ADSORPTION-DESORPTION PROCESSES IN

DEFENSE AGAINST CHEMICAL,

BIOLOGICAL, RADIOLOGICAL, NUCLEAR
AND EXPLOSIVE THREATS
Olga Jaki, Zoran Jaki, Danijela Randjelovi, Ivana Joki, Milo
Frantlovi
olga@nanosys.ihtm.bg.ac.rs
IHTM Institute of Microelectronic Technologies
and Single Crystals, University of Belgrade, Serbia
1
OTEH 2012
Outline
Introduction: CBRNe threats
IHTM research of adsorption-desorption
processes in the context of defence
technologies against CBRNe threats
Analytical models, tools and databases
Simulation results
Conclusion
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OTEH 2012
Introduction/CBRNe threats - sources
Chemical, biological, radiological and nuclear agents and explosive
agents (CBRNe) are potentially highly lethal, even if their amounts in
the environment are minuscule, could be used in terrorist actions and
may be encountered by military personnel on a variety of occasions,
during intentional attacks or accidental exposure.
Possible contaminants are airborne and they may be gases, vapors,
or aerosols (small solid and liquid particles). Most biological and
radiological agents are aerosols, whereas most chemical warfare
agents are gaseous.
Toxins poisonous substances produced by living things
Comon for all sources: attacks may be improvised utilizing a large
number of readily available industrial hazardous substances!!!

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OTEH 2012
Introduction/ CBRNe threats & trends
Relevant world conventions
The Geneva Protocol for the Prohibition of the Use in War of
Asphyxiating, Poisonous or Other Gases, and of Bacteriological
Methods of Warfare a few paragraphs
The Biological Weapons Convention (BWC), 1972 four pages
The Chemical Weapons Convention (CWC), 1993 200 pages
United Nations Security Council resolution 1540, 2004 obliges
countries for implementation measures (outreach through meetings, The
International Union of Pure and Applied Chemistry (IUPAC) activities)
International governance of materials and technologies that could be
used to create biological or chemical weapons is a key tool in reducing
possible biological and chemical threats.
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Introduction/CBRNe threats & IHTM-CMTM
5
PREVENTION

PROTECTION

DECONTAMINA
TION
SENSORS

MEMBRANES

ADSORPTION
FILTERS
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IHTM-CMTM/sensors, membranes, adsorbents
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AD processes / modelling
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Theoretical model for multicomponent adsorption
Ideal gas striking rate and rate equation for
the number of adsorbed molecules:
Important physical parameters
7
,
,
, , ,
a i
d i
k
g i f i a i
k
A A A

+

,
, , , , ,
d
d
a i
a i g i f i d i a i
N
k N N k N
t
=
,
1
1
1
2
r
a i i j
j i B
R p
m k T
u
t
=
| |
=
|
|
\ .

, , ,
1
d
1
d
2
r
a i s i a i
i j
j i i B
N A N
p
t
m k T
o
u
t t
=
| |
= |
|
\ .

,
max
, , 0, , ,
,
1
2
s i
i B
a i d i i a i s i
s i i B
i
p V k T
k k N N n A
n V m k T
o
t
t
= = = =
AD processes / numerical database
OTEH 2012
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Important physical parameters from the designers
point of view
,
max
, , 0, , ,
,
1
2
s i
i B
a i d i i a i s i
s i i B
i
p V k T
k k N N n A
n V m k T
o
t
t
= = = =
well known constants like pi, Boltzmann constant
system parameters that can be tailored through the design process
like pressure, volume and temperature
parameters, scarce in literature data, are very cumbersome to find and
implement: the sticking coefficient, mean residential time of adsorbed
molecules (through the desorption energy) and the surface density of
adsorbed molecules in case of mono and multi site adsorption
New methods are developed for the estimation of missing data!
Military gadgets / structure design
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Key points:
good knowledge on physical parameters of chemical warfare agents
good knowledge on material and structural properties of the adsorbent,
both at the surface and in bulk
This includes the knowledge of the effective area and surface
functionalization that are of interest for adsorption dynamics.
There may be three large groups of adsorbents with different properties,
depending on their overall purpose:
materials for sorbent filters,
materials for decontamination and
materials for highly sensitive sensors
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Physical parameters/ surface densities
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Ar
O
2

H
2

C
6
H
6

a)
b)
c)
Binding site
Adsorption
Desorption
He
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Surface densities/ prefferable orientations
Different gases with complex non-spherical molecules
have different molecular projected area on the surface.
But it is also true that complex non-spherical molecules of
the same gas have different molecular projected areas on
the surface, depending on their orientation at the moment
of adsorption on the surface
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NO2 SO2
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Prefferable orientations/ Tabun Sarin Soman
The molecule structure was first obtained using the information available
in the PubChem Substance and Compound online database through the
unique chemical structure identifier CID.
The molecular projected surface area was then determined using the
geometry and calculator plug-ins of the software Marvin 5.9.3, 2012,
ChemAxon.
The molecular projected areas were finally utilized to determine the
surface density of adsorbed molecules
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Molecular projected areas/nerv agents
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Substance
(CID)
Formula
MPA
(A
2
/molecule)
Tabun GA (6500) C
5
H
11
N
2
O
2
P 29.93-49.57
Sarin GB (7871) C
4
H
10
FO
2
P 26.66-42.02
Soman GD (7305) C
7
H
16
FO
2
P 33.99-52.51
Cyclosarin GF
(64505)
C
7
H
14
FO
2
P 29.37-53.87
Agent VX
(178033)
C
11
H
26
NO
2
PS 50.31-82.82

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Molecular projected areas/vesicants
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Substance
(CID)
Formula
MPA
(A
2
/molecule)
Sulfur Mustard HD
(10461)
C
4
H
8
Cl
2
S 19.82-45.64
Lewisite L
(5372798)
C
2
H
2
AsCl
3
26.15-39.51

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Surface functionalization/desorption energy
The bond between the adsorbate
molecules and the surface has
been modeled as
very weak (_._),
weak (.),
stronger (---) and
very strong (_)
via change of the sticking
probability (directly proportional to
adsorption rate) and desorption
energy (counter proportional to
desorption rate) and the results for
the number of adsorbed molecules
are shown in logarithmic scale
15

10
-15
10
-10
10
-5
10
11
12
13
14
15
l
o
g
(
N
a
)



[
m
o
l
e
c
u
l
e
s
]

Sulfur mustard
T=300 K
V=3 lit
p=0.01 bar
A=100 mm
2

t [s]
3 kcal/mol
5 kcal/mol
7 kcal/mol
10 kcal/mol
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Surface area/the effect of augmentation
16

10
-15
10
-10
10
-5
6
8
10
12
14
16
t [s]
l
o
g
(
N
a
)



[
m
o
l
e
c
u
l
e
s
]

Tabun
T=300 K, V=3 lit
p=0.01 bar
E
d
=5kcal/mol
1 mm
2

10
2
mm
2

10
4
mm
2

10
6
mm
2

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Conclusion
AD processes within the context of CBRNe agents are addressed
Core defence technologies where our research can contribute
gas sensors (early detection of CBRNe agents)
decontamination adsorbents (remediation)
The analysis was performed from the designers point of view
(effective surface area, surface material, functionalization).
Similar facilities are required for the development of both: sensing
and decontamination structures and devices
Crucial part of the design of devices:
nanostructuring
surface functionalization
The improvement of the properties of devices
the increase of the effective surface
target-specific binding
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Acknowledgments
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This work has been supported by the Serbian
Ministry of Education and Science through the
project TR 32008.
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