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Estudos Do Equilíbrio de Adsorção de Soluções Aquosas Diluídas de Poluentes Aromáticos em Carbono Ativado A Diferentes Temperaturas
Estudos Do Equilíbrio de Adsorção de Soluções Aquosas Diluídas de Poluentes Aromáticos em Carbono Ativado A Diferentes Temperaturas
S D
relationship between the sorbate and the adsorbent (activated
n/b
carbon) most commonly used. Langmuir and Freundlich iso- q0aC be
Marczewski and Jaroniec type qe Å . [6]
therms are the most common, and sometimes piecewise 1 / aC be
equations are used for a selected range of concentration
where implementation of only one expression fails badly. He has also used a second-order polynomial function for
the Freundlich isotherm equation to compensate for the cur-
Adsorption Isotherms vature on the logarithmic plot. The coefficient n can be
BET is a special form of Langmuir isotherm which can written as n1 / ln(C ne 2 ) and the equilibrium isotherm is
account for multilayer adsorption. All the assumptions relat-
ing to surface uniformity, distribution of sites, and negligible qe Å kC ne Å kC ne 1/ n 2 ln C e . [7]
influence of the occupied site on neighboring sites are the
same as for Langmuir monolayer adsorption. The energy for Jossens et al. (14) have correlated equilibrium concentra-
a monolayer is different from that for the second or other tion of sorbate to the adsorbed amount on the adsorbent
layers, which is equivalent to energy of liquification. The (capacity). This equation can be reduced to Henry’s law at
BET equation for physical adsorption is given as low capacities:
q0aCe q0
qe Å . [1] Ce Å exp(a2q be ). [8]
(CS 0 Ce )(CS 0 Ce (1 0 a)) a1
Radke and Prausnitz (7) have proposed a slight modifica- Temperature Effects
tion to the Langmuir equation, introducing another coeffi- In some of the proposed equilibrium equations, a tempera-
cient which has improved the fit to their experimental data: ture term has been introduced. These equations are most
often used to evaluate adsorption behavior at constant tem-
q0aCe perature. Parker (13) has reported an nth order exponential
qe Å . [2]
1 / aC be isotherm function for multilayer adsorption, which has n /1
coefficients. As the number of coefficients increases, the
Toth (11) has modified the Langmuir equation to reduce possible degree of fitness improves:
the error between experimental data and predicted values of
F H S DJ G
N i
equilibrium adsorption data. The application of his equation CS
qe Å q0 exp 0 ∑ ai RT ln . [9]
is best suited to multilayer adsorption similar to BET iso- Ce
iÅ1
therms which is a special type of Langmuir isotherm and
has very restrictive validity (12). The Toth correlation is If this equation is limited to a single term with an arbitrary
given as exponent, this equation reduces to the Dubinin–Astakov
equation (15) which has been successfully used by Parker
q0aCe (13) for his experimental adsorption data of 1,1,2-trichloroe-
qe Å . [3]
(1 / aC be ) 1 / b thene on activated carbon at 257C:
Ce Å F q0 uL13
H 10u S 1 0 (1 0 L31 ) u
L13 / (1 0 L13 ) u DG DS Å D0 exp S D
k qe
q0
. [15]
F
1 exp 0
L31 (1 0 L31 ) u
0
(1 0 L13 ) u
1 0 (1 0 L31 ) u L13 / (1 0 L13 ) u
, G [11] By comparing Eqs. [14] and [15], qe can be related to
temperature. Furuya et al. (24) have explained intraparticle
mass transport by two parallel mechanisms, pore and surface
where the Henry’s law constant H is defined by H Å diffusions, which are similar direct linear functions of tem-
lim (qe /Ce ) and u Å qe /q0 . perature. The diffusion coefficients are related to each other
Cer0 by the following equation:
The second theory is the Ideal Adsorbed Solution theory
for gaseous adsorption, which has been further developed by DP
De Å DS / . [16]
O’Brien and Myers (18) for calculation of multicomponent (dqe /dCe ) rP
equilibrium from pure component data. They have proposed
an expression for a single-component isotherm data by a Integration of Temperature Term in Correlation
Langmuir equation with a first-order correction: Equation [13] has been further developed to take into
account of the effect of the variation of temperature on equi-
qe Å q0 S aCe
1 / aCe
/
s 2aCe (1 0 aCe )
2(1 / aCe ) 3 D . [12]
librium adsorption expressions. Considering the condensa-
tion analogy, the equilibrium concentration of sorbate is re-
lated to temperature. For condensation phenomenon, the
Gibbs free energies for both phases, liquid and vapor, are
It seems that adsorption data from dilute solutions and equal at equilibrium and the vapor pressure is expressed as
also for gaseous adsorption can best be represented by either a function of temperature as d ln P/dT Å g /T 2 . The equilib-
Langmuir or modified Langmuir isotherms. Equations [1– rium concentration of sorbate is assumed to be represented
6] are all different modified forms of the Langmuir equation. by a similar function of temperature, which results in the
Khan et al. (6) have put forward a generalized equation equation
for multicomponent adsorption and have tested it on pub-
lished data for bisolute solutions. In their later work Khan q0aCe ( 0 g /T / d )
et al. (10) have compared different types of multicomponent qe Å , [13a]
[1 / aCe ( 0 g /T / d )] b
isotherms on their experimental data and concluded that the
generalized equation could represent the experimental data where g and d are arbitrary constants and g can be used for
most accurately with minimum average percentage error. the evaluation of heat of adsorption. In the present work
The generalized model for a single solute could be formu- experimental data have been obtained by conducting experi-
lated in the form of the simple expression ments at different temperatures for single solute adsorption
on activated carbon from aqueous solutions. Various types
q0aCe of reported equilibrium isotherm equations with this general-
qÅ . [13] ized form have been tested for the present data and also for
(1 / aCe ) b
the published data to determine the best possible equation
for the entire single adsorption data. The influence of various
To incorporate the influence of temperature on adsorption,
variables, the adsorbent, the concentration of sorbate, the
Kapoor et al. (19) have presented a review of existing mod-
solution pH, and the temperature, has been investigated.
els of the concentration dependence of the surface diffusion
coefficient, DS , in gas–solid systems. The model proposed EXPERIMENTAL
by Gilliland et al. (20) has also been widely used to explain
the dynamics of adsorption for dilute aqueous solutions Hydro-Anthrasit H (activated carbon) of bulk density 540
(21, 22), kg m03 , particle porosity of 0.485, and surface area of 3000
m2 g 01 was washed with hot deionized water and was dried concentrations were determined by UV absorption using
at 1107C to remove excessive moisture. Double-distilled and 8700 series Unicom UV/V spectrophotometer. No addi-
deionized water was used for the preparation of solutions of tional buffers were added; the pH of solutions varied from
different solutes, phenol, p-chlorophenol, and p-nitrophenol 4 to 6 for the selected range of concentration during the
of analytical reagent grade supplied by Aldrich Chemicals. course of the present research for phenol and phenol deriva-
The initial concentration of these compounds for the prepara- tives.
tion of stock solution for adsorption isotherm determination
was 1000 ppm (g m03 ) which was double-checked by volu- RESULTS AND DISCUSSION
metric titration (25). A specified quantity, 0.2 dm3 , of differ-
ent solutions with known initial concentration containing a Yenkie and Natarajan (3) have experimentally investi-
measured amount of activated carbon was taken in a 0.25 gated the influence of different adsorbents on the adsorption
dm3 Erlenmeyer flask and sealed with a screw cover. The of aromatic compounds from dilute aqueous solutions. The
flasks, including a blank one, were kept in a shaker–incuba- properties of the different adsorbents in experimental use
tor at a controlled temperature for a minimum period of 24 are listed in Table 1. It is noted from the experimental data
h for high temperatures and a maximum period of 72 h that phenol, benzoic acid, o-cresol, and p-methoxyphenol
for low temperatures. The samples were filtered through a have shown high selectivity for adsorbent 1 due to the sur-
Whatman filter paper number 42 next day and equilibrium face charge, which facilitated the adsorption of solutions
FIG. 1. (a) Comparison of different adsorbents for the adsorption of benzoic acid from dilute aqueous solution (3). (b) Comparison of the adsorption
of different aromatic sorbates from dilute aqueous solutions on adsorbent 4 (F200) (3).
AID
JCIS 5041
/
TABLE 2
Comparison of Different Isotherms for Single Organic Solutes in Aqueous Medium for Different Adsorbents (Yenkie and Natarajan, 1991)
6g30$$5041
Solute qo a % err k n % err qo a b % err qo H L13 L31 % err qo a s % err qo a b % err
1
Aniline 1.64 3.60 9.39 1.54 0.65 18.6 1.38 3.83 1.47 6.13 1.36 2.81 0.12 2.02 3.60 1.79 0.62 2.89 6.85 8.14 0.68 3.12 6.8
Phenol1 1.85 4.19 11.0 2.02 0.67 26.0 1.43 4.79 1.45 7.10 1.47 4.32 0.16 1.92 5.00 2.11 0.73 2.71 8.20 9.64 0.75 3.26 8.0
Benzoic acid1 2.25 4.16 2.52 2.06 0.48 8.79 2.19 3.72 1.18 1.83 2.1 4.42 0.17 1.98 2.87 3.5 0.98 1.71 1.3 4.02 2.14 1.41 1.3
p-Methoxyphenol1 1.56 38.3 6.29 1.98 0.28 8.29 1.79 51.2 0.86 1.15 1.91 10.1 0.001 6.07 10.7 1.89 19.5 1.34 1.83 0.902 89.2 0.85 1.1
o-Cresol1 1.83 17.7 4.87 2.36 0.41 15.5 1.94 18.6 0.93 4.25 2.04 13.1 0.04 3.51 11.4 2.58 5.93 1.48 4.55 1.42 24.6 0.91 4.1
Aniline2 1.57 2.75 6.16 1.32 0.66 16.4 1.54 2.67 1.14 5.6 1.74 1.61 0.04 3.36 5.60 1.57 2.75 0.001 6.20 2.47 1.71 1.33 5.7
Phenol2 1.57 2.75 6.16 1.32 0.66 16.4 1.54 2.67 1.14 5.6 1.74 1.61 0.04 3.36 5.60 1.57 2.75 0.001 6.20 2.47 1.71 1.33 5.7
Benzoic acid2 1.86 6.35 2.17 1.92 0.47 9.81 1.86 6.35 1.01 2.2 1.96 4.84 0.074 2.84 5.30 2.79 1.99 1.43 1.68 1.82 6.54 0.988 2.1
p-Methoxyphenol2 1.69 13.5 3.40 1.82 0.33 9.15 1.76 16 0.90 1.68 1.89 1.81 0.006 3.75 8.10 2.39 4.52 1.51 1.90 1.21 21.8 0.885 1.65
o-Cresol2 1.72 12.3 10.7 1.94 0.36 3.93 1.93 98.5 0.669 3.8 2.93 5.75 0.001 7.16 7.90 1.92 9.16 1.14 9.46 0.289 273 0.668 3.9
10-16-97 13:03:11
Aniline3 1.92 3.51 2.1 1.74 0.52 6.32 1.81 3.2 1.18 1.92 1.35 6.62 1.57 0.01 1.20 2.81 0.75 1.93 1.86 4.29 1.43 1.68 1.70
Phenol3 1.73 5.4 3.2 1.66 0.48 12.7 1.68 4.97 1.13 2.40 1.65 5.71 0.22 1.99 5.12 2.72 1.33 1.64 2.33 2.61 3.34 1.24 2.50
Benzoic acid3 3.11 2.72 10 2.52 0.57 15.4 2.67 2.51 1.77 6.8 2.35 0.088 0.005 1.52 2.85 1.02 0.38 6.07 7.52 29.3 0.26 5.84 7.40
p-Methoxyphenol3 1.65 29.2 12.1 1.93 0.28 5.21 1.87 71.4 0.80 3.6 2.10 14.6 0.001 7.05 8.88 1.98 16.5 1.50 4.10 0.56 208.0 0.776 3.40
o-Cresol3 2.29 8.16 2.1 1.57 0.42 8.18 2.45 8.64 0.94 1.85 2.61 5.2.0 0.039 3.12 4.20 3.38 3.05 1.33 1.60 1.93 10.7 0.91 1.70
coida
Aniline4 1.76 2.57 2.76 1.58 0.71 10.3 1.77 2.58 0.98 2.85 1.27 4.67 1.67 0.034 3.64 2.47 1.12 1.12 2.85 1.74 2.61 0.991 2.76
Phenol4 1.67 3.19 9.88 1.6 .679 20 1.4 3.43 1.41 7.75 1.46 3.1 0.12 2.37 9.37 1.67 3.18 1 1 1004 10.0 6.15 0.825 2.54 8.70
Benzoic acid4 2.07 4.81 0.75 2.05 0.52 8.64 2.08 4.84 0.989 0.73 2.13 9.39 0.33 2.08 1.46 3.03 1.73 1.31 1.00 1.98 5.08 0.975 0.73
p-Methoxyphenol4 1.31 26.4 8.71 1.45 0.24 3.24 1.44 80.7 0.812 2.40 1.55 17.82 0.001 7.56 8.82 1.57 15.2 1.47 1.45 1.21 21.8 0.885 1.65
o-Cresol4 1.786 9.3 4.38 1.925 0.39 6.1 1.88 12.23 0.84 2.35 2.07 6.0 0.03 3.75 5.67 2.1 5.88 1.01 2.35 0.989 20.85 0.80 2.41
KHAN, ATAULLAH, AND AL-HADDAD
Aniline5 1.74 3.31 6.36 1.585 0.61 15.0 1.53 3.32 1.403 4.63 1.474 2.49 0.132 2.00 4.26 2.09 .607 2.512 4.75 7.43 0.71 2.82 4.81
Phenol5 1.46 5.93 7.54 1.468 0.547 22.79 1.26 3.82 1.62 5.54 1.465 3.05 0.118 2.39 9.40 2.305 1.202 1.915 4.42 3.09 2.57 1.52 4.42
Benzoic acid5 2.81 3.115 5.79 2.78 0.679 13.39 2.57 3.11 1.21 5.38 2.43 7.88 0.515 1.379 7.20 2.803 3.115 1 1 1004 5.79 6.524 1.274 1.787 5.3
p-Methoxyphenol5 1.678 25.4 6.37 1.92 0.296 7.67 1.825 34.97 0.862 3.07 1.98 9.83 0.003 5.52 12.41 2.076 11.71 1.402 3.32 0.945 59.81 0.842 3.04
o-Cresol5 1.98 16.76 9.72 2.41 0.357 6.17 2.34 49.97 0.0718 5.164 1.868 38.83 2.38 1 1 1004 17.445 2.263 11.34 1.12 7.08 1.01 44.14 0.795 5.12
Aniline6 1.448 7.251 3.24 1.59 0.478 9.54 1.52 8.31 0.874 1.98 1.701 1.255 0.012 3.62 4.32 1.73 4.57 .952 2.10 0.895 13.36 0.815 2.03
Phenol6 1.687 4.345 20.4 1.72 0.653 34.0 1.22 5.26 1.66 13.61 1.388 1.468 0.035 2.354 15.0 0.533 0.555 6.63 14.42 12.69 0.545 4.31 13.9
Benzoic acid6 3.10 3.94 12.27 3.29 0.666 25.0 2.097 4.991 1.684 7.53 2.276 7.34 0.331 1.171 3.33 0.881 0.544 6.71 9.10 21.20 0.537 4.227 8.70
p-Methoxyphenol6 1.98 17.1 3.54 2.21 0.316 9.13 2.05 19.1 0.938 2.695 2.204 14.76 0.026 4.021 12.62 2.93 4.77 1.62 1.606 1.548 24.35 0.914 2.48
o-Cresol6 1.934 36.0 13.34 2.56 0.31 6.36 2.44 93.67 0.759 4.43 1.98 80.1 2.59 0.022 26.31 2.33 19.67 1.43 6.92 98.79 0.983 0.814 4.77
Note. Superscripts 1–6 refer to adsorbent. See Table 1 for descriptions and origins.
ADSORPTION STUDIES OF AROMATIC POLLUTANTS 159
FIG. 2. (a) Comparison of different isotherm equations for the adsorption of p-chlorophenol from aqueous solution (7). (b) Comparison of different
isotherm equations for the adsorption of toluene from dilute aqueous solution (4).
having pH values lower than 7. Aniline solution has pH lected concentration range. A FORTRAN program has been
value higher than 7 and has shown minimum adsorbence for used for the estimation of coefficients for the reported corre-
the above reported adsorbent 1, while on adsorbent 3, it was lations based on nonlinear optimization technique (27). All
highly adsorbed due to its surface structure. the isotherm equations with the generalized expression (Eq.
The surface heterogeneity and chemical nature of the ad- [13]) have been tried and the results are given in Table 2.
sorbent surface are important factors for the determination The value of the mean absolute percentage error É[qe (experi-
of the influence of pH on the adsorption of single solute mental) 0 qe (predicted)]/qe (experimental) 1 100É has
systems. It has been discussed (26) that high pH depresses been selected as a test criterion for the fit of the correlation.
the equilibrium amount adsorbed but neutral salt addition Equations [2] and [13] which are not very different from
increases adsorption. The buffers have unnoticeable influ- each other, represent the data for the whole reported experi-
ence or adsorption. Ionization of the sorbates at high pH mental concentration range with minimum average percent-
values and changes in the nature of the solid surface with age error. The physical significance for each constant in
pH are responsible for the above reported results. The change these equations has been explained by Martinez and Basmad-
in selectivity with pH value indicates that electrostatic inter- jian (28). Equation [13] is a simplification of a generalized
action between surface and sorbate ions are very important equation put forward by Khan et al. (6) and successively
at high values of pH but specific interaction becomes more used for bisolute systems due to its unique characteristic that
significant with decreasing pH. it can cover both extreme cases, Langmuir and Freundlich
In Fig. 1a, the adsorption data for benzoic acid on six type isotherms. The amount adsorbed is a binomial function
different adsorbents are shown for comparison and in Fig. of equilibrium concentration and can accommodate all dif-
1b the selectivity of various sorbates for a specific granular ferent types of variations where other correlations fail.
activated carbon (adsorbent 4) is given. Phenol and aniline The comparison of different isotherms for adsorption of
sorbates have less adsorption than benzoic acid, o-cresol, p-chlorophenol (7) and toluene (4) from aqueous solutions
and p-methoxyphenol due to polarity, molecule structure, on activated carbon over a wide concentration range is
mass, and size. Yenkie and Natarajan (3) have presented shown in Figs. 2a and 2b and the coefficients for all reported
their data using Langmuir and Freundlich isotherms for se- isotherms are tabulated in Table 3. Figure 2a has an enlarged
% err
2.6
3.7
1.5
1.6
7.0
13
3.2
8.23
tion range there is a large average percentage error for almost
(1 / aCe)b
all isotherms with the exception of Eqs. [2] and [13], where
Present model
0.8
0.85
0.55
0.84
0.86
1.71
0.88
1.01
qoaCe
b
the average percentage error is within an acceptable limit.
For almost all systems the numerically evaluated values
155.0
258.0
482.0
99.0
3.53
3.96
40.7
1427.0
qe Å
a
of the saturated amount adsorbed q0 , using Eqs. [1–6] and
Note. Sorbates and references are as follows: toluene (4); acetone, p-cresol, and p-chlorophenol (7); benzene, n-pentanol, 4n-propylphenol, and 4-methylphenol (33).
[13], have the same order of magnitude. The values of the
0.9
1.65
0.11
0.82
5.93
0.28
0.94
0.89
Langmuir coefficient a also have behavior similar to that
qo
observed for q0 with very few exceptions. In Table 5, the
% err
2.3
2.5
7.3
17.0
6.43
6.58
6.87
13.1
coefficients for Dubinin–Astakov equation (Eq. [10a]) and
the generalized equilibrium expression (Eq. [13a]) for dif-
IAS model (1983)
1.25
1.16
1.73
1.81
1.83
0.84
1.59
1.87
ferent sorbates at specified experimental temperature range
s
Eq. [12]
293.0
108.0
26.7
0.16
12.2
15.5
2.28
14.1
does not represent experimental data adequately with an av-
Comparison of Different Isotherms for Single Organic Solutes in Aqueous Solution
2.33
2.64
3.84
0.55
1.82
1.32
qo
5.0
11
45.0
16.0
7.3
24.3
75.0
25.7
8.1
9.0
0.9
0.03
0.19
2.57
3.69
L31
VST model (1985)
1.95
0.19
2.19
0.02
6135.0
78.4
0.01
0.01
L13
2.98
2055.0
17.3
86.0
35.1
2.39
5.16
14.2
39.0
0.98
qo
7.0
3.6
8.5
2.58
1.94
1.35
1.42
12.5
0.6
0.9
0.86
0.85
1.27
0.85
0.67
1.01
qoaCe
670.0
503.0
60.4
1.95
83.6
12.2
63.8
qe Å
5.4
5.4
13.0
6.56
16.5
12.3
15.3
32.1
0.2
0.6
0.27
0.58
0.17
0.38
0.32
0.35
Table 6.
7.3
8.3
5.81
20.9
13.1
17.5
13.3
6.36
1 / aCe
2.58
0.49
1.47
0.88
qo
n-Pentanol
Benzene
Acetone
Toluene
Ammoniaa 249 0.224 6.998 5.554 1.267 0.404 18.26 0.397 4.65 0.9 3.78 0.388 4.538 0.87 3.8
Ammoniaa 273 0.068 6.878 2.278 .881 0.441 9.26 0.111 4.72 0.916 1.888 0.098 5.136 0.884 1.9
Ammoniaa 303 0.024 6.045 6.525 .23 0.659 5.68 0.271 0.844 0.585 2.69 0.21 0.903 0.459 2.9
Ammoniaa 353 0.020 2.070 12.13 .068 0.683 3.98 23.31 0.07 0.323 4.029 1.87 0.047 0.331 4.02
Ammoniaa 424 0.018 0.660 14.6 0.031 .58 9.92 98.7 0.031 0.421 9.93 1.186 0.028 0.419 9.81
Isobutaneb 298 2.833 1.724 5.258 1.08 0.131 7.01 4.79 1.44 0.945 2.385 4.924 1.3 0.943 2.37
Isobutaneb 323 1.750 1.520 7.57 .914 0.132 7.02 6.169 1.091 0.911 5.29 6.504 0.902 0.908 5.4
Isobutaneb 373 0.312 1.352 7.76 .363 0.318 17.85 0.466 1.052 0.936 8.36 0.391 1.149 0.949 7.86
a
(29).
b
(30).
Parker (13) used the Dubinin–Astakov equation (Eq. [10]) differential molar adsorption enthalpy,
for the evaluation of adsorption potential, adsorption poten-
tial distribution, adsorption enthalpy, and adsorption entropy bA b / aaeT
(Fig. 6). The equations for the following functionalities DHads Å 0 ,
ab
were developed by Jaroniec et al. (15) and are given as
adsorption potential,
and differential molar adsorption entropy
A Å RT ln
CS
CeS D or RT ln S
fT / c
Ce D ,
DSads Å 0
aae A 10 b
, [10a]
b
adsorption potential distribution,
x(A) Å abA b 01 exp( 0aA b ), where ae is the thermal coefficient of the maximum capacity
FIG. 3. (a) Comparison of different isotherm equations for the adsorption of isobutane (gas) at different temperatures (30). (b) Comparison of
different isotherm equations for the adsorption of ammonia (gas) for different temperatures on activated carbon (29).
TABLE 5
Comparison of Different Absorption Correlations for Different Temperatures
Isobutane1 298–373 4.659 2.13 1 1008 2512.7 04506.4 1.741 13.48 1.018 632.18 04747.9 019.91 0.915 6.4
Ammonia2 249–424 176.345 3.88 1 1005 1316.4 8235.3 1.155 14.37 4.13 210.16 03365.7 019.81 0.839 12.4
Phenol3 293–353 3.302 1.01 1 10025 264.92 94.22 5.59 11.54 2.756 2523.4 01358.8 012.91 0.962 11.57
Phenol4 303–328 23.762 4.93 1 1009 152.17 27921 1.947 14.79 4.5 1 1005 40.88 0193.99 17.543 0.515 6.4
p-Chlorophenol4 303–328 3.258 9.79 1 10021 38.69 3368.9 4.47 6.09 0.842 3.623 0285.6 2.217 0.802 3.54
p-Nitrophenol4 298–328 6.55 8.67 1 1002 0.131 09.71 0.272 8.17 1.83 135.94 0209.03 01.989 0.92 7.26
Propanol5 273–343 3 5.27 1 1004 0.528 2.839 0.938 15.21 0.155 45.44 01690.8 09.557 0.524 9.07
Propionitrile5 273–343 2.996 1.61 1 1007 5.527 34.842 1.702 7.4 0.143 38.651 02488.1 011.313 0.505 9.47
Cobalt phthalocyanin6 293–333 0.647 1.67 1 1003 3308.7 35519 0.5 15.47 0.046 34.231 056.787 21.49 0.895 10.54
Note. Superscripts 1–6 refer to the following references, respectively: 1, Cochran et al. (30); 2, Brunauer (29); 3, Bhatia et al. (34); 4, Present work.
5, Radke and Prausnitz (7); 6, Leitao et al. (12).
and CS is saturated solubility and the characteristic energy well to the generalized isotherm correlation and have shown
is related to the coefficient a as equal to a 01 / b . minimum deviation between predicted and measured values.
The experimental data for different temperatures have From this correlation a unique value of DHads has been evalu-
been analyzed using the Dubinin–Astakov equation (Eq. ated for a given sorbate–adsorbent system, confirming
[10a]) and the generalized equation (Eq. [13a]) for the eval- monolayer surface coverage.
uation of differential molar enthalpy, DHads , and entropy,
DSads . The accuracy of the values is dependent on the degree CONCLUSION
of fitness, which can be judged by comparing average per-
centage error. The value of ae has been calculated from Surface heterogeneity, pore structure, and surface charge
liquid density obtained from ‘‘Physical and Thermodynami- are important factors in determining the adsorption charac-
cal Properties of Pure Chemicals’’ (32) as a function of teristics of an adsorbent for a particular sorbate–adsorbent
temperature, and CS has been assumed to be a linear function system. For a given adsorbent, the adsorption phenomenon
of temperature, (CS Å cT / f ), for a narrow range of for different sorbates is a strong function of solubility, activ-
experimental temperature. The values of differential molar ity (intermolecular forces), polarity, and molecule structure,
enthalpy of adsorption, DHads , for different sorbate–adsor- mass, and size. The hydrophilic and hydrophobic nature of
bent systems have been plotted in Fig. 5b. The calculated the molecules of chemicals (sorbates) is also important when
value of DHads using Eq. [10a], increases with increased aqueous solutions are used for adsorption.
loading of adsorbent. This behavior is not in accordance In general, the high values of pH suppress adsorption
with commonly used isotherms except for BET multilayer on activated carbon, but addition of neutral salts expedites
adsorption, where DHads is higher for the first monolayer adsorption. The influence of pH is attributed to the electro-
and gradually decreases as the second or multilayers are static interaction between the adsorbent surface and the sor-
formed. All the experimental and published data have fitted bate molecule or ion.
TABLE 6
Differential Molar Enthalpy and Entropy of Adsorption
FIG. 4. (a) Comparison of different isotherm equations for the adsorption of propanol at different temperatures from the aqueous solution on activated
carbon. (b) Comparison of different isotherm equations for the adsorption of cobalt phthalocyanine (dye) for different temperatures from the dilute
aqueous solution on activated carbon.
Most of the reported data cover a very limited concentra- fit for the entire data. Equation [13] can cover both funda-
tion range; for high equilibrium concentrations, the pub- mental type isotherms, Freundlich for aCe & 1 and Langmuir
lished isotherm equations have large deviations, with the for b approaching unity.
exception of Eq. [2] and [13], which have shown the best The temperature influence for gaseous adsorption is given
FIG. 5. (a) Comparison of different isotherm equations for the adsorption of phenol for different temperatures from the aqueous solution on activated
carbon. (b) Comparison of different differential molar enthalpies of adsorption of various sorbates as function of relative adsorption.
Greek Letters
ae Thermal coefficient of [K 01 ]
maximum adsorbed
amount
g Constant in Eq. [13a] [K 01 ]
d Constant in Eq. [13a]
FIG. 6. The chemical structure of cobalt phthalocyanine (dye) adsorbed
DHads Differential molar heat of [kJ kmol 01 ]
from the dilute aqueous solution on activated carbon. adsorption
DSads Differential molar entropy [kJ kmol 01 K]
of adsorption
in terms of equilibrium pressure as d ln Pe Å ( DHads / k Constant in Eq. [15]
RT 2 )dT. This equation has been introduced in the general- L13 , L31 Wilson parameter for
ized isotherm equation and successfully used in relating the interaction between
experimental data at different temperatures for adsorption in solute and solvent
both gaseous and dilute aqueous medium with minimal error. u Relative adsorption [qe /q0 ]
The other equation which has temperature dependency (Eq. s Constant in Eq. [12]
[10a]) has also been tried to represent the experimental data. n Constant in Eq. [6]
This adsorption equation for the value of constant, b equal to j Constant in Eq. [14]
unity, would relate temperature to equilibrium concentration, f Constant in Eq. [10a] [mol m03 ]
Ce , and amount adsorbed, qe , as qe /q0 Å (Ce / cT / f ) aRT . c Constant in Eq. [10a] [mol m03K 01 ]
The exponential equation has a poor fit and predicted value x Adsorption potential
of differential heat of adsorption has showed an increase distribution (Eq. [10a])
with the increase of loading of adsorbent.
NOMENCLATURE REFERENCES
1. Crittenden, J. C., Hand, H. B., Arora, H., and Lykins, B. W., Jr., J.
Am. Water Works Assn. 79, 74 (1987).
a, a1, a2 Constants in Eqs. [1–12]. 2. Noll, K. E., Gounaris, V., and Hou, W., ‘‘Adsorption Technology for
Air and Water Pollution Control,’’ Lewis Publishers, Chelsea, MI,
A Adsorption potential RT ln(Ce /CS ) 1992.
b Constant in Eqs. [2–13] 3. Yenkie, M. K. N., and Natarajan, G. S., Sep. Sci. Technol. 28, 661
Ce Equilibrium concentration [mol m03 ] (1991).
CS Concentration to form a [mol m03 ] 4. Chatzopoulos, D., Varma, A., and Irvine, R. L., AIChE J. 39, 2027
monolayer on adsorbent (1993).
5. Fritz, W., and Schlunder, E. U., Chem. Eng. Sci. 29, 1279 (1974).
surface 6. Khan, A. R., Al-Waheab, I. R., and Al-Haddad, A., Environ. Tech. 17,
De Effective diffusional [m2 s 01 ] 13 (1996).
coefficient for adsorbent. 7. Radke, C. J., and Prausnitz, J. M., Ind. Eng. Chem. Fund. 11, 445
D0 Constant in Eq. [15] (1972).
DP Pore diffusional coefficient [m2 s 01 ] 8. Fritz, W., and Schlunder, E. U., Chem. Eng. Sci. 36, 721 (1981).
9. Sheindrof, C., Rebhun, M., and Sheintuch, M., J. Colloid Interface Sci.
DS Surface diffusional [m2 s 01 ] 79, 136 (1981).
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DSO Constant in Eq. [14] 2102 (1997).
H Henry’s law constant lim (qe /Ce ) 11. Toth, J., Acta Chim. Acad. Sci. Hung. 69, 311 (1971).
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J. Chem. Eng. 70, 690 (1992).
n, n1, n2 Constant in Eq. [7] 13. Parker, G. R., Jr., Adsorption 1, 113 (1995).
Pe Equilibrium pressure of [kPa] 14. Jossens, L., Prausnitz, J. M., Fritz, W., Schlunder, E. U., and Myers,
sorbate gas A. L., Chem. Eng. Sci. 33, 1097 (1978).