LEC

Adsorption isotherms
04.08

Related concepts Separator for magnetic bars 35680.03 1

Adsorbent and adsorbate, Henry, Freundlich and Langmuir Precision balance, 620 g 48852.93 1
adsorption isotherms, volumetry. Burette 50 ml, lateral stopcock 36513.01 1
Volumetric flask 1000 ml, IGJ24/29 36552.00 1
Principle Volumetric flask 250 ml, IGJ14/23 36550.00 6
In general, the term adsorption is used to describe the attach- Volumetric pipette, 10 ml 36578.00 1
ment of gases or dissolved substances to the surface of a solid Volumetric pipette, 25 ml 36580.00 1
or liquid. At constant temperature,the quantity of adsorbed sub- Volumetric pipette, 50 ml 36581.00 1
stances is a function of the type of system investigated and the Volumetric pipette, 100 ml 36582.00 1
partial pressure and / or concentration of the substance con- Graduated pipette, 25 ml 36602.00 1
cerned. This correlation is described by a number of adsorption Pipettor 36592.00 1
isotherms. Their validity is to be investigated experimentally. Pipette dish 36589.00 1
Erlenmeyer IGJ29/32, 250 ml 46126.00 6
Tasks Stopper, PP, for IGJ 29/32 47508.00 6
Determine the residual equilibrium concentrations of citric acid Erlenmeyer flask, wide neck, 250 ml 36134.00 7
after stirring solutions of differing initial concentrations with a Glass beaker, 100 ml, tall 36002.00 7
constant mass of activated carbon. Use the measurement Funnel, glass, do = 55 mm 34457.00 7
results to determine which of the adsorption isotherms is valid Circular filters, d = 90 mm 32977.03 1
for the given system. Pasteur pipettes 36590.00 1
Rubber bulbs 39275.03 1
Spoon 33398.00 2
Equipment Wash bottle, 500 ml 33931.00 1
Retort stand, h = 750 mm 37694.00 2 Citric acid, 250 g 30063.25 1
Burette clamp, roller mounting 37720.00 1 Caustic soda solution, 1.0 M, 1000 ml 48329.70 1
Filtration stand for 2 funnels 33401.88 1 Phenolphthalein, 1% solution, 100 ml 31714.10 1
Magnetic stirrer, mini 47334.93 2 Activated carbon, granular, 500 g 30011.50 1
Magnetic stirrer bar, l = 30 mm 46299.02 2 Water, distilled, 5 l 31246.81 1

Fig. 1. Experimental set-up.

PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen P3040801 1
 LEC
Adsorption isotherms
04.08

Set-up and procedure Type and strength of the interactions allow a differentiation to be
Set up the experiment as shown in Fig. 1. made between physicosorption (weak van der Waals forces,
Prepare 1000 ml of 1.0 molar citric acid solution by dissolving very low adsorption enthalpies, a number of multilayers of the
210.16 g of citric acid in distilled water and topping the volu- adsorbed substance) and chemisorption (chemical bonds, sub-
metric flask off to the calibration mark. Pipette the volumes of stantial adsorption enthalpies, monolayers of the adsorbed sub-
this stock solution (Vst) that are listed in Table 1 into separate stance).
clean 250 ml volumetric flasks and top the flasks off to the cali- Adsorption and desorption represent an equilibrium, the position
bration mark. of which is temperature-dependent. Adsorption is accompanied
Pour 100 ml each of the six concentration series solutions into by a decrease in surface tension and the liberation of heat of
separate 250 ml Erlenmeyer flasks containing exactly 3.00 g of adsorption so that, acc. to Le Chatelier’s principle for exothermic
activated carbon. Slip a magnetic stirrer bar into each flask. Seal processes, adsorption must decrease with increasing tempera-
the flasks, then stir the solutions in them vigorously for approxi- ture.
mately 30 minutes and filter them. Titrate the sample volumes V1 The quantity adsorbed is further dependent on the concentration
of the respective filtrates, as given in Table 1, with 1.0 molar of the substance in the contacting phase, and on the size of the
sodium hydroxide solution using phenolphthalein as indicator. adsorbing surface. As the value of the latter is very difficult to
Titrate 10 ml of the 1.0 molar citric acid stock solution V0 simi- determine, however, the quantity of the substance adsorbed
larly to check the initial concentration. nB,ads is related to the mass of the adsorbent mA which is pro-
portional to the size of the adsorbing surface:
Vst / ml V1 / ml
nB,ads
250.0 10 g
(1)
mA
187.5 10
125.0 25 where
g Adsorption molality
62.5 25
25.0 50 The type and degree of adsorption are functions of the chemical
nature of the adsorbent and the adsorbate as well as of the
12.5 50
adsorbate temperature and concentration (for dissolved sub-
stances) or partial pressure (for gases). The correlation between
Table 1: Volumes of stock solution for the preparation of the the adsorption molality and the free equilibrium concentration of
concentration series Vst and the sample volumes after B at constant temperature is described by a number of adsorp-
filtration V1 for the determination of the equilibrium con- tion isotherms.
centration of citric acid Freundlich empirically determined an adsorption isotherm in
1907:
Theory and evaluation
As a result of the action of attractive forces between exposed
g
abB;eq (2)
particles, gases or dissolved substances B attach themselves
reversibly to the surfaces of solid phases A (adsorption).
where
cB;eq Equilibrium concentration of B
A + B ABads
a, b System-dependent constants

Fig. 2: Investigation of the adsorption isotherm for the citric Fig. 3: Confirmation of the validity of the adsorption isotherm
acid/active carbon system for the citric acid/active carbon system

2 P3040801 PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen
 LEC
Adsorption isotherms
04.08

The logarithmic expression of this With very low equilibrium concentrations (K cB,eq < 1) the iso-
therm (5) simplifies to
lg g = lg cB;eq + lg a (2.1)
g = gmax K cB,eq = K’ cB,eq (5.2)
allows simple graphic evaluation and thus the determination of
the constants a and b (Fig. 4). which is Henry-Dalton’s law. Thus the adsorption molality g is
linearly correlated with cB,eq.
With increasing coverage of the surface, g strives towards a lim- In contrast, at very high equilibrium concentrations (K cB,eq > 1),
iting value gmax, i.e. monolayer formation. The quotient of the the adsorption molality tends toward a concentration indepen-
real (g) and the maximum (gmax) adsorption molality is defined as dent limiting value gmax:
the degree of coverage .
g = gmax (5.3)
g
®
(3)
gmax To check which adsorption isotherms are valid in the investigat-
ed case, determine which expressions of adsorption molality (g,
Taking this into consideration, the adsorption isotherm can be 1/g, lg g) correspond to relationships (5.2), (5.1) and (2.1) as
derived by examining the kinetics of adsorption and desorption. functions of the corresponding equilibrium concentrations (cB,eq,
The adsorption velocity is proportional to the product of the con- 1/cB,eq, lg cB,eq).
centrations of the reaction partners, i.e. of the molecules of the The initial (cB,0) and equilibrium concentration (cB,eq) which are
adsorbate and the free positions on the surface of the adsor- required for the evaluation can be calculated from the volume of
bent. When  represents the degree of coverage, then 1 -  is the volumetric flask VK = 250 ml and the volumes of NaOH of
the amount of free adsorbent surface. known concentration cNaOH required to neutralise the sample
volumes VNaOH,0 and VNaOH,1 of citric acid solution, taking the
tribasicity of the absorbed material (citric acid) into account by

kads cB 11  ® 2  kdes ®
d cB
 (4) applying the following relationships:
dt

where cNaOH VNaOH,0 Vst

cB,0
(6.1)
cB Concentration of B in the solution 3 V0 VK
kads, kdes Rate constants of the adsorption and desorption,
respectively cNaOH VNaOH,1
cB,eq
(6.2)
3 V1
For the case of an established adsorption (-dcB/dt = 0),
Langmuir’s adsorption isotherm follows (Fig. 2): The adsorption molality g can be determined from the following
correlation, which is derived from equation (1)
gmax K cB,eq
g

1cB,0  cB,eq 2 · Vs
(5)
1  K cB,eq nB,ads
g

(7)
mA mA
where
cB,eq Equilibrium concentration of B in solution
K kads / kdes = constants where
Vs = 100 ml, system volume
The correlation between adsorption molality and equilibrium mA = 3.00 g = mass of adsorbent
concentration can be linearized by rearranging:
Data and results
1 1 1 1 The linear correlation between the logarithms of the equilibrium

·  (5.1)
g gmax · K cB,eq gmax concentration cB,eq and the adsorption molatity g demonstrated
in Fig. 3 confirms the exclusive validity of Freundlich’s adsorp-
In the region of the validity of the isotherm (5), the graphic plot of tion isotherm in the investigated concentration range. The con-
1/g as a function of the reciprocal equilibrium concentration stant b = 0.172, which corresponds to the slope of the regres-
1/cB,eq gives a straight line with a slope of 1/gmax K and the ordi- sion lines, lies in the range of values expected for granulated
nate segment 1/gmax. activated carbon (0.1 < b < 1.0).

PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen P3040801 3
 LEC
Adsorption isotherms
04.08

4 P3040801 PHYWE series of publications • Laboratory Experiments • Chemistry • © PHYWE SYSTEME GMBH & Co. KG • D-37070 Göttingen