Mathematical Modelling

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Mathematical Modelling

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2.1) Introduction:

A chemical plant should operate at a specific steady state condition known as the operating

conditions. However, the plant undergoes dynamics or transient behavior either when the

process is under the influence of disturbances or when the operating condition is changed.

Steady state: means all process variables are stationary, i.e. not changing with time.

Dynamic: means some or all process variables are changing with time.

Hence, since a typical plant undergoes frequent dynamic operation it is necessary to implement

control strategy to restore the steady state operation, i.e. to maintain the plant around its

operating condition.

Mathematical modelling of a process involves developing equations which attempt to describe

the dynamic behaviour of the system/process. These equations are based on the conservation

laws: total mass, component, energy, and momentum.

behaviour and response to various inputs without unexpected hazards. Behaviour can be

determined before constructing the actual plant. Models can also be used to determine

chemical kinetic mechanisms and parameters from laboratory reaction data. Aids in

scale-up calculations.

which are based on the model of the process.

To design the control strategy for a new process. The model allows alternate control

strategies to be evaluated.

settings prior to start-up of a new process. Studying the effects of and the requirements

for expansion projects. It is easier, cheaper, and safer to conduct studies on a

mathematical model than experimentally on an operating unit.

To design the control law. Exploring the sizing and arrangement of process equipment for

dynamic performance; studying the interactions of various parts of the process;

simulating start-up and shut-down procedures, and emergency situations and

procedures.

periodically so that the plant maximises profits and minimises costs.

2.3) Modeling Principles

Conservation Law

Change in (S)

within system All that adds to (S) All that removes from (S)

time S can be any one time of the following time

quantities:

The quantity

Total Mass

Component Mass (Mole)

Total Energy

Momentum

Water in

Water in

Pump

Tank

Water out

Water in 2

1 Pump 3 Tank 4

Water in Water out

Suppose that in the above system x kg/sec of water enters the tank through stream 1 and

y kg/sec through stream 3. How much water is expected to leave through stream 3 ?

(x +y) kg/sec

This is obtained by the law of conservation of mass which states that mass can neither be

created nor destroyed:

through system boundary through system boundary

or in short:

time

output

time

or

input

output

0

time time

3

Water in

2 Tank 4

Water in Water out

You would have (x + y) kg/sec of water going in and (x + y) – a kg/sec of water leaving.

Where is the remainder of the water?

It accumulates in the tank. accumulation is the rate of change of holdup within the system. It may

be positive (material is increasing), negative (material is decreasing), or zero (steady-state).

change inmas of material toal fowof material into sy tem toal fow of material out of sy tem

Several different conventions may be used to denote the flow-rate of a species in a stream:

The total mass flow-rate is denoted as M

The mass flow-rate of species j is denoted as Mj

The volumetric flow-rate of species j is denoted as Fj

Consider each term in the continuity equation:

Term 2:

total mass input through boundary

time

dm j

dt

M i

Now the fluid would normally enter the system through a conduit of some sort ie via a pipe or a

duct, etc. To obtain an indication of the changing mass flow into the system we can measure the

volumetric flow-rate. Units of volumetric flow-rate: {dV/dt) = [volume/time] = [m3/s].

The volumetric flow-rate is measured by using a rotameter, an orifice plate, a weir, etc.

The units we measure are: m3/s

m3 kg kg

s m3 s

mass flow-rate = volumetric flow-rate density

or

M

inlets

i ρ i Fi

If we cannot measure the volumetric flow-rate of the fluid we may be able to measure the

velocity of the fluid entering the pipe.

The units of velocity are: m s-1

m kg m2 kg

s m3 s

M

i vi ρ A

If the fluid flowing through the pipe is a gas then convert known stream volumes or volumetric

flow-rates to mass or molar quantities, using tabulated densities or gas law. In mass balance

equations, the mass or molar quantities are required. However, in industry it is easier to measure

the volumetric flow-rate using on-line instruments such as rotameters or differential pressure

gauges. We need to convert these volumetric flow-rates to mass or molar flow-rates. We do this

by using the following equation:

mass m

ρ

volume V

m ρV

ρV

or n

M

For gases, it is easier to measure the pressure, temperature and volumetric flow-rate, than the

mass or moles of gas. To obtain the mass or moles we use the following equation:

We assume that the gas is ideal:

PV nRT

PV

N

RT

and

M W PV

M

RT

d Mi M W PV

M i

i

dt RT

M

M PV

i W i

RT

Term 3:

total mass output through boundary

time

dMo

dt

M o

M

outlets

o ρ

outlets

o

V o

Term 1:

accumulati on of mass within system

time

dM

dt

expression for the change in mass of the fluid within the container. It is not normally possible to

measure the change in mass directly. Instead one measures the change in volume of the fluid

within the container. A conversion from volume to mass is therefore required:

The units we measure are: m3/s

m3 kg kg

s m3 s

time dt dt

substituting the various expression into the total mass balance gives:

d ρV

dt

ρ F

inlets

i i ρ F

outlets

o o

2.3.2.1) Introduction:

Unlike total mass, chemical components are not conserved when a chemical reaction occurs –

some species are consumed while others are generated. Before defining the mole balance we

consider a few related terms.

making up the species.

Chemical Reaction: A chemical reaction is said to occur when a detectable number of

molecules of a species have lost their chemical identity to form a new

species.

Chemical species can lose their identities via one of three ways:

or atom fragments.

Combination: where one molecule/atom combines with another molecule/ atom.

Isomerization: where a new species is formed simply by the change in

configuration of the atoms making up the species.

Homogeneous Reaction: A reaction that takes place in one phase alone.

Heterogeneous Reaction: A reaction that requires at least 2 phases to proceeds at the rate it

does.

Reactors: A reactor is a vessel in which a chemical reaction occurs.

Irreversible Reaction: a reaction that proceeds only in one direction and continues in that

direction until the reactants are exhausted.

Reversible Reaction: a reaction that can proceed in either direction, depending on the

concentrations of reactants and products relative to their

corresponding equilibrium concentrations.

Batch Reactor:

In this type of reactor, reactants are initially charged into the reactor and left to react for a certain

period. The resultant mixture is then discharged. This type of reactor results in an unsteady

operation – composition of a particular species changes with time. At any instant the

composition/concentration is uniform throughout the reactor.

Semi-Batch Reactor:

Or

Continuous Reactors

This reactor has both input and output streams. Since the reactor contents is well stirred the

composition of the output stream is equivalent to that of the composition within the reactor. This

type of reactor is also known variously as a continuous stirred tank reactor (CSTR), back mix

reactor (BMR), or mixed flow reactor (MFR). These reactors are normally run at steady-state.

PIPE

This type of reactor consists of a cylindrical pipe or tube – it is therefore called a tubular reactor.

It is normally operated at steady-state. The flow of fluid through the reactor is smooth – there is

no element of fluid mixing with that before or after it. There is no radial variation in concentration

– element moves through reactor as a plug – therefore also called a plug flow reactor (PFR).

The reactants are continually consumed as they move down the reactor.

Catalytic Reactors:

aA + bB cC + dD

The rate of reaction for the above reaction is defined as the number of moles of species A

reacting (disappearing) per unit time per unit base. Since species A is a reactant, its

concentration will decrease with time. The symbol for the rate of reaction is consequently: -rA.

The rate of the above reaction can also be expressed in relation to other species involved in the

reaction – if we consider species D, then the rate of reaction is expressed as the number of

moles of species D formed (generated) per unit time per unit base. Since species D is a product,

its concentration will increase with time. The symbol for the rate of reaction is consequently: r D.

Note: -rA and rD are related by the stoichiometric equation. This will be discussed in more detail

in later sections.

The “base” mentioned above is dependent on the reacting system:- If the system is

homogeneous then the base is considered to be the volume of the reacting fluid. In fluid-solid

systems the base could be one of mass of solid, surface area of solids, or volume of solids.

rj = f1(temperature) f2(composition)

= [kA(T)] [f2(CA, CB, CC, . . . )

Notes:

1) k is not strictly a constant – it depends on the temperature of the reacting system.

This will be discussed in more detail in a later section.

2) The rate expression is an algebraic equation.

Before determining the form of the concentration term in a rate expression, we need to define

certain terms.

The effect of concentration on the reaction rate is almost always determined experimentally. An

elementary reaction is one for which the rate expression can be obtained directly from the

stoichiometric reaction equation. If we consider the following reaction to be elementary:

aA + bB cC + dD

-rA = k CAa CBb wrt species A

or

-rB = k’ CAa CBb wrt species B

or

+rC = k’’ CAa CBb wrt species C

or

+rD = k’’’ CAa CBb wrt species D

stoichiometric equation and the rate expression. Consider the following reaction:

H2 + Br2 2HBr

This reaction is considered non-elementary because its rate expression turns out to be

k C C0.5

rHBr 1 H2 Br

2

C

k HBr

2 C

Br2

The molecularity of an elementary reaction refers to the number of atoms, ions, or molecules

involved (colliding) in the rate-limiting step of the reaction. This has been found have values of

one (unimolecular), two (bimolecular) and sometimes three (termolecular).

The order of a reaction refers to the powers to which the concentrations are raised in the rate

expression. For example, consider the following rate expression:

-rA = kA CA CB

This reaction is of order with respect to component A, and of order with respect to

component B. The overall order of the reaction is n, where n = + .

Note: the order of a reaction (both with respect to a component and overall) need not be an

integer.

Zero-order: -rA = kA

First-order: -rA = kA CA

Second-order: -rA = kA CA2

Third-order: -rA = kA CA3

The rate law gives the relationship between reaction rate and concentration:

k is not truly a constant – it is merely independent of the concentration of the species

involved in the reactor.

k(T) = Ae-E/RT

E is the activation energy [J/mol; cal/mol]

R is the gas constant [8.314 J/mol K; 1.987 cal/mol K]

T is the absolute temperature [K]

Fj Fj

Fjo

dN j

dt

N ji

N jo Gj Gj

For a product there is no consumption term and for a reactant there is no generation term.

Consider the generation or production term Gj.

moles moles

Gj volume rj V

time time volume

Now rj is the rate of reaction which depends on the concentration. Since the concentration

may not be the same throughout the reactor we divide the reactor into unit volumes and

find the rate of reaction in each unit volume. Then the total generation or consumption is

the sum of the generation or consumption in each of these unit volumes.

V

Gj m

r jm Vm

r dV

0

j

V

dN j

dt

N ji

N jo

r dV

0

j

Introduction:

Similar to that of mass or matter, the law of conservation of energy states that energy can

neither be created nor destroyed, but can be transformed from one form to another.

Kinetic Energy, EK

Kinetic energy is the energy a system possesses because of a velocity difference between it and

its surrounding at rest:

F x

m [kg]

parallel to the direction of the force. During this displacement the velocity increases from an

initial velocity vo to a final velocity v.

Force, F ma

du

where a acceleration

dt

2 2 2 2 2

du dx 1

F dx m a dx m dx m du m u du m u 22 u12

dt dt 2

1 1 1 1 1

If the initial velocity 0 and the final velocity u then then the kinetic energy is given by;

1

EK m u2 [N.m], [J]

2

EK ˆ 1 2

The specific kinetic energy E K u

m 2

The gravitational potential energy is the energy associated with a certain mass of fluid owing to

its vertical position in the earth’s gravitational field.

Consider an object of mass m whose centre of gravity is thrust vertically upward to a height z 2

above its original level z1 by a vertical force F.

2

mg

Z2

mg Z1

2

EP

1

m g dz m g z 2 z1 J

EP

Eˆ

P g z 2 z1

m

EP

If z1 0 and z 2 z then E ˆ

P gz J/kg

m

Internal Energy, U

The internal energy is the stored energy a system possesses by virtue of the atomic and

molecular energy of the matter of which it is constituted. The internal energy of a body of gas,

containing a certain quantity of molecules, is the sum of the energies represented by the random

molecular translational motion, their molecular rotational and vibrational bond energies and the

submolecular energies of the orbiting electrons. The potential energy due to the force of

attraction between the molecules also contribute towards the total internal energy. In the case of

liquids and solids the relative contribution of the different energies changes drastically. In solids

there is no rapid random motion of its molecules or atoms but only a slow process of diffusion.

The internal energy is an extensive property since it is proportional to the mass of the system in

question.

Translational:

Vibrational:

Rotational:

The internal energy of a system cannot be measured, but can be calculated from other variables

that can be measured, such as pressure, temperature, and volume. The internal energy per unit

V̂

mass is called the specific internal energy (Û) [kJ/kg]. It is a function of both temperature and

volume:

Û = Û(T, V)

Û Û

dÛ T dT V̂ dV̂

V̂ T

temperature of a system is changed (with the volume maintained constant), the specific internal

energy changes as follows:

Û Û

(kJ/kg)

T

T (oC)

The slope of the curve at any temperature is called the specific heat capacity at constant volume

Ĉ v ˆ dU

Cv

dT

ˆ

dU Cv dT

T2

ˆ

ΔU

C

T1

v dT

Work Energy:

There are several types of work that one may consider: Flow Work, Displacement Work, and

Shaft Work.

Work is a form of energy in transition or motion. When a system does work on its surroundings,

it transfers to it a certain quantity of energy. Similarly, when the surroundings do work on a

system, the energy level of the system rises.

Work done to the system is negative

dt

Flow work is done on a system when an amount of fluid flows through the system’s boundary

(control surface) into the system. Alternately, this is the work done on the fluid at the inlet to the

system – forcing the fluid into the system against the pressure of the system at the inlet:

x

Flow Pi Pi

If P = pressure [N/m2],

A = cross-sectional area [m2],

M = mass of fluid [kg],

x = distance [m]

M = mass flow rate [kg/s]

then

Flow work (Wf) = Fx

= P A x

= P V

= P V M

dWf

P Vˆ M

dt

Displacement Work:

Displacement work is the work done whenever a force acts through a distance

P F

where F is the component of the force acting in the direction of the displacement dx.

Consider the compression or expansion of a fluid in a cylinder by the movement of a piston. The

force exerted by the piston of the fluid is equal to the product of the piston area and the pressure

of the fluid. The displacement of the piston is equal to the volume change of the fluid divided by

the area.

V

dW P A d

A

or, since A is constant:

dW P dV

V2

W P dV

V1

This equation must be integrated if the work for a finite process is required:

The term shaft work is used to indicate work done by or on the fluid flowing through a piece of

equipment and transmitted by a shaft which protrudes from the equipment and which either

rotates or reciprocates. Therefore the term is taken to mean the work done which is

interchanged between the system and the surroundings through the shaft. The equipment may

include centrifugal pumps, turbines, reciprocal compressors, etc.

dQ

Heat [kJ]

dt

When a hot object is brought into contact with a cold object, the hot object becomes colder and

the cold object becomes warmer. We can assume that something has been transferred from the

hot object to the cold object – this something is called heat (Q). One important observation about

heat is that it always flows from a higher temperature to a lower one. The rate of heat transfer

from one body to another is proportional to the temperature difference between the bodies – the

temperature difference is the driving force for the transfer of heat.

Heat only exists in transit from one body to another, or between the system and the surrounding.

When energy in the form of heat is added to a body it is stored not as heat but as kinetic and

potential energy of the atoms and molecules making up the body.

In many thermodynamic analyses the sum of the internal energy U and the product of pressure

(P) and volume (V) appears. Because the sum U + PV occurs so frequently it is convenient to

give the combination a name, enthalpy, and a distinct symbol, H.

H = U + PV

The enthalpy per unit mass is called the specific enthalpy, Ĥand is an intensive property.

ˆ

H ˆ PV

U ˆ

Ĥ = Ĥ( T, P)

ˆ

H ˆ

ˆ

dH dT H dP

T P

P T

system is changed (with the pressure maintained constant), the enthalpy changes as follows:

Ĥ Ĥ

(kJ/kg)

T

T (oC)

The slope of the curve at any temperature is called the specific heat capacity at constant volume

Ĉ

P

ˆ

dH

CP

dT

ˆ

dH CP dT

T2

ˆ

ΔH ˆ H

H2

ˆ

1

T1

CP dT

It is important to note that one cannot calculate the absolute enthalpy – only changes in enthalpy

or the enthalpy relative to some reference state can be determined:

Ĥ2

Ĥ1

Ĥref reference

Initial state Final state

of system of system

= (Ĥ2 – Ĥref) (Ĥ1 – Ĥref)

= Ĥ2 Ĥ1

ˆ C dT

dH P

T2

ˆ

H C

T1

P dT

CP a bT cT 2

T2

ˆ

ΔH

T

CP dT

T2

a bT cT 2

dT

T

T2

T2 T3

aT b c

2 3 T1

a T2 T1

b

2

T2

2

T1

2

c

3

T2

3

T1

3

If the temperature range (T2 – T1) is large (> 50 oC) then the above equation is used. If the

temperature range (T2 – T1) is small (< 50 oC) then one can use the mean heat capacity:

ˆ C ΔT

ΔH P

ˆ T T ΔHˆ T ΔH

ΔH ˆ T

1 2 2 1

C

P T2 T2 Tref C

P T1 T1 Tref

Consider a liquid at some fixed temperature T1 with its upper surface exposed to a gas. The

liquid molecules are held in the liquid phase by various attractive forces. These molecules have

some energy and are in constant. If the temperature of the liquid is increased to some

temperature above T1 then the energy of the molecules will increase. Some molecules will have

gained sufficient energy to overcome the attractive forces and will consequently enter the vapour

phase. This phenomenon is known as vapourisation. The net rate of vapourisation is the

difference between the rate which molecules escape from the liquid phase and the rate at which

vapour molecules collide with the liquid surface are recaptured into the liquid phase.

The vapourising molecules will take with them some energy – the average energy of the liquid

phase will thus be reduced. There is a gain in enthalpy associated with the transition from liquid

to vapour at constant temperature. This enthalpy change is called the latent heat of

vapourisation.

The reverse of this process (when vapour molecules lose some energy and enter the liquid

phase) is called condensation and the enthalpy change associated with this process is called the

latent heat of condensation.

A similar consideration applies for the transition from solid to liquid (for example, when ice melts

to form a liquid).

Latent Heat of Fusion: ΔĤfheat required to melt a unit amount of solid at constant T

and P

Latent Heat of Vapourisation: ΔHˆ heat required to vapourise a unit amount of liquid at

v

constant T and P

Latent Heat of Sublimation: ˆ

ΔHs heat required to vapourise a unit amount of solid at

constant T and P

ΔHˆ

Latent Heat of Condensation: c

heat loss when a unit amount of vapour condenses to liquid

at constant T and P

ˆ

ΔH ˆ

ΔH

ΔĤ Enthalpy

condensation vapourisat ion

ˆ

ΔH fusion

Temperature (K)

W T To

o

Po

Ûo

Q Vo

Û

M

Ti i

Pi

Ûi

Vi

M i

Zi Z Zo

The law of conservation of energy states that energy can neither be created nor destroyed – it

can only be transformed from one form to another. This law is based on physical observations

and is not subject to mathematical proof. In its application to energy transformations on earth,

there is no known exceptions. The law of conservation of energy (or continuity equation),

therefore, reduces to:

accumulati on of energy within system

. . . . (1)

t im e t im e t i m e

time

Consider each of the terms in turn:

Term 1:

d 1

U M v M g z

dt 2

2

d

dt

ˆ 1 2

U 2 v g z M

Term 2:

flow of energy into system

time

ˆ 1 2 dMi dQ

Ui v i g zi

2 dt dt

ˆ 1 2

Ui v i g zi M i Q

2

time

ˆ 1 2 dMo dWT

Uo v o g z o

2 dt dt

ˆ 1

Uo v o g z o Mo 2

W

Substituting (2), (3), and

(4)2into (1) gives:

T

d ˆ 1 2 1 2 1

U v gz M Uˆ i v i gzi M i Uˆ o v o2 gzo M o Q W

T

dt 2 2 2

The above equation is true for a single inlet and single outlet. For multiple inlets and multiple

outlets the above equation becomes:

d ˆ 1 2

dt 2

U v gz M

inlets

ˆ

1 2

2

Ui v i gz i M

i

outlets

ˆ

1 2

2

Uo v o gz o M

o

Q

W T

M

ρV

In terms of measurable quantities, we know that

d ˆ 1 2 ˆ 1 2 ˆ 1 2

U v gz M

dt 2

inlets

Ui v i gz i ρ iFi

2

Uo v o gz o ρ o Fo

outlets 2

W

Q

T

Special Cases:

Steady-State Systems:

d ˆ 1 2

U gz v m 0

dt 2

and M

The mass flowrates M can be replaced by their steady - state flowrate

i o

equivalent s : m or n

Therefore, we have:

inlets

ˆ

1 2

2

Ui v i gzi mi

outlets

ˆ

1 2

2

Uo v o gzo mo

Q

W T 0

OR

inlets

ˆ

1 2

2

Ui v i gzi ni

outlets

ˆ

1 2

2

Uo v o gzo no

Q

W T 0

Closed Systems:

For closed systems there is no transfer of mass across the system boundary.

M 0 and

M 0

i o

d ˆ 1 2 W

U gz v M Q T

dt 2

ˆ 1 2 ˆ 1

U gz 2 v M U gz v 2 M Q WT

2 t1

t2

[Û + g z + ½ v2]M = Q – W

U + Ep + EK = Q – W

U = Q – W

Flow work is done on the fluid at the system inlet (forcing the fluid into the system against a

system pressure PI). This is negative work and is given by:

ˆ M

Pi V

i i

Flow work is also done on the fluid at the system outlet (forcing the fluid out of the system

against an outlet pressure Po). This is positive work and is given by:

ˆ M

Poi V

o o

W ˆ M

Po V ˆ M

Pi V

f o o i i

W W W

T S f

The energy balance ˆ M ˆM

WS Po V o o Pi Vi i

d ˆ 1 2 1 2 1

U v gz M Uˆ i v i gzi M i Uˆ o v o2 gzo M o

W

Q

T

dt 2 2 2

therefore, becomes:

d ˆ 1 2 ˆ 1 2 ˆ 1 2 ˆ ˆ

U v gz M Ui v i gz i Mi Uo v o gz o Mo Q WS Po Vo Mo Pi Vi Mi

dt 2 2 2

d ˆ 1 2 ˆ ˆ 1 v 2 gz M

U

ˆ P V

ˆ 1 2

U v gz M Ui Pi Vi i i i o o o v o gz o Mo Q WS

dt 2 2 2

d ˆ 1 2 ˆ 1 2 ˆ 1 2

U v gz M Hi v i gz i Mi Ho v o gz o Mo Q WS

dt 2 2 2

For multiple inlets and multiple outlets:

d ˆ 1 2 ˆ ˆ 1 v 2 gz M ˆ ˆ 1 v 2 gz M

U v gz M

dt 2

inlets

H i Pi V

i

2

i i

i

outlets

H o Po V

o

2

o o

o

W

Q

S

d ˆ 1 2 ˆ ˆ 1 v 2 gz ρ F ˆ ˆ 1 v 2 gz ρ F Q

dt U 2 v gz M H i Pi Vi

2

i i i i H o Po V o

2

o o o o

W

S

inlets outlets

Consider an open system having one input and one output stream. Assume the system to be at

steady state and the mass flow rate to be M. Assume further that the liquid is incompressible so

that

V̂i V̂o V̂ 1

The equation

d ˆ 1 2 1 2 1

U v gz M Uˆ i v i gz i Mi Uˆ o v o2 gz o Mo Q W

T

dt 2 2 2

becomes

ˆ 1 2 ˆ 1 2

0 Hi v i gzi M Ho v o gzo M Q Ws

2 2

ˆ ˆ 1 v 2 gz M ˆ ˆ 1 v 2 gz M

0 Ui Pi Vi i i Uo Po Vo o o Q Ws

2 2

0 Uˆ

o -U

ˆ M

i

Po Pi

M g z o z i M

1 2

v o v i2 M Q Ws

ρ 2

ˆM ΔP 1

0 ΔU M g Δz M Δv 2 M Q Ws

ρ 2

M

ˆ Q ΔP 1 Ws

0 ΔU g Δz Δv 2

M ρ 2 M

Now ΔUˆ Q M is the friction loss or heat that is generated as a result of friction.

ΔP Δv W

g Δz f s

ρ 2 M

For systems where there is no frictional loss and where there is no shaft work:

ΔP Δ v2

g Δz 0

ρ 2

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