FILM THEORY

The simplest conceptualization of the gas-liquid transfer process is attributed

to Nernst (1904). Nernst postulated that near the interface there exists a stagnant
film. This stagnant film is hypothetical since we really don't know the details of the
velocity profile near the interface.

In this film transport is governed essentially by molecular diffusion. Therefore, Fick's

law describes flux through the film.

If the thickness of the stagnant film is given by d n then the gradient can be
approximated by:

Cb and Ci are concentrations in the bulk and at the interface, respectively.

At steady-state if there are no reactions in the stagnant film there will be no

accumulation in the film (Assume that D = constant) -- therefore the gradient must be
linear and the approximation is appropriate.

And:

Calculation of CI is done by assuming that equilibrium (Henry's Law) is attained

instantly at the interface. (i.e., use Henry's law based on the bulk concentration of
the other bulk phase.) Of course this assumes that the other phase doesn't have a
"film". This problem will be addressed later. So for the moment::

A problem with the model is that the effective diffusion coefficient is seldom constant
since some turbulence does enter the film area. So the concentration profile in the
film looks more like:

The equation for film mass transfer starts from bulk phase mass balance for adsorption
followed by film-surface diffusion model equation.

Bulk phase mass balance for batch adsorption

For a batch adsorption process the bulk (liquid) phase mass balance can be expressed as,

V(c0 - cb) = mqt

(1)

Where:
c0 = the initial adsorbate concentration in the bulk solution
cb = the instantaneous (at time t) adsorbate concentration in the bulk solution
V = the volume of the bulk solution
m = the adsorbent mass
qt = the instantaneous amount adsorbed by unit mass of adsorbent or the adsorbed phase
concentration at time t
When adsorption reaches equilibrium, Eq (1) becomes,

V(c0 _ ce) = mqe

(2)

Where:
ce = the equilibrium bulk phase concentrations.
qe = the equilibrium adsorbed phase concentrations.

Filmsurface diffusion model

For a spherical adsorbent the filmsurface diffusion (the filmsolid diffusion or the
homogeneous surface diffusion) model can be expressed as,
qr Ds 2 qr
= 2
(r
)
t
r
r r

(3)

with the initial and boundary conditions:

t = 0, qr = 0
(4)

r = 0,

qr
r

r = R,

qr
p Ds
=k f ( c bc s )
r

=0
(5)

(6)
where :
r = the radial coordinate
R = the adsorbent radius
qr = the adsorbed phase concentration at r
Ds = the surface diffusion coefficient
kf = the film mass transfer coefficient
p = the adsorbent particle density
cs = the liquid phase concentration at the adsorbent surface
*cs is related to the adsorbed phase concentration at the adsorbent surface qs by the
adsorption isotherm equation.
The average adsorbed phase concentration in the adsorbent or the amount adsorbed per unit
mass of adsorbent at time t is given by,
R

qt =

3
q r 2 dr
3 r
R 0

qt is related to the bulk phase concentration cb by Eq (1)

(7)

The two key parameters in the filmsurface diffusion model are the film mass transfer
coefficient kf and the surface diffusion coefficient Ds. The usual method for obtaining kf and
Ds is to match the numerical solution of the filmsurface diffusion model equations
(3-7) along with the bulk phase mass balance equation (1)

Estimation of film mass transfer coefficient

From the bulk phase mass balance equation (1) and film surface diffusion model (3-7) it can
be shown that the adsorption rate is related to the film mass transfer coefficient by,
d q t V d c b 3 k f
=
=
( c c )
dt
m dt R p b s

(8)

Initially (t = 0) cb = c0 and cs = 0 (for finite film mass transfer resistance or finite kf), the
initial adsorption rate r0 is defined and becomes,
r o=

( ddtq )
t

Then

kf=

t=0

R p ro
3 co

3 k f co
R p

(9)

(10)

Eq (10) provides the relationship for evaluating the film mass transfer coefficient through the
initial adsorption rate and is used in the present study. Ocampo-Perez et al. determined the
initial adsorption rate by using the bulk phase concentration change between t = 0 and t = 1
min. Kim et al. (8) estimated the film mass transfer coefficient by neglecting cs in Eq. (8) for
very short adsorption time (less than 5 min). Since adsorption often takes place very fast
initially, it may be difficult to measure the bulk concentration change (or the adsorbed
amount) very accurately in a very short time (e.g., in 1 min). We here propose that the initial
adsorption rate be estimated in the following way. First an early adsorption stage in the
adsorption process is identified which, we suggest, corresponds to the range of the adsorbed
amount (qt) from zero to about half of the equilibrium value (qe). Then the early-stage kinetic
data are fitted with an early-stage kinetic equation for which we suggest the following
equation
q r=

Where:
r0 = the initial adsorption rate
a = fitting parameters to be determined

r ot
1+at

(11)

For linear regression equation (11) may be written as

t 1 a
= + t
qt r o r o

(12)

ro is then obtained by plotting the early-stage kinetic data in the form of t/qt versus t.
*Eq. (11) is used only for the early adsorption stage (thus called the early-stage kinetic
equation) and for the purpose of obtaining the initial adsorption rate.

ABSTRACTS
A new simplified method is presented for estimating the film mass transfer and
the surface diffusion coefficients from batch adsorption kinetic data without solving
partial differential equations. The film mass transfer coefficient is determined from
the initial adsorption rate which is estimated by fitting the kinetic data in the early
adsorption stage to the early-stage kinetic equation. The surface diffusion coefficient
is related to the late-stage adsorption rate constant which is estimated by fitting the
late-stage kinetic data to the late-stage kinetic equation. The method is applied to
four different adsorption systems in the literature. The predicted kinetics obtained

with the estimated film mass transfer and surface diffusion coefficients shows a
reasonable agreement with the experimental kinetics. To design fixed-bed adsorbers,
kinetic parameters such as the fluid-film mass transfer coefficient and intraparticle
diffusivity are required. The fluid-film mass transfer coefficient is usually estimated by
theoretical and/or empirical equations. Most of the equations were derived from
experimental data obtained through techniques other than adsorption. Thus, values
estimated from empirical equations are unreliable to use for adsorption systems. The
fluid-film mass transfer coefficients (k F) were determined experimentally from
adsorption uptake curves measured under conditions of low Reynolds numbers. The
experimental kF values were compared with several empirical equations, such as
Carberry equation. The experimental values were found to be always 4/3 of the
Carberry and Yoshida et al. equation. The experimental k F values were converted
into modified kF values (=kF_av = kFP/S), and compared with these equations. The
particle void (P) and shape factor (S) were introduced into the particle surface area
(aV) for experimental values to modify the area where mass transfer at the fluid-film
boundary surrounding adsorbent particles affects. Those k F values were nearly
identical, suggesting that only mass transfer around particle pores contributes to the
kF value for adsorbent particles. To represent the mass transfer at fluid film
appropriately, kFaV should be employed, since the error of aV is included in kF value.