제3장

Rate Laws
and Stoichiometry
Booker T. Washington

“Success is measured not so

much by the position one
has reached in life, as by
the obstacles one has
overcome while trying to
succeed”

An African-American Scholar and Inventor

 Objectives
After completing Chapter 3, reader will be able to:

 Write down a rate law, and define reaction order and

activation energy.
 Set up a stoichiometric table for both batch and flow systems
and express concentration as a function of conversion.
 Calculate the equilibrium conversion for both gas and liquid
phase reactions.
 Write down the combined mole balance and rate law as a
function of conversion.
 Set up a stoichiometric table for reactions with phase change.
 Part 1
Rate Laws
 3.1 Basic Definitions
 Homogeneous reaction is one that involves only one phase.
Heterogeneous reaction involves more than one phase. (reaction
usually occurs at or very near the interface between the phase)

 Reversible reaction can proceed in either direction, depending on

the concentration of reactants and products relative to the
corresponding equilibrium concentration.

 Irreversible reaction is one that proceeds in only one direction and

continues in that direction until the reactions are exhausted. An
irreversible reaction behaves as if no equilibrium condition exists.
Strictly speaking, no chemical reaction is completely irreversible.
However, for many reactions, the equilibrium point lies so far to the
product side that these reactions are treated as irreversible reaction.
 Basic Definitions

 Molecularity of a reaction is the number of atoms, ions or

molecules involved in a reaction step.

 The term, unimolecular, bimolecular, and termolecular refer

to reactions involving, respectively, one, two, or three atoms
(or molecules) interacting in any one reaction step.
Example of Elementary Reaction

2 NO  O2  2 NO 2
H2  I2  2 HI
92 U 238
 90Th 234
 2 He 4

NaOH  CH 3 Br  CH 3OH  NaBr

 3.1.1 Relative Rates of Reactions
If the rate law depends on more than one species, we MUST relate the
concentrations of different species to each other. A stoichiometric table presents
the stoichiometric relationships between reacting molecules for a single reaction.

aA + bB cC + dD (2-1)

In formulating our stoichiometric table, we shall take species A as our basis of

calculation (i.e., limiting reactant) and then divide through by the stoichiometric
coefficient of A. In order to put everything on a basis of “per mole of A.”

b c d
A B 
 C  D (2-2)
a a a
The relationship can be expressed directly from the stoichiometry of the reaction.

rA rB rC rD
   (3-1)
a b c d
 3.1.1 Relative Rates of Reactions

Example: 2NO + O2 2NO2

rNO rO2 rNO 2

 
2 1 2

If rNO2= 4 mol/m3-sec rNO= -4 mol/m3-sec

rO2= -2 mol/m3-sec
 3.2 Reaction Order and Rate Law

Let take A as the basis of calculation

a species A is one of the reactants that is disappearing as a result
of the reaction. The limiting reactant is usually chosen as our
basis for calculation.

The rate of disappearance of A, -rA, depends on temperature and

composition and it can be written as the product of the reaction
constant k and

 rA (T , C )  k A (T ) fn (C A , C B ...) 

Rate raw (Kinetic expression) : the algebraic equation that relates –rA to the species
concentration
3.2.1 Power Law Models and Elementary Rate Laws

The dependence of the reaction rate –rA on the concentration of

the species is almost without exception determined by
experimental observation.

The order of a reaction refers to the powers to which the

concentrations are raised in the kinetic rate law.

 
 rA  k A C CA B
(3-3)

 order with respect to reactant A

 order with respect to reactant B
n (=) : the overall order of the reaction
 Unit of Specific Reaction Rate

The unit of the specific reaction rate, kA,

vary with the order of the reaction.

A  products

(Concentration)1-n
k=
Time
 Unit of Specific Reaction Rate

mol
Zero - order :  rA  k A {k }  (3-4)
( dm ) 3  s

1
First - order :  rA  k A C A {k }  (3-5)
s

( dm ) 3
Second - order :  rA  k A C A2 {k }  (3-6)
mol  s

( dm 3 / mol ) 2 (3-7)
Third - order :  rA  k A C A3 {k } 
s
 Elementary and Non-elementary Reaction

Kinetic rate raw

Elementary reaction Non-elementary reaction

O + CH3OH  CH3O  + OH  CO + Cl2  COCl2

-rO = k CO CCH3OH  rCO  kC CO C Cl3 /22

1st order w.r.t. atomic oxygen 1st order w.r.t. carbon monoxide
1st order w.r.t. methanol 3/2 order w.r.t. chorine
overall is 2nd order reaction overall is 5/2 order reaction

In general, first- and second-order reactions are more commonly observed.

 Elementary Reaction

An elementary reaction is one that evolves a single step such as the

bimolecular reaction between oxygen and methanol

O + CH3OH  CH3O  + OH 

The stoichiometric coefficients in this reaction are identical to the

powers in the rate law.

-r O = k CO CCH3OH
The reaction is 1st order in oxygen radical and 1st order in methanol;
therefore, we say both the reaction and rate law are elementary.
 Determination of Reaction Rate Law

It is important to remember that the rate laws are

determined by experimental observation! They
cannot be deduced from reaction stoichiometry.

They are function of the reaction chemistry and not

the type of reactor in which the reactions occur.

Even though a number of reactions follow elementary

rate laws, at least as many reactions do not. One must
determine the reaction order from the experiments or
from literature.
Example of Rate Law
Example of Rate Law
 Apparent Reaction Order
Sometimes reactions have complex rate expressions that cannot be separated
into solely temperature-dependent and concentration-dependent parts.
Pt
2N2O 2N2 + O2
k N 2O C N 2O
 rN 2 O  Kinetic rate raw
 C O2
1  k NO

Limiting conditions: depending on oxygen concentration

(1) 1  k C O2 :  rN 2 O  k N 2O C N 2O “apparent” 1st-order w.r.t. N2O

1st order overall

k N 2O C N 2O “apparent” reaction-order
(2) 1  k C O2 :  rN 2O  -1 w.r.t. O2 , +1 w.r.t. N2O,
k C O2 overall apparent zero order
 3.2.2 Nonelementary Rate Laws and Reactions

H2 + Br2 2HBr CH3CHO CH4 + CO

Non-elementary reaction (free radical) Non-elementary reaction (free radical)

gas-phase decomposition of acetaldehyde
@500oC

1/ 2
k1C H 2 C Br
 rH 2  2
 rCH 3CHO  kC CH
3/ 2
3 CHO
k 2  C HBr / C Br2
3.2.2 Nonelementary Rate Laws and Reactions
In many gas-solid catalyzed reactions, it is sometimes preferable to write the
rate law in terms of partial pressures rather than concentrations.

C6H5CH(CH3)2 C6H6 + C3H6

cumene benzene propylene

C B + P

Langmuir-
k ( PC  PB PP / K C )

 rC  Hinshelwood
1  K A PC  K B PB kinetics

KC = the pressure equilibrium constant [atm]

KB = the adsorption constants [atm-1]
k = the specific reaction rate [mol/kg cat·s ·atm]
3.2.2 Nonelementary Rate Laws and Reactions
At equilibrium, -r’C =0; the rate law for the reversible reaction is indeed
thermodynamically consistent:
k ( PC  PB PP / K C )
 rC  0 
1  K A PC  K B PB
Solving for Kp yields
PBe PPe
KC 
PCe
which is identical to the expression obtained from thermodynamics.
To express the rate of decomposition of cumene, -r’C as a function of conversion,
replace the partial pressure with concentration, using the ideal gas law:

pC  C C RT
and then express concentration in terms of conversion.
 3.2.3 Reversible Reactions
All rate raws for reversible reactions must reduce to the
thermodynamic relationship relating the reacting species
concentrations at equilibrium. At equilibrium, the rate of reaction is
identically zero for all species (i.e., -rA=0). For the general reaction

aA + bB cC + dD

The concentrations at equilibrium are related by the thermodynamic

relationship for the equilibrium constant KC.

c d
C Ce C De
KC  a b [( mol / dm 3 ) d  c  b  a ]
C Ae C Be
 3.2.3 Reversible Reactions
2C6H6 C12H10 +H2

2B D +H2

The rate of disappearance of benzene The rate of formation of benzene

2C6 H6 kB
C12 H10  H2 C12 H 10  H 2 k
B
2C 6 H 6

rB , forward  kB CB2 rB , reverse  k  B C D C H 2

The net rate of formation of benzene

rB  rB , net  rB , forward  rB , reverse

rB   k B C B2  k  B C D C H 2
 3.2.3 Reversible Reactions
The rate law for the rate of disappearance of benzene

 2 kB 
 rB  k B C  k  B C D C H 2
2
B  k B  C B  C D C H 2 
 kB 
 2 CDCH 2 
 rB  k B  C B  
 KC 
kB
 K C  concentrat ion equilibriu m constant
kB
thermodynamically consistent with the equilibrium constant

C De C H 2 e
2B D +H2 KC  2
C Be
We need to check
 2 CDC H 2 
 rB  k B  C B  
 KC 
whether the above rate law is thermodynamically consistent at equilibrium.

At equilibrium, -rB=0,

 2 C De C H 2 e 
 rB  0  k B  C Be  
 KC 
Rearranging, we obtain
identical
C De C H 2 e
KC  2
C Be
 Thermodynamically Consistent with Equilibrium Constant

2B D +H2
The rate of formation of diphenyl is
 2 C DC H 2 
 rD  k D  C B   (3-15)
 KC 
Using the relationship
rA r r r
 B  C  D
a b c d

We can obtain the relationship between the various specific reaction rates,
kB, kD:
rD rB k B  2 C DC H 2 
   C B   (3-16)
1 2 2  KC 

kB
kD 
2
Temperature Dependence of Concentration Equilibrium Constant

Appendix C, Eq (C-9)

 H Rx  1 1 
K C (T )  K C (T1 ) exp    
 R  T1 T 

Exothermic
KC reaction KC Endothermic
reaction

T T
3.3 k : The specific Reaction Rate (the Rate Constant)
A

The specific reaction rate is always referred to that species in the

reactions and normally should be subscripted w.r.t. that species. The
reaction rate constant k is not truly a constant, but is merely
independent of the concentrations of the species involved in the
reaction.

The quantity k is also referred to as the specific reaction rate (constant).

It is almost always strongly dependent on temperature. In gas-phase
reactions, it depends on the catalyst and total pressure. In liquid
systems, it depends on the total pressure, ionic strength and choice of
solvent.

These other variables normally exhibit much less effect on the specific
reaction rate than temperature does with the exception of supercritical
solvents, such as supercritical water.

In this text, it will be assumed that kA depends only on temperature.

 Arrhenius equation
Activation energy, J/mol or cal/mol

Specific reaction rate (constant)

E

k A (T )  Ae RT
Absolute
Temperature, K
frequency factor
or Gas constant
pre-exponential 8.314 J/mol · K
factor
mathematical number 1.987 cal/mol · K
e=2.71828… 8.314 kPa · dm3/mol · K
 Arrhenius equation
E

k A (T )  Ae RT

A
high E

kA kA
Low E

Slope= -E/R

T (K) 1/T (K-1)

T  0, kA  0
T  , k A  A
 Activation energy
Activation energy E :
a minimum energy that must be possessed by reacting
molecules before the reaction will occur.

E The fraction of the collisions between

 molecules that together have this minimum
e RT
energy E (the kinetic theory of gases)

Activation energy E is determined experimentally by

carrying out the reaction at several different
temperature.
E1
ln k A  ln A   
R T 
Activation energy
A+BC A-B-C AB+C
 Azo Dye

0~5oC
HNO3 NO2 3H2 NH2 HNO3 N=N-Cl
H2SO4 Pd/C* HCl

Aniline Benzene
bp=184oC diazonium

0~5oC
OH
OH
0~5oC

OH

-N=N-
-N=N- -OH

Yellow Bright red

(4-hydroxyl phenol) azobenzene mp=132oC
Example 3-1. Determination of the Activation energy

Decomposition of benzene diazonium chloride to give chlorobenzene and N2

Cl
N=N Cl
+ N2

Calculate the activation energy using following information for this first-order
E 1
log k A  log A   
2.3R  T 
T(K) k (s -1 ) 1/T (K -1 ) k (s -1 )
313 0.00043 0.003195 0.00043
319 0.00103 0.003135 0.00103
323 0.00180 0.003096 0.00180
328 0.00355 0.003049 0.00355
333 0.00717 0.003003 0.00717
 Finding the activation energy
Plot (ln k) vs (1/T)
0.01
k (sec-1)

0.001

Slope = -E/2.3R

0.0001
0.0030 0.0031 0.0032
1/T (K-1)
 Finding the activation energy
Plot (ln k) vs (1/T)
To use the decade method,
E 1 choose 1/T1 and 1/T2 so that k2=0.1 k1.
log k1  log A   
2.3R  T1  Then, log(k1/k2)=1

E 1 When k1=0.005 : 1/T1=0.003025

log k 2  log A    When k2=0.0005 : 1/T2=0.00319
2.3R  T2 
Therefore,
k2 E 1 1
log     
k1 2.3R  T2 T1  (2.3)(R) log(k2 / k1 )
E
(2.3)( R ) log(k 2 / k1 ) 1/ T2  1/ T1
E (2.3)(8.314 J / mol  K )(1)
1 / T2  1 / T1 
(0.00319 0.003025) / K
 116 kJ / mol  28.7 kcal / mol
 Finding the activation energy
Plot (ln k) vs (1/T)
0.01

0.005
k (sec-1)

0.001

0.0005

0.0001
0.0030 0.0031 0.0032
0.003025
1/T (K-1) 0.00319
 Activation energy

The larger the activation energy, 0.01

the more temperature-sensitive

is the rate of reaction.

k (sec-1)
Typical values of 1st order gas- 0.001
Low E
phase reaction

Frequency factor ~ 1013 s-1 High E

Activation energy ~ 300 kJ/mol 0.0001
0.0030 0.0031 0.0032

1/T (K-1)
 Specific reaction rate
E

k  Ae RT E 를 알고 나면 실험
하지 않은 어느 온도
E 에서의 k 값을 구할

k0  Ae RT0 수 있다.

Taking the ratio

 E  1 1 
k  k 0exp    
 R  T0 T 
3.4 Present Status of Our Approach to Reactor Sizing and Design

Design Equations
Differential Algebraic Integral
form form form

Batch dX X dX
N A0   rAV t  N A0 
dt 0  rAV

CSTR FA 0 X
V 
 rA

dX X dX
PFR FA 0   rA V  FA 0 
dV 0  rA

dX X dX
PBR FA 0   rA W  FA 0 
dW 0  rA
 Design Isothermal Reactor

CHAPTER 3
Design isothermal reactor

 rA  kC Aa C Bb

-rA=g(X)

stoichiometry
Cj = f(X)
CHAPTER 2

Nj = f(X)
V= f(X)
 Part 2
Stoichiometry
 Stoichiometric Table
If the rate law depends on more than one species, we MUST relate the
concentrations of different species to each other. A stoichiometric table presents
the stoichiometric relationships between reacting molecules for a single reaction.

aA + bB cC + dD (2-1)

rA rB rC rD
   (3-1)
a b c d
In formulating our stoichiometric table, we shall take species A as our basis of
calculation (i.e., limiting reactant) and then divide through by the stoichiometric
coefficient of A
b c d
A B 
 C  D (2-2)
a a a

In order to put everything on a basis of “per mole of A.”

 3.5 Batch System

t=0
NA0 t=t
NB0 NA
NB
NC0 NC
ND0 ND
Ni
Ni0
b c d
A B
 C  D
a a a

Batch reactors are primarily used for the production

of specialty chemicals and to obtain reaction rate data
in order to determine reaction rate laws and rate law
parameters such as k, the specific reaction rate.
 3.5 Batch System
t=0
At time t=0, we will open the reactor NA0
NB0
and place a number of moles of NC0
t=t
NA
species A, B, C, D, and I (NA0, NB0, ND0
NB
Ni0
NC0, ND0, and NI0, respectively) NC
ND
Ni
Species A is our basis of calculation. b c d
A B
 C  D
a a a

NA0 is the number of moles of A initially present in the reactor.

NA0X moles of A are consumed as a result of the chemical reaction.
NA0-NA0X moles of A remaining in the system.
The number of moles of A remaining in the reactor after conversion X

NA = NA0 - NA0X = NA0(1-X)

 Determination of the number of moles of B

To determine the number of moles of

species B remaining at time t (after NA0X
moles of A have reacted). For every mole
of A that reacts, b/a moles of B must A
b
B
c d
 C  D
reacted; a a a

The number of moles of B remaining in the system, NB

moles of A reacted

b
N B  N B0  N A0 X
a

moles of B initially moles of B disappeared

 Stoichiometric table
To determine the number of moles of
each species remaining after NA0X
moles of A have reacted, we form the
stoichiometric table (Table 3-3). A
b
B
c d
 C  D
a a a

This stoichiometric table presents the following information.

Column 1: the particular species

Column 2: the number of moles of each species initially present
Column 3: the change in the number of moles brought about by
reaction
Column 4: the number of moles remaining in the system at time t.
 Stoichiometric Table for a Batch System

Species Initially Change Remaining

(mol) (mol) (mol)
A N A0  ( N A0 X ) N A  N A0  N A0 X
b b
B N B0  ( N A0 X ) N B  N B 0  N A0 X
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 D 0  N A0 X
a a
I (inert ) N I 0 NI  NI0
d c b 
Total NT 0 N T  N T 0      1 N A0 X
a a a 
N T  N T 0  N A 0 X
The total number of moles per mole of A reacted

b c d
A B 
 C  D
a a a
The total number of moles in the system, NT

d c b 
NT  NT 0      1 N A0 X
a a a 
 NT 0  N A 0 X

d c b Change in the total number of moles

    1 mole of A reacted
a a a
 Design Isothermal Reactor

CHAPTER 3
Design isothermal reactor

 rA  kC Aa C Bb

-rA=g(X)
CA =f(X)
CHAPTER 2

Nj = f(X)
V= f(X)
 3.5.1. Concentration of each species

NA N A 0 (1  X )
CA    rA  kC Aa C Bb
V V
NB N B 0  (b / a ) N A 0 X
CB   CA =f(X)
V V
NC N C 0  (c / a ) N A0 X Nj = f(X)
CC   V= f(X)
V V
ND N D 0  (d / a ) N A0 X
CD  
V V
 3.5.1. Concentration of each species

N i0 Ci0 yi0
i   
N A0 C A0 y A0

NA N A 0 (1  X )
CA  
V V
NB N B 0  (b / a ) N A 0 X N A 0  B  (b / a ) X 
CB   
V V V
NC N C 0  (c / a ) N A0 X N A 0  C  ( c / a ) X 
CC   
V V V
ND N D 0  (d / a ) N A0 X N A 0  D  ( d / a ) X 
CD   
V V V
 3.5.2 Volume as a function of conversion

N B ( X ) N B 0  (b / a ) N A 0 X N A 0  B  (b / a ) X 
CB   
V (X ) V (X ) V (X )

We need V(X) to obtain CB=f(X)

- For liquids, volume change with reaction is negligible

when no phase changes are taking place. (V=V0)

-For gas-phase reactions, the volumetric flow rate most often

changes during the course of the reaction due to a change
in the total number of moles or in temp. or pressure.
3.5.2 Constant-Volume Batch Reaction Systems

Constant volume system (=constant density system):

(1) The lab bomb calorimeter reactor: the volume within the vessel
is fixed and will not change. V=V0

(2) A constant-volume gas-phase isothermal reaction occurs when

the number of moles of products equals the number of moles of
reactants. (Ex: water-gas shift reaction, CO+H2O  CO2+H2)

(3) For liquid-phase reactions taking place in solution, the solvent

usually dominates the situation. As a result, changes in the
density of the solute do not affect the overall density of the
solution significantly and therefore it is essentially a constant-
volume reaction process: Most liquid-phase organic reactions,
except polymerization.
Constant Volume Batch Reactor
 Constant Volume System

For Liquid phase reactions (or isothermal and isobaric gas-phase

reactions with no change in the total number of moles)
b c d
A B
 C  D
a a a

-rA = f(C)  rA  k A C A C B

Eq. (3-26)

 b 
-rA = f(X)  rA  k A C A2 0 (1  X )  B  X 
 a 
Levenspiel plot
 Example 3-2: Liquid-Phase Reaction

Soap consists of the sodium and potassium salts of various fatty

acids as oleic, stearic, palmitic, lauric, and myristic acids. The
saponification for the formation of soap from aqueous caustic
soda and glyceryl stearate is as follow.

3NaOH + (C17H35COO)3C3H5  3C17H35COONa + C3H5(OH)3

Letting X represent the conversion of sodium hydroxide (the

mole of sodium hydroxide reacted per mole of sodium hydroxide
initially present), set up a stoichiometric table expressing the
concentration of each species in terms of its initial concentration
and the conversion of X.
 Example 3-2 Stoichiometric Table
3NaOH + (C17H35COO)3C3H5  3C17H35COONa + C3H5(OH)3
1 1
A B
 C  D
3 3

Species Initially Change Remaining Concentrat ion

(mol) (mol) (mol) (mol/m 3 )
A N A0  ( N A0 X ) N A0 (1  X ) C A0 (1  X )
1  X  X
B N B0  ( N A0 X ) N A0   B   C A0   B  
3  3  3
C NC0 ( N A0 X ) N A0 ( C  X ) C A0 ( C  X )
1  X  X
D N D0 ( N A0 X ) N A0   B   C A0   B  
3  3  3
I (inert ) N I 0 NI0 CI 0

Total NT 0 0 NT  NT 0
 Example 3-3: What is the limiting reactant?
3NaOH + (C17H35COO)3C3H5  3C17H35COONa + C3H5(OH)3

Having set up stoichiometric table in Example 3-2, one can now

readily use it to calculate the concentrations at a given conversion. If
the initial mixture consists solely of sodium hydroxide at a
concentration of 10 mol/L and of glyceryl stearate at a concentration
of 2 mol/L, what is the concentration of glycerine when the
conversion of sodium hydroxide is (a) 20% and (b) 90%?

Solution

Only the reactants NaOH and (C17H35COO)3C3H5 are initially present;

therefore, C=D=0.
 Example 3-3: What is the limiting reactant?
3NaOH + (C17H35COO)3C3H5  3C17H35COONa + C3H5(OH)3

(a) For 20% conversion of NaOH:

X   0 .2 
C D  C A 0    10    0 .67 mol / L
 3  3 
 X   2 0 .2 
C B  C A 0   B    10     1 .33 mol / L
 3   10 3 
(b) For 90% conversion of NaOH:
X   0 .9 
C D  C A 0    10    3 mol / L
 3   3 
 X   2 0 .9 
C B  C A 0   B    10      1 mol / L
 3   10 3 

Ooops! Negative concentration impossible! What went wrong?

glyceryl stearate is limiting reactant. All the glyceryl stearate is used
up before 90% of the NaOH could be reacted.
 Example 3-3: What is the limiting reactant?

3NaOH + (C17H35COO)3C3H5  3C17H35COONa + C3H5(OH)3

10 mol/L 2 mol/L

glyceryl stearate is limiting reactant

It is important to choose the limiting

reactant as the basis of calculation.
 3.6 Flow Systems
Entering Leaving
FA0 FA
FB0 FB
b c d
FC0 A B
 C  D FC
FD0 a a a FD
FI0 FI

Definition of FA moles/time moles

concentration CA    (3-27)
for flow system
 liters/time liter

Fi 0 C i 0 v0 Ci0 yi0
i    
F A0 C A0 v0 C A0 y A0
3.6.1 Equations for Concentrations in Flow Systems

Batch System
Flow System

NA N A 0 (1  X )
CA   FA FA0
V V CA   (1  X )
 
NB N B 0  (b / a ) N A 0 X FB F  (b / a ) F A 0 X
CB   CB   B0
V V  
NC N C 0  (c / a ) N A0 X FC F  (c / a ) F A0 X
CC   CC   C0
V V  
FD FD 0  ( d / a ) F A 0 X
ND N D 0  (d / a ) N A0 X CD  
CD    
V V
 Stoichiometric Table for a Flow System

Feed rate Change Effluent rate

Species to reactor in reactor from reactor
(mol/time) (mol/time) (mol/time)

A FA 0  (FA0 X) FA  FA0( 1  X)
b  b 
B FB 0  ΘB FA0  (FA0 X) FB  FA0  ΘB  X 
a  a 
c  c 
C FC 0  ΘC FA0  (FA0 X) FC  FA0  ΘC  X 
a  a 
d  d 
D FD 0  ΘD FA0  (FA0 X) FD  FA0  ΘD  X 
a  a 
I(inert) FI 0  ΘI Fa 0 FI  FA0ΘI

d c b 
Total FT 0 FT  FT 0      1  F A 0 X
a a a 
Table 3-4 FT  FT 0  F A 0 X
 3.6.2 Liquid-Phase Concentrations
Entering Leaving
FA0 FA
FB0 FB
b c d
FC0 A B
 C  D FC
FD0 a a a FD
FI0 FI

FA F A0
CA   (1  X )  C A 0 (1  X )  rA  kC Aa C Bb
 0
b
C B  C A0 ( B  X ) (3-27)
a CA = f(X)

FA = f(X)
v=f(X)
 3.6.3 Change in the Total Number of Moles
with Reaction in the Gas Phase
(1) Gas-phase reactions often do not have an equal number of product
and reactant moles. In flow systems where this type of reaction occurs,
the molar flow rate will be changing as the reaction progress. The
volumetric flow rate will also change due to molar flow change.

N2 + 3H2 2NH3

(2) The combustion chamber of the internal-combustion engine

(3) The expanding gases within the breech and barrel of a firearm as it
is fired.
 Batch Reactor with Variable Volume
Individual concentrations can be determined by expressing the volume V for
batch system (or volumetric flow rate v for a flow system) as a function of
conversion using the following equation of state.
PV  ZN T RT (3-30)

T = temperature, K
P = total pressure, atm (kPa; 1 atm=101.3 kPa)
Z = compressibility factor
R = gas constant = 0.08206 dm3·atm/gmol · K

This equation is valid at any point in the system at any time. At time t=0,

P0V 0  Z 0 N T 0 RT 0 (3-31)

Dividing (3-30) by (3-31) and rearranging yields

 P0 T  Z  NT
V  V0     (3-32)
Z N
 P  T0  0  T0
 Stoichiometric Table for a Batch System

Species Initially Change Remaining

(mol) (mol) (mol)
A N A0  ( N A0 X ) N A  N A0  N A0 X
b b
B N B0  ( N A0 X ) N B  N B 0  N A0 X
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 D 0  N A0 X
a a
I (inert ) N I 0 NI  NI0
d c b 
Total NT 0 N T  N T 0      1 N A0 X
a a a 
N T  N T 0  N A 0 X
 Volume as a function of conversion
variable-volume batch reactor

The total number of moles in the system, NT

N T  N T 0  N A 0 X (3-33)

We divide through by NT0

NT N
 1  A 0 X  1  y A 0 X  1  X (3-34)
NT 0 NT 0
where yA0 is mole fraction of A initially present. If all the species in the
generalized reaction are in the gas phase, then

d c b
    1 (3-23)
a a a

change in the total number of moles 총몰수 변화

 =
mole of A reacted 반응한 A의 몰수
 Volume as a function of conversion
variable-volume batch reactor
Eq (3-34) is further simplified by letting

  y A0  (3-35)

NT  NT 0 (3-36)
NT
 1  X 
NT 0
NT 0 X

N Tf  N T 0
@ X=1, NT=NTf  완전전환에서의 총몰수 변화

NT 0 반응기에 공급된 총몰수

Change in the total number of moles for complete conversion


Total moles fed
 Volume as a function of conversion
variable-volume batch reactor
Eq (3-34) is further simplified by letting
d c b  N A0
      1  y A0 
a a a  NT 0 (3-35)

  y A0  (3-36)

change in the total number of moles for complete conversion


total number of moles fed to the reactor

Eq (3-32) now becomes

P T  Z  NT  P0 T  Z 
V  V0  0     V 0    (1   X ) (3-37)
Z N Z 
 P  T0  0  T0  P  T0  0 
 Volume as a function of conversion
variable-volume batch reactor

In gas-phase systems that we shall be studying, the temperature and

pressure are such that the compressibility factor will not change
significantly during the course of the reaction; hence Z0~Z. For a batch
system the volume of the gas at any time t is

 P0  T
V  V0   (1   X ) (3-38)
 P  T0

Eq (3-38) applies only to a variable-volume batch reactor. If the reactor

is a rigid steel container of constant volume, then of course V=V0. For a
constant-volume container, V=V0, and Eq. (3-38) can be used to
calculate the pressure inside the reactor as a function of temperature and
conversion.
3.4 Present Status of Our Approach to Reactor Sizing and Design

Design Equations
Differential Algebraic Integral
form form form

Batch dX X dX
N A0   rAV t  N A0 
dt 0  rAV

CSTR FA 0 X
V 
 rA

dX X dX
PFR FA 0   rA V  FA 0 
dV 0  rA

dX X dX
PBR FA 0   rA W  FA 0 
dW 0  rA
 Volume as a function of conversion
variable-volume flow system

To derive the concentration of the species in terms of conversion for a

variable-volume flow system, we shall use the relationships for the total
concentration. The total concentration at any point in the reactor is

FT P
CT   (3-39)
 ZRT
At the entrance to the reactor
FT 0 P0 (3-40)
CT 0  
0 Z 0 RT 0
Taking Eq (3-40)/Eq(3-39) and assuming Z~Z0,

 FT  P0  T 
   0    
 P T  (3-41)
 FT 0   0
 Concentration as a function of conversion
variable-volume flow system

We can express the concentration equation of species j for a flow system in terms
of conversion:

Fj Fj  FT 0  F j  P   T0 
Cj        
  FT P T0    0  F  P  T
 0    T  0  
 FT 0 P0 T 

 Fj  P   T0 
C j  C T 0  
 P
 
 T (3-42)
 FT  0  

The total molar flow rate is just the sum of the molar flow rates of each of the
species in the system and is
n
FT  F A  FB  FC  FD  FI      F j 1
j
 Volume as a function of conversion
variable-volume flow system

From Table 3-4, the total molar flow rate can be written in terms of X

FT  FT 0  F A 0 X (3-43)

FT 0  F A 0 X  P0  T
  0   (3-44)
FT 0  P  T0
 FA0  P0  T  P0 T
  0  1  X     0 1  y A 0 X  
 FT 0   P  T0  P  T0

 P0 T
   0 1   X   (3-45)
 P  T0
 Volume as a function of conversion
variable-volume flow system
The concentration of species j is
F j  F j 0  v j ( FA0 X )

Fj

 FA0  j  v j X 
Cj 

 P0  T
   0 1   X  
 P  T0

Cj 

FA0  j  v j X 
(3-46)
 P T 
 0  1   X  0 
 P T0 
 Some Definitions
d c b 총몰수 변화
    1 =
a a a 반응한 A의 몰수

N Tf  N T 0 완전전환에서의 총몰수 변화
  y A0   =
NT 0 반응기에 공급된 총몰수

N T  N T 0  N A 0 X

NT N A0
 1 X  1  y A 0 X  1  X
NT 0 NT 0

NT
 1  X
NT 0
 Expressing concentration b c d
A B 
 C  D
a a a
as a function of conversion
Liquid Phase Gas Phase
Flow Batch Batch Flow
FB NB NB FB
CB  CB  CB  CB 
 V V 
N P T FT P0 T
No Phase Change V  V0 T 0   0
  0 V  V0 Constant N T 0 P T0 FT 0 P T0
Volume F F
N B N T 0 P T0 P T0
CB  CB  B T 0
V  V0 N T V 0 P0 T FT  0 P0 T
N B P T0 F P T0
C B  CT 0 C B  CT 0 B
N T P0 T FT P0 T
 b 
C B  C A0   B  X 
 a 
No Phase Change or No Semipermeable Membranes

  y A0   P  T 
v  v0 (1  X ) 0  
d c b   P  T0 
      1  b 
a a a  C A0   B  X 
 a  P  T0
P CB   
CT 0  0 1  X P T
RT 0  0 

y A 0 P0 isothermal Isothermal + No P
C A0 
RT 0
 b   b 
C A0   B  X  No P C A0   B  X 
 a  P  a 
CB  CB 
1  X P0 1  X
pp112
 Concentration as a function of conversion
variable-volume gas flow system

Table 3-4

F F (1  X ) F A 0 (1  X )  T0  P (1  X )  T0  P
C A  A  A0     C A0  
   0 (1   X )  T  P0 (1  X )  T  P0

F F   (b / a) X  F   (b / a ) X   T0  P  C   B  (b / a ) X  T0  P



C B  B  A0 B  A0 B   A0   P 
   0 (1   X ) T  P0  1  X T  0 

FC FA0 C  (c / a) X  F   ( c / a ) X   T0  P    ( c / a ) X  T0  P 
CC    A0 C    C A0  C   

   0 (1   X ) T  P0  1  X  T  P0 
FD FA0  D  (d / a) X  F A 0  D  ( d / a ) X   T0  P    ( d / a ) X  T0  P 
CD       C A0  D   
   0 (1   X ) T P
 0 1  X 
  T  P0 
FI FA0 I F A 0  I  T0  P C A 0  I  T0  P
CI        
   0 (1   X )  T  P0 1  X  T  P0

pp114
Example 3-5: Determination of Cj=hj(X)
for a Gas-Phase Reaction

Isothermal
  B  ( b / a ) X  P  T0 
C B  C A0    
 1  X  P0  T 
Example 3-5: Determination of Cj=hj(X)
for a Gas-Phase Reaction

A B C

y A0  0.28
 1 1 F A0 X
  1 1   FT  FT 0  F A 0 X  FT 0 
2 2 2
Concentrations as a function of conversion
 1
SO 2  O 2  SO 3
2
0.25

N2
Concentration (mol/dm3)

0.20

0.15

SO3
0.10
SO2

0.05
O2

0.00
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X
 Reaction rates as a function of conversion

1
SO 2  O 2  SO 3
2

 rA  kC A C B

(1  X )(  B  0 .5 X )
 kC A2 0
(1   X ) 2
2 (1  X )( 0 .54  0 .5 X )

(1  0 .14 X ) 2
 1
SO 2  O 2  SO 3
2
60

 rA  kC A C B
50
(1  X )(  B  0 .5 X )
 kC A2 0
40 (1   X ) 2
2 (1  X )( 0 .54  0 .5 X )
(-1/rA)

30 
(1  0 .14 X ) 2

20

10

0
0.0 0.2 0.4 0.6 0.8 1.0

Conversion, X
Example 3-6: Calculating the Equilibrium Conversion
 Homework #3

1. P3-2A except (g)

2. P3-8C
3. P3-10A
4. P3-11A
5. P3-16B