Chemical Engineering Science, 1974, Vol. 29, pp. 1279-1282. Pergamon Press.

Printed in Great Britain

Simultaneous adsorption equilibria of organic solutes in dilute aqueous solutions on

activated carbon

(Received 26 October 1973)

The use of activated carbon to remove persistent organic ing equations are available for determining the concentra-
pollutants from waste waters has received great attention tions:
in recent years. In the design of such water purification
facilities, equilibrium adsorption information is required. X,=&E, (1)
Most of the published papers in this field are dealing
with the effectiveness of adsorption for removing a single
solute from water[l-31. However, waste waters contain
more than one component[B, so that as a next step the
simultaneous adsorption equilibria of solutions containing X, and X, are the concentrations of p-nitrophenol and
two solutes have to be studied. phenol, E. and ES.. are the absorbances at 317 nm and
212nm, respectively. m. and m, are the slopes of the
EXPERIMENTAL calibration lines of p-nitrophenol at 317 mn and 212 nm,
The usual procedure was to pipette a 200 ml volume of respectively and m2 is the slope of the calibration line of
aqueous solution of p-nitrophenol and phenol of a given phenol at 212 nm.
concentration (1 to 10 mmolell) into 250 ml bottles, each
containing a carefully weighed quantity of carbon. The RESULTS AND DISCUSSlON

bottles were then shaken continuously for three to four
days, and after equilibrium was reached a sample was
taken from each bottle for analysis.
The concentrations were determined by ultraviolet
spectrophotometry.
Because p-nitrophenol has a characteristic absorbancy
at 317 mu and phenol doesnt absorb at this wave length,
but otherwise the peaks of both substances coincide at
212nm, and furthermore a superposition of the absor-
bances exists over the total wave length range, the follow-
The relative amount of solute (Y$) adsorbed on the carbon
at equilibrium can be calculated from the mass balance
equation
K =j$,-X) (3)
and was plotted vs X, to yield the adsorption isotherm.
Figures 1 and 2 show the adsorption equilibria of
p-nitrophenol and phenol for the ratio of solution to car-
bon quantity L/K = O-5l/g. If instead of the initial con-

/ I I I / I
0 I 2 3 4 5 6

Equilibrium concentration X,. T

Fig. 1. Adsorption isotherms of p-nitrophenol in the presence of phenol at 20C.

1279
 1280 Shorter Communications

4s

Equilibrium concentration X,, 7mmole

Fig. 2. Adsorption isotherms of phenol in the presence of p-nitrophenol at 20C.

centrations X0 the equilibrium concentrations X are cho- where Y; is the amount of solute 1 adsorbed from a
sen as parameters for these curves, one obtains a rep- separate solution of the same total concentration.
resentation of the adsorption equilibrium, which is then With only a single solute present, Eq. (4) is reduced to
independent of the ratio L/K (Figs. 5 and 6).
The data in Figs. 1 and 2 indicate, that the mutual inter-
ference of the two solutes is very different, even though
the adsorbed amounts of both solutes from the pure solu-
tion is about the same order of magnitude. There is only a which becomes the correlation suggested by Radke and
weak competition in adsorptive capacity of p-nitrophenol Prausnitz[ll], if b,, = b,,- 1 and c, = 1:
in the presence of phenol, whereas the uptake of phenol is a ,oX,10
very much reduced by the addition of p-nitrophenol. Y, =
1 + a,,X,blo-
In order to describe the adsorption isotherms
mathematically, some well-known relationships [S-7] Furthermore, the Freundlich equation
were tested, but there was no satisfying agreement with
the measured data.
Therefore a general empirical equation for calculating
the adsorption equilibria of organic solutes in aqueous sol-
ution is suggested as follows: yields from Eq. (8) in the special case that the parameter
c, is identically zero, and for b,, = b,, = c, = 1 one obtains

in which Yj is the amount of solute i, adsorbed per unit

weight of carbon at equilibrium concentration X in a
solution containing n solutes.
This equation includes some well-known relationships
as special cases.
For bjO= b<i= cj = 1 it becomes the Langmuir equation

y;= aioX
(5)
1+ 2 a,X
i-1
which has been used in many cases for describing adsorp-
tion isotherms of two solutes& 8, 9, lo].
For a bisolute system Eq. (4) reduces for solute 1 to
ataX, %
Y, = 65)
c, + a,,X,Q + a12Xzb~z
which contains the relationship of Jager and Erdijs [7] as a
special case x0.77
2
.
y, = yJ1 Fig. 3. Plot of X,,/Y, vs. XZ0,i7used to determine the
-X + a12X2
(7)
coefficient hZ in Eq. (12).
 Shorter Communications 1281

the Langmuir equation

y, _ aJL (11)
1 + a,,X,
The applicability of Eq. (4) was tested by experimental
data for equilibrium adsorption of p-nitrophenol and
phenol from mixed solutions.
The Freundlich equation gives the best fit of the experi-
mental data of the pure solutes so that the parameter c, is
consequently identical zero. Then for solute 2 (phenol)
and analogous for solute 1 (p-nitrophenol) Eq. (6) reduces
* to
10-l I I I I I I I I
162 2 5 16 2 5 IO0 2 5 IO
(12)

4 with az2= 1.
Rewriting Eq. (12) using a2 = azo and b2 = b, - b,
4. of the intercepts
determine the coefficients

Fig. 5. Comparison of experimental data with the isotherms curve fitted by Eq. (4).

Y,
2

0 I 2 3 4 5 6 7

X,

Fig. 6. Comparison of experimental data with the isotherms curve fitted by Eq. (4).

CES VOL. 29 NO. S-O

1282 Shorter Communications

a2 is the coefficient and ba the exponent in the Freundlich NOTATION

equation, which can be determined by measurements with X, equilibrium concentration in the water phase of the
the pure solutions. solute i, mmole l-
If Eq. (12) holds, then experimental values of X,, initial concentration in the water phase of the solute
Xzb2+*zz/Y2plotted vs Xzb22 should give straight lines. i, mmole I-
with a slope equal to l/a, and intercepts equal to Y, amount of the solute adsorbed on the carbon at
u2,/a2 Xlbzl, for varied XI. Because these lines have to run equilibrium per unit mass of adsorbent, mmole g-
parallel, according to Eq. (13), bZ2is fixed (Fig. 3). L volume of solution, 1
If the intercepts (multiplied with a*) are log-log plotted K mass of carbon, g
versus the concentration of solute 1, a straight line should
be obtained, as illustrated in Fig. 4. Then from this graph Znstitut fiir Thernzische W. FRITZ
the constants a2, and b,, may be determined. Verfahrenstechnik E.-U. SCHLUENDER
Thus, the following relationships were found for der Universitiit Karlsruhe,
p-nitrophenol (1) and phenol (2) solved in water: Deutschland

3.25X, I REFERENCES
(14)
y1 = x, +0.0185X; Cl1 Heil G., Dissertation University of Karlsruhe 1971.
PI Schwuger M. J., Jilntgen H. and Peters W., Chem.
with Zng. Techn. 1%8 40 903.
a, = 3.25; b, = 0.13; b,, = 1-O; [31 Digiano F. A. and Weber W. J., J. Wat. Poll. Control
a,2 = 0.0185; b,, = l-20 Fed. 1973 45 713.
141 Sontheimer H., Chemie in unserer Zeit 1972 6 175.
and [51 Butler J. A. V. and O&rent C., J. phys. Chem. 1930
34 2841.
2.16X, bl Erdiis E. and Jgger L., Coil. Czech. Chem. Comm.
Y2 = (1% 1959 24 2851.
XF + 14X,oO
I71 Jgger L. and Erdiis E., Coil. Czech. Chem. Comm.
with 1959 24 3019.
[81 O&rent C., J. Chem. Sot. 1932 p. 613.
a2 = 2.16; bz = 0.23; bz2 = 0.77; [91 Weber W. J. and Morris J. C., J. Am. Wat. Wks. Ass.
a>, = 14; bx, = 0.70. 1964 56 447.
HOI Cooney D. 0. and Strusi F. P., Znd. Engng Chem.
Figs. 5 and 6 show that the experimental data are in good Fundls 1972 11 123.
agreement with Eqs. (14) and (15), respectively. r111 Radke C. J. and Prausnitz J. M., Znd. Engng Chem.
In order to check the general validity of Eq. (4) further Fundls 1972 11 445.
experiments have to be carried out with different kinds of t121 Freundlich H., Z. physik. Chem. 1907 57 385.
activated carbon and several solutes. [131 Langmuir J., J. Am. Chem. Sot. 1916 38 2221.

Chemical Engineering Science, 1974, Vol. 29, pp. 1282-1286. Pergamon Press. Printed in Great Britain

Dispersion of solutes in non-Newtonian laminar flow through a circular tube-

Eyring model fluid

(Received 23 May 1973; accepted 15 November 1973)

The dispersion of solute in a solvent flowing through a exists, where R is the radius of the tube, ii, is the mean
circular cross-section was first described by G. I. Taylor fluid velocity, and D is the molecular diffusivity.
in 1953[l-31. In this study, he considered two limiting con- The conditions under which an approximate solution of
ditions: [ll dispersion of a tracer material due to convec- the diffusion equation is valid are
tion only,
_ and r21 disoersion due to the combined effects
of convection and ra&al diffusion. Under the second con-
dition, Taylor concluded that for laminar flow, an effec-
tive dispersion coefficient
k _ Rqx where L is the length of the tube over which concentra-
480 tion changes are appreciable. Since that time, numerous