Evaluation of Metal Organic Frameworks

for Desulfurization
by
MORLA VYAS
Department of Chemical Engineering
Indian Institute of Technology, Guwahati
May, 2012
OUTLINE
INTRODUCTION
OBJECTIVES
LITERATURE REVIEW
EXPERIMENTAL WORK
RESULTS AND DISCUSSIONS
CONCLUSIONS
INTRODUCTION
Environment
Air Pollution
Sulfur Emissions
Combustion of Fuels Combustion of Fuels
Gasoline and Diesel Fuels
Can`t we reduce these Emissions ????
Yes
Environmental Regulations
Euro III ( Concentration of [S] < 150 ppm)
Euro IV ( Concentration of [S] < 25 ppm)
INDIA
BS III ( Concentration of [S] < 150 ppm)
BS IV ( Concentration of [S] < 50 ppm)
Is there any methods to maintain these Sulfur concentrations ????
Methods Like
Oxidative and Bio Desulfurization
Ultra sound assisted Desulfurization
Extraction
Hydro Desulfurization Hydro Desulfurization
Adsorption
The first three methods are good at regulating the
sulfur concentrations but these are not able to meet
the present environmental regulations
HDS as an Conventional Technology
Principle: Converts Sulfur in to H
2
S
Advantages :
Sulfur concentrations to less than 50 ppmvery effectively
Eliminates non aromatic sulfur compounds
Disadvantages :
Requires high temperatures (~ 898 K) Requires high temperatures (~ 898 K)
Requires high pressures (60 100 atm)
High operating costs
Frequent catalyst poisoning
Ineffective in eliminating aromatic sulfur species like
Benzothiophene
Dibenzothiophene
4,6-DMDBT
Decrease in octane ratings ( due to increase in temperature
for the removal of organic sulfur species)
Here Comes Liquid Phase Adsorption
Advantages:
Requires Low temperature and low pressures (ambient conditions)
Hydrogen is not required
Low energy demands for the process
Potential to regenerate the spent adsorbent
Reduction of oil loss in the beds
Importance:
Selectively removes sulfur compounds from transportation fuels
by the pi-complexation ( a weak chemica bond) adsorption.
Refractory sulfur compounds bind strongly to the pi-
complexation sorbents because of a better electron donation and
back donation ability[01]
[01]Ralph T. Yang,Desulfurization of Transportation Fuels by Adsorption, Vol. 46, No. 2, pp.
111150, 2004
Adsorbents like :
Activated Carbon
Silica gel
Activated Alumina
Carbon Molecular sieves
Zeolites
Metal organic Frameworks
MOFs Consist of metal cations linked by polyfunctional organic linkers yielding
porous three-dimensional networks.
Advantages:
High Surface Area
Easy Regeneration
Tunable structures
OBJECTIVE:
This Project focuses on
Synthesis and characterizing the adsorbents
Choosing the better adsorbent based on the effective removal of sulfur
species
Investigation of relationship between structures of the adsorbent
framework and sulfur adsorption
S. No Type of
Adsorbent
Sulfur
Species
removed
Work done Results at
optimum
conditions
References
1.
Cu-BTC-
MOF
Thiophene
and Tetra
hydro
thiophene
(THT)
Investigated Zn
containing MOF`s and Cu
containing MOF`s
(prepared by electro
chemical methods) and
found Cu containing
MOF`s having higher
potential towards the
78 wt% of the
sulfur content
was removed
from the
Thiophene based
oils and 86 wt%
for THT based
oils
Sabine
Achmann
et.
al ,2010[2]
Literature Survey
potential towards the
removal of thiophenes and
THT in low sulfur
gasoline and diesel fuels.
oils
2.
Copper
containing
MOF
Benzothiop
hene,
Thiophene
and tetra
hydro
thiophene
Investigated Al
containing MOF`s ,Fe
containing MOF`s and Cu
containing MOF`s and
observed C300 has high
adsorption capacity.
The extent of
DBT at
temperatures
close to ambient
is eight times
higher on C300
MOF`s
G.Blanco-
Brieva et.
al , 2011
[3]
S. No Type of
Adsorbent
Sulfur
species
removed
Work done Results at
optimum
conditions
References
3.
Ag+/Al-
MSU-S
Benzo
thiophenes
and Di
Benzo
thiophenes
(DBT)
Investigated Ag+
exchanged mesoporous
material Al-MSU-S for
gasoline containing 600
ppmw of BT and DBT
The sulfur
species were
brought to less
than 10 ppmws
Chunmei
Meng et. al
2010 [4]
Contd
4.
Activated
Carbon
Fibre
BT,DBT
before
HDS and
after HDS
4-
MDBT;4-6
DMDBT;
2,4,6-
TMDBT
Activated carbon ber
(ACF) was selected in this
study asan adsorbent
because it showed rather
low pressure drop and
high performance among
the activated carbon
materials and the twice
use of bed is possible
Removed the
sulphur content
from 300 ppms
to less than 10
ppms
Yosuke Sano
et. al 2005
[5]
S. No Type of
Adsorbent
Sulfur
species
removed
Work done Results at
optimum
conditions
References
5
Activated
carbon
Impregnate
d with CuCl
and PdCl
2
4,6-
dimethyl
di benzo
thiophene,
BT,DBT
Considered JP-5, a jet
fuel that has sulphur
content of 1172 ppm and
investigated metal
impregnated oxides,
zeolite 5A,13X,Y zeolites
of various
65% sulphur
adsorption
capacity was
observed for
first
regeneration
Hermen A.
Zinnen
1999 [6]
Contd
of various
metal cation forms..
regeneration
and 54% for
second
regeneration
Sulfur Species
We have chosen Dibenzothiophene as our sulfur species
Why Dibenzothiophene????
Structure
Two benzene rings
Single sulfur atom (Hindered)
At very High temperatures (~900
o
C) DBT can At very High temperatures (~900
o
C) DBT can
be removed
But at those temperatures the aromaticity
will be lost.
Hence, Liquid phase adsorption explored
3 Dimensional structure of DBT
Source : Ben mills et al.,
Metal organic Frameworks
We have chosen three different MOFs
Cu-BTC
Cr-BDC
MIL-53 (Al)
What is the Importance of Choosing these MOFs????
Cu-BTC
Coordinatively unsaturated metal center
Stable structure Stable structure
Cr-BDC
Open metal centers
High surface area and large pore volume
MIL-53 (Al)
Stable structure
Partially saturated metal center
Flexible framework
This Involves
Synthesis
Characterization
Adsorption Equilibrium Measurements
Synthesis:
Experimental Work
Adsorbent Reactants Temperature
(K)
Time
(h)
Product Recovery
Cu-BTC
[7]
[Cu
3
(BTC)
2
], [Cu
(NO
3
)
2
.3H
2
O ,
Ethanol, DMF,
Methanol and
Deionized water
373 10
Filtration and Soxhleted
with methanol, for
removal of excess DMF.
Product is dried in hot air
oven at 353 K
Adsorbent Reactants Temperature
(K)
Time
(h)
Product Recovery
Cr-BDC
[8]
Cr(NO
3
)
3
.9H
2
O ,
BDC, Hydrofluoric
acid, DMF,ethanol
& Deionized water
493 8
Filtration and Washed
thoroughly with DMF
and dried in oven at 423
K in hot air oven for
overnight. For 200 mg of
373 20 the product,15 ml of
ethanol is added.
MIL 53(Al)
[9]
Al(NO
3
)
2
.9H
2
O,
Terephthalic acid,
DMF, and
Deionized water
493 72
Filtration and Washed
with Deionized water. For
removal of excess BDC
1 gm of product is added
with 25 ml of DMF and
keep for heating at 333 K
for 15 h
0
10
20
30
40
25 225 425
W
e
i
g
h
t
,

m
g
Temperature , C
Characterization
Thermo Gravimetric analysis plot for Cu-BTC MOF
0
2
4
6
8
10
12
14
16
18
20
0 100 200 300 400 500 600
W
e
i
g
h
t
,

m
g
Temperature C
Thermo Gravimetric analysis plot for Cr-BDC MOF
Thermo Gravimetric Analysis
0
2
4
6
8
10
12
14
16
0 200 400 600 800
W
e
i
g
h
t
,

m
g
Temperature (
o
C)
Thermo Gravimetric analysis plot for MIL-53(Al) MOF
Metal Organic
Framework
BET Surface
Area (m
2
/gm)
Pore
volume
(cm
3
/gm)
Cu-BTC
1668 0.828
Cr-BDC
3300 1.38
MIL-53 (Al)
1215 0.59
Textual Properties of Metal Organic frameworks
Adsorption Equilibrium Measurements:
To study the behavior of Metal organic Frameworks in Liquid phase adsorption,
we followed a definite Protocol
Protocol Involves Six Steps:
Preparation of Synthetic Fuel mixtures
Synthesizing the Metal organic Framework Synthesizing the Metal organic Framework
Activating the Metal organic Framework
Loading the MOF to the fuel mixtures
Equilibrating the Fuel mixture
Analyzing the Fuel mixture
Equilibrium Experiments for Liquid phase adsorption
Allowed to distribute
Done by shaking at 200 rpm in an Incubator shaker
Time estimated for equilibration is 24 hrs
Adsorbent was filtered and the clear solution is collected
This unknown concentration (After adsorption) was analyzed in analyzing equipments This unknown concentration (After adsorption) was analyzed in analyzing equipments
Finally we will get the extent of adsorption done by measuring the removal of the
subjected species on to the adsorbent.
Isotherms were plotted to understand the behavior of the adsorbents at different
temperatures and to identify conditions for which high adsorption capacities can be
obtained.
Sulfur Analysis
These can be carried out on
The fuel mixture need to be analyzed before and after the Adsorption, to know
the extent of adsorption
We prepared Concentrations ranging from 100 ppm(S) to 6000 ppm(S) for our
analysis
These can be carried out on
High Performance Liquid Chromatography
UV-Visible Spectrophotometer
GC/MS Spectroscopy
Determination of DBT concentrations in UFLC (Ultra Fast Liquid Chromatography):
Results and Discussion:
Column selected: C-18
(ZORBAX-ODS)
Wavelength range : 220 nm
Detector:UV-Visible
Stationary phase (A):
Deionised water (HPLC grade)
Typical chromatogram for DBT+ n-heptane (500ppmw DBT) mixture using UFLC
Deionised water (HPLC grade)
Mobile phase (B): Methanol
(HPLC grade)
Flow rate (A): 0.2 ml/min
Flow rate (B) : 0.8 ml/min
Pressure : 13.9 Mpa
Amount injected: 0.10 ml
Observation:
Compound of interest dibenzothiophene is detected at the
retention time of 16-17.5 minutes( Retention Time) range.
Contd.
Calibration Plot:
y = 1E-05x + 1.6411
R = 0.998
0
100
200
300
400
500
600
700
800
900
1000
p
p
m
w

D
B
T
Analysis:
50 ppmw DBT 950ppmw DBT
A plot of ppmw DBT verses
these chromatogram areas
gives the required calibration
plot.
0
0 20000000 40000000 60000000 80000000 100000000
Area
Calibration plot of dibenzothiophene + n-heptane fuel mixture [11]
Observation:
From the trend line pattern it is obvious that analysing equipment is best suitable for the
concentrations ranging upto around 900 ppmw DBT
[11]P.Poddar Adsorptive Desulfurization of Liquid Fuels, BTP thesis,Dept of chemical engineering,IITG
Contd.
Dibenzothiophene on Cu-BTC:
0
20
40
60
80
100
120
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(

g

S
/

k
g

M
O
F
)
298 K
313 K
328 K
Experiments were conducted
at three different
temperatures
298 K
313 K
328 K
0
0 1000 2000 3000 4000 5000
Concentration, ppmwS
Adsorption isotherms of DBT on Cu-BTC at 298 K, 313 K and 328 K
Observation:
It is evident
that adsorption
potential of this
material is
higher at 313 K
than on 298 K
and still lesser
for 328 K
Reasons:
At low temperatures, the adsorption process is basically
governed by weak Van der Waals forces
At higher temperatures Chemisorption, and probably chemical
reaction [12] is dominant showing in increase in adsorption
potentials
[12] Zhang ZY, Adsorptive removal of aromatic organosulfur compounds over the modied NaY zeolites. Appl Catal B:
Environ 2008;82:110
Contd.
Dibenzothiophene on Cr-BDC:
0
20
40
60
80
100
120
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(
g
S
/

k
g

M
O
F
)
298 K
313 K
328K
Experiments were conducted
at three different
temperatures
298 K
313 K
328 K
0
0 1000 2000 3000 4000 5000
Concentration, ppmwS
Adsorption isotherms of DBT on Cr-BDC at 298 K, 313 K and 328 K
Observation:
It is evident
that adsorption
potential of this
material is
slightly higher at
313 K than on
298 K and still
lesser for 328 K
Reasons:
At low temperatures, the adsorption process is basically
governed by weak Van der Waals forces
At higher temperatures Chemisorption, and probably chemical
reaction [12] is dominant showing in increase in adsorption
potentials
Contd.
Dibenzothiophene on MIL-53 (Al):
0
20
40
60
80
100
120
140
0 1000 2000 3000 4000
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(

g
S
/

k
g

M
O
F
)
298 K
313 K
328 K
Reasons:
At low
temperatures, the
adsorption process is
Experiments were conducted
at three different
temperatures
298 K
313 K
328 K
0 1000 2000 3000 4000
Concentration, ppmwS
Adsorption isotherms of DBT on MIL-53 (Al) at 298 K, 313 K and 328 K
adsorption process is
basically governed by
weak Van der Waals
forces
Observation:
It is evident that adsorption potential of this material is slightly higher at 313
K than on 298 K and lesser for 328 K
Adsorption potentials at 298 K and 313 K haven`t shown significant changes,
resembling that there is no effect of chemisorptions at 313K
Contd.
Correlation of MOFs based on Temperature Kinetics:
0
20
40
60
80
100
120
140
0 1000 2000 3000 4000 5000
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(
g
S
/

k
g

o
f

M
O
F
)
Concentration, ppmwS
Cu-BTC
Cr-BDC
MIL-53(Al)
Observation:
MIL-53 (Al) is having more
adsorption capacity than other
two mofs
Cu-BTC is competitive with
MIL-53 (Al) because of its still
adsorbing potentials
0
20
40
60
80
100
120
140
0 2000 4000 6000
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(

g
S
/

k
g

o
f

M
O
F
)
Concentration, ppmwS
Cu-BTC
Cr-BDC
MIL-53 (Al)
Correlation among the adsorption isotherms of DBT on the three MOFs (Cu-BTC, Cr-BDC and MIL-53 (Al) ) at 298 K.
Correlation among the adsorption isotherms of DBT on the three MOFs (Cu-BTC, Cr-BDC and MIL-53 (Al) ) at 313 K.
Observation:
Same trend is observed at
313 K
Contd.
Correlation of MOFs based on Temperature Kinetics:
0
20
40
60
80
100
120
140
A
m
o
u
n
t

A
d
s
o
r
b
e
d

(

g
S

/

k
g

o
f

M
O
F
)
Cu-BTC
Cr-BDC
MIL-53 (Al)
0
0 1000 2000 3000 4000 5000
Concentration, ppmwS
Correlation among the adsorption isotherms of DBT on the three MOFs (Cu-BTC, Cr-BDC and MIL-53 (Al) ) at 328 K.
Observation:
MIL-53 (Al) is having more adsorption capacity than other two mofs
Cu-BTC is less competitive with MIL-53 (Al) at this temperature (328 K)
Contd.
0
20
40
60
80
100
120
140
290 300 310 320 330
E
x
t
e
n
t

o
f

a
d
s
o
r
p
t
i
o
n

(

g
S
/

k
g

M
O
F
)
MIL-53 (Al)
Cu-BTC
Cr-BDC
Variation of Adsorption amounts:
290 300 310 320 330
Temperature K
Variation of dibenzothiophene (DBT) adsorption capacity for Cr-BDC and MIL-53 (Al) at
equilibrium concentration (3400 ppmwS) and Cu-BTC at 3400 ppmwS
Observation:
No distinct pattern is noticed
Extent of adsorption is maximum at 313 K for Cu-BTC and Cr-BDC
Extent of adsorption at 298 K , 313 K and 328K are more or less equal for MIL-53 (Al)
Contd.
Comparison with existed Sorbents:
40
60
80
100
120
140
E
x
t
e
n
t

o
f

A
d
s
o
r
p
t
i
o
n

(

g

S
/

k
g

S
o
r
b
e
n
t
)
Extent of DBT adsorption at 298 K (2500 ppmw S) for Cu-BTC, Cr-BDC,MIL-53 (Al), MOF-5,
MOF-177, MOF-505 [13] , Y-Zeolites[03], Activated carbons[14]
[13] Adam J. Matzger, Liquid Phase Adsorption by Microporous Coordination Polymers: Removal of Organosulfur
Compounds, J. AM. CHEM. SOC. 2008, 130, 69386939
[14]
0
20
MIL-53 (Al) Cu-BTC Cr-BDC MOF-5 MOF-505 MOF-177 Y-Zeolites Activated
Carbon
E
x
t
e
n
t

o
f

A
d
s
o
r
p
t
i
o
n

(

g

S
/

k
g

S
o
r
b
e
n
t
)
Sorbents
Why this higher and lower adsorption amounts ???
Factors effecting adsorption
Surface areas
pore volumes
Liquid phase adsorption
Impact of structure Impact of structure
Role of metals
Role of ligands
Role of host-guest interactions
Comparison with existed Sorbents: Surface areas
Sorbents
Metal
involved
Ligand
BET
Surface
Area
(m
2
/gm)
Pore volume
(cm
3
/gm)
Amount Adsorbed
(g S / kg Sorbent)
Dibenzothiophene
Cu-BTC Copper
1,3,5-
benzenetricarboxylic
acid
1668 0.828 68.1
Cr-BDC Chromium
1,4-
benzenedicarboxyli
c acid
3300 1.38 57.3
1,4-
MIL-53 (Al) Aluminium
1,4-
benzenedicarboxyli
c acid
1215 0.59 118.6
MOF-5[13] Zinc
1,4-
benzenedicarboxyli
c acid
2900 1.04 40
MOF-177[13] Zinc
1,3,5-
benzenetribenzoate
4630 1.69 20
MOF-505[13] Copper
3,3,5,5-
biphenyltetracarbox
ylic acid
1830 0.71 35
[13] Adam J. Matzger, Liquid Phase Adsorption by Microporous Coordination Polymers: Removal of Organosulfur
Compounds, J. AM. CHEM. SOC. 2008, 130, 69386939
Contd.
Reasons behind higher and lower adsorption:
Role of Cation on the S-M (Sulfur-Metal) interactions with alter in Ligand
40
60
80
100
E
x
t
e
n
t

o
f

A
d
s
o
r
p
t
i
o
n

(

g
S
/

k
g

o
f

M
O
F
)
298 K
313 K
298 K 313 K
328 K
328 K
Observation:
Here the Cation Copper
( Cu
2+
) is same for both
the Materials
0
20
40
Cu-BTC Cu-DABCO Cu-BTC Cu-DABCO Cu-BTC Cu-DABCO
E
x
t
e
n
t

o
f

A
d
s
o
r
p
t
i
o
n

(

g
S
/

k
g

o
f

M
O
F
)
Metal organic frameworks
298 K 313 K
328 K
Possess greater (S-M)
interactions and leads to
higher adsorption for Cu-
BTC than on Cu-DABCO
Extent of DBT adsorption at equilibrium (3500 ppmw S) for Cu-BTC and
Cu-DABCO [11]
[11]P.Poddar Adsorptive Desulfurization of Liquid Fuels, BTP thesis,Dept of chemical engineering,IITG
Contd.
Reasons behind higher and lower adsorption:
Role of Ligand on the S-M (Sulfur-Metal) interactions with alter in Cation
40
60
80
100
120
140
E
x
t
e
n
t

o
f

a
d
s
o
r
p
t
i
o
n

(
g

S
/

k
g

o
f

M
O
F
)Observation:
Here the Cation
Aluminium(Al
3+
) and
Iron (Fe
2+
) is different for
both the Materials
But the ligands are
identical
0
20
MIL-53 (Al) MIL-53 (Fe)
E
x
t
e
n
t

o
f

a
d
s
o
r
p
t
i
o
n

(
g

S
/

k
g

o
f

M
O
F
)
Metal organic frameworks
Extent of DBT adsorption at equilibrium (3500 ppmw S) for MIL-53(Al)
and MIL-53(Fe) [03]at 313K
identical
Thus possess 6 times
higher adsorption for
MIL-53 (Al) than on MIL-
53 (Fe)
[03] G.Blanco-Brievaa, Effectiveness of metalorganic frameworks for removal of refractory organo-sulfur compound
present in liquid fuels, Fuel Vol:90, 2011
Conclusion:
In this study
The metal organic frameworks Cu-BTC, Cr-BDC and MIL-53 (Al) were
synthesised and characterisation of these frameworks were also carried out.
The metal organic frameworks Cu-BTC, Cr-BDC and MIL-53 (Al) were
synthesised and characterisation of these frameworks were also carried out.
Explored Sulfur adsorption measurements on these MOFs
Our studies explored that these MOFs have promising adsorption
potentials than existing Sorbents employed for desulfurization of organo
sulfur compounds till yet
MIL-53 (Al) has higher adsorption potentials than Cu-BTC and Cr-BDC
Cu-BTC is more competitive with MIL-53 (Al) than Cr-BDC due to its still
adsorbing capacities
It was explored that the structure of these organo sulfur compounds plays an important
role along with the structure of MOF and other parameters like -Complexation and pore
volumes and surface areas in deciding the adsorption potentials of these MOFs employed
in this work
It has been demonstrated that the extent of dibenzothiophene (DBT) adsorption at
temperatures close to ambient (304 K) is higher for all three mofs employed in this work
The very high adsorption capacity of these (MIL-53(Al)) and Cu-BTC) substrates makes it a
potential candidate to be employed in the removal of remaining refractory S-compounds in
Contd.
potential candidate to be employed in the removal of remaining refractory S-compounds in
previously desulfurized liquid fuels.
Future work
Evaluating these organo sulfur compounds like BT(benzothiophene) and DBT(
dibenzothiophene) on mofs like MOF-74 with change in metal (w.r.t. Mg,Ni, and Co),
which is showing higher adsorption potentials for CO
2
adsorption till now.
Flow-through experiments and determination of the selectivity of these materials
for BT and DBT in the presence of other aromatic compounds found in fuels are can be
made to assess the practicality of desulfurization by adsorption to MOFs.
References
[2] Sabine Achmann, Gunter Hagen, Martin Hmmerle, Itamar Malkowsky, Christoph Kiener, Ralf
Moos, Sulfur Removal from Low sulphur Gasolineand Diesel Fuel by Metal Organic
Frameworks, Chem. Eng. Technol. 2010, 33, No. 2, 275280
[3] G.Blanco-Brievaa, J.M. Campos-Martina, S.M. Al-Zahrani and J.L.G. Fierroa, Effectiveness of
metalorganic frameworks for removal of refractory organo-sulfur compound present in liquid
fuels, Fuel Vol:90, 2011
[4]Chunmei Meng, Yunming Fang, Lijun Jin, Haoquan Hu, Deep desulfurization of model
gasoline by selective adsorption on Ag+/Al-MSU-S , Catalysis Today 149 (2010) 138142
[5] Yosuke Sano, Kazuomi Sugahara, Ki-Hyouk Choi, Yozo Korai, Isao Mochida , Two-step
adsorption process for deep desulfurization of diesel oil , Fuel 84 (2005) 903910 adsorption process for deep desulfurization of diesel oil , Fuel 84 (2005) 903910
[6] Hermen A. Zinnen Removal of organic sulphur compounds from FCC Gasoline using
Regenerable Adsorbents, US Patent number 5,935,422 Aug 10 1999
[7] Pradip C Ph.D. Thesis, Indian Institute of Technology, Guwahati, 2009
[8] Pradip chowdhury, Chaitanya Bikkina, and Sasidhar Gumma* Gas adsorption properties of
the Chromiumbased Metal Organic Framework MIL 101 J.Phys.Chem.C 2009, 113, 6616-6621
[9] Rowsell, J. L. C., and Yaghi, O. M., Metalorganic frameworks: a new class of porous
materials, Micropor. Mesopor. Mater., 73, 3-14 (2004)
Chemisorption:
-Complexation:
The DewarChattDuncanson model is a model in organometallic chemistry , which
Chemisorption is a sub-class of adsorption , driven by a chemical reaction occurring at the
exposed surface.
A new chemical species is generated at the adsorbent surface (e.g. corrosion, metallic oxidation).
The strong interaction between the adsorbate and the substrate surface creates new types of
electronic bonds ionic or covalent, depending on the reactive chemical species involved
Back up
The DewarChattDuncanson model is a model in organometallic chemistry , which
explains the type of chemical bonding between an alkene and a metal (pi-complex) in
certain organometallic compounds.
The model is named after Michael J.S. Dewar , Joseph Chatt and L.A. Duncanson
The pi-acid alkene donates electron density into a metal d-orbital from -symmetry
bonding orbital between the carbon atoms.
The metal donates electrons back from (a different) filled d-orbital into the empty
antibonding orbital. Both of these effects tend to reduce the carbon-carbon bond order,
leading to an elongated C-C distance and a lowering its vibrational frequency.[14]
[14] Olefin co-ordination compounds. Part III. Infra-red spectra and structure: attempted preparation of
acetylene complexes J. Chatt and L. A. Duncanson, J. Chem. Soc., 1953,
Back up: for UFLC
ZORBAX-ODS: [10]
Highly retentive reversed phase liquid chromatographic column packing based on the ZORBAX
Microparticulate silica support
This bonded phase packing is formed by the monomolecular bonding of octadecysilane groups
to the surface of the particles
Maximum surface area coverage is maintained to produce these columns with exceptional
reproducibility of performance
C-18 bonded phases are well established for the seperation of non polar and low polarity solutes
Stronger retentive power for non polar compounds
Choice of Mobile phase: Methanol [10]
As our fuel mixture is basically a non polar mixture, we need our compound to be retended by
the column
So, we need a partially aqueous solvents to serve our purpose
Methanol is a strong organic solvent and it is chosen as our mobile phase
An increase in the retention is basically governed by increasing the water content of the mobile
phase
Hence we have chosen the binary mixture composition of flow as
Methanol : 0.8ml/min
Deionised water : 0.2ml/min
[10] Instrumental Liquid chromatography: A practical manual on High performance liquid chromatography, by N.A Parris