Water Res. Vol. 19. No. 4. pp. 491~t95. 1985 0043-1354 85 53.00 + 0.

00
Printed in Great Britain. All rights reserved Copyright ~ 1985 Pergamon Press Ltd

THE ADSORPTION OF VARIOUS POLLUTANTS FROM

AQUEOUS SOLUTIONS ON TO ACTIVATED CARBON
G. MCKAV *, M. J. BINO: and A. R. ALTAMEMI"
*Department of Chemical Engineering, Queen's University, Belfast, Northern Ireland and
-'Royal Scientific Society, Amman, Jordan

(Received July 1984)

Abstract--The ability of activated carbon, Filtrasorb 400, to adsorb various pollutants from aqueous
solutions has been studied. The pollutants investigated are phenol, p-chlorophenol, sodium dodecyl
sulphate, mercuric ions and chromic(Ill) ions. The saturation adsorption capacity of the activated carbon
for the pollutants is 213,434, 361, 35 and 138 mg g- i for phenol, p-chlorophenol, sodium dodecylsulphate,
chromium(IlI) and mercuric(ll) respectively. Equilibrium isotherm analyses were undertaken using
Langmuir and Freundlich equations.

Key words--adsorption, activated carbon, water pollution, equilibrium isotherms, phenol, p-

chlorophenol, sodium dodecyl sulphate, mercuric ions, chromium(III) ions

NOMENCLATURE plants. In the trivalent state chromium is not believed

a = Langmuir constant (dm 3mg -L)
c = dimensionless liquid phase concentration
Co = initial concentration of pollutant in solution
(mg dm- ~)
C, = Concentration of pollutant in solution at equilibrium
(rag din-3)
K = Langmuir constant (dm 3 g-~)
K r --- Freundlich constant (mg g-t )
m = concentration of carbon in solution (g dm -3)
M --- mass of carbon (g)
N = Freundlich exponent
q = dimensionless solid phase concentration
Q,--- concentration of pollutant in the carbon (mgg -~)
r = dimensionless separation factor
X = weight of pollutant adsorbed (rag).
INTRODUCTION
Activated carbon adsorption offers one of the most
efficient processes available for removing certain or-
ganics and inorganics from wastewater. The capacity
of activited carbon for a certain type of pollutant is
important for designing adsorption contacting sys-
tems. The aim of the present work is to determine the
adsorption capacity of activated carbon for a number
of substances in aqueous solution, namely, phenol,
chlorophenol, dodecyl hydrogen sulphate sodium salt
(SDS), Hg 2+ and Cr 3+.
Phenolic compounds (Lewis, 1980) are discharged
in wastewaters from industries such as refineries, gas
undertakings, pharmaceutical and pesticide (Nem-
erow, 1971) manufacturers etc. SDS is widely used in
many applications as in lube oils to stabilize anti:
oxidants in photographic developers, tin plating and
many others.
Certain inorganic pollutants can create severe
problems in conventional wastewater treatment
to be toxic but it does inhibit the growth of micro-
organisms in activated sludge processes. Trivalent
chromium is discharged f r o m tanneries and certain
metal treatment plants.
Mercury ions, Hg -'+, in industrial effluents are
frequently related to the discharge of effluent from
battery cell manufacturers and chloralkali plants
(Cowley et aL, 1966; Caban and Chapman, 1972).
Mercury is most toxic to man in its methylated form
and certain microorganisms in water are capable of
the conversion of mercury to methyl mercury.
A series of experiments have been performed in this
work to assess the capacity of activated carbon, Type
Filtrasorb 400, to adsorb several contaminants from
aqueous solutions. Adsorption isotherms have been
determined and analysed according to the Langmuir
and Freundlich equations.
EXPERIMENTAL
Materials
The solutes used were obtained from BDH chemical
suppliers. The isotherms were all conducted using distilled
water and all the chemicals studied were readily soluble in
water.
The granular activated carbon was Filtrasorb 400 and it
was supplied by Chemviron Ltd. Table 1 shows the physical
properties of this carbon.
The carbon was milled in a ball mill and then sieved into
various particle size ranges as shown in Table 2. The sieved
carbon was washed with distilled water to remove fines and
dried to constant weight at 105:C. Drying for 24h was
usually sufficient to maintain constant weight, after which
the carbon was kept in a desiccator.
Analysis
Phenol and p-chlorophenol absorb ultraviolet radiation
at ).,~x = 270 and 280nm respectively. A Perkin-Elmer
Model 550-S spectrophotometer was used to determine
concentrations of phenol and p-chlorophenol. Dodecylhy-

491
492 G. McKAY et al.

Table I. Physical properties of Fihrasorb 400

Total surface area [(N., BET method)m: kg-'] (I.05--1.2) x 106
Solid phase density (kg m -J) 2100
Particle density (wetted in water) (kg m -~) 1300-1400
Porosity 0.38
Iodine number 1000-1100
Methylene Blue number 260-300

Table 2. Carbon particle size range were observed to become slightly turbid after 4 days
Particle size Average particle of contact with carbon. This was attributed to some
range diameter (dp)
Mesh size (~m) (~m) sort of bacterial growth in the solution and in partic-
65 150-250 200 ular the liquid-solid interface. Therefore, a procedure
48 250--355 303 whereby a vigorous shaking of adsorbent/solution
35 355-500 428 mixtures of all solutes, except p-chlorophenol, for 2
28 500-710 605
20 710-1000 855 days was found enough to attain equilibrium, p-
Chlorophenol, on the other hand did not develop
such complications and a contact time of up to 4
drogen sulphate (SDS) concentrations were measured usmg weeks was found necessary to establish equilibrium
Beckman Model 915-B Total Organic Carbon Analyser. using a much lower degree of agitation.
Hg2~ and Cr 3* were determined using Perkin-Elmer 300 Adsorption isotherms of the studied organic com-
atomic absorption spectrophotometer. Mercury concen-
trations were measured by the sodium borohydrate pounds were of the Langmuir form and typical of
flameless technique, while Cr 3" was determined using an those encountered in the adsorption of most organic
air/acetylene flame. compounds from dilute aqueous solutions (Weber
Experimental and Morris, 1964; Glasstone, 1951; McKay, 1982).
Stock solutions of the adsorbates were prepared with Adsorption isotherms of mercuric and chromic ions
distilled water in the desired initial concentration and were of the Freundlich type. Figures 1-5 show the
subsequent concentrations were made by dilution. Ad- adsorption isotherms of the studied adsorbates; Figs
sorption isotherms were obtained by shaking a fixed weight
1, 2, 4 and 5 show isotherms for different particle size
of carbon with 0.05 dm ~ of pollutant solution of known
initial concentration. Various solute concentrations were ranges and Fig. 3 shows the effect of changing pH on
used and the system was allowed sufficient time to reach the adsorption of Cr 3+ ions.
equilibrium. The effect of carbon particle size was also The effect of pH on the adsorption of Cr 3+ was
studied. The adsorbed amounts were calculated from: studied to a limited extent and is shown in Fig. 3.
x Co-C Cr 3÷ tends to form a precipitate at pH higher than
Q~ (1)
M rn pH 5.0 and therefore adsorption by carbon is difficult
where to quantify at the higher pH value of 5.7 and the
m = g carbon dm -3 " t r u e " adsorption at this pH is masked by precip-
itation. Consequently only the data at pH 5 are
RESULTS AND DISCUSSION analysed to determine the isotherm constants.
The adsorption curves in Figs 1, 2, 4 and 5 indicate
Equilibrium isotherms a particle size effect. The difference in adsorption
Adsorption at equilibrium conditions was deter- capacity with particle size is small but significant, it
mined for each pollutant separately. Phenol solutions is not proportional to the external surface area of the

200

///. 00<.m,

100
O 605
T • 18°C

I I I I I
100 200 300 400 500
C, (mg din-31
Fig. 1. Adsorption isotherms for phenol on carbon.
 Adsorption of pollutants on to carbon 493

5oo~ 75

400 i" 50
o•O57 • 50
dp • 303/t.m

3O0
S
~A
dp(~m)

0 200
d
o / T - 18"C

"~'------"
/.~ A 303 25
~ 428
• 605 o / ~
• 855
x 200 T-20"C
x [ I
100 200
Ce ( mg dm -3 )

100 Fig. 3. Effect ofpH on the adsorption isotherm for Cr 3~ on

carbon.

particles. Consequently, the effect is difficult to ex-

I I I
100 200 3OO 400 plain. It is possible that the adsorbate molecules may
be unable to penetrate all the internal pores within
Ce(mg dm -3 )
the carbon particles. The greater the diffusion path
Fig 2 Adsorption isotherms for pochlorophenol on (proportional to particle radius), the more difficult
carbon.

150 o
o
A

[
100
E:n

d
5O

I I
0 50 100
C, (mg dm "3)

Fig. 4. Effect of particle size for the adsorption of Hg -'÷ on carbon.

400

300
A-----'--- dp (,u.m)

>/K
/ oo
:
20O
6 • 428
• 605

100
T , 27"C

I I I I I I I
100 200 300 400 500 600 700
Ce (rag dm-3)
Fig. 5. Adsorption isotherms for sodium dodecyl sulphate on carbon.
494 G. McKAY et al.

becomes complete saturation of the particle; the so L

greater will be the probability that the solute mole- 0.3

cules will come up against pores too small for the
solute to penetrate. Alternatively it is possible that
the fine particles are derived from the highly activated
outer portion of the granules of carbon and the
coarser particles are from the less activated inner
core.
Equations (2) and (3) represent the Langmuir and
the Freundlich equations respectively.
X KC,, u
Q, = - - = 9 - - (2)
;vl 1 + aC~
0.1
Z
O = 7 ~ = K F C,t.,.v. (3)

Figures 6 and 7 show the Langmuir isotherm plots

for phenol and chlorophenol. The linear forms of
;o
Langmuir and Freundlich isotherms are given by 1 I I
equations (4) and (5) respectively. 50 100 150
Ce ( m g d m -3 )
The Freundlich plots for four of the adsorbates on
to carbon, size range 500-710/~m, are shown in Fig. 8. Fig. 7. Linearized Langmuir plot for p-chlorophenol
adsorption.
As the isotherms reach saturation and monolayers
are formed the Freundlich plots are not applicable 2.B~
but up to monolayer formation the plots in Fig. 8 are
linear.
C~ 1 a
X/M = -K + K C¢ (4)

X 1
In ]-~ = In Kr + ~ In C,. (5) 16 . ~
~, Phenol
The Langmuir and Freundlich isotherm constants 1.2 o /P - ChloropheooI
• Mercuric ions
of the relevant adsorbates are listed in Table 3. • Sodium dodecyl sulphate
The theoretical plots shown in Fig. 9 show that I I
both Freundlich and Langmuir equations are in 1.0 2.0
log C,
agreement with experimental results for low values of
C,. The Langmuir isotherm gives the best agreement Fig. 8. Freundlich isotherm plots for the adsorption of
phenol, p-chlorophenol, mercuric ions and sodium dodecyl
over the whole adsorption range since it predicts the sulphate on to carbon (500-710pm).

0.006 "~ ~ ~- ~'-

/ ^( ." ." / / / /
l 2' ,'.," / / / /
0.50 • " 0.6 -i I d / / / / I
I I 0.5

0.4

025
/ 5 (
/
I I I
i i
0 02 0 4 0.6 0.8 1.0
0 50 100

Ce (rag drn-3) c
Fig. 9. Dimensionlessconcentration isotherms on functions
Fig. 6. Linearized Langmuir plot for phenol adsorption on of separation factor. C) SDS, r = 0.006: A Hg2", r = 0.17;
carbon. • Cr 3-, r =0.23.
 Adsorption of pollutants on to carbon 495

Table 3. Langrnuir and Freundlich constants for activated carbon.

de 500-710~m =

Langmuir Freundlich
K
a K "a Kr 1
Pollutant (din3m8-' ) (dm~g-K) (mgg-L) (mgg-t )
Phenol 0.10 21.3 213 50 0.26
p-Chlorophenol 0.1-14 62.50 434 126 0.25
SDS 0.180 65.06 361 72 0.27
Cr3" 0.015 0.52 35 2.3 0.'4Z
Hg"* 0.034 4.68 138 20 0.46

experimentally observed monolayer coverage better
than the exponentially increasing Freundlich iso-
therm. The theoretically predicted Langmuir mono-
layer coverages, defined by the K/a ratio in Table 3,
are 213, 434, 361, 35 and 138mgg -t carbon for
phenol, p-chlorophenol, sodium dodecyl sulphate,
chromic and mercuric ions.
There is a large difference in the monolayer ad-
sorption capacities between phenol and chloro-
phenol. Although chlorophenol is a larger organic
molecule than phenol, its adsorption capacity is
around 400 mg g-' carbon, having a small particle
size dependence, whereas the adsorption capacity of
phenol is around 210-230mgg -~ carbon. T h e
difference in adsorption capacities must therefore be
linked to the solute adsorbent bonding. The presence
of the chlorine atom produces a more polar charge
over the molecule and enhances its affinity for ad-
sorption at the carbon surface.
Effect of isotherm shape
The influence of isotherm shape on whether ad-
sorption is "favourable" or "unfavourable" has been
considered Weber and Chakravorti (1974). For the
Langmuir-type adsorption process the isotherm
shape can be classified by a term "r" a dimensionless
constant separation factor.
1
r = - -
1 + aC0"
Values of r < 1.0 represent favourable adsorption
and values greater than 1.0 represent unfavourable
adsorption.
The results for three of the adsorption systems,
namely, sodium dodecyl sulphate, Hg -'+ and Cr ~+ are
shown in Fig. 9 in the form of the dimensionless
isotherm. The r values for all three systems are
favourable.
Theoretical isotherms
The theoretical isotherms can be obtained from
equations (2) and (3) for Langmuir and Freundlich
analysis. The theoretical results are compared with
the experimental results in Fig. 10. The agreement
between experimental values and theoretical data is
good over most of the isotherm except at high Ce
values where the Langmuir gives the best fit.
CONCLUSION
The adsorption capacity of five pollutants in
ous solutions on to activated carbon has been studied.
The Langmuir and Freundlich constants have been
determined. The Langmuir monolayer adsorption
capacities for phenol, p-chlorophenol, sodium do-
decyl sulphate, mercuric ions and chromium ions on
to carbon are around 213, 434, 361, 138 and
(6) 35 mg g - ' respectively. The capacities show a small
particle size dependence possibly due to the fact that
the solute molecules cannot completely penetrate all
the pores within the carbon particles.

REFERENCES
Caban R. and Chapman T. W. (1972) A.I.Ch.E.J! 18, 892.
Cowley W. E. et al. (1966) Chem. Engng 345.
Glasstone S. (1951) Textbook of Physical Chemistry, 2nd
Edition. Macmillan, London.
Lewis W. M. (1980) Developments in Water Treatment.
Applied Science, London.
McKay G. (1982) J. Chem. Technol. Biotechnol. 32, 759.
Nemerow N. L. (1971) Liquid Wastes from Industry--
L_____ I I ' 1
Theories, Practices and Treatment. Addison-Wesley,
100 200 3(30 400 Philippines.
Ce (mq dm -3) Weber T. W. and Chakravorti R. K. (1974) A.LCh.E.JI 20,
228.
Fig. 10. Comparison of theoretical isotherms for phenol. A Weber W. J. Jr and Morris J. C. (1964) J. sanit. Engng Div.
Experimental; © Langmuir; • Freundlich. Am. Soc. cir. Engrs 90, 79.