Governing Equations for

Multicomponent Systems
ChEn 6603
1 Wednesday, January 11, 12
Outline
Preliminaries:
Derivatives
Reynolds transport theorem (relating Lagrangian and Eulerian)
Divergence Theorem
Governing equations
total mass, species mass, momentum, energy
weak forms of the governing equations
Other forms of the energy equation
! the temperature equation
Examples
Couette ow - viscous heating
Batch reactor
2 Wednesday, January 11, 12
Derivatives

t
D
Dt
d
dt
Time-rate of change at a xed position in space.
Time-rate of change as we move through space with arbitrary
velocity (not necessarily equal to the uid velocity)
Time-rate of change as we move through space at the
uid mass-averaged velocity.
D/Dt is known as the
material derivative or
substantial derivative
dx
dt
= v
dx
dt
= v
x
,
dy
dt
= v
y
,
dz
dt
= v
z
D
Dt


t
+v
T = sin(t) + x + 5y Example: Can you have a
steady ow eld
where d/dt is
unsteady?
dT
dt
= cos(t) +u
a
x
+ 5u
a
y
DT
Dt
= cos(t) + v
x
+ 5v
y
d
dt
=

t
+
dx
dt
=

t
+
dx
dt

x
+
dy
dt

y
+
dz
dt

z
=

t
+u
a

3 Wednesday, January 11, 12
For a continuous eld !(x,t) we relate the Lagrangian and Eulerian descriptions as
Reynolds Transport Theorem

Let ! be any eld function that is continuous in space and time.

V(t)
An Eulerian volume dened
arbitrarily in space and time.
May have ux through boundaries
since it is NOT a closed system!
A Lagrangian volume that denes
a closed system for !
V

(t)
Closed system:
V

(t)
dened by u
!
Lagrangian vs. Eulerian
What does each
term represent?
dS
a
V(t
o
)
V

(t
o
)
V

(t
o
t)
V
b
(t
o
) = V(t
o
)
d
dt
Z
V

(t)
dV =
Z
V(t)

t
dV +
Z
S(t)
u

adS

also known as the Leibniz formula

4 Wednesday, January 11, 12
Intensive & Extensive Properties
B - extensive quantity
b - intensive quantity (B per unit mass)
!b - B per unit volume
Note: if ! and b are continuous functions then so is !b.
Reynolds Transport
Theorem with !=!b:
B =
Z
V
b dV
d
dt
Z
V
b
(t)
b dV
| {z }
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
bu
b
adS
!bu
b
=n
b
Mass ux of b
Note: if we use moles rather than
mass, we obtain the partial molar
properties (also intensive)
dS
a
V(t
o
)
V

(t
o
)
V

(t
o
t)
This equation will help us derive balance
equations for mass, momentum, energy.
5 Wednesday, January 11, 12
The Lagrangian Volume Problem
dx
1
dt
= v
1
dx
2
dt
= v
2
dx
dt
= u
a
Reynolds transport theorem
Relates a closed Lagrangian
system moving at ub to an open
Lagrangian system moving at u
a
.
Relates a closed Lagrangian system
moving at ub to an Eulerian system.
d
dt
Z
V
b
(t)
b dV
| {z }
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
n
b
adS
d
dt
Z
V
b
(t)
b dV =
d
dt
Z
V
a
(t)
b dV +
Z
S
a
(t)
j
a
b
adS
=
Z
V(t)
b
t
dV +
Z
S(t)
n
b
adS
= mass diffusive ux of b relative
to reference velocity u
a
.
j
a
b
In a multicomponent system, we have
many velocities! That means that we have
different denitions of the Lagrangian
volume for each property b!
dS
a
V(t
o
)
V

(t
o
)
V

(t
o
t)
n
b
= bu
b
= bu
a
+j
a
b
6 Wednesday, January 11, 12
The Divergence Theorem
Also called Gauss theorem, Ostrogradskys
theorem or the Gauss-Ostrogradsky theorem
Z
S(t)
q adS =
Z
V(t)
qdV
For any vector eld q,
This is very useful when moving
from macroscopic (integral) balances
to differential balances.
Using the divergence theorem, we can rewrite
the Reynolds Transport Theorem as
d
dt
Z
V
b
(t)
b dV =
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
n
b
adS
=
Z
V(t)

b
t
+ n
b

dV
mass ux of b.
n
b
= bu
b
= bu
a
+j
a
b
Can also be written for
scalar & tensor elds:
Z
V(t)
dV =
Z
S(t)
adS
Z
V(t)
dV =
Z
S(t)
adS
useful for
transforming
the momentum
equations
(p & ")
7 Wednesday, January 11, 12
1. Dene B and b.
2. Determine dB/dt (change in B in a closed system) This typically comes from
some law like Newtons law, thermodynamics laws, etc.
Using a closed system is the most convenient for deriving the equations, but
note that each B has a (potentially) different denition for the system.
3. Construct the governing equations in Lagrangian or Eulerian form.
Deriving Transport Equations for Intensive Properties
Lagrangian Form:
Eulerian Form:
from step 2
If you need to use an open
Lagrangian system, see the notes on
the Lagrangian volume Problem.
d
dt
Z
V
b
(t)
b dV =
dB
dt
=?
d
dt
Z
V
b
(t)
b dV =
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
n
b
adS
8 Wednesday, January 11, 12
Total Mass (Continuity)
Mass:
dS
a
V(t
o
)
V
b
(t
o
t)
V
b
(t
o
)
Eulerian forms:
Total mass is constant
in a closed system
d
dt
Z
V

(t)
dV =
dm
dt
= 0
What denes ? V

(t)
Reynolds
transport
theorem
d
dt
Z
V
b
(t)
b dV =
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
n
b
adS
0 =
Z
V(t)

t
dV +
Z
S(t)
n
t
adS
0 =

t
+ n
t
0 =

t
+ v
0 =

t
+ u +
n
X
i=1
j
u
i
You will explore various forms of the
continuity equation in your homework...
Lagrangian form of the
continuity equation.

Helps us move between

Lagrangian and Eulerian...
B = m, b =
B
m
= 1
9 Wednesday, January 11, 12
Lagrangian & Eulerian - A Very Simple Example
What is the density in a piston-cylinder system as a function of time?
Eulerian: Lagrangian:
d
dt
Z
V

(t)
dV =
dm
dt
= 0
1. Initial conditions: bottom of cylinder air at STP
2. Adiabatic system
3. Constant composition in space and time.
4. Spatially uniform density
5. h(t) = h0 + L/2 [ 1+cos("t) ] - this is a simplied description
-see http://en.wikipedia.org/wiki/Piston_motion_equations
6. Closed system (no valves)
Assumptions:
key
step!
What level of description do we have of the velocity field
in the cylinder? Is it adequate to answer the question?
m = V = R
2
h
dm
dt
=
d
dt

R
2
h

= 0

t
= n
t
= (v) = v
Z
V(t)

t
dV =
Z
V(t)
v dV =
Z
S(t)
v adS
V(t)

t
= R
2
v

t
=
v(t)
h(t)
Hom
ework: show that these are equivalent.
Cylinder stroke: 30 cm
Head height: h0 = 2 mm
10 Wednesday, January 11, 12
Eulerian forms:
Species Mass
b =
i
B = m
i
= m
i
In a closed system,
the mass of species i
changes only due to
chemical reaction:
dS
a
V(t
o
)
V
b
(t
o
t)
V
b
(t
o
)
si - mass reaction rate per unit volume.
NOTE: this is for a closed system on species i.
Is this the same system as for species j?
d
dt
Z
V
b
(t)
b dV =
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
n
b
adS
Z
V(t)
s
i
dV =
Z
V(t)

i
t
dV +
Z
S(t)
n
i
adS

i
t
= n
i
+s
i
Lagrangian form of species conservation.
d
dt
Z
V

i
(t)

i
dV =
dm
i
dt
=
Z
V

i
(t)
s
i
dV

Note that uxes appear in the Eulerian form.

If the total ux is not readily available, we

decompose it into convective and diffusive
components, ni=!iv+ji...

The total continuity equation is readily

obtained by summing the species equations.
11 Wednesday, January 11, 12
Species Balance Example: Stefan Tube
cx
i
t
=
c
i
t
= N
i

i
t
=

i
t
= n
i
,
At steady state (1D),
Species balance equations (no reaction):
T&K Example 2.1.1
Air
Liquid
Mixture
z =
z = 0
Convection-
diffusion balance...
n
i
=
i
N
i
=
i
Z
V(t)
s
i
dV =
Z
V(t)

i
t
dV +
Z
S(t)
n
i
adS

i
t
= n
i
+s
i
V - the volume we choose
for the integral balance.
Given: composition
at z=0, z=l.
12 Wednesday, January 11, 12
Momentum - Pure Fluid
Newtons second
law of motion:
Lagrangian integral form of
the momentum equations
Eulerian forms
dS
a
V(t
o
)
V
b
(t
o
t)
V
b
(t
o
)
B = mv
b =
mv
m
= v
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
bu
b
adS
m
dv
dt
=
Z
S(t)
( a + pa) dS +
Z
V(t)
f dV
Recall, for a pure uid, there exists
a single unique system velocity, v.
v
t
= vv p +f
Z
V(t)
v
t
dV +
Z
S(t)
vv adS =
Z
S(t)
( a + pa) dS +
Z
V(t)
f dV
dB
dt
= m
dv
dt
=
X
F
Extenal
13 Wednesday, January 11, 12
Momentum Example: Steady Stirred Tank
Choose the liquid-tank & liquid-air interface as the
volume over which we will perform the balance.
Z
V(t)
v
t
dV +
Z
S(t)
vv adS =
Z
S(t)
( a + pa) dS +
Z
V(t)
f dV
Z
S(t)
vv adS
Z
S(t)
a + padS
Z
V(t)
f dV
at steady state this term must be zero
only nonzero if we have ow across the surface
(therefore zero for this situation)
Stresses at the surfaces are nonzero if there are nonzero
velocity gradients. What balances this force? What happens if it
is not balanced?
f=g - acceleration due to gravity. How is this force balanced?
Z
V(t)
v
t
dV
14 Wednesday, January 11, 12
Momentum - Multicomponent Mixtures
What velocity denes the momentum?
species specic momentum
(momentum per unit
volume for species i)
n
X
i=1

i
u
i
=
n
X
i=1

i
u
i
= v
total specic momentum
(total momentum per
unit volume)
What velocity advects the momentum?
n
X
i=1
m
i
u
i
= m
n
X
i=1

i
u
i
= mv
species momentum
(momentum for species i)
total
momentum
B = mv, b =
B
m
= v
Velocity is an intensive quantity,
momentum per unit mass
It seems reasonable that a mass-averaged velocity would
advect the mass-averaged velocity (specic momentum)...
15 Wednesday, January 11, 12
Differences from pure uid momentum equation:

body force term includes forces acting on each species

velocity is a mass-averaged velocity!

Eulerian forms
d
dt
Z
V
b
(t)
b dV
| {z }
dB
dt
=
Z
V(t)
b
t
dV +
Z
S(t)
bu
b
adS
Newtons second
law of motion:
dB
dt
= m
dv
dt
=
X
F
Extenal
Body forces may
act differently on
different species:
F =
n

i=1

i
f
i
fi : acceleration
on species i.
Lagrangian integral form of
the momentum equation
Z
V(t)
v
t
dV =
Z
S(t)
vv adS
Z
S(t)
( a + pa) dS +
Z
V(t)
n
s
X
i=1

i
f
i
dV
v
t
= (vv) p +
n
s
X
i=1

i
f
i
Reynolds
transport
theorem
m
dv
dt
=
Z
S
v
(t)
( a + pa) dS +
Z
V
v
(t)
n
s
X
i=1

i
f
i
dV
16 Wednesday, January 11, 12
Total Internal Energy
B = E
0
= me
0
b = e
0
First law of
thermodynamics:
q - total diffusive heat ux (more later)
! - stress tensor
fi - body force on species i.
Rate of
viscous work
done on the
system
Rate of
pressure work
done on the
system
Rate of body
force work done
on the system
Total heat ux
out of the system
Lagrangian
Form:
dE
0
dt
=
dQ
dt
+
dW
dt
What would q include?
dW
dt
=???
What is the rate of work done
on the closed system?
specic
kinetic
energy
specic
internal
energy
E
0
- total internal energy (kinetic and internal energy)
dQ
dt
=
Z
S
e
0
(t)
q adS
e
0
=
1
2
v v + e
=
1
2
v v
p

+ h
dE
0
dt
=
Z
V
e
0
(t)
e
0
dV =
Z
S
e
0
(t)
q adS
Z
S
e
0
(t)
( v + pv) adS +
Z
V
e
0
(t)
n
s
X
i=1
f
i
n
i
dV
Note: here we have assumed
that the mass averaged velocity
is the appropriate one...
17 Wednesday, January 11, 12
Total Internal Energy (cont.)
time rate of
change of total
internal energy
in the volume
advective transport of
total internal energy
across the surfaces
Energy
dissipation from
viscous and
pressure work
on the system
work done by
body forces due
to both advection
and diffusion
Eulerian Integral Form:
Lagrangian Form:
Reynolds Transport Theorem:
Eulerian Differential form:
Z
V
b
(t)
b dV =
Z
V(t)
b
t
dV +
Z
S(t)
bu
b
adS
e
0
t
+ e
0
v = q ( v + pv) +
n
X
i=1
f
i
n
i
Energy
transfer
from heat
ux
Z
V(t)
e
0
t
dV +
Z
S(t)
e
0
v adS =
Z
S(t)
(q + v + pv) adS +
Z
V(t)
n
s
X
i=1
f
i
n
i
dV
dE
0
dt
=
Z
V
e
0
(t)
e
0
dV =
Z
S
e
0
(t)
q adS
Z
S
e
0
(t)
( v + pv) adS +
Z
V
e
0
(t)
n
s
X
i=1
f
i
n
i
dV
18 Wednesday, January 11, 12
Recap of Governing Equations
Continuity:
Momentum:
Species mass:
Total Internal
Energy:
This set of equations is the
most frequently used set for
many engineering applications.
Thermodynamics: solve for
T from !
i
, p and e
0
.
h =
n
X
i=1
h
i

i
h
i
= h

i
+
Z
T
T

i
c
p,i
(T)dT
Diffusive uxes - require constitutive relationships.
Pressure - requires equation of state.
Chemical source terms - requires a chemical mechanism relating T, p, !
i
to s
i
.
E
u
l
e
r
i
a
n

G
o
v
e
r
n
i
n
g

E
q
u
a
t
i
o
n
s

i
n

T
e
r
m
s

o
f

a

M
a
s
s
-
A
v
e
r
a
g
e
d

V
e
l
o
c
i
t
y

t
= v

i
t
=
i
v j
i
+ s
i
v
t
= (vv) p +
n
s
X
i=1

i
f
i
e
0
t
= e
0
v q ( v + pv) +
n
X
i=1
f
i
n
i
19 Wednesday, January 11, 12
The Heat Flux - a preview
Contributions:
Fourier term (due to !T )
Diffusing species carry energy: #h
i
j
i

Species gradients (in absence of
species uxes) can move energy!
!Dufour Effect - typically ignored
!ugly.
Radiative heat ux: "#T
4
(or more
complicated)
More soon...
q = q
Fourier
+q
Species
+q
Dufour
q
Fourier
= T
e
0
t
= e
0
v q ( v + pv) +
n
X
i=1
f
i
n
i
q
Species
=
n
X
i=1
h
i

i
(u
i
v),
=
n
X
i=1
h
i
j
i
20 Wednesday, January 11, 12
Mass vs. Molar Equations
Equations can be written in molar form as well.
can be derived using Reynolds Transport Theorem.
Sometimes it is more convenient.
! ideal gas at constant T, p, no reaction
Typically when solving the momentum equations, the mass
form is used.
sometimes the molar form of the species equations are used when
momentum is not being solved

t
= v
c
t
t
= c
t
u +
n
X
i=1
s
i
M
i
mass form
molar form
21 Wednesday, January 11, 12
Weak Forms of the Governing Equations
The weak form of a governing equation is obtained by subtracting the continuity equation.

t
+ v = 0

t
+v + v = 0
D
Dt
+ v = 0
D
Dt


t
+v
Example: species

D
i
Dt
= j
i
+s
i
Strong form or
conservative form
Weak form or
nonconservative form

i
t
+
i
v = j
i
+s
i

i
t
+
i

t
+v
i
+
i
v =

t
+ v

i
t
+v
i

=
substitute
continuity
22 Wednesday, January 11, 12
Strong & Weak Forms - Summary
Strong Form Weak Form

t
+ v = 0
D
Dt
= v

i
t
+
i
v = j
i
+s
i

D
i
Dt
= j
i
+s
i

Dv
Dt
= p +
n
X
i=1

i
f
i
e
0
t
+ (e
0
v) = q ( v)
(pv) +
n
X
i=1
f
i
n
i

De
0
Dt
= q ( v)
(pv) +
n
X
i=1
f
i
n
i
Continuity
Species
Momentum
Total internal
energy
D
Dt


t
+v
v
t
+ (vv) = p +
n
X
i=1

i
f
i
23 Wednesday, January 11, 12
Forms of the Energy Equation
Total internal energy equation:
Internal energy equation:
e
0
t
= e
0
v q ( v + pv) +
n
X
i=1
f
i
n
i
Enthalpy equation:
h
t
=
Dp
Dt
(hv) : v q +
n
X
i=1
f
i
j
i
e
0
= e +k = e +
1
2
v v
subtract kinetic energy equation
from total internal energy equation
e
t
+ (ev) = : v p v q +
n
X
i=1
f
i
j
i
h = e +
p

=
h
t
=
e
t
+
p
t
24 Wednesday, January 11, 12
Temperature Equation (1/2)
Coefcient of thermal
expansion
(from equation of state)
dh =
n
X
i=1

T,p
d
i
+

h
T

i
,p
dT +

h
p

T,
i
dp
Species enthalpies Heat capacity (function of T, ")
dh =
n
X
i=1
h
i
d
i
+c
p
dT +

V (1 T) dp
h
i

T,p
c
p
=

h
T

i
,p
=
n
X
i=1

i
c
p,i

h
p

T,
i
=

V T

V
T
!
p,
i
=

V (1 T)
Thermodynamics: choose T, p, !
i
as independent variables.
Then the enthalpy differential is:

1

V
T
!
p,
25 Wednesday, January 11, 12
dh =
n
X
i=1
h
i
d
i
+c
p
dT +

V (1 T) dp
Solve for dT and multiply by !:
c
p
dT = dh (1 T) dp
n
X
i=1
h
i
d
i
Substitute and simplify...
Notes:
For an ideal gas, $=1/T.
If body forces act equally on species, then #f
i
"j
i
= 0.
q includes the term #h
i
j
i
. The net term is thus #j
i
"!h
i
.
c
p
DT
Dt
= T
Dp
Dt
: v q +
n
X
i=1
h
i
( j
i
s
i
) +
n
X
i=1
f
i
j
i
Temperature Equation (2/2)

Dh
Dt
=
Dp
Dt
: v q +
n
X
i=1
f
i
j
i
D
i
Dt
= j
i
+s
i
26 Wednesday, January 11, 12
1e2 1 1e2 1e4
10
10
10
5
10
0
10
5
(s
1
)
d
T
/
d
t

(
K
/
s
)


Air 300K
Steam 600K
Hg 600 K
Example: Viscous Heating
Is Couette ow isothermal?
v
x
= 0
v
x
= v
H
x
y
c
p
DT
Dt
= T
Dp
Dt
: v q +
n
X
i=1
h
i
( j
i
s
i
) +
n
X
i=1
f
i
j
i
y = 0
y =
v
y
= 0,
v
x
x
= 0
v
x
y
=
v
x
t
=
v
x
v
x
x

v
x
v
y
y


xx
x


xy
y

p
x
+g
x

xy
y
= 0
xy
= constant =
v
x
y
=
v
x
= ( y) + v
H
c
p
T
t
= T
p
t

xy
v
x
y
T
t
=

xy
c
p
v
x
y
,
=

2
c
p
,
=

c
p

2
M
o
m
e
n
t
u
m

b
a
l
a
n
c
e
A
r
e

t
h
e

a
s
s
u
m
p
t
i
o
n
s

v
a
l
i
d
?
assume steady
pressure eld
what happened
to the convective
terms?
27 Wednesday, January 11, 12
Example: Batch Reactors
Derive the equations describing a well-mixed batch reactor.
Assumptions:
Well-mixed (no spatial gradients).
Constant volume.
Closed system.
How do we simplify and solve these equations?
Z
V(t)

t
dV =
Z
S(t)
v adS
Z
V(t)

i
t
dV =
Z
S(t)

i
v adS +
Z
V(t)
s
i
dV
Z
V(t)
v
t
dV =
Z
S(t)
(vv + ) adS
Z
S(t)
padS
n
X
i=1
Z
V(t)

i
f
i
dV
Z
V(t)
e
0
t
dV =
Z
S(t)
(e
0
v q v + pv) adS +
n
X
i=1
Z
V(t)
f
i
n
i
dV
28 Wednesday, January 11, 12