Entropy GMS IrrevThermo PDF

GMS Equations From
Irreversible
Thermodynamics
ChEn 6603
References
• E. N. Lightfoot, Transport Phenomena and Living Systems, McGraw-Hill, New York 1978.
• R. B. Bird, W. E. Stewart and E. N. Lightfoot, Transport Phenomena 2nd ed., Chapter 24
McGraw-Hill, New York 2007.
• D. Jou, J. Casas-Vazquez, Extended Irreversible Thermodynamics, Springer-Verlag, Berlin 1996.
• R. Taylor, R. Krishna Multicomponent Mass Transfer, John Wiley & Sons, 1993.
• R. Haase, Thermodynamics of Irreversible Processes, Addison-Wesley, London, 1969.
Monday, February 27, 12 1

Outline
Entropy, Entropy transport

Entropy production: “forces” & “fluxes”
• Species diffusive fluxes & the Generalized Maxwell-Stefan Equations
• Heat flux
• Thermodynamic nonidealities & the “Thermodynamic Factor”
Example: the ultracentrifuge
Fick’s law (the full version)
Review

A Perspective
Reference velocities Goal: obtain a more general
• Allows us to separate a species form of the GMS equations
flux into convective and that represents more
diffusive components. physics
Governing equations • Body forces acting differently
• Describe conservation of mass, on different species (e.g.
momentum, energy at the electromagnetic fields)
continuum scale. • Nonideal mixtures
GMS equations • Large pressure gradients
• Provide a general relationship (centrifugal separations)
between species diffusion fluxes
and diffusion driving force(s).
• So far, we’ve assumed:
‣ Ideal mixtures (inelastic collisions)
‣ “small” pressure gradients
Entropy
n
X Chemical potential
Entropy differential: T ds = de + pdv µ̃i d!i µ̃i = µi /Mi per unit mass
i=1
e Internal energy
Total (substantial/material) derivative:

D
⇥ +v·⇤
v Specific volume
Dt t
n
X
Ds De Dv D!i
T⇢ =⇢ + p⇢ µ̃i ⇢
Dt Dt Dt i=1
Dt
= 1/v
n
X
Ds De p D⇢ D!i
T⇢ =⇢ µ̃i ⇢
Dt Dt ⇢ Dt i=1
Dt
n
De X D D⇤i
⇢ = r·q ⌧ : rv pr · v + fi · ji = ⇤·v = ⇤ · ji + ⇥i
Dt Dt Dt
i=1

Entropy Transport
n n
Ds p
T⇥ = ⇤·q ⌅ : ⇤v p⇤ · v + fi · ji + ⇥⇤ · v µ̃i ( ⇤ · ji + ⇤i ) ,
Dt i=1
⇥ i=1
n n n
= ⇤·q ⌅ : ⇤v + fi · ji + µ̃i ⇤ · ji µ̃i ⇤i ,
i=1 i=1 i=1
chain rule...
( ⇥) = ⇥+⇥
⇧ ⇤ n
⌅⌃ ⇥ n ⇥ n n
Ds 1 ⌥ 1 ⌥ µ̃i 1 1⌥ 1⌥
⇥ = ⇤· q µ̃i ji +q · ⇤ ji · ⇤ ⌅ : ⇤v + f i · ji µ̃i ⇤i
Dt T i=1
T i=1
T T T i=1 T i=1
⌦ ↵ ⌦ ↵
Transport of s Production of s

⇧ ⇤ n
⌅⌃ ⇥ n ⇥ n n
Ds 1 ⌥ 1 ⌥ µ̃i 1 1 ⌥ 1 ⌥
⇥ = ⇤· q µ̃i ji +q · ⇤ ji · ⇤ ⌅ : ⇤v + f i · ji µ̃i ⇤i
Dt T i=1
T i=1
T T T i=1 T i=1
⌦ ↵ ⌦ ↵
Transport of s Production of s
Ds
Now let’s write this in the form: =
⇤ · js + ⇥s
⇥ Dt
⇤n
1
js = q µ̃i ji diffusive transport of entropy
T i=1
⇥ ⇧ n ⇥ ⇧ n ⇧ n
1 µ̃i 1 1 1
⇥s = q · ⇤ ji · ⇤ : ⇤v + fi · j i
production
µ̃i ⇥i ,
of entropy
T i=1
T T T i=1 T i=1
⇧n ⇤ ⇥ ⌅ n
q µ̃i 1 1 1⇧
= · ⇤ ln T ji · ⇤ fi : ⇤v µ̃i ⇥i
T i=1
T T T T i=1
⇥ ⇥
µ̃i µ̃i T 1 µ̃i 1
= + p+ T,p µ̃i ,
T T T T p T Note that we
⇥ haven’t “completed”
1 1 µi
= p + T,p µ̃i , the chain rule here.
T Mi p We will apply it to
⇥
1 V̄i species later...
= p + T,p µ̃i
T Mi
n
⇤ ⇥ n
⇤
V̄i
T ⇥s = q · ⇤ ln T ji · ⇤T,p µ̃i + ⇤p fi : ⇤v µ̃i ⇥i
Mi
i=1 ⌃ ⇧⌅ ⌥ i=1
i
Look at this term
(entropy production due to species diffusion)
Part of the Entropy Source Term…
n ⇥ n
⇤ n
⌅
⇧ V̄i ⇧ 1 ⇧ Why can we add this “arbitrary” term?
ji · ⇥T,p µ̃i + ⇥p fi = ji · i ⇥p + ⇥k fk What does this term represent?
Mi
i=1 ⌥⌃ i=1 k=1
i
n n
" ✓ ◆ n
#!
X X V̄i 1 X
ji · i = ⇤i (ui v) · ⇥T,p µ̃i + ⇥p fi + ⇤k fk ,
i=1 i=1
Mi
k=1 ji = ⇥i (ui v)
0 2 31
i xi
n B 6 !7C =
X B 6 Xn
7C Mi M
= B(ui v) · 6 ⇤k fk 7C
B 6ci ⇥T,p µi + (⇥i ⇤i )⇥p ⇤i fi 7C ,
i=1 @ 4 k=1 5A i = ci V̄i
| {z }
cRT di µi
n
X µ̃i =
Mi
= cRT di · (ui v),
i=1 V̄i Partial molar
Xn volume.
1
= cRT di · ji
i=1
⇤i
n
⇥ From physical reasoning (recall di n
⇤
cRT di = ci ⇥T,p µi + (⇤i ⌅i )⇥p ⌅ i ⇥ fi ⌅k fk represents force per unit volume
di =0
driving diffusion) or the Gibbs-
k=1 i=1
Duhem equation,

The Entropy Source Term - Summary
Ds From the previous slide:
= ⇤ · js + ⇥s
Dt n n
di · ji
n
⇥ ji · i = cRT
1 ⇤ i=1 i=1 i
⇥
js = q µ̃i ji n
⇤
T i=1 cRT di = ci ⇥T,p µi + (⇤i ⌅i )⇥p ⌅ i ⇥ fi ⌅k fk
k=1
n
⇤ ⇥ n
⇤
V̄i
T ⇤s = q · ⇤ ln T ji · ⇤T,p µ̃i + ⇤p fi ⌅ : ⇤v µ̃i ⇤i
Mi
i=1 ⌃ ⇧⌅ ⌥ i=1
i
n
⇤ n
⇤
cRT
= q · ⇤ ln T di · ji ⌅⌃ :⇧⌅⇤v⌥ µ̃i ⇤i
⌃ ⇧⌅ ⌥ ⇥i
i=1 3 i=1
1 ⌃ ⇧⌅ ⌥ ⌃ ⇧⌅ ⌥
2 4
Interpretation of each term???

σs ∼ Forces ⋅ Fluxes
n n
cRT
T ⇤s = q · ⇤ ln T di · ji ⌅ : ⇤v µ̃i ⇤i
i=1
⇥i i=1
Fundamental
Flux, J Force, F
principle of s = J F q ⇥ ln T
irreversible
thermodynamics:
ji ⇥i di
cRT
⇥v
Fluxes are functions of: J = J (F1 , F2 , . . . , F⇥ ; T, p, i )

⇥
⇤ J
• Thermodynamic state variables: J = F⇥ + O (F⇥ F⇤ )
F⇥
T, p, ωi. ⇥
⇤ J
• Forces of same tensorial order L ⇥ F⇥ L ⇥
F⇥
(Curie’s postulate) ⇥
L = L⇥
‣ What does this mean? ⇥
‣ More soon… Lαβ - Onsager (phenomenological) coefficients

Species Diffusive Fluxes
Tensorial order of “1” any Flux: J q ji
vector force may contribute. Force: F ⇥ ln T cRT
⇥i di ⇥v
Index form: n-1 dimensional matrix form

From irreversible thermo:
n
X1 cRT
ji = Lij
⇢j
dj Li qr ln T (j) = ⇥ [L] (d) + ⇥ ln T ( q )
j=1
Fick’s Law:
n
X1 Dij - Fickian diffusivity
ji = ⇢ Dij dj DiT r ln T (j) = ⇢ [D ] (d) DT r ln T
DiT - Thermal Diffusivity
j=1
Generalized Maxwell-Stefan Equations:

n
X ✓ ◆ n
X
xi xj ji jj
di = r ln T xi xj T
ij ⇢(d) = [B on ](j) r ln T [⌥](DT )
⇥Ðij ⇤i ⇤j
j6=i j6=i
✓ T ◆
1 Di DiT
T
ij =
Ðij ⇥i ⇥j

Constitutive Law: Heat Flux
Tensorial order of “1” any Flux: J q ji
vector force may contribute. Force: F ⇥ ln T cRT
⇥i di ⇥v
n
cRT
q= Lqq ⇥ ln T Lqi di
i=1 i
Choose Lqq=λT to “Dufuor” effect - mass driving

obtain “Fourier’s Law” force can cause heat flux!
Usually neglected.
n
X Xn X n ✓ ◆
cRT D xi xj ji
T
jj here we have substituted
q= rT + hi j i + the RHS of the GMS
| {z } ⇥i Ðij ⇥i ⇥j
i=1 i=1 j6 = i equations for di.
Fourier | {z } | {z }
Species Dufour
Note: the Dufour effect
is usually neglected.
The “Species” term is typically included here, even though it does not come from
irreversible thermodynamics. Occasionally radiative terms are also included here...
Observations on the GMS Equations
n n
xi Jj xj Ji
di = ⇥ ln T xi xj T
ij
j=1
cDij j=1
n
⇥
⇤
cRT di = ci ⇥T,p µi + (⇤i ⌅i )⇥p ⌅ i ⇥ fi ⌅k fk
k=1
What have we gained? Onsager coefficients themselves

• Thermal diffusion (Soret/Dufuor) not too important from a
& its origins. “practical” point of view.
‣ Typically neglected. Still don’t know how to get the
• “Full” diffusion driving force binary diffusivities.
‣ Chemical potential gradient (rather than
mole fraction). More later.
‣ Pressure driving force.
‣ When will φi ≠ ωi? More later.
‣ Body force term.
‣ Does gravity enter here?

T&K §2.2
The Thermodynamic Factor, Γ ⇥

n
⇤
xi 1 i
di = ⇥T,p µi + (⇥i ⇤i )⇥p fi ⇤k fk
RT ct RT ct RT
k=1
µi = µi (T, p, xj ) n
xi xi ⌅1 ⇧µi
n
⇥1 µi T,p µi = xj ,
T,p µi = xj RT RT j=1
⇧xj T,p,
j=1
xj T,p,
P
n 1 γ - Activity coefficient
xi ⌅ ⇧ ln i xi Many models available
= RT xj ,
µi (T, p) = µi + RT ln i xi RT j=1 ⇧xj T,p, (see T&K Appendix D)
n 1
⇥ ⇤
⌅ ⇧ ln xi ⇧ ln i
= xi + xj ,
j=1
⇧xj ⇧xj T,P,
n 1
⇥ ⇤
⌅ ⇧ ln i
= ⇥ij + xi xj ,
j=1
⇧x j T,p,
⇤ ln i
ij ⇥ij + xi n
⌅1
⇤xj T,p,
= ij xj
j=1
n
⇥
⇤1 1
n
⇤
i Note: for p = c RT
di = ij ⇥xj + (⇥i ⇤i )⇥p fi ⇤k fk t
ct RT ct RT ideal gas,
j=1 k=1

T&K §2.3.3
Example: The Ultracentrifuge

Used for separating mixtures based on components’ molecular weight.
Consider a closed system...

depleted in
dense species
⌦
f = fi = 2
r
For a closed centrifuge (no flow) with a known

initial charge, what is the equilibrium species profile?
⇥ i steady, 1D, ni
Species equations: = ⇥ · ni + si no reaction r
=0
⇥t
ni = i vr + ji,r = 0 ji,r = Ji,r = 0
n
X xi Jj xj Ji
GMS Equations: di = =0
j=1
cDij
The generalized diffusion driving force: !
n
X1 n
X
1 ⇤i
di = ij rxj + (⇥i ⇤i )rp fi ⇤k fk
j=1
ct RT ct RT
k=1
n
!
X1 dxj 1 dp ⇤i
n
X
0= ij + (⇥i ⇤i ) ⇥2 r ⇤ k ⇥2 r
j=1
dr ct RT dr ct RT
k=1
n
X1 dxj 1 dp
ij = (⇤i ⇥i )
j=1
dr ct RT dr
For an ideal gas mixture, φi = xi, and Γij = δij.

dxi 1 dp We don’t know dp/dr or xi0
= ( i xi )
dr ct RT dr (composition at r = 0).

dxi 1 dp
= ( i xi )
dr ct RT dr
Species mole balance:
Z rL Z rL * indicates the
cxi 2 r dr = c⇤ x⇤i 2 r dr initial condition
(pure stream).
0 0
Z rL 2
r Must know p(r) and
For species i, p xi r dr = p⇤ x⇤i L
0 2 xi(r) to integrate this.
Species mole balance constrains the species profile solution

(dictates the species boundary condition)
n
X
⇤ v
Momentum: = ⇥ · ( vv) ⇥·⌧ ⇥p + ⇥i fi
⇤t i=1
n
X
at steady state dp
= ⇥i fr,i = 2
r The momentum equation
(no flow): dr i=1 gives the pressure profile,
but is coupled to the species
dp 2 pM 2 We don’t know p0 equations through M.
= r= r
dr RT (pressure at r = 0).

Total mole balance (at equilibrium):
Z Z
c dV = c⇤ dV * indicates the initial condition (pure stream).
V V
Z rL 2 p
r c=
cr dr = c⇤ L dV = L2 rdr
0 2 RT
Z rL 2
r
pr dr = p⇤ L Substitute p(r) and solve this for p0...
0 2
Total mole balance constrains the pressure solution
(dictates the pressure boundary condition)
Solve these dxi M dp pM 2

= ( i xi ) 2 r = 2
r= r Note: M couples all of the
equations: dr RT dr RT
Z rL Z rL equations together and
2 2
With these r r makes them nonlinear.
p xi r dr = p⇤ x⇤i L pr dr = p⇤ L
constraints: 0 2 0 2
Option A: Option B:
1. Guess xi0, p0. Try to simplify the problem
2. Numerically solve the ODEs for xi, p. by making approximations.
3. Are the constraints met? If not,
return to step 1.
Note: for tips on solving ODEs numerically in Matlab, see my wiki page.
Example: separation of Air into N2, O2.
• Centrifuge diameter: 20 cm • Air initially at STP
Approximation Level 1 Approximation Level 2

• Approximate M as constant, (MO2+MN2)/2, for
• Approximate M as constant,
the pressure equation only. This decouples the (MO2+MN2)/2, for the species
pressure solution from the species and gives an and pressure equations.
easy analytic solution for pressure profile.
• Obtain a fully analytic solution
• Solve species equations numerically, given the for both species and pressure.
analytic pressure profile.
0.25
1e1 1000 RPM 1,000 RPM
0.2
1
50,000 RPM
O2 Mole Fraction
50,000 RPM 0.15
100,000 RPM
p (atm)
1e−2
0.1
100,000 RPM
500,000 RPM
1e−4 150,000 RPM 0.05 numeric

fully numeric
constant M
approximate 1
approximate 2
0
0 0.02 0.04 0.06 0.08 0.1 0 0.02 0.04 0.06 0.08 0.1
r (m) r (m)

Fick’s Law (revisited)
⇤n ⇥ n
⇤
xi xj ji jj
di = ⇥ ln T xi xj T
ij
j=1
⇥Dij ⇤i ⇤j j=1
n
⇤ n
⇤
xj Ji xi Jj
=
cDij
⇥ ln T xi xj T
ij J= c[B] 1
(d) ⇥ ln T (DT )
j=1 j=1
⇥ This is the same [B] matrix as
n
⇤1 n
1 i
⇤ before (T&K eq. 2.1.21-2.1.22)
di = ij ⇥xj + (⇥i ⇤i )⇥p fi ⇤k fk
j=1
ct RT ct RT
k=1
Ignoring thermal diffusion,

⇥p
(J) = c[B] 1
[ ](⇥x) [B] 1
((⇥) (⇤)) [B] 1
[⇤] ((f ) [⇤](f + fn ))
⇤ ⇥ ⌅ RT
⇤ ⇥ ⌅ ⇤RT ⇥ ⌅
1
2 3
Notes: [D]=[B]-1[Γ]
For ideal mixtures: [Γ]=[I]
In the binary case: D11=Γ11Ð12
How do we interpret each term?

When is each term important?
Review:
Where we are, where we’re going…
Accomplishments Still Missing:
• Defined “reference velocities” and • Models for binary diffusivities.
“diffusion fluxes” ‣ Given a model, we are good to go!
• Governing equations for Roadmap:
multicomponent, reacting flow.
• Models for binary diffusivities.
‣ mass-averaged velocity…
(T&K Chapter 4) - we won’t
• Established a rigorous way to cover this...
compute the diffusive fluxes from
• Simplified models for
first principles.
multicomponent diffusion
‣ Can handle diffusion in systems of
arbitrary complexity, including: • Interphase mass transfer (surface
‣ nonideal mixtures, EM fields, large pressure discontinuities)
& temperature gradients, multiple species,
chemical reaction, etc.
• Turbulence - models for diffusion
in turbulent flow.
• Simplifications for ideal mixtures,
negligible pressure gradients, etc. • Combined heat, mass, momentum
transfer.
• Solutions for “simple” problems.

Entropy GMS IrrevThermo PDF

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GMS Equations From

Monday, February 27, 12 1

Entropy, Entropy transport

Monday, February 27, 12 2

Total (substantial/material) derivative:

Monday, February 27, 12 4

Monday, February 27, 12 5

Monday, February 27, 12 7

Interpretation of each term???

Monday, February 27, 12 8

Fluxes are functions of: J = J (F1 , F2 , . . . , F⇥ ; T, p, i )

‣ More soon… Lαβ - Onsager (phenomenological) coefficients

Monday, February 27, 12 9

Index form: n-1 dimensional matrix form

Generalized Maxwell-Stefan Equations:

Monday, February 27, 12 10

Choose Lqq=λT to “Dufuor” effect - mass driving

What have we gained? Onsager coefficients themselves

Monday, February 27, 12 12

The Thermodynamic Factor, Γ ⇥

Monday, February 27, 12 13

Example: The Ultracentrifuge

Consider a closed system...

For a closed centrifuge (no flow) with a known

ni = i vr + ji,r = 0 ji,r = Ji,r = 0

For an ideal gas mixture, φi = xi, and Γij = δij.

Monday, February 27, 12 15

Species mole balance constrains the species profile solution

Monday, February 27, 12 16

Solve these dxi M dp pM 2

Approximation Level 1 Approximation Level 2

1e−4 150,000 RPM 0.05 numeric

Monday, February 27, 12 18

Ignoring thermal diffusion,

How do we interpret each term?

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