FUNDAMENTAL OF

MASS TRANSFER

Mass Transfer (CHE 308)

Dr. Mehrab Mehrvar,, P.Eng.

g
Department of Chemical Engineering
Ryerson University, Toronto,
Ontario, Canada

Mass Transfer
Definition
Transport of one component from a
region of higher conc. to that of a lower
conc.

Applications:
Distillation
Extraction
Ion Exchange
... Fundamental of Mass Transfer 2

1
 Mass Transfer Operations: Refinery

Columns: Distillation, Extraction, Leaching, Stripping/Absorption, .

3
H-Exchanger, Dryer, cooling towers // Pumps, Compressors, valves

Distillation
Columns

2
 Hydrocarbons
Distillation
Column

Crude Oil

Vapor & Liquid Flows

3
 Schematic Diagram of Distillation Column

Inside the
Distillation Column

Objective: Design the

column sizing the height,
diameter, trays, flows,
structure, etc..
8

4
 Bubbling Trays

Objective:
Design trays,
tray spacing,
height of weir,
flows.

Caps &
Bubbles

10

5
Lab scale distillation

1: Heat source
2: Still pot
3: Still head
4: Thermometer/Boiling point temperature
5: Condenser
6: Cooling water in
7: Cooling water out
8: Distillate/receiving flask
9: Vacuum/gas inlet
10: Still receiver
11: Heat control
12: Stirrer speed control
13 Stirrer/heat
13: Sti /h t plate
l t
14: Heating (Oil/sand) bath
15: Stirrer bar/anti-bumping granules
16: Cooling bath.

11

Molecular Mass Transfer

Molecular Diffusion:
Macroscopic transport of mass, independent of any
convection effects within the system.
Due to:
Ci
Pi
i
vi (Potential Grad.)

Fundamental of Mass Transfer 12

6
 Concentrations
n
Total Mass Conc. i
i 1

Mass Fraction A A &

n
A i 1
n

i i 1

i 1

A
Molar Conc. c A Ideal Gas c A PA

MA RT
n
Total Mole Conc. c ci
i 1
Ideal Gas c P
RT
Fundamental of Mass Transfer 13

Mole Fraction
cA
liquid and solids xA
c
cA
gases yA
c
cA pA
ideal gas (Daltons law) yA
c P

n n
Also: yi xi 1
i 1 i 1

Fundamental of Mass Transfer 14

7
 Example 1.1 to 1.3

Fundamental of Mass Transfer 15

Velocities & Fluxes

Diffusion vs. Bulk Flow

mass-avg velocity:
l it
n n
i vi i vi n
v i 1n i 1 i vi
i i 1
i 1

molar-avg
g velocity:
y n n
ci vi ci vi n
V i1n i 1
xi vi
ci c i 1
i 1

Fundamental of Mass Transfer 16

8
 Mass & Molar flux with respect to
coordinates that are fixed in space
mass flux: ni i vi

tot. mass flux: n v

molar flux: N i ci vi

t t molar
tot. l flux:
fl N cV

Fundamental of Mass Transfer 17

Mass & Molar diffusion flux

with respect to mass-avg velocity

mass diff. flux: ji i (vi v)

n
and ji 0
j 1

molar diff. flux: J i ci (vi V )

n
and Ji 0
j 1

Fundamental of Mass Transfer 18

9
 Mass and Molar flux of species i
mass flux:
ni ji i v ji i n

molar flux:

N i J i ciV J i yi N (20)

Fundamental of Mass Transfer 19

Maxwell-Stefan (MS) Relations

From momentum balance for an ideal binary gas mixture
@ T,P=const.:

net forces on = rate of change of

species 1 /unit vol momentum of type 1/unit vol

= avg. amount of momentum no. of 1-2 collisions/

exchanged in one collision unit vol per unit time

(p1 ) y1 y2 v1 v2
And p1 f12 y1 y2 v1 v2

f12 = empirical parameter analogous to a friction factor or drag

Fundamental of Mass Transfer 20
coeff.

10
 Define inverse drag coeff. (MS diffusivity): D12 P / f12

and MS Eq.:
p1 y y v v
d1 1 2 1 2
P D12

where d1 is driving force for diffusion of i in an ideal gas mixture

at T & P const.

Fundamental of Mass Transfer 21

Similarly: p2 y y v v
d2 1 2 2 1
P D 21

since the system

y pressure
p (P)
( ) is constant across the
diffusion path:
y1 y2 v1 v2
y1
D12

y1 y2 v2 v1
y 2
D 21

Example 1.5

Fundamental of Mass Transfer 22

11
 MS Diff Eqs for multicomponent sys.
n yi y j vi v j
di i 1,2,...,n - 1
j 1 D ij
i terms
in t off molar
l fluxes
fl using
i Ni=civi
n yi N j y j N i
di i 1,2,..., n - 1 (26)
j 1 c D ij

in terms of diff fluxes using Ni=Ji+yiN

n yi J j y j J i
di i 1,2,..., n - 1 (27)
j 1 c D ij
n

d
i 1
i 0
Fundamental of Mass Transfer 23

For ideal gas mixture:

D ij D ji

Also, from Eq (27), for a binary mixture of ideal

gases:
J1 c D12 d1 c D12y1

Fundamental of Mass Transfer 24

12
 for non-ideal fluids:
G
Chemical Potential : i
n
i T , P , n j ( n j ni )

and i io,T , P RT ln(( xi )

i RT ln xi
xi
i RT
xi
xi
i RT
xi
d
i RT i
xi

Fundamental of Mass Transfer 25

Therefore, for non-ideal fluids, the driving force for

diffusion:
x
d i i T , P i
RT

in terms of activity coefficients (i) & mole fraction

gradients: n 1
d i ij x j xi (31)
j 1
where thermodynamic factor matrix is given by:
ln i
ijj ijj xi
x j T ,P ,

ij (Kronecker delta) is: ij 1 if i j

ij 0 if i j
Fundamental of Mass Transfer 26

13
 Combining Eqs (26), (27), and 31 give:

n xi J j x j J i n xi N j x j N i
xi i 1,2,...,n - 1
j 1 c D ij j 1 c D ij
(E 34)
(Eq

For a multicomponent mixture of ideal gases:

n yi J j y j J i n yi N j y j N i
yi i 1,2,...,n - 1
j 1 c D ij j 1 c D ij
(E 35)
(Eq

Fundamental of Mass Transfer 27

For a binary mixture, Eq (34) becomes:

J1 c D12x1 (Eq 36)

where thermodynamic
y factor is:
ln 1
1 x1 (Eq 37)
x1
for liquid mixtures are evaluated from is. For
example, for a regular:
ln 1 Ax22 A 1 x1
2
(Eq 38)

and Eq (37) becomes:

1 2 Ax1 x2 (Eq 39)
Fundamental of Mass Transfer 28

14
 Ficks First Law for Binary Mixtures
Adolf Fick (1855), same time as MS
For a binary mixture in an isothermal, isobaric sys.:
J1 cD12x1 (Eq 40)
D12 = diffusivity or diffusion coeff

recall (MS): J1 c D12x1 (36)

Then: D12 D12 (41)

for ideal systems, = 1, then

D12 D12 (42)
Fundamental of Mass Transfer 29

Diffusion Coefficients
Dimension: [L2/s]

Experimental
p or semi-theoretical expressions
p

Range:
gases: 0.5 - 1.0 m2/s

liquids:
li id 0 5
0.5 - 1.
1 0
m2/s
/

solids: 0.5 - 1.0 m2/s

Fundamental of Mass Transfer 30

15
 DAB for binary ideal gas systems
Hirschfelder Eq for Low to Moderate pressures:
0.00266T 3 / 2
DAB (43)
PM 1AB/ 2 AB
2
D
1
1 1
where M AB 2
M A M B
DAB = diff coeff [m2/s]
MA, MB = molecular weights
g of A & B
T = Temp, K
P = Pressure, bar
AB = collision diameter, a Lennard-Jones parameter, Ao
D = diffusion collision integral, [ ]
Fundamental of Mass Transfer 31

and: a c e g
D
(T ) exp(dT ) exp( fT ) exp(hT * )
* b * *

where:
T*= T/AB a = 1.06036 b = 0.15610
c = 0.19300
0 19300 d = 0.47635
0 47635 e = 1.03587
1 03587
f = 1.52996 g = 1.76474 h = 3.89411

for binary systems of nonpolar molecular pairs:

A B
AB & AB A B
2
AB = energy of molecular interaction [erg]

See Appendix B for Lennard-Jones parameters.

Fundamental of Mass Transfer 32

16
 In the absence of exp. data:
1.18Vb1/ 3 & A / 1.15Tb

where
( Boltzman constant) = 1.38 erg/K

Vb = molar volume as liquid at its n.b.p. [cm3/gmole] (Table 1.1)

For non-listed, then use: Vb 0.285Vc1.048

Tb = n.b.p
b T Temp

if Vc is not available, the atomic volume of each element present are

added together as per the molecular formula of the compound.
(Table 1.2)
Fundamental of Mass Transfer 33

For Low to Moderate pressures similar to Eq (43), but

using empirical constants (Wilke-Lee):

DAB
3.03 0.98 / M 10 T
1/ 2
AB
3 3/ 2
(49)
PM 1AB/ 2 D2
AB

All parameters are the same as Eq (43).

Fundamental of Mass Transfer 34

17
 DAB for liquids
Stoke-Einstein Equation for infinite dilution diff
coefficient (theoretical):
T
o
DAB (50)
6 rA B
where
rA = solute particle radius
B = solvent viscosity

Good for colloidal particles or large round molecules through

a solvent which behaves as a continuum relative to the
diffusing species.

Fundamental of Mass Transfer 35

Other empirical correlations:

General Form: o
DAB B
f (VA ) (51)
T
f(VA) = a function of the molecular volume of diffusing
solute.

Wilke-Chang Eq (for nonelectrolytes in an infinitely

dilute solution - doubt about using it at >100 Poise of
solvent):
o
DAB B 7.4 108 ( B M B )1/2
(52)
T VA0.6
DoAB = [cm2/s]
VA = solute molar volume @ n.b.p. [cm3/mol] = 75.6 cm3/mol for water as solute
B = association factor for solvent B, [ ]
= 2.26 for water as solvent
= 1.9 for methanol as solvent
B = viscosity of solvent [cP] Fundamental of Mass Transfer 36

18
 Hayduk-Minhas Eqs for dilute solutions:
Solutes in aqueous solutions:

o
DAB 1.25 108 VA0.19 0.292T 1.52 B (53)
9.58
1.12
VA

DoAB = [cm2/s]
VA = solute molar volume @ n.b.p. [cm3/mol] = 75.6 cm3/mol for water as solute
B = viscosity
i it off water
t [cP]
[ P]

Fundamental of Mass Transfer 37

Nonaqueous (nonelectrolyte) solutions:

VB0.27 T 1.29 B0.125

8
D o
AB 1.55 10 (54)
VA0.42 B0.92 A0.105
0 105

= surface tension @ n.b.p. [dyn/cm]

Fundamental of Mass Transfer 38

19
If values of are not known, use:

Pc2 / 3Tc1/ 3 (0.132 c 0.278)(1 Tbr ) 11/ 9 (55)

Tbr ln( Pc / 1.013)
c 0.90761
1 Tbbr
Tbr Tb / Tc

=surface tension @ n.b.p. [dyn/cm]

Pc = critical ppressure [[bar]]
Tc = critical temp. [K]
Tb = normal boiling temp. [K]

Fundamental of Mass Transfer 39

Notes in using Eq (54):

do not use for viscous solvents (>20 cP).

if solute is water, a dimer value of VA should be used

(VA = 37.4 cm3/mol).

If solute is an organic acid and solvent is other than

water, methanol, or butanol, the acid should be
considered a dimer with twice the expected value of
VA.

F
For nonpolar
l solutes
l t diffusing
diff i iinto
t monohydroxy
h d
alcohols, the values of VB should be multiplied by a
factor equal to 8B where B is the solvent viscosity in
cP.

Fundamental of Mass Transfer 40

20
DAB for Concentrated Liquid Solutions

Reid et al. ((1987)) :

D
D12 D12
o x2 o x1
21

(56)
D12 D12

Fundamental of Mass Transfer 41

Example 1.4 to 1.9

Fundamental of Mass Transfer 42

21
 Effective Diffusivity in Multicomponent Mixtures

MS eqs in multicomponent systems become very

complicated. Then Di,eff is used.

The rate of diff of i depends only on its own

composition gradient:

J i cDi ,eff xi i 1,2,

1 2 ... , n (57)

Fundamental of Mass Transfer 43

Di,eff in a multicomponent gas mixture:

n
N i yi N j
j 1
Di ,eff (58)
y j N i yi N j
n 1
j 1 D ij
j i
relations
l ti between
b t Ns
N mustt be
b know.
k

Special Case:
all components are stagnant except 1 (all Nis =0
except N1):
1 y1 1
1 eff
D1, n
n
(60)
yi y 'i
D1i
D1i
i 2 i 2
yi
where: y 'i i 2,3, .. ,n (61)
1 y1
Fundamental of Mass Transfer 44

22
 Example 1.11: Calculation of Effective
Diffusivity in a Multicomponent Gas Mixture
Catalytic cracking of NH3:

1 3
NH 3 catalyst
t lt N 2 H 2
2 2

@ one place in the apparatus @ 1 bar & 300 K :

NH 3 (1) 40%
N 2 ((2)) 20%
H 2 (3) 40% (by volume)
D1 , eff ?

Fundamental of Mass Transfer 45

SOLUTION
n
N i yi N j N1 N2 N3
j 1
Di ,eff (58)
1
y j Ni yi N j
n

j 1 D ij
j i

catalyst

1 3
binary diffusivities: NH 3 catalyst
N 2 H 2
(by Wilk-Lee Eq) 2 2
N1 N 2 N 3
D12 D12 0.237 cm 2 / s
1 1/ 2 3 / 2
D13 D13 0.728 cm 2 / s
and :
3
N j N1 N 2 N 3 N1
j 1
Fundamental of Mass Transfer 46

23
 Substitute in Eq (58):
n
N i yi N j
j 1
Di ,eff (58)
y j N i yi N j
n
1

j 1 D ij
j i

N1 1 y1
D1,eff
y2 N1 1 / 2 y1 N1 y3 N1 3 / 2 y1 N1

D12 D13
0.457 cm /s2
/

Fundamental of Mass Transfer 47

Example 1.12: Calculation of Effective Diffusivity in a

Multicomponent Stagnant Gas Mixture
NH3 is absorbed from a mixture of NH3 (1) = 40%, N2 (2) =
20% and H2 (3) =40% (by volume) by contact with a 2 N
sulfuric acid solution @ 1 bar and 300 K.
D1,eff=?:
?:

SOLUTION:
From example 1.11:
D12 D12 0.237 cm 2 / s
D13 D13 0.728 cm 2 / s

Fundamental of Mass Transfer 48

24
 Eq 60:
1 yi
D1,eff where: y 'i i 2,3, .. ,n
n
y 'i 1 y1
D1i
i 2
y2 0.2
y '2 0.333
1 y1 1 0.4
y3 0.4
y '3 0.667
1 y1 1 0.4
1
D1,eff 0.431 cm 2 / s
y '2 y '3

D12 D13

Fundamental of Mass Transfer 49

Di,eff in a multicomponent liquid mixture:

Perkins-Geankoplis Eq for dilute solute diffusing into a

homogeneous solution of mixed solvents (Error <20%):

n
D1o,eff M0.8 x j D1oj 0j .8 (61)
j 2

where:
Do1,eff = eff. diff. [cm2/s]
DoAj = infinite dilution diff of solute A into solvent j [cm2/s]
s = [cP]

Fundamental of Mass Transfer 50

25
 In case of CO2 as solute into mixed solvents, use
Takahashi et al. Eq (Error <4%):

1/ 3 1/3
M n j
D o
xjD o
(62)
CO2 ,eff
V
CO2 j V
M j 1
j CO2
j

VM & Vj = molar volume of mixture and pure j @ T [cm3/mol]

Fundamental of Mass Transfer 51

Example 1.13

Fundamental of Mass Transfer 52

26
 MOLAR FLUX AND
EQUATION OF CONTINUITY
Continuity Equation for component A (Bird, Stewart,
Lighfoot, 2002):

ci
Ni Ri 0 i 1,2, ... , n (64)
t

Cartesian (Rectangular) Coordinates:

N i ,x N i ,y N i ,z
Ni i 1,2, ... , n (65)
x y z

Fundamental of Mass Transfer 53

Equation of Continuity of i in various coordinate systems:

Cartesian (Rectangular) Coordinates:

c i N i, x N i , y N i, z
Ri i 1,2, ... , n
t x y z

Cylindrical Coordinates:

ci 1
rNi,r 1 N i, N i,z R i i 1,2, ... , n
t r r r z

Spherical
p Coordinates:

N i,
ci 1 2
2
t r r

r N i,r
1
rSin
N i,Sin 1
rSin
Ri

i 1,2, ... , n
Fundamental of Mass Transfer 54

27
 Equation of Continuity of i for constant and DAB:
Cartesian (Rectangular) Coordinates:

c i c i c c 2c 2c 2c
v x v y i v z i D AB 2i 2i 2i R i
t x y z x y z

Cylindrical Coordinates:

c i ci 1 c i c 1 ci 1 2 c i 2 c i
vr v v z i D AB r 2 2 R i
t r r z r r r r
2
z

p
Spherical Coordinates:
ci ci 1 c i 1 c i
vr v v
t r r rSin
1 c 1 c 1 2ci
D AB 2 r 2 i 2 Sin i 2 2 Ri
r r r r Sin r Sin 2
Fundamental of Mass Transfer 55

Special Case:
One dimensional steady-state molecular diffusion in
z-direction in Cartesian Coordinates:

ci
Ni Ri 0 i 1,2, ... , n (66)
t
0 (no chem rxn)
0 (st-st)
Therefore:
Ni 0 (67)
OR
dN i,z
0 i 1,2, ... , n (68)
dz

Fundamental of Mass Transfer 56

28
 Therefore:

Ni=Ni,z=constant i=1,2, , n

N
i 1
i constant (69)

More Examples for concentration distribution and

molar flux.

Fundamental of Mass Transfer 57

Steady-State Molecular Diffusion in Gases

St-st diffusion only in z-direction w/o chem rxn in a
binary mixture:

Recall

N i J i ciV J i yi N (20)

J1 cD12x1 (40)

Fundamental of Mass Transfer 58

29
 For binary mixture:
dy A
N A cDAB yA NA NB (70)
dz

dy A dz

N A y A N A N B cDAB

For gases @ T,P=constant, c & DAB = constant

for st
st-st
st one
one-dimensional
dimensional diffusion:
n
Ni & N
i 1
i constant (69)

Fundamental of Mass Transfer 59

B.C.s:

@ z=z1 y=yA1
@ z=z2 y=yA2

Solving:
1 N A y A2 ( N A N B ) z
ln (74)
( N A N B ) N A y A1 ( N A N B ) cDAB

NA
y A2
N A cDAB N A N B
NA ln (75)
N A NB z NA y
N A N B A1

Fundamental of Mass Transfer 60

30
 Define Molar Flux Fraction:

NA
A (76)
N A NB

Therefore:
cDAB A y A2
N A A ln (77)
z A y A1

F bi
For binary ideal
id l gas mixture:
i
DAB P A y A2
N A A ln (78)
RTz A y A1

Fundamental of Mass Transfer 61

Example 1.16: Production of Nickel Carbonyl: St-st,

one-dimensional binary flux calculation

Ni(CO)4 (g) is produced by passing CO (g) @

1atm & 323 K over a nickel slab:
Ni ( s ) 4CO ( g )
Ni (CO ) 4 ( g )
RXN is very rapid.
Gases diffuse through a film of 0.625 mm thick.
@ bulk gas phase: CO=50% (mole)
DAB=20.0 mm2/s

FIND:
molar flux of nickel carbonyl [mole/m2 of solid surface-s]
Fundamental of Mass Transfer 62

31
 SOLUTION

50% CO (B) , 50% Ni(CO)4 (A)

2 Gas film
NB NA z=0.625 mm
323 K
0% CO , 100% Ni(CO)4 1 atm
1
Ni ( s ) 4CO ( g )
Ni (CO ) 4 ( g )
NB
NA DAB P A y A2
4 N A A ln (78)
and : RTz A y A1
2
N j N A N B 3 N A
j 1

NA NA 1
N A 0.189 mol/m 2 - s
A
N A N B 3N A 3

Fundamental of Mass Transfer 63

Steady-State Molecular Diffusion in Liquids

St-st diffusion only in z-direction w/o chem rxn in a
binary mixture:

Recall (general form) eq (70) for liquids:

dx A dz
(70)
N A x A N A N B cDAB

In case of liquids,
q c & DAB =f(position)#constant
(p )
Eq. (75) (solution for Eq (70) for c & DAB = constant)
is used with an avg of c & DAB for dilute solutions.

Fundamental of Mass Transfer 64

32
 o
DAB A xA2
NA A ln (96)
z M avg A xA1

Special cases:
St-st diffusion of A through stagnant B:
NA=const. & NB =0, A=1
Eq (96) becomes: o
DAB ln1 xA2
NA
z M avg 1 xA1

Define Log-Mean
g g for x:
Average
xB2 xB1
xBM (98)
xB
ln 2
xB
1
Fundamental of Mass Transfer 65

Therefore:

o
DAB
NA
zxBM

xA1 xA2
M avg
(97)

St-st
St st equimolar counter
counter-diffusion:
diffusion:
NA=-NB & N= NA+NB=0
Eq (70) becomes:
dx A dz

N A x A N A N A cDAB

For avg c and DAB:

o
DAB
NA xA xA2
z M avg 1
(99)

Fundamental of Mass Transfer 66

33
 Example 1.19: St-st Molecular Diffusion in Liquids

A crystal of chalcanthite (CuSO4.5H2O) dissolves in a

large tank of pure water @ 273 K. Estimate the rate at
which the crystal dissolves by calculating the flux of
CuSO4 from the crystal surface to the bulk solution.
Assume that molecular diffusion occurs through a liquid
film uniformly 0.01 mm thick surrounding the crystal.

Solubility of chalcanthite in water @ 273 K = 24.3 g of

crystal/100 g of water and the density of the
corresponding
p g saturated solution is 1,140
, g 3.
kg/m

Diffusivity of CuSO4 in dilute aqueous solution @ 273 K

can be estimated as 3.6 10-10 m2/s. The density of pure
liquid water @ 273 K is 999.8 kg/m3.
Fundamental of Mass Transfer 67

SOLUTION
CuSO4 .5 H 2O( s )
CuSO4 ( aq ) 5 H 2O(l )

CuSO4 = A & H2O = B

NB=5NA
NA NA 1
NA A 0.167
N A N B N A 5N A 6

NB pure water

1 2
liquid film
Fundamental of Mass Transfer 68

34
 o
DAB A xA2
N A A ln (96)
z M avg A xA1
xA20 (pure water @ side 2)
xA1:

MCuSO4 =159.63 , M CuSO4.5H2O =249.71

Solubility of crystal in Water = 24.3 g crystal / 100 g H2O

basis =100 g H2O (24.3 g CuSO4.5H2O : crystal)

Mass of CuSO4 = (24.3 g crystal) (159.63 g CuSO4 ) / (249.71 g crystal)
= 15.53 g
Mass of hydration water in crystal = 24.3
24 3 - 15.53
15 53 = 8.77
8 77 g
Total mass of water = 100 + 8.77 = 108.77 g
15.53
x A1 159 .63 0.0158
15.53 108.77

159.63 18
69

Calculation of the film average molar density:

@ Point 1:

Mavg,1 = (0.0158)(159.63)+(1-0.00158)(18)=20.24 kg/kgmol

therefore: 1/M1= 11,140/20.24

140/20 24 = 56 32 kgmol/m3
56.32

@ Point 2:
2/M2= 999.8/18 = 55.54 kgmol/m3

(/M)av = (56.32 + 55.54)/2 = 55.93 kgmol/m3

Substituting into Eq (96):

NA=3.342 10-5 kgmol/m2-s
Fundamental of Mass Transfer 70

35
 Analogies among Molecular Momentum,
Heat, and Mass Transfer
Flow past a stationary fat plate:
Momentum Transfer:
du
d
(121)
dz
OR
d u d u
(122)
dz dz

Recall
R ll Ficks
Fi k First
Fi Law:
L
dxA
J A cDAB (40)
dz
dc
DAB A
Fundamental of Mass Transfer
dz 71

Heat Transfer:
dT
q k (124)
dz
OR
k d TCP d TCP
q (125)
CP dz dz

Dimensionless Numbers in Momentum, Heat, and

Mass Transfer:

Sc (124)
DAB
CP
Pr (126)
k
Sc
Le (127)
DAB Pr

Fundamental of Mass Transfer 72

36