Chapter 18

Shell Mass Balance:

Concentration Distribution in
Laminar Flow
⚫ In §17.1, the discussion of Fick's (first) law of diffusion
was given in terms of mass units: mass concentration, and
mass flux.
⚫ In this section we extend the previous discussion to
include molar units.
⚫ When chemical reactions are involved, molar units are
usually preferred.
⚫ When the diffusion equations are solved together with the
equation of motion, mass units are usually preferable
⚫ In this chapter we show how steady-state diffusion problems may
be formulated by shell mass balances. The procedure used here is
virtually the same as that used previously:
⚫ A mass balance is made over a thin shell perpendicular to the
direction of mass transport, and this shell balance leads to a
first-order differential equation.
⚫ Into this expression we insert the relation between mass flux
and concentration gradient (Fick’s law), which results in a
second-order differential equation for the concentration
profile.
⚫ The integration constants that appear in the resulting
expression are determined by the boundary conditions on the
concentration and/or mass flux at the bounding surfaces
⚫ For simplicity, we shall in this chapter use the combined
mole flux NA- that is, the number of moles of A that go
through a unit area in unit time, the unit area being fixed
in space.
⚫ We shall relate the molar flux to the concentration
gradient by Eq. 18.0-1, where for the z-component is
A B
⚫ Eq 18.0-1 shows that diffusional mass flux A is calculated
by considering convective mass flux of A. When
components A move in the restricted space, some of
components B also moves because the space previously
occupied by components B is now filled by components
A. Therefore, the diffusion of components A due to
concentration gradient is affected by convection of
combined components A and B.
⚫ When chemical reactions occur, we distinguish between
two reaction types: homogeneous, in which the chemical
change takes place in a fluid, and heterogeneous, in which
the chemical change takes place only in a restricted
region, such as the surface of a catalyst.
⚫ Not only is the physical picture different for
homogeneous and heterogeneous reactions, but there is
also a difference in the way the two types of reactions are
described mathematically.
⚫ The rate of production of a chemical species by
homogeneous reaction appears as a source term
(production term) in the differential equation obtained
from the shell balance, just as the thermal source term
appears in the shell energy balance.
⚫ The rate of production by a heterogeneous reaction, e.g.
that involving catalyst, on the other hand, appears not in
the differential equation, but rather in the boundary
condition at the surface on which the reaction occurs.
 reactants
products
catalyst A→ 2 B

heterogeneous reaction
⚫ In §18.1 with a statement of the shell balance and the
kinds of boundary conditions that may arise in solving
diffusion problems.
⚫ In §18.2 a discussion of diffusion through a stagnant
film (of B) is given, this topic being necessary to the
understanding of the film models of diffusional
operations in chemical engineering. NB = 0. This occurs
when the space is large enough that components B is at
rest.
⚫ In §18.3 a discussion of equimolar counter diffusion is
given. It happens in a mixture system where the mixture
is in very restricted space, NB = -NA
§18.1. SHELL MASS BALANCES;
BOUNDARY CONDITIONS
⚫ The law of conservation of mass of species A in a binary
system is written over the volume of the shell in the
form
⚫ .

⚫ The conservation statement may, of course, be

expressed in terms of moles. The chemical species A
may enter or leave the system by diffusion (i.e., by
molecular motion) and also by motion of the fluid (i.e.,
by convection), both of these being included in NA. In
addition, species A may be produced or consumed by
homogeneous chemical reactions.
⚫ After a balance is made on a shell of finite thickness by
means of Eq. 18.1-1, we then let the thickness become
infinitesimally small. As a result of this process a
differential equation for the mass (or molar) flux is
generated.
⚫ If, we substitute the expression for the mass (or molar)
flux in terms of the concentration gradient into this
equation (Fick’s law), we get a differential equation for
the concentration.
⚫ When this differential equation has been integrated,
constants of integration appear, and these have to be
determined by the use of boundary conditions.
⚫ The boundary conditions are very similar to those used
in heat conduction (see §10.1):
⚫ The concentration at a surface can be specified; for
example, xA = xA0
Gas B
⚫ The mass flux at a surface can be specified; for
shell
example, NAz = NA0 . z

Liquid A
⚫ If diffusion is occurring in a solid, e.g. pores, it may
happen that at the solid surface substance A is lost to
a surrounding fluid stream according to the relation
Gas B
⚫ in which NA0 is the molar flux at the surface, CA0 is
the surface concentration, cAb is the concentration in
the bulk fluid stream, and the proportionality solid
constant kc is a "mass transfer coefficient.“ with
pores
 §18.2. DIFFUSION THROUGH A
STAGNANT GAS FILM
⚫ Now we analyze the diffusion system shown in Fig.
18.2-1 in which liquid A is evaporating into gas B.
We imagine there is some device that maintains the
liquid level at z = z1.
Gas B
⚫ Right at the liquid-gas interface, the gas-phase
concentration of A, expressed as mole fraction, isz shell
xAi. This is taken to be the gas-phase concentration
of A corresponding to equilibrium with the liquid at z
the interface. That is, xAi is the vapor pressure of A
Liquid
divided by the total pressure, pAvap/pt (xAi = pA/pt), A
provided that A and B form an ideal gas mixture and
that the solubility of gas B in liquid A is negligible
(gas B is only in gas phase).
xA + xB = 1

shell

Stagnant gas
film
⚫ A stream of gas mixture A-B of concentration xA2 flows
slowly past the top of the tube, to maintain the mole
fraction of A at xA2 for z= z2. The entire system is kept at
constant temperature and pressure. Gases A and B are
assumed to be ideal.
⚫ We know that there will be a net flow of gas upward
from the gas-liquid interface.
⚫ To simplify the problem, we assume that there is no
dependence of velocity on the radial coordinate.
⚫ When this evaporating system attains a steady state, there
is a net motion of A away from the interface and the
species B is stationary (stagnant). Hence the molar flux
of A is given by Eq. 18.0-1 with NBz = 0 (diffusion of A
with convection of A in stationery B). Solving for NAz, we
get

⚫ A steady-state mass balance (in molar units) over an

increment z of the column states that the amount of A
entering at plane z equals the amount of A leaving at
plane z + z:
⚫ Here S is the cross-sectional area of the column. Division
by S z and taking the limit as z → 0 gives

⚫ Substitution of Eq. 18.2-1 into Eq. 18.2-3 gives

⚫ For an ideal gas mixture the equation of state is p = cRT, so

that at constant temperature and pressure c (total mole/vol)
must be a constant. Furthermore, for gases DAB is very
nearly independent of the composition. Therefore, cDAB can
be moved to the left of the derivative operator.
⚫ .

⚫ This is a second-order differential equation for the

concentration profile expressed as mole fraction of A.
Integration with respect to z gives

⚫ A second integration then gives

⚫ If we replace C1 by -ln K1, and C2 by -ln K2 Eq. 18.2-7
becomes –ln (1 – xA) = - lnK1.z – lnK2

⚫ The two constants of integration, K1, and K2 may then be

determined from the boundary conditions
⚫ B.C. 1:
⚫ B.C. 2:
⚫ When the constants have been obtained, we get finally
⚫ The profiles for gas B are obtained by using xB = 1 - xA.
The concentration profiles are shown in Fig. 18.2-1.
⚫ It can be seen there that the slope dxA/dz is not constant
although NAz is constant (see Eq. 18.2-6); this could have
been anticipated from Eq. 18.2-1.
⚫ Once the concentration (non-linear) profiles are known,
we can get average values and mass fluxes at surfaces.
For example, the average concentration of B in the region
between z2 and z1, is obtained as follows:
 shell

Stagnant gas
film
 d = d((z-z1)/(z2-z1))
= dz/(z2-z1)

⚫ .

⚫ in which  = (z – z1)/(z2 - z1) is a dimensionless length

variable. This average may be rewritten as

,ln

⚫ That is, the average value of xB in gas bulk is the

logarithmic mean, (xB)ln of the terminal concentrations,
xB1 and xB2.
Variables: xB and z Variables: z only
* How to modify Eq. 18.2-1 (differential form for
diffusion through stagnant film) to algebraic form?
xB = 1 - xA
derived from concentration
,ln distribution eq.
⚫ The rate of mass transfer at the liquid-gas interface -that
is, the rate of evaporation-may be obtained from Eq. 18.2-
1 as follows See next slide for the derived from
derivation to get this equality mass flux eq.

⚫ By combining Eqs. 18.2-13 and 18.2-14 we get finally

,avg

⚫ This expression (algebraic form) gives the evaporation

rate in terms of the characteristic driving force xA1 - xA2
derived from mass balance
 Derivation to Equation 18.2-14

⚫ d(a/ln a)/d=a
⚫ d(a)/d = a ln a Eq. 18.2-11
⚫ a = (xB2/xB1)
⚫  = (z-z1)/(z2-z1)
⚫ (1-xA) = xB
⚫ At z=z1,1/(xB1).dxB/dz = [d((xB2/xB1))/dz]/(z2-z1) =
a ln a/(z2-z1) = a(z1-z1)/(z2-z1) ln a/(z2-z1) = ln a/(z2-z1)
⚫ By expanding the solution in Eq. 18.2-15 in a Taylor series,
we can get = (1/x ) B ln,avg

⚫ The expression in front of the bracketed expansion is the result

that one would get if the convection term were entirely
omitted in Eq. 18.0-1. The bracketed expansion then gives the
correction resulting from including the convection term. Then,
diffusion through a stagnant gas film changes to equimolar
counter diffusion
Example 18.2-1. Diffusion with a
Moving Interface
⚫ We want now to examine a problem that is slightly
different from the one just discussed. Instead of
maintaining the liquid-gas interface at a constant height, we
allow the liquid level to subside as the evaporation
proceeds, as shown in Fig. 18.2-3. Since the liquid retreats
very slowly, we can use a quasi-steady state method with
confidence.
⚫ SOLUTION
⚫ First we equate the molar rate of evaporation of A from the
liquid phase with the rate at which moles of A enter the gas
phase:
,avg
In algebraic
form
,avg
 ,avg

⚫ Here (A) is the density of pure liquid A and MA is the

molecular weight. On the right side of Eq. 18.2-17 we have
used the steady-state evaporation rate evaluated at the
current liquid column height (this is the quasi-steady-state
approximation). This equation can be integrated to give

constant
,avg

⚫ in which h(t) = z1 (0) – z1(t) is the distance that the interface

has descended in time t, and H = z2 - z1 (0) is the initial
height of the gas column.
⚫ When we abbreviate the right side of Eq. 18.2-18 by
1/2Ct, the equation can be integrated and then solved for
h to give

⚫ One can use this experiment to get the diffusivity from

measurements of the liquid level as a function of time.
Example 18.2-2. Determination of
Diffusivity (with constant interface z1)
⚫ The diffusivity of the gas pair O2-CCl4 is being
determined by observing the steady-state evaporation of
carbon tetrachloride into a tube containing oxygen, as
shown in Fig. 18.2-1.
⚫ The distance between the CCl4 liquid level and the top of
the tube is z2 – z1 = 17.1 cm. The total pressure on the
system is 755 mm Hg, and the temperature is 0°C. The
vapor pressure of CCl4 at that temperature is 33.0 mm Hg.
The cross-sectional area of the diffusion tube is 0.82 cm2.
It is found that 0.0208 cm3 of CCl4 evaporate in a 10-hour
period after steady state has been attained.
⚫ What is the diffusivity of the gas pair O2-CCl4?
⚫ SOLUTION
⚫ Let A stand for CCl4 and B for O2. The molar flux of A is
then

⚫ Then from Eq. 18.2-14 we get.

in gas phase, p = cRT

xA is assumed to
be zero at the top
or xB = 1 or pB2 =
ptot = 755 mmHg
 §18.3. EQUIMOLAR COUNTER
DIFFUSION
In a mixture system where the mixture is in very restricted
volume, there may be equimolar counter diffusion between
components A and B where NA = -NB. By applying Equation
18.0-1 some equations can be derived in the case of NA=-NB.

NA = - NB (equimolar counter diffusion)