Supplementary Information for

Isosteric Heats of Gas and Liquid Adsorption

Santiago Builes and Stanley I. Sandler1
Department of Chemical and Biomolecular Engineering
University of Delaware, Newark DE 19716

Adsorption isotherms for the system pentane-hexane-isooctane

The adsorption isotherms for the solutions of pentane-hexane-isooctane on silicalite in

terms of the mole fraction and the concentration are shown in Figure S1. In addition, in Figure
S2 is shown the excess adsorption isotherm in terms of the mole fraction for the same system.

Concentration C6 [mol/L] Mole fraction C6

0.12 0.08 0.04 0.00 0.020 0.015 0.010 0.005 0.000
1.0 1.0
[mmol/g]

0.8
[mmol/g]
Uptake [mmol/g]

0.8
Uptake [mmol/g]

0.6 0.6
Loading

Loading

0.4 0.4

0.2 0.2

0.0 0.0

Figure S1. Adsorption isotherms on silicalite at 277 K (squares) and 300 K (circles) for pentane
(open symbols) and hexane (closed symbols) as functions of their, mole fraction (right) and
concentration.

1
Corresponding author, sandler@udel.edu
Figure S2. Excess adsorption isotherm on silicalite at 277 K (squares) and 300 K (circles) for
pentane (open symbols) and hexane (closed symbols) as functions of their mole fraction.

Calculation of the excess enthalpy for MeOH-Water

mix
The experimental data of the heat of mixing ( ∆H ) for methanol/water mixtures can be
used to compute the excess enthalpy term, given by the following relationship for binary
mixtures.
e l l ,* mix d ∆H mix
H = H −H
1 1 1 = ∆H + x2 (S1)
dx1
e l l ,* mix d ∆H mix
H = H −H
2 2 2 = ∆H − x1
dx1

The experimental data is the enthalpy of mixing at constant temperature and pressure, and
varying mole fraction. The enthalpy of mixing for the mixture of methanol water has been
measured by different authors at different temperatures and different ranges of composition.1-3
The experimental data for the enthalpy of mixing was fit to the Redlich-Kister expansion.
N
∆H mix = ( x1 − x12 ) ∑ ak ( 2 x1 − 1)
k
(S2)
k ≥0

where N are the number of terms used in the expansion, and ak are the parameters of the
expression. Once the number of parameters is set, the equation can be differentiated analytically
to obtain the excess enthalpy (eqn. S1). The experimental data was correlated using the Redlich-
Kister expansion with 4 parameters (N=3). The values of the parameters were determined by the
least squares regression of the experimental data.
Figure 3a in the manuscript shows the experimental data at 298K and 313K and Figure
3b of the manuscript shows the calculated values of the excess enthalpy of methanol using eqn.
(S1).
Using the data for the adsorption isotherms in terms of the mole fraction (Figure 4 in the
manuscript) is possible to relate the values of the excess enthalpy to the loading. Figure S3
shows the excess enthalpy of methanol as a function of the loading of methanol on silicalite.

Figure S3. Excess enthalpy of methanol as a function of the adsorbed amount of methanol on
silicalite in a mixture of methanol-water at different temperatures.

The values of the excess enthalpy up to 1.8 mmol/g of adsorbed methanol seem to follow
a straight line. And the values at the intermediate temperature (305 K) could be calculated as the
averages of the values at 298K and 313K; for zero coverage the average value is -7.0 kJ/mol and
for an uptake of 1.8 mmol/g the average value is about -5.5 kJ/mol.

REFERENCES

(1) Gmehling, J. Excess enthalpies for 1,1,1-trichloroethane with alkanes, ketones, and esters
J. Chem. Eng. Data 1993, 38, 143-146
(2) Dohnal, V.; Roux, A.; Hynek, V. Limiting partial molar excess enthalpies by flow
calorimetry: Some organic solvents in water J. Solution Chem. 1994, 23, 889-900
(3) Bose, E. Calorimetric Studies Z. Phys. Chem 1907, 58, 585-624