Microscopic Mass Balance

Mathematical Modeling in Chemical Engineering

1
It is established for a control volume (CV).
Rate of mass
flow into
CV
Rate of mass
flow out of
CV
Rate of mass
generation/consumption
inside CV
Rate of change
of mass in
CV

=
-
Mathematical Modeling in Chemical Engineering
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Consider volume element AxAyAz in Cartesian coordinates
y
z
x
y
y+Ay
x
z
x+Ax
z+Az
CV

x, y, z
x+Ax, y+Ay, z+Az
Ax
Az
(U
x
)
x
(U
x
)
x+Ax

Ay
Assume no mass generation/consumption in control volume
Use areas perpendicular to the flow streams in all directions
( ) ( ) { } ( ) ( ) ( ) ( ) { }
t
z y x U U y x U U z x U U z y
z z
z
z
z
y y
y
y
y
x x
x
x
x
c
c
A A A = A A +
)
`

A A + A A
A +
A +
A +


Mathematical Modeling in Chemical Engineering
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x -axis :
Rate of mass in at x = x : (u
x
)|
x
AyAz
Rate of mass out at x = x+Ax : (u
x
)|
x+Ax
Ay Az

Inlet and outlet flow rates in the y and z directions can be written
similarly.

Mass accumulation in the (CV) : Ax

AyAz /t
Substitution of these terms into the mass balance equation gives
By dividing the entire equation by AxAyAz, we get
( ) ( )
( ) ( )
( ) ( )
t

z
U U
y
U U
x
U U
z z
z
z
z y y
y
y
y
x x
x
x
x
c
c
=
A

+
A

+
A

A +
A +
A +
( )
( )
( )
)
`

c
c
+
c
c
+
c
c
=
c
c
z
U
y
U
x
U
t
z
y
x

Mathematical Modeling in Chemical Engineering
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By taking the limits as Ax, Ay, and Az approach zero, we obtain
Equation of continuity, which describes the rate of change of density
at a fixed point resulting from the changes in the mass velocity
Convenient using the Nabla (divergence) operator (V)
Collecting all derivatives of on the left-hand side
) . ( - U
t

c
c
V =
|
|
.
|

\
|
+ + = + + +
z y x z y x t c
c
c
c
c
c

c
c
c
c
c
c
c
c
z
y
x
z y x
U
U
U
U U U
z y x t Dt
D
c
c
c
c
c
c
c
c
z y x
U U U + + + =
Mathematical Modeling in Chemical Engineering
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) . ( - U
Dt
D
V =

The left-hand side of this equation is the substantial derivative of density

It should be noted that, the mass balance can be performed for a
volume of any arbitrary shape.
When is constant (incompressible fluid)
Hence, (V.u) = 0 or
0 , 0 , 0 , 0 = = = =
z y x t c
c
c
c
c
c
c
c
0 = + +
z
u
y
u
x
u
z
y
x
c
c
c
c
c
c
Mathematical Modeling in Chemical Engineering
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Example 1:
Mass Balance for Fluid Flow through Cylindrical Pipe
A fluid is flowing through a constant-diameter cylindrical
pipe. The flow is turbulent, therefore we can assume
plug-flow conditions. There are no radial gradients in
velocity or any other properties. However, axial gradients
exist.
We want to study the unsteady-state mass balance for
the fluid.
Mathematical Modeling in Chemical Engineering
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Solution:
Since, there can be gradients in the axial direction (x) this
is a microscopic system. Being an unsteady-state flow,
the velocity and the density of the fluid can change as a
function of two independent variables: time (t) and
position (x).
x
x=0
x=L
u
A
r
Assumptions:
Plug-flow conditions
exist
There are no radial
gradients
Properties of fluid are
constant

x x+Ax
u
Ax
Control
volume
Mathematical Modeling in Chemical Engineering
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t
) x A (
uA uA
x x
x
x
x
c
c
=
+
A total mass balance over a CV of constant
cross-sectional area A and thickness Ax:
Dividing by (AAx) gives:
t

x
u u
x x x
c
c
=

+
Taking limit as Ax 0:
t

x
) u (
c
c
=
c
c

0
x
) u (
t

=
c
c
+
c
c
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Initial and Boundary Conditions
Initial Condition(s):
0 t @ C ) t , x ( C
0 A
= =
For an unsteady-state problem the behavior
(temperature, concentration, velocity,...etc) of a
system under consideration must be known at some
instant of time.
In many cases this is taken to be the situation at the
beginning.
For the mass transfer:
Mathematical Modeling in Chemical Engineering
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The concentration (C
A
) or mole fraction (X
A
) at a
surface may be specified to be a constant (C
A0
or X
A0
)
or a function of space or time.
Boundary Conditions
1. Prescribed Surface Concentration
0) t all (at L x @
0) t all (at 0 x @
0) t all (at 0 x @
0
0
> = =
> = =
> = =
L A
A
A
X X
X X
C C
direction) - x the in position the (x =
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The mass flux at or across the surface of a system
may be given/known.
2. Prescribed Mass Flux
L x @ N
x
C
D N
0
A
A
AB A
= =
c
c
=
L x @ N
x
X
D C N
0
A
A
AB T A
= =
c
c
=
constant) C (If
T
=
D
AB
= diffusion coefficient
C
T
= total concentration
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The surface is impermeable. No mass transfer may
take place
3. Impermeable Surface (No mass flux)
L x @ 0
x
C
D N
A
AB A
= =
c
c
=
L x @ 0
x
C
A
= =
c
c
or
L x @ 0
x
X
A
= =
c
c
(if C
T
= constant)
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Substance A is lost to the surrounding fluid stream
from a solid surface:
4. Solid-Fluid Interface
L x @ ) C C ( k N
AF AS c 0 A
= =
N
A0
= mass flux of A at solid surface
C
AS
= concentration of A at solid surface
C
AF
= concentration of A at fluid stream
K
c
= mass transfer coefficient
Mathematical Modeling in Chemical Engineering
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5. Chemical Reaction
The rate of chemical reaction at the surface may be
specified.
L x @ C k N
A R 0 A
= =
If A is consumed at the surface by a 1
st
order rxn:
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6. Mass Transfer at the Gas-Liquid Interface
The gasous substance A is weakly soluble in liquid
B:
0 x @
H
p
X
A
A
= =
H = Henrys constant
p
A
= partial pressure of A
Mathematical Modeling in Chemical Engineering
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7. Mass Transfer at the Gas-Solid Interface
Gaseous substance A dissolves in solid B:
0 x @ Sp C
A 0 A
= =
C
A0
= concentration of A in solid at interface
p
A
= partial pressure of gas adjoining interface
S = solubility of A in solid
Mathematical Modeling in Chemical Engineering
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A tubular reactor with a constant cross-sectional area is
used to carry out the first order reaction R S. The
concentration of R (C
R
) decreases with axial distance from
the entrance of the reactor as R is consumed, while the
concentration of S increases as it is generated. Density (),
velocity (u) and concentration (C
R
) can all vary with time
and axial position. We assume plug-flow conditions, so
that the radial gradients of density, velocity and
concentration can be ignored.
We want to derive a mathematical equation defining the
concentration of R as a function of time and axial position
by application of the mass balance law.
Mass Balance for a Tubular Reactor
Mathematical Modeling in Chemical Engineering
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Tubular reactor with first order reaction
What kind of a system is this reactor?
Microscopic
system
Concentration changes as function of the axial
position of the reactor (Concentration gradient exists
in x-direction)
u
A
C
R0
C
S0
R S
k
R

u
A
C
R
C
S
Mathematical Modeling in Chemical Engineering
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Plug-flow conditions
No radial concentration gradient
Fluid properties are constant
Assumptions:
x x+Ax
x=0 x=L
u(t,x)
(t,x)
C
R
(t,x)
Ax
u
A
C
R0
(t)
x
Control
volume R S
r
Mathematical Modeling in Chemical Engineering
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Component mass balance of R over CV
Molar flow rate of R in at x =x
Molar flow rate of R out at x = x +Ax

Rate of consumption of R in CV

Rate of change of R in the CV

x
R R
) uAC AN ( +
x x
R R
) uAC AN (
+
+
x A kC V r
R R
=
t
) xC A (
R
c
c
Since R is consumed kC
R
AAx is (-)
Remember the sign convention!
) xC A (
dt
d
) x A C k ( ) uAC AN ( ) uAC AN (
R R R
x x
R R
x
R R
= + + +
+
) xC A (
dt
d
) x A C k ( ) uAC AN ( ) uAC AN (
R R R
x x
R R
x
R R
= + + +
+
Mathematical Modeling in Chemical Engineering
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0 C k )
x
C
D (
x x
) uC (
t
C
R R
R
RS
R R
= +
c
c
c
c

c
c
+
c
c
Dividing by AAx, and taking limit as Ax 0
) C (
dt
d
) C k (
x
) uC N ( ) uC N (
R R R
x x
R R
x
R R
= +
+ +
+
t
C
C k
x
N
x
) uC (
R
R R
R R
c
c
=
c
c

c
c

x
C
D N
R
RS R
c
c
= Insert Ficks Law
Mathematical Modeling in Chemical Engineering
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0 C k
x
C
D
x
) uC (
t
C
R R
2
R
2
RS
R R
= +
c
c

c
c
+
c
c
This is a partial differential equation.
It requires 1 IC and 2 BCs for solution.
Steady-state:
0 t / C
R
= c c
0 C k
x
) uC (
x
C
D
R R
R
2
R
2
RS
= +
c
c
+
c
c

0 C k
x
) C (
u
x
C
D
R R
R
2
R
2
RS
= +
c
c
+
c
c

coeff.s) const. with ODE linear order (2

nd
If u = constant
What type of
differential eqn. is this?
If D
RS
is constant
Mathematical Modeling in Chemical Engineering
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For convenience:
0 C k
x
C
u
x
C
D
R
2
2
= +
c
c
+
c
c

D D and C C
RS R

Solution of ODE:
0
2
= + +
R
k um Dm
Characteristic equation:
D
Dk u u
m
R
2
4
2
2 , 1

+
=

Characteristic roots:
How do we solve this ODE?
Mathematical Modeling in Chemical Engineering
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B
1
and B
2
are constants
Can be determined from BCs.
0 x @ C C : 1
0
= = BC
L x @ 0 : 2 = =
dx
dC
BC
x m
2
x m
1
2 1
e B e B C + =
2 1 0
B B C + =
L m L m
e B m e B m
2 1
2 2 1 1
0 + =
x m
L m L m
L m
x m
L m L m
L m
e
e m e m
e m C
e
e m e m
e m C
C
2
2 1
1
1
2 1
2
2 1
1 0
2 1
2 0

=
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Solve these algebraic eqns to obtain:
L m L m
L m
e m e m
e m C
B
2 1
2
2 1
2 0
1

=
L m L m
L m
e m e m
e m C
B
2 1
1
2 1
1 0
2