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Fick's Law: A Derivation

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Introduction
Fick’s law is a special case of the governing equation for the diffusion velocity, u A . Even though the
governing equation for u A is not well known, Fick’s law is something that everyone knows. This can be
demonstrated by the opening lines of a paper by Onsager (1945) where one finds:

“Diffusion in a liquid system of two components is governed by Fick’s law1

Ji = − D∇ci (i = 1, 2) (1)

where c1 , c 2 denote the concentrations per unit volume, and J1 , J 2 the flows in
corresponding units.”
1. Fick, A. Pogg. Ann. 94:59 1855.

Analysis
Our derivation of Eq. 1 begins with the fundamental axiom for the mass of species A that can be
expressed in the form (Whitaker, 2012, Figure 2; Truesdell and Toupin, 1960, Sec. 159)
∂ ρA .(ρ A v A )
+ ∇= r=
A , A 1, 2,..., N (2)
∂t
while the supplemental axiom is given by
A= N

∑A =1
rA = 0 (3)

Equation 2 is often referred to as the species continuity equation and it can be used to derive the total
continuity equation. This is obtained by summing Eq. 2 over all species in order to obtain
∂ρ
+ ∇. (ρv ) = 0 (4)
∂t
in which ρ and v are defined by
=A N=A N

=A 1=A 1
ρ =
∑ ρA , v =
∑ ωAv A , ωA = ρA ρ (5)

The species velocity, v A can be decomposed into the mass average velocity, v , and the mass diffusion
velocity, u A , according to
vA = v + uA , A = 1, 2,..., N (6)
Use of this representation in Eq. 2 leads to
∂ ρA
+ ∇. (ρ A v ) = ∇. (ρ Au A ) + rA , A = 1, 2,..., N (7)
∂t
The molar form of this result is obtained by the use of
Page 1
 =ρA cA =
MA , rA R A=
MA , A 1, 2, ..., N (8)
which leads to the following versions of Eqs. 2 and 3
∂ cA
+ ∇. (c A v ) = ∇. J A + RA , A = 1, 2,..., N (9)
∂t
=JA =
cA u A , A 1, 2,..., N (10)
A= N

∑A =1
RA M A = 0 (11)

In order to determine the diffusion velocity, u A , we need the governing differential equation for u A which
is developed in the following paragraphs. Here we should keep in mind that our objective is to obtain a
representation for the diffusive flux, J A , that leads to what Onsager (1945) identified as Fick’s law.
The two fundamental axioms for the laws of continuum mechanics (linear and angular momentum)
can be expressed as (Whitaker, 2009b; Truesdell and Toupin, 1960, Sec. 215)
B=N
∂
∂t
(ρ Av A ) + ∇ ⋅ (ρ Av Av A ) = ρ Ab A + ∇ ⋅ TA +
∑B =1
PAB + rA v∗A (12)

= =
T
TA TA , A 1, 2, ..., N (13)
The two supplemental axioms were given by Whitaker (2009b) in the form
=A N=B N

=
∑∑
A 1=B 1
PAB = 0 (14a)

A= N

∑A =1
rA v∗A = 0 (14b)

however, Truesdell and Toupin (1960, Eq. 215.5) and Truesdell (1969, Eq. 5.12) state these two
supplemental axioms as a single supplemental axiom given by
=A N=B N =A N

=
∑∑
A 1=B 1
PAB +
=
∑
A 1
rA v∗A =
0 (15)

In the absence of any experimental verification of Eqs. 14, it seems prudent to accept Eq. 15 as opposed
to the more restrictive form given by Eqs. 14; however, both representations lead to the same result in this
analysis.

Page 2
 The total linear momentum equation is obtained by summing Eq. 12 over all species and imposing the
two supplemental axioms given by Eqs. 14 or the single supplemental axiom given by Eq. 15. This leads
to
A= N
∂
∂t
(ρ v ) + ∇ ⋅ (ρ v v ) = ρ b + ∇ ⋅ T − ∇.
∑
A =1
ρA u A u A (16)

in which the following definitions have been employed

=A N=A N=A N

=A 1 =A 1=
ρv =
A 1
∑ ρA v A , ρb=
∑ ρA b A , T=
∑ TA (17)

Our objective at this point is to use Eqs. 12 and 16 to obtain the governing equation for the diffusion
velocity, u A . We begin with the following representation for the species A stress tensor

TA =− p A I + τ A , A =1, 2,..., N (18)

in which p A is the partial pressure defined by

pA = ρ2A ( ∂ e A ∂ ρ A ) s , ρ , A = 1, 2,..., N (19)

B , ρC ,..., ρ N

Here eA represents the internal energy of species A per unit mass (Whitaker, 2017). The total stress
tensor is given by the sum of Eqs. 18 that takes the form
T = − pI + τ (20)
in which the following definitions have been used
=A N=A N=A N

=T
=A 1=A 1=A 1
=
∑
TA , p =
∑
pA , τ
∑τ A (21)

The total pressure is also defined by

p = ρ2 ( ∂e ∂ρ ) s , ρ (22)
B , ρC ,..., ρN

in which e is the total internal energy per unit mass (Whitaker, 1977). This representation for the total
pressure requires that
A= N

ρ ( ∂e ∂ρ ) s , ρ
2
=
B , ρC ,..., ρN ∑A =1
ρA2 ( ∂ e A ∂ ρA ) s , ρ
B , ρC ,..., ρN
(23)

and the proof of this result is given by Whitaker (2009b, Appendix B).
It is important to recognize that the application of Eqs. 18 and 20 requires an assumption of local
thermodynamic equilibrium (Batchelor, 1967, Sec. 3.4), and this should be satisfactory for many, but not
all, mass transfer processes.

Page 3
Diffusion Velocity
Our next step in the derivation of Eq. 1 requires the development of the governing equation for the
mass diffusion velocity, u A . We begin by multiplying Eq. 2 by the species velocity to obtain

 ∂ρ 
vA  A =+ ∇ ⋅ (ρ A v A )  =
rA v A , A 1, 2, ...., N (24)
 ∂t 
and then subtract this equation from Eq. 12 to obtain
B=N
 ∂ vA
ρA 
 ∂t

+ v A ⋅∇v A  =

ρ Ab A + ∇ ⋅ TA +
∑B =1
(
PAB + rA v∗A − v A ) (25)

Next we multiply Eq. 4 by the mass average velocity to obtain

∂ρ 
v + ∇. (ρv )  = 0 (26)
 ∂t 
and then subtract this equation from Eq. 16 to obtain
A= N
 ∂v
ρ
 ∂t

+ v.∇v  =

ρ b + ∇ ⋅ T − ∇.
∑A =1
ρ Au Au A (27)

Multiplication of this result by the mass fraction, ω A , and the use of the first of Eqs. 21 leads to

A = N 
 ∂v
ρA 
 ∂t

+ v ⋅∇v  =


ρ Ab + ω A∇ ⋅ 
∑
 A = 1
( TA − ρ Au Au A )

(28)

We now subtract this result from Eq. 25 to obtain the desired governing differential equation for u A given
by
 ∂u 
ρ A  A + v A ⋅∇u A + u A ⋅∇v  = ρ A (b A − b)
 ∂t 

A = N 
+ ∇ ⋅ TA 
− ω A∇ ⋅ 
∑
 A = 1
( TA − ρ Au Au A )

(29)

B=N

+
∑
B =1
(
PAB + rA v∗A − v A , ) A = 1, 2,..., N − 1

Page 4
We now make use of the proposal given by Eq. 18 along with the definitions given by Eqs. 21 to obtain
the following form of the governing equation for the diffusion velocity
 A= N 
 ∂u A
ρA 
 ∂ t

+ v A ⋅∇u A + u A ⋅∇v  − ω A∇ ⋅



 A=1
∑ρ Au Au A  =


− ( ω A∇ ⋅ τ − ∇ ⋅ τ A )

(30)
B= N

− ∇p A + ω A∇p + ρ A (b A − b) +
∑
B =1
(
PAB + rA v∗A − v A )
Simplification of this result has been explored by Whitaker (1986, pages 9-17; 2009a, Secs. 2.6 & 2.7)
using order of magnitude estimates. Such estimates suggest but do not confirm the conditions necessary
for the simplification of Eq. 30, and more detailed studies would be welcome. A plausible set of
restrictions (Whitaker, 2009b, Sec. 1.2) is given by
∂u A
R1. ρA << ∇p A (31a)
∂t

R2. ρ A ( v A ⋅ ∇u A + u A ⋅ ∇v ) << ∇p A (31b)

A= N

R3. ω A∇ ⋅
∑
A =1
ρ Au Au A << ∇p A (31c)

R4. ( ωA∇ ⋅ τ − ∇ ⋅ τ A ) << ∇p A (31d)

R5. (
rA v∗A − v A ) << ∇p A (31e)

Here R1, R2, etc. refer to restrictions that can lead to constraints (Whitaker, 1988) if reliable estimates of
the terms are available. Some examples of constraints are given by Whitaker (1986). When these five
restrictions are imposed on Eq. 30, and we accept the plausible assumption that small causes give rise to
small effects (Birkoff, 1960), we obtain
B=N

∇p A − ω A∇p − ρ A (b A=
− b)
∑
B =1
PAB , =A 1, 2,..., N − 1 (32)

Truesdell (1962, Eq. 7) represents the left-hand side of this result by p d A and cites Hirschfelder, Curtiss
& Bird (1954) as the source. Curtiss & Bird (1999, Eq. 7.6) represent the left hand side of
Eq. 32 by cRT d A and refer to it as the generalized driving force for diffusion.
At this point we dispense with all electrical effects (del Río and Whitaker, 2016) as indicated by
R6. ρ A (b A − b) << ∇p A (33)

and we assume that ω A∇p can be neglected on the basis of

Page 5
R7. ω A∇p << ∇p A (34)
Imposing these two restrictions on Eq. 32 leads to
B=N

∇p =
A ∑
B =1
PAB , =
A 1, 2,..., N − 1 (35)

For ideal gas and liquid mixtures, the partial pressure can be expressed as
pA = xA p (36)
If we impose the restriction given by
R8. p∇x A >> x A∇p (37)
we can express Eq. 35 in the form
B=N

∇x=
A ∑
B =1
p −1PAB , =
A 1, 2,..., N − 1 (38)

From dilute gas kinetic theory, we know that PAB gas

is given by

x A xB
Ideal gas mixture: PAB = pgas (vB − v A ) , A =1, 2,..., N − 1 (39)
gas DAB
This result can be obtained by comparing Eq. 32 of this work with Eqs. 7.3-27 and 7.4-48 of Hirschfelder,
Curtiss and Bird (1954) and neglecting the effect of thermal diffusion. At this point we need a
representation for PAB liq , and one possibility is to use Eq. 39 as a model. This leads to

x A xB
Ideal liquid solution: PAB liq
= pliq ( vB − v A ) , A =1, 2,..., N − 1 (40)
DAB
where it is understood that all the terms on the right side are associated with a liquid solution. It should
be clear that Eq. 40 represents an empirical expression for the diffusive force, PAB liq , and that DAB
represents an empirical coefficient to be determined by experiment.

Binary Liquid Systems

Binary systems are often used to introduce the phenomena of diffusion, and we will follow that
approach here. For a binary system, Eqs. 38 and 40 take the form
x A xB ( v B − v A )
0 = − ∇x A + (41)
DAB
and we think of this as the governing differential equation for v A . The value of v B is available from a
solution for v and v A which can be used in the second of Eqs. 5 to obtain

Page 6
 1
=
vB ( v − ω Av A ) (42)
ωB
For a binary system, the two mass continuity equations are given by Eqs. 7 that we repeat here as
∂ρ A
+ ∇ ⋅ (ρ Av ) = − ∇ ⋅ (ρ Au A ) + rA (43a)
∂t
∂ ρB
+ ∇. (ρ B v ) = − ∇. (ρ B u B ) + rB (43b)
∂t
We need to determine u A , u B and v in order to solve these equations. Given the form of Eqs. 43 it will
be convenient to express Eq. 41 in terms of mass diffusion velocities, and the use of Eq. 6 leads to
x A xB (u B − u A )
0 = − ∇x A + (44)
D AB

For a binary system, Eqs. 5 and 6 provide

ω Au A + ωB u B = 0 (45)
and this can be used in Eq. 44 to obtain
1 x A xB
0 = − ∇x A − (ω Au A ) (46)
DAB ω AωB
Multiplying and dividing the second term by the total density allows us to express this result as
1 x A xB
0 = − ∇x A − (ρ Au A ) (47)
ρDAB ω AωB
Here we have a mixed-mode representation in which the mass diffusive flux, ρ Au A , is expressed in terms
of the gradient of the mole fraction, ∇x A , along with the mixed-mode term, x A xB ω AωB .
At this point we need to make use of the following representations for the mass fraction, the mole
fraction, and the mean molecular mass. These are given by
ω A =ρ A ρ , x A =c A c , M =x A M A + xB M B (48a)

ωB =ρ B ρ , xB =cB c , M =xB M B + x A M A (48b)

in which M A represents the molecular mass of species A and M B represents the molecular mass of
species B . In addition to these results, we make use of
cA =
ρA M A , cB =
ρB M A , c =
ρ M (49)
to obtain the following relations between the mole fractions and the mass fractions

=
xA
cA
=
cAM
=
(ρ A MA)M
=
M
ωA (50a)
c ρ ρ MA

Page 7
 =
xB
cB
=
cB M
=
(ρB MB )M
=
M
ωB (50b)
c ρ ρ MB
Next we make use of the following relations
1 ωA ω
∇x A = − ∇x B , ωB = 1 − ω A , = + B (51)
M MA MB
along with several algebraic steps to arrive at
M2
=
∇x A ∇ω A (52)
M AM B
Substitution of this expression for the gradient of the mole fraction of species A into Eq. 47 leads to
M2 1 x A xB
0 = − ∇ω A − (ρ Au A ) (53)
M AM B ρDAB ω AωB
From Eqs. 50 we see that
x A xB M2
= (54)
ω AωB M AM B
and Eq. 53 simplifies to
jA = ρ Au A = − ρDAB ∇ω A (55)
This result can be used with the first of Eqs. 49 to obtain
ρ Au A = (c Au A ) M A = − ρDAB ∇ω A (56)
If we assume that the density is constant
A1. ρ =constant (57)
Eq. 56 can be used to obtain the following result
(c Au A ) =− DAB ∇ ( ρω A M A ) =− DAB ∇c A (58)

We now make use of Eq. 10 to obtain the classic form of Fick’s law given by Onsager (1945) for a binary
liquid system
Fick’s law: JA =− DAB ∇c A (59)
Use of this result in Eq. 9 leads to
∂cA  ρ =constant
+ ∇ ⋅ (c A v ) = ∇ ⋅ ( DAB ∇c A ) + RA ,  (60a)
∂t  binary system
while the analysis for species B leads to the analogous result given by
∂ cB  ρ =constant
+ ∇ ⋅ (cB v ) = ∇ ⋅ ( DAB ∇cB ) + RB ,  (60b)
∂t  binary system

Page 8
Rather than accept this result on the basis of the assumption given by Eq. 57, it would be better to impose
the restriction given by
R9. ω A∇ρ << ρ∇ω A (61)
This reminds us that there is a constraint (Whitaker, 1988) associated with Eqs. 60 that has yet to be
developed. The multi-component version of Eq. 60 is given elsewhere (Whitaker, 2009b, Sec. 6.3) and it
is limited by the multi-component version of Eq. 61.

Conclusions
In this note we have derived Fick’s law for a binary liquid system. The derivation is based on the
axiomatic statements for the species mass and momentum of a binary system. These mass-based
quantities provide a rigorous foundation for the mole-based species transport equations that dominate the
analysis of processes involving convection, diffusion and chemical reaction.

Nomenclature
bA body force per unit mass exerted on species A, N/kg
b body force per unit mass exerted on the mixture, N/kg
cA molar concentration of species A, moles/m3
c total molar concentration, moles/m3
DAB DBA , gas-phase binary diffusion coefficient for species A and B, m2/s

DAB DBA , liquid-phase binary diffusion coefficient for species A and B , m2/s
eA internal energy of species A per unit mass, kcal/kg
A= N

e
∑A =1
ω A eA , total internal energy per unit mass, kcal/kg

g gravitational body force per unit mass, N/kg

I unit tensor
jA ρ Au A , mass diffusive flux of species A, kg/ m2s
JA c Au A , mixed-mode diffusive flux of species A, moles/ m2s
MA molecular mass of species A, g/mole
M x A M A + xB M B , mean molecular mass of a binary mixture, g/mole
N number of molecular species
PAB force per unit volume exerted by species B on species A, N/m3

Page 9
 A= N

p
∑A =1
p A , total pressure, N/m2

pA partial pressure of species A, N/m2

rA net mass rate of production of species A owing to homogeneous reactions, kg/m3s
RA net molar rate of production of species A owing to homogeneous reactions, moles/m3s
t time, s
TA stress tensor for species A, N/m2
A= N

T
∑A =1
TA , total stress tensor for the mixture, N/m2

uA v A − v , mass diffusion velocity, m/s

vA velocity of species A, m/s
A= N

v
∑A =1
ω A v A , mass average velocity, m/s

v∗A velocity associated with the net rate of production of species A momentum owing to chemical
reaction, m/s
xA c A / c , mole fraction of species A

Greek Letters
ρA mass density of species A, kg/m3
ρ total mass density, kg/m3
µ viscosity, N/m2s
τ viscous stress tensor, N/m2
τA viscous stress tensor for species A, N/m2
ωA ρ A / ρ , mass fraction of species A

References
Birkoff, G. 1960, Hydrodynamics, A Study in Logic, Fact, and Similitude, Princeton University Press.

Batchelor, G.K. 1967, An Introduction to Fluid Mechanics, Cambridge University Press.

Page 10
 Bird, R.B., Stewart, W.E. and Lightfoot, E.N. 2002, Transport Phenomena, Second Edition, John Wiley
and Sons, Inc., New York.

Curtiss, C.F. and Bird, R.B. 1999, Multicomponent diffusion, Ind. Eng. Chem. Res. 38, 2515-2522.

del Río, J. A. and Whitaker, S. 2016, Diffusion of charged species in liquids, Scientific Reports, 6, 35211.

Hirschfelder, J.O., Curtiss, C.F. and Bird, R.B. 1954, Molecular Theory of Gases and Liquids, John Wiley
& Sons, Inc.

Onsager, L. 1945, Theories and problems of liquid diffusion, Ann. N.Y. Acad. Sci. 46, 241-265.

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Truesdell, C. 1969, Rational Thermodynamics, McGraw-Hill Book Company.

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