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• Directional Quantity
DC/ Dx dC/dx
DC
c
Dx J D - Fick’s first law
x
ey Jy
D=D0exp(-Qd/RT)
Jx here Q is the activation energy for the process: [J/mol];
Jz
ex Do is temperature-independent pre-exponential
ez constant: [m2/s]
NONSTEADY-STATE DIFFUSION
Example: diffusion from a finite volume through a membrane into a finite volume.
The pressures in the reservoirs involved change with time as does,
consequently, the pressure gradient across the membrane.
FICK’s SECOND LAW
Consider a volume element (between x and
x+dx of unit cross section) in a diffusion system.
The flux of a given material into a volume
element (Jx) minus the flux out of the element
volume (Jx+dx) equals the rate of material
accumulation in the volume:
x
C
J x J x dx dx
Using a Taylor series we can expand Jx+dx: t
J x 1 2J x 2 C is the average species concentrat ion
J x dx Jx dx dx
x 2 x 2
in the volume element
Accordingly, as dx0 and using And if D does not vary with x we have
Fick’s First Law: The formulation of Fick’s Second Law:
C C C 2C
(D ) D 2
x x t t x
EX: NON STEADY STATE DIFFUSION
• Copper diffuses into a semi-infinite bar of aluminum.
C(x,t)
Cs Boundary conditions:
C C 2
For t=0, C=C0 at 0 x
D 2
t x For t>0, C=Cs at x=0
t3 C=C0 at x =
t2
t t1
Co o
position, x
• General solution:
x
C(x, t) Co
1 erf
2 Dt
Cs Co
Error Function
2 z
y2
erf (z) e dy z x / 2 Dt
0
The terms erf and erfc stand for error function and complementary error
function respectively - it is the Gaussian error function as tabulated (like
trigonometric and exponential functions) in mathematical tables. (see Table
5.1, Callister 6e).
Rate = K·exp(-Q/RT)
where K is a pre-exponential constant (independent of temperature),
Q- the activation energy, R the universal gas constant and T the absolute temperature
Energy
Assumptions:
Molecular transfer without convection (natural or forced),
i.e. no motion as a whole (otherwise additional term
should be added);
Λ – mean free pass << L – characteristics length of the
problem (otherwise Knudsen diffusion);
T=constant (otherwise Onsager's equations for thermo-
diffusion);
The concentration of this admixture should be small and
the gradient of this concentration should be also small; or
we have to consider only binary system; or diffusion
coefficients are equal to all components;
It means that ji depends on the gradient of only Ci !!
(otherwise Onsager's multicomponent diffusion) .
Convection
Now, if we have motion of the system as a whole,
which is characterized by linear velocity 𝑣Ԧ than:
𝑗Ԧ = −𝐷 ∙ 𝑔𝑟𝑎𝑑𝐶 + 𝑣Ԧ ∙ 𝐶 (2)
The special importance the Stefan Flux has for the process of evaporation
and condensation.
The average velocity for each component (i) can be defined as:
𝑗
𝑢𝑖 = 𝐶𝑖 (3)
𝑖
The average velocity of the Brownian Motion equals to zero, thus 𝑢𝑖 is an
average velocity of directional movements of the media. The value of this
velocity depends on the coordinate system and only 𝑢𝑖 − 𝑢𝑘 is invariant.
The overall flux rate is a sum of the directional rates of each component, thus
molar velocity:
σ 𝑗Ԧ𝑖 σ 𝑢𝑖 𝐶𝑖
𝑉𝑉 = σ 𝐶𝑖
= σ 𝐶𝑖
=σ 𝑥𝑖 𝑢𝑖 (4)
Diffusion Flux
We can also represent the flux using partial pressures:
𝐷𝑖 𝑣
𝑗Ԧ𝑖 = − 𝑔𝑟𝑎𝑑𝑝𝑖 + 𝑃 (5)
𝑅𝑇 𝑅𝑇 𝑖
𝐷 𝑣
σ𝑖 𝑗Ԧ𝑖 = − 𝑔𝑟𝑎𝑑𝑃 + 𝑃 (7)
𝑅𝑇 𝑅𝑇
If P=const than:
𝑣 𝑅𝑇 σ 𝑗Ԧ𝑖
σ𝑖 𝑗Ԧ𝑖 = 𝑃 and 𝑣Ԧ = σ𝑖 𝑗𝑖 =σ (8)
𝑅𝑇 𝑃 𝐶𝑖
𝐷∙𝑃 𝐶1 +𝐶2
𝑢1 − 𝑢2 = ∙ 𝛻𝑝1 = − D∙ 𝛻𝐶1 (13)
𝑝1 𝑝2 𝐶1 𝐶2
* which for multicomponent case has the following general form:
Josef Stefan’s evaporation– diffusion tube
A vertical tube is partly filled
with a liquid, which in turn
evaporated and the vapor flowed
out of the tube at the open end.
The tube portion above the
liquid level contained a (binary)
mixture consisting of the
surrounding gas (air) and the
vapor, generated on the liquid–
gas interface.
Due to evaporation, the liquid
level fell, and the process was
unsteady, even if all other
parameters were kept constant.
Under these conditions, Stefan
derived equations for calculating
the concentration distribution
along tube length and the
evaporation rate of the liquid.
The Stefan solution (1)
Stefan started by applying the momentum and continuity equations to diffusion in the
gaseous area above the liquid level. The gas mixture and its components were treated as ideal
gases, and the total pressure and temperature are constant through out the whole
system. The origin of the coordinate x is the plane of the upper tube end, and the position of
the liquid level is denoted by L. The gas mixture contained two components, and the
Stefan equations describing the diffusion process are:
0
(14)
(15)
The indices1and 2 refer to the mixture components1(vapor) and2 (gas); t is the time,
while A12 and A21 represent the resistance coefficients.
The Stefan solution (2)
Adding equations (14): Adding equations (15) and
accounting (16):
(16)
(17)
0
Now to solve (14) and (15) Stefan used the boundary condition at the
moving liquid–gas interface where evaporation is taking place: As the
components are not consumed while passing the interface, their fluxes
(𝒏𝟏ሶ 𝒂𝒏𝒅ሶ 𝒏𝟐ሶ ) are the same on both sides of the interface:
(18)
2G
where uI denotes the velocity of the interface; the indices L, G and I stand
for liquid, gas, and interface, respectively.
Adding equations (18):
and considering that the interface is impermeable to gas(component 2) and the liquid does
not move, so c 2L=0, and u1L =0 , hence
(19)
Boundary condition
(17)
(20)
where, for reason of simplicity we have omitted some indices, and set:
Note that Eq. (20) is obtained from the boundary conditions at the interface, but due to Eq.
(17) it is valid in the whole diffusion space.
The Stefan solution (3)
(21) (15)
Differentiating Eq.(21) with respect to x and combining with Eq. (15) for
component 1 gives the relation :
(21a)
(22)
At x=0, the equation is satisfied automatically; Let us consider boundary condition at x=L ;
it is assumed that the concentration c1I depends only on temperature (saturation
concentration of vapor),it is independent of time t when the temperature is constant. Thus:
(23)
And comparing with (21) we may conclude that: 𝜑 𝑡 = −(𝑐1 𝑢1 )𝐼 at x=L and from (20):
(24)
Finally, combining Eqs. (23) and (24) gives the additional boundary condition relation:
𝜕𝑐1𝐼 𝑐−𝑐1𝐼 𝑑𝐿
𝑥=𝐿 𝐷12 - ∙ 𝑐𝐿 =0 (25)
𝜕𝑥 𝑐 𝑑𝑡
The Stefan solution (4)
So we have:
(21)
𝜕𝑐1𝐼 𝑐−𝑐1𝐼 𝑑𝐿
𝑥=𝐿 𝐷12 - ∙ 𝑐𝐿 =0 (25)
𝜕𝑥 𝑐 𝑑𝑡
0
(26)
where the constants B and a are to be determined from the boundary conditions at x=L,
and (26) becomes:
and with (25)
And thus
(27)
The Stefan solution (4)
So we have: (27)
Stefan then proceeded to discuss the case when the molar liquid density was much larger than the gas
density, namely, cL>>c, and b=(cL-c)/c becomes very large. He simplified the integral (27),
From this equation the following expression for the position of the interface was deduced :
(27)
Stefan compared this expression with an expression he derived in an earlier paper (Stefan, 1873) under
the assumption of a constant evaporation rate (fixed interface):
(28)
Eq. (27) rests on the assumption c10=0, that is, p10=0. Assuming in this equation cL>>c1L, cL>>c1I, it
becomes identical with Eq.(28).
Slattery & Mhetar Solution
Let us consider a vertical tube, partially filled For simplicity, let us replace the finite
with a pure liquid A. gas phase with a semi-infinite gas that
For time t < 0, this liquid is isolated from the occupies all space corresponding to z2 > 0:
Z2
remainder of the tube, which is filled with a
gas mixture of A and B, by a closed diaphragm. G(gas) at t =0 for all z2 > 0:
The entire apparatus is maintained at a
constant temperature and pressure (neglecting X (A)=X (Ao) (1)
the very small hydrostatic effect).
X (A) - mole fraction of species A
At time t = 0, the diaphragm is carefully
in the gas phase;
opened, and the evaporation of A commences.
X (Ao) - initial mole fraction of
Let us assume that A and B form an ideal-gas species A in the gas phase
mixture. This allows us to say that the molar
density c in gas phase is a constant 0 The liquid gas phase interface
throughout the gas phase. Z3
is a moving plane
We also assume that B is insoluble in A.
We wish to determine the concentration Z2 = h(t) (2)
L(liquid)
distribution of A in the gas phase as well as the
position of the liquid-gas phase interface as and at z2 = h for all t > 0:
functions of time.
X(A)= X(A)e q. (3)
Slattery & Mhetar Solution (2)
Equations (1) and (2) suggest that we seek a solution to this problem of the form
V1= V3 =0
V2= V2 (t, z2) (4)
X(A)= X (A)(t, Z2) .
V - molar averaged velocity of gas phase; V2 - Z2 component of the molar averaged velocity
of gas phase. Since c can be taken to be a constant and since there is no homogeneous chemical
reaction, the overall differential mass balance requires:
𝝏𝑽𝟐
Z2 =𝟎 (5)
𝝏𝒁𝟐
G(gas) which implies:
V2=V2(t) (6)
The overall mass balance at interface requires at Z2=h:
L(liquid)
Slattery & Mhetar Solution (3)
It means that at Z2=h:
𝒄
𝑼𝟐 = − 𝒄(𝑳) −𝒄 ∙ 𝑽𝟐 (9)
𝒄(𝒄∙𝑿 𝑨 −𝒄(𝑳) )
𝑱 𝑨 𝟐 = ∙ 𝑽𝟐 (10)
𝒄−𝒄(𝑳)
𝝏𝑿(𝑨)
𝑱 𝑨 𝟐 = 𝒄 ∙ 𝑿(𝑨) ∙ 𝑽𝟐 -𝒄 ∙ 𝑫𝟏𝟐 (11)
𝝏𝒁𝟐
(𝒄−𝒄 𝑳 ) 𝝏𝑿(𝑨)
at Z2=h 𝑽𝟐 = 𝑫 (12)
𝒄 𝑳 (𝟏−𝑿 𝑨 𝒆𝒒 ) 𝟏𝟐 𝝏𝒁𝟐
(𝒄 𝑳 −𝒄) 𝝏𝑿(𝑨)
𝑽𝟐 = − 𝒄 𝑳 (𝟏−𝑿 𝑫 𝑨𝑩 𝝏𝒁 ∣𝒛𝟐=𝒉 (13)
𝑨 𝒆𝒒 ) 𝟐
Slattery & Mhetar Solution (3)
We concluded that everywhere :
(𝒄 𝑳 −𝒄) 𝝏𝑿(𝑨)
𝑽𝟐 = − 𝒄 𝑳 (𝟏−𝑿 𝑫 𝑨𝑩 𝝏𝒁 ∣𝒛𝟐=𝒉 (13)
𝑨 𝒆𝒒 ) 𝟐
Now equation, which reflects the continuity of the fluxes, or so-called differential
mass balance for A species, equires:
𝝏𝑿(𝑨) 𝒄 𝑳 −𝒄 𝝏𝑿 𝝏𝑿 𝑨 𝝏𝟐 𝑿(𝑨)
+ − 𝒄 𝑳 𝟏−𝑿 𝑫𝑨𝑩 𝝏𝒁𝑨 ∣𝒛𝟐=𝒉 ∙ − 𝑫𝑨𝑩 =0 (14)
𝝏𝒕 𝑨 𝒆𝒒 𝟐 𝝏𝒁𝟐 𝝏𝒁𝟐
𝑧2 ℎ
With substitutions: 𝜂 = and 𝜆 = (15)
4𝐷𝐴𝐵 𝑡 4𝐷𝐴𝐵 𝑡
eq. (14) becomes:
(16)
where
(𝒄 𝑳 −𝒄) 𝝏𝑿(𝑨) 𝒕
𝝋= − 𝒄 𝑳 (𝟏−𝑿 ∙ ∣𝒛𝟐=𝒉= - 𝟐𝑽𝟐 (17)
𝑨 𝒆𝒒 ) 𝝏𝒁𝟐 𝑫𝑨𝑩
(20)
(21)
Solution (6)
𝑐
(21) 𝑈2 = − 𝑐 𝐿 −𝑐 ∙ 𝑉2 (9)
Let us characterized the rate of evaporation by the position of phase interphase z2=h(t)
𝑑ℎ 𝐷𝐴𝐵
= 𝑈2 = 𝜆 (22)
𝑑𝑡 𝑡
𝜆
𝜑 = 2(𝑐 𝐿 − 𝑐) 𝑐 (23)
Now we have to solve for a given system, (21), (23) we can find 𝝋 and
𝝀 𝐚𝐧𝐝 𝐭𝐡𝐚𝐧 𝐟𝐢𝐭 𝐭𝐡𝐞 𝐞𝐱𝐩𝐞𝐫𝐢𝐦𝐞𝐧𝐭𝐚𝐥 𝐡 = 𝐡 𝐭 𝐝𝐚𝐭𝐚
Notes:
(21)
From eq. (21), we see that, in the limit X (A)e q → X (A)o, the dimensionless molar averaged
velocity 𝜑 →0, and the effects of diffusion-induced convection can be neglected (V2=0).
If one simply says that V2=0 and uses Fick's second law, even though the overall jump
mass balance (7) suggests that this is unreasonable, it can be shown that:
(22)
And only this equation should be solved to follow experimental h=h(t) data.
Let us consider two liquids to emphasize this effect. Methanol has a relatively low vapor
pressure at room temperature, and we anticipate that the effects of diffusion-induced
convection will be small. Methyl formate has a larger vapor pressure, and the effects of
diffusion-induced convection can be anticipated to be larger.
Solving eqs. (21) and (23) simultaneously, we found
Example (1) l= -1.74 x 10 -4
For Evaporation of 𝝋= -0.208.
From Fig. 1 below , it can be seen that the predicted
Methanol height of the phase interface follows the
T = 25,4 C experimental data closely up to 2500 s. As the
p = 1.006 × 105 Pa concentration front begins to approach the top of
X (methanol)eq.= 0.172 the tube, we would expect the rate of evaporation to
be reduced. Note that neglecting diffusion-induced
X(methanol)o = 0
convection results in an under prediction of the rate
D (methanol,air) == 1.558 x 10 -5 m2/s of evaporation.
(corrected from 1.325 × 10 -5 m2/s at
0ºC and 1 atm (Washburn, 1929, p. 62)
using a popular empirical correlation
(Reid et al., (1987) The Properties of
Gases and Liquids, 4th Ed. McGraw-
Hill, New York, U.S.A.1987, p. 587);
c(L)= 24.6 kgmol/ 3
(Dean, J. A. (1979) Lange's Handbook of
Chemistry, 12th ed. McGraw-Hill, New York,
U.S.A. pp. 7 271. 10 89),
c=0.0411 kg mol/m 3 The lower curve gives the position of the phase interface h (mm)
(Estimated for air from Dean, 1979, p. 10- 92)). as a function of t (s) for evaporation of methanol into air at
T = 25.4ºC and p = 1.006 x 105 Pa. The upper curve is the same
case derived by arbitrarily neglecting convection.
Example (2) Solving eqs. (21) and (23) simultaneously, we found
l= -1.84 x 10 -3
For Evaporation of 𝝋= -1.44.
Methyl Formate: From Fig. 2, it can be seen that the predicted
T = 25,4 C height of the phase interface follows the
experimental data closely over the entire range
p = 1.011 × 105 Pa
of observation. Once again, neglecting diffusion-
X (mformate)eq.= 0.784 induced convection results in an
X(methanol)o = 0 underprediction of the rate of evaporation
D (mformate,air) == 1.020 x 10 -5 m2/s
(corrected from 0.872 × 10 -5 m2/s at C
and 1 atm (Washburn, 1929, p. 62)
using a popular empirical correlation
(Reid et al., (1987) The Properties of
Gases and Liquids, 4th Ed. McGraw-
Hill, New York, U.S.A.1987, p. 587);
c(L)= 16.1 kgmol/ 3
(Dean, J. A. (1979) Lange's Handbook of
Chemistry, 12th ed. McGraw-Hill, New York,
U.S.A. pp. 7 271. 10 89),
c=0.0411 kg mol/m 3
(Estimated for air from Dean, 1979, p. 10- 92)). The lower curve gives the position of the phase interface h (mm)
as a function of t (s) for evaporation of methyl formate into air
at T = 25.4ºC and p = 1.011 x 105 Pa. The upper curve is the same
case derived by arbitrarily neglecting convection.