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Part I

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1. Introduction to Mass Transfer
and Diffusion
Part
2. Molecular Diffusion in Gasses I

3. Molecular Diffusion in Liquids

4. Molecular Diffusion in Biological


Solutions and Gels Part

5. Molecular Diffusion in Solids II

6. Unsteady State Diffusion

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7. Convection Mass Transfer Part

Coefficients II

8. Mass Transfer Coefficients


for various geometries Part
9. Mass Transfer to Suspensions III

of Small Particles

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1. Introduction to Mass Transfer and
Diffusion
1.1 Fick’s law for molecular diffusion
2. Molecular Diffusion in Gasses
2.1 Equimolar counterdiffusion in gases
2.2 General case for diffusion of gases A
& B plus convection
2.3 Special case for A diffusing through
stagnant, nondiffusing B

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2.4 Diffusion through a varying cross-
sectional area
2.5 Diffusion coefficient for gases
3. Molecular Diffusion in Liquids
3.1 Introduction
3.2 Equation for diffusion in liquids
3.3 Diffusion coefficients for liquids
3.4 Prediction of diffusivities in liquids

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 Mass transfer occurs:

Water evaporates Sugar dissolves &


into still air. diffuses to the
surrounding solution.
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 Mass transfer occurs:

Liquid-liquid
extraction

Crystallization

Distillation

Drying
bblee@UniMAP Adsorption 7
 Molecular diffusion (transport):
 the transfer or movement of
individual molecules through a fluid
by means of the random, individual
movements of the molecules.

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Low
concentration

Figure 6.1-1:
Schematic
diagram of
molecular
diffusion
High
process.
concentration
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 Consider:
 the diffusion of molecules when the
whole bulk fluid is not moving but is
stationary.
 due to a concentration gradient.
 The Fick’s law equation:
The mole fraction of
A in mixture of A & B
* dxA
J AZ cDAB Distance, m
dz
Total concentration The molecular diffusivity of
of A &B (kg mol/m3) the molecule A in B, m2/s
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 If c is constant, then cA=cxA,
cdxA = d(cxA)=dcA

 For constant total concentration:

* dcA
J AZ DAB
dz

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Example 6.1-1

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Example 6.1-1

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Example 6.1-1

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2.1 Equimolar Counterdiffusion in Gases
 Two gases A & B at constant total
pressure P in two large chambers
connected by a tube where molecular
diffusion at steady state is occurring.

Figure 6.2-1:
Equimolar
counterdiffusion
of gases A and B
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 Stirring in each chamber keeps the
concentrations in each chamber uniform.
 The partial pressure pA1>pA2 and pB2>pB1.
 Molecules of A diffuse to the right and
B to the left.
 Since the total pressure P is constant
throughout, the net moles of A
diffusing to the right must equal to the
net moles of B to the left.

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 This means that J *
J *
A B
 Writing Fick’s law for B for constant c,
* dcB
J B DBA
dz
 Now since P=pA+pB = constant, then
c cA cB
 Differentiating both sides, dc dc A dc B
dc=0, dc A dc B
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 Equating the equations,
* dcA * dcB
J A DAB J B ( )DBA
dz dz
 Finally, DAB DBA Molecular
diffusivity
 This shows that for a binary gas
mixture of A & B,
 the diffusivity coefficient DAB for A
diffusing into B is the same as DBA
for B diffusing into A.
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Example 6.2-1

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Example 6.2-1

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 The diffusion flux J*A occurred because
of the concentration gradient.
 The rate at which moles of A passed a
fixed point to the right (positive flux).
 This flux can be converted:

* 2 m kgmol A
J ( kg mol A / s.m ) v AD c A
A 3
s m
where vAD is the diffusion velocity of A
(m/s).
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 Consider when the whole fluid is moving
in bulk or convective flow to the right.
 The molar average velocity of the whole
fluid relative to a stationary point is vM
m/s.
 Component A is still diffusing to the
right, but now its diffusion velocity,
vAd is measured relative to the moving
fluid.

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 To a stationary observer A is moving
faster than the bulk of the phase, since
its diffusion velocity vAd is added to that
of the bulk phase vM.
 The velocity of A relative to the
stationary point is the sum of the
diffusion velocity & the average or
convective velocity:
vA v Ad vM
Where vA – velocity of A relative to a
stationary point.
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vA
vAd vM

 Multiplying by cA,
c Av A c Av Ad c Av M
NA
(kgmol A/s,m2) J*A
 Let N be the total convective flux:
N cv M NA NB
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 So, * cA
NA J A NA NB
c
Equimolar
 Since J*A is Fick’s law, counterdiffusion
dxA cA
NA cDAB N A NB
dz c
dxB cB
NB cDBA N A NB
dz c
NA = -NB
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 In the evaporation of a pure liquid (e.g.
benzene (A) at the bottom of a narrow
tube, where a large amount of inert or
nondiffusing air (B) is passed over the top.
Figure 6.2-2a:
Diffusion of A
through stagnant,
nondiffusing B: (a)
benzene
evaporating into air
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 The benzene vapor (A) diffuses through
the air (B) in the tube.
 The boundary at the liquid surface at
point 1 is impermeable to air, since air is
insoluble in benzene liquid.
 Air (B) cannot diffuse into or away from
the surface.
 At point 2 the partial pressure pA2=0,
since a large volume of air is passing by.

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 In the absorption of NH3 (A) vapor which
is in air (B) by water.
 The water surface is impermeable to
the air, since air is only very slightly
soluble in water.
Figure 6.2-2:
Diffusion of A through
stagnant, nondiffusing
B. (b) ammonia in air
being absorbed into
water.
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 thus, since B cannot diffuse, NB = 0.
dxA cA
NA cDAB NA 0
dz c
Convective flux of A
 Keeping the total pressure P constant,
substituting P
c
RT
p A x A P
cA pA
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c P 29
 Then, DAB dpA pA
NA NA
RT dz P
pA DAB dp A
NA 1
P RT dz
z2 pA 2
DAB dpA
N A dz
z1
RT p A1
1 pA P
DAB P P pA 2
NA ln
RT z2 z1 P pA1
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 A log mean value of the inert B is defined:
P pA1 pB1 pA 2 pB 2
pB1 P pA1 pB 2 P pA 2
pB 2 pB1 pA1 pA 2
 Then, PBM
ln pB 2 pB1 ln P pA 2 P pA1

DAB P
NA pA1 pA 2
RT z2 z1 pBM

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EXAMPLE 6.2-2

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EXAMPLE 6.2-2

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EXAMPLE 6.2-3

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EXAMPLE 6.2-3

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 So far, the cross-sectional area A m2
through which the diffusion occurs has
been constant with varying distance z.
 In some situations the area A may vary.

NA kg moles of A / s
NA
A
 At steady state, N A will be constant
but not A for a varying area.
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2.4.1 Diffusion from a sphere
 The evaporation of a drop of liquid, the
evaporation of a ball of naphthalene, and
the diffusion of nutrients to a sphere-like
microorganism in a liquid.
Figure 6.2-3a:
A sphere of fixed
radius, r1 (m) in
an infinite gas
medium.
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NA NA
NA
A 4πr 2

 Since this is a case of A diffusing through


stagnant, nondiffusing B:
NA DAB dpA
NA
4πr 2
RT 1 pA P dr
 Note that dr was substituted for dz.
 Integrating between r1 and some point r2
a large distance away:
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r2 pA 2
NA dr DAB dpA
dr
4π r1
r 2
RT p A1
1 pA P
NA 1 1 DAB P P pA 2
ln
4π r1 r2 RT P pA1
 r2>>r1, 1/r2≈0.

NA DAB pA1 pA 2
NA1
4πr12
RTr1 pBM
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 If pA1 is small compared to P (a dilute gas
phase), pBM≈P,
2r1=D1 (diameter),
cA1=pA1/RT
2DAB
N A1 c A1 c A 2
D1
 This equation can be used for liquids,
where DAB is the diffusivity of A in the
liquid.

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Example 6.2-4

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Example 6.2-4

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 If the sphere is evaporating, the radius r
of the sphere decreases slowly with time.
 The time it takes for the sphere to
evaporate completely can be derived by
assuming pseudo-steady state and by
equating the diffusion flux equation,
where r is now a variable, to the moles
of solid A evaporated per dt time and per
unit area as calculated from a material
balance.

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Original
Density of sphere radius
the sphere
2
p r RTpBM
A 1
tF
2M ADAB P pA1 pA 2
Molecular
weight
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2.5.1 Experimental determination of
diffusion coefficients
 To evaporate a pure liquid un a narrow
tube with a gas passed over the top (see
Fig 6.2-2a).
 The fall in liquid level is measured with
time and the diffusivity calculated:
2
p r RTpBM
A 1
DAB
2M At F P pA1 pA 2
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 The common method is the two-bulb
method (N1).
Figure 6.2-4:
Diffusivity
measurement of
gases by the
two-bulb
method.
Pure gas A is added to V1 and pure B to V2
at the same pressures.
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 The valve is opened, diffusion proceeds
for a given time, and then the valve is
closed and the mixed contents of each
chamber are sampled separately.
 Assumptions:
Neglecting the capillary volume &
assuming each bulb is always of a
uniform concentration.

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Quasi-steady-state diffusion in the
capillary, Concentration Concentration
of A in V2 at of A in V1 at
time t time t

* dc DAB c 2 c1
J A DAB
dz L
 The rate of diffusion of A going to V2 is
equal to the rate of accumulation in V2:
* DAB c 2 c1 A dc2
AJ A V2
L dt
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 The average value cav at equilibrium can
be calculated by a material balance from
the starting composition c10 and c20 at
t=0:
0 0
V1 V2 cav Vc
1 1 Vc
2 2

 A similar balance at time t gives,


V1 V2 cav V1c1 V2c 2

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 Rearranging & integrating between t=0 &
t=t,

cav c2 DAB V1 V2
0
exp
cav c2 L A V2V1
 if c2 is obtained by sampling at t, DAB
can be calculated.

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 Some typical data are given in Table 6.2-
1, Perry & Green (1984) and Reid et al.,
(1938).
Table 6.2-1: Diffusivity coefficient of gases at
101.32 kPa Pressure

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 The diffusivity of a binary gas mixture in
the dilute gas region, that is, at low
pressure near atmospheric, can be
predicted using the kinetics theory of
collision with another molecule, which
implies that
momentum is
conserved.

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 The final relation for predicting the
diffusivity of a binary gas pair of A & B
molecules is:
7 3/ 2 1/ 2
1.8583x10 T 1 1
DAB
Pζ AB ΩD ,AB
2
MA MB

Average A collision integral based on


collision the Lennard-Jones
diameter potential

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 The above equation is relatively
complicated to use (σAB is not available
or are difficult to estimate).
7 1.75 1/ 2
1.00x10 T 1 M A 1 MB
DAB 1/ 3 1/ 3 2
p Σν A Σν B
Sum of structural
volume increments

Note: DAB α 1/P, DAB α T1.75,


DAB α T1.75/P
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Table 6.2-2: Atomic diffusion volumes for use
with Fuller et al., method.

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Example 6.2-5

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Example 6.2-5

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3.1 Introduction
 Diffusion of solutes in liquids is
important in many industrial processes:

Solvent Gas
extraction absorption Distillation 58
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 Diffusion in liquids also occurs in nature:

Diffusion of
Oxygeneration of water in blood
rivers and lakes by
the air
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 It should be apparent that the rate of
molecular diffusion in liquids is
considerably slower than in gases.
 The molecules of the diffusing solute
A will collide with molecules of liquid B
more often and diffuse more slowly
than in gasses.
 The diffusion coefficient in a gas will
be on the order of magnitude of about
105 times greater than in a liquid.

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 The flux in a gas is being only 100 times
faster,
since the concentrations in liquids are
considerably higher than in gases.
 Since the molecules in a liquid are
packed together much more closely
than in gases, the density & resistance
to diffusion in a liquid are much greater.
 the attractive forces between
molecules play important role in
diffusion.
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 Diffusion of liquids: the diffusivities are
often dependent on the concentration of
the diffusing components.
3.2.1 Equimolar counterdiffusion
 An equation similar to gases at steady
state [NA=-NB]:
DAB c A1 c A 2 DAB cav x A1 x A 2
NA
z2 z1 z2 z1
Kg mol Concentration of
Mole fraction of
m2/s A (kg mol A/m ) A at point 1.
3
A/s.m2
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at point 1. 62
Average
 cav defined by density of
ρ ρ1 ρ2 the
cav 2 solution
M av M1 M2
(kg/m3)
Average total Average molecular weight
concentration of of the solution at point 1
A+B (kg mol/m3) (kg mass / kg mol)
 The average value of DAB may vary some
with concentration, &
 the average value of c may vary with
concentration
 Linear average of c is usually used. 63
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 A dilute solution of propionic acid (A) in a
water (B) solution being contacted with
toulene.
Only the propionic acid (A) diffuses
through the water phase (B), to the
boundary & then into the toluene phase.
The toulene-water interface is a
barrier to diffusion of B and NB = 0.
 Substituting
P ρA1 pBM
cav c A1 xBM
RT RT P
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 For liquids at steady state:
DAB cav
NA x A1 x A2
z2 z1 xBM
xB 2 xB1
xBM
ln( xB 2 xB1 )
 Note xA1+xB1=xA2+xB2=1.0
 For dilute solution, xBM is close to 1.0
 c is essentially constant.
DAB c A1 c A 2
NA
z2 z1
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Example 6.3-1

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Example 6.3-1

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3.2.3.1 Experimental determination of
diffusivities
 A relatively dilute solution & a slightly
more concentrated solution are placed in
chambers on opposite sides of a porous
membrane of sintered glass (see Fig6.3-1).
Figure 6.3-1:
Diffusion cell for
determination of
diffusivity in a
liquid
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 Quasi-steady-state diffusion in the
membrane is assumed:
Concentration in the lower Concentration in the
chamber at a time, t upper chamber
Fraction of area
of the glass open
to diffusion

c c'
NA εDAB
ηδ
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 Combining & integrating:
Initial concentrations

c0 c'0 2εA
ln c c' DAB t
ηδV
Final concentrations
Cell constant
Note: For liquids, unlike gases, the
diffusivity DAB does not equal DBA.
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 Table 6.3-1: experimental diffusivity
data for binary mixtures in the liquid
phase are given.
 The diffusivity values are quite small and
in the range of about 0.5x10-9 to 5x10-9
m2/s for relatively nonviscous liquids.
 Diffusivities in gases are larger by a
factor of 104-105.

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Table 6.3-1:
experimental
diffusivity data
for binary
mixtures in the
liquid phase are
given.

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 The Stokes-Einstein equation was derived
for a very large spherical molecule (A)
diffusing in a liquid solvent (B) of small
molecules.
Stokes’ law was used to describe the
drag on the moving solute molecule.
Diffusivity,
K
m /s
2
9.96x10 T 16
DAB Solute molar
μV 1/ 3
volume at its
Viscosity, A
normal boiling
Pa.s or kg/m.s point, m3/kgmol
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 The Wilke-Chang correlation can be used
for most general purposes, where the
solute (A) is dilute in the solvent (B).
1/ 2 T
DAB 1.173 x10 16
θM B
μBVA0. 6

Association
Molecular weight
parameter Solute molar
of solvent B
of the volume at the
solvent Viscosity of B, boiling point
Pa.s or kg/m.s (Table 6.3-2)
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 The association parameter (φ):
φ φ
Water 2.6 Benzene 1.0
Methanol 1.9 Ether 1.0
Ethanol 1.5 Heptane 1.0
Unassociated 1.0
solvents

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Example 6.3-2

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Example 6.3-2

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