CHAPTER 13
ADSORPTION OF ORGANIC
COMPOUNDS
Vernon L. Snoeyink, Ph.D.
Ivan Racheff Professor of Environmental Engineering
Department of Civil and Environmental Engineering
University of Illinois at Urbana-Champaign
Urbana, Illinois
R. Scott Summers, Ph.D.
Professor of Environmental Engineering
Civil, Environmental, and Architectural Engineering
University of Colorado
Boulder, Colorado
Adsorption of a substance involves its accumulation at the interface between two
phases, such as a liquid and a solid or a gas and a solid. The molecule that accumu-
lates, or adsorbs, at the interface is called an adsorbate, and the solid on which
adsorption occurs is the adsorbent. Adsorbents of interest in water treatment
include activated carbon; ion exchange resins; adsorbent resins; metal oxides,
hydroxides, and carbonates; activated alumina; clays; and other solids that are sus-
pended in or in contact with water.
Adsorption plays an important role in the improvement of water quality. Acti-
vated carbon, for example, can be used to adsorb specific organic molecules that
cause taste and odor, mutagenicity, and toxicity, as well as natural organic matter
(NOM) that causes color and that can react with chlorine to form disinfection by-
products (DBPs). NOM is a complex mixture of compounds such as fulvic and
humic acids, hydrophilic acids, and carbohydrates.The aluminum hydroxide and fer-
ric hydroxide solids that form during coagulation will also adsorb NOM.Adsorption
of NOM on anion exchange resins may reduce their capacity for anions (see Chap-
ter 9),but ion exchange resins and adsorbent resins are available that can be used for
efficient removal of selected organic compounds. Calcium carbonate and magne-
sium hydroxide solids formed in the lime softening process have some adsorption

ADSORPTION THEORY
Adsorption Equilibrium
Adsorption of molecules can be represented as a chemical reaction:
A + B ⇔ A⋅B
where A is the adsorbate, B is the adsorbent, and A⋅B is the adsorbed compound.
Adsorbates are held on the surface by various types of chemical forces such as
hydrogen bonds, dipole-dipole interactions, and van der Waals forces. If the reac-
tion is reversible, as it is for many compounds adsorbed to activated carbon,
molecules continue to accumulate on the surface until the rate of the forward reac-
tion (adsorption) equals the rate of the reverse reaction (desorption). When this
condition exists, equilibrium has been reached and no further accumulation will
occur.
Isotherm Equations. One of the most important characteristics of an adsorbent is
the quantity of adsorbate it can accumulate. The constant-temperature equilibrium
relationship between the quantity of adsorbate per unit of adsorbent q
e
and its equi-
librium solution concentration C
e
is called the adsorption isotherm. Several equa-
tions or models are available that describe this function (Sontheimer, Crittenden,
and Summers, 1988), but only the more common equations for single-solute adsorp-
tion, the Freundlich and the Langmuir equations, are presented here.
13.2 CHAPTER THIRTEEN
The Freundlich equation is an empirical equation that is very useful because it
accurately describes much adsorption data.This equation has the form
q
e
= KC
e

. For fixed values of K and C
e
, the smaller the value of 1/n, the stronger is the
adsorption bond.As 1/n becomes very small, the capacity tends to be independent of
C
e
and the isotherm plot approaches the horizontal level; the value of q
e
then is
essentially constant, and the isotherm is termed irreversible. If the value of 1/n is
large, the adsorption bond is weak, and the value of q
e
changes markedly with small
changes in C
e
.
The Freundlich equation cannot apply to all values of C
e
, however. As C
e
increases, for example, q
e
increases (in accordance with Equation 13.1) only until the
adsorbent approaches saturation.At saturation, q
e
is a constant, independent of fur-
ther increases in C
e
, and the Freundlich equation no longer applies. Also, no assur-
ance exists that adsorption data will conform to the Freundlich equation over all

neglected in the model development), and other factors.
Factors Affecting Adsorption Equilibria. Important adsorbent characteristics
that affect isotherms include surface area, pore size distribution, and surface chem-
q
max
bC
e
ᎏ
1 + bC
e
1
ᎏ
n
ADSORPTION OF ORGANIC COMPOUNDS 13.3
13.4 CHAPTER THIRTEEN
FIGURE 13.1 Pore size distributions for different acti-
vated carbons. (Source: Lee, Snoeyink, and Crittenden,
1981.)
istry.The maximum amount of adsorption is proportional to the amount of surface
area within pores that is accessible to the adsorbate. Surface areas range from a few
hundred to more than 1500 m
2
/g, but not all of the area is accessible to aqueous
adsorbates.The range of pore size distributions in an arbitrary selection of GACs is
shown in Figure 13.1.A relatively large volume of micropores (pores less than 2 nm
diameter d) (Sontheimer, Crittenden,and Summers, 1988) generally corresponds to
a large surface area and a large adsorption capacity for small molecules, whereas a
large volume of mesopores (2 < d < 50 nm) and macropores (d > 50 nm) is usually
directly correlated to capacity for large molecules.The fulvic acid isotherms in Fig-
ure 13.2 are for the same activated carbons whose pore size distributions are shown

the molecule can gain entrance to the pores. When an increase in size causes the
molecule to be excluded from some pores, however, adsorption capacity may
decrease as solubility decreases. As molecular size increases, the rate of diffusion
within the activated carbon particle decreases, especially as molecular size
approaches the particle’s pore diameter.
The affinity of weak organic acids or bases for activated carbon is an important
function of pH. When pH is in a range at which the molecule is in the neutral form,
adsorption capacity is relatively high. When pH is in a range at which the species is
ionized, however, the affinity for water increases and activated carbon capacity
accordingly decreases. Phenol that has been adsorbed on activated carbon at pH
below 8, where phenol is neutral, can be desorbed if the pH is increased to 10 or
above, where the molecule is anionic (Fox, Keller, and Pinamont, 1973). If adsorp-
tion occurs on resins by means of the ion exchange mechanism, the specific affinity
of the ionic adsorbate for charged functional groups may also cause good removal.
The inorganic composition of water also can have an important effect on the
extent of NOM adsorption, as shown in Figure 13.3 for fulvic acids (Randtke and
Jepsen, 1982). After 70 days, a small GAC column was nearly saturated with fulvic
acid. Addition of CaCl
2
at this point resulted in a large increase in adsorbability of
fulvic acid, as reflected in the reduced column effluent concentration. After 140
days, elimination of the CaCl
2
resulted in desorption of much of the fulvic acid. Cal-
cium ion apparently associates (complexes) with the fulvic acid anion to make ful-
vic acid more adsorbable (Randtke and Jepsen, 1982; Weber, Voice, and Jodellah,
1983). Presumably many other divalent ions can act in similar fashion, but calcium
is of special interest because of its relatively high concentration in many natural
waters. Similar effects are expected for other anionic adsorbates, but salts are not
expected to have much effect on the adsorption of neutral adsorbates (Snoeyink,

important effect on the performance of adsorption columns. The nonadsorbable
fraction cannot be removed regardless of the column design, whereas the strongly
adsorbable fraction may cause the effluent concentration to slowly approach the
influent concentration.
Competitive Adsorption in Bisolute Systems. Competitive adsorption is impor-
tant in drinking water treatment because most compounds to be adsorbed exist in
solution with other adsorbable compounds. The quantity of activated carbon or
other adsorbent required to remove a certain amount of a compound of interest
13.6 CHAPTER THIRTEEN
FIGURE 13.3 Effects of calcium chloride addition and withdrawal on column per-
formance (pH = 8.3; TOC = 5.37 mg/L, peat fulvic acid buffer = 1.0 mM NaHCO
3
).
(Source: Randtke and Jepsen, 1982.)
from a mixture of adsorbable compounds
is greater than if adsorption occurs with-
out competition, because part of the
adsorbent’s surface is utilized by the
competing substances.
The extent of competition on activated
carbon depends upon the strength of
adsorption of the competing molecules,
the concentrations of these molecules,
and the type of activated carbon. Some
examples illustrate the possible mag-
nitude of the competitive effect. Jain
and Snoeyink (1973) showed that as
p-bromophenol (PBP) equilibrium con-
centration increased from 10
−4

have been observed in full-scale GAC systems. Effluent concentrations in excess of
influent concentrations can be prevented through careful operation. Crittenden et
al. (1980) showed that the magnitude of the displacement decreased when the value
of C
eff
/C
inf
was lowered at the time the second compound was introduced. Thus, a
reasonable strategy to prevent the occurrence of an undesirable compound at a con-
centration greater than the influent is (1) to monitor the column for that compound
and (2) to replace the activated carbon before complete saturation at the influent
concentration occurs (i.e., before C
eff
= C
inf
).
A number of isotherm models have been used to describe competitive adsorp-
tion.A common model for describing adsorption equilibrium in multiadsorbate sys-
tems is the Langmuir model for competitive adsorption, which was first developed
by Butler and Ockrent (1930) and which is presented in the fourth edition of this
book (Snoeyink, 1990). This model is based on the same assumptions as the Lang-
muir model for single adsorbates. Jain and Snoeyink (1973) modified this model to
account for a fraction of the adsorption taking place without competition. This can
happen if the adsorbates have different sizes and only the smaller adsorbate can
enter the smaller pores (Pelekani and Snoeyink, 1999), or if some of the surface
functional groups adsorb one compound but not the other.Other models that can be
used to describe and predict competitive effects are the Freundlich-type isotherm of
Sheindorf, Rebhun, and Sheintuck (1981) and the ideal adsorbed solution theory of
Radke and Prausnitz (1972) described in the next section. The latter has proven to
be applicable to a large number of situations.

C
0
= 1245 ng/L
C
0
= 150 ng/L
Single-Solute Isotherm
FIGURE 13.6 Effect of initial concentration on MIB capacity in Lake
Michigan water. (Source: Gillogly et al., 1998b.)
musty odor compound, is lower in natural water than in distilled water, and that this
capacity is further reduced as initial concentration decreases (Gillogly et al., 1998b).
It is important to have a procedure to predict capacity as a function of initial con-
centration, because the capacity of activated carbon depends in such an important
way on initial concentration and because the concentrations of trace organic com-
pounds vary widely in natural waters. The ideal adsorbed solution theory (IAST)
can be used for this purpose. The following two equations, based on the IAST as
developed by Radke and Prausnitz (1972) and modified by Crittenden et al. (1985)
to include the Freundlich equilibrium expression, describe equilibrium in a two-
solute system,
C
1,0
− q
1
C
c
−
΂΃
n
1
= 0 (13.4)

)/C
c
C
1,0
and C
2,0
= initial liquid phase concentrations of compounds 1 and 2
C
1,e
and C
2,e
= equilibrium concentrations of compounds 1 and 2
K
1
and K
2
= single-solute Freundlich parameters for compounds 1 and 2
1/n
1
and 1/n
2
= single-solute Freundlich exponents for compounds 1 and 2
C
c
= carbon dose
These equations show the relationship between the initial concentration of each
adsorbate, the amount of adsorbed compound per unit weight of carbon, and the
carbon dose. The Freundlich parameters are derived from single-solute tests in
organic-free water.
In natural waters, the organic matter present is a complex mixture of many dif-

i
= single-solute Freundlich parameters for compound i
These equations can be solved simultaneously to determine the concentrations for
each component assumed to be in solution.
Crittenden et al. (1985) used this fictive component approach to describe the
adsorption of a target compound in the presence of NOM. With a single-solute
isotherm of the target compound and experimental results from isotherms measured
Α
N
i = 1
n
j
q
j
ᎏ
n
i
K
i
q
i
ᎏ
Α
N
j = 1
q
j
n
1
q

q
1
ᎏ
q
1
+ q
2
ADSORPTION OF ORGANIC COMPOUNDS 13.9
13.10 CHAPTER THIRTEEN
FIGURE 13.7 EBC model results for atrazine isotherms in Illinois ground-
water. (Source: Reprinted with permission from D. R. U. Knappe et al. 1998.
“Predicting the capacity of powdered activated carbon for trace organic com-
pounds in natural waters.” Environmental Science & Technology, 32:1694–1698.
Copyright 1998 American Chemical Society.)
using the natural water, parameters for each of the fictive components were found
through a best-fit search procedure. These results were then applied to describe the
adsorption of other compounds in that water.
The IAST was applied to the problem of trace organic adsorption in natural
waters by Najm, Snoeyink, and Richard (1991) using a procedure that was subse-
quently modified by Qi et al. (1994) and Knappe et al. (1998). These researchers
assumed that the background organic matter that competed with the trace com-
pound could be represented as a single compound, called the equivalent background
compound (EBC). This approach involved the determination of the single-solute
isotherm for the trace compound, and an isotherm in natural water for the trace
compound at two different initial concentrations. A search routine was used to find
the Freundlich parameters K and 1/n and the initial concentration C
0
for the EBC
that gave the observed amount of competition. For example, Figure 13.7 shows
isotherms determined for atrazine in organic-free water and in Illinois groundwater

the equilibrium concentration of the trace compound can be calculated from the
equation q = (C
0
− C
e
)/C
c
. This approach was used to determine the predicted
isotherm for atrazine at an initial concentration of 8.3 µg/L, shown in Figure 13.7,
which compares very well with the measured data. It is interesting to note that at an
equilibrium concentration of 1 µg/L, there is a 63 percent reduction in capacity for
atrazine as the initial concentration is reduced from 176 to 8.3 µg/L.
An important modification of the EBC model was developed by Knappe et al.
(1998), who found that the amount of adsorption on a unit mass of activated carbon
was directly proportional to the initial concentration of that trace compound in an
adsorption test if (1) the Freundlich exponents for the trace compound 1/n
1
and the
EBC 1/n
2
both fall between 0.1 and 1, as is generally the case, and (2) the solid-phase
concentration of the background organic matter is much in excess of that of the
trace compound, which also is often true.When these two approximations hold, the
IAST model simplifies to
q
1
= C
1,0
΄
C

n
1
K
1
1
ᎏ
q
2
ADSORPTION OF ORGANIC COMPOUNDS 13.11
FIGURE 13.8 Percent MIB remaining as a function of PAC dose.
(Source: Gillogly et al., 1998b.)
Graham et al. (1999) independently derived a different form of Eq. 13.7 and
applied it using the EBC approach to adsorption of MIB and geosmin from four nat-
ural waters. The same EBC parameters [K = 1.35 (µg/mg)(L/µg)
1/n
and 1/n = 0.20]
were found to be applicable to both MIB and geosmin and, at different initial con-
centrations (15 to 51 µg/L), to all four natural waters. For three of the four natural
waters, the EBC initial concentration was about 0.45 percent of the TOC initial con-
centration.
These results allow the following general procedure to be used to determine
adsorption capacity for a trace compound in natural water:
1. Determine one adsorption isotherm for the trace compound in natural water at a
sufficiently low initial concentration.
2. Plot the data on a log-log percent remaining versus carbon dose plot.
3. Use this isotherm plot to determine the carbon dose required for any desired per-
cent removal for any initial concentration that satisfies the assumptions.
An important question now is what concentration is sufficiently low that the
assumptions made in developing the percent remaining versus carbon dose plot are
valid. Research to date has shown that MIB (Gillogly et al., 1998b) and geosmin

the boundary layer of water surrounding the adsorbent particle. The transport
occurs through diffusion if the adsorbent is suspended in quiescent water such as
a sedimentation basin, or through turbulent mixing such as during turbulent flow
through a packed bed of GAC,or when PAC is being mixed in a rapid mix unit or
flocculator.
2. External (film) resistance to transport Adsorbates must be transported by
molecular diffusion through the stationary layer of water (hydrodynamic bound-
ary layer) that surrounds adsorbent particles when water is flowing past them.
The distance of transport, and thus the time for this step, is determined by the
flow rate past the particle. The higher the flow rate, the shorter the distance.
3. Internal (pore) transport After passing through the hydrodynamic boundary
layer, adsorbates must be transported through the adsorbent’s pores to available
adsorption sites. Intraparticle transport may occur by molecular diffusion
through the solution in the pores (pore diffusion), or by diffusion along the
adsorbent surface (surface diffusion) after adsorption takes place.
4. Adsorption After transport to an available site, an adsorption bond is formed
between the adsorbate and adsorbent.This step is very rapid for physical adsorp-
tion (Adamson, 1982) and as a result one of the preceding diffusion steps will
control the rate at which molecules are removed from solution. If adsorption is
accompanied by a chemical reaction that changes the nature of the molecule, the
chemical reaction may be slower than the diffusion step and thereby control the
rate of compound removal.
The transport steps occur in series, so the slowest step, called the rate-limiting step,
will control the rate of removal. In turbulent flow reactors, a combination of film dif-
fusion and pore diffusion very often controls the rate of removal for some of the
types of molecules to be removed from drinking water. Initially, film diffusion may
control the rate of removal, and after some adsorbate accumulates within the pore,
pore transport may control the rate of removal. The mathematical models of the
adsorption process, therefore, usually include both steps.
Both molecular size and adsorbent particle size have important effects on the

large activated carbon particles in a column may not be used because the time inter-
val between activated carbon replacements is not sufficient for equilibrium to be
achieved.
Mass Transfer Zone and Breakthrough Curves for Packed Bed Reactors. The
region of an adsorption column in which adsorption is taking place, the mass trans-
fer zone (MTZ), is shown in Figure 13.10a. The activated carbon behind the MTZ
has been completely saturated with adsorbate at C
e
= C
0
, and the amount adsorbed
per unit mass of GAC is (q
e
)
0
.The activated carbon in front of the MTZ has not been
exposed to adsorbate, so solution concentration and adsorbed concentration are
both zero. Within the MTZ, the degree of saturation with adsorbate varies from 100
percent (q = [q
e
]
0
) to zero. The length of the MTZ, L
MTZ
, depends upon the rate of
adsorption and the solution flow rate. Anything that causes a higher rate of adsorp-
tion, such as a smaller carbon particle size, higher temperature, a larger diffusion
coefficient of adsorbate, and/or greater strength of adsorption of adsorbate (i.e., a
larger Freundlich K value), will decrease the length of the MTZ. In some circum-
stances, L

L
critical
ᎏ
Q/A
13.14 CHAPTER THIRTEEN
When C
B
is greater than the minimum detectable concentration, the critical depth is
less than L
MTZ
and its value can be determined as shown in a later section (see Fig-
ure 13.14 and related discussion).
The breakthrough curve is a plot of the column effluent concentration as a func-
tion of either the volume treated, the time of treatment, or the number of bed vol-
umes (BV) treated (BV = V
B
/V, where V
B
is the volume treated).The number of bed
volumes is a particularly useful parameter because the data from columns of differ-
ent sizes and with different flow rates are normalized. A breakthrough curve for a
single adsorbable compound is shown in Figure 13.11. The shape of the curve is
affected by the same factors that affect the length of the MTZ, and in the same way.
Anything that causes the rate of adsorption to increase will increase the sharpness of
the curve, while increasing the flow rate will cause the curve to “spread out” over a
larger volume of water treated. The breakthrough curve will be vertical if L
MTZ
= 0,
as shown in Figure 13.10b. As shown in Figure 13.11, the breakthrough capacity,
defined as the mass of adsorbate removed by the adsorber at breakthrough, and the

= 1. Breakthrough curves shown in later sections (see Fig-
ures 13.15 and 13.22, for example) also illustrate some of these effects.
GAC ADSORPTION SYSTEMS
Characteristics of GAC
Physical Properties. A wide variety of raw materials can be used to make acti-
vated carbon (Hassler, 1974), but wood, peat, lignite, subbituminous coal, and bitu-
minous coal are the substances predominately used for drinking water treatment
carbons in the United States. Both the physical and chemical manufacturing pro-
cesses involve carbonization (conversion of the raw material to a char) and activa-
tion (oxidation to develop the internal pore structure). With physical activation,
carbonization, or pyrolysis, is usually performed in the absence of air at tempera-
tures less than 700°C, while activation is carried out with oxidizing gases such as
mass of GAC in column
ᎏᎏᎏᎏ
volume treated to breakthrough V
B
mass
ᎏ
volume
13.16 CHAPTER THIRTEEN
FIGURE 13.11 Adsorption column breakthrough curve.
steam and CO
2
at temperatures of 800 to 900°C. Chemical activation combines car-
bonization and activation steps. Patents describing carbonization and activation pro-
cedures are given by Yehaskel (1978).
Various characteristics of activated carbon affect its performance.* The particle
shape of crushed activated carbon is irregular, but extruded activated carbons have a
smooth cylindrical shape. Particle shape affects the filtration and backwash properties
of GAC beds. Particle size is an important parameter because of its effect on rate of

sity and is typical of activated carbon during normal operation unless it becomes
destratified during backwashing. The latter is an important parameter because it
determines how much activated carbon must be purchased to fill a filter of given size.
The particle density wetted in water is the mass of solid activated carbon plus the
mass of water required to fill the internal pores per unit volume of particle. Its value
for GAC typically ranges from 1300 to 1500 kg/m
3
(90 to 105 lb/ft
3
) and it determines
the extent of fluidization and expansion of a particle of given size during backwash.
Particle hardness is important because it affects the amount of attrition during
backwash, transport, and reactivation. In general, the harder the activated carbon,
the less the attrition for a given amount of friction or impact between particles.Acti-
vated carbon hardness is generally characterized by an experimentally determined
hardness or abrasion number, using a test such as the ASTM Ball Pan Hardness Test
that measures the resistance to particle degradation upon agitation of a mixture of
activated carbon and steel balls (American Society for Testing Materials, 1988). The
relationship between the amount of attrition that can be expected when activated
carbon is handled in a certain way and the hardness number has not been deter-
mined, however.
Adsorption Properties. A number of parameters are used to describe the adsorp-
tion capacity of activated carbon (Sontheimer, Crittenden,and Summers, 1988).The
molasses number or decolorizing index is related to the ability of activated carbon to
adsorb large-molecular-weight color bodies from molasses solution, and generally
correlates well with the ability of the activated carbon to adsorb other large adsor-
bates. The iodine number (American Society for Testing Materials, 1988) measures
the amount of iodine that will adsorb under a specified set of conditions, and gener-
ally correlates well with the surface area available for small molecules. Other num-
bers have been developed for specific applications, such as the carbon tetrachloride

(1988). These data can be used to judge relative adsorption efficiency. The K values
of isotherms that have nearly the same values of 1/n show the relative capacity of
adsorption. For example,if a GAC column is satisfactorily removing 2-chlorophenol
[K = 51 (mg/g)(L/mg)
1/n
and 1/n = 0.41], the removal of compounds with larger val-
ues of K and approximately the same concentration will very likely be better. (An
exception might occur if the organic compounds adsorb to particles that pass
through the adsorber.) If the 1/n values are much different, however, the capacity of
activated carbon for each compound of interest should be calculated at the equilib-
rium concentration of interest using Equation 13.1, because the relative adsorbabil-
ity will depend on the equilibrium concentration. The use of isotherm values to
estimate adsorber life and PAC usage rate will be discussed later.
GAC Contactors
GAC contactors can be classified by the following characteristics: (1) driving
force—gravity versus pressure; (2) flow direction—downflow versus upflow;
(3) configuration—parallel versus series; and (4) position—filter-adsorber versus
postfilter-adsorber.
GAC may be used in pressure or gravity contactors. Pressure filters enclose the
GAC and can be operated over a wide range of flow rates because of the wide vari-
ations in pressure drop that can be used. An advantage of these filters is that they
can be prefabricated and shipped to the site.A disadvantage is that the GAC cannot
be visually observed with ease. Gravity contactors are better suited for use when
wide variations in flow rate are not desirable because of the need to remove turbid-
ity, when large pressure drops are undesirable because of their impact on operation
costs, and when visual observation is needed to monitor the condition of the GAC.
For many systems the decision between pressure or gravity contactors is made on
the basis of cost. Medium-size and large systems normally use gravity contactors.
Water may be applied to GAC either upflow or downflow, and upflow columns
may be either packed bed or expanded bed. Downflow columns are the most com-

†
Fluoranthene 664 0.61
†
Aldrin 651 0.92
†
PCB-1232 630 0.73
†
β-Endosulfan 615 0.83
†
Dieldrin 606 0.51
†
p-Dichlorobenzene 588 0.691 *
1,3,5-Trichlorobenzene 586 0.324 *
Alachlor 482 0.257 *
m-Dichlorobenzene 458 0.63 *
m-Dichlorobenzene 458 0.63 *
Hexachlorobenzene 450 0.6
†
Pentachlorophenol 443 0.339 *
Pentachlorophenol 436 0.34 *
Oxamyl 416 0.793 *
Anthracene 376 0.7
†
p-Chlorotoluene 376 0.34 *
4-Nitrobiphenyl 370 0.27
†
m-Xylene 343 0.614 *
Styrene 334 0.479 *
Fluorene 330 0.28
†

Acifluorofen 236 0.198 *
Metolachlor 233 0.125 *
13.20 CHAPTER THIRTEEN
TABLE 13.1 Freundlich Adsorption Isotherm Parameters for Organic Compounds
(Continued)
Compound K (mg/g)(L/mg)
1/n
1/n Reference
DDE 232 0.37
†
Acridine yellow 230 0.12
†
p-Xylene 226 0.418 *
Benzidine dihydrochloride 220 0.37
†
β-BHC 220 0.49
†
n-Butylphthalate 220 0.45
†
n-Nitrosodiphenylamine 220 0.37
†
Dibromochloropropane (DBCP) 220 0.501 *
Silvex 215 0.38 *
Phenanthrene 215 0.44
†
Bromobenzene 213 0.364 *
Dimethylphenylcarbinol 210 0.34
†
Dinoseb 209 0.279 *
4-Aminobiphenyl 200 0.26

2,4,6-Trichlorophenol 155 0.4
†
β-Naphthylamine 150 0.3
†
Simazine 150 0.227 *
2,4-Dinitrotoluene 146 0.31
†
2,6-Dinitrotoluene 145 0.32
†
4-Bromophenyl phenyl ether 144 0.68
†
Tetrachlorethene 143 0.516 *
p-Nitroaniline 140 0.27
†
1,1-Diphenylhydrazine 135 0.16
†
Aldicarb 133 0.402 *
Naphthalene 132 0.42
†
1-Chloro-2-nitrobenzene 130 0.46
†
p-Chlorometacresol 124 0.16
†
1,4-Dichlorobenzene 121 0.47
†
Benzothiazole 120 0.27
†
Diphenylamine 120 0.31
†
Guanine 120 0.4

†
4-Nitrophenol 76 0.25
†
Acetophenone 74 0.44
†
1,2,3,4-Tetrahydronaphthalene 74 0.81
†
1,2,3-Trichloropropane 74 0.613 *
Ethylene thiourea 73 0.669 *
Adenine 71 0.38
†
Dibenzo |a,h| anthracene 69 0.75
†
1,1,1,2-Tetrachlorethane 69 0.604 *
Nitrobenzene 68 0.43
†
2,4-D 67 0.27 *
Isophorone 63 0.271 *
Methyl isobutyl ketone 61 0.279 *
3,4-Benzofluoranthene 57 0.37
†
Trichloroethene 56 0.482 *
2,4,5-Trichlorophenoxy acetic acid 55 0.21 *
Trichloroacetic acid 52 0.216 *
2-Chlorophenol 51 0.41
†
o-Anisidine 50 0.34
†
Benzene 50 0.533 *
Dibromochloromethane 47 0.636 *

bon usage rate mayberelatively high.Alternatively,columns may bearrangedin series
so that the MTZ is entirely contained within the downstream columns after the lead
column has been saturated with the influent concentration.When the activated carbon
is replaced in the lead column,the flow is redirected so that it goes through the freshest
activated carbon last.Thus, the activated carbon“moves”countercurrent to the flow of
ADSORPTION OF ORGANIC COMPOUNDS 13.23
TABLE 13.1 Freundlich Adsorption Isotherm Parameters for Organic Compounds
(Continued)
Compound K (mg/g)(L/mg)
1/n
1/n Reference
Dalapon 23 0.224 *
1,2-Dibromoethane 23 0.471 *
1,2-Dibromoethene (EDB) 22 0.46 *
Endothall 22 0.329 *
Bromodichloromethane 22 0.655 *
Phenol 21 0.54
†
1,2-Dichloropropane 19 0.597 *
Methyl ethyl ketone 19 0.295 *
1,1-Dichloroethene 16 0.515 *
trans-1,2-Dichloroethene 14 0.452 *
1,1,1-Trichloroethane 13 0.531 *
Diquat 12 0.242 *
cis-1,2-Dichloroethene 12 0.587 *
Bis(2-Chloroethoxy) methane 11 0.65
†
Uracil 11 0.63
†
Benzo |g,h,i| perylene 11 0.37

†
N-Dimethylnitrosamine 6.8 × 10
−5
6.6
†
* Speth and Miltner, 1998.
†
Dobbs and Cohen, 1980/Faust and Aly, 1983.
water, and lower activated carbon usage
rates are achieved than with single-stage
contactors. Series configuration is best
utilized when the effluentcriterionis very
low compared to the influent concentra-
tion (Wiesner, Rook, and Fiessinger,
1987). The increased cost of plumbing
counters the cost benefit of reduced acti-
vated carbon usage rate, however, espe-
cially when more than two columns must
be used in series.
When parallel-flow activated carbon
adsorbers are operated in staggered
mode, they can also be used to decrease
the activated carbon usage rate from
that which is possible with a single-stage
contactor (Westrick and Cohen, 1976;
Roberts and Summers, 1982). Because
the effluent from each of the units is
blended, each unit can be operated until
it is producing a water with an effluent
concentration in excess of the treated

the rate of adsorption in columns. If the rate of adsorption is controlled by intra-
particle diffusion, the time to reach equilibrium with a given solution concentration
in a column approximates that for a batch test. With all other factors constant,
decreasing particle size will decrease the time required to achieve equilibrium and
will decrease the length of the MTZ in a column. Thus, to improve adsorption effi-
ciency and to minimize the size of column required, the particle size selected for a
contactor should be as small as possible.
The rate of head loss buildup caused by particle removal may limit the size of
GAC that can be used in adsorbers.The smaller the GAC, the higher the initial head
loss and rate of head loss buildup; thus, cost of energy and availability of head have
an important influence on the GAC size selected for a design.Additionally, if a filter-
adsorber is constructed by replacing media in an existing rapid filter, turbidity
removal efficiency generally increases as the GAC size decreases. If the medium is
too small, however, the rate of head loss buildup because of particle accumulation
becomes excessive, and the net water production will be too small for cost-effective
operation.The filters also become difficult to clean by backwashing.
The commercial sizes of GAC are typically characterized by a relatively large
uniformity coefficient of up to 1.9. This large coefficient causes the bed to restrat-
ify more easily after backwashing. This large uniformity coefficient also requires
that greater percent expansion of the adsorber be used during backwash in order
to expand the bottom media (Graese, Snoeyink, and Lee, 1987a). Some GAC fil-
ters use GAC with a small uniformity coefficient (∼1.3) in deep beds to improve
depth removal of turbidity and to increase net water production (Graese,
Snoeyink, and Lee, 1987b). Mixing of the media in these filters undoubtedly is
more than in filters with large uniformity coefficients, so they should not be used
in applications where desorption from the mixed GAC will require early GAC
replacement.
Common practice is to use 12 × 40 US Standard mesh (1.68 × 0.42 mm) or similar
activated carbon in postfilter adsorbers, because backwashing is rarely required due
to head loss buildup.This carbon size also is commonly used in filter-adsorbers when