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Objectives

REACTION ENGINEERING CKB 20104

CHAPTER 1 MOLE BALANCE

Upon the completion of this chapter, students are able to: Define the rate of chemical reaction Apply mole balance equation in reactors systems Identify the commercial / industries reactor system

CHAPTER 1 MOLE BALANCE

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

Introduction

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Introduction
Reaction? Occurs when a chemical species lost its chemical identity and a new compound forms Kind Chemical Identity Number Configuration

Introduction
Reaction? decomposition
reactant product + by-product

Reaction Rate
3 ways combination
reactant + reactant product

isomerization

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1.1 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

1.1 DEFINITION OF REACTION RATE Consider species A: A B

Independent of the reaction system (batch, CSTR, plug flow, etc.) 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)CA].

1.1 DEFINITION OF REACTION RATE Consider species A:

1.1 DEFINITION OF REACTION RATE

REACTANT PRODUCT

EXAMPLE 1

Given reaction as

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] It is a function of concentration, temperature, pressure and types of catalyst (if any)

Therefore 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

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1.1 DEFINITION OF REACTION RATE

REACTAN T PRODUC T

1.1 DEFINITION OF REACTION RATE

Consider the reaction

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.

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: 1. 2. 3. 4. 5. 6. 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? What is -rB?

1.1 DEFINITION OF REACTION RATE

REACTAN T PRODUC T

1.1 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;

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.

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1.1 DEFINITION OF REACTION RATE For example given the reaction of A+ B C + D Based on Power Law Model, the reaction rate, -rA is given as

1.1 DEFINITION OF REACTION RATE

A reaction follows an ELEMENTARY RATE LAW if the REACTION ORDER of EACH REACTANT is IDENTICAL with the STOCHIOMETRIC COEFFICIENT of THE REACTANT for the reaction as written. Example: For reaction of A + B C+D The rate law would be -rA = k CA CB For reaction of 2NO + O2 2NO2 The rate law would be -rNO = k CNO2 CO

- rA = k(CA C B )
where k = specific reaction rate constant

1.1 DEFINITION OF REACTION RATE

1.1 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 the rate equation is -rA = kCA1CB2. 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

- rA = k(C A C B )
CA and CB is function of concentrations of component A and B (mol/L) The exponent of and 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

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1.1 DEFINITION OF REACTION RATE

EXAMPLE: Given the reaction as A + 2B C CASE 2 1. If stated the reaction obeys a NONELEMENTARY 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

1.2 THE GENERAL MOLE BALANCE

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

Exiting molar flow rate of A (mol/time) = Rate of generation of A (mole/time.vol) Rate of accumulation of A within system (moles/time)

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

+ reaction within system (moles/time)

Rate of generation of A by chemical

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

1.2 THE GENERAL MOLE BALANCE

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

+
+ +

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)

In

Generation
V

Out FA

= Accumulation = dNA/dt

Moles Balances

FAO

G A = A A .dV Gr

FA o F A + rA .dV =

dN A dt

Basic Equation for Chemical Reaction Engineering

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1.3 TYPES OF REACTOR IN INDUSTRY BATCH REACTORS

Types of Reactor in Industry

Key Characteristics unsteady-state operation (by definition) no spatial variation of concentration or temperature (wellmixed) mainly used for small scale operation suitable for slow reactions mainly (not exclusively) used for liquid-phase reaction has neither inflow nor outflow of reactants or products while reaction is carried out, FAO = FA = 0

1.3 TYPES OF REACTOR IN INDUSTRY

Batch Reactor Continuous Continuous stirred tank reactor (CSTR) Tubular reactor Simple batch Industrial CSTR Tubular reactor Fixed/ Packed bed Fluidized bed

1.3 TYPES OF REACTOR IN INDUSTRY BATCH REACTORS

Batch volume equation

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Models Development: Batch System

1.3 TYPES OF REACTOR IN INDUSTRY CONTINUOUS STIRRED TANK REACTOR

0 FAo + GA = dNA/dt + FA

Knowing that : GA = rAV Thus, dNA rA V =

dt
NA

(differential form) (integral form)

t=

N Ao

dNA rA V

CSTR Volume Equation

1.3 TYPES OF REACTOR IN INDUSTRY CONTINUOUS STIRRED TANK REACTOR

Models Development: CSTR System

FAo

CSTRs are also known as back-mix reactors

FA

Key Characteristics steady state operation used in series no spatial variation of concentration or temperature (well-mixed) mainly used for liquid phase reaction suitable for viscous liquid Reactants are continuously introduced into the reactor while products are continuously removed.

0 FAo + GA = dNA/dt + Thus, FAo + rAV = FA

V= FAo FA (rA )

FA

(algebraic form)

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1.3 TYPES OF REACTOR IN INDUSTRY PLUG FLOW REACTOR

Models Development: PFR System

V V + V

FAo

Gj

FA

0 FAo + GA = dNA/dt + FA FA|V + rA V = FA|V+V Key Characteristics steady-state operation consists of a cylindrical pipe which the reactants and products can flow through spatial variation in axial direction but not in radial direction suitable for fast reaction mainly used for gas phase reaction temperature control may be difficult there are no moving parts (FA|V+V - FA|V ) / V = rA Taking the limit as V0,
dFA = rA dV
FA

(differential form) (algebraic form)

V=

FAo

dFA (rA )

1.3 TYPES OF REACTOR IN INDUSTRY PLUG FLOW REACTOR

Summary
Differential Algebraic Equation Equation Batch Integral Equation
NA

Remarks Conc. changes with time but is uniform within the reactor. Reaction rate varies with time. Conc. inside reactor is uniform. (rA) is constant. Exit conc = conc inside reactor.

dNA = (rA )V dt

t=

NA0

dNA (rA )V

CSTR

V=

FA0 FA (rA )
FA

PFR

dFA = rA dV

V=

FA0

dFA (rA )

Concentration and hence reaction rates vary spatially.

PFR Volume Equation

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Thank you

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