Chapter 4:

Material Balance for

Chemical Reactors

What do we need?

Modeling and design of chemical reactors is based on

equation describing

mass transfer (Continuity equation)

heat transfer (Energy equation)

momentum transfer (Momentum equation)

chemical reaction (Rate equation)

These differential equations must be solved subject to the

appropriate initial and boundary conditions

Mass transfer implies motion

Aj

z
y

Fixed
coordinate
system

zu

uj
y

Ak

uk
Moving
coordinate
system

Average velocities
Let u j be the velocity of A j w.r.t. a fixed coordinate system
n

u
j

Local mass average velocity:

u=

j=1
n

M c u
j

j=1

(1)

j=1
n

c u
j

Local molar average velocity:

u* =

j=1
n

c
j=1

c u
j

j=1

(2)

Diffusion velocities
To characterize the motion of species A j relative to the
local motion of the stream, we need to introduce new
relative velocities:
Diffusion velocity w.r.t. u:

uj u

Diffusion velocity w.r.t u* :

u j u*

Fluxes
Fluxes relative to mass average or molar average velocity:
j j = j u j u

(3)

(4)

J j =c j u j u

(
J =c ( u

)
u )

j*j = j u j u*
*
j

(5)
(6)

kg
Units: 2
m s
mol
Units: 2
m s

Fluxes
Fluxes relative to fixed coordinate system:
n j = j u j

(7)

N j =c j u j

(8)

c u
j

Note that :
and

u* =

j=1

j=1

c
c
n
n
c
u* = j u j = x j u j
j=1 c
j=1

How are these fluxes related?

ci n
J =ci ui ci u = ci ui c j u j
c j=1
*
i

But,
N i =ci ui

ci
and xi =
c

Then
n

J*i = N i xi N j

(9)

j=1

Also:

J
j=1

*
j

=0

( Prove it! )

Diffusion in binary systems

Fick's First Law:
J*A =-cDABx A

(10)

From eqn. (9) we have:

J*A = N A x A ( N A + N B )
Thus
N A = J*A + x A ( N A + N B )
N A = -cDABx A + x A ( N A + N B ) (11)

Things to remember
Careful!
N A = -cDABx A
ONLY when
NA + NB = 0

Question:

Why

J*A =-cDABx A

and not

J*A =-DABcA ??

Things to remember

Diffusive fluxes are only defined relative to a convective flux

or the total flux!

Diffusive and convective fluxes are NOT independent! They

must sum to NA.

Ficks 1st Law has limitations. Everything changes for

multicomponent systems!

Multicomponent systems
Diffusion in a multicomponent system of ideal gases is described
by the Stefan-Maxwell equations:
n

1
xi =
xi N j x j N i
j=1 cDij

(12)

For a binary system:

1
1
x A =
xAN A xAN A ) +
xAN B xBN A )
(
(
cDAA
cDAB
cDABx A = x A N B x B N A

cDABx A = x A N B (1 x A ) N A
cDABx A = x A N B + x A N A N A
N A = cDABx A + x A ( N B + N A )

Multicomponent systems
For some (but not all) systems, we may be able to define
effective binary diffusivities Dim than do not depend on the
other species. The Stefan-Maxwell equations then become:

1
xi N j x j N i
j=1 cDim

xi =

cDimxi = xi N j x j N i
j=1

j=1

j=1

cDimxi = xi N j N i x j
n

N i = cDimxi + xi N j
j=1

(13)

Conservation of mass

A k
B

Conservation of mass
Volume element
y
(xyz)
fixed in space

A k
B

x
x
y

Conservation of mass
Volume element
y
(xyz)
fixed in space

A k
B

x
x
y
Amount of A Amount of A Amount of A Amount of A
introduced removed reacted per = accumulated

per unit time per unit time unit time per unit time

Conservation of mass
Volume element
y
(xyz)
fixed in space

A k
B

x
x
y

Input of A across face at x:

n Ax x yz

Output of A across face at x + x:

n Ax

x+x

yz

Conservation of mass
Volume element
y
(xyz)
fixed in space

A k
B

x
x
y

Input of A across face at y:

n Ay xz

Output of A across face at y + y:

n Ay

y+y

xz

Conservation of mass
Volume element
y
(xyz)
fixed in space

A k
B

x
x
y

Input of A across face at z:

n Az z xy

Output of A across face at z + z:

n Az z+z xy

Conservation of mass
Volume element
y
(xyz)
fixed in space

A k
B

x
x
y

Rate of production of A by chemical reactions:

Accumulation of mass of A in volume element:

rA xyz
A
xyz
t

Conservation of mass
Finally:

A nAx nAy nAz

+
+
+
= rA

t x
y
z

Units?

or
A
+ n A = rA
t
A
+ A u A = rA
t
Since this a binary mixture with 1 reaction:
B
+ B u B = rA
t

(14)
(15)

(16)

Conservation of mass
By adding (15) and (16) and noting that
rA + rB = 0
from the conservation of mass, we finally obtain:

+ u = 0
t

(17)

Eulerian form of continuity equation

Conservation of mass
If we work with moles:
cA
+ N A = RA*
t
cB
+ N B = RB*
t

(18)
(19)

Add (18) and (19) to get

since

c
+ cu* = RA* + RB*
t
??

(20)

N A + N B = cA u A + cB u B = cu*

Conservation of mass
Using equation (11) [ Fick's Law]:
cA
+ cDABx A + x A ( N A + N B ) = RA*
t
cA
+ ( cDABx A ) + x A cu* = RA*
t

cA
+ cA u* + ( cDABx A ) = RA*
t

(21)

Conservation of mass
Note that:

n A = cDABx A + gA ( n A + n B )
n A = cDABx A + gA u
n A = cDABx A + A u

(22)

From (22) and (14)

A
+ A u + ( DABgA ) = rA
t
And since
jA = DABgA
A
+ A u + jA = rA
t
Dividing by M A we obtain
cA
+ cA u + J A = RA*
t

(23)
(24)
(25)

(26)

Multicomponent systems

And since

) (

c j
+ c j u + J j = R*j
t

(27)

J j = D jmc j

(28)

) (

c juy
c j uz
c j c j u x
+
+
+
=
t x
y
z
c j
c j
c j

*
=
D
+
D
+
D
+
R
jm
jm
jm
j
x
x y
y z
z

(29)

Assumptions

The only contribution to mass flux Ji comes from

concentration gradients.

Additional contributions may come from

pressure gradients (centrifuge);

external forces acting unequally on different species (ionic

solutions);

temperature gradients (thermal diffusion or Soret" effects).

These are usually small but can be enhanced by steep
temperature gradients

Assumptions

The continuity equation assumes perfectly ordered flow.

Turbulent flow introduces an additional flux that can also be

expressed as proportional to the concentration gradient eddy diffusivity.

The two fluxes are summed to obtain an effective diffusivity.

When we have highly turbulent flow, the molecular diffusion is

negligible and the effective diffusivity is the same for all
species.

Simplifications

Tubular Reactors

Empty tubes

Flow in one direction

Under isothermal conditions, major gradients exist only in the

axial direction

Then, we may use average values of variables over the cross

section of the reactor:

1
= d

Tubular reactors
Assuming
1. turbulent flow and
2. constant diffusivity

c j c j uz
2 c j
+
= D j,m 2 + R*j
t
z
z

(1)

Additional assumptions:
1. Steady state
2. Diffusion term is negligible

( )=R

d c ju
dz

*
j

(2)

Tubular reactors
Let Ac be the constant cross sectional area of the tube. Then:
Q = uAc

Volumetric flow rate:

( ) = d (c Q) = d (c Q) = R

d c ju
dz

Ac dz

dV

*
j

(4.66)

and since c jQ = N j :

Units?

dN j
= R*j
dV

(4.67)

Gas phase reactions

Ideal Gas Law:
P
c j = RT
j

N
j

RT
Q=
P

P
=

RT

(4.69)

Nj
P Nj
cj =
=
Q RT N j
j

(4.70)

Liquid phase reactions

M = N jM j

Total mass flow:

M = Q

(4.71)

d M jN j
dN j
*
(4.67) M j
= M j Rj
= M j R*j
dV
dV
Sum over j:

d M jN j

dV

= M j R*j
j

dM
= 0 and M ( 0 ) = M feed
dV

Liquid phase reactions

Total mass flow is constant w.r.t. axial position!
Chemical reaction cannot change mass flow!

Mass flow rate:

Mf
Q=

(4.72)

Q = Qf

(4.73)

If the liquid density is constant: ( z ) = f

Time spent in reactor: =V Q

If Q is constant:

( ) = Q dc

d c jQ
dV

dc j
=
= R*j
dV d
j

(4.74)

Well-mixed reactors
Q2

Rj
V
Q1
c j1

S1

S2

cj2

Well-mixed reactors
Start with the continuity equation:
c j
+ c j u + J j = R*j
t
Concentrations are uniform in well-mixed reactor!
Integrate over the entire volume of the reactor:
c j
*
dV
=

c
u
dV

J
dV
+
R
j
j
V t
V
V
V j dV

From Gauss divergence theorem:

d
*
c
dV

c
u
dS
=

c
u
dS

j
dS
+
R
j
j mn
j n
in
j dV

dt V
S
S
S
V
Surface of control volume may move with time

Well-mixed reactors
( ) = c (u

dt

d c jV

u
dS

j
dS
+
R
)
n
mn
in j dV =
S

= c j1u1S1 c j 2u2 S2

(1)

jin dS + R*j V

S1 +S2

(2)

(3)

where
S1 ,S2 : open end surfaces of control volume
u1 ,u2 : average velocities over cross sectional areas
The integral term (2) is usually negligible compared to term (1).

Well-mixed reactors
( ) = (c
dt

d c jV

*
u
S

c
u
S
+
R
j1 1 1
j2 2 2
jV

Batch reactor: No fluid enters or leaves the reactor

( )=RV

d c jV
dt

CSTR: c j1u1S1 = c j, f Q f
c j 2u2 S2 = c jQ j

*
j

(4.5)

Inlet molar flow rate

Outlet molar flow rate

( )=c

d c jV
dt

*
Q

c
Q
+
R
j, f
f
j j
jV

(4.36)