SCOPES

CKB 20104 REACTION ENGINEERING

CHAPTER 1: MOLE BALANCE

1.1 Definition of reaction rate 1.2 The general mole balance 1.3 Types of reactor in industry

OBJECTIVES
Define the rate of chemical reaction Apply mole balance equation in reactors systems Identify the commercial / industries reactor system

INTRODUCTION
What is reaction?
Occurs when a chemical species lost its chemical identity and a new compound forms Kind Chemical Identity Number Configuration

INTRODUCTION
How does reaction occur?
decomposition
reactant product + by-product

DEFINITION OF REACTION RATE

The reaction rate is the rate at which a species loses its chemical identity per unit volume Can be expressed either as: 1. The rate of disappearance of a reactant or 2. The rate of appearance of a product

3 ways

combination
reactant + reactant product

isomerization

DEFINITION OF REACTION RATE

Consider species A:

DEFINITION OF REACTION RATE

(iii) It is a function of concentration, pressure, temperature, and types of catalyst (if any) (iv) Used to relate the rate of reaction, - rA, to the concentration of reacting species and to the temperature at which the reaction occurs [e.g. -rA = k(T)CA2]

(i) The rate of reaction, -rA is the number of moles of A reacting (disappearing) per unit time per unit volume [e.g. mol/dm3.s] (ii) Independent of the reaction system (batch, plug flow, etc.)

DEFINITION OF REACTION RATE

REACTANT PRODUCT

DEFINITION OF REACTION RATE

REACTANT PRODUCT

Example 1:
Given reaction as

rA = The rate of formation of species A per unit volume -rA = The rate of a disappearance of species A per unit volume rB = The rate of formation of species B per unit volume -rB = The rate of disappearance of species B per unit volume

For reactants, the rate of disappearance is a positive (+) number. For products, the rate of disappearance is a negative (-) number because they are being formed and not disappearing.

DEFINITION OF REACTION RATE

REACTANT PRODUCT

DEFINITION OF REACTION RATE

Consider the reaction

A + 2 B 3C
in which the rate of disappearance of A is 5 moles of A per dm3 per second at the start of the reaction. At the start of the reaction What is -rA? What is the rate of formation of B? What is the rate of formation of C? What is the rate of disappearance of C? What is the rate of formation of A, rA? 6. What is -rB?
1. 2. 3. 4. 5.

For reactants, the rate of formation is a negative (-) number because they are disappearing and not being formed. For products, the rate of formation is a positive (+) number.

DEFINITION OF REACTION RATE

1. -rA is the rate of disappearance of A

DEFINITION OF REACTION RATE

3. C is a product that is being formed three times as fast as A is disappearing. Because C is a product is being formed, its rate of formation is positive.

rA = 5 mol / dm .s
2. For every one mole of A that disappears, two moles of B disappear. Reactant B is a is disappearing twice as fast as reactant A. B is being used up therefore its rate of formation is a negative number.

rC = 15 mol / dm 3 .s
4. The rate of disappearance of C is -rC. Because C is a product, its rate of disappearance, -rC, is a negative number

rB = 10 mol / dm 3 .s

rC = 15mol / dm3 .s

DEFINITION OF REACTION RATE

5. A is a reactant that is being used up therefore its

DEFINITION OF REACTION RATE

The rate law is an equation which links the reaction rate with concentrations or pressures of reactants and constant parameters Determined from the experiments observations and gives the rate of reaction as a function of reacting species concentration and temperature

rate of formation is negative

rA = 5 mol / dm 3 .s
6. -rB is the rate of disappearance of B

rB = 10 mol / dm 3 .s

DEFINITION OF REACTION RATE

For example given the reaction of
A +B C+D

DEFINITION OF REACTION RATE

A +B C+D

- rA = k(C A n C B m )
CA and CB is function of concentrations of component A and B (mol/L) The exponent of n and m are called the reaction orders The order of reaction with respect to a certain reactant is defined, as the power to which its concentration term in the rate equation is raised

Based on the Power Law Model, the reaction rate, -rA is given as

- rA = k(C A C B )
where k is known as the specific reaction rate (constant)

DEFINITION OF REACTION RATE

A reaction follows an elementary rate law if the reaction order of each reactant is identical with the stoichiometric coefficient of the reactant for the reaction as written.
Example: C+D For reaction A + B The rate law would be -rA = k CA CB

DEFINITION OF REACTION RATE

EXAMPLE: Given the reaction as A + 2B C CASE 1 1. If stated the reaction follows elementary rate law, then the rate law and order of reaction can be obtained from the stoichiometric coefficient. 2. Therefore for the above reaction, the rate equation is -rA = k[A]1[B]2 3. The reaction order with respect to A would be 1 and with respect to B would be 2, the total reaction order would be 2 + 1 = 3

For reaction of 2NO + O2 2NO2 2 C The rate law would be -rNO = k CNO O2

DEFINITION OF REACTION RATE

EXAMPLE: Given the reaction as A + 2B C CASE 2 1. If stated the reaction obeys a non-elementary rate law, therefore the rate equation cannot be determined by looking at the stoichiometric coefficient. 2. Additional information are needed from experimental works or literature to deduce the rate law and the order of reaction

DEFINITION OF REACTION RATE

A +B C+D

The overall reaction order could be deduced by referring to the units of k

[k ] = (time )1 (concentration )1n

Zero order: First order: Second order: -rA = k

{k} = mol/(dm)3.s
-rA = kCA

{k} = 1/s
-rA = kCA2 or -rA = kCACB

{k} =

(dm)3/mol.s

DEFINITION OF REACTION RATE ZERO ORDER REACTION

The zero order rate law for the general reaction is written as Integrate of both sides gives C A =C A0 kt

DEFINITION OF REACTION RATE FIRST ORDER REACTION

The first order rate law for the general reaction, is written as

dC A =k dt

dC A = kC A dt

dC A = kdt CA

Plotting CA versus t will give a straight line with slope -k.

Integrating above equation to yield

ln

C A0 = kt CA

Plotting ln (CA0 / CA) against t creates a straight line with slope k

ln

C A0 CA

DEFINITION OF REACTION RATE SECOND ORDER REACTION

The second order rate law for the general reaction is given by

THE GENERAL MOLE BALANCE

Rate of generation of A (mol/time) Entering molar flow rate of A (mol/time) Number of moles of A inside the system volume Volume (e.g. m3)

dC A 2 = kC A dt
A plot of 1 / CA vs t produces a straight line with slope k and intercept 1 / CA0

dC A kdt 2 = CA
1 1 = kt C A CA 0

Separating the variables and integrating gives

Exiting molar flow rate of A (mol/time) Rate of generation of A (mole/time)

1 CA
Rate of flow of A INTO the system (moles/time) Rate of generation of A + reactionby chemical within system (moles/time) Rate of flow of A OUT of the system (moles/time)

Rate of accumulation of A within system (moles/time)

THE GENERAL MOLE BALANCE

Rate of flow of A Into the system (moles/time)

TYPES OF REACTOR IN INDUSTRY

+
+ +

Rate of generation of A by chemical reaction within system (moles/time)

Rate of flow of A Out of the system (moles/time)

Rate of accumulation of A within system (moles/time)

Types of Reactor

In FAO

Generation
V

Out FA

= Accumulation = dNA/dt

G A =GAA .dV r

FLOW SYSTEM CSTR PFR

BATCH SYSTEM

FA o F A + rA .dV =

dNA dt

Basic Equation for Chemical Reaction Engineering

TYPES OF REACTOR IN INDUSTRY BATCH REACTORS

Characteristics: 1. Usually used for small scale operation, for testing new processes that has not been fully developed, manufacturing of expensive products, etc. 2. Has neither inflow nor outflow of reactants or products while reaction is carried out, FAO = FA = 0 3. Typically used for liquid phase reactions

TYPES OF REACTOR IN INDUSTRY BATCH REACTORS

Batch volume equation

TYPES OF REACTOR IN INDUSTRY CONTINUOUS STIRRED TANK REACTOR (CSTR)

Characteristics: 1. Normally run at steady state and assumed to be perfectly mixed. 2. No spatial variations in concentration, temperature or reaction rate throughout the vessel. 3. Reactants are continuously introduced into the reactor while products are continuously removed.

TYPES OF REACTOR IN INDUSTRY CONTINUOUS STIRRED TANK REACTOR (CSTR)

CSTR Volume Equation

TYPES OF REACTOR IN INDUSTRY PLUG FLOW REACTOR (PFR)

Characteristics: 1. Consists of a cylindrical pipe which the reactants and products can flow through 2. Normally operated at steady state and there is no radial variation in concentration but varies continuously in the axial direction.

TYPES OF REACTOR IN INDUSTRY PLUG FLOW REACTOR (PFR)

PFR Volume Equation