Mathematical Modeling of Chemical Engineering Systems

Module 2

CENG3001: Process Dynamics & Control

Academic Year 2010 – 2011

Dr. Luca Mazzei

 Balance Equations

To write a balance equation, we must first define the control volume.

Control Volume

Generation
In + Out
Accumulation

System Boundary
 Balance Equations

The balance equation takes the form:

IN
OU T GEN  ACC
IN property flow rate into the control volume
OU T  property flow rate out of the control volume
GEN  property generation rate inside the control volume
ACC  property accumulation rate inside the control volume

ACC is present only if the system is not in stationary state. GEN is present
only if the property can be generated (GEN ¡ 0) or destroyed (GEN   0).

In chemical processes
total mass and total energy cannot be generated!
 Balance Equations

ACC  IN
OU T GEN
For a given control volume, this becomes:

amount of θ accumulated
time interval
 amount of θ in
time interval

amount of θ out
time interval
amount of θ generated
time interval

Remember: GEN is positive if θ is produced and negative if θ is destroyed.

Depending on the physical property θ and the problem at hand, ACC, IN ,
OU T and GEN take different analytical expressions.
 Total Mass Balance

ACC  IN
OU T GEN
X
 
XX

In chemical processes the total mass is not generated. This means that it is
neither produced nor destroyed.

For a given control volume, the total mass balance equation is:

amount of mass accumulated

time interval
 amount
time interval
of mass in amount of mass out
time interval

The total mass of fluid can enter and leave the control volume only by
convection; no other mechanisms are present.

IN and OU T only by convection.

 Example: Total Mass Balance
F0 ( t ) ρ0 ( t )

h (t ) V (t ) = A h (t )

CSTR F (t ) ρ (t )

Assumptions
Tank is perfectly mixed. This means that the generic variable θ has the
same value throughout the system and depends only on time: θ  θptq.
 Example: Total Mass Balance
F0 ( t ) ρ0 ( t )

IN  F0 ρ0 ; OU T  Fρ
h (t ) V (t ) = A h (t ) GEN 0
CSTR F (t ) ρ (t )

ACC  mpt dtq
mptq

dt
 dm
dt
 dpdt
V ρq
 A dpdthρq
dpV ρq
dt
 F0 ρ0
F ρ (1)
 Example: Total Mass Balance

How many equations do we have?

dpV ρq
dt
 F0 ρ0
F ρ ñ 1 equation

How many variables appear in this equation?

F0 , ρ 0 input variables (forcing functions) that must be specified;

V, F, ρ  output variables (these are the problem unknowns).

Is the model consistent? How many degrees of freedom are there once we
have specified the system forcing functions?

3 unknowns
1 equation  2 degrees of freedom

Two equations are missing. Which other equations can we still write?
 Example: Total Mass Balance

We need a constitutive equation to determine the fluid density.

If the fluid is a liquid, we can assume that the density is constant; if it is a

gas, we can use the ideal gas law or a more complex constitutive equation.
Assuming that it is a liquid, we have:

ρ  ρ0 0
dρ
; (2)
dt
Whence, from equation (1):

dpV ρq
dt
 ρ dV
dt
 F0 ρ0
F ρ  ρ pF0
F q ñ dV
dt
 F0
F
The fluid density disappears from the differential equation; accordingly, ρ is
no longer an unknown output variable. Equation (2) reduces the degrees of
freedom to one. However, one equation is still missing.
 Example: Total Mass Balance

We need to specify how the flow out of the tank is to be set.

Suppose we do not control the outflow. The system self-regulates. How?

F0 ( t ) ρ0 ( t ) p ≈ patm + ρ gh

p = patm

p = patm

h (t ) V (t ) = A h (t )

CSTR F (t ) ρ (t )
Δp ( F ) = ρ gh
A
 Example: Total Mass Balance
F0 ( t ) ρ0 ( t ) p ≈ patm + ρ gh

p = patm

p = patm

h (t ) V (t ) = A h (t )

CSTR F (t ) ρ (t )
Δp ( F ) = ρ gh
A

The pressure drop ∆p through the pipe (concentrated plus distributed) is a

function of F . ∆p is equal to ρg pV {Aq; thus, it is:

∆ppF q  ρg pV {Aq ñ F  f pV q
This equation reduces the system degrees of freedom to zero.
 Example: Total Mass Balance
F0 ( t ) ρ0 ( t ) p ≈ patm + ρ gh

p = patm

p = patm

h (t ) V (t ) = A h (t )

CSTR F (t ) ρ (t )
Δp ( F ) = ρ gh
A

Without control the system self-regulates, and we cannot control the flow
rate F . This is because we cannot change the function F  f pV q.

How can we control this system?

 Example: Total Mass Balance
F0 ( t ) ρ0 ( t )

hm ( t ) h sp ( t )
−+
ε
Controller
h (t ) V (t ) = A h (t )

CSTR ρ (t ) F = f (V )

• We install on the outlet line a control valve that regulates the flow.
• A level controller operates the valve to keep the fluid level in the tank
equal to hsp ; thus, V and F are related.
p q describes the level controller and the control valve.
• f V
 Example: Total Mass Balance

How many equations do we have?

dV
dt
 F0
F ; F  f pV q ñ 2 equations

How many variables appear in this equation?

F0  input variable (forcing function) that must be specified;

F, V  output variables (these are the problem unknowns).
Is the model consistent? How many degrees of freedom are there once we
have specified the system forcing function?

2 unknowns
2 equations  0 degrees of freedom

 Component Mass Balance

ACC  IN
OU T GEN

In chemical processes the mass of a generic component A can be produced

(if A is a product) or destroyed (if A is a reactant).

For a given control volume, the component mass balance equation is:

amount of mass accumulated

time interval
 amount
time interval
of mass in amount of mass out
time interval

amount of mass generated

time interval

When writing component mass balance equations, you might find it more
convenient to use molar instead of mass units. Why?
 Component Mass Balance

The component mass can enter and leave the control volume by convection
(bulk flow associated with the mixture average velocity) and diffusion (flow
relative to the mixture average velocity).

IN and OU T by convection and diffusion.

$
& mass: Avρ ωi  F ρ ωi  F ρ i
Convective flow rate
%

moles: Avc xi F c xi  F ci
$
'
'
' p
q
& mass: A vi v ρ ωi 
ADi ρ BBωzi
Diffusive flow rate
p
vq c xi 
ADi c BBxzi
'
'
'
% moles: A vi

In this course, we shall consider problems where diffusion is negligible.

 Example 1: Component Mass Balance
F0 ( t ) ρ0 ( t ) A→ B
c A 0 ( t ) cB 0 ( t ) rA = − k A c A
rA  molestimeof Avolume
produced

kA cA
IN  F0 cA0 ; OU T  F cA
h (t ) V (t ) = A h (t )
F (t ) ρ (t )
GEN  rA V 
V kA cA
CSTR
c A ( t ) cB ( t )
A

ACC  n A pt dtq
nA ptq

dt
 dndtA  dpVdtcAq  A dphc
dt
Aq

dpV cA q
dt
 F0 cA0
F cA
V kA cA (3)
 Example 1: Component Mass Balance
F0 ( t ) ρ0 ( t ) A→ B
dpV cA q
c A 0 ( t ) cB 0 ( t ) rA = − k A c A
dt
 F0 cA0
F cA
V kA cA
dpV cB q
 F0 cB0
F cB V kA cA
h (t ) V (t ) = A h (t ) dt
F (t ) ρ (t )
CSTR
c A ( t ) cB ( t )
A

We want to show that summing these two equations gives the total mass
balance, equation (1):

dpV ρq
dt
 F0 ρ0
F ρ
 Example 1: Component Mass Balance

Multiply the mass balance equation of component A, equation (3), by its

molar weight MA . Then, do similarly for component B.

dpV MA cA q
dt
 F0 MA cA0
F MA cA
V kA MA cA
dpV MB cB q
dt
 F0 MB cB0
F MB cB V kA MB cA

Summing the equations yields:

dpV ρq
dt
 F0 ρ0
F ρ
V kA pMA
MB q cA
since it is:

ρ0  MA cA0 MB cB0 and ρ  MA cA MB cB

 Example 1: Component Mass Balance

We expected to obtain the equation:

dpV ρq
dt
 F0 ρ0
F ρ
Instead, we have obtained:
dpV ρq
dt
 F0 ρ0
F ρ
V kA pMA
MB q cA
How can we explain the difference?

AÑB ñ MA  MB ñ V kA pMA
MB q cA 0
ó
The two equations coincide!
 Example 2: Component Mass Balance

F0 ( t ) ρ0 ( t ) A→ B→C
c A 0 ( t ) cB 0 ( t ) rA = − k A c A
cC 0 ( t ) rB = k A c A − k B cB
rB  molestimeof Bvolume
produced
 kA cA
kB cB
IN  F0 cB0 ; OU T  F cB
h (t ) V (t ) = A h (t )

CSTR
F (t ) ρ (t ) GEN  V pkA cA
kB cB q
c A ( t ) cB ( t )
A cC ( t )

ACC  n B pt dtq
nB ptq

dt
 dndtB  dpVdtcB q  A dphc
dt
Bq

dpV cB q
dt
 F0 cB0
F cB V pkA cA
kB cB q
 Example 2: Component Mass Balance

The mass balance equations of components A and C are similar to equation

(3). Therefore, we have:

dpV cA q
dt
 F0 cA0
F cA
V kA cA
dpV cB q
dt
 F0 cB0
F cB V pkA cA
kB cB q

dpV cC q
dt
 F0 cC0
F cC V kB cB

Multiplying each equation by the molar weight of the respective component

and then summing gives:

dpV ρq  
dt
 F0 ρ0
F ρ
V kA pMA
MB q cA k B pM B
MC q cB
 Example 2: Component Mass Balance

But, given the reaction stoichiometries, MA  MB  MC and therefore we

obtain the total mass balance equation (1).

Summary
For systems involving n chemical components, write:
• either the total mass balance equation and n
1 component mass
balance equations
• or n component mass balance equations.
Remember:
• summing the n component mass balance equations yields the total mass
balance equation;
• the n 1 mass balance equations for total mass and component mass
are not independent;
• n components ñ n independent mass balance equations.