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MULTICOMPONENT MONOLAYER GAS ADSORPTION:

THE EFFECT OF MOLECULAR SIZE AND THE


NUMBER OF BINDING SITES ON SORPTION RATES
O. Jaki1, Z. Jaki1, . upi1, D. Ranelovi1, Lj. Kolar-Ani2
1
Institute of Chemistry, Technology and Metallurgy, University of Belgrade
Njegoeva 12, 11000 Belgrade, Serbia, olga@nanosys.ihtm.bg.ac.rs
2
Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16,
11000 Belgrade, Serbia, lkolar@ffh.bg.ac.rs
Abstract. Multicomponent monolayer gas adsorption on solid surfaces is studied.
Master equations for multicomponent gas adsorption are formulated. Sorption rates
and the number of free binding sites for each gas species are modeled using
physical parameters of the system. The procedure for estimation of surface density
of adsorbed molecules is explained and demonstrated on some industrial and
semiconductor gases. These results may be used for adsorption based sensor
design/technology or related fundamental research.
Introduction
The development in micro and nano technologies leads to the fabrication of
new micro and nano structures whose functioning depends highly on adsorptiondesorption processes. That dependence can be crucially favorable like for instance
in adsorption-based (bio)chemical plasmonic sensors , or very undesirable like in
microresonators where adsorption-induced mass fluctuations provoke frequency
instabilities .
In this work we focus on modeling adsorption-desorption process, its constants
and parameters, in order to set-up a model suitable for analyzing multicomponent
gas adsorption on solids in time span from the beginning till the equilibrium is
reached and afterwards. This model could be used in many analytical applications
where adsorption-desorption processes play important role in both detection and
measurement.
Theory
Starting premises are similar to that of Langmuir's: the surface is homogenous;
all molecules of the same gas species are alike. Molecules in gas phase behave as
ideal gas; adsorbed molecules do not collide or interact and do not form multilayer
islands. Average residential time of adsorbed particles is the same for all particles
of the same gas. The flux of arrivals of gas molecules of the species i, Ra,i, onto the
solid surface is proportional to its partial pressure, pi, and free surface
r

1
Ra ,i
pi 1 j
(1)

2 mi k B T
j 1

Here, j are fractions of occupied surfaces for each of r surrounding gases, mi is


mass of a single molecule of ith gass, kB is Boltzmann constant, T is temperature.
The rate of desorption of the species i onto the solid surface is proportional to
its number of adsorbed molecules, Na,i, and inversely proportional to their mean
residential time i . According to the ideal gas law, the final expression for rate
equation of the number of adsorbed molecules for each gas is then
r
r

d N a ,i
A s ,i
N a,i A s ,i k BT
N a ,i

pi 1 j

N g ,i 1 j

dt
V
2 mi
i
i
2 mi k BT
j 1
j 1
(2)
where s,i is sticking probability of adsorption for ith gass, Ng,i is the number of free
gas molecules, A is surface area and V is gas chamber volume. In order to be able
to find the solution for the number of adsorbed molecules for each gas or to
conduct the stochastic analysis of this process, one must transform equation (2)
into a more suitable form.
Results
Adsorption-desorption process is usually studied as a second order reaction,
according to the following stoichiometric equation
ka
Ag A f
Aa
(3)
k
d

and the corresponding differential equation:


dN a ,i
(4)
ka ,i N g ,i N f ,i kd ,i N a ,i
dt
where a free gas molecule Ag and a free adsorption center Af reversibly transform
into an adsorbed molecule Aa, with an adsorption rate ka and a desorption rate kd
and the number of free adsorption centers for the species i is Nf,i.
Equations (2) and (4) were analyzed with respect to surface densities of
adsorbed molecules for different gases. In case of multi-component environment
with r gases, one has r parallel reactions, each of which obeys differential equation
r n

d N a ,i s,i
N a ,i
k BT
s ,i

N 0,i N a ,i N a ,i max
N a , j

dt
ns ,iV 2 mi
i
j 1 ns , j

(5)
s ,i
piV
k BT
1
max
ka ,i
k d ,i
N 0,i
N a ,i
ns ,i A
ns ,iV 2 mi
k BT
i
N0,i is the overall number of molecules of the species i in the system, Na,imax is
the number of places that molecules of the species i would take to fully populate
surface A in monolayer and ns,i is the maximal surface density of adsorbed
molecules. As we can see from eq. (4) the adsorption rate constant and the
maximum number of binding sites for the species i depend on its molecular size
through the surface density.

The constants and parameters in eq. (5) are necessary for further analysis
(deriving time evolutions of the number of adsorbed molecules or its mean,
determining equilibrium coverages...). In order to provide the surface density of
adsorbed molecules the following procedure is used:
The molecule structure is obtained using the chemical structure information
available in the PubChem Substance and Compound database through the unique
chemical structure identifier CID. Then, molecular projected surface area was
obtained using Marvin 5.9.3, 2012, ChemAxon (http://www.chemaxon.com), fig.1.

a.)

b.)

c.)

Fig. 1. Maximal and minimal projection areas of a.) carbon monoxide b.) chlorine and c.)
hexane in A2 (8.13 11.01, 9.62 16.70, 21.59 40.59), respectively.

Since spheres cannot cover rectangular areas completely, molecular projected


surface areas were corrected by a factor of 4/, before being inversed in order to
give the number of adsorption centers per unit area for that species. The obtained
data were compared with the experimental results from , as shown in table 1.
Table 1. The maximum number of binding sites in 1018 molecules/m2.
gas
ref
our data

CH4
6.3
6.52

CO
6.6
7.15

N2
6.6
7.5

Ar
7.7
7.08

O2
7.7
7.34

CO2
6.1
6.52

Hence, molecules of different gas species occupy different number of free


adsorption centers when adsorbing onto the same surface. Moreover, molecules of
the same gas, that have strongly unisotropical geometry, like chain carbohydrates,
can also have different estimates of potentially free places for themselves. In that
case, we may assume that there are some preferable orientations for adsorption .
Conclusion
Procedure has been proposed for the estimation of the number of binding sites,
parameter needed for the stochastic and deterministic analysis of multicomponent
adsorption. Obtained data were approved by experimental values from literature.
Acknowledgement. This work was funded by Serbian Ministry of Education and Science
through the projects TR 32008, III 45001, and ON 172015.

References:
[1] I. Abdulhalim, M. Zourob and A. Lakhtakia, 2008, Electromagn., 28, 214-242.
[2] Z. Djuri, I. Joki, M. Djuki and M. Frantlovi, 2010, Microelec. Eng., 87,
1181-1184.

[3] D. Do, 1998, Adsorption Analysis: Equilibria and Kinetics, Imperial College
Press, London.
[4] I. Langmuir, 1918, J. American Chem. Soc., 40, 1361-1403.