Predicting Fick- and Maxwell-Stefan diffusivities

in liquids
Thijs J.H. Vlugt
Professor and Chair Engineering Thermodynamics
Delft University of Technology, The Netherlands
t.j.h.vlugt@tudelft.nl,

http://homepage.tudelft.nl/v9k6y
August 13, 2012

Fluid Phase Equilibria, 2011, 301, 110-117.

Chem. Phys. Lett., 2011, 504, 199-201.
J. Phys. Chem B, 2011, 115, 8506-8517.
J. Phys. Chem B, 2011, 115, 10911-10918.
J. Phys. Chem B, 2011, 115, 12921-12929.
Ind. Eng. Chem. Res., 2011, 50, 4776-4782.
Ind. Eng. Chem. Res., 2011, 50, 10350-10358.

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Collaborators

Xin Liu (RWTH Aachen University, Delft)

Sondre K. Schnell (Delft)
Andre Bardow (RWTH Aachen University, Delft)
Signe Kjelstrup (NTNU, Delft)
Dick Bedeaux (NTNU, Delft)
Jean-Marc Simon (Dijon)

Thijs J.H. Vlugt

[1]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

(Empirical) Fick formulation for multicomponent diffusion

Ji = ct

n1
X
k=1

Dik xk

n components, (n 1)2 Fick diffusivities

Pn

i=1 Ji

=0

(molar reference frame)

Dij 6= Dji for n > 2

Dij strongly dependent on the mole fractions x1 xn
Dij can become negative for n > 2
multicomponent Dij unrelated to binary counterpart
R. Krishna and J.A. Wesselingh, Chem. Eng. Sci., 1997, 52, 861-911.

[2]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Maxwell-Stefan formulation at constant T, p

di =

n
n
X
X
xii
xiJj xj Ji
xixj (uj ui)
=
=
RT
Dij
ct
Dij

j=1,j6=i
j=1,j6=i

Ji = uici = uixict
n
X
i=1

xii = 0

Gradient in chemical potential as driving force di

n components, n(n 1)/2 MS diffusivities,
Dij > 0

Dij =
Dji

(Onsagers reciprocal relations)

Dij is less composition dependent than Fick diffusivities
Possibility to predict
Dij using theory...

[3]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Diffusion coefficients depend on concentration!

(a)

10

C2mimCl-H2O
H2O-C2mimCl
C4mimCl-H2O
H2O-C4mimCl

IL /(10

-9

-1

m s )

H2O-C8mimCl
C8mimCl-H2O

0.1

0.01
0.0

0.2

0.4

0.6

x CnmimCl

0.8

1.0

[4]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Vignes equation in ternary systems

Dij

xj 1 xj
x 1 xk
xi 1 xi
Dijk )
Dij ) (
(
Dij ) (

Recommended in chemical engineering

Is it any good?
x 1

What about
Dijk

? Models for this in literature:

q
xj 1 xi 1
D
Dij
ij
q
xk 1 xk 1
D
Djk
ik
j
i
 x x+x
 x x+x


xk 1
x
1
i
j
i
j
Dik
Djkk

xi
xj
xk 1
xk 1
D
+
D
xi + xj ik
xi + xj jk

x 1

x 1

x 1

x 1

x 1

= (
Dikk

WK (1990)

Dijk

KT (1991)

Dijk

VKB (2005)

Dijk

DKB (2005)

Dijk

RS (2007)

Dijk

x 1

x 1

Djkk

x 1

Dijj

xi 1 1/4
Dij
)

[5]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[6]

(Open?) Questions
Is the quality of Vignes increased/decreased by a particular model choice for
xk 1
D
?
ij
x 1

Which of the predictive models for

Dijk
(if any...)
x 1

VKB and DKB suggest that

Dijk
the ratio xi/xj . Is this correct?
x 1

WK (1990)

k
D
ij

KT (1991)

k
D
ij

x 1

x 1

VKB (2005)

k
D
ij

DKB (2005)

k
D
ij

RS (2007)

k
D
ij

x 1

x 1

is best for a certain system?

does not exist, i.e. its value depends on

r

x 1

x 1

j
i
D
ij D
ij
q
xk 1 xk 1
D
ik D
jk


 xj
 xi 
xk 1 xi +xj
xk 1 xi +xj
D
D
ik
jk

xj
xi
xk 1
xk 1
D
+
D
ik
jk
xi + xj
xi + xj

k
(D
ik

x 1

x 1

k
D
jk

x 1

j
D
ij

x 1 1/4

i
D
ij

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Obtaining Maxwell-Stefan diffusivities from MD

ij

1
1
lim
6N m m t

1
3N

dt

*N
i
X
l=1

* N
i
X
(rl,i(t + m t) rl,i(t))
l=1

Nj

k=1

vl,i(0)

(rk,j (t + m t) rk,j (t))

Nj

k=1

vk,j (t)

Note: ij = ji (Onsager)
Krishna & Van Baten, Ind. Eng. Chem. Res., 2005, 44, 6939-6947.

[7]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Obtaining ternary Maxwell-Stefan diffusivities from MD

D
12

B
A + (x1 + x3 )
C
x1 D

2
11 23 x2 12 x3 21 + 11 x3 22 11 x3 x2 22 + 11 23 x2 11 x3 x2 32
2
2
2
+11 33 x2 13 x1 22 x1 x3 11 22 + 13 22 x1 x1 31 x3 22 + 33 x1 22
2
+12 23 x1 + 12 x3 x2 21 + 13 x1 x2 22 + 12 x3 31 x2 + 13 x2 21 13 x2 21
2
2
2
13 x2 31 + x1 12 x3 21 x1 12 23 + x1 32 x3 21 x1 32 23 + 13 x1 x2 32
+x1 11 23 x2 + x1 31 23 x2 12 x1 23 x2 12 x1 33 x2 x1 13 x2 21
x1 33 x2 21

12 x3 13 x2 x1 x3 12 + x1 x2 23 x1 x3 32 + x1 x2 33

2
11 23 x2 12 21 x3 + x3 11 22 x2 x3 11 22 + 11 23 x2 x2 x3 11 32
2
2
2
+11 33 x2 13 22 x1 x1 x3 11 22 + x1 13 22 x1 x3 31 22 + x1 22 33
2
+x1 12 23 + x2 x3 12 21 + x1 x2 13 22 + x2 x3 12 31 + x2 13 21 x2 13 21
2
2
2
x2 13 31 + x1 x3 12 21 x1 12 23 + x1 x3 32 21 x1 32 23 + x1 x2 13 32
+x1 x2 11 23 + x1 x2 31 23 x1 x2 12 23 x1 x2 12 33 x1 x2 13 21
x1 x2 33 21

3
2
2
22 x3 23 x2 22 x3 x2 + 23 x2 x2 12 x3 + 13 x2 x2 32 x3 + 33 x2

[8]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[9]

Limit when xk 1 (1)

ii

=
kk

ij,j6=i

1
3N

dt
0

Ni
X
l=1

vl,i(0)

Ni
X

+
vg,i(t)

g=1

Z
Ni
dt hvi,1(0) vi,1(t)i
3N 0
xiCii
+
Nk
Nk
Z *X
X
1
vg,k (t)
dt
vl,k (0)
3N 0
g=1
l=1
1
3N

dt
0

*N
k
X
l=1

+
vl,k (0) vl,k (t)

1
3N

xk Ckk + xk N Ckk
+
Nj
Ni
Z *X
X
1
dt
vl,i(0)
vk,j (t)
3N 0
l=1
k=1
Z
NiNj
dt hv1,i(0) v1,j (t)i
3N 0
N xixj Cij

dt
0

*N
Nk
k
X
X
l=1 g=1,g6=l

+
vl,k (0) vg,k (t)

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[10]

Limit when xk 1 (2)

Set a = xj /xi and xk = 1 xi xj , fill in the equations for ii, jj , kk , ij ,
ik , jk and take the limit xk 1
Final result (after a lot of math):

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[11]

Limit when xk 1 (2)

Set a = xj /xi and xk = 1 xi xj , fill in the equations for ii, jj , kk , ij ,
ik , jk and take the limit xk 1
Final result (after a lot of math):
x 1

x 1

Dijk

x 1

k
k
Di,self
Dj,self

x 1

k
Dk,self
+ Cx

?
Cx = N (Cij Cik Cjk + Ckk
)

which is independent of xj /xi !! (Note: Cx converges to a finite value when

N ).
When cross-correlation are neglected:
x 1

x 1

Dijk

x 1

k
k
Di,self
Dj,self

x 1

k
Dk,self

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Ternary system of WCA particles that only differ in mass

x 1

Prediction
MD b
AD a
Prediction
MD c
AD a
Prediction
MD d
AD a
Prediction
MD e
AD a
a

incl. Cx
1.401
1.411
1%
0.310
0.318
2%
3.344
3.348
0%
0.172
0.172
0%

3
MS diffusivity D
12
Cx = 0
WK
KT
1.441
1.296
0.952
1.411
1.411
1.411
2%
8%
32%
0.315
0.390
0.248
0.318
0.318
0.318
1%
23%
22%
3.288
1.296
0.682
3.348
3.348
3.348
2%
61%
80%
0.161
0.389
0.101
0.172
0.172
0.172
7%
126% 42%

VKB
0.952
1.411
32%
0.248
0.318
22%
0.682
3.348
80%
0.101
0.172
42%

DKB
0.952
1.411
32%
0.248
0.318
22%
0.683
3.348
80%
0.101
0.172
42%

absolute difference normalized with corresponding value from MD simulations

= 0.2; M1 = 1; M2 = 1.5; M3 = 5; x1/x2 = 1; x3 = 0.95; T = 2
c
= 0.5; M1 = 1; M2 = 1.5; M3 = 5; x1/x2 = 1; x3 = 0.95; T = 2
d
= 0.2; M1 = 1; M2 = 1.5; M3 = 100; x1/x2 = 1; x3 = 0.95; T = 2
e
= 0.5; M1 = 1; M2 = 1.5; M3 = 100; x1/x2 = 1; x3 = 0.95; T = 2
b

RS
1.111
1.411
21%
0.311
0.318
2%
0.940
3.348
72%
0.198
0.172
15%

[12]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Increasing the mass of the solvent (M3)

1000

rho
0.1
== 0.1
rho
0.2
== 0.2
rho
0.3
== 0.3
rho
0.4
== 0.4
rho
0.5
== 0.5

12

100

10

0.1
1

10

100

1000

M3
x 1

x 1

k
D
ij

x 1

k
k
Di,self
Dj,self
x 1

k
Dk,self

10000

[13]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[14]

(1) n-hexane / (2) cyclohexane / (3) toluene

x1 1b
x2 1c
x3 1d
a

MS Diffusivity/(109 m2s1)
x 1
MD simulation
Prediction of
Dijk
D23
incl. Cx ADa Cx = 0

4.07
4.12
1%
3.78
D13
incl. Cx ADa Cx = 0

2.19
2.21
1%
2.69
incl. Cx ADa Cx = 0
D12

2.99
2.93
2%
2.82

ADa
7%
ADa
23%
ADa
6%

absolute difference normalized with corresponding value from MD simulations

b
598 n-hexane molecules; 1 cyclohexane molecule; 1 toluene molecule
c
1 n-hexane molecule; 598 cyclohexane molecules; 1 toluene molecule
d
1 n-hexane molecule; 1 cyclohexane molecule; 598 toluene molecules
298K, 1 atm.

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[15]

(1) ethanol / (2) methanol / (3) water

x 1

Prediction of
D23
MD b
AD a
Prediction of
D13
MD c
AD a
Prediction of
D12
MD d
AD a

incl. Cx
2.68
2.68
0%
3.17
3.24
2%
5.01
4.76
5%

Dijk /(109 m2s1)

Cx = 0 WK
KT
VKB
1.57
2.07
1.25
1.25
2.68
2.68
2.68
2.68
41%
23% 53% 53%
2.07
1.20
2.04
2.04
3.24
3.24
3.24
3.24
36%
63% 37% 37%
1.06
1.78
1.72
1.72
4.76
4.76
4.76
4.76
78%
63% 64% 64%

DKB
1.32
2.68
51%
2.06
3.24
37%
1.73
4.76
64%

RS
1.61
2.68
40%
1.56
3.24
52%
1.75
4.76
63%

absolute difference normalized with corresponding result from MD simulations

b
168 ethanol molecules; 1 methanol molecule; 1 water molecule
c
1 ethanol molecule; 248 methanol molecules; 1 water molecule
d
1 ethanol molecule; 1 methanol molecule; 598 water molecules
298K, 1 atm. Lennard-Jones+electrostatics (Ewald summation)

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[16]

Consistent multicomponent Darken

Darken equation for a binary system (1945)
Dij = xiDj,self + xj Di,self

Generalized Darken for multicomponent system (empirical)

xi
xj
D
=
D
+
ij x + x j,self x + x Di,self
i
j
i
j
Multicomponent Darken (Ind. Eng. Chem. Res., 2011, 50, 10350-10358.)
Dij = Di,self Dj,self

n
X
i=1

xi
Di,self

derived by assuming that velocity cross-correlations are much smaller than

velocity self-correlations
for n = 2, multicomponent Darken reduces to binary Darken
x 1

for a ternary system for xk 1, our equation for

Dijk

is recovered

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Converting Fick and Maxwell-Stefan diffusivities

Fick
[Dij
] = [Bij ]1[ij ]

n
X
xi
xj
Bii =
+
D
Dij
in j=1,j6=i
!
1
1

Bij = xi
D
Din
ij

ij = ij + xi

lni
xj

T,p,

Fick
Note: molar reference frame for [Dij
]

with i = 1, , (n 1)
with i, j = 1, , (n 1) i 6= j

[17]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Obtaining Fick diffusivities (1)



ln 1
x1

p,T

c2 (G22 + G11 2G12)

1 + c2x1 (G22 + G11 2G12)

hNN i hNihN i

hNihN i
c
Z
 V T
 2
g (r) 1 r dr
= 4
0
Z
 NV T
 2
g (r) 1 r dr
4
= v

with c = hNi /v and h i denotes an average in the V T ensemble

G : Total Correlation Function Integral (TCFI)
Kirkwoord and Buff, J. Chem. Phys., 1951, 19, 774-778.

[18]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Obtaining Fick diffusivities (2)

1

[g(r) 1] r2dr

Rr

2
3

4
0

= 1, = 1
= 2, = 2
= 1, = 2

8
r/[]

10

12

14

[19]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Obtaining Fick diffusivities (3)

Thijs J.H. Vlugt

[20]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Obtaining Fick diffusivities (4)

periodic

non-periodic

[21]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Obtaining Fick diffusivities (5)

Thijs J.H. Vlugt

[22]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Obtaining Fick diffusivities (6)

0.0
0.5

1.0
1.5
2.0
= 1, = 1
= 2, = 2
= 1, = 2

2.5
3.0
0.0

0.1

0.2
0.3
1/L/[1/]

0.4

0.5

[23]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Obtaining Fick diffusivities (7)

Lt/[]
10

20

30

40

11
22
12
11
22
12
11
22
12
11
22
12

R/[]
4.503

5.000

6.023

6.027

from g(r)
-0.977
-1.633
-0.275
-1.508
-2.456
-0.429
-1.552
-2.577
-0.428
-1.574
-2.555
-0.455

new method
-1.601
-2.686
-0.440
-1.594
-2.601
-0.464
-1.600
-2.602
-0.461
-1.600
-2.621
-0.463

[24]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Acetone-tetrachloromethane (1)
1.1
Thiswork,
work 298K
(MD)
this

1.0

Experiments298K
experiment,

0.9

0.8
0.7
0.6
0.5
0.4
0.0

0.2

0.4

0.6

x1
298K, 1atm

0.8

1.0

[25]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Acetone-tetrachloromethane (2)

this
Thiswork
work
exp
- Hardt et al
Experiments
exp
- Babb et al
Experiments
Darken
+ LBV
Prediction
by Eqs. (8, 17, 18)

4
3

D Fick / (10

-9

m 2 s -1 )

2
1
0
0

298K, 1atm

0.2

0.4

x1

0.6

0.8

[26]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

Chloroform(1)-Acetone(2)-Methanol(3) (x2 = x3)

298K, 1atm

[27]

Predicting Fick- and Maxwell-Stefan diffusivities in liquids

Thijs J.H. Vlugt

[28]

Conclusions

Transport diffusion coefficients depend on concentration

Molecular Dynamics and theory are useful tools for developing predictive models
for calculating transport diffusivities
A consistent multicomponent Darken equation was developed
A new way was found for computing ij from Molecular Dynamics simulations,
thereby bridging the gap between experiments and simulations