Chapter 3 - Rate Laws and Stoichiometry

LOGO 3
CHAPTER
RATE LAWS AND

STOICHIOMETRY
Relative rates of reaction
aA + bB cC + dD
rA rB rC rD

E.g.
a b c d
2NO + O2 2NO2
If NO2 is being formed at a rate of 4 mol/m3.s, rNO2 =
4 mol/m3.s
www.themegallery.com
rNO rO rNO
2
2
2 1 2
24mol / m 3 s
rNO 4mol / m 3 s
2
14mol / m 3 s
rO 2mol / m 3 .s
2
2 Company Logo
Rate Law
What is rate law?
- an algebraic equation that relates reaction rate to
species concentration
- Rate law is a behavior of a reaction
(-rA) = [k (T)] [f (CA, CB, ..)]

k is a specific reaction rate (rate constant )

determined by Arrhenius equation
Ea / RT
k Ae
Reaction Rate Constant -
Arrhenius Law
strongly dependent on temperature
A - frequency factor (same unit as rate

Ea / RT
constant k
k Ae Ea - Activation energy
R - Universal gas constant, 8.314 J/mol.K
T Temperature (K)
Activation Energy Ea ?
the energy barrier that reactants must overcome for
a reaction to proceed.
Example:
A + BC A-B-C AB + C
ABC
Potential Energy
A + BC
AB + C
Reaction coordinate Company Logo

Activation Energy
1
ln = ln

Ea / RT
k Ae 1
l = l
2.3
Rxn 1: High Ea

Slope =

Rxn 2: Low Ea
1/T
Reaction Order
Consider the following reaction:
A+B C+D
The rate law can be written as follows:
(-rA) = k CACB
= reaction order with respect to species A

= reaction order with respect to species B
n = + = overall order of reaction
2A + B 3C
A reaction follows an elementary rate law if
the reaction orders just happen to agree
with the stoichiometric coefficients for the
reaction as written.
E.g. if the above reaction follows an
elementary rate law
-rA = kACA2CB
Species A = Second order,
Species B = First order,
overall = third order.
Company Logo
Units of Reaction Rate
Constant
The units of k depends on the reaction order. You can find
out the overall order of reaction from units of k
units of k = units of (rA ) /units of conc. terms
Reaction Order Rate Law k unit

Zero -rA=kA mol/dm3.s
One -rA=kACA s-1
Two -rA=kACA2 (dm)3/mol.s
Three -rA=kACA3 (dm3/mol)2.s-1

Elementary and Non-
Elementary Reactions
In the previous example, i.e., aA + bB cC + dD
The rate law (in terms of the rate of consumption of A) was written as:
(-rA) = k CA CB
Now, if = a and = b , the reaction is considered to

follow an elementary rate law.
Elementary Reaction
CNBr + CH3NH2 CH3Br + NCNH2
(-rCNBr) = k CCNBr CCH3NH2
Non-elementary
CO + Cl2 COCl2 (-rCO) = k CCO CCl2 3/2
Reaction Rates for Reversible
Reactions
General reaction:
aA bB cC dD
Thermodynamic equilibrium
relationship:
c d
CCe CDe Kc equilibrium constant
KC a b
CAe CBe Unit: (mol/dm3) d+c-b-a
Reaction Rates for Reversible
Reactions
kB
Reaction: 2B D + H2 B = Benzene
k-B D = Diphenyl
H2 = Hydrogen
Rate of disappearance of Benzene is
-rB,forward = kB CB2 -------------- Eq. 3-11
Rate of formation of Benzene is

rB,reverse = k-B CD CH2 ------------ Eq. 3-12
Net rate of formation of Benzene:

rB = rB, reverse + rB, forward
rB = -kB CB2 + k-B CDCH2
Multiply both sides by -1, we obtain rate law for the rate of
disappearance of benzene, -rB :
-rB = kB CB2 - k-B CDCH2
k
rB k B C B2 B C D C H 2
kB
2 CDCH 2
rB k B C B -------------- Eq. 3-14
KC
k
where B K C concentration equilibrium constant
kB
At equilibrium , - rB 0
2 C DeC H 2e
rB 0 k B C Be
K C
C DeC H 2e Same as thermodynamic
KC
C Be2 equilibrium relationship
Write rate of formation of diphenyl in terms of
concentration:
2 CDCH 2
rD k D C B -------------- Eq. 3-15
KC
Using relationsh ip of relative rates of reaction :
rA r r r
B C D
a b c d
For rB and rD
rD rB k B 2 CDCH 2
C B -------------- Eq. 3-16
1 2 2 KC
combine (3 - 15) & (3 - 16), we get relationsh ip between k D and k B
kB
kD We can obtain k for other species
2
Stoichiometry
Introduction
Stoichiometric Table
Batch System
Constant Volume
Flow System
Constant Volume
Variable Volume
Why Stoichiometric Table is
Needed?
- We have shown how rate law can be expressed as a

function of concentration, so we need to only express

concentration as a function of conversion to size a
reactor.
- Use stoichiometric table which represents the
stoichiometric relationship between reacting molecules
for a single reaction.
Continued
Now we can design or size the

reactor!
4 Components:
Column 1 : particular species
Column 2 : number of moles initially present
Column 3 : change in number of moles
Column 4 : number of moles remaining
For every moles of A that reacts, b/a

moles of B must react
moles B reacted
moles B reacted moles A reacted
moles A reacted
b
( N Ao X )
a
Some Useful Definitions
1. Net mole change for the reaction
For above reaction, let us define a term , which represents net change in total
number of moles per mole of A reacted
d c b
1
a a a
2. Relationship between and initial mole fraction of A
Change in total number of moles to attain complete conversion of A

Total number of moles of all species fed to the reactor

N AO
y A0
NTO
3. Theta (i) - to factor NAO in each expressions for concentration
N io Fio Cio yio

i
N Ao FAo C Ao y Ao
Expression from Mole to
Concentration
From stoichiometric table, we have Ni = f(X). The
concentration of individual species (reactants and products)
can be calculated if we know the volume occupied by the
reaction mixture.
Ni
Concentration in Batch Reactors : Ci
V
N A N Ao (1 X )
CA
V V
b N Bo b b
N Bo N Ao X N Ao ( X ) N Ao ( B X )
NB a N a a
CB Ao

V V V V
Now, Do for the Rest of
Species!!
c N Co c c
N Co N Ao X N Ao ( X ) N Ao (C X )
NC a N a a
CC Ao

V V V V
d N Do d d
N Do N Ao X N Ao ( X ) N Ao ( D X )
ND N Ao a
CD a a
V V V V
Batch System-Constant
Volume, V = Vo
N Ao (1 X )
CA C Ao (1 X )
V
b
N Ao ( B X )
a b
CB C Ao ( B X )
V a
c
N Ao ( C X )
a c
CC C Ao ( C X )
V a
d
N Ao ( D X )
a d
CD C Ao ( D X )
V a
Stoichiometric Table Batch
System-Constant Volume
Example 3-2
The saponification for the formation of soap from
aqueous caustic soda and glyceril stearate is
3NaOH (C17H35COO)3 C3H5 3C17H35COONa C3H5 (OH)3
Letting X represent the conversion of sodium

hydroxide (the moles 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 X.
Example 3-3
Having set up stoichiometric table , one can now

readily use it to calculate the concentrations at a
given conversion. If the initial mixture consists of
NaOH at a concentration of 10 mol/dm3 and of
glyceril stearate ((C17H35COO)3C3H5) at a
concentration of 2 mol/dm3, what is the
concentration of glycerine when the conversion of

NaOH is (a) 20% and (b) 90%?
Stoichiometric Table Flow
System -Constant Volume
Variable Volume System
Flow System
-frequently occurred in gas phase reaction which do
not have an equal number of product and reactant
mole.
N2+3H2 2NH3
Batch System
-example is in combustion chamber of internal

combustion engine
-For variable volume system, the first 4 column in

stoichiometric table are not changed, only the last
column of concentration is changed
Expression of Volume Function as
Conversion -Gas Phase for variable
volume system
Po T
Batch System
V Vo (1 X )
P To
Po T
Flow System v vo (1 X )
P To
Isobaric and Isothermal
Flow System
Po T
v vo (1 X )
P To
if Isobaric condition ( P=P0)
T
v vo (1 X )
To
if Isothermal (T=To) and Isobaric
v vo (1 X )
Concentration of Species
FB
The concentration of species B is CB

FB FB 0
b
FA0 X FA0 B b X
a a
Po T
v vo (1 X )
P To
b
FAo ( B
X)
a To P
Therefore, CB
vo (1 X ) T Po
b
C Ao ( B X)
a To P

(1 X ) T Po
Same for others species

Stoichiometric Table for Variable
Volume in Flow system

Chapter 3 - Rate Laws and Stoichiometry

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Chapter 3 - Rate Laws and Stoichiometry

Загружено:

Авторское право:

Доступные форматы

LOGO 3

RATE LAWS AND

(-rA) = [k (T)] [f (CA, CB, ..)]

k is a specific reaction rate (rate constant )

A - frequency factor (same unit as rate

Reaction coordinate Company Logo

Consider the following reaction:

= reaction order with respect to species A

Reaction Order Rate Law k unit

Zero -rA=kA mol/dm3.s

One -rA=kACA s-1

Two -rA=kACA2 (dm)3/mol.s

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

Now, if = a and = b , the reaction is considered to

Rate of formation of Benzene is

Net rate of formation of Benzene:

- We have shown how rate law can be expressed as a

function of concentration, so we need to only express

Now we can design or size the

For every moles of A that reacts, b/a

Change in total number of moles to attain complete conversion of A

Total number of moles of all species fed to the reactor

N io Fio Cio yio

Letting X represent the conversion of sodium

per mole of sodium hydroxide initially present),

Having set up stoichiometric table , one can now

concentration of glycerine when the conversion of

-example is in combustion chamber of internal

-For variable volume system, the first 4 column in

if Isothermal (T=To) and Isobaric

Same for others species

Вам также может понравиться