4.

Introduction to Heat & Mass Transfer

This section will cover the following concepts:
A rudimentary introduction to mass transfer.
Mass transfer from a molecular point of view.
Fundamental similarity of heat and mass transfer.
Application of mass transfer concepts:
- Evaporation of a liquid layer
- Evaporation of a liquid droplet

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Mass Transfer:
Mass-Transfer Rate Laws:
Ficks Law of Diffusion: Describes, in its basic
form, the rate at which two gas species diffuse
through each other.
For one-dimensional binary diffusion:
m
A
,1

mass flow of A
per unit area

4. Heat & Mass Transfer

= YA (m
A+m
B)

,
1
mass flow of A
associated with bulk
flow per unit area

dYA
DAB
 , dx1

mass flow of A
associated with
molecular diffusion

(4.1)

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 A is transported by two means: (a) bulk motion of

the fluid, and (b) molecular diffusion.
Mass flux is defined as the mass flowrate of
species A per unit area perpendicular to the flow:
m
A=m
A /A

(4.2)

m
A has the units kg/(s m2 ).
The binary diffusivity, or the molecular diffusion
coefficient, DAB is a property of the mixture and
has units of m2 /s.
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 In the absence of diffusion:

m
A = YA (m
A+m
B ) = YA m

Bulk flux of species A

(4.3a)

where m
is the mixture mass flux.
The diffusional flux adds an additional component
to the flux of A:
dYA
DAB
Diusional flux of A, m
A,di
dx
(4.3b)
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 Note that the negative sign causes the flux to be

postive in the x-direction when the concentration
gradient is negative.
Analogy between the diffusion of heat (conduction) and molecular diffusion.
- Fouriers law of heat conduction:
dT

Qx = k
(4.4)
dx
Both expressions indicate a flux (m
A,di or Q x )
being proportional to the gradient of a scalar quantity [(dYA /dx) or (dT /dx)].
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 A more general form of Eqn 4.1:

A+m
B ) DAB YA
m
A = YA (m

(4.5)

symbols with over arrows represent vector quantities. Molar form of Eqn 4.5

N A = A (N A + N B ) cDAB A

(4.6)

where N A , (kmol/(s m2 ), is the molar flux of

species A; A is mole fraction, and c is the molar concentration, kmol/m3 .
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 Meanings of bulk flow and diffusional flux can be

better explained if we consider that:
m

= m
A + m
B
,1
,1
,1

mixture
mass flux

species A
mass flux

(4.7)

species B
mass flux

If we substitute for individual species fluxes from

Eqn 4.1 into 4.7:
dYA
dYB
m
= YA m
DAB
+ YB m
DBA
dx
dx
(4.8a)
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 Or:
dYA
dYB
m
= (YA + YB )m
DAB
DBA
dx
dx
(4.8b)
For a binary mixture, YA + YB = 1; then:
dYA
dYB
DAB
DBA
=0
 , dx1  , dx1
diffusional flux
of species A

In general

4. Heat & Mass Transfer

(4.9)

diffusional flux
of species B

m
i =0
8

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 Some cautionary remarks:

- We are assuming a binary gas and the diffusion is a result of concentration gradients
only (ordinary diffusion).
- Gradients of temperature and pressure can
produce species diffusion.
- Soret effect: species diffusion as a result of
temperature gradient.
- In most combustion systems, these effects are
small and can be neglected.

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Molecular Basis of Diffusion:

We apply some concepts from the kinetic theory of
gases.
- Consider a stationary (no bulk flow) plane
layer of a binary gas mixture consisting of
rigid, non-attracting molecules.
- Molecular masses of A and B are identical.
- A concentration (mass-fraction) gradient exists in x-direction, and is sufficiently small
that over smaller distances the gradient can
be assumed to be linear.
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 Average molecular properties from kinetic

of gases:
p 8k T Q1/2
Mean speed
B
of
species
A
v molecules =
mA
pn Q
Wall collision
1
A
frequency
of
A
ZA molecules per unit area =
v
4 V
1
Mean free path =
2(ntot /V ) 2
Average perpendicular distance
2
from
plane
of
last
collision
to
a plane where next collision occurs =
3
4. Heat & Mass Transfer

12

theory

(4.10a)
(4.10b)
(4.10c)
(4.10d)

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where
kB : Boltzmanns constant.
mA : mass of a single A molecule.
(nA /V ): number of A molecules per unit volume.
(ntot /V ): total number of molecules per unit volume.
: diameter of both A and B molecules.

Net flux of A molecules at the x-plane:

m
A=m
A,(+)xdir m
A,()xdir
4. Heat & Mass Transfer

13

(4.11)

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 In terms of collision frequency, Eqn 4.11 becomes

m
A
,1

Net mass
flux of
species A

(ZA )xa
 , 1

mA

Number of A
crossing plane x
originating from
plane at (xa)

(ZA )x+a
 , 1

mA

Number of A
crossing plane x
originating from
plane at (x+a)

(4.12)
Since mtot /Vtot , then we can relate ZA to
mass fraction, YA (from Eqn 4.10b)
1 nA mA
1
ZA mA =

v = YA
v
4 mtot
4

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14

(4.13)

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 Substituting Eqn 4.13 into 4.12

1
m
A =
v (YA,xa YA,x+a )
4

(4.14)

With linear concentration assumption

dY
YA,xa YA,x+a
=
dx
2a
YA,xa YA,x+a
=
4/3

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(4.15)

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 From the last two equations, we get

v dYA
m
A =
3 dx

(4.16)

Comparing Eqn. 3.16 with Eqn. 3.3b, DAB is

DAB = v/3

(4.17)

Substituting for v and , along with ideal-gas

equation of state, P V = nkB T
3
2 p kB
T Q1/2 T
DAB =
(4.18a)
3
2
3 mA
P
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or
DAB T 3/2 P 1

(4.18b)

Diffusivity strongly depends on temperature and is

inversely proportional to pressure.
Mass flux of species A, however, depends on
DAB , which then gives:
DAB T 1/2 P 0 = T 1/2

(4.18c)

In some practical/simple combustion calculations,

the weak temperature dependence is neglected and
D is treated as a constant.
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Comparison with Heat Conduction:

We apply the same kinetic theory concepts to the
transport of energy.
Same assumptions as in the molecular diffusion
case.
v and have the same definitions.
Molecular collision frequency is now based on the
total number density of molecules, ntot /V ,
p
Q
1 ntot
Average wall collision
Z = frequency per unit area =
v (4.19)
4 V
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 In the no-interaction-at-a-distance hard-sphere

model of the gas, the only energy storage mode
is molecular translational (kinetic) energy.
Energy balance at the x-plane;
Net energy flow
in xdirection

kinetic energy flux

with molecules
from xa to x

kinetic energy flux

with molecules
from x+a to x

Q x = Z (ke)xa Z (ke)x+a
ke is given by

4. Heat & Mass Transfer

3
1
2
v = kB T
ke = m
2
2
20

(4.20)

(4.21)

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heat flux can be related to temperature as

3

Qx = kB Z (Txa Tx+a )
2

(4.22)

The temperature gradient

dT
Tx+a Txa
=
dx
2a

(4.23)

Eqn. 4.23 into 3.22, and definitions of Z and a

p n Q dT
1
Q x = kB
v
(4.24)
2
V
dx
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Comparing to Eqn. 4.4, k is

Q
p
1
n
k = kB
v
2
V

(4.25)

In terms of T and molecular size,

p k3 Q1/2
1/2
B
k=
T
3 m 4

(4.26)

Dependence of k on T (similar to D)
k T 1/2

(4.27)

- Note: For real gases T dependency is larger.

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Species Conservation:
One-dimensional control volume
Species A flows into and out of the control volume as a result of the combined action of bulk
flow and diffusion.
Within the control volume, species A may be created or destroyed as a result of chemical reaction.
The net rate of increase in the mass of A within
the control volume relates to the mass fluxes and
reaction rate as follows:

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dmA,cv
 dt
, 1

Rate of increase
of mass A
within CV

= [m
A A]x [m
A A]x+x + m
AV
 , 1
 , 1 
,
1
Mass flow
of A into
CV

Mass flow
of A out
of the CV

Mass prod.
rate of A
by reaction

(4.28)

- where
- m
A is the mass production rate of species A
per unit volume.
- m
A is defined by Eqn. 4.1.

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 Within the control volume mA,cv = YA mcv =

YA Vcv , and the volume Vcv = A x; Eqn. 4.28

(YA )
YA =
Ax
= A YA m
DAB
t
x x

=
YA
A YA m
DAB
+m
A Ax
x x+x
(4.29)
Dividing by Ax and taking limit as x 0,
(YA )

YA =
=
YA m
DAB
+m
A
t
x
x
(4.30)
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 For the steady-flow,

d 
dYA =
YA m
DAB
=0
m
A
dx
dx

(4.31)

Eqn. 4.31 is the steady-flow, one-dimensional

form of species conservation for a binary gas mixture. For a multidimensional case, Eqn. 4.31 can
be generalized as

m
A

m
A
= 0 (4.32)
,1
 , 1
Net rate of
species A production
by chemical reaction

4. Heat & Mass Transfer

Net flow of species

A out of
control volume

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Some Applications of Mass Transfer:

The Stefan Problem:

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 Assumptions:
- Liquid A in the cylinder maintained at a
fixed height.
- Steady-state
- [A] in the flowing gas is less than [A] at the
liquid-vapour interface.
- B is insoluble in liquid A
Overall conservation of mass:
A+m
B
m
(x) = constant = m

4. Heat & Mass Transfer

29

(4.33)

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Since m
B = 0, then
m
A=m
(x) = constant
Then, Eqn.4.1

(4.34)

now becomes

dYA
m
A = YA m
A DAB
dx

(4.35)

Rearranging and separating variables

m
A
dYA

dx =
DAB
1 YA
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(4.36)

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Assuming DAB to be constant, integrate Eqn.

4.36
m
A

x = ln[1 YA ] + C
(4.37)
DAB
With the boundary condition
YA (x = 0) = YA,i

(4.38)

We can eliminate C; then

m
=
Ax
YA (x) = 1 (1 YA,i ) exp
DAB
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31

(4.39)

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 The mass flux of A, m

A , can be found by letting
YA (x = L) = YA,
Then, Eqn. 4.39 reads
DAB  1 YA, =
m
A=
ln
L
1 YA,i

(4.40)

Mass flux is proportional to D, and inversely

proportional to L.

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Liquid-Vapour Interface:
Saturation pressure
PA,i = Psat (Tliq,i )

(4.41)

Partial pressure can be related to mole fraction and

mass fraction
YA,i

Psat (Tliq,i ) M WA
=
P
M Wmix,i

(4.42)

- To find YA,i we need to know the interface

temperature.
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 In crossing the liquid-vapour boundary, we maintain continuity of temperature

Tliq,i (x = 0 ) = Tvap,i (x = 0+ ) = T (0) (4.43)
and energy is conserved at the interface. Heat is
transferred from gas to liquid, Q gi . Some of this
heats the liquid, Q il , while the remainder causes
phase change.
Q gi Q il = m(h
vap hliq ) = mh
fg (4.44)
or

Q net = mh
fg
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34

(4.45)
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Droplet Evaporation:

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 Assumptions:
- The evaporation process is quasi-steady.
- The droplet temperature is uniform, and the temperature is assumed to be some fixed value below
the boiling point of the liquid.
- The mass fraction of vapour at the droplet surface
is determined by liquid-vapour equilibrium at the
droplet temperature.
- We assume constant physical properties, e.g., D.

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Evaporation Rate:
Same approach as the Stefan problem; except
change in coordinate sysytem.
Overall mass conservation:
m(r)

= constant = 4r2 m

(4.46)

Species conservation for the droplet vapour:

dYA
m
A = YA m
A DAB
dr

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37

(4.47)

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 Substitute Eqn. 4.46 into 4.47 and solve for m,

DAB dYA
m
= 4r
1 YA dr
2

(4.48)

Integrating and applying the boundary condition

YA (r = rs ) = YA,s

(4.49)

- yields
(1 YA,s ) exp [m/(4D

AB r)
YA (r) = 1
exp [m/(4D

AB rs )]
(4.50)
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 Evaporation rate can be determined from Eqn.

4.50 by letting YA = YA, for r :
 (1 Y

=
)
A,
m
= 4rs DAB ln
(1 YA,s )

(4.51)

In Eqn. 4.51, we can define the dimensionless

transfer number, BY ,
1 YA,
1 + BY
1 YA,s
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39

(4.52a)

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or

YA,s YA,
BY =
1 YA,s

Then the evaporation rate is

m
= 4rs DAB ln (1 + BY )

Droplet Mass Conservation:

dmd
= m

dt
where md is given by
md = l V = l D3 /6
4. Heat & Mass Transfer

40

(4.52b)

(4.53)

(4.54)

(4.55)
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where D = 2rs , and V is the volume of the

droplet.
Substituting Eqns 4.55 and 4.53 into 4.54 and differentiating
dD
4DAB
=
ln (1 + BY )
dt
l D

(4.56)

Eqn 4.56 is more commonly expressed in term of

D2 rather than D,
dD2
8DAB
=
ln (1 + BY )
dt
l
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41

(4.57)

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 Equation 4.57 tells us that time derivative of

the square of the droplet diameter is constant.
D2 varies with t with a slope equal to RHS of
Eqn.4.57. This slope is defined as evaporation
constant K:
8DAB
K=
ln (1 + BY )
(4.58)
l
Droplet evaporation time can be calculated from:
80

dD2 =

Kdt

(4.59)

Do2
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8td

42

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which yields
td = Do2 /K

(4.60)

We can change the limits to get a more general

relationship to provide a general expression for the
variation of D with time:
D2 (t) = Do2 Kt

(4.61)

Eq. 4.61 is referred to as the D2 law for droplet

evaporation.

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43

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D2 law for droplet evaporation:

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