C HBr / C Br2

rN 2O
i) CO2
1>>

ii) CO2
1<<

k CO2

+ O2

k N 2O C N 2O
1 k CO2

k CO2 rN O kN OCN O
2

2N2

kN2OCN2O
rN2O
k CO2

## Pseudo-first order with

respect to nitrous oxide
Apparent reaction order:
-1 with respect to O2
1 with respect to N2O
Overall zero order

Rate Law
Examples of Forms of Rate Law and Units of Reaction Rate Constant
Zero-order:

rA k A

mol
mol
rA 3

k
A
3

dm

sec

dm sec

mol
dm 3 sec

First-order:

[k]=sec-1
Second-order:

dm 3
k

mol sec
Third-order:

dm 6
k 2
mol sec

rA k AC A

mol
1
mol mol
rA 3

C
3
A
A
3

sec
dm sec

dm dm sec

rA k AC A2
2
dm 3
mol
mol
2 mol
rA 3

A
A

dm sec
mol sec
dm dm sec

rA k AC A3
3
dm 6
mol
mol
3 mol
rA 3

A
A

2
9

dm sec
mol sec
dm dm sec

Rate Law

1
What is the reaction rate law for the reaction: A B C
2
if the reaction is elementary?
Calculate the rates of A, B, and C in a CSTR where the concentrations
are
CA = 1.5 mol/dm3, CB = 9 mol/dm3 and kA = 2 (dm3/mol)(1/2)(1/s).

## Rate Law for Reversible Reactions

One more limit condition for reversible reactions: Equilibrium State
The state in which the concentrations of the reactants and products
have no net change over time
The rate of reaction is identical for all species and equal zero -rA 0
aA

bB

k
k-1

cC

dD

## k= Forward reaction rate constant

k-1 = Reverse reaction rate constant

At thermodynamic equilibrium:

c
d
CCe
C De
KC a b
C Ae C Be

KC is an equilibrium constant

Units

(5)

mol
3
dm

d c b a

## The equilibrium constant characterise: equilibrium concentration of all species

ratio between rates of forward and
reverse reactions

k forward
k
KC

k reverse k -1

(6)

## Rate Law (Reversible Reaction)

thermodynamic
equilibrium relationship

c
d
CCe
C De
KC a b
C Ae C Be

## Kinetic rate law for reversible

reaction must be consistent
with

with specified rate law of
forward and reverse
reactions

## An elementary reversible reaction

A

kA

k-A

A
Forward reaction A
B
Reaction rate with respect to species A

rA k AC A
rA k AC A
Reverse reaction B

k-A

disappearance of species A

(7)

formation of species A

(8)

## Reaction rate with respect to species A

rA k AC B

formation of species A

(9)

## Rate Law (Reversible Reaction)

The overall rate of formation of
species A r r
r
A

A, forward

A, reverse

k AC A k A C B

(10)

## rA rA, forward rA,reverse

k AC A k AC B k A ( C A

KC

k forward
k

k reverse k -1

k A
CB )
kA

## Rate law for elementary monomolecular reversible reaction:

C
rA k A (C A B )
KC
Check of the consistency with thermodynamic equilibrium:
A

kA

k-A

At equilibrium:

## Thermodynamics tells that:

KC

C Be
C Ae

rA 0 k A (C Ae

CBe
After rearranging:C Ae
KC
C
K C Be
C Ae

(11)

(12)

CBe
)
KC

## Write the rate law for the elementary reaction

Here kfA and krA are the forward and reverse specific reaction rates both
defined with respect to A.

Stoichiometry

Stoichiometry
Stoichiometry provides information on relative quantities of reactants
and products in chemical reactions.

and excess in our previous lecture.

## Rate of reaction ri is a variable in all the design equations for

reactors. Rate of reaction is a function of thermodynamic quantities
such as temperature and also concentration of the species.
Conversion of the limiting reactant is a function of the concentration
and therefore rate of reaction is a function of the conversion: ri=f(Xi).
To evaluate the integrals associated with the design equations of
the form
the functional form of ri(X) has to be found.
Stoichiometry provides a solution for this challenge.
rate law

rA f (C j )

C j h j (X )

rA g (X )

## Conversion: Revision of concepts

Mole Balance for Different Reactors
Reactor Type

Batch

Differential

N A0

Algebraic

dX
rAV
dt

Integral

t N A0

X A (t )

dX
rAV

FA 0 X
(rA ) exit
C X
A0
( rA )exit
V

CSTR

PFR

FA0 dX
rA
dV

V FA0

C A0

X out

X in
X out

X in

PBR

FA0 dX
rA
dW

W FA0

dX
rA

dX
rA

X out

X in

dX
rA

Stoichiometry: Extent
Relative quantities (extent)
Reaction

Initial quantities

Quantities remaining at
t=t

Quantities reacted

0

## Therefore the relative quantities are given by the following equation

0

[13]

The extent E of the reaction is the relative number of moles reacted/ generate

## Stoichiometry: Relative rates

Relative reaction rates
Reaction

Rates

Rate of disappearance of A =
Rate of disappearance of B =
Rate of appearance of C

=
= =

[14]

## Stoichiometry: Stoichiometric table

Constructing stoichiometric table

t=0
NA0
NB0
NC0
ND0
NI0

t=t
NA
NB
NC
ND
NI

## Reaction was terminated at time t when

the conversion of the limiting reactant A
reached X. Composition of the product:
NA, NB, NC, ND and NI moles of substances
A, B, C, D and I, respectively
From the definition of conversion

= 0 0
moles of A
moles of A in
a system volume introduced into the

at conversion X system volume

## For every mole of A reacted, b/a moles of B must react

moles B reacted

b
b
moles A reacted ( N A0 X )
a
a

moles of A

reacted when

conversion reached X

A +

t N A0

X A (t )

Species

Initially
(mol)

Change
(mol)

NA0

( N A0 X )

NB0

NC0

ND0

NI0

Total

NT0

b c d

1 N A0 X
a a a

b
( N A0 X )
a
c
( N A0 X )
a
d
( N A0 X )
a

dX
rAV

Remaining
(mol)

N A N A0 N A0 X
b
N A0 X
a
c
N C N C 0 N A0 X
a
d
N D N D0 N A0 X
a
N B N B0

NI NI0
d c b
NT NT 0 1 N A0 X
a a a

## Stoichiometry: Stoichiometric table

Total number of moles changed
The total number of moles of all active species (reactants and products) at
conversion X of species A:
= 0 +

+ 1 0

[15]

reacted
=

+ 1

= 0 + 0

0
0

= 0 + 0
where
= /

## We will introduce concentrations in the

stoichiometric table using:
=

= +

[16]

## Stoichiometry: Stoichiometric table

Expressing all in terms of NA0
In order to define all concentrations on a basis per mole of A we
introduce the parameter :
N
C
y
i i 0 i 0 i 0
[17]
N A0 C A0 y A0
The final equation for concentration of species B:

CB

N B 0 ( b / a )N A0 X B N A0 ( b / a )N A0 X

V
V

CB

N A0 B (b / a) X
V

[18]

A +

()

## b/a B c/a C + d/a D

= 0
0

Initially
(mol)
A

NA0

N B 0 B N A0

NC 0 C N A0

N D 0 D N A0

N I 0 I N A0

Total NT0

Change
(mol)

( N A0 X )

Remaining
(mol/dm3)

(mol)

N A N A0 N A0 X

CA

N A 0 (1 X)
V

b
N

X C N A0 B (b / a) X
( N A0 X ) B
A0
B
a B

a
V
c
c

N A0 C (c / a) X
( N A0 X ) N C N A0 C X
C

a
a C

V
d
d
( N A0 X ) N D N A0 D X C N A0 D (d / a) X
a
a D

V
NI0
NI NI0
CI
V
N T N T 0 N A0 X

## Constant-Volume (or Density) Reaction Systems

Sealed vessel (gas phase reaction)
~Example:
Laboratory bomb calorimeter
(to measure the heat of combustion
of a particular reaction)

## Isothermal gas-phase reaction with no change in the total number of moles

(ideal gas law applies)
~ Example: coal gasification
PV nRT
CO

+ H2O

CO2 + H2

V nR

T
P

## Liquid phase reaction in an incompressible solvent

(except polymerizations)
~ Solvent dominates
~ Changes in the density of the solute do not affect
the overall density of the solution significantly

A +

()

## b/a B c/a C + d/a D

= 0
0

Initially
(mol)

Change
(mol)

Remaining
(mol)

(mol/dm3)

NA0

( N A0 X )

N A N A0 N A0 X

C A C A0 (1 X )

NB0
NC0

ND0

NI0

N B N A0 B X
a

N C N A0 C X
a

N D N A0 D X
a

NI NI0

CB C A0 B (b / a) X

b
( N A0 X )
a
c
( N A0 X )
a
d
( N A0 X )
a

Total

NT0

N T N T 0 N A0 X

CC C A0 C (c / a) X
CD CA0 D (d / a ) X
CI CI 0

A +

Rate law

rA kCACB

## b/a B c/a C + d/a D

C A C A0 (1 X )

CB CA0 B (b / a) X

rA kCA0 (1 X ).CA0 B (b / a) X
rA kC2 A0 (1 X )B (b / a) X
Design Equation

F X
V A0
(rA ) exit

V FA0

X out

X in

dX
rA

rA f (X )

## Stoichiometric Table: Example

A component of soap (sodium stearate) is produced by saponification of glyceryl
stearate with aqueous caustic soda according the following equation:

3 NaOH + (C17H35COO)3C3H5

3 C17H35COONa + C3H5(OH)3

Production is carried out in a batch reactor. The initial mixture consists solely of sodium
hydroxide at a concentration of 10 mol/dm3 and glyceryl stearate at a concentration
of 2 mol/dm3. What is the concentration of glycerine when the conversion of sodium
hydroxide is (a) 20% and (b) 90%?

## Stoichiometric Table: Flow system

Stoichiometric Table for Flow Systems
Entering
FA0
FB0
FC0
FD0
FI0

A +

Leaving
FA
FB
FC
FD
FI

Flow systems

Batch System

## FA FA0 FA0 X FA0 ( 1 X )

N A N A0 N A0 X N A0 (1 X )
Nj0

fluxes
Replaced by

Nj

Fj0
Fj

Cj

Fj
q

moles / time
moles

[19]

+ +

## Concentrations of species A, B, C, and D in terms of entering molar

flow rate (FA, FB, FC, FD), the conversion X, and the volumetric flow
rate

CA

FA FA0

(1 X )
q
q

CB

FB FB 0 (b / a ) FA0 X

q
q
[20]

CC

FC FC 0 (c / a ) FA0 X

q
q

CD

FD FD 0 (d / a ) FA0 X

q
q

The parameter :

Fi 0 Ci 0v Ci 0
y

i0
FA0 C A0v C A0 y A0

## Stoichiometric Table: Flow system

Stoichiometric Table for Flow Systems
Species

Initially
(mol / time)

Change
(mol / time)

( FA0 X )

FA0

FB 0 B FA0 b ( F X )
A0
a
c
( FA 0 X )
FC 0 C FA0
a
d
( FA 0 X )
FD0 D FA0
a

C
D
I

FI 0 I FA0

Total

FT0

Remaining
(mol / time)

FA FA0 (1 X )
b

FB FA0 B X
a

FC FA0 C X
a

FD FA0 D X
a

FI FA0 I

d c b
FT FT 0 1 FA0 X
a a a
FT FT 0 FA0 X

## Stoichiometric Table: Flow system

Stoichiometric Table for Flow Systems (Liquid-Phase Reactions)

For liquid-phase reactions, the volumetric flow rate does not practically
change in the course of reaction: v = v0 = Const

FA0
(1 X ) C A0 (1 X )
q0

FA FA0 (1 X )

CA

FB FA0 B X
a

C B C A0 B X
a

FC FA0 C X
a

C C C A0 C X
a

FD FA0 D X
a

C D C A0 D X
a

## Therefore for a given rate law we have: rA g ( X )

Stoichiometric Table

+ +

## Volume Change with Reaction

For most batch and liquid-phase reactions and some gas-phase reactions
the volumetric flow rate or reaction volume does not change, however:
volume (or volumetric flow rate) will change in the following situations:

number of moles

d c b
1 0
a a a

## Batch system with variable volume

N2

3H2

2NH3

Stoichiometric Table
Volume Change with Reaction
The first four columns of the stoichiometric tables are always valid
Assumptions concerning a volume change were made when expressing
concentration in terms of conversion

## Expressing volume as a function of conversion V = f (X) (Batch Systems)

Equation of State is a fundamental equation for gas systems:
PV ZNT RT
time = 0

[21]
Z = a compressibility factor
NT = an overall number of moles in a gas mixture
[22]

P0V0 Z 0 N T 0 RT0

## By dividing equation (21) by equation (22):

PV
Z NT T

P0V0 Z 0 NT 0 T0

V V0

P0 Z
N
T

T
P Z 0 N T 0 T0

[23]

Stoichiometric Table
Volume Change with Reaction in a Batch System

V V0

P0 Z
N
T

T
P Z 0 N T 0 T0

conversion:

N T N T 0 N A0 X

[24]

N
NT
1 A0 X 1 y A0 X
NT 0
NT 0

## yA0 is the molar fraction of

species A in an initial
[25]
mixture

## change in total number of moles for complete conversion

total number of moles fed to the reactor
[26]

N
d c b N
1 A0 A0 y A0
NT 0
a a a NT 0
Equation [25] now becomes:

Equation [23]:

NT
1 y A0 X 1 X
NT 0

V V0

[27]

P0 Z T

(1 X )
P Z 0 T0

[28]

Stoichiometric Table
Volume Change with Reaction in a Batch System

V V0

P0 Z T

(1 X )
P Z 0 T0

## In gas-phase systems, at the certain ranges of temperatures and pressures

the compressibility factor does not change significantly during the course of
the reaction: Z0Z
The volume of gas mixture for a variable volume batch reactor at any
time/conversion:
V V0

P0
T
(1 X )
P
T0

## If the reactor is a rigid steel container of constant volume, then:

V V0
and equation [29] can be used to calculate the pressure change as a
function of T and X

[29]

## Stoichiometric Table: Flow system

Volume Change with Reaction in a Flow System

## Consider the total concentration at

any point within the reactor:
CT

FT
Pq
P

q qZRT ZRT

## At the entrance to the

reactor:
P0
CT 0
Z 0 RT0

[30]

FT P0 T

FT 0 P T0

FT FT 0 FA0 X

[33]

F
FT
1 A0 X 1 y A0 X 1 X [34]
FT 0
FT 0
[31]

## Taking the ratio of the equations

(31) and (30) and assuming that
Z0Z:
q q0

## Total molar flux rate as a

function of conversion in a
continuous reactor:

[32]

## Volumetric flow rate as a function

of conversion can be obtained by
combining the equations (32) and
(34) :
q q0 (1 X )

P0 T

P T0

[35]

## Stoichiometric Table: Flow system

Concentrations as a Function of Conversion

q q0 (1 X )

P0 T

P T0

## If the volumetric flow rate is known as a function of conversion, then the

concentration of any species in a flow system can be defined as a function
of conversion:
Cj

Fj
q

## Molar flow rate of each species as a function of conversion is:

F j FA0 j S j X
Thus:

Cj

Cj

FA0 ( j S j X )
q0 (1 X )

P T0

P0 T

C A0 ( j S j X ) P T0

(1 X )
P0 T

[36]

## Stoichiometric Table: Flow system

+

Cj

C A0 ( j s j X ) P T0

(1 X )
P0 T

## Stoichiometric Table for a Variable-Volume Gas Flow System

Initially
(mol/time)

Change
(mol/time)

Remaining
(mol/time)

A
B
C
D
I

FA0

(mol/volume. time)

1 X P T0

C A C A0
(
1

X
)

P0 T
(b / a) X P T0

C B C A0 B
(1 X ) P0 T

( FA0 X )

FA FA0 (1 X )

FB 0 B FA0

b
( FA0 X )
a

FC 0 C FA0

c
( FA 0 X )
a

FB FA0 B X
a

FC FA0 C X
a

(c / a ) X
CC C A0 C
(1 X )

P T0

P0 T

FD0 D FA0

d
( FA 0 X )
a

FD FA0 D X C D C A0 D (d / a) X
(1 X )
a

P T0

P0 T

FI 0 I FA0

FI FA0 I

CI

C A0 I P T0

(1 X ) P0 T

## Stoichiometric Table: Flow system-Example

A mixture of 28% SO2 and 72% air is charged to a flow reactor in which SO2 is
oxidized.

2 SO2 + O2 2 SO3
Calculate concentrations of all species at the following conversion of SO2: 0; 0.25;
0.5; 0.75; 1, if the total pressure is 1485 kPa and the temperature is constant at
227oC. Note that air composition is 21% O2 and 79% N2.
Solution

2 SO2 + O2 2 SO3
+

1

2

## Stoichiometric Table: Flow system-Example

The elementary gas phase reaction
k1

3A + 2B 3 C +5 D
is carried out in a flow reactor operated isothermally at 427C and 28.7 atmospheres.
Pressure drop can be neglected. Express the rate law and the concentration of each
species as a function of conversion and as a function of the total molar flow rates. The
entering volumetric flow rate is 10 dm3/s and the specific reaction rate,k is 200
dm12/mol4s. The feed is equal molar in A and B.

Solution

## Volume change (Flow system) -Example

The elementary gas phase reaction
k

1
3A + 2B
3 C +5 D

is carried out in a flow reactor operated isothermally at 427C and 28.7 atmospheres.
Pressure drop can be neglected. Express the rate law and the concentration of each
species as a function of conversion and as a function of the total molar flow rates. The
entering volumetric flow rate is 10 dm3/s and the specific reaction rate is 200 dm12/mol4s.
The feed is equal molar in A and B.

## Volume change (Flow system) -Example

The elementary gas phase reaction
k

1
3A + 2B
3 C +5 D

is carried out in a flow reactor operated isothermally at 427C and 28.7 atmospheres.
Pressure drop can be neglected. Express the rate law and the concentration of each
species as a function of conversion and as a function of the total molar flow rates. The
entering volumetric flow rate is 10 dm3/s and the specific reaction rate is 200 dm12/mol4s.
The feed is equal molar in A and B.

Summary