Beruflich Dokumente
Kultur Dokumente
2
or
,
_
,
_
,
_
m e m A e
Q C Q K Q
2 2 2 2
"#.2'
Where,
e
Q
6 Amount of adsorbate adsorbed per unit amount of adsorbent at
equilibrium/
m
Q
6 Amount of adsorbate adsorbed per unit amount of adsorbent required for
monolayer adsorption "limiting adsorbing capacity'/
A
K 6 ,onstant related to enthalpy of adsorption/
e
C
6 ,oncentration of adsorbate solution at equilibrium.
4.6.1.2 Freundlich Isotherm
The 0reundlich isotherm is derived by assuming a heterogeneous surface with a non-
uniform distribution of heat of adsorption over the surface. The heat of adsorption in
many instances decreases in magnitude with increasing e!tent of adsorption. This decline
in heat of adsorption is logarithmic, implying that adsorption sites are distributed
e!ponentially with respect to adsorption energy. This isotherm does not indicate an
adsorption limit when coverage is sufficient to fill a monolayer.
The equation that describes such isotherm is 0reundlich +sotherm, given as
n
e F e
C K Q
2
or
e F e
C
n
K Q ln
2
ln ln +
"#.4'
Where,
F
K and n are the constants/
e
C
6 the concentration of adsorbate solution at equilibrium.
The 0reundlich equation is most useful for dilute solutions over small concentration
ranges. +t is frequently applied to the adsorption of impurities from a liquid solution onto
activated carbon. A high M
0
and high Nn3 value is an indication of high adsorption
throughout the concentration range. A low M
0
and high Nn3 indicates a low adsorption
throughout the concentration range. A low Nn3 value indicates high adsorption at strong
solute concentration "9emr et al., 4$22'.
4.6.1.3 Temkin Isotherm
Temin and )yBhev considered the effects of some indirect adsorbate&adsorbent
interactions on adsorption isotherms and suggested that because of these interactions the
heat of adsorption of all the molecules in the layer would decrease linearly with coverage.
The Temin isotherm has been used in the following formC
' " e e C A Ln
b
RT
q
or
' " ' " e e C Ln
b
RT
A Ln
b
RT
q +
"#.8'
Where, ( 6
b
RT
The adsorption data can be analyBed according to equation. A plot of q
e
versus lnC
e
enables the determination of the constants A and B. The constant B is related to the heat
of adsorption "9emr et al., 4$22'.
4.6.2 ERROR ANALYSIS
The use of =4 is limited to solving linear forms of isotherm equations, which measures
difference between e!perimental data and theoretical data in linear plots only, but not the
errors in isotherm curves.
)urely, from a comparison of the correlation coefficients "=4 values' for the lineariBed
models, it can be seen that higher weightage is given to the higher C
e
value data points,
thus giving a better fit correlation to the higher C
e
value data points. Due to the inherent
bias resulting from lineariBation, error functions of non-linear regression basis are
employed to evaluate the isotherm constants and compare them with the less accurate
lineariBed analysis values. Three different error functions of non-linear regression basin
were employed in this study to find out the best-fit isotherm model to the e!perimental
equilibrium data. The values of error functions used in the adsorption of phenol using
banana peel activated carbon are given in table :.4.
4.6.2.1 The Hybrid Fractional Error Function H!"#I$%
5O(=+D is given as
"#.#'
This error function was developed ")orter and >cMay, 2???' to improve the fit of the
A=K method at low concentration values. +nstead of n as used in A=K, the sum of the
fractional errors is divided by "n-p' where p is the number of parameters in the isotherm
equation. The values of 5O(=+D error functions are given in Table :.4, for activated
carbon from banana peels.
4.6.2.2 &ar'uardt(s )ercent *tandard $e+iation &)*$%
>)SD has been used by a number of researchers in the field "Seidel and Pelbin, 2?I?' to
test the adequacy and accuracy of the model fit with the e!perimental data. +t has some
similarity to the geometric mean error distribution, but was modified by incorporating the
number of degrees of freedom. This error function is given as
,
_
n
i
i
meas e
calc e meas e
q
q q
p n
2
4
,
, ,
' " 2
2$$ "#.7'
4.6.2.3 *um o, the *'uares o, the Errors **E%
The Sum of the Squares of the Krrors "SSK' function is given as
"#.:'
Where, q
e,calc
is equilibrium capacity obtained by calculating from the model "mg&g'
q
e,e!p
is e!perimental data of the equilibrium capacity "mg&g'
n is the number of data points
4.6.2.4 *um o, the -bsolute Errors *-E%
The Sum of the Absolute Krrors "SAK' function is given as
"#.<'
Where, q
e,calc
is equilibrium capacity obtained by calculating from the model "mg&g'
q
e,e!p
is e!perimental data of the equilibrium capacity "mg&g'
n is the number of data points.
( )
,e!p ,
2
,e!p
2$$
n
e e calc
i
e
i
q q
HYBRID
n p q
1
]
( )
4
, ,e!p
2
n
e calc e
i
i
SSE q q
,e!p ,
2
n
e e calc
i
i
SAE q q
"#.?'
Where, q
e,calc
is equilibrium capacity obtained by calculating from the model "mg&g'
q
e,e!p
is e!perimental data of the equilibrium capacity "mg&g'.
+f data from the model are similar to the e!perimental data, 4 will be a small number,
while if they differ, 4 will be a bigger number. Therefore, it is necessary to analyBe the
data set using the non-linear ,hi-square test to confirm the best-fit isotherm for the
sorption system.
3./ ADSORPTION PRACTICES
Adsorption systems are run either on batch or on continuous basis. The following
te!t gives a brief account of both types of systems as in practice.
3./.1 .ATCH ADSORPTION SYSTEMS
+n a batch adsorption process, the adsorbent is mi!ed with the solution to be
treated in a suitable reaction vessel for the stipulated period of time, until the
concentration of adsorbate in solution reaches an equilibrium value. Agitation is
( )
,e!p ,
2
,e!p
2$$
n
e e calc
i
e
i
q q
ARE
n q
generally provided to ensure proper contact of the two phases. After the equilibrium is
attained the adsorbent is separated from the liquid through any of the methods available
lie filtration, centrifugation or settling. The adsorbent can be regenerated and reused
depending upon the need.
3./.2 CONTIN+O+S ADSORPTION SYSTEM
The continuous flow processes are usually operated in fi!ed bed adsorption columns.
These systems are capable of treating large volumes of waste wasters and are widely used
for treating domestic and industrial wastewaters. They may be operated either in the up
flow columns or down flow column. ,ontinuous counter current columns are generally
not used for wastewater treatment due to operational problems.
0luidiBed beds have higher operating costs hence are not common in use. Wastewater
usually contains several compounds which have different properties and which are
adsorbed at different rates. (iological reactions occurring in the column may also
function as filter bed, retaining solids entering with the feed. As a result of these and
other complicating factors, laboratory or pilot plant studies on specific wastewater to be
treated should be carried out. The variables to be e!amined include type of adsorbent,
liquid feed rate, solute concentration in feed and height of adsorbent bed.
3.0 FACTORS CONTROLLIN1 ADSORPTION
The amount of adsorbate adsorbed by an adsorbent from aqueous solution is
depend upon a number of factors which are discussed below.
9ature of Adsorbent
Adsorbent dose
p5 of Solution
,ontact Time
+nitial ,oncentration of Adsorbate
Temperature
Degree of Agitation.
3.0.1 NAT+RE OF ADSOR.ENT
The adsorption capacity of an adsorbent depends upon its physicochemical
characteristics, specific surface area and its affinity to adsorbate. Adsorption capacity is
directly proportional to the e!posed surface of the adsorbent. 0or the non-porous
adsorbents, the adsorption capacity is inversely proportional to the particle diameter
whereas for porous material it is practically independent of particle siBe. 5owever, for
porous substances particle siBe affects the rate of adsorption "Srivastava et al., 4$2$'.
3.0.2 ADSOR.ENT DOSE
The removal increases rapidly with an increase in the adsorbent dose. An increase in the
sorption with an increase in the adsorbent dose can be attributed to the increase in the
mesoporous surface area available for sorption and hence, the availability of more
adsorption sites. 5owever, the unit adsorption decreases with an increase in dose "m'.
The decrease in sorption capacity per unit weight of adsorbent is because of the fact that
an increase in the sorbent dose at a constant concentration and volume leads to the
saturation of sorption sites through the sorption process "Shula et al., 4$$4/ Ou et al.,
4$$8/ Hataye et al., 4$$:/ Hataye et al., 4$$<d'. Also, particle-particle interaction such as
aggregation at higher m leads to a decrease in the total surface area of the sorbent and an
increase in the diffusional path length "Shula et al., 4$$4/ Hataye et al., 4$$:/ Hataye et
al., 4$$<d'. The incremental uptae of adsorbate is very small after a particular dose, as
the surface concentration and the bul solution concentration of adsorbate come to
equilibrium to each other.
3.0.3 pH OF SOL+TION
The surface charge as well as the degree of ioniBation is affected by the p5 of the
solution. Since the hydrogen and hydro!yl ions adsorb readily on the adsorbent surface,
the adsorption of other molecules and ions is strongly affected by p5. Penerally a surface
adsorbs anions favourably at low p5 and cations at high p5 "Shrivastava et al., 4$2$'.
3.0.4 CONTACT TIME
+n physical adsorption, most of the adsorbate species are adsorbed within a short
interval of contact time. 5owever, strong chemical binding of adsorbate with adsorbent
requires a longer contact time for the attainment of equilibrium. Available adsorption
results reveal that the uptae of adsorbate species is fast at the initial stages of the
contact period, and thereafter, it becomes slower near the equilibrium. +n between these
two stages of the uptae, the rate of adsorption is found to be nearly constant. This may
be due to the fact that a large number of active surface sites are available for adsorption at
initial stages and the rate of adsorption is a function of available vacant site. During the
course of adsorption, the concentration of the available vacant sites decreases and the
repulsion between solute molecules on the surface and solution increases thereby
reducing the adsorption rate "Srivastava et al., 4$2$'.
3.0.* INITIAL CONCENTRATION OF ADSOR.ATE
A given mass of adsorbent can absorb only a fi!ed amount of adsorbate. So the
initial concentration of the adsorbate in the solution is very important. The Q removal
in adsorption decreases with an increase in adsorbate initial concentration. (ut the
adsorption capacity of the adsorbent increases with an increase in initial concentration
because, the resistance to the uptae of solute from the solution decreases with an
increase in the solute concentration also the driving force is increases with increasing
concentration "Hataye et al. 4$$I'.
3.0., TEMPERAT+RE
Temperature dependence of adsorption is of comple! nature. Adsorption
processes are generally e!othermic in nature and the e!tent and rate of adsorption in most
cases decreases with increasing temperature. This trend may be e!plained on the basis of
rapid increase in the rate of desorption or alternatively e!plained on the basis of He-
,hatelierRs principle. Some of the adsorption studies show increased adsorption with
increasing temperature. This increase in adsorption is mainly due to an increase in
number of adsorption sites caused by breaing of some of the internal bonds near the
edge of the active surface sites of the adsorbent. When the adsorption process is
controlled by the diffusion process, then the sorption capacity increases with an increase
in temperature due to endothermicity of the diffusion process. An increase in temperature
results in an increased mobility of the ions and a decrease in the retarding forces acting
on the diffusing ions. This results in enhancement in the sorption capacity of the
adsorbents "Shrivastav et al., 4$2$'.
3.0./ DE1REE OF A1ITATION
Agitation in batch adsorption is important to ensure proper contact between the adsorbent
and the adsorbate in the solution. At lower agitation speeds, the stationary liquid film
around the particle is thicer and the resistance to transport is large. Thus, the process is
e!ternal mass transfer controlled. With the increase in agitation "or proper mi!ing' this
film thicness decreases and the film resistance to mass transfer gets reduced and after a
certain agitation speed, the process becomes intraparticle diffusion controlled. Whatever
is the e!tent of agitation, the solution inside the pores remains unaffected and hence, for
intraparticle mass transfer controlled processes agitation has no effect on the rate of
adsorption.
The adsorption isotherm is the most e!tensively employed method for representing
the equilibrium states of an adsorption system. +t can give useful information regarding
the adsorbate, the adsorbent, and the adsorption process. +t helps in the determination of
the surface area of the adsorbent, the volume of the pores, and their siBe distribution, the
heat of adsorption, and the relative absorbability of a gas or a vapor on a given adsorbent.
"(ansal and Poyal'