Topic 3 - Theory

Rate Laws and Stoichiometry

Fogler, Chapters 3-4

• Rate Laws
o Reaction Orders
o Arrhenius Equation

• Stoichiometry
o Stoichiometric Table
o Stoichiometry based on Concentration
o Stoichiometry based on Molar Flowrates

Slide 2
Introduction
• Last topic: if we have the rate of reaction as a function of conversion,
–rA = f(X), we can calculate reactor volumes necessary to achieve a
specified conversion for flow systems and the time to achieve a given
conversion in a batch system.
• However usually –rA = f(X) is not able to be determined directly from
raw data.
• This week we will show how to obtain the rate of reaction as a function
of conversion.
• This relationship between reaction rate and conversion will be obtained
in two steps.
o Step 1: define the rate law, which relates the rate of reaction to temperature and the
concentrations of the reacting species.
o Step 2: define concentrations for flow and batch systems and develop a
stoichiometric table so that one can write concentrations as a function of conversion.
• By combining Steps 1 and 2, we see that the rate can be expressed as a
function of conversion and use the techniques of Week 1 to design
reaction systems.
The Algorithm

How to find −𝑟𝐴 = 𝑓 𝑋

Step 1: Rate Law −𝑟𝐴 = 𝑔 𝐶𝑖

Step 2: Stoichiometry 𝐶𝑖 = ℎ 𝑋

Step 3: Combine to get −𝑟𝐴 = 𝑓 𝑋

Slide 4
Specific Rate Constant, kA
kA is strongly dependent on temperature
k A (T) = Ae −E RT Arrhenius Equation
Where :
A = Pre-exponential factor or frequency factor (1/time)
E = Activation energy, J/mol or cal/mol
R = Gas constant, 8.314 J/mol K (or 1.987 cal/mol K)
T = Absolute temperature, K

Taking ln of E 1
lnk = lnA −
both sides: R  T  ln k
-E/R
To determine activation energy E, run
the reaction at several temperatures,
and plot ln k vs 1/T. Slope is –E/R
1/T

Slide 8
Arrhenius Equation

• The Arrhenius equation can be put in a most useful form by finding the
specific reaction rate at a temperature T0, that is:
𝑘(𝑇0) = 𝐴𝑒−𝐸/𝑅𝑇0
and at a temperature T:
𝑘(𝑇) = 𝐴𝑒−𝐸/𝑅𝑇
and taking the ratio to obtain:
𝑘 𝑇 −𝐸 1− 1 −𝐸 1− 1
= 𝑒 𝑅 𝑇 𝑇0 or 𝑘(𝑇) = 𝑘(𝑇0)𝑒 𝑅 𝑇 𝑇0
𝑘 𝑇0
• Hence, if we know the specific reaction rate k(T0) at a temperature, T0,
and we know the activation energy, E, we can find the specific reaction
rate k(T) at any other temperature, T, for that reaction.

Slide 9
Slide 10
Stoichiometry

• We shall set up Stoichiometry tables using species A as our

basis of calculation in the following reaction.
𝑏 𝑐 𝑑
𝐴+ 𝐵→ 𝐶+ 𝐷
𝑎 𝑎 𝑎
• Stoichiometric tables express the concentration as a function
of conversion.
• We will combine Ci = h(X) with the appropriate rate law to
obtain -rA = f(X).
• A is the limiting reactant.

Slide 14
Slide 15
Stoichiometry
For the reaction 2NO + O2 → 2NO2 the rate of O2
disappearance is 2 mol/dm3•s (-rO2= 2 mol/dm3•s).

What is the rate of formation of NO2?

rj
Hint: − rA =
j
rNO
−rO =
2 (2 1)
2
( )= r
→ 2 −rO
2 NO2

 mol  mol
→ 22 = r
 NO2 → 4 = r NO
3 3 2
 dm  s  dm  s

ie. rNO2 = 4 mol/dm3•s

Slide 16
Stoichiometry

NA = NA 0 − NA 0 X
• For every mole of A that reacts, b/a moles of B react. Therefore
moles of B remaining:
N b 
b
NB = NB0 − N A0 X = NA 0   B0
− X
a  NA0 a 
• Let ΘB = NB0 / NA0

• Then: N = N   −b X 
B A0 B
 a 
c 
c 
NC = NC 0 + N A 0 X = N A 0 C
+ X
a  a 

Slide 17
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

Slide 19
Stoichiometry Constant Volume Batch

• Suppose −r = k C 2 C
A A A B

• Constant Volume Batch: V = V0

𝑏
𝐶𝐴 = 𝐶𝐴0 1 − 𝑋 and 𝐶𝐵 = 𝐶𝐴0 Θ𝐵 − 𝑎 𝑋
2 𝑏
⇒−𝑟𝐴 = 𝑘𝐴 𝐶𝐴0 1 − 𝑋 𝐶𝐴0 Θ𝐵 − 𝑋
𝑎
𝑏
= 𝑘𝐴 𝐶𝐴0 3 1 − 𝑋 2 Θ𝐵 − 𝑋
𝑎

b
• Equimolar feed:  B = 1 Stoichiometric feed:  B =
a

Slide 20
Stoichiometry Constant Volume Batch

− r = k C 2
C
• Hence, if A A A B , then
𝑏
3
−𝑟𝐴 = 𝑘𝐴𝐶𝐴0 1−𝑋 2 Θ𝐵 − 𝑋 Constant Volume Batch
𝑎

• and we have − rA = f (X )

1
− rA

Slide 21
Flow System – Stoichiometry

Slide 22
Flow System – Stoichiometry Table

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=FA0ΘI ---------- FI=FA0ΘI
FT0 FT=FT0+δFA0X
Fi0 C  C y d c b
Where: i = = i0 0 = i0 = i0 and  = + − −1
FA0 C A0 0 C A0 y A0 a a a
FA
Concentration – Flow System CA =


Slide 23
Flow System – Stoichiometry

FA
• Concentration Flow System: C A =

• Liquid Phase Flow System:  = 0

Liquid Systems
FA FA0 (1− X ) = C (1− X )
CA = = Flow Liquid Phase
 0 A0

N B N A0  
  B − X  = C A0   B − X 
b  b 
CB = =
V V0  a   a 
etc.

Slide 24
Liquid Systems

• If the rate of reaction were −𝑟𝐴 = 𝑘𝐴𝐶𝐴𝐶𝐵

then 𝐶𝐴 = 𝐶𝐴0 1 − 𝑋 and 𝐶𝐵 = 𝐶𝐴0 Θ𝐵 − 𝑋

𝑎
𝑏
⇒ −𝑟𝐴 = 𝑘𝐴𝐶𝐴0 1 − 𝑋 𝐶 𝐴0 Θ𝐵 − 𝑋
𝑎
2 𝑏 FA
= 𝑘𝐴 𝐶𝐴0 1 − 𝑋 Θ𝐵 − 𝑋
𝑎 −
• This gives us − rA = f (X )
X

Slide 25
Slide 27
Gas Phase Flow System

where
𝑑 𝑐 𝑏
𝛿 = + − −1
𝑎 𝑎 𝑎
change in total number of moles
𝛿=
mole of A reacted
𝑑 𝑐 𝑏 𝐹𝐴0
𝜀= + − −1 = 𝑦𝐴0 𝛿
𝑎 𝑎 𝑎 𝐹𝑇0

change in total number of moles for complete conversion

𝜀=
total number of moles fed to the reactor

Slide 29
Topic 3 – Theory: Summary

• From this lecture you should be able to:

1. Relate the rates of reaction of species in a reaction to each
other;
2. Write the rate law in terms of concentrations;
3. Use the Arrhenius Equation to find the rate constant as a
function of temperature;
4. Write the rate law solely in terms of conversion and the
reaction rate parameters, (e.g., k, KC) for both liquid-
phase and gas-phase reactions.

Slide 32