APPLICATION

S OF GAS
CHROMATOGRAPH
Y
Edited by Reza
Davarnejad
and Mahboubeh
Jafarhan!
Applications of Gas Chromatography
Edited by Reza Davarnejad and Mahboubeh Jafarkhani
Published by InTech
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Copyright 2012 InTech
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A""i!ation# of 2a# Chro%ato)ra"hy,
Edited by Reza Davarnejad and Mahboubeh Jafarkhani
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Content#
Preface $II
Cha"ter 1 Gas Chromatography Application
in %upercritical &luid !'traction Process 1
Reza Davarnejad and Mo#tafa 8e#havarz Moraveji
Cha"ter / Interaction Parameters of %urfactant
i'tures by In"erse Gas Chromatography 1(
Eeuterio 9ui# Aran!ibia, 0abo C' ,!huz and ,u#ana M' 3ardavid
Cha"ter & Applications of Chromatography )yphenated
Techni*ues in the &ield of +ignin Pyrolysis ,1
,hubin :u, 2aojin 9v and Rui 9ou
Cha"ter ; #egradation Phenomena of
-eforming Catalyst in #I-.C&C /0
8i%ihiko ,u)iura
Cha"ter 5 -ecent %trategies in 1rganic -eactions
Cataly2ed by Phase Transfer Catalysts
and Analy2ed by Gas Chromatography 34
0' A' <ivekanand and Ma(69in) :an)
Cha"ter 7 P1P and PA) in 5i2erte +agoon6 Tunisia 11(
Trabe#i ,ouad, 3en A%eur :aid, Deroui!he Abdekader,
Cheikh Moha%ed and Dri## Moha%ed Ridha
0refa!e
This book presents a critical review of various chromatography techniques for a
limited number of processes. Most techniques are illustrated by examples.
The processes described are necessarily limited to those which appear to the authors to
have the greatest validity and practical use. Wherever possible, we have included
recommendations delineating the best techniques for analyzing each sample.
Recommended techniques are often illustrated by detailed examples.
Although the book is intended to serve primarily the practicing engineer, especially
the process or chemical engineer, other engineers (such as environmental engineers)
and chemists concerned with analyzing techniques may fnd it useful.
Most new techniques are still empirical in nature, although there are often theoretical
bases for the correlation; wherever possible, the theory is outlined to provide the user
with the foundation of the proposed chromatography techniques.
Special thanks are due to all respectful authors for their excellent contributions to this
book and to Ms. Martina Durovic and Ms. Daria Nahtigal for extensive assistance and
support.
Reza Davarnejad and Mahboubeh Jafarkhani
Department of Chemical Engineering,
Faculty of Engineering,
Arak University
Iran
1
Gas Chromatography Application in
Supercritical Fluid Extraction Process
Reza Davarnejad
*
and Mostafa Keshavarz
Moraveji Department of Chemical Engineering, Faculty of
Engineering, Arak University, Iran
1. Introduction
There are two types of application for gas chromatography (!" in the
s#percritical $#id e%traction process& as chromatography is a type of
s#percritical e%traction apparat#ses which can separate a component from a
m#lti'component mi%t#re d#ring s#percritical e%traction& Therefore( this
application can be the alternative to conventional gas chromatography(
which needs high temperat#res for the evaporation of the feed mi%t#re and
for li)#id chromatography( where li)#id solvents may be replaced& This process
res#lts in a di*erent transport velocity along the stationary phase for
di*erent molec#les& Molec#les having wea+ interaction forces with the
stationary phase are transported )#ic+ly while others with strong interactions
are transported slowly& ,eside the interactions with the stationary phase( the
solvent power of the mobile phase determines the distrib#tion of the
components& -#rthermore( s#percritical gases have a high solvent power
and e%ert this solvent power at low temperat#res&
.nother application of ! in s#percritical fl#id e%traction is consideration and
analysis of e%traction prod#ct& The obtained prod#cts from vario#s types of
s#percritical apparat#ses (s#ch as phase e)#ilibri#m and rate test apparat#s"
sho#ld be analyzed& /owever( di*erent types of analyzer can be #sed b#t( the
conventional ! with a s#itable col#mn has widely been recommended&
.ltho#gh several col#mns for detecting a lot of components have been designed
and fabricated by some companies b#t d#e to lac+ing of s#itable col#mns for
some components or #nclear pea+s obtained from some col#mns( an e%tra
process (s#ch as esteri0cation of the fractionated fish oil" before ! analyze
is sometimes re)#ired& 1n this application( the samples obtained from the
s#percritical e%traction apparat#s are not #nder press#re or their press#res have
bro+en down by a damper (in online !"&
1n this chapter both types of ! application in s#percritical $#id e%traction with
e%amples will be ill#strated&
2. Gas chromatography apparatus
1n s#percritical $#id chromatography (2-!" the mobile phase is a s#percritical
gas or a near critical li)#id& !ompared to gas chromatography (!"( where
a gas is #nder ambient
*
!orresponding
.#thor
2 Applications of Gas Chromatography
press#re (for e%ample in the second type of apparat#s applied in s#percritical
process"( and li)#id chromatography (3!"( where a li)#id is #sed as mobile
phase( the solvent power of the li)#id mobile phase in 2-! can be varied
by density( e&g&( by press#re changes at constant temperat#re& 2ol#bility
increases in general with press#re #nder s#percritical conditions of the
mobile phase( temperat#re sensitive compo#nds can be processed& The
chromatographic separation can be carried o#t at constant press#re (isobaric
operation" or with increasing press#re (press#re programmed"& 1n addition(
temperat#re can be varied& 2-! has one more adj#stable variable for
optimization of el#tion than ! or 3! (,r#nner(
4556"& . s#percritical $#id has properties similar to a gas and also similar to a
li)#id& 7hile
density and solvent power may be compared to those of li)#ids( transport
coe8cients are
more those of a gas& 2-!( beca#se of its mobile phase( can cover an
intermediate region
between ! and 3!( as ill#strated in -ig#re 4 with respect to density and
di*#sion
coe*icient& -or preparative and prod#ction scale operations( 2-! has the
advantage of easy
separation of mobile phase from separated compo#nds& . disadvantage is
that strongly
polar and ionic molec#les are not dissolved by s#percritical gases(
which can be advantageo#sly #sed in 2!- (,r#nner( 4556"&
-ig& 4& .reas for the di*erent mobile phases in chromatographic separations
with respect to component properties (2choenma+ers and 9#n+( 45:;"&
Most gases which can be #sed in 2-! are non'polar& Therefore( polar
s#bstances of a feed mi%t#re can only be el#ted by adding a polar modi0er&
<olar gases li+e ammonia or s#lf#r dio%ide are reactive compo#nds #nder
press#re the e)#ipment m#st be able to withstand corrosive conditions& =n
the other hand( carbon dio%ide is easy to handle and safe& <olar modi0ers(
3 Gas Chromatography Application in Supercritical Fluid Extraction Process
which are easier to handle than ammonia or s#lf#r dio%ide may instead be
applied& To ma+e e*ective #se of the possibilities of 2-!( allowable press#res
sho#ld be high&
4 Applications of Gas Chromatography
!omposition of the mobile phase can s#bstantially in$#ence separation in 2-!
(,r#nner(
4556"& Retention times of s#bstances may be very m#ch di*erent d#e to
polarity or other physico'chemical properties of the components of the
mobile phase& <ic+el (45:>"
investigated large di*erences in the separation of aromatic hydrocarbons with
!=
?
( @
?
=( !
A
/
:
and !
A
/
>
&
ases applied in 2-! are mostly non'polar& The polarity of carbon dio%ide at low
densities is comparable to that of n'he%ane and at higher densities to that
of methylene chloride& @itro#s o%ide and the al+anes b#tane or pentane behave
similar& <olar s#bstances are el#ted only after long retention times and in
broad pea+s even not at all& 1n these cases( a polar modi0er( added to the
gaseo#s mobile phase( introd#ces the necessary polarity to the mobile
phase& The modi0er then determines the el#tion se)#ence( which can be
changed by the amo#nt and the type of modi0ers (,r#nner( 4556"&
7ith increasing content of a modi0er in the mobile phase( retention times
become shorter& -or polycyclic aromatic compo#nds( 3eyendec+er et al. (45:>"
investigated the in$#ence of
4&6'dio%ane as modi0er on n'pentane as mobile
phase&
Temperat#re and press#re can be employed in s#percritical chromatography as
parameters for in$#encing separation characteristics& Temperat#re directly
determines vapor'press#re of the feed components and density of the
mobile phase and( indirectly( adsorption e)#ilibri#m& 7ith higher
temperat#res( vapor'press#res of the feed components increase e%ponentially&
Density decreases proportionally to temperat#re if conditions are far from
critical( b#t in the region of the critical point of the mobile phase( which is the
main area of application of 2-!( density varies dramatically with temperat#re&
The solvent power of the mobile phase( which increases with density( is therefore
changed s#bstantially in this region& The in$#ence on chromatographic
separation depends on the relative importance of these two e*ects( if other
conditions remain #nchanged (,r#nner( 4556"&
<ress#re mainly in$#ences density of the mobile phase& 7ith increasing
press#re( the in$#ence of temperat#re is diminishing( since density varies less
with temperat#re at higher press#res (,r#nner( 4556"& 2-! allows the
variation of temperat#re and press#re for optimizing separation conditions
as well as d#ring the separation process itself& 2#ch an operational mode
is called press#re and temperat#re programming& Temperat#re
programming is well +nown from gas chromatography( b#t is less common in
2-!( since press#re programming can be very e*ective& <ress#re and
temperat#re programming may be combined to density programming (,r#nner(
4556"&
1n preparative chromatography( conditions are +ept constant d#ring separation(
since feed mi%t#res of several injections may be on their way at the same
time in the col#mn& The el#tion of s#bstances of di*erent molec#lar weight in
isobaric 2-! separations is better than in isothermal !( since vapor press#re
is not so important in 2-!& !ompared to 3!( the tendency of pea+
broadening is lower in 2-!( since diff#sion coe8cients are far higher
(,r#nner( 4556"&
-low rate of the mobile phase is a f#rther important parameter which a*ects the
n#mber of theoretical stages in chromatographic separations& D#e to the low
viscosity of near critical mobile phases( $ow rate in 2-! can be high( and
5 Gas Chromatography Application in Supercritical Fluid Extraction Process
n#mber of theoretical stages remains nearly constant over a wide range
of $ow rate& . more detailed disc#ssion of
Applications of Gas Chromatography
chromatographic f#ndamentals and especially analytical applications of 2-!
can be fo#nd in the ab#ndant literat#re on analytical 2-! (ere et al&( 45:?B
3ee and Mar+ides( 455CB 2mith( 45::B 7enclawia+( 455?B 7hite( 45::"&
The apparat#s (as shown in -ig#re ?" consists of the separation col#mn as central
part in a temperat#re controlled environment (4"( the reservoir for the mobile
phase (?"( a #nit for establishing( maintaining and controlling press#re (A"( an
optimal #nit for adding a modi0er (6"( the injection part for introd#cing the feed
mi%t#re (D"( a meas#ring device (detector" for determining concentration of the
el#ted s#bstances (>"( a sample collection #nit (;"( a #nit for processing the
mobile phase (:" and another one for processing data and controlling the total
apparat#s (5" (,r#nner( 4556"&
The $ow of the s#percritical gas #nder press#re is maintained by long'stro+e
piston'p#mps( reciprocating piston'p#mps or membrane'p#mps which
deliver the mobile phase in li)#e0ed form& The fl#id is then heated to
s#percritical conditions before entering the col#mn& <ress#re and $ow rate
m#st be +ept as constant as possible in order to maintain constant conditions
for separation and to achieve a stable base line in the chromatogram&
=scillating p#mps therefore can have three heads which deliver at di*erent
times or a p#lsation dampener in order to minimize p#lsation (,r#nner( 4556"&
-ig& ?& -low scheme of apparat#s for 2-! (,r#nner(
4556"&
2.1 Columns
!ol#mns for chromatographic separation with s#percritical are chosen(
li+e other chromatographic col#mns( according to the needs of the separation&
-or analytical p#rposes the choice is between pac+ed and capillary col#mn&
!apillary col#mns are #sed with a length between 4C m and ?D m& <ress#re
drop is low compared to li)#id mobile phases& Therefore( capillary col#mns
with inner diameters of DC to 4CC Em can be #sed and a high
! Gas Chromatography Application in Supercritical Fluid Extraction Process
n#mber of theoretical stages veri0ed& 2eparations with capillary col#mns can be
nearly as e*ective as in gas chromatography& 7hile in early applications steel
capillaries had been #sed in 2-!( since 45:C( f#sed silica capillary col#mns
have replaced the steel capillaries& 2tationary phases mostly stem from
polysilo%anes and polyglycols& -re)#ently #sed stationary phases have been
listed in the literat#re (,r#nner( 4556"&
9nder conditions of 2-!( the compo#nds of the stationary phases may be slightly
sol#ble in the mobile phase and are therefore 0%ed by lin+ing them by chemical
reactions& @#mero#s pac+ed col#mns are available( many from /<3!
applications& @ormal phase chromatography (polar stationary phase(
non'polar mobile phase" and reverse phase chromatography (non'polar
stationary phase( polar mobile phase" are applied( b#t are not as important in
2-! as in /<3!( since a polar mobile phase in 2-! involves a polar modi0er&
Most separations in 2-! are carried o#t with #nmodi0ed silica gel or chemically
modified silica gel as stationary phase (,r#nner( 4556"& -or pac+ed col#mns
particles are available with diameters in the range of A to 4CC Em& -or analytical
p#rposes particles in the range of A to D Em have a high separation power in a
pac+ing and enable a high linear velocity of the mobile phase leading to short
retention times& -or preparative p#rposes particles in the range of ?C to 4CC
Em are #sed (,r#nner( 4556"&
2pecial filling techni)#es are necessary to ens#re a homogeneo#s
pac+ing& 2aito and Fama#chi (2aito et al.( 45::B 2aito and Fama#chi( 45::B
2aito et al&( 45:5" and Fama#chi and 2aito (Fama#chi et al&( 45::B Fama#chi
and 2aito( 455C" applied col#mns of ; to ?C mm diameter( <err#t (45:?(
45:A( 45:6" a col#mn of >C mm inner diameter and >CC mm length with
particles of 4C'?D Em( .l+io et al. (45::" a 5CC mm long col#mn with 6C'A> Em
diameter particles&
The length of the col#mn is dependent on the allowable press#re drop&
<ress#re drop #s#ally is in the range of 4 to 6 M<a for ?DC mm& 1n this range for
the press#re drop capillary factors are nearly independent of press#re drop as
demonstrated by 2choenma+ers et al. (45:>"& To avoid #nacceptable press#re
drop( 2aito et al. applied a recycling techni)#e (2aito et al.( 45::B 2aito and
Fama#chi( 45::B 2aito et al.( 45:5"& . cycle p#mp transports the el#ted
s#bstances several times to the beginning of the col#mn& Th#s( the separation
power of the col#mn can be enhanced( witho#t increasing press#re drop& <ea+
broadening occ#rs d#e to the cyclic operations&
2.2 Detectors
Detection of a s#bstance is necessary in analytical and preparative
chromatography& 1n general( the same detectors are #sed as in gas and li)#id
chromatography& 2election of a detector depends on the )#antity of
s#bstance available and the chemical nat#re the compo#nd& . $ame
ionization detector (-1D" detects s#bstances down to nanogram )#antities&
,etween two electrodes a voltage of ACC G and a hydrogen $ame are
maintained& 1f a s#bstance with at least one carbon'hydrogen bonding is el#ted
from the col#mn to the detector( it is b#rned and ions are formed( which leads to
a c#rrent between the electrodes& The c#rrent is ampli0ed and processed as a
signal for the concentration of the s#bstance& @early all s#bstances can be
detected& Response factors mainly di*er according to n#mber of carbon atoms(
therefore calibration is easy (,r#nner( 4556"&
" Applications of Gas Chromatography
The #ltraviolet spectroscopy detector (9G" is a nondestr#ctive detector(
which can be applied at col#mn press#re& 1t is widely #sed( b#t is
limited to s#bstances with chromophoric gro#ps& 2at#rated hydrocarbons(
fatty acids and glycerides may be di8c#lt to detect )#antitatively& These
s#bstances may be detected with a refractive increment detector (R1D"( where
the variation of refractive inde% of the mobile phase ca#sed by dissolved
s#bstances is applied for detection& =ther detectors are the $#orescence
detector and the light'scattering detector (,r#nner( 4556"&
1n a light'scattering detector the mobile phase is intensively mi%ed with an
inert gas and heated while $owing downward a t#be (9pnmoor and
,r#nner( 45:5B 9pnmoor and ,r#nner( 455?"& The inert gas and the
temperat#re increase red#ce solvent capacity of the mobile phase& The el#ted
s#bstances precipitate and are carried o#t droplets or particles into the detection
chamber& 1nto this chamber a t#ngsten lamp delivers visible light( which is
dispersed by droplets or particles& The dispersed light is detected by a
photom#ltiplier #nder an angle of >CH& The signal is proportional to the mass
of light'scattering particles& Therefore( the light'scattering detector acts as mass
detector and its signal is independent on chromatographic gro#ps& 1t can be
applied for detection of chromatographic and non' chromatographic
s#bstances in a mi%t#re( as for e%ample( in fatty acids and glycerides
(,r#nner( 4556"&
2. Expansion o! mo"ile phase and sample collecting system
1n analytical 2-!( the mobile phase is either e%panded after or before
detection& Downstream to a detector( which is operated #nder col#mn
press#re( e%pansion can be achieved by normal e%pansion valves& They can
act as bac+ press#re reg#lators may be controlled by a central #nit& .t
interesting alternative to an e%pansion valve was designed by 2aito and
Fama#chi( who #se time'controlled opening and closing of an #nrestricted
t#be for e%pansion& This has the advantage that bloc+ing of the t#be by
precipitating s#bstances is avoided& .nother e%pansion techni)#e was
adapted from !I . glass capillary is formed into long( thin capillary( as so'
called restrictor& <roblems with bloc+ing and diffic#lties with reprod#cible
man#fact#ring of the restrictors are disadvantages of this sol#tion& 1n analytical
2-! e%pansion techni)#es are determined by detection needs& The amo#nt of
s#bstances is small and can easily be handled& The )#antity of the mobile phase
is not small and it m#st be recycled& To avoid bac+mi%ing( the recycled mobile
phase m#st be totally free from any dissolved s#bstances& 1n most cases they
will be in the range of C&4 or even C&C4J (,r#nner( 4556"& Then( separation
methods for the dissolved s#bstances from the mobile phase become important&
-ig#re A shows a chromatographic system proposed by <err#t (45:?( 45:A(
45:6"& .fter el#tion and detection( the mobile phase together with the
dissolved s#bstance is heated and e%panded& ,y these means the solvent
power of the mobile phase is red#ced and the s#bstance precipitatesB it is
collected in one of several collecting vessels( one for each s#bstance& The
s#bstances are removed after s#*icient )#antities of each of the s#bstances
have acc#m#lated after several injections& ,efore the e%panded mobile phase
can be recycled by a cycle p#mp( it is passed thro#gh an adsorbing bed( where
remaining )#antities of the dissolved s#bstances and other #n wanted
s#bstances (as( for e%ample( water" are removed& .s in any solvent cycle( ma+e
#p gas m#st be added( and a small part of the solvent m#st be removed
for disposal or for special cleaning (,r#nner( 4556"&
# Gas Chromatography Application in Supercritical Fluid Extraction Process
1n preparative 2-! so far mostly e%tracts from plants li+e lemon peel oil(
tocopherols from wheat germ or #bichinones have been treated& 9nsat#rated
fatty acids from 0sh oil( mostly processed as esters( is a s#bject investigated
heavily in recent years (Davarnejad et al.( ?CC:"&
-ig& A& -low scheme of a preparative 2-! with recycle of the mobile phase
(<err#t( 45:?(
45:A(
45:6"&
More specialized applications deal with polymers or the fractionation of coal tar&
,erger and
<err#t (45::" have reviewed the applications of
preparative 2-!&
2.# In$ection techni%ues
1njection of the mi%t#re to be separated is accomplished for analytical p#rposes
by sample loops which may be 0lled at ambient press#re and are injected into
the flow of the mobile phase by switching a m#ltiposition valve in the
appropriate position& 2#ch valves can be man#fact#red as linear moving or
rotating valve( as shown in -ig#re 6&
-or preparative separations the feed is p#mped by metering p#mps into the
$ow of the mobile phase& 1ntensive mi%ing can be achieved in line by static
mi%ers& =ther possibilities comprise a col#mn( where the mi%t#re is placed
#nder ambient press#re and is then el#ted by the mobile phase and transported
to the separation col#mn( or a combination with a gas e%traction #nit& The
e%tract of the gas e%traction process can be directly passed thro#gh the
chromatographic col#mn& The separated s#bstances can be collected& The
e%tract from an e%traction #nit is dil#ted with respect to the interesting
compo#nds& 1t can be collected on a col#mn and after some time transported to
the chromatographic separation (,r#nner( 4556"& This operational mode is
$% Applications of Gas Chromatography
ill#strated in -ig#re D&
$$ Gas Chromatography Application in Supercritical Fluid Extraction Process
-ig& 6& M#ltiposition'valves for injection of samples into a 2-! (,r#nner( 4556"&
$2 Applications of Gas Chromatography
-ig& D& !o#pling of 2-E with 2-!& !oncentration of compo#nds in a
collecting col#mn
(Fama#chi and 2aito(
455C"&
.ccording to this type of apparat#s( some e%amples in details have been shown
by ,r#nner
(4556
"&
. General gas chromatography apparatus
The obtained prod#cts from vario#s types of s#percritical apparat#ses
(s#ch as phase e)#ilibri#m and rate test apparat#s" sho#ld be analyzed&
/owever( di*erent types of analyzer can be #sed( b#t the conventional !
with a s#itable col#mn has widely been recommended& .ltho#gh several
col#mns for detecting a lot of components have been designed and
fabricated by some companies( b#t d#e to lac+ing of s#itable col#mns for
some components or #nclear pea+s obtained from some col#mns( an e%tra
process (s#ch as esteri0cation of the fractionated 0sh oil" before ! analyze is
re)#ired& 1n this application( the samples obtained from the s#percritical
e%traction apparat#s are not #nder press#re or their press#res have bro+en
down by a damper (in the online !"&
2ince this type of apparat#s has been e%plained in detail in the other chapters(
therefore an e%ample from its application is ill#strated in this section&
$3 Gas Chromatography Application in Supercritical Fluid Extraction Process
.1 &riacylglycerols analysis
.1.1 Introduction
Most of the fatty acids of palm oil are present as triacylglycerols (T.s"&
The di*erent placements of fatty acids and fatty acid types on the glycerol
molec#le prod#ce a n#mber of di*erent T.s& .bo#t ; to 4C percent of
sat#rated T.s are predominantly tripalmitin (Karles+ind and 7olff( 455>"
and the f#lly #nsat#rated triglycerides constit#te > to 4? percent
(Karles+ind and 7ol*( 455>B Ki$i( 45:4"& The T.s in palm oil are partially
de0ned most as of the physical characteristics of the palm oil s#ch as
the melting point and crystallization behavior (2ambantham#rthi et al.(
?CCC"& Detailed information abo#t Malaysian tenera palm oil T.s have been
given in vario#s references (2ambantham#rthi et al.( ?CCCB Kifli( 45:4B 2ow(
45;5"& -ato#h et al. (?CC;" st#died the s#percritical e%traction of T.s from
b#*alo b#tter oil #sing carbon dio%ide solvent& They concl#ded that increasing
the press#re and temperat#re of the e%traction led to increasing the solvating
power of the s#percritical carbon dio%ide& 1n these st#dies( the T.s were
e%tracted d#ring the early stage of the fractionation thereby creating low'
melting fractions& !onversely( T.s were concentrated in the fractions (i&e&
high'melting fractions" obtained towards the end of the process&
.ccording to the literat#re( mole fraction sol#bility data of p#re triacylglycerols in
!=
?
were reported at temperat#res of 6C( >C and :C H! in the range of 4C
'4C
to
4C
'?
(2oares et al.( ?CC;"& These data depended on the type of triacylglycerols
and operating press#re& That means high press#re had a good e*ect on
sol#bility of triacylglycerols in !=
?
& -#rthermore( tricaprylin had the higher
sol#bility in !=
?
(aro#nd 4C
'?
at high press#res" than the rest (Kensen and
Moller#p( 455;B ,amberger et al.( 45::B 7eber et al.( 4555"&
1n this research( phase e)#ilibri#m of T.s from cr#de palm oil in s#b
and slightly s#percritical !=
?
is st#died& -or this p#rpose( the samples
obtained from the phase e)#ilibri#m s#percritical fl#id e%traction apparat#s
are caref#lly analyzed by a /<3! in terms of T.s&
.1.2 Experiment
A&4&?&4 Materials and
methods
!r#de palm oil and !=
?
(55&55J" respectively as feed and solvent were
p#rchased from 9nited =il <alm 1nd#stries( @ibong Tebal( Malaysia and Mo%
2dn& ,hd& 4(A'dipalmitoyl'?' oleoyl'glycerol (55J" (<=<"( 4(?'dioleoyl'A'
palmitoyl'rac'glycerol (55J" (<==" and 4(?' dioleoyl'A'stearoyl'rac'glycerol
(55J" (2==" as standards were p#rchased from 2igma' .ldrich& .cetone
(55&:J" and acetonitrile (55&55J" as solvent and mobile phase were
obtained from K&T&,a+er and -isher 2cientific( respectively&
The phase e)#ilibri#m s#percritical $#id e%traction apparat#s and calc#lations
proced#re have been shown and e%plained in detail in the references
(Davarnejad( ?C4CB Davarnejad et al.( ?C4CB Davarnejad et al.( ?CC5"&
The operating conditions were set at 4C&:( ;&C( ?&; and 4&; M<a for temperat#re
of :C H!( 44&4(
;&>( >&4 and 4&4 M<a for temperat#re of 4CC H! and ;&6( D&6( A&A and C&> M<a for
temperat#re of 4?C H!&
$4 Applications of Gas Chromatography
-or T.s analysis( the following stages are carried o#t step by step #sing a
/<3! (brandI 2himadz#( KapanB modelI 4C 2eries" which is e)#ipped with a
capillary col#mn (.glient 3ichrosphere R<'4:?DCL6 mn" and oven temperat#re
is also set at DC H!&
4& The standard sol#tions of <==( <=< and 2== with concentrations of 4C( ?D
and DC ppm are prepared by dil#ting these chemicals with acetone
separately& These sol#tions are prepared by dil#ting these chemicals which
are initially prepared at a concentration of
?CC ppm&
?& . mobile phase containing ;DJ acetone and ?DJ acetonitrile (vMv" is
prepared&
A& The chromatography interface( vac##m degasser( p#mp (3!':. p#mp with
ma%im#m $ow rate of 4DC cm
A
Mmin" and refractive inde% (R1"
detector are switched on respectively&
6& The comp#ter( printer and ! are
switched on&
The /<3! diagram obtained from each sample is shown as following and
compared with the diagrams obtained from the standard materials& Then(
by applying the standard e)#ationI
2amples concentration (ppm"Nsample areaMstandard area
L
standard
concentration
2amples concentration in terms of each s#bstance is
calc#lated&
2== <=< <==
-ig& >& /<3! chromatogram of cr#de palm oil T.s for vapor phase at press#re
of D&6 M<a and temperat#re of 4?C H!&
.1. 'esults and discussion
Two'phase e)#ilibri#m data based on different T.s are ill#strated in
Tables 4'A as followingI
$5 Gas Chromatography Application in Supercritical Fluid Extraction Process
Pre""u
re
#MPa$
TN:C
H!
L!%u!d
&ha"e' CO
(
)o*e fra+,!on
-a&or
&ha"e' CO
(
)o*e fra+,!on
4C&: C&5 4
;&C C&5 4
?&; 4 4
4&; 4 4
TN4CC H!
44&4 4 4
;&> 4 4
>&4 4 4
4&4 4 4
TN4?C H!
;&6 C&5 4
D&6 C&5 4
A&A 4 4
C&> 4 4
Table 4& Two'phase e)#ilibri#m calc#lated data based on !=
?
at :C(4CC and
4?C H! in order to <=< analysis
Pre""u
re
#MPa$
TN:C
H!
L!%u!d
&ha"e' CO
(
)o*e fra+,!on
-a&or
&ha"e' CO
(
)o*e fra+,!on
4C&: C&5 4
;&C C&5 4
?&; 4 4
4&; 4 4
TN4CC H!
44&4 4 4
;&> 4 4
>&4 4 4
4&4 4 4
TN4?C H!
;&6 C&5 4
D&6 C&5 4
A&A 4 4
C&> 4 4
Table ?& Two'phase e)#ilibri#m calc#lated data based on !=
?
at :C(4CC and
4?C H! in order to <== analysis
Pre""u
re
#MPa$
TN:C
H!
L!%u!d
&ha"e' CO
(
)o*e fra+,!on
-a&or
&ha"e' CO
(
)o*e fra+,!on
4C&: C&5 4
;&C C&5 4
?&; 4 4
4&; 4 4
TN4CC
H!
44&4 C&5 4
;&> 4 4
>&4 4 4
4&4 4 4
TN4?C
H!
;&6 C&5 4
D&6 C&5 4
A&A 4 4
C&> 4 4
Table A& Two'phase e)#ilibri#m calc#lated data based on !=
?
at :C(4CC and
4?C H! in order to 2== analysis
The mole fractions of !=
?
in the e)#ilibri#m s#percritical e%traction of the <=<
s#bstance for the li)#id and vapor phases are shown in Table 4& The <=<
s#bstance mole fractions in the vapor phase increased with increasing the
press#re at :C H!& This trend was also observed in the li)#id phase& .
reg#lar trend was not observed in the vapor and li)#id phases at 4CC H! and
4?C H!& 1t seems that high temperat#res (s#ch as 4CC H! and 4?C H!" to ca#se
this irreg#larity however( the ma%im#m sol#bility was carried o#t at 4?C H!
which is reasonable beca#se high temperat#re increases T.s sol#bilities in !=
?
(2oares et al.( ?CC;"& The ma%im#m sol#bility of <=< s#bstance in !=
?
was
observed at :C H! and 4C&: M<a( at
4CC H! and ;&> M<a as well as at 4?C H! and D&6 M<a( respectively& The optim#m
conditions
aro#nd these operating regions for the ma%im#m sol#bility of the <=< s#bstance
were at
4?C H! and D&6
M<a&
The mole fractions of !=
?
in the e)#ilibri#m s#percritical e%traction of the <==
s#bstance for the li)#id and vapor phases are shown in Table ?& The <==
s#bstance mole fractions in the vapor phase increased with increasing the
press#re at :C H!& This trend was also observed in the li)#id phase& .
reg#lar trend was not observed in the vapor and li)#id phases at 4CC H! and
4?C H!& 2ince <== is from T.s gro#p( this s#bject is reasonable as it was
legitimized for <=<& The ma%im#m sol#bility of the <== s#bstance was observed
at ;&>
M<a and 4CC H! as well as at D&6 M<a and 4?C H!( respectively& The optim#m
conditions aro#nd these operating regions for the ma%im#m sol#bility of the
<== s#bstance was observed at 4?C H! and D&6 M<a&
The mole fractions of !=
?
in the e)#ilibri#m s#percritical e%traction of the 2==
s#bstance for the li)#id and vapor phases are shown in Table A& The 2==
s#bstance mole fractions in
the vapor phase increased with increasing the press#re at :C H!B this
trend was also observed in the li)#id phase& . reg#lar trend was not
observed in the vapor and li)#id phases at 4CC H! and 4?C H!& 2ince 2== also
is from T.s gro#p( this s#bject is reasonable as it was legitimized for <=< and
<==& The ma%im#m sol#bility of the 2== s#bstance was observed at ;&> M<a
and 4CC H! as well as at D&6 M<a and 4?C H!& The optim#m conditions aro#nd
these operating regions for the ma%im#m sol#bility of the 2== s#bstance
was observed at 4?C H! and D&6 M<a&
The e%perimental res#lts showed that altho#gh highest e%traction #sing !=
?
was observed at 4?C H! and D&6 M<a for all of the T.s s#bstances b#t(
ma%im#m sol#bilities at the mentioned operating conditions were obtained for
<=< (yN4"( <== (yN4" and 2== (yN4" respectively& The obtained res#lt was
con0rmed by the overall concl#sion which stated that the fats and oils
composed of shorter chain fatty acids are more sol#ble than those with
longer chain fatty acids (-ato#h et al.( ?CC;"& 2oares et al. (?CC;" also
ill#strated that high temperat#re had a desired e*ect on T.s sol#bility in
!=
?
as this o#tp#t was obtained from the c#rrent research as well where this
statement s#pported the res#lts above&
Tan et al. (?CC:" also con0rmed that high temperat#re had a positive
e*ect on T.s e%traction #sing !=
?
& They observed that mono#nsat#rated
fatty acids (s#ch as <=<" had a ma%im#m yield of e%traction in s#percritical !=
?
as this o#tp#t was obtained from c#rrent research& That means <=< had a higher
sol#bility in !=
?
in comparison with <== and 2==& .ltho#gh they proposed
high press#res for s#percritical e%traction of T.s b#t they cond#cted their
e%periments at operating press#res more than 4C M<a and they st#died yield
of e%traction&
.1.# Conclusions
1n the m#t#al sol#bility st#dy of T.s from cr#de palm oil which is
related to the e%periment( it was shown that by #sing the s#percritical $#id
e%traction process( the highest mole fraction percentage of T.s sol#bility was
obtained at appro%imately ?&?J (at D&6 M<a and 4?C H!"& .ccording to o#r
calc#lations( the data slightly varied in seventh or eighth decimal points for
the reported data d#e to the chromatography in$#ence& 1n order to the
calc#lations proced#re( the signi0cant part of these calc#lated data
(sol#bility data" is prepared from the press#re increments& -#rthermore( high
temperat#re increased T.s sol#bility in !=
?
&
#. 'e!erences
.l+io( M& /arvala T& Komppa( G& (45::"& <reparative scale
s#percritical $#id chromatography& 1nI <err#t( M& (ed&" Proceedings of

nd
International !ymposium on !upercritical Fluids&
,amberger( T& Eric+son( K&!& !ooney( !&3& K#mar( 2&K& (45::"& Meas#rement
and model prediction of sol#bilities of p#re fatty acids( p#re
triglycerides( and mi%t#res of triglycerides in s#percritical carbon
dio%ide( ". Chemical # Engineering Data( Gol& AA( @o& A( pp& A?;OAAA&
,erger( !& <err#t( M& (45::"& <#ri0cation de molec#les dPinteret
biologi)#e par
chromatogra0e preparative avec el#ant s#percriti)#e( $echnoscope
%iofutur( Gol& ?D( pp& A':&
,r#nner( & (4556"& as E%tractionI an 1ntrod#ction to -#ndamentals of
2#percritical -l#ids and the .pplication to 2eparation <rocesses( 2pringer(
C'A:;'546;;'A( @ew For+&
Davarnejad( R& Kassim( K&M& .hmad( Q& 2ata( 2&.& (?CC5"& 2ol#bility of R'
carotene from cr#de palm oil in high temperat#re and high press#re
carbon dio%ide( ". Chemical # Engineering Data( Gol& D6( @o& :( pp& ??CC'
??C;&
Davarnejad( R& .hmad( Q& 2ata( 2&.& Moraveji( M&K& .hmadloo( -& (?C4C"& M#t#al
sol#bility st#dy in s#percritical fl#id e%traction of tocopherols from cr#de
palm oil #sing !=
?
solvent( International ". &olecular !ciences( Gol& 44(
@o& 4C( pp& A>65'A>D5&
Davarnejad( R& Kassim( K&M&( .hmad( Q& 2ata 2&.& (?CC:"& E%traction of
0sh oil by fractionation thro#gh the s#percritical carbon dio%ide( ".
Chemical # Engineering Data( Gol& DA( @o& 5( pp& ?4?:'?4A?&
Davarnejad( R& (?C4C"& <hase e)#ilibri#m st#dy of R'carotene(
tocopherols and
triacylglycerols in s#percritical $#id e%traction process from cr#de palm
oil #sing
carbon dio%ide as a solvent( <hD& thesis( 9niversiti 2ains Malaysia(
Malaysia& -ato#h( .&E& Mahran( .& El'hando#r( M&.& 2ingh( R&K& (?CC;"&
-ractionation of b#ffalo
b#tter oil by s#percritical carbon dio%ide& '($( Gol& 6C( @o& 4C( pp& 4>:;'
4>5A&
ere( D& ,oard( R& Mc'Manigill( D& (45:?"& <arameters of
2#percritical -l#id
!hromatography 9sing /<3! !ol#mns( /ewlett'<ac+ard( 6A'D5DA'
4>6;(
.vondale( <ennsylvania&
Kensen( !&,& Moller#p( K& (455;"& <hase e)#ilibria of carbon dio%ide and
tricaprylin( ".
!upercritical Fluids( Gol& 4C( @o& ?( pp& :;O5A&
Karles+ind( .& 7olff( K<& (455>"& 1nI vol#me 4I <roperties( <rod#ction and
.pplications( 1ntercept 3imited( .ndover( 9K&
Ki$i( /& (45:4"& 2t#dies on palm oil with special reference to interesteri0cation&
<hD& Thesis( 9niversity of 2t .ndrews( 2cotland&
3ee( M&3& Mar+ides( K&E& (eds" (455C"& .nalytical s#percritical $#id
chromatography and e%traction( Proceedings of Chromatography( <rovo(
9tah&
3eyendec+er( D& 3eyendec+er( D& 2chmitz( -&<& Klesper( E& (45:>"&
!hromatographic behavior of vario#s el#ents and el#ent mi%t#res
in the li)#id and in the s#percritical state& ". Chromatography A( Gol&
A;4( pp& 5A'4C;&
<err#t( M& (45:?"& Demande de brevet francais( @o&
:? C5 >65& <err#t( M& (45:A"& ,revet E#ropean( @o&
CC 55 ;>D&
<err#t( M& (45:6"& 92 <atent( @o& 66 ;: ;?C&
<ic+el( K&/& (45:>"& !hromatogra0sche 9nters#ch#ngen mit /och+ompressiblen
Mobilen
<hasen( Dissertation( 9niversitSt Erlangen'@Trnberg&
2aito( M& Fama#chi( F& /ondo( T& 2enda M& (45::"& 3aboratory scale
preparative s#percritical chromatography in
recycle operationI instr#mentation and
applications& 1nI <err#t( M& (ed&"( Proceedings of
nd
International
!ymposium on !upercritical Fluids&
2aito( M& Fama#chi( F& (45::"& Recycle chromatography with s#percritical carbon
dio%ide as
mobile phase( ". )igh *esolution Chromatography( Gol& 44( @o& 4C( pp& ;64'
;6A&
2aito( M& Fama#chi( F& 1nomata( K& Kott+amp( 7& (45:5"& Enrichment of
tocopherols in
wheat germ by directly co#pled s#percritical $#id e%traction with semi'
preparative s#percritical chromatography( ". Chromatographic !cience(
Gol& ?;( @o& ?( pp& ;5':D&
2aito( M& Fama#chi( F& (455C"& 1solation of tocopherols from wheat germ oil by
recycle semi' preparative s#percritical $#id chromatography( ".
Chromatography A( Gol& DCD( @o&
4( pp& ?D;'?;4&
2choenma+ers( <&K& Gerhoeven( -&!&!&K&& (45:>"& E*ect of press#re on
retention in s#percritical fl#id chromatography with pac+ed col#mns( ".
Chromatography A( Gol&
A?D( pp& A4D'A?:&
2ambantham#rthi( R&( 2#ndram( K Tan( F&.& (?CCC"& !hemistry and
biochemistry of palm oil( Progress in 'ipid *esearch( Gol& A5( @o& >( pp&
DC;'DD:&
2choenma+ers( <&K& 9#n+( 3&& (45:;"& 2#percritical $#id chromatography'recent
and f#t#re developments& European Chromatography +e,s( Gol& 4( @o& A(
pp& 46'??&
2mith( R&M& (ed&" (45::"& 2#percritical -l#id !hromatography( Roy 2oc !hem(
3ondon& 2oares( ,&M&!& amarra( -&M&!& <aviani( 3&!& onUalves( 3&.&&
!abral( -&.& (?CC;"&
2ol#bility of triacylglycerols in s#percritical carbon dio%ide( ".
!upercritical Fluids(
Gol& 6A( @o& 4( pp& ?D'A4&
2ow( /<& (45;5"& Modification in the chemical composition of palm oil by physical(
chemical
and biochemical treatment( <hD& thesis( 9niversiti 2ains Malaysia(
Malaysia&
Tan( T&K& Kinap( 2& K#snadi .&E& .bd#l /amid( @&2& (?CC:"& E%traction of cocoa
b#tter by s#percritical carbon dio%ideI optimization of operating
conditions and e*ect of
particle size( ". Food 'ipids( Gol& 4D( @o& ?( pp& ?>A'?;>&
9pnmoor( D& ,r#nner( & (45:5"& Retention of acidic and basic compo#nds
in pac+ed
col#mn s#percritical $#id chromatography( Chromatographia( Gol& ?:( @o&
5'4C( pp&
665'6D6&
9pnmoor( D& ,r#nner( & (455?"& <ac+ed col#mn s#percritical $#id
chromatography with
light scattering detection& 1& =ptimization of parameters with
a carbon dio%ideMmethanol mobile phase( Chromatographia( Gol& AA( @o&
D'>( pp& ?DD'?>C&
7eber( 7& <et+ov( 2& ,r#nner( & (4555"& Gapor li)#id e)#ilibria and calc#lations
#sing the Redlich'Kwong'.spen'e)#ation of state for tristearin(
tripalmitin( and triolein in !=
?
and propane( Fluid Phase E-uili.ria( Gol&
4D:( pp& >5D';C>&
7enclawia+( ,& (ed&" (455?"& .nalysis with 2#percritical -l#idsI
E%traction and
!hromatography( 2pringer( ,erlin /eidelberg @ew For+ 3ondon <aris
To+yo
/ong Kong ,arcelona ,#dapest&
7hite( !&M& (ed&" (45::"& Modern 2#percritical -l#id !hromatography( /Tthig(
/eidelberg
,asel @ew For+&
Fama#chi( F& 2aito( M& /ondo( T& 2enda( M& Milet( K&3& !astiglioni( E& (45::"&
!o#pled s#percritical fl#id e%traction's#percritical $#id
chromatography #sing pre'
concentrationMseparation col#mnI .pplication to fractionation of lemon
peel oil& 1nI <err#t( M& (ed&" Proceedings of
nd
International !ymposium
on !upercritical Fluids&
Fama#chi( F& 2aito( M& (455C"& -ractionation of lemon'peel oil by semi'
preparative s#percritical $#id chromatography( ". Chromatography A(
Gol& DCD( @o& 4( pp& ?A;'
?6>&
2
Interaction Parameters o! Sur!actant
(ixtures "y In)erse Gas Chromatography
Ele#terio 3#is .rancibia
4
( <ablo !& 2ch#lz
?
and 2#sana M& ,ardavid
4
/
I+0UI+1A 2 C1+ICE$2 FACE$ 3 U+$2 $ucum4n,

I+0UI!U* 3 C1+ICE$ 3F0 3U+! 3 %ahia

%lanca,
Argenti
na
1. Introduction
1nverse as !hromatography (1!" is an acc#rate and versatile techni)#e for
determining a variety of properties of different materials (Goel+el( .& et al&(
?CC5"& 1! has also shown to be an e*ective way to determine thermodynamic
properties in polymer materials( especially to obtain -lory'/#ggins interaction
parameters( which can be #sed to calc#late energy densities interaction
(,
?A
" in polymer'polymer systems& These parameters have been
employed for eval#ating thermodynamic miscibility in polymer mi%t#res
(Deshpande( et al&(
45;6B 3ezcano( et al&(
455D"&
The major diffic#lty in those determinations relies on the dependence of the
parameters obtained on the solvents #sed as probe sol#tes& 1n spite of the fact
that the relations obtained from interaction st#dies thro#gh 1! can be
applied to miscible systems( the st#dies in systems that present partial or
total inmiscibility have been made in several polymer systems (D#( et al&(
4555B Qhi+#an( !& V 7alsh( D&K&( 45:A"&
The relation from which ,
?A
data are obtained describes a ternary system as a
simple balance of the corresponding binary ones& 1t is well +nown their small
contrib#tion to this relation (Et%eberria( et al&( 4556( 455D"& ,esides( the
interaction parameter is several orders of magnit#de smaller than that of
the retention property determined by 1!& .n attempt to red#ce the
#ncertainty in the ,
?A
parameter has led to establish an ade)#ate selection
of probe sol#tes (Et%eberria et al&( ?CCC"& These a#thors have also demonstrated
that the res#lts obtained from 1! as well as from static techni)#e are similar
when !=
?
is #sed as a probe sol#te&
.s indicated by several a#thors( the polymer'polymer interaction parameter
determined by 1! shows a clear dependence on the solvent #sed as a
probe& 1n order to solve this problem( di*erent methods have been
proposed (El'/ibri( et al&( 45::B Et%eberria( et al&(
4556( ?CCCB -aroo)#e( V Deshpande( 455?B /#ang( ?CCAa( ?CCAbB <rolongo( et
al&( 45:5B Qhao(
V !hoi(
?CC4"&
-aroo)#e and DeshpandePs proposed methodology (-aroo)#e( V Deshpande(
455?" has allowed the determination of reliable polymer'polymer interaction
parameters by 1!& /#angPs later proposal (/#ang( ?CCAa( ?CCAb" based on a
methodology similar to the latest
$" Applications of Gas Chromatography
has been applied to several systems and has been compared with the previo#s
methodology #sing retention data in polymer materials (,enabdelghani( et al&(
?CC>"&
1n the case of li)#id crystals( they have been thoro#ghly investigated as
stationary phases by gas li)#id chromatography (3!" from an analytical
point of view (Kanini( et al&( 45;DB Kanini( et al&( 45:CB Martire( et al&( 45>:"&
They have also been #sed in st#dies of sol#tion thermodynamic( by inverse
gas chromatography (1!" of sol#tes in li)#id crystals (!3" and in polymer li)#id
crystals (!3<" at infinite dil#tion (!how V Martire( 45;4B Romanns+y V #illet(
4556B Romanns+y( et al&( 4556B 2hillcoc+ V <rice( ?CC6"&
/#ang et al& (/#ang( et al&( ?CC;" has st#died the sol#tion properties of a series
of organic sol#tes in li)#id crystals #sing 1! thro#gh activity coefficients and
free energy transference of sol#te between mesophases and an isotropic phase&
1n these systems( constant val#es of free energy of transference have been
obtained applying latticePs model of polymer sol#tions (-lory( 45DA" and -loryPs
treatment of li)#id crystals (-lory( 45D>B -lory( 45:6"& The treatment of the data
obtained via 1! in order to get thermodynamic properties #sing -loryPs classic
model has been more fre)#ently applied to mesophases than to -loryPs li)#id
crystal model& 1n the derivation of this model( the e%pression that
corresponds to the non'combinatory contrib#tion has been discarded (.be V
-lory( 45;:B -lory V .be( 45;:"B th#s( the interaction parameter
4(?
between
probe sol#te and stationary phase( that represents the energy e%change of
interactions( has not been incl#ded& This might be one of the reasons beca#se
the interaction parameter is obtained preferably by -loryPs classic model of
polymers&
2ince the probe sol#te is at near in0nite dil#tion( the order of the li)#id crystal
phase is not destroyed by the probe sol#te incl#sion& The accessibility of
the probe molec#les in a mesophase co#ld be limited by its ordering& This
means that the main interaction occ#rs with the hydrocarbon chains of the
bilayers and the interactions are mainly of dispersive character& 7e can
estimate the degree of interaction sol#te O stationary phase by -lory
/#gginsP interaction parameter obtained by 1! #sing s#rfactants as stationary
phase&
The amphiphilic molec#lar str#ct#re of s#rfactants has a signi0cant in$#ence in
the crystals phase str#ct#re& The pac+ing of the s#rfactants is prod#ced so that
the liphophilic gro#ps of the di*erent molec#les are associated with every
lipophilic region& Their hydrophilic gro#ps are e)#ally associated within the polar
region& 1n this way( they form the so called bilayers which are #s#ally formed
in crystals of simple or do#ble hydrocarbon chain s#rfactants& 2ome
s#rfactant crystals do not melt in a li)#id phase directly b#t go thro#gh
anhydro#s li)#id crystal phases (thermotropic li)#id crystals" before reaching the
isotropic li)#id state& The li)#id crystals of anhydro#s s#rfactants are
thermotropic since they res#lt only from the temperat#re increase on anhydro#s
crystals (3a#ghlin( 4556"&
This chapter is part of a series of wor+s done in this laboratory( where several
s#rfactant properties s#ch as sol#bility parameters( s#rfactant's#rfactant
interaction parameters in several systems made #p by cationic s#rfactants of
di*erent hydrocarbon length chain have been determined by 1! (,ardavid( et
al&( ?CCA( ?CC;B <roverbio( ?CCAB 2chaefer( ?CC:"&
The vast majority of the wor+s related to s#rfactant mi%t#res have been
made at low concentration in a)#eo#s sol#tions& The mi%ing of di*erent types
of s#rfactants gives rise to synergies that provide the opport#nity to optimize
$# &nteraction Parameters of Surfactant 'ixtures (y &n)erse Gas Chromatography
prod#ct performance& -or s#rfactant mi%t#res the characteristic phenomena
are the formation of mi%ed monolayers at the
2% Applications of Gas Chromatography
interface and mi%ed micelles in the b#l+ sol#tion& 1n s#ch sol#tions( adsorption
behavio#r( aggregatesP microstr#ct#re( and rheological properties can be
manip#lated to tailor the properties of the di*erent prod#cts&
1n ionic anhydro#s s#rfactant systems( the str#ct#res of li)#id crystals and
crystals are based on the sim#ltaneo#s f#l0llment of two +inds of
interactionsI van der 7aals interactions in the hydrocarbon bilayers and
the electrostatic interactions in the ionic bilayers& 2ometimes( steric
interactions can appear in the hydrocarbon bilayers( and polar interactions or
hydrogen bonds can appear in the ionic bilayers (2ch#lz et al&( 455>"& .
combination of these interactions can be especially disclosed in mi%ed
amphiphiles systems( and their st#dy can lead to a better #nderstanding of their
in$#ence in the formation and stability of the microstr#ct#res mentioned above&
The cationic s#rfactants mi%ed systems are becoming more important and in
the f#t#re additional comple% form#lation a and m#ltiple technological prod#cts
will be re)#ired& The e%tension to a thermodynamic appro%imation of
m#lticomponents incl#ding additional phenomena li+e sol#bility will allow the
establishment of more comple% systems (/olland V R#bingh( 455C"& There is not
m#ch information abo#t st#dies of cationic s#rfactant mi%t#re phases (Garade(
et al&( ?CC:"( or the miscibility of p#re s#rfactant mi%t#res (,ardavid( et al&(
?CC;( ?C4C" that allow resemblance to the behavio#r of s#rfactant mi%t#res
interactions in mi%ed micelles&
1n this chapter we present the res#lts obtained from the st#dy of miscibility
of cationic s#rfactant mi%t#res of three systems made #p by mi%t#res of
s#rfactants of e)#al polar head and di*erent hydrocarbon chains by
determining s#rfactant's#rfactant interaction parameters thro#gh 1!& The
implementation of this techni)#e has also allowed #s to analyze the #se of
two methodologies of meas#rement in order to obtain the parameter ,
?A
for
cationic s#rfactants and to contrast them with the ones obtained in polymeric
materials& 7ith this wor+ we hope to enlarge the information abo#t the
behavio#r of p#re s#rfactant mi%t#res( and analyze the non'ideality degree in
the mi%t#res and its possible ca#ses&
2. Experimental
2.1 (aterials
Dodecylpyridini#m chloride (D<!"( /e%adecylpyridini#m bromide
(!etylpyridini#m bromide (!<,""( Dodecyltrimethylammoni#mbromide
(DT.,"( =ctadecyl trimethylammoni#m bromide (=T.,"(
(.ldrich( analytical grade( 92." Didodecyldimethylammoni#m
bromide (DD.," and Dioctadecyldimethylammoni#m bromide (D=D.,"
(2igma( analytical grade( 92." were #sed as received& .ll probe sol#tes were
chromatographic )#ality or reagent grade and were #sed witho#t f#rther
p#ri0cation&
2.2 Di!!erential Scanning Calorimetry *DSC+
D2! was performed on a <er+in Elmer D2! > calorimeter( between ?5A and
D?A K( with a scanning rate of 4C degree min
W4
and #sing samples of DO4C mg
for p#re s#rfactants and 4CO
4D mg for materials collected over chromatography s#pport& The instr#ment was
calibrated with indi#m&
2$ &nteraction Parameters of Surfactant 'ixtures (y &n)erse Gas Chromatography
2. In)erse Gas Chromatography *IGC+
<#re s#rfactants and their mi%t#res were #sed as stationary phase and
deposited on !hromosorb 7 or ( .7( >CM:C( which was employed as solid
s#pport& The col#mn 0ller was prepared #sing methanol as a solvent in a
rotary evaporator #nder a $ow of dry nitrogen and was +ept in a dry
atmosphere before 0lling the col#mns (stainless steel pipes"& The col#mn was
loaded and conditioned for 4 h at A>A K #nder a $ow of carrier gas& The
amo#nt of stationary phase on the s#pport was determined by calcinations
of abo#t one gram of material& The data employed in the specific retention
vol#me comp#tation were obtained by #sing a col#mn 4CC cm long( 4M6
inch e%ternal diameter( and the pac+ing characteristics are incl#ded in Table 4&
2ystem DD., (?" O D=D., (A"
2tationary phase Mass pac+ing 3oading(wMw" 7eight fraction
(g" (J" (w
?
"
DD., (?" X D=D., (A" ;&?>DA 5&4? C&CCCC
DD., (?" X D=D., (A" ;&>6A? 5&?? C&4>6A
DD., (?" X D=D., (A" ;&:>A6 5&?A C&A?:4
DD., (?" X D=D., (A" ;&C?>: 5&DA C&DCA;
DD., (?" X D=D., (A" ;&C5C> 5&>C C&;A?D
DD., (?" X D=D., (A" ;&::D> 5&44 4&CCCC
2ystem D<! (?" O !<, (A"
2tationary phase Mass pac+ing 3oading(wMw" 7eight fraction
(g" (J" (w
?
"
D<! (?" X !<, (A" 4A&?A4: ;&66 C&CCCC
D<! (?" X !<, (A" 4?&54;D ;&:? C&4D5:
D<! (?" X !<, (A" 4?&5CD> ;&;? C&A6>4
D<! (?" X !<, (A" 4?&>56D ;&6? C&D6C5
D<! (?" X !<, (A" 4?&5?6C ;&A5 C&;D5C
D<! (?" X !<, (A" 4?&D:AD ;&64 4&CCCC
2ystem DT., (?" O =T., (A"
2tationary phase Mass pac+ing 3oading(wMw" 7eight fraction
(g" (J" (w
?
"
DT., (?" X =T., (A" ;&?AC4 4C&C5 C&CCCC
DT., (?" X =T., (A" >&;56; 4C&C6 C&44C?
DT., (?" X =T., (A" ;&6?6C 4C&C? C&A>D?
DT., (?" X =T., (A" ;&A?:4 5&55 C&D5>A
DT., (?" X =T., (A" ;&?A5? 44&>6 C&:AA4
DT., (?" X =T., (A" ;&C;6> 4C&CA 4&CCCC
Table 4& !ol#mn loading data and the weight fraction at the di*erent mi%t#res&
The retention time meas#rement for each sol#te was performed with a /ewlet
<ac+ard( /<
>:5C series( ! 2ystem( e)#ipped with a $ame ionization detector (-1D"& !ol#mn
temperat#re was meas#red in a range between A6A&4 and 6CA&4 K with an 1ron'
!onstantan thermoco#ple
g s
22 Applications of Gas Chromatography
placed in the direct environment of the col#mn& The temperat#re stability d#ring
e%periments was Y C&? K& The employed sol#tes were n'he%ane( n'
heptane( n'octane( n'nonane( cyclohe%ane( methylcyclohe%ane( benzene(
tol#ene( ethyl acetate( dichloromethane( trichloromethane and carbon
tetrachloride& @itrogen was #sed as carrier gas&
-low rates were meas#red at the beginning of each e%periment with an air'
jac+eted soap 0lm $owmeter placed at the o#tlet of the detector& 1nlet
press#res were meas#red with a micrometry syringe (tro#gh the injector
sept#m" which was connected to an open branch merc#ry manometer& To
ens#re that the res#lts were independent of sample size and $ow rate and
those meas#rements were being made at in0nite dil#tion the #s#al chec+s
were made (!onder V Fo#ng( 45;:"& 2ol#tes were injected with 4C Zl /amilton
syringes( as steam in e)#ilibri#m with p#re li)#id& -or all the sol#tes and for all
the range of stationary phase concentrations the pea+s were symmetric& The
injector was +ept at 6?A K and the detector at
6DA
K&
Retention times (t
R
" were meas#red with a !hem 2tation system and the
retention speci0c vol#mes (G
C
g
" were calc#lated with the following relationship
(!onder V Fo#ng( 45;:"I
5
C

6

F
f
_
?;A&4D
_
(
t

t
)

(
p
C
p
,
)
_
(4"
g
,

$
* C
p

,
f
,
C
,
where j is the Kames'Martin compressibility correction factor( p
C
represents the o#tlet col#mn press#re( -
f
is the $ow rate meas#red at
press#re p
C
and temperat#re T
f
( w is the mass of the stationary phase into the
col#mn and p
w
is the water vapo#r press#re at T
f
B t
C
is the dead time( which
was meas#red by #sing the methane pea+ obtained with the -1D&
. Data reduction
2peci0c retention vol#mes were 0tted to the e)#ation (!onder V
Fo#ng( 45;:"I
ln5
C
)
C
M *$ + cons
tan t
(?"
where /
s
is the sorption heat& The val#es obtained for /
s
( as well as their
respective standard deviations( were calc#lated #sing Mar)#artd'3evenbergPs
algorithm (Mar)#artd(
45>A" and can be seen in Table ?& Gal#es of standard deviations in /
s
smaller
than 4&D J are obtained in the regression of specific retention val#es vs& 4MT(
altho#gh most of the val#es were near 4&C J&
The meaning of /
s
depends on the physical state of the stationary phase& -or a
solid( /
s
correspond to the molar adsorption enthalpy& -or the li)#id
mesophase( it was ass#med that the sol#te is dissolved in the stationary phase
so /
s
corresponds to the molar sol#tion enthalpy&
The average per cent error val#es /
s
for DDD., is C&:: %( and C&;6% for
D=D.,& -or the D<,'!<, systems the average error J is C&;5 % for D<! and for
!<, is 4&?C %& -inally( for the mi%ed systems DT.,'=T., the average error in
23 &nteraction Parameters of Surfactant 'ixtures (y &n)erse Gas Chromatography
/
s
val#es is generally bigger than the previo#s ones and from the calc#lated
val#es we get a val#e of 4&A: % for the average error in DT., and of 4&4C % for
the val#es in =T.,&
2ystem DDD.,'
D=D.,
DDD., D=D.,
/
s
t /
s
t Di*erence
n'/e%ane ?:&; C&A AC&; C&A ?&C
n'/eptane AA&6 C&6 A6&: C&6 4&6
n'=ctane A:&> C&? A5&A C&A C&;
,enzene AA&D C&? AA&; C&6 C&?
Tol#ene A;&D C&6 A;&> C&? C&4
!yclohe%ane ?5&: C&6 A4&4 C&? 4&A
Methylcyclohe%ane AA&> C&? AA&> C&? C&C
Dichloromethane AA&? C&A A?&A C&A 'C&5
Trichloromethane 6A&: C&6 6A&6 C&? 'C&6
!arbon tetrachloride AD&D C&? A6&A C&? '4&?
Ethyl acetate AA&A C&A A?&> C&4 'C&;
2ystem D<!'
!<,
D<! !<,
/
s
t /
s
t Difference
n'/e%ane ?5&D C&4 ?;&6 C&D '?&4
n'/eptane AA&> C&? A4&: C&D '4&:
n'=ctane A:&4 C&? AD&5 C&6 '?&?
,enzene A?&5 C&A AC&? C&A '?&;
Tol#ene A;&A C&? AD&4 C&> '?&>
!yclohe%ane ?5&: C&? ?;&? C&6 '?&>
Methylcyclohe%ane A?&? C&A AC&D C&D '4&;
Dichloromethane A4&6 C&6 ?;&4 C&? '6&A
Trichloromethane 6C&6 C&A AD&5 C&A '6&D
!arbon tetrachloride AA&5 C&A A4&6 C&? '?&D
Ethyl acetate A4&> C&6 ?:&> C&A 'A&C
2ystem DT.,'=T.,
DT., =T.,
/
s
t /
s
t Di*erence
n'heptano AD&C C&D AA&4 C&A '4&5
n'=ctano A5&6 C&? A:&6 C&6 '4&C
n'nonano 6A&A C&; 6C&; C&D '?&>
,enceno A:&D C&? AD&? C&6 'A&A
Tol#eno 6?&> C&: A5&C C&D 'A&>
!yclohe%ane AC&5 C&> ?:&; C&A '?&?
Methylcyclohe%ane AA&D C&> A4&A C&6 '?&?
Dichloromethane AA&: C&? AC&: C&A 'A&C
Trichloromethane 6;&? C&: 6A&4 C&6 '6&4
!arbon tetrachloride A6&; C&: A?&D C&6 '?&?
Ethyl acetate AA&> C&A ?5&; C&A 'A&5
Table ?& 2ol#tion heat (+K&mol
'4
" and standard deviations for of the s#rfactant
mi%t#res&
_

C
.ctivity coef0cients at in0nite dil#tion in terms of mole fraction were
obtained by the following e%pression (<rice et al&( ?CC?"I

?;A&4D*
p
C
(
%
5
)
ln
i
ln
5
C
p
C
&
4 44 4
*$
(A"
g 4
?
where M
?
stands for molar mass of s#rfactant( p
4
C
( G
4
stands for vapo#r
press#re and molar vol#me of p#re sol#te& ,
44
is the second virial
coe8cient for sol#teOsol#te interactions&
<atterson (<atterson et al&( 45;4" s#ggested #sing the weight fraction( w( in
which case e)#ation (A" may be replaced by e%pressionI

?;A&4D*
p
C
(
%
5
)
ln
i
ln
5
C
p
C
&
4 44 4
*$
(6"
g 4
4
where M
4
is the molar mass of the sol#te&
The -lory'/#ggins theory of non'athermal sol#tions givesI

4
_ _
ln a
4

(
ln
a
4
)
+
(
ln a
4
)

ln
4
+

+
? (D"
com.& noncom.&

r
,
,
i
where the vol#me fraction( ( is de0ned in terms of the speci0c
vol#mes&
-or the limiting case in which
4
tends to #nity( #sing the e)#ations (6" and
(D"( the probe sol#te's#rfactant -lory'/#ggins interaction parameter(
4i
( can
be calc#lated from the specific retention vol#mes( GH
g
( by the e%pression
(!onder V Fo#ng( 45;:B Deshpande( et al&(
45;6
"I

?;A&4D*v p
(
%
5
)
_
5 _

4i
ln

5
C
p
C
5
i

4 44 4
*$



4

4

5
(>"

g 4 4
,
,
i ,
where v
i
stands for the speci0c vol#me of the s#rfactant e%perimentally
meas#red in the laboratory&
The vapo#r press#res were comp#ted #sing .ntoine e)#ations and the
coe8cients were ta+en from Riddic+( ,#nger and 2a+ano (Riddic+( et al&(
45:>"& The sol#te densities at di*erent temperat#res were estimated from
Dreisbach[s compilation (Dreisbach( 45DD"& The second virial coe8cient of the
sol#tes was calc#lated by Tsonopo#los[s correlation #sing critical constants
tab#lated in Reid et al& (Reid et al&( 45:>"&
7hen the stationary phase is a s#rfactant mi%t#re( E)#ation (;" allows to
determine the ternary probe sol#te (4"'s#rfactant (?"'s#rfactant (A" interaction
parameter(
4(?A"
( ass#ming an additive speci0c vol#me for the s#rfactant
mi%t#re(
m
Nw
?

?
X w
A

A
where w
i
is the weight fraction of s#rfactant i in
the mi%t#re (Deshpande( et al&( 45;6"&

5

?;A&4D*
(

,
?
v
?
+ ,
A
v
A )

_

p
C
(
%
44
5
4 )

_

5 _
5 _
_


ln


4

4
4

4

4

(;"
4( ?A"
5
C
p
C
5


*$

?

5
,

A

5
,

g 4
4
,
,
? A
,
where
i
stands for the vol#me fraction for i component in the stationary
phase& G
i
is the molar vol#me of component i in the mi%t#re&
=n the contrary( ass#ming the 2cott'Tompa appro%imation (Tompa( 45D>"( which
describes a ternary system as a simple balance of the corresponding binary
systems it is possible to calc#late the s#rfactant's#rfactant interaction
parameter(
?A
( byI

5
4
_
(:"
4( ?A" ? 4? A 4A ? A ?A

5
? ,
.s it has been indicated by di*erent a#thors( the polymer'polymer interaction
parameter determined by 1! shows a clear dependence on the solvent #sed
as a probe& 1n order to solve this problem( di*erent methods have been
proposed& The -aroo)#e and Deshpande (-aroo)#e( V Deshpande( 455?" and
the /#ang (/#ang( ?CCAa( ?CCAb" methodologies will be applied to retention
data obtained from the #se of s#rfactant anhidro#s mi%t#res in order to carry
o#t a comparative analysis of the behavio#r of these methodologies in
the determination of s#rfactant's#rfactant interaction parameters&
-aroo)#e and Deshpande (-aroo)#e( V Deshpande( 455?" methodology gives a
reliable tr#e interaction parameter after a rearrangement of E)& (:"I

4( ?A"

4A
1

?
(

4?

4A
)

1

1
]

1

1

?A
1
(5"
5
4
5
4
? A
? ]
. plot of the left side of this e%pression vers#s the 0rst term of the right'hand
side yields a lineal f#nction from whose slope
?
can be calc#lated and from the
intercept
?A
can be
obtained& The physical meaning of the slope was interpreted in terms of an
e*ective average col#mn composition that the sol#tes are probing&
/#ang (/#ang( ?CCAa( ?CCAb"et& al& have proposed an alternative rearrangement
of E)&( :"I

1 1

4( ?A" +

? 4? A 4A
1

?A
(4C"
5
4
5
4
? A 1

5
? ]
. linear plot can be obtained from the left'hand side vs& first term of right'side
of E)&(4C"
allowing that the interaction parameter can be
obtained&
1n both methodologies( if the conditions given by .l'2aigh and M#n+ (.l'2aigh
V M#n+(
45:6" are obeyed( the s#rfactant's#rfactant interaction parameter can be
calc#lated thro#gh the speci0c retention vol#me witho#t calc#lating the
individ#al parameter&
The val#es of the s#rfactant's#rfactant interaction parameters can be analyzed
as
?A
MG
?
or as
?A
when m#ltiplied by G
?
( or as the e)#ivalent )#antity ,
?A
N RT
(
?A
MG
?
" (in K&cm
'A
" called energy density&
#. 'esults and discussion
#.1 Sur!actants as stationary phases
1n this chapter both D2! and 1! were #sed to con0rm the stationary phase
stability with temperat#re& The phase transition temperat#res were
determined with D2! on p#re s#rfactants between ?5A and D?A K& The same
techni)#e was also employed to analyze the thermal behavio#r of both
s#rfactants deposited over the solid s#pport in a 4C J (wMw" percentage(
appro%imately&
!how and Martire (!how V Martire( 45;4" compared 1! and D2! st#dies on
two azo%y li)#id crystals and reported no meas#rable adsorption effects from
the interface above a 0lm thic+ness of 4CC nm& 7it+iewicz (Rayss( K& et al&(
45:C" reported s#rface orientation e*ects #p to depth of ? nm( b#t in a later
wor+ reported constant speci0c retention vol#mes above a stationary phase
loading of above DJ (Marcinia+ V 7it+iewicz( 45:4"& Qho# et al& (Qho#( 4556"
in the ! and 1R st#dy of li)#id crystal deposited on di*erent types of silica
have shown that for a percentage #nder of ; J of the stationary phase loading(
the ln Gg vs
4MT plot did not show discontin#ity& The loading #sed in this wor+ was near of
4C J on
!hromosorb 7 in all the
cases&
The retention diagram of ln Gg vs 4MT for sol#te probes in D=D., and DD.,
coated on !hromosorb 7( @.7( >CM:C( is shown in -ig#re 4 (,ardavid( et
al&( ?CC;"& -or both s#rfactants( speci0c retention vol#mes were obtained
between ACA K and 6?A K& =n heating the crystalline solid( the retention
decreases #ntil the crystalline solid'to'li)#id crystal transition is reached&
Then there is a large increase in retention( which once the system phase
change 0nished( decreases with increasing temperat#re& -or DD., and
D=D., changes in retention are observed at A6A&4 K and AD:&4 K respectively&
-ig& 4& The retention diagram for sol#te probes in DD., (a" and D=D., (b"
coated on
!hromosorb 7& 2ol#tesI (\"( tol#eneB (]"( carbon tetrachlorideB (^"(
n'octane&
D2! meas#rements of the phase transition temperat#re for DD., y D=D.,
have been described in the literat#re (2ch#lz( et al&( 4556( 455:"& The
e%perimental meas#rements for DD., (,ardavid( et al&( ?CC;"( D2! analysis
shows a temperat#re transition between the solid phase and li)#id crystal
mesophase thro#gh two pea+s at AA>&: K and A65&? K& These val#es were
coincident with those obtained in bibliography (2ch#lz( et al&( 4556"& The
0rst pea+
*
e
m
p
e
r
a
t
u
r
e

+
,
-
corresponds to the melting of hydrocarbon tails of DD., and that at A65&? K
corresponds to the melting of the DD., polar heads bilayer giving an
anhydro#s lamellar li)#id crystal which in some circ#mstances (i&e&( when
lamellae are parallel to the slide s#rface" appears as pse#do'isotropic& There is
another phase transition at 66D&5 K that co#ld be the transition to isotropic
li)#id& D2! val#es in the literat#re have been informed #p to 66D&5 K&
D2! analysis for p#re D=D., shows a phase transition at A>4&: K (,ardavid( et
al&( ?CC;"& .ccording to the literat#re (2ch#lz( et al&( 4556" this transition
corresponds to the melting of D=D., crystals to a li)#id which was named a
pse#doisotropic li)#id (2ch#lz( et al&( 455:"& 7e have not detected in o#r
thermogram the hydrocarbon tails transition temperat#re( perhaps beca#se
both transitions (i&e&( the melting of the polar and the apolar layer" occ#r at
almost the same temperat#re giving an overlapping of their pea+sB b#t we have
detected another transition temperat#re at 6A5&A K that we considered as
the transition from mesophase to isotropic li)#id& The transitions for DD., and
D=D., in literat#re (2ch#lz( et al&( 4556( 455:" were st#died #p to smaller
temperat#res than o#rs& DD., and D=D., s#pported on !hromosorb 7
@.7 show a slight displacement toward smaller temperat#res with
respect to p#re s#rfactants& There is previo#s information abo#t
discrepancies in the res#lts when li)#id and s#pported samples are analyzed by
D2!( with lower val#es of transition temperat#re for the last ones (2hillcoc+ V
<rice( ?CCA"&
The systems D<! and !<,( either p#re or mi%ed( are lamellar mesophases at the
wor+ing temperat#re (3a#ghlin( 455C"& The obtained res#lts tro#gh D2! in p#re
s#rfactant samples for the change from crystal phase to li)#id crystal phase is
one pea+ at A6A&4 K and others two pea+s at 6A>&4 K and D4A&4 K for D<!
(,ardavid( et al&( ?C44"&
1n the case of !<, one pea+ is at AA5&6 K and the other two at 6?4&; K and D4:&4
K ( ,ardavid( et al&( ?C44"& 7hen the s#rfactants are deposited on
chromatographic s#pport (!hromosorb ( .7( >CM:C" the val#es obtained
thro#gh D2! f or the phase changes are at
3%
34%
32%
3%%
2"%
%. % % . 2 %. 4 % . %. " $ . %
/ e ig h t f r a c tio n o f 0 P C +
1
2
-
-ig& ?& <hase transition temperat#re for the s#rfactant mi%t#res D<!'!<,
deposited on the solid s#pport as f#nction of the weight fraction of component
? (D<!"&
AA5&4 K for D<! and at AAD&5 K for !<,& 1n -ig#re ? we have incl#ded the
val#es of phase transition temperat#re for the s#rfactant mi%t#res deposited on
the solid s#pport as f#nction of the weight fraction of component ? (D<!"
( ,ardavid( et al&( ?C44"&
7hen the st#died system consists of DT., and =T., either p#re or mi%ed(
deposited on !hromosorb 7( prod#ced lamellar mesophases at wor+
temperat#re (3a#ghlin( 455C"& D2! e%periments showed the phase changes from
crystal to li)#id crystal occ#rring at A;?&D K for DT., and at A;:&4 K for =T.,
(,ardavid( et al&( ?C4C"& 1! meas#rements of the retentive behavior of n'
octane and tol#ene between AA:&4 and 6?A&4 K indicate (in the ln Gg vs& 4MT
plot" retention changes at A>:&4 K for DT., and A;A&4 K for =T.,& The anhydro#s
crystal to lamellar phase transition in p#re dodecyltrimethylammoni#m
chloride (DT.!" occ#rs at abo#t AD>&4 K (,lac+more V Tiddy( 455C"& Ta+ing
into acco#nt the e*ect of changing the co#nterion( the agreement is good&
The D2! techni)#e is very acc#rate in determining the p#re component
properties and the 1! res#lts can be #sed as s#pplement to the D2! res#lts in
the case of s#rfactant deposited on solid s#pport& The val#es of transition
temperat#res obtained by 1! are always lower than those obtained by D2!(
and even more when the very start detection method is #sed to obtain the
transition temperat#re by means of gas chromatography (,enabdelghani( et
al&(
?CC>B @astasovic V =njia( ?CC:B 2hillcoc+ V
<rice( ?CCA"&
.ccording to these res#lts( it is possible to point o#t that both p#re
s#rfactants and their mi%t#res appear as a lamellar mesophase at the wor+ing
temperat#re (A::'6CA K"& Th#s( we can infer that the probe sol#tes dissolve
in a stationary phase formed by an ordered str#ct#re of lamellar
mesophase&
#.2 Interaction parameter in mixtures
The systems st#died( which are made #p by cationic s#rfactants
deposited on !hromosorb 7 or ( being either p#re or mi%ed( appear as
lamellar mesophase at wor+ temperat#re (3a#ghlin( 455C" and their
temperat#res of transition phases have been determined by D2! and 1!&
1n two systems we have #sed !hromosorb 7( >CM:C( with a charge close to 4C
J of stationary phase( and when !hromosorb ( >CM:C was #sed( the
percentage of charge of stationary phase was close to ; J& These val#es are
considered to be ade)#ate for this type of chromatographic s#pport (!onder V
Fo#ng( 45;:B @astasovic
V =njia( ?CC:"& To ens#re that the res#lts were independent of sample size and
$ow rate and since meas#rements were being made at infinite dil#tion( the
#s#al chec+s were made (!onder V Fo#ng( 45;:"&
.s shown by Et%abarren et al& (Et%abarren( et al&( ?CC?"( in polymeric materials
the polymer' probe sol#te interaction parameters depend on the polymer
molec#lar mass in intermediate concentration zones( and this dependence
vanishes at very high concentration as in the case presented in 1!& These
concl#sions have lead #s to analyze the behavio#r in s#rfactant mi%t#res
which present molec#lar mass that are m#ch lower than those of the
polymers with TompaPs appro%imation (Tompa( 45D>" to ternary systems in -lory
/#gginsPs theory&
.s pointed o#t in the introd#ction( the meas#rements made in li)#id state
thro#gh 1! allow the determination of thermodynamic properties (Deshpande(
et al&( 45;6"( especially of interaction parameters that play an important
role in determining the miscibility of
mi%t#res& The behavio#r of s#rfactant mi%t#res has been determined by 1!
allowing the e%perimental determination of s#rfactant's#rfactant interaction
parameters in systems with di*erent characteristics (,ardavid( et al&( ?CC;(
?C4C( ?C44"&
@egative val#es of ,
?A
are indicative of attractive interactions and hence higher
miscibility& =n the contrary( positive val#es of ,
?A
wo#ld indicate rep#lsive
interactions between the two polymers and they are related to immiscibility (.l'
2aigh V M#n+( 45:6B ,enabdelghani( et al&( ?CC>B Deshpande( et al&( 45;6B
Di<aola',aranyi V& Degre( 45:4B Et%eberria et al&( ?CCCB 2hi V 2creiber( 4554"&
-rom a theoretical point of view( this parameter sho#ld be constant with the
concentration& @evertheless( it has fre)#ently been fo#nd that its val#e
changes with concentration (Et%eberria( et al&( 4556"&
Thro#gh 1! (,ardavid( et al&( ?CC;" we have st#died the system DD.,
(didodecyldimethyl ammoni#m bromide" and D=D., (dioctadecyldimethyl
ammoni#m bromide"( which are two twin tailed s#rfactants( the system DT.,
(Dodecyltrimethyl ammoni#m bromide" and =T.,
(=ctadecyltrimethylammoni#m bromide" (,ardavid( et al&( ?C4C" and the system
D<! (Dodecylpyridini#m chloride" and !<, (/e%adecylpyridini#m bromide"
(,ardavid( et al&(
?C44"& The val#es of ,
?A
obtained in the former were positive in all the range of
concentration and at all temperat#res& They were also indicative of high
inmiscibility and they coincided with the behavio#r of these s#rfactant mi%t#res
in a)#eo#s sol#tions (-eitosa( et al&( ?CC>"& This is not s#rprising beca#se the
str#ct#re of anhydro#s lamellar li)#id crystals formed by melting the crystals
m#st f#l0ll the same conditions that lamellar mesophases formed in a)#eo#s
sol#tions( i&e&( polar headgro#ps m#st be in polar layers and the chains in apolar
bilayers&
1n the system DT., and =T., most of the val#es in ,
?A
are negative for
each st#died temperat#re& @egative val#es of ,
?A
s#ggest that the interaction
between s#rfactants is more favo#rable as DT., concentration increases&
There are some precedents in a)#eo#s sol#tions in which these s#rfactants
form mi%ed micelles (.+isada( et al&( ?CC;B 2ch#lz( et al&(
?CC>
"&
1n the system D<! and !<, all the ,
?A
val#es are positive in the range of
concentration and temperat#re st#died& These val#es are lower than the ,
?A
val#es obtained in the DD., and D=D., system& To o#r +nowledge( st#dies of
mi%t#res D<! and !<,( neither p#re nor a)#eo#s sol#tion( have not been
carried o#t&
1n this mi%t#re of s#rfactants deposited on a solid s#pport( an ordering can be
e%pected d#e to the fact that the polar head wo#ld be directed to a solid
s#rface& There is some indication that the pyridini#m head gro#p may interact
specifically with s#rface sites( most li+ely by hydrogen bonding (-#erstena# V
Kia( ?CC6"& Th#s it is e%pected that the rep#lsion between the co#nter ions and
the 'electron clo#d on the pyridini#m ring together with lower charge on
nitrogen atom is responsible for high 'val#e of s#ch s#rfactants ( being the
micelle ionization degree"( higher than their trial+ylammoni#m co#nter'parts
(,hat( et al&( ?CC;"& This wo#ld e%plain the di*erence in the behavio#r in these
systems&
.s #s#al( in polymer mi%t#res increasing the temperat#re the interactions
become wea+erB th#s the val#es of ,
?A
become more positive at
higher temperat#res (,enabdelghani( et al&( ?CC>"& . similar behavio#r can be
observed in the systems with the s#rfactants st#died&
#. Faroo%ue,Deshpande and -uang methodology
-aroo)#e and Deshpande (-aroo)#e( V Deshpande( 455?" and /#angPs
(/#ang( ?CCAa(
?CCAb" methodologies have been shown to be effective and reliable to
determine the interaction parameter
?A
in polymers by 1!( since these
parameters were )#estioned beca#se of their dependence on the probe sol#tes
#sed&
7e have applied the thermodynamic relations determined by 1! for polymer
mi%t#res to anhydro#s s#rfactant mi%t#res and have proved that the res#lts
obtained show a behavio#r that is coherent among the systems st#died&
2imilarly( we have proved that the res#lts are coherent with some res#lts
obtained in a)#eo#s sol#tions of cationic s#rfactants& 1tPs worth noting that the
e)#ations #sed in the meas#rement of ,
?A
wo#ld be only valid for miscible
mi%t#res( altho#gh they have been applied s#ccessf#lly to several
systems that show immiscibility (D#( et al&( 4555B Qhi+#an( V 7alsh(
45:A"& ,enabdelghani et al& (,enabdelghani( et al&( ?CC>" have carried o#t
an analysis of both methodologies in a st#dy of phase behavio#r of
poly(styrene'co'methacrylic acid"Mpoly(?(>'dimethyl'4(6'phenylene o%ide"
thro#gh 1! of polymer mi%t#res&
They have concl#ded that both methods show similar interaction parameter
val#es and that both can be considered as reliable to determine the tr#e polymer
mi%t#re parameters&
The possibility to co#nt with e%perimental data in three binary systems of
anhydro#s s#rfactants( their molar vol#me and to devise a method to classify
miscibility in mi%t#res has led #s to apply both methodologies to s#rfactant
mi%t#res& ,esides( this allows #s to prove if both methods can be #sed in these
types of s#bstances&
1n Table A we have incl#ded the val#es obtained from the intercept( its
errors and the correlation coe8cients with the lineal 0tting of the data applied
to the e)#ations (5 and 4C" #sing both methodologies for the system DD., O
D=D.,& This system presents positive val#es of ,
?A
that indicate the presence
of immiscibility in this mi%t#re&
2everal observations can be made on the obtained val#es& -irst( the interception
val#es in this system (DD., O D=D.,"( are nearly e)#al for both
methodologies& 9sing /#angPs methodology the errors are the do#ble or
larger& The correlation coe8cients of the lineal regression are e%cellent in
/#angPs methodologies in contrast to -aroo)#e y DeshpandePs (-'D"
(-aroo)#e( V Deshpande( 455?" which are good&
These res#lts are similar to those obtained from the comparison between
both methods made by ,enabdeghani et al& (,enabdelghani( et al&( ?CC>" in
the system <oly(styrene'co' methacrylic acid" O <oly(?(>'dimethyl'4(6'
phenylene o%ide"( which have led them to concl#de that both methods are
reliable to calc#late interaction parameter val#es in polymer mi%t#res with
miscible and immiscible regions&
1n Table 6 we have incl#ded the system D<! O !<,( which also presents positive
val#es of ,
?A
that indicate the presence of immiscibility in this mi%t#re(
where the sit#ation is di*erent& 1n general( the intercept val#es are lower
#sing /#angPs method and errors are higher (0ve times or more" than those
determined by -'D method& 2omething pec#liar appears at a minor
percentage of component A (!<,"& .t all temperat#res the obtained intercept
val#es are similar and the errors obtained by /#ang are slightly higher&
A>A&4 K
- ' D
/#ang
w
?
(DDD.," ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4>6A 4:&>6 4&?: C&5;;5 4:&54 A&6C C&5555
C&A?:4 45&5: ?&CD C&55C? 45&>4 ?&D4 C&5555
C&DCA; 4:&A6 6&5C C&5;5> 4;&AC >&4D C&555>
C&;A?D 4;&C> 6&D4 C&55?> 4D&C6 A&>A C&555:
.verage A&4: A&5?
A;A&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4>6A ?4&44 ?&5D C&5?>C ?4&A6 D&4> C&555;
C&A?:4 ?A&D6 A&44 C&5:4? ?A&64 D&4C C&555;
C&DCA; ?4&:4 A&:A C&55CC ?C&D; >&A4 C&555>
C&;A?D ?C&>? 6&>A C&55A4 45&6C >&CD C&555>
.verage A&>A D&>D
A:A&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4>6A ?D&5D 4&:C C&5DA: ?;&4; ;&4> C&555>
C&A?:4 ?;&:> ?&4? C&55C: ?:&AC D&46 C&555:
C&DCA; ?>&6; A&:C C&554? ?D&?; ;&>: C&555D
C&;A?D ?6&6: ;&:4 C&5:C4 ?D&>: 4A&>5 C&55:4
.verage A&:: :&6?
A5A&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4>6A A?&D5 6&A4 C&:D:C AD&CC :&?6 C&555D
C&A?:4 AA&;> A&64 C&5:AD AD&A? D&C5 C&555:
C&DCA; AA&A> 6&?4 C&55C> A6&>C ;&C6 C&555>
C&;A?D AC&5> >&4? C&554C AA&A6 4C&>4 C&555C
.verage 6&D4 ;&;6
6CA&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4>6A 6C&DC A&6: C&:5A> 6?&?: 4?&>6 C&5554
C&A?:4 64&45 D&C5 C&5>:6 6?&6D 4?&4: C&5554
C&DCA; A5&;> >&C5 C&5:6; 6C&66 4A&?6 C&55::
C&;A?D A;&6C ;&;D C&5::> A5&6A 4:&;? C&55;6
.verage D&>C 46&45
Table A& 1ntercepts (ord"( standard deviations ("( and correlation
coef0cients (r
?
" in the system DDD., O D=D.,&
A6:&4 K - ' D /#ang
w
?
(D<!" ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4D5: 5&64 A&6> C&5:6> 6&56 44&6D C&555C
C&A6>4 :&6: A&:6 C&5566 A&4; 44&6> C&555C
C&D6C5 :&>> 6&:D C&55D: A&D6 4C&4? C&555C
C&;D5C 4?&C; A&:4 C&55:6 4C&46 6&6C C&5555
.verage 6&C: 4C&;>
AD:&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4D5: 4D&AC D&A5 C&5DD; 4?&A6 4D&A5 C&55:?
C&A6>4 46&:C A&>C C&55DC :&;> 4?&A: C&55:5
C&D6C5 4A&A> A&:? C&55;D ;&46 44&6? C&5554
C&;D5C 4;&;6 A&DC C&55:> 4>&DC A&:; C&5555
.verage 6&C: 4C&;>
A>:&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4D5: 4:&?: A&54 C&5:6> 4C&D> ?A&A5 C&55>6
C&A6>4 4:&D4 ?&55 C&55D? 4C&?A 4;&:6 C&55;5
C&D6C5 4>&>; A&:6 C&55;> ;&A5 4>&A; C&55:?
C&;D5C ?4&5A ?&:> C&5554 45&D; A&C; C&5555
.verage A&6C 4D&4;
- ' D /#ang
A;:&4 K ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&4D5: ?C&DC ;&D4 C&5>;> ;&AA 6;&?5 C&5:;6
C&A6>4 ?4&6? 6&:4 C&556? ;&DA AD&5> C&55?D
C&D6C5 4:&5C 6&;: C&55;6 ?&>D A?&6: C&55A5
C&;D5C ?A&:D 4&:4 C&555; 4;&DA :&?; C&555D
.verage 6&;A A4&CC
Table 6& 1ntercepts (ord"( standard deviations ("( and correlation
coef0cients (r
?
" in the system D<!O !<,&
1n /#angPs method the correlation coe*icients for all percentages and at all
temperat#res are greater than C&555 and in the method - O D the val#e of these
coe8cients is between C&5D and C&555&
1n Table D( the val#es obtained from the intercept( their error and correlation
coefficients from the lineal 0tting of the data for the system DT., O =T., are
incl#ded& This system presents a partial miscibility in accordance with the
val#es of ,
?A
obtained by - O D( the intercept val#es determined by both
methodologies present major di*erences between the systems st#diedB all the
val#es determined by - ' D are negative e%cept for the 0rst val#es at the last two
temperat#res&
A::&4 K - ' D /#ang
w
?
(DT.," ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&44C? '>&A4 6A&D4 C&5;>A 4?&6D :4&?A C&5D6:
C&A>D? '4A&D? 6A&?; C&556C C&6D :C&:: C&5D>6
C&D5>A '4D&?C 64&C; C&5;6D '?&:4 ;6&?A C&5>A?
C&:AA4 '4A&:5 6D&4D C&5D?A '4&;? :C&?? C&5D>>
.verage 6A&?D ;5&46
A5A&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&44C? '4&?C A5&;C C&5;A4 4:&:6 :C&;6 C&5D6:
C&A>D? '5&>? A5&;6 C&556: D&;5 ;5&6? C&5D;D
C&D5>A '44&A4 64&4A C&5;A? ?&>> :?&CD C&5D65
C&:AA4 '5&5: 64&:? C&5>A? A&A4 :4&C6 C&5DD:
.verage 6C&>C :C&:4
A5:&4 K - ' D /#ang
w
?
ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&44C? ?&66 A>&5> C&5;4> ??&5; :4&>6 C&5DA>
C&A>D? 'D&;; A>&D6 C&5;DC 4C&DA ;5&D: C&5D;A
C&D5>A ';&:; A:&4C C&5;CD ;&D: :?&A: C&5D66
C&:AA4 'D&5; A:&D6 C&5A>6 :&44 :?&;4 C&5D6D
.verage A;&DA :4&D:
- ' D
/#ang
6CA&4 K ord&4C
6
t&4C
D
r _ ord&4C
6
t&4C
D
r _
C&44C? D&:5 AA&5> C&5>;6 ?>&DA :?&C? C&5DA6
C&A>D? 'A&?D A6&;5 C&554A 46&?5 :?&;; C&5DA:
C&D5>A 'D&?: AD&56 C&5646 4C&:5 :>&?C C&5DC>
C&:AA4 'A&CD A;&C; C&5D;5 4?&4? ::&?> C&56:;
.verage AD&66 :6&:4
Table D& 1ntercepts (ord"( standard deviations ("( and correlation
coef0cients (r
?
" in the system DT.,'=T.,&
1n /#angPs methodology( the only negative intercept val#es correspond to those
of the last two weight fractions at the 0rst temperat#re( b#t in this
methodology the val#es show incoherence at the di*erent temperat#res& The
highest errors appear in /#angPs method (close to the do#ble" and the
correlation coefficients are good and similar in both methodologies (C&56
'C&55 in -'D and C&56'C&5> in /#ang"&
1n all systems we can point o#t that the major errors correspond to /#angPs
methodology( with a good correlation of the lineal regression in this method&
This behavio#r is similar to that obtained by ,enabdelghani et al&
(,enabdelghani( et al&( ?CC>" in polymers( and as
pointed o#t by these a#thors( this co#ld be d#e to the fact that the e%perimental
points fitted in /#angPs method are far from the intercept and its
determination is s#bject to a major error& The enlargement of the val#es
that correspond to the intercept in /#angPs methodology leads to the
d#plication of errors and to res#lts that are less n#merically stable in relation to
-'D methodology&
1t is worth mentioning that besides the intrinsic errors of the chromatographic
method in the determination of the parameter
?A
MG
?
(obtained from a delicate
balance between a ternary system (
4(?(A"
" and two binary systems (
4?
and

4A
""( there wo#ld be e%perimental errors of the method as pointed o#t by
Et%eberria et al& (Et%eberria et al&( ?CCC"& =ne way of red#cing the #ncertainty in
the val#es of ,
?A
is an ade)#ate selection of probe solvents& 1n this way( we
have tried to cover all the possible chemical str#ct#res and polarities( avoiding
the tests with similar retention among the retentive possibilities in this type of
s#rfactant& 7e have incl#ded hydrocarbons in the probe sol#tes altho#gh they
are not recommended for the e%perimental determination of polymer
interaction parameters (Et%eberria et al&( ?CCC"&
1n Table ?( we have incl#ded val#es of sol#tion enthalpies obtained of the
retention time data vs& 4MT( their errors at a level of reliability of 5D J and
the di*erences between the val#es of sol#tion enthalpies for each of the
systems st#died& 1n general terms we can point o#t that the system DD., O
D=D., presents the slightest di*erences between /H
s
( and the minor error
among the systems st#died& ,esides( both stationary phases wo#ld show a
major apolar character d#e to the major density of hydrocarbon chain& The
other two systems present similar val#es of sol#tion heat and the highest val#es
in the component with a minor hydrocarbon chain&
7e have calc#lated the average errors in the sol#tion heat of the systems
st#died( which are also incl#ded in Table ?& Th#s( we can observe that the
system DD., O D=D., presents a minor average error in the sol#tion heat of
C&:4 J( the system D<! O !<, is intermediate with an average val#e of 4&C4 J
and the third system DT., O =T., presents a major val#e of 4&?4 J& The third
system presents the lower val#es of G
C
g
among the systems we st#died and the
major e%perimental errors in this retention parameter& The percentage val#es of
the errors in the system DT., O =T., are very di*erent from those
calc#lated in the other systems following the method - O D( and there is a large
di*erence in the errors obtained from a retention time correlation as a f#nction of
4MT&
7e have observed that in the res#lts determined in the three systems by
/#angPs methodology (/#ang( ?CCAa( ?CCAb" the val#e of the slope shows that
when the withdrawal from the #nit is greater( the di*erence between the
intercept val#es is bigger in both methodologies&
1n Table > we have incl#ded the val#es obtained from the di*erences between
the intercept val#es determined by both methods in the systems st#died and
the slope calc#lated by /#angPs methodology for the 0rst val#es of
temperat#re&
.s it can be seen in Table >( the highest val#es of the differences between
intercept val#es are visible when the deviation of the slope from the #nit is
major& 7e have plotted the val#es of the di*erences between the ordinate
val#es in the method -'D (-aroo)#e( V Deshpande( 455?" and in /#angPs
methodology (/#ang( ?CCAa( ?CCAb" as a f#nction of the
slope determined by /#angPs method& -ig#re A shows that in the systems
DD.,'D=D., and D<!'!<,( the dots rest on a straight line( with a major
concentration of the val#es closeness to the #nitary slope val#e& 7hen the
slope val#es are higher( the di*erences between both methods are greater&
DD.,OD=D.,
system
A>A&4 K =rd&4C
6
w
?
-'D /#ang Di*erence /#ang slope
C&4>6A 4:&>
6
4:&5
4
'
C&?;
4&CC
C
C&A?:4 45&5
:
45&>
4
C&A
;
4&CC
>
C&DCA; 4:&A
6
4;&A
C
4&C
6
4&C4
A
C&;A?D 4;&C
>
4D&C
6
?&C
?
4&C?
A
D<!'!<,
system
A6:&4 K =rd&4C
6
w
?
-'D /#ang Di*erence /#ang slope
C&4D5: 5&6
4
6&5
6
6&6
;
4&CA
;
C&A6>4 :&6
:
A&4
;
D&A
4
4&C6
D
C&D6C5 :&>
>
A&D
6
D&4
?
4&C6
6
C&;D5C 4?&C
;
4C&4
6
4&5
A
4&C4
:
DT.,'=T.,
system
A::&4 K =rd&4C
6
w
?
-'D /#ang Di*erence /#ang slope
C&44C? '
6&A4
4?&6
D
'
4>&;>
C&:5C
:
C&A>D? '
A&D?
C&6
D
'
4A&5;
C&:5C
A
C&D5>A '4D&?C '
?&:4
'
4?&A5
C&:;5
D
C&:AA4 '4A&:5 '
4&;?
'
4?&4;
C&:D>
A
Table >& Differences of the val#es between the intercept val#es
determinate by both methodologies and the slope calc#lated by /#angPs
methodology&
The dots corresponding to the system DT.,'=T.,( are in a part of the graph
opposite to the val#es fo#nd in the other two systems& 1n this system( it can
be observed the higher di*erences between the ordinate val#es( the major
errors in both methodologiesB the errors in /#angPs method are twice as big as
those fo#nd in -'D( the correlation coe8cients are similar and the slopes in
/#angPs method are minor than the #nit&
1n general terms( we can point o#t that the -'D method is n#merically more
stable than /#angPs methodology in these systems& This wo#ld be d#e to the
algebraic treatment of the depart#re e%pression& The higher val#es of the
correlation coe*icient in the regression are the res#lt from the scale e%pansion
in /#angPs methodology&
.s a concl#sion( in these systems the res#lts of the comparison between the
methodologies are in agreement with what ,enabdelghani et al&
(,enabdelghani( et al&( ?CC>" said& 7e also fo#nd that when the val#e of
withdrawal of the slope from the #nit in /#angPs method is higher( the val#es
are less reliable and there are higher errors than in the method of -'D&
-ig& A& Di*erences between the ordinate val#es in the method -'D and
in /#angPs methodology as a f#nction of the slope determined by
/#angPs method&
.. Conclusions
The st#died systems were different mi%t#res of anhydro#s cationic s#rfactants(
deposited on solid s#pport( that has been #sed as stationary phases in 1! and
the res#lts were analyzed in term of mi%t#res miscibility&
The determination of the thermodynamic miscibility was realized by the
val#es of s#rfactant's#rfactant interaction parameters obtained by the
same method #sed in polymeric materials&
The comparative #se of two phenomenological methodologies allowed #s to
calc#late the s#rfactant's#rfactant interaction parameter in anhydro#s cationic
s#rfactant mi%t#resB the obtained res#lts were similar to those obtained by
,enabdelghaie et al& (,enabdelghani( et al&( ?CC>" in polymeric materials&
7e also fo#nd that when the val#e of withdrawal of the slope from the #nit in
/#angPs method is higher( the val#es are less reliable and there are major
errors than in the method of -'D&
/. Ac0no1ledgments
This wor+ was sponsored by !19@T (!onsejo de 1nvestigaciones de la
9niversidad @acional de T#c#m`n" and partially by 9@2& E&3&.& is a member
of !=@1!ET (!onsejo @acional de 1nvestigaciones !ienta0cas y Tbcnicas de la
Rep#blica .rgentina"&
2. 'e!erences
.be( .& V -lory( <&K&( (45;:"& 2tatistical thermodynamics of mi%t#res of rodli+e
particles& ?&
Ternary systems& &acromolecules( 44( 44??'44?>
.l'2aigh( Q& F&( V M#n+( <&( (45:6"& 2t#dy of polymer'polymer interaction
coe8cients in polymer blends #sing 1nverse as !hromatography&
&acromolecules( 4;( :CA'
:C5
.+isada( /& ( K#wahara( K&( Koga( .&( Motoyama( /& V Kaneda( /&( (?CC;"& 9n#s#al
behavior of !M! for binary mi%t#res of al+yltrimethylammoni#m
bromidesI Dependence on chain length di*erence& ". Colloid Interface
!ci.( A4D( >;:'>:6
,ardavid( 2& M&( 2ch#lz( <& !& V .rancibia( E& 3&( (?CCA"& 2ol#bility parameter
determination of cationic s#rfactant by 1nverse !& Chromatographia( D;(
D?5'DA?
,ardavid( 2& M&( 2ch#lz( <& !& V .rancibia( E& 3&( (?CC;"& 1! st#dies of
binary cationic
s#rfactant mi%t#res& ". Colloids Interface !ci.( A4>( 446'44;
,ardavid( 2& M&( 2ch#lz( <& !& V .rancibia( E& 3&( (?C4C"& Miscibility of anhydro#s
cationic s#rfactant mi%t#res& ". &ol. 'i-uids( 4D>( 4>D'4;C
,ardavid( 2&M&( 2ch#lz( <&!& V .rancibia( E&3&( (?C44"& 1nteraction parameter of
anhydro#s cationic s#rfactant mi%t#res by 1!& .cepted in the ". !olution
Chemistry (?C44"
,enabdelghani( Q&( Et%eberria( .&( Djado#n( 2&( 9r#in( K& K& V 9riarte( !&( (?CC>"&
The phase behavio#r of poly(styrene'co'methacrylic acid"Mpoly(?(>'
dimethyl'4(6'phenylene o%ide" by 1nverse as !hromatography& ".
Chromatog. A( 44?;( ?A;'?6D
,hat( M& .&( Dar( .& .&( .min( .&( Rashid( <& 1& V Rather( & M&( (?CC;"&
Temperat#re dependence of transport and e)#ilibri#m properties of
al+ylpyridini#m s#rfactants in a)#eo#s sol#tions& ". Chem. $hermodyn.(
A5( 4DCCO4DC;
,lac+more( E& 2& V Tiddy( & K& T& ( (455C"& =ptical microscopy( m#ltin#clear
@MR (
?
/(
46
@ and
AD
!l" and c'ray st#dies of dodecyl'and
he%adecyl'trimethylammoni#m chlorideMwater mesophases& 'i-uid
Crystals( :( 4A4'4D4
!how( 3& !& V Martire( D& E&( (45;4"& Thermodynamics of sol#tions with
li)#id crystal solvents& 111& Molec#lar interpretation of sol#bility in
nematogenic solvents& ". Phys. Chem&( ;D( ?CCD'?C4D
!onder( K& R& V Fo#ng( !& 3&( (45;:" Physicochemical &easurement .y 7as
Chromatography(
7iley( @ew For+
Deshpande( D& D&( <atterson( D&( 2creiber( /& <& V 2#( !& 2&( (45;6"&
Thermodynamic interactions in polymer
2ystems by as'3i)#id'!hromatography& 1G&
1nteractions between components in a mi%ed stationary phase&
&acromolecules(
;( DAC'
DAD&
Di<aola',aranyi( & V Degre( <&( (45:4"& Thermodynamic characterization of
polystyrene' poly(b#tyl methacrylate" blends& &acromolecules( 46( 46D>'
46>C&
Dreisbach( R& R&( (45DD" Advances Chemistry !eries( p#blishing by .&!&2& D#( d&(
!hen( 7& V M#n+ <&( (4555"& 1nverse as !hromatography& :& .pparent
probe dependence of

?A
P for a poly(vinil chloride"'poly(tetramethylene glycol" blend&
&acromolecules( A?(
4D46'
4D4:
El'/ibri( M& K&( !heng( 7&( V M#n+( <&( (45::"& 1nverse as
chromatography& >&
Thermodynamics of poly('caprolactone"'polyepichlorohydrin
blends&
&acromolecules( ?4(
A6D:'A6>A
Et%abarren( !&( 1riarte( M&( 9riarte( !&( Et%eberria( .& V 1r#in( K& K&( (?CC?"&
<olymer'solvent interaction parameters in polymer sol#tions at high
polymer concentrations& ". Chromatogr. A( 5>5( ?6D'?D6
Et%eberria( .&( 9riarte( !&( -ernandez',erridi( M&K& V 9r#in( K&K&( (4556"& <robing
polymer'
polymer interaction parameters in miscible blends by 1nverse
as
!hromatographyI 2olvent effects& &acromolecules( ?;(
4?6D'4?6:
Et%eberria( .&( 1riarte( M&( 9riarte( !&( V 1r#in( K& K&( (455D"& 3attice -l#id Theory and
1nverse as !hromatography in the analysis of polymer'
polymer interactions& &acromolecules( ?:( ;4::';45D
Et%eberria( .&( Et%abarren( !& V 1r#in( K& K&( (?CCC"& !omparison between static
(sorption" and dynamic (1!" methods in the determination of
interaction parameters in polymerMpolymer blends& &acromolecules(
AA( 544D'54?4
-aroo)#e( .& M& V Deshpande( D& D&( (455?"& 2t#dies of polystyrene'
polyb#tadiene blend system by inverse gas chromatography& Polymer(
AA( DCCD'DC4:&
-eitosa( E&( .lves( -& R&( @iemiec( .&( Real =liveira( M& E&!& D&( !astanheira( E&
M& 2& V
,aptista( .& 3& -&( (?CC>"& !ationic liposomes in
mi%ed didodecyldimethylammoni#m bromide and
dioctadecyldimethylammoni#m bromide a)#eo#s dispersions
st#died by Di*erential 2canning !alorimetry( @ile Red -l#orescence(
and T#rbidity& 'angmuir( ??( AD;5'AD:D
-lory( <& K&( (45DA" <rinciples of Polymer Chemistry( !ornell 9niversity <ress( 1thaca
(@F"
-lory( <& K&( (45D>"& 2tatistical thermodynamics of semi'$e%ible chain molec#les&
<roc& R& 2oc&( 3ond& .( ?A6( >C';A
-lory( <& K& V .be( .&( (45;:"& 2tatistical thermodynamics of mi%t#res of rodli+e
particles& 4&
Theory for polydisperse systems& &acromolecules( 44(
4445'44??
-lory( <& K&( (45:6"& Molec#lar theory of li)#id crystals& 'i-uid Crystal Polymers I.
Advances in
Polymer !cience, D5(
4'A>
-#erstena#( D& 7& V Kia( R&( (?CC6"& The adsorption of al+ylpyridini#m chlorides
and their e*ect on the interfacial behavior of )#artz& Colloids and
!urfaces A8 Physicochem. Eng. Aspects( ?DC( ??AO?A4
/olland( <& M& V R#bingh( D& @&( (455C" 1n Cationic !urfactantsB /olland( <& M& V
R#bingh( D&
@& ( Eds&B 2#rfactant 2cience 2eriesB Marcel De++er( @ew
For+( 5ol. A;
/#ang( K& !&( (?CCAa"& .nalysis of the thermodynamic compatibility of poly(vinyl
chloride"
and nitrile r#bbers from 1nverse as !hromatography& ". Appl. Polym. !ci.(
:5( 4?6?'
4?65
/#ang( K& !&( (?CCAb"& Determination of polymer'polymer interaction
parameters #sing
1nverse as !hromatography& ". Appl. Polym. !ci.( 5C( >;4'>:C
/#ang( K& !&( !oca( K& V 3anger( 2& /&( (?CC;"& 3i)#id crystal sol#tions at in0nite
dil#tionI 2ol#te phase transfer free energy and sol#bility parameter
variations at phase conversion temperat#res. Fluid Phase E-uili..( ?DA(
6?'6;
Kanini( & M&( Kohnston( K& V Qielins+i( 7& 3& Kr&( ( 45;D"& 9se of a nematic li)#id
crystal for
gas' li)#id chromatographic separation of polyaromatic hydrocarbons&
Anal. Chem.(
6;( >;C' >;6
Kanini( & M&( Manning( 7& ,&( Qielins+i( 7& 3& Kr&V M#schi+( M&( (45:C"&
as'li)#id chromatographic separation of bile acids and steroids on a
nematic li)#id crystal& ". Chromatogr.( 45A( 666'6DC
3a#ghlin( R& &( (455C"& Cationic !urfactants( <hysical !hemistry( Ed&
R#bingh( D& @& V /olland( <& M&( Marcel De++er( @ew For+
3a#ghlin( R&( (4556"& $he a-ueous phase .ehaviour of surfactants( .cademic
<ress 1nc&( 2an
Diego( !.
3ezcano( E& &( <rolongo( M& & V 2alom !oil( !&( (455D"& !haracterization of the
interactions in the poly(6'hydro%ystyrene"Mpoly(s'caprolactone"
system by 1nverse as !hromatography& Polymer( A>( D>D'D;A
Marcinia+( 7& V 7it+iewicz( Q&( (45:4"& E*ect of the amo#nt of li)#id crystal and
type of s#pport on some properties of the li)#id crystalline
stationary phase's#pport system& ". Chromatogr. ( ?C;( AAA'A6A
Mar)#artd( D& 7&( (45>A"& .n .lgorithm for 3east'2)#ares Estimation of
@onlinear
<arameters& !IA& "ournal on Applied &athematics 44 (?" 6A4O664
Martire( D& E&( ,lasco( <& .&( !arone( <& E&( !how( 3& !&V Gicini( /&( (45>:"&
Thermodynamics of sol#tions with li)#id'crystal solvents& 1& . as'3i)#id
!hromatographic st#dy of cholesteryl myristate& ". Phys. Chem.( ;?(
A6:5'A65D
@astasovic( .& ,& V =njia( .& E&( (?CC:"& Determination of glass temperat#re of
polymers by
1nverse as !hromatography& ". Chromatog. A( 445D( 4'4D
<atterson( D&( Tewari( F&,& ( 2chreiber( /&,& V #illet( K&E&( (45;4"& .pplication of
as'3i)#id
!hromatography to the thermodynamics of <olymer 2ol#tions&
&acromolecules ( 6(
AD>'AD5
<rice( & K&( /ic+ling( 2& K& V 2hillcoc+( 1& M&( (?CC?"& .pplications of
1nverse gas !hromatography in the st#dy of li)#id crystalline stationary
phases& ". Chormatogr. A( 5>5( 45A'?CD
<rolongo( M& &( Masegosa( R& M& V /orta( .&( (45:5"& <olymer'polymer
interaction
parameter in the presence of a solvent& &acromolecules( ?? 6A6>'6AD4
<roverbio( Q& E&( ,ardavid( 2& M&( .rancibia( E& 3& V 2ch#lz( <& !&( (?CCA"&
/ydrophile' lipophile balance and sol#bility parameter of cationic
s#rfactants& Colloids and !urf. A, Physicochem. Eng. Aspects( ?46( 4>;'
4;4
Rayss( K&( 7it+iewicz( Q& ( 7a+sm#ndz+i( .& V Dabrows+i( R&( (45:C"& Effect of the
s#pport s#rface on the str#ct#re of the 0lm of li)#id crystalline
stationary phase& ". Chromatgr. A., 4::( 4C;'44A
Reid( R& !&( <ra#snitz( K& M& V <oling( ,& E&( (45:>"& $he properties of 7ases and
'i-uids( 6
th
Ed&( Mcraw'/ill( @ew For+
Riddic+( .& R&( ,#nger( 7& ,& V 2a+ano( T& K&( (45:>"& 1rganic !olvents&
Techni)#es of
!hemistry( 6
th
Ed&( 7iley'1nterscience( @ew For+
Romanns+y( M& V #illet( K& E&( ( 4556"& The #se of 1nverse as
!hromatography to st#dy li)#id crystalline polymers& Polymer( AD( D:6'
D:5
Romanns+y( M& ( 2mith( <& -&( #illet( K& E& V ri8n( .& !&( (4556"& 2olvent
interactions with an insol#ble li)#id'crystalline polyester&
&acromolecules( ?;( >?5;'>ACC
2chaefer( !& R& de( R#iz /olgado( M& E& -& de V .rancibia( E& 3&( (?CC:"& E*ective
sol#bility parameters of s#crose monoester s#rfactants
obtained by 1nverse as !hromatography& Fluid Phase E-uili..( ?;?(
DA'D5
2hi( Q& /& V 2creiber( /& <&( (4554"& =n the application of 1nverse as
!hromatography to interactions in mi%ed stationary phases&
&acromolecules( ?6( AD??'AD?;
2hillcoc+( 3& M& V <rice( & K& ( (?CCA"& 1nverse as !hromatography st#dy of
poly(dimethyl
silo%ane"'li)#id crystal mi%t#res& Polymer( 66( 4C?;'4CA6
2hillcoc+( 3& M& V <rice( & K& ( (?CC6"& 1nteractions of solvents with low molar
mass and side chain polymer 3i)#id !rystals meas#red by 1nverse as
!hromatography& ". Phys. Chem. %( 4C:( 4>6CD' 4>646
2ch#lz( <& !& ( <#ig( K& E& ( ,arreiro( & V Torres( 3& .& ( 4556" & Thermal
transitions in s#rfactant' based lyotropic li)#id crystals& $hermochimica
Acta ?A4( ?A5'?D>
2ch#lz( <&!&( .brameto( M&( <#ig( K&E&( 2oltero'Martanez( -&.& V onz`lez'.lvarez( .&(
(455>"&
<hase ,ehavior of the 2ystems n'Decanephosphonic .cid '
7ater and n' Dodecanephosphonic .cid' 7ater& 'angmuir, 4?( AC:?'
AC::
2ch#lz( <& !& ( Rodrig#ez( K& 3&( 2oltero'Martinez( .& <#ig( K& E& V <roverbio( Q&
E&( (455:"&
<hase behavio#r of the dioctadecyldimethylammoni#m bromide'water
system& ". $hermal Anal.( D4( 65'>?
2ch#lz( <& !&( Rodrag#ez( K& 3&( Minardi( R& M&( 2ierra( M& ,& V Morini( M& .&(
(?CC>"& .re the mi%t#res of homologo#s s#rfactants ideale ". Colloid #
Interface !ci.( ACA( ?>6'
?;4
Tompa( /&( (45D>"& Polymer !olutions( ,#tterworths( 3ondon Garade( D&(
.rama+i( K& V 2t#benra#ch( !&( (?CC:"& <hase diagrams of waterO
al+yltrimethylammoni#m bromide systems& Colloids !urf. A8
Physicochem. Eng. Aspects( A4D( ?CD'?C5
Goel+el( .&( 2trzemiec+a( ,&( .dams+a( K& V Milczews+a( K&( (?CC5"&
1nverse as
!hromatography as a so#rce of physicochemical data& ". Chromatogr. A(
4?4>( 4DD4'
4D>>
Qhao( 3& V !hoi( <&( (?CC4"& Determination of solvent'independent
polymer'polymer interaction parameter by an improved 1nverse as
!hromatographic approach& Polymer( 6?( 4C;D'4C:4
Qhi+#an( !& V 7alsh( D& K&( (45:A"& 1nverse as !hromatography for the st#dy of
one phase
and two phase polymer mi%t#res& Eur. Polym. ".( 45( D45' D?6
Qho#( F& 7& ( Karoniec( M&( /ann( & 3& V ilpin( R& K&( (4556"& as
!hromatographic and 1nfrared st#dies of 6P'cyano'6'biphenyl 6'(6'
pentenylo%y"benzoate coated on poro#s silica& Anal. Chem&( >>( 46D6'
46D:

Applications o! Chromatography -yphenated

&echni%ues in the Field o! 3ignin Pyrolysis
2h#bin 7#( aojin 3v and R#i
3o# !outh China University of
$echnology, China
1. Introduction
D#e to the #rgency of the c#rrent world energy s#pply'and'demand sit#ation( the
need for clean so#rces of energy is receiving an increasing attention& 1n the
framewor+ of a f#t#re s#stainable development( biomass is one of the most
often considered so#rces of renewable energy (,ridgewater et al&( 4555"& There
are many ways of converting biomass into #sef#l prod#cts and energy( s#ch
as direct comb#stion processes( thermochemical processes( biochemical
processes( and agrochemical processes etc& =f these( pyrolysis forms the foc#s
of this st#dy (,ridgewater( ?CC6B Mohan et al&( ?CC>"& The pyrolysis of
lignocell#lose is very comple%( primarily d#e to the inherent comple%ity of
the s#bstrate( which changes contin#o#sly both chemically and
str#ct#rally thro#gho#t the decomposition process (/osoya et al&( ?CC;B 3v et
al&( ?C4Ca"&
The chemical str#ct#re and major organic components in biomass are e%tremely
important in biomass pyrolysis processes& Knowledge of the pyrolysis
characteristics of the three main components is the basis and th#s
essentially important for a better #nderstanding of biomass thermal
chemical conversion& 3ignin is one of the main components of woody
biomass( and the worldwide prod#ction of technical lignins as a by'prod#ct from
chemical p#lping processes stands at appro%imately DC million tMyr (/ar#mi et
al&( ?C4C"& /owever( it is merely #sed as f#el to recover energy in conventional
p#lping ind#stry& =nly recently( with the #pcoming foc#s on biore0neries(
lignin has gained new interest as chemical reso#rces&
.nalytical pyrolysis is a well'+nown techni)#e to analyse lignin pyrolysis and
vario#s a#thors p#blished di*erent analytical methods to determine
decomposition characteristics of lignin& Many researchers presented that the
pyrolysis of lignin primarily occ#rred in a wide temperat#re range (?CC'
>CC
o
!" by means of thermogravimetric analysis method (Domang#ez et al&(
?CC:B 3v et al&( ?C4Cb"& 2ome researchers (3i# et al&( ?CC:B 7ang et al&(
?CC5" also compared the pyrolysis behavior of lignin from di*erent tree
species #sing
thermogravimetryO-o#rier transform infrared spectroscopy (TO-T1R"&
<yrolysisOgas chromatographyMmass spectrometry (<y'!MM2"( which is an
advanced pyrolysis methods combined with hyphenated separation and
detection systems (i&e& !'M2"( is often #sed for st#dying degradation
mechanisms of lignin beca#se of its strong ability to identify the pyrolysis
prod#cts (.ti+a et al&( ?CC;B 7indt et al&( ?CC5"&
42 Applications of Gas Chromatography
=n lignin pyrolysis( their prod#ct analysis( and f#rther deriving the crac+ing
mechanism( many researchers have done considerable wor+s& -or e%ample(
,a#mlin et al& (?CC>" have reported the res#lts of e%periments performed on
the flash pyrolysis of two types of lignins( i&e& +raft lignin and organocell lignin(
to prod#ce hydrogen& @owa+ows+ia et al& (?C4C" presented an international
st#dy of fast pyrolysis of lignin& Kegers and Klein (45:D" had reported that
vario#s catechol (4(?'dihydro%ybenzene"( o'cresol (?'methylphenol" and other
phenols prod#cts go along with the formation of g#aiacols d#ring the co#rse of
lignin pyrolysis( the yields of those prod#cts are di*erent corresponding to the
di*erent +inds of lignin and pyrolysis conditions& .ccording to ,ritt et al&
(455D"( lignin pyrolysis occ#rred mainly by a free'radical reaction
mechanism& The relative distrib#tion of prod#cts is dependent on pyrolysis
conditions( s#ch as so#rces of raw materials( pyrolysis temperat#re( heating
rate( pyrolysis atmosphere( and catalyst etc& (arcia et al&( ?CC:"&
To s#m #p( there have already emerged lots of st#dies abo#t lignin pyrolysis(
and their foc#s and concerns were also varied& ,#t so far( to o#r +nowledge(
limited information is available in the literat#re concerning the prod#ct
generation and distrib#tion reg#larities of lignin pyrolysis #nder the
in$#ence of parameters li+e temperat#res and catalysts& Therefore( the
objectives of this wor+ were to attempt to carry o#t fast pyrolysis of several
lignin samples (one enzymaticMmild acidolysis lignin and two technical lignins
were #sed" and analyse the prod#cts by <y'!MM2( in order to 0rstly
establish the potential of this method for lignin processing and secondly to
investigate the e*ects of temperat#re and catalysts on lignin pyrolysis&
2. -yphenated techni%ues
1n the case of samples originating in the real world( each of the techni)#es has a
place( and often several m#st be #sed in order to obtain a complete
overview of the nat#re of the sample&
The #se of m#ltiple techni)#es and instr#ments( which allow more than one
analysis to be performed on the same sample at the same time( provide
powerf#l methods for analyzing comple% samples (Kealey V /aines( ?CC?"& 1f
the instr#ments are combined so that the analyses are done essentially at the
same time( this is called a sim#ltaneo#s approach and is often written with a
hyphen( so that they may be referred to as hyphenated techni)#es( for e%ample
gas chromatography'mass spectrometry (!'M2" and gas
chromatography' infrared spectrometry (!'1R"& ,y #sing many techni)#es in
combinations( the advantages to the analyst in the additional information(
time saving and sample thro#ghp#t are considerable&
2.1 Gas Chromatography,(ass Spectrometry *GC,(S+
The #se of chromatographic techni)#es to separate mi%t#res is one of the most
important analytical tools& The separated components may then be identified
by other techni)#es& Mass spectrometry is the most important of these&
2.1.1 Separation
as chromatography( is a common type of chromatography #sed in analytic
chemistry for separating and analyzing compo#nds that can be vaporized
witho#t decomposition& Typical
43 Applications of Chromatography 2yphenated *echni3ues in the Field of 4ignin Pyrolysis
#ses of ! incl#de testing the p#rity of a partic#lar s#bstance( or separating the
di*erent components of a comple% mi%t#re( s#ch as bio oil&
7hen #sed to prepare p#re compo#nds from a mi%t#re( ! can separate
the volatile components of mi%t#res by di*erential migration thro#gh a col#mn
containing a li)#id or solid stationary phase (-#( ?CC:"& 2ol#tes are transported
thro#gh the col#mn by a gaseo#s mobile phase and are detected as they are
el#ted& 2ol#tes are generally el#ted in order of increasing boiling point( e%cept
where there are speci0c interactions with the stationary phase& .n elevated
temperat#re( #s#ally in the range DC'ADC
o
!( is normally employed to ens#re
that the sol#tes have ade)#ate volatility and are therefore el#ted reasonably
)#ic+ly&
2.1.2 Identi!ication
Mass spectrometry (M2" is an analytical techni)#e in which gaseo#s ions formed
from the molec#les or atoms of a sample are separated in space or time and
detected according to their mass'to'charge ratio( mMz (2par+man( ?CCC"& 1t is
#s#ally #sed for determining masses of particles( for determining the
elemental composition of a sample or molec#le( and for el#cidating the
chemical str#ct#res of molec#les( s#ch as phenols( aldehydes( and other
chemical compo#nds&
The M2 principle consists of ionizing chemical compo#nds to generate charged
molec#les or molec#le fragments and meas#ring their mass'to'charge ratios&
The n#mbers of ions of each mass detected constit#te a mass spectr#m& The
spectr#m provides str#ct#ral information and often an acc#rate relative
molec#lar mass from which an #n+nown compo#nd can be identified or a
str#ct#re confirmed&
2.1. Com"ination
as chromatography'mass spectrometry (!'M2" is a common combined
techni)#e( comprising a gas chromatograph (!" co#pled to a mass
spectrometer (M2"( by which comple% mi%t#res of chemicals may be
separated( identi0ed and )#anti0ed& . schematic diagram of a !'M2 is
shown in -ig& 4& 1n this techni)#e( a gas chromatograph is #sed to separate
different compo#nds& This stream of separated compo#nds is fed online
into the ion so#rce( a metallic filament to which voltage is applied& This 0lament
emits electrons which ionize the compo#nds& The ions can then f#rther
fragment( yielding predictable patterns& 1ntact ions and fragments pass into
the mass spectrometer[s analyzer and are event#ally detected (.dams( ?CC;B
3ee V E#gene( ?CC6"&
This ma+es it becoming an ideal tool of choice for the analysis of the h#ndreds of
relatively low molec#lar weight compo#nds fo#nd in biomass pyrolysis li)#id
prod#cts (bio oil"& 1n order to ma+e a compo#nd be analysed by !'M2( it
m#st be s#8ciently volatile and thermally stable& 1n addition( f#nctionalised
compo#nds may re)#ire chemical modification (derivatization" prior to analysis(
to eliminate #ndesirable adsorption e*ects that wo#ld otherwise a*ect the
)#ality of the data obtained (7#( ?CCD"& ,io oil samples are #s#ally needed
to be solvent e%tracted( and dehydrated before !'M2 analysis&
The prepared sample sol#tion is injected into the ! inlet where it is vaporized
and swept into a chromatographic col#mn by the carrier gas& The sample
$ows thro#gh the col#mn and the compo#nds comprising the mi%t#re of
interest are separated by virt#e of their
44 Applications of Gas Chromatography
-ig& 4& 2chematic of a !'M2
system
relative interaction with the coating of the col#mn (stationary phase" and the
carrier gas (mobile phase"& The latter part of the col#mn passes thro#gh a
heated transfer line and ends at the entrance to ion so#rce (-ig& 4" where
compo#nds el#ting from the col#mn are converted to ions& Then the ions are
separated in a mass analyser (0lter"& .fter that( the ions enter a detector the
o#tp#t from which is ampli0ed to boost the signal& The detector sends
information to a comp#ter that records all of the data prod#ced( converts
the electrical imp#lses into vis#al displays and hard copy displays& 1n
addition( the comp#ter also controls the operation of the !'M2 system&
2.2 Pyrolysis,Gas Chromatography4(ass Spectrometry *Py,GC4(S+
<yrolysis'gas chromatographyMmass spectrometry (<y'!MM2"( which
e%tends the combination to incl#de three distinct techni)#es( is an
instr#mental method that enables a reprod#cible characterisation of the
intractable and involatile macromolec#lar comple%es fo#nd in virt#ally all
materials in the nat#ral environment (,#ll( ?CCD"& 1t di*ers from !' M2 in the
type of sample analysed and the method by which it is introd#ced to the !'M2
system& 1nstead of the direct injection of a highly re0ned organic sol#tion( a few
amo#nt (#s#allyfmg" of the original nat#ral material (e&g& soil( sediment(
biomass etc&" is analysed directly (Kin et al&( ?CC5"&
45 Applications of Chromatography 2yphenated *echni3ues in the Field of 4ignin Pyrolysis
7hen analyzed( the samples are 0rst inserted into a )#artz chamber in a
pyrolysis #nit (-ig&
?" that is then heated resistively in an o%ygen free environment at a pre'set
temperat#re for a n#mber of seconds (e&g& >CCH! for 4Cs"& This res#lts in a heat
mediated cleavage of chemical
bonds within the macromolec#lar str#ct#res of interest prod#cing a s#ite of low
molec#lar weight chemical moieties( which is indicative of specific types of
macromolec#le (e&g& lignin( cell#lose( hemicell#loses etc&"& This mi%t#re of
compo#nds is then swept into the analytical col#mn of the ! and !'M2
proceeds as normal&
-ig& ?& 2chematic of a <yroprobe combined with !'M2
system
,eca#se of its high sensitivity( a rapid analysis time( and less sample
pretreatments( the analytical techni)#e of <yO!MM2 is widely #sed to
research chemical str#ct#re and pyrolysis characteristics of biomass and its
three main components (i&e& lignin( cell#lose( and hemicell#lose"( to e%amine
reaction prod#cts of biomass thermal degradation (Meier V -ai%(
4555"( and to investigate fast pyrolysis of biomass and on'line analysis of
the pyrolysis
vapors (-ahmi et al&( ?CC;B @owa+ows+i V
Kones( ?CC:"
. Experimental
.1 (aterials
The enzymaticMmild acidolysis lignin (EM.3" was isolated from Moso bamboo by
means of enzymaticMmild acidolysis method previo#sly described (7# V
.rgyropo#los( ?CCAB 3o# V 7#( ?C44"( and the so called enzymaticMmild
acidolysis lignin was obtained&
Technical al+ali lignin (.3" and acid hydrolysis lignin (./3" were isolated from
bagasse blac+ li)#or and bagasse respectively( according to o#r previo#s
4 Applications of Gas Chromatography
reports (7# et al&( ?CC:B Tan( ?CC5"&
4! Applications of Chromatography 2yphenated *echni3ues in the Field of 4ignin Pyrolysis
Elemental analysis of three types of lignin was implemented in a Gario E3
elemental analyzer and an 1!< ind#ctively co#pled plasma emission
spectrometer& Table 4 lists the res#lts of the elemental analysis( from
which the = content can be calc#lated by difference&
=rganic Elements
M
wtJ
1norganic elements M ppm
! / @ 2 .l !a @a Mg Mn K Qn !# -e
EM.3
.3
./3
D:&;6 D&;? ?&D:
C&C>
>?&?C ;&A; C&C;
C&>D
D&;A 4&?> :C&45 C&A; ' 4?&DC 46&6D A&;5
4C5&4C
' A:4&;5 ??>&;C ?>&4A A&D> :C>&?; 5&:;
A?&:4 :5&:4
Table 4& Elemental analysis of the lignin
samples
.2 Analytical pyrolysis
-ast pyrolysis of prepared samples was carried o#t in a <yO!MM2 system( which
incl#des a K/<OA model !#rieOpoint pyrolyzer (!D2D?CC( 92." and a 2himadz#
d<?C4C <l#s gas chromatograph'mass spectrometer (Kapan"& The pyrolyzer
consisted of an ind#ctive heated coil to heat the samples and was capable of
maintaining #p to 4?CC
o
! temperat#re with a heating rate of appro%imately
4C
o
!g ms
'4
from room temperat#re to the terminal temperat#re( with
heli#m as both p#rge gas and carrier gas&
=n the basis of the thermal behaviors of EM.3 (3o# V 7#( ?CC:"( the pyrolysis
temperat#re of EM.3 samples was set at A?Ch!( 6CCh!( >CCh!( and :CCh!(
respectively& .ppro%imately
C&4mg of each sample was pyrolyzed& <yrolysis reactions were carried o#t
with an event time of 4Cs( and the obtained pyrolysis prod#cts were then
analyzed by !'M2&
The pyrolysis prod#cts were separated in a D,ODM2 (.gilent Technologies( 92."
capillary col#mn (ACmLC&?DmmLC&?DEm"& The split ratio of ;CM4 and linear
velocity of 6C&Ccmg s
'4
was #sed& The ! oven was heated from DCh! to ?DCh!
at a heating rate of 4Ch!Mmin( and then maintained for another ?min& The
injector temperat#re was ?DCh!& The mass spectrometer was operated in the E1
mode #sing ;CeG of electron energy& The mass range mMz 6D'DCC was scanned&
1denti0cation of the pyrolysis compo#nds was achieved by comparison of their
mass fragment with <er+in Elmer @12T CD mass spectral library& -or
)#alitative and )#antitative analysis of the pyrolysis prod#cts( a more
detailed e%planation based on a practical e%ample will be given&
. Catalytic pyrolysis
1n order to st#dy the e*ect of catalysts on EM.3 pyrolysis( sodi#m chloride (@a!l"
of metal salt and perm#tite of zeolite were selected to serve as the
catalyst& The catalysts were previo#sly s#bject to high temperat#re treatment
#nder @
?
atmosphere at :CC
o
! for >h to ens#re the decomposition reaction of
catalysts did not happen d#ring lignin pyrolyzing& The additive amo#nt of each
catalyst was set to be DJ( 4CJ( and ?CJ based on weight( and the catalyst
and lignin were gro#nd and mi%ed together evenly before #sed for e%periment&
.s lignin pyrolysis reaction was complete at :CC
o
!( so the catalytic pyrolysis
temperat#re of EM.3 was set at :CC
o
! to better investigate the impact of the
additive catalysts on prod#cts&
4" Applications of Gas Chromatography
#. 'esults and discussion
#.1 Identi!ication o! pyrolysis products
.ccording to the previo#s introd#ction of !'M2( both )#alitative and
)#antitative analysis of the pyrolysis compo#nds can be achieved with !'M2
easily& -or e%ample( -ig& A shows T1! chromatogram of ,amboo lignin
pyrolysis at >CCh!( in which each pea+ shown a compo#nd prod#ced
d#ring lignin pyrolysis process& .n e*ective and e*icient way to )#alitative
identify these pea+s is to compare its e%perimental mass spectr#m against
a library of comp#terized mass spectra (Mistri+( ?CC6"&
-ig& A& Total ion chromatograms of ,amboo EM.3 pyrolyzed at
>CCh!
1n o#r e%periment analysis( identification of the pyrolysis compo#nds was
achieved by comparison of their mass fragment with <er+in Elmer @12T CD
mass spectral library& -ig& 6 shows e%amples of identi0ed pea+s of some
major pyrolysis prod#cts by searching comp#terized spectra library& 1n addition(
by means of spectral libraries( more information abo#t identi0ed compo#nds
can be obtained( s#ch as compo#nd name( molec#lar form#la( str#ct#ral
form#la( and molec#lar weight( etc&
d#antitative analysis of lignin pyrolysis prod#cts can be obtained in terms of
pea+ areas or pea+ heights( both of which are +nown as semi')#antitative
method& .ltho#gh it can not be acc#rately determined the content of a certain
compo#nd witho#t standard samples( it does can be #sed to compare the
relative content of each or each +inds of compo#nds( and get the increase or
decrease tendencies of a certain +inds of compo#nd with pyrolysis parameters
by their pea+ area percentage& This is why many researchers have been
st#dying biomass pyrolysis by #sing <y'!MM2& =f co#rse( for precise
)#anti0cation of certain components of bio'oil derived from pilot laboratory
e)#ipment or factory( it is recommended to #se internal or e%ternal
standards( or by standard addition or internal normalization& /owever( at
present( in order to st#dy the trends or reg#larities of lignin pyrolysis prod#cts
with the e%perimental conditions( )#antitative information obtained from
integrated pea+ areas are the most reliable and convenient&
4# Applications of Chromatography 2yphenated *echni3ues in the Field of 4ignin Pyrolysis
-ig& 6& 2ome e%amples of mass spectra identified by
searching libraries
#.2 E!!ect o! temperature on E(A3 pyrolysis
,ased on the analysis method described earlier( )#antitative information of
bamboo EM.3 pyrolysis prod#cts at di*erent temperat#res are presented in
Table ?& .s can be seen from Table ?( The major compo#nds
derived from p'hydro%yphenylpropanoid( g#aiacylpropanoid( and
syringylpropanoid of lignin #nits d#ring pyrolytic reactions( were mainly
classified as the heterocycles (?(A'dihydrobenzof#ran"( phenols( and a small
amo#nt of acetic acid& The yield of phenolic compo#nds increased with an
increase of pyrolysis temperat#re( and the highest fraction of phenols was
D>&6AJ at >CC
o
!&
.mong these pyrolysis prod#cts( the small molec#le compo#nds of vanillin and
acetic acid generated as a res#lt of the bond crac+ing of interlin+age !
i
O!
R
of
lignin phenylpropane( and the brea+age of !
i
O!
R
can ind#ce the prod#ction of
carbo%ylic acid and carbon dio%ide (Fang et al&( ?C4C"& ,ond brea+age of the
side chains of lignin str#ct#ral #nits can lead to generate degradation
prod#cts with the new hydro%yl and carbonyl gro#ps& Th#s( with the contents of
the hydro%yl and carbonyl gro#ps increasing( the side chains of aromatic
compo#nds connected to i'carbonyl( i'carbo%yl or ester gro#ps appeared
(3o# et al&(
?C4Ca
"&
1n all the identi0ed prod#cts( ?( A'dihydrobenzof#ran (D)%F" acco#nted for
the largest )#antity( in addition( other compo#nds s#ch as ethenylg#aiacol( ?(
>'di'tert'b#tyl'p'cresol (D$%C"( A( D'dimetho%yacetophenone (D&AP"(
metho%ye#genol etc& also acco#nt for considerable amo#nt& 2ome of these
selected compo#nds with higher yields d#ring lignin pyrolysis and their
chemical str#ct#res are shown in -ig& D( and their yield distrib#tions varying
with pyrolysis temperat#re are presented in -ig& >& The yields of obtained
compo#nds possessing the syringyl #nit str#ct#re (metho%ye#genol(
syringol( and syringaldehyde" and ?( A'dihydrobenzof#ran (D)%F" are shown in
-ig& >(a" and the yield of compo#nds possessing g#aiacyl #nit str#ct#re
(ethenylg#aiacol( vanillin( E'isoe#genol( and sinapylaldehyde" are shown in -ig&
>(b"&
A?C
o
! 6CC
o
! >CC
o
! :CC
o
!
pO/ydro%yphenols <henol
'
b ' 4&>4 ?&55
o'!resol ' ' ' 4&>:
p'!resol ' ' 4&C4 A&D:
?(>'Di'tert'b#tyl'p'cresol
(D$%C"
>&54 D&:5 ?&4C 4&>;
?(6'%ylenol ' ' ' C&::
p'Ethylphenol ' ' C&;6 4&D5
?'.llylphenol ' ' ' 4&:6
#aiacols #aiacol ' ' A&;: 4&C:
p'Methylg#aiacol ' ' 4&6D 4&;?
Ethenylg#aiacol :&4: 5&?? ;&?A A&4>
Ganillin ' ?&;> ?&>6 ?&D4
E'isoe#genol ' 4&55 ?&>> ?&CC
2inapylaldehyde ' 4&DC 4&5> ?&C4
!oniferylalcohol ' D&A6 5&65 '
2yringols 2yringol ' A&D; 5&>5 6&DA
Methylsyringol ' ' ?&5: A&C4
2yringaldehyde ' ?&A> ?&6? 4&6D
Metho%ye#genol 6&>D D&>; D&C> ?&A5
.cetosyringone ' ' ' 4&?A
/eterocycles ?(A'Dihydrobenzof#ran
(D)%F"
>>&?> D>&>? A>&CD 45&4D
=thers .cetic acid
A(;'Dimethylnonane
'
'
'
'
'
'
C&5
;
'
A(D'Dimetho%yacetophenone
(D&AP"
6&C5 D&4C >&>A ?&?C
m'<hthalic acid ' ' ' 5&>5
p'pP'1sopropylidenebisphenol
(IP%P"
' 6&6> D&;? ;&:5
.llylphthalate C&:5 C&5; 4&A; ?&>5
Tetracosane ' ' ' A&>D
?'<henylb#tyrophenone ' ' ' ?&>4
Dipropylene giycol dibenzote ' ' ' 4&>A
Dotriacontane ' ' ' 6&:5
5% Applications of Gas Chromatography
!ompo#nd class
!ompo#nds
Field( .rea percent (J"
a
a
based on the integrated areasB
b
not detected&
Table ?& <rod#cts identification from bamboo EM.3 pyrolysis
5
i
e
l
d
.

6
5
i
e
l
d
.

6
5
i
e
l
d
.

6
-ig& D& <rod#cts with higher yields in EM.3 pyrolysis
$2 !%
777777DHBF Methoxyeugenol
Syringol
$%
Syringaldehyde %
"
5%
4%

3%
4
2%
2
$%
3%% 4%% 5%% %% !%% "%%
*emperature. C +a-
$%
Ethenylguaiacol
Vanillin
E-isoeugenol
"
Sinapylaldehyde

4
2
3%% 4%% 5%% %% !%% "%%
*emperature. C +(-
-ig& >& <rod#ct Fields distrib#tion varied with pyrolysis
temperat#re
1t can be seen from -ig& > that almost all of the compo#nds derived from EM.3
pyrolysis appeared at 6CC
o
!( e%cept for D)%F( metho%ye#genol( and
ethenylg#aiacol emerged earlier at abo#t ACC
o
!& The formation fraction of
metho%ye#genol( syringaldehyde( ethenylg#aiacol( and vanillin reached a
ma%im#m at 6CC
o
!( then( the yields of these compo#nds decreased with the
increment of temperat#re( which may be beca#se the secondary
decomposition too+ place at high temperat#res& The highest yield of ?( A'
dihydrobenzof#ran (D)%F" was
>>&?>J at A?C
o
!( as pyrolysis temperat#re increased to :CC
o
!( the yield of D/,-
decreased rapidly to 45&4DJ& This con0rms that in lignin pyrolysis process( the
ma%im#m formation of D)%F occ#rred at aro#nd ACC
o
! (3o# et al&(
?C4Cb"& The yield of E'isoe#genol and sinapylaldehyde increased slowly
beca#se their chemical str#ct#res possessed the do#ble bonds of side chain
and the benzene rings formed conj#gated system( th#s became more stable
even at high temperat#re&
#. E!!ect o! catalysts on E(A3 pyrolysis
The e*ects of catalysts on the yield of prod#cts from EM.3 pyrolysis were st#died
in detail& The )#antitative analysis of pyrolysis prod#ct based on the
integrated areas is shown in Table A( and the yield distrib#tions of val#able
prod#ct are present in -ig& ;&
Field( .rea percent
(J"
X%<erm#tite
.3
DJ 4CJ ?CJ DJ 4CJ ?CJ
as !arbon dio%ide ' ' D&4: ?&5> 4D&?4 4D&:A
4:&A4
,enzenes ,enzene ' 4&4> 4&AD 4&D5 4&?D 4&A5 4&:?
Tol#ene ' 4&:A 4&6C ?&>? ?&4A ?&?6 ?&C?
m'cylene ' C&;? C&;6 4&?D C&:A 4&?; C&56
2tyrene ' C&5D ' ' C&:4 ' '
<henol ?&55 A&54 6&6C >&4; D&?5 D&>6 D&;5
pO/ydro%yphenols o'!resol 4&>: 4&D5 ?&C6 A&?C 4&:A ?&?;
4&:5 p' !resol A&D: A&?C A&5>
>&CA 6&A4 D&?> 6&>D o'.llylphenol '
C&5C ?&CD 4&44 4&D? ?&?; 4&AD m'
cylenol C&:: 4&4C 4&;4 ?&DC 4&>C ?&C;
?&46 p'Ethylphenol 4&D5 ?&DA
A&4D 6&;> ?&4; ?&;: ?&:5
,#tylated
hydro%ytol#ene
' 4&C6 4&>A 4&66 4&CC 4&C6 4&C5
#aiacols o'#aiacol 4&C: C&:D 4&:D 4&;> 4&;; 4&?; 4&?5
Metho%yl phenol 4&;? A&A4 D&;C >&A; 4&D4 C&:4 4&AD
?'Dihydro%ytol#ene ' ?&>C A&?C 6&>> 4&;6 ?&5; 4&5:
p'Ginylg#aiacol ' A&:6 6&?C 6&C6 D&4D ?&A5 6&:6
Ganillin ?&D4 C&:> 4&?C 4&4C 4&D6 4&55 4&D5
E9:;'isoe#genol ?&CC ?&?A ?&DD A&44 ?&A; ?&?? 4&5;
'/ydro%yisoe#genol ' C&:D C&5C C&5? C&>> 4&CC 4&?A
.cetog#aiacone ' ' ' ' C&>? C&>D C&:A
-er#lic acid ' :&6C 6&5A A&>D C&>C C&6: C&A;
2yringols 2yringol 6&DA 4&A? 4&55 4&4: D&?D 6&56 6&A6
A(6'
Dimetho%yphenol
' 4&C; 4&;C 4&:> ' ' '
Metho%ye#genol ?&A5 4&AD 4&C? C&:4 ?&?5 4&>> 4&>A
2yringaldehyde 4&6D 5&A? ?&66 4&?D C&A> C&66 4&D4
.cetosyringone 4&?A ' ' ' C&:? C&:> 4&6?
#aiacylacetone ' 4&D> ' ' ' ' '
!atechols 6'Ethylcatechol ' ' 4&C; 4&C6 4&44 C&:6 C&;6
A'Mmethyl'4(?'
benzenediol
' ?&?: A&D6 A&;; ' ' '
?(A'
/eterocycle
s
Dihydrobezof#ra
n
(D)%F"
45&4D 4>&AC 4D&6A 4A&C: ?4&D6
?A&;: ?6&45
=thers .cetic acid C&5; 4&:5 A&DC D&:6 A&D; A&>: 6&C4
-#rf#ral ' C&5; 4&C; 4&A5 4&C: 4&CA C&56
4(?(6'
Trimetho%ybenzene
' 4&C; ?&C4 4&A? ?&:; ?&A6 ?&?>
A(D'
Dimetho%yacetoph
en one (D&AP"
?&?C A&DD ?&D? 4&5> A&4? ?&?? ?&4D
DJ 4CJ ?CJ DJ 4CJ ?CJ
p'pP'
1sopropylidenebisph ;&:5 ?&54 4&A: 4&CC ' ' '
enol (IP%P"
Dib#tyl phthalate 4&>A C&5C 4&64 C&;; ' ' '
6'/ydro%y'A(D'
dimetho%ybenzohy
dr
' A&>? 4&46 C&;: ' ' '
azide
!ompo#nd class
!ompo#nds
Field( .rea percent
(J"
EM EM.3 X%@a!l
EM.3
.3
X%<erm#tite
Table A& <rod#cts identification from EM.3 pyrolysis with catalysts at :CC
o
!
!
Acetic acid

5
4
3
2
$
!
Phenol

5
4
3
8aCl
Permutite
$9
%6 56 $%6 2%6
29%
%6 56 $%6 2%6
$92
Furfural
Benzene
$95
%9"
$9%
%94
%95
%9%
%6 56 $%6 2%6
%9%
%6 56 $%6 2%6
(a"
-ig& ;& !ontin#ed
5
i
e
l
d
.
6
2" 5
DHBF
Ethylphenol
24
4
2%
3
$
2
$2
49%
%6 56 $%6 2%6
$
295
%6 56 $%6 2%6
395
39%
DMAP
Methoxyeugenol
29%
$95
295
29%
%6 56 $%6 2%6
(b"
$9%
%95
%6 56 $%6 2%6

5
4
3
2
$
395
Syringol
%6 56 $%6 2%6
295
29%
$95
$9%
%95
$%
Vanillin
%6 56 $%6 2%6
39%
295
29%
$95
E(Z!i"oeugenol
"
Syringaldehyde

4
2
%
%6 56 $%6 2%6
$%
#PBP
"

4
2
%
%6 56 $%6 2%6
%6 56 $%6 2%6
$%
"
Ferulic acid

4
2
%
%6 56 $%6 2%6
0osage of
catalyst
(c"
-ig& ;& <rod#ct Fields distrib#tion varied with di*erent dosages of catalyst
5
i
e
l
d


4

6
.dditive @a'salt and perm#tite promoted the formation of small molec#les& The
amo#nt of acetic acid( phenol( f#rf#ral( and benzene varying with dosage of
catalyst is shown in -ig&
;(a"& 1t revealed that yields of acetic acid( phenol( f#rf#ral( and benzene
increased with an increase of the dosage of two catalysts( and the two catalysts
in EM.3 pyrolysis promoted the generation of benzene and f#rf#ral& 7hen
the dosage of perm#tite was DJ( the formation rate of acetic acid( phenol(
and f#rf#ral were the most distinct( as the amo#nt of perm#tite f#rther
increased( the increase in yield of them was not obvio#s& /owever( as the
amo#nt of @a!l increased( the yield enhanced considerably& 1n short( the
addition of two catalysts promoted the cleavage of lignin and the generation of
small molec#le compo#nds&
1t can be obtained( from -ig& ;(b"( that with the additive catalyst increasing from
DJ to ?CJ( perm#tite has a signi0cant role in promoting the formation of D)%F
from 45&4DJ to ?6&45J( however( @a!l catalyst was e*ective to red#ce the
prod#ction of D)%F from 45&4DJ to
4A&C:J& =n the yields of ethylphenol( D&AP( and metho%ye#genol d#ring EM.3
catalytic pyrolysis( the catalysts of perm#tite and @a!l had the same
impact& !ompared with perm#tite( @a!l catalyst had more prono#nced e*ect to
improve or s#ppress the generation of ethylphenol( D&AP( and metho%ye#genol&
-ig& ;(c" shows that when @a!l catalyst was DJ( prod#ct of syringaldehyde and
fer#lic acid reached their ma%im#m yield( while with f#rther increase in the
amo#nt of catalyst( the yield decreased& This was similar to that of D&AP shown
in -ig& ;(b"&
Two +inds of phenolsP generation trends (i&e& g#aiacols and syringols" a*ected by
variations of temperat#re and catalysts are shown in -ig& :& ,oth g#aiacols and
syringols reached their ma%im#m yields at >CC
o
!& The catalytic e*ects of
@a!l and perm#tite for improving g#aiacols were the most prominent at
dosage of DJ( however( the catalytic e*ect of perm#tite for syringols was
not obvio#s&
Guaiacols
3%
Syringol
Guaiacols
3%
Syringols
8aCl
999999999Permutite
2% 2%
$% $%
% %
3%% 4%% 5%% %% !%% "%%
&emperature 4
o
C
% 56 $%6 2%6
Dosage o! catalyst
-ig& :& The total amo#nt of g#aiacols and syringols with pyrolysis
conditions
To s#m #p( the impact of di*erent catalysts on the selectivity of pyrolysis
prod#cts is di*erent& !ompared with perm#tite( the effect of catalyst @a!l was
considered to be more signi0cant& Two types of catalysts added to EM.3 can
promote the generation of small molec#le compo#nds( s#ch as carbon
dio%ide( acetic acid( benzene series( f#rf#ral( and phenol etc& Meanwhile(
add catalysts to EM.3 made macromolec#lar lignin degrade to small
molec#le compo#nds more thoro#ghly&
Phenols
2eterocycles
:en;enes
Easters
5
i
e
l
d

4

6
5
i
e
l
d

4

6
5
i
e
l
d

4

6
5
i
e
l
d

4

6
#.# E!!ect o! temperature on technical lignin pyrolysis
<yrolysis st#dies of two types of technical lignin were also started by means of
<y'!MM2 analysis& The pyrolysis temperat#re selection was based on their
thermal degradation behaviors (Tan et al&( ?CC5B 7# et al&( ?CC:"( respectively&
.ccording to precio#sly introd#ced method( identification information of
pyrolysis prod#cts at different temperat#res for two types of technical lignin is
presented in Table 6 and D& <yrolysis prod#cts from technical lignin can be
classified into benzenes( phenols( aromatic heterocyclics (mainly ?( A'
Dihydrobenzof#ran"( esters and trace acids& The lignin derived phenols can be
f#rther classi0ed into molec#les with g#aiacyl( syringyl( and pO hydro%yphenyl
aromatic moieties( and were de0ned as g#aiacols( syringols( pO
hydro%yphenols( respectively& Fields distrib#tion of each type of prod#ct
changed with pyrolysis temperat#re are plotted in -ig& 5&
.s the pyrolysis temperat#re rise( the heterocyclics red#ced( while phenolic
compo#nds content increased& The ma%im#m content of ?( A'
Dihydrobenzof#ran emerged at abo#t
A;D
o
!'6CC
o
!& .t >CC
o
!( the highest yields of phenols for .3 and ./3 were
D;&54J and
D?&44J( respectively& .s the temperat#re increased f#rther( both of their
yields were
red#ced& This characteristic is consistent with that of
EM.3&
%
4%
Guaiacols
Syringols
p72ydroxyphenols
3%
4%
2%
2%
$%
%
2%% 3%% 4%% 5%% %% !%% "%%
&emperature 4
o
C
(a" .3
%
2%% 3%% 4%% 5%% %% !%% "%%
&emperature 4
o
C
Phenols
2eterocycles
%
:en;enes
Easters
4%
Guaiacols
4%
Syringols
p72ydroxyphenols
3%
2%
2%
$%
%
2%% 3%% 4%% 5%% %% !%% "%%
&emperature 4
o
C
(b" ./3
%
2%% 3%% 4%% 5%% %% !%% "%%
&emperature 4
o
C
-ig& 5& <rod#ct Fields distrib#tion varied with pyrolysis temperat#re
Field( .rea percent (J"
!ompo#nd class !ompo#nds
,enzenes ,enzene
Tol#ene
4(?(6'
Trimetho%ybenzene pO/ydro%yphenols
<henol
?'
Methylphenol
6 (or A"'Ethylphenol
6'(?'.llyl"'phenol
#aiacols ?'Metho%yphenol
?'Metho%y'6'methylphenol
A'Metho%ycatechol
6'Ethyl'?'metho%yphenol
?'Metho%yl'6'vinylphenol
Ganillin
?'Meho%y'A'(?' allyl"'phenol
!oniferylalcohol
2yringols ?(>'Dimetho%yphenol
2yringaldehyd
e
?(>'Dimetho%y'6'(?'allyl"'
phenol
6'/ydro%y'A(D'
dimetho%yacetylbenz
ene
/eterocycles ?(A'Dihydrobenzof#ran (D)%F"
Esters
<henyl glyo%ylate'?
[acetyl benzene ester
?;C
o
! 6CC
o
! >CC
o
! :CC
o
!
' ' ' C&55
' ' ' 4&C>
' ' >&D: ?&:5
' ' 4&6? A&65
' ' 4&;5 6&65
' ' 4&:4 ?&A4
' ' ?&?> 4&D:
' ' >&4? 4&D:
'
'
'
'
'
A&;
6
4&6
6
'
' ' 4&:6 C&:C
4?&65 ?;&;6 4A&>C 4?&:>
' ' 4&D: '
' A&6A >&C6 4&:?
' ' ' ?&C>
' ?&?? ;&6A 6&:;
' ' C&5D '
' 5&4D :&CC ?&;;
' ' 4&AA C&5A
6D&?A 65&45 ?D&C5 ?5&?;
6?&?: ?&56 4&;> ;&?;
' ' ?&4: 4C&A6
' ' ' 4&;?
=thers A(D'Dimetho%y acetophenone ' D&A? >&;; 6&>>
<almitinicaci
d
' ' ' C&:C
Table 6& <rod#cts identification from .3
<yrolysis
.romatic esters decreased with temperat#re increasing( while benzenes
compo#nd only emerged at high pyrolysis temperat#re( with a little increase&
/eterocyclic compo#nds and esters decrease with temperat#re increasing&
This was mainly d#e to their poor thermal stability( ca#sing these two types of
compo#nds cleaved into smaller molec#lar( more stable phenols or aromatic
compo#nds at higher temperat#re&
.s abo#t the phenolic prod#cts( it can be seen from -ig& 5 that( the g#aiacols
and syringols trends were similar to that of total phenols( while pO
hydro%yphenols had a f#rther increasing trend as the temperat#re increases&
This may be beca#se the branched'chains of the relatively larger molec#les of
phenols (s#ch as some g#aiacols and syringols" ca#se f#rther crac+ing as
the temperat#re increases( which res#lting the increase of p'
hydro%yphenols&
-ig& 4C shows the contents of g#aiacols( syringols and pOhydro%yphenols of three
types of lignin pyrolyzed at >CC
o
!& .s can be seen from the 0g#re( compared
with that of ./3( the g#aiacols prod#ced from EM.3 and .3 pyrolysis was m#ch
higher (?5&?4J( A?&5?J"( while the ./3 prod#ced the highest pO
hydro%yphenols (45&4>J"& .ccording to the str#ct#ral analysis of the three
types lignin (Tan( ?CC5"( this prod#ct distrib#tion depends )#alitatively on the
relative content of three basic str#ct#re #nits of lignin&
!ompo#nd class !ompo#nds
Fie
?DC
o
ld( .rea
A;D
o
!
percen
t
(J"
:CC
o
,enzenes ,enzene ' ' ' 4&>5
Tol#ene
4(?(6'Trimetho%ybenzene
'
'
'
'
'
D&>
A
?&C
:
' 4(?(A'Trimetho%yl'D'tol#ene ' ' 4&AC '
pO
/ydro%yphenols
<henol ' ' ?&:A D&C:
p'!resol ' ' A&65 5&AD
6'Metho%ylphenol
?( 6'Dimethylphenol
'
'
'
'
A&A
;
'
'
4&A
; 6 (or A"'Ethylphenol ' ' D&4: >&D>
?'.llylphenol ' ' 4&?A ?&4;
6'(?'<ropenyl"'phenol ' ' ' 6&?5
?(>'Ditert'b#tyl'6'methyl
phenol
?5&66 4A&4D A&C> D&C;
#aiacols ?'Metho%y'6'methylphenol ' ' A&>6 '
6'Ethyl'?'metho%yphenol ' ' ?&4A '
?'Metho%yl'6'vinylphenol >&54 5&45 ;&6: A&;4
Ganillin ' ?&46 4&;> '
?'Metho%yl'6'(4'propenyl"'
phenol
' C&5D ?&6: '
2yringols ?(>'Dimetho%yphenol
2yringaldehyde
'
'
'
4&?
A
:&4
5
'
'
'
?(>'Dimetho%y'6'(?'allyl"'
phenol
' ?&D4 ;&?; 4&4>
6'/ydro%y'A(D'
dimetho%yacetylbenzene
' ' ' 4&>;
/eterocycles ?(A'Dihydrobenzof#ran
(D/,-"
DD&C6 >>&?: A6&;C ?>&:6
?( A'Dihydro'?'
methylbenzof#ran
' ' 4&CC 4&>;
Esters
=thers
A',#tenevalerate
Dib#tyl phthalate (D,<"
4(A',#tadiene
'
:&>
4
'
'
6&D
>
'
'
4&D
C
'
4&>
C
'
;&>
.cetic acid ' ' ' 4&44
!yclopentanone ' ' ' 4D&>:
A(D'Dimetho%y acetophenone ' ' A&;> 4&?A
Table D& <rod#cts identification from ./3
<yrolysis
3ignin pyrolysis prod#cing high val#e'added phenolic chemicals is a new
direction in the f#t#re research& The highest content of phenolic compo#nds
occ#rred at >CC
o
!( meanwhile the content of heterocyclics and esters were
minimal( th#s had the least effect on the desired phenols& 1f the temperat#re
was controlled in a reasonable range in the ind#strial prod#ction
process( fast pyrolysis of technical lignin co#ld prod#ce more phenols&
=
i
e

d

>

?
EMA9
&0
A9
A@9
/0
10
0
2uaia!o# ,yrin)o# "A@ydro*y"heno#
-ig& 4C& <henols contents of three types of lignin pyrolysis
at >CC
o
!
#.. E!!ect o! catalysts on technical lignin pyrolysis
The e*ects of metal ion catalysts( s#ch as !a=( K
?
!=
A
( @a
?
!=
A
( @a!l and
Qn!l
?
( on the pyrolysis reactions of the two types of technical lignin were
previo#sly st#died by #sing thermogravimetric analysis and their apparent
activation energy were calc#lated by !oats' Redfern method (!oats V Redfern(
45>6"& 1t was fo#nd that the e*ects of these catalysts on both of two types of
technical lignin are similar& The apparent activation energy co#ld be red#ced
by the adding catalysts& 1n addition( the pea+ temperat#res of lignin
decomposition shifted to lower temperat#re region when adding catalysts( and
th#s accelerate the lignin pyrolysis reaction& The pyrolysis temperat#re of
two types of technical lignin co#ld be e*ectively red#ced by the addition of
K
?
!=
A
( while the yield of co+e pyrolyzed from .3 and ./3 co#ld be greatly
red#ced by the addition of @a!l and !a=( respectively&
1n order to f#rther st#dy the e*ect of catalyst on the distrib#tion of pyrolysis
prod#cts( for each +ind of technical lignin( two catalysts( whose effect had
been proven to be more obvio#s by T analysis( were selected for lignin <y'
!MM2 test( i&e& K
?
!=
A
and @a!l were selected for .3( while K
?
!=
A
and !a=
were selected for ./3& 1n e%periment( K
?
!=
A
and !a= were mi%ed with lignin
as previo#sly described( while @a!l was #sed by immersion and adsorption
(Tan( ?CC5"&
<rod#cts analysis of .3 catalytic pyrolysis at >CC
o
! is listed in Table >( and the
prod#ct distrib#tion is shown in -ig& 44& 1t can be seen( the .3 pyrolysis
prod#cts changed dramatically after adding the K
?
!=
A
catalyst& The ?( A'
Dihydrobenzof#ran (D)%F" that possessed the highest content previo#sly
was not fo#nd in this condition( and the phenols content was red#ced to
4C&4;J& 1nstead( there have emerged a large n#mber of polycyclic aromatic
compo#nds (are #s#ally e%ceed two benzene rings of <./s" and high molec#lar
weight long'chain al+anes compo#nds& This indicates that K
?
!=
A
can e*ectively
promote the cleavage of heterocyclic compo#nds( b#t also facilitate f#rther
condensation of pyrolysis prod#cts( which generate large amo#nts of
naphthalene'based compo#nds&
The e*ects of @a!l on lower D)%F and phenols content( increase polycyclic
aromatic compo#nds yields are similar to that of K
?
!=
A
( b#t its effect is less
dramatic& 1n addition( both two catalysts have led to the r#pt#re of lignin
al+yl side'chain( and prod#ced some long'chain al+ane compo#nds&
.3 X4CJK
?
!=
A
X4J@a!l
,enzenes 4(?(6'Trimetho%ybenzene >&D: A&;
C
A&C>
pO
/ydro%yphenos
<henol 4&6? ' '
?'Methylphenol 4&;5 ' '
6 (or A"'Ethylphenol 4&:4 ' '
6'(?'.llyl"'phenol
6'/ydro%y'A'
metho%yphenylacetyl
?&?
>
'
'
A&D
5
'
4>&4
6 #aiacols ?'Metho%yphenol >&4? A&4
?
6&::
?'Metho%y'6'methylphenol
A'Metho%ycatechol
'
A&;
6
'
'
6&?
;
'
6'Ethyl'?'metho%yphenol 4&:6 ' ?&4C
?'Metho%yl'6'vinylphenol 4A&>C ' A&5?
Ganillin 4&D: ' '
?'Meho%y'A'(?' allyl"'phenol >&C6 ' '
2yringols ?(>'Dimetho%yphenol ;&6A A&6
>
>&;4
2yringaldehyde C&5D ' '
?(>'Dimetho%y'6'(?'allyl"'phenol :&CC ' ?&AD
6'/ydro%y'A(D'
dimetho%yacetylbenzene
4&AA ' '
/eterocycles
<./
?(A'Dihydrobenzof#ran
(D)%F" <henanthrene
?D&C
5
'
'
;&6
C
?4&D
D
'
?'@aphthalene acid methyl
ester
' 44&5: ;&;6
?'@aphthalene'4'b#tanone ' ;&4
4
?&5:
4'<henyl naphthalene ' 44&;A ?&::
?'.cetonaphthone ' A&5
5
?&>C
6(D(5(4C'Tetrahydropyrene ' >&4
;
'
4(6'?'(?'Dinaphthyl"'b#tanone ' ;&C
6
A&A5
6'(?'@aphthyl"'6'+etob#tyric
acid
' >&;
5
'
Esters
<henyl glyo%ylate'? [acetyl
benzene
ester
4&;> ' '
,enzoic acid( phenylmethyl
ester
?&4: 4&6
6
'
6'Methyl'benzoic acid
cyclob#tyl
eater
' ?&5
5
'
?(A'dimethyl'?'he%adecylenic
acid
' ' 4&C5
.l+anes
5'=ctadecenoic acid methyl
ester n'@icosane
'
'
'
4&>
4
4&D
5
'
/e%atriacontane ' ?&6
?
'
Triacontane ' A&5
C
A&:C
=thers Methanol ' ?&C
:
'
Docosa'4A'en'4'ol ' ?&4
6
?&6:
4'Triacontanol
A(D'Dimetho%y acetophenone
'
>&;
;
;&A
6
'
>&6
:
'
!ompo#nd class !ompo#nds
Field( .rea percent (J"
Table >& <rod#cts identification from .3 pyrolysis with catalysts at >CC
o
!
5
i
e
l
d

4

6
5
i
e
l
d

4

6
50
70
A9
B10? 8 C$
/ &
50
B1? -aC
;0
&0
/0
10
0
3enzene# D@3. 0heno# 0A@ Akane# E#ter#
Compounds
-ig& 44& E*ect of catalysts on .3
pyrolysis
Table ; lists the prod#cts of ./3 pyrolysis with or witho#t catalyst& .nd -ig& 4?
shows the prod#ct distrib#tion plotted accordingly& -rom the 0g#re it can be
clearly seen that( the catalytic performance of !a= and K
?
!=
A
to ./3 pyrolysis
was mainly lies in emerging lots of small molec#le compo#nds( partic#larly for
!a=& This is beca#se the catalyst !a= can e*ectively improve the volatile
yield of ./3( and red#ce the co+e prod#ction& 1n addition( adding !a= also
increased the prod#ction of heterocyclic compo#nds( while red#cing the
phenols content&
70
A@9
B10? Ca$
B10? 8 C$
/ &
;0
&0
/0
10
0
,%a %oe!ue# 3enzene# D@3. 0heno#
Compounds
-ig& 4?& E*ect of catalysts on ./3
pyrolysis
1n this regard( the e*ect of K
?
!=
A
on ./3 pyrolysis is j#st the opposite& 2ame as
that to .3( K
?
!=
A
red#ced heterocyclics content of ./3 pyrolysis prod#cts& The
difference is that( for ./3( it did not ma+e f#rther condensation of pyrolysis
prod#cts to form <./s( b#t facilitate the fract#re of aromatic compo#nds
side chains( leading to prod#ced more phenolic compo#nds&
-rom this it can be seen( as the di*erent str#ct#re of lignin( the catalytic e*ect
of a catalyst on di*erent lignins also may be di*erent& The e*ect of K
?
!=
A
on
phenolic compo#nds yield from two technical lignins pyrolysis is a good proof&
!ompo#nd class
!ompo#nds
Field( .rea percent
(J"
./3 X4CJ!a=
X4CJK
?
!=
A
2mall
molec#les
,enzenes
pO
/ydro%ypheno
Methanol
Ginyl methyl ether
'
'
>&>
>
'
'
4&A
4
Methyl acetate
?',#tanone
'
'
'
?&;
:
?&4
A
'
lycollic aldehyde ' 4&4D '
.cetic acid ' 4&54 ?&4
A
Meto%ybenzene
4'Ginyl'6'metho%ybenzene
4'Ethyl'6' metho%ybenzene
'
'
'
'
C&5
D
'
C&;
6
'
C&6
4(?'Dimetho%ylbenzene ' ' C&D
>
4(?'Dimetho%yl'A'tol#ene ' ' 4&4
5
4(?(6'Trimetho%ylbenzene D&>A ?&>A C&>
A
4(?(A'Trimetho%yl'D'tol#ene 4&AC ' '
s
<henol ?&:A ?&:; 5&;
A
?'Methyl phenol ' C&;D 4&;
4
p'!resol A&65 4&:> 4&D
A
6'Metho%ylphenol
6'Ginylphenol
A&A
;
'
'
'
'
4&A
A
6 (or A"'Ethylphenol D&4: ?&:5 A&6
6
?'.llylphenol 4&?A ' '
6'/ydro%y'A'
methylphenylacetyl
' 5&>D 5&6
C
?(>'Ditert'b#tyl'6'methyl
phenol
A&C> ' '
#aiacols ?'Metho%yphenol ' 6&C> 4C&D?
?'Metho%y'6'methylphenol A&>6 6&6? A&?
C
6'Ethyl'?'metho%yphenol ?&4A 4&>> ?&A
?
?'Metho%yl'6'vinylphenol ;&6: A&?5 C&;
:
Ganillin 4&;> ' '
?'Metho%yl'6'(4'propenyl"'
phenol
?&6: ' 4&;
4
2yringols ?(>'Dimetho%yphenol :&45 6&A5 4>&A4
?(>'Dimetho%y'6'(?'allyl"'
phenol
;&?; 4&>6 '
/eterocycles ?(A'Dihydrobenzof#ran
(D/,-"
A6&;C 6?&;4 ?;&D?
?( A'Dihydro'?'
methylbenzof#ran
4&CC ' '
Esters
=thers
Dib#tyl phthalate (D,<"
4(6'Dio%ane
4&D
C
'
'
?&D
?
'
'
p'1sopropyl benzaldehyde
A(D'Dimetho%y
acetophenone
'
A&;
>
4&?
C
'
4&A
A
'
Table ;& <rod#cts identification from ./3 pyrolysis with catalysts at >CC
o
!
.. Conclusion
<yrolysis of several types of lignins was investigated by #sing <y'!MM2( with
the foc#s mainly on the e*ects of temperat#res and catalysts& 2ignificant
di*erences in terms of yields of pyrolysis prod#cts and phenolic compo#nds were
observed&
-or lignin pyrolysis( temperat#re is an important parameter( and has a signi0cant
impact on both the type and the content of pyrolysis prod#cts& /igh
temperat#re (above >CC
o
!" #ndo#btedly favored the thermal chemical
conversion of lignin& .nd as the temperat#re increases( pyrolysis prod#cts
tend to be more diversified& The ?( A'Dihydrobenzof#ran #s#ally emerged at
low pyrolysis temperat#re and reached its highest yield at abo#t A?C
o
!'
6CC
o
!& .s the temperat#re increased f#rther( the yield of ?( A'Dihydrobenzof#ran
decreased( while the phenolic compo#nds increased dramatically& .t >CC
o
!( the
ma%im#m content of phenolic compo#nds from lignin pyrolysis can reach #p to
D:J&
The impact of catalysts and its dosage on EM.3 pyrolysis mainly re$ected in the
prod#ct distrib#tion( while for technical lignin the impact of catalysts are
more evident in the increase of new pyrolysis prod#cts& ,oth @a!l and
perm#tite can promote the generation of small molec#le compo#nds d#ring
EM.3 pyrolysis( s#ch as acetic acid( benzene series( f#rf#ral( and phenols
etc&( and the yields of those prod#cts increase with an increase of catalyst
dosage& /owever( the impact of the two catalysts on the selectivity of ?( A'
Dihydrobenzof#ran is opposite& The addition of K
?
!=
A
res#lted in the
dramatically decrease of heterocycles and yielded large amo#nts of
naphthalene'based compo#nds for the al+ali lignin& 7hile the same e*ect was
not happened for the acid hydrolysis lignin( b#t relatively increase the phenols
and small molec#les yields&
/. Ac0no1ledgment
This wor+ is s#pported by the Major 2tate ,asic Research Development
<rogram of !hina (5;A <rogram" (@o& ?CC;!,?4C?C4"( the @ational /igh
Technology Research and Development <rogram of !hina (:>A <rogram"
(@o& ?CC;..CDQ6D>"( and the @at#ral 2cience -o#ndation of !hina (@2-!( @=&
?44;>C5D"&
2. 'e!erences
.dams( R&<& (?CC;"& Identi<cation of Essential 1il Components %y 7as
Chromatography=&ass
!pectrometry (6
th
edition"( .ll#red <#b !orp&( 12,@ 4'5A?>AA'?4'5( 1llinois(
92.
.ti+a( =&( Eri+a( M&( V Rogbrio( 2& et al& (?CC;"& <yrolysis'!MM2 and TMM2
2t#dy of
Mediated 3accase ,iodeligni0cation of E#calypt#s lob#l#s Kraft <#lp&
". Anal.
Appl. Pyrolysis( Gol&;:( @o&?( (March ?CC;"( pp& ?AA'?6?( 122@ C4>D'?A;C
,a#mlin( 2&( ,ro#st( -&( V ,azerbachi( -& et al& (?CC>"& <rod#ction of /ydrogen by
3ignins
-ast <yrolysis& International "ournal of )ydrogen Energy, Gol&A4( @o&4D(
(December
?CC>"( pp& ?4;5'?45?( 122@ CA>C'A455
,ridgwater( .&G&( Meier( D& V Radlein( D& (4555"& .n =verview of -ast <yrolysis of
,iomass&
1rganic 7eochemistry( Gol&AC( @o&4?( (December 4555"( pp& 46;5'465A(
122@ C46>'
>A:C
,ridgwater( .&G& (?CC6"& ,iomass -ast <yrolysis& $hermal !cience, Gol&:( @o&?(
(March ?CC6"(
pp& ?4'DC( 122@ CAD6'5:A>
,ritt( <&-&( ,#chanan( .&!& V Thomas K&,& et al& (455D"& <yrolysis Mechanisms
of 3igninI 2#rface'1mmobilized Model !ompo#nd 1nvestigation of .cid'
!atalyzed and -ree' Radical Reaction <athways& ". Anal. Appl. Pyrolysis(
Gol&AA( (.pril 455D"( pp& 4'45( 122@ C4>D'?A;C
,#ll 1&D& (.pril ?CCD"& <yrolysis gas chromatography mass spectrometry
(<yM!MM2"( 1nI
$echni-ues( ?;&C6&?CCD( .vailable from
httpIMMwww&bris&ac&#+MnerclsmsfMtechni)#esMpyro&html
!oats( .&7& V Redfern( K&<& (45>6"& Kinetic <arameters from
Thermogravimetric Data&
+ature( Gol&?C4( (Kan#ary 45>6"( pp& >:'>5( 122@ CC?:'C:A>
Domang#ez( K&!&( =liet( M&( V .lonso( M&G& et al&( (?CC:"& Thermal 2tability and
<yrolysis
Kinetics of =rganosolv 3ignins =btained from E#calypt#s lob#l#s&
Industrial
Crops and Products( Gol&?;( @o&?( (March ?CC:"( pp& 4DC'4D>( 122@ C5?>'
>>5C
-ahmi( R&( ,ridgewater( .&G& V Thain( 2&!& (?CC;"& <rediction of Klason 3ignin
and 3ignin
Thermal Degradation <rod#cts by <yO!MM2 in a !ollection of 3oli#m and
-est#ca
rasses& ". Anal. Appl. Pyrolysis( Gol&:C( @o&4( (.#g#st ?CC;"( pp& 4>'?A(
122@ C4>D'?A;C
-#( R&@& (?CC:"& 1vervie, of Chromatographic Analysis (?
nd
edition"( !hemical
1nd#stry <ress(
12,@ 5;:;DC?D>65::( ,eijing( !hina
arcia( <&M&( 7ang( 2& V 2hen( K& et al& (?CC:"& E*ects of Temperat#re on The
-ormation of
3ignin'derived =ligomers d#ring the -ast <yrolysis of Mallee 7oody
,iomass&
Energy # Fuels& Gol&??( @o&A( (March ?CC:"( pp& ?C??O?CA?( 122@ C::;'
C>?6
/ar#mi( /&( 2atoshi( K& V Tats#hi+o( F& et al& (?C4C"& !onversion of Technical
3ignins to
.mphiphilic Derivatives with /igh 2#rface .ctivity& "ournal of (ood
Chemistry and
$echnology( Gol&AC( @o&?( (May ?C4C"( pp& 4>6'4;6( 122@ C?;;'A:4A
/osoya( T&( Kawamoto( /& V 2a+a( 2& (?CC;"& <yrolysis ,ehaviors of
7ood and 1ts
!onstit#ent <olymers at asi0cation Temperat#re& ". Anal. Appl.
Pyrolysis( Gol&;:(
@o&?( (March ?CC;"( pp& A?:'AA>( 122@ C4>D'?A;C
Kegers( /&E& V Klein( M&T& (45:D"& <rimary and 2econdary 3ignin <yrolysis
Reaction
<athways& Ind. Eng. Chem. Process Des. Dev.( Gol&?6( @o&4( (Kan#ary
45:D"( pp& 4;A'
4:A( 122@ C45>'6ACD
Kin( c&&( /#ang( 3&F& V 2hi( F& (?CC5"& Pyrolysis 7as Chromatography2&ethod
and Application
(4
st
edition"( !hemical 1nd#stry <ress( 12,@ 5;:;4??C6>D>;( ,eijing(
!hina
3ee( &R& V E#gene -& ,& (?CC6"& &odern Practice of 7as Chromatography (6
th
edition"( 7iley'
1nterscience( 12,@ C'6;4'??5:A'C( @ew Kersey( 92.
3i#( d&( 7ang( 2&R& V Qheng( F& et al&( (?CC:"& Mechanism 2t#dy of 7ood 3ignin
<yrolysis by #sing TO-T1R .nalysis& ". Anal. Appl. Pyrolysis( Gol&:?( @o&4(
(May ?CC:"( pp& 4;C'
4;;( 122@ C4>D'?A;C
3o#( R& V 7#( 2&,& (?CC:"& <yrolysis !haracteristics of Rice 2traw EM.3&
Cellulose Chem.
$echnol.( Gol&6?( @o&;':( (December ?CC:"( pp& A;4'A:C( 122@ CD;>'5;:;
3o#( R&( 7#( 2&,& V 3v( &K& (?C4Ca"& -ast <yrolysis of EnzymaticMMild .cidolysis
3ignin from
Moso ,amboo& %io*esources( Gol&D( @o&? (March ?C4C"( pp& :?;':A;( 122@
45AC'?4?>
3o#( R&( 7#( 2&,& V 3v( &K& (?C4Cb"& E*ect of !onditions on -ast <yrolysis of
,amboo 3ignin&
". Anal. Appl. Pyrolysis( Gol&:5( @o&?( (@ovember ?C4C"( pp& 454'45>( 122@
C4>D'?A;C
3o#( R& V 7#( 2&,& (?C44"& <rod#cts <roperties from -ast <yrolysis of
EnzymaticMMild
.cidolysis 3ignin& Applied Energy( Gol&::( @=&4( (Kan#ary ?C44"( pp& A4>'
A??( 122@
CAC>'?>45
3v( &K&( 7#( 2&,&( V 3o#( R& (?C4Ca"& Kinetic 2t#dy of the Thermal
Decomposition of
/emicell#lose 1solated from !orn 2tal+& %ioresources( Gol&D( @=&?( (.pril
?C4C"( pp&
4?:4'4?54( 122@ 45AC'?4?>
3v( &K&( 7#( 2&,&( 3o#( R& V Fang( d& (?C4Cb"& .nalytical <yrolysis
!haracteristics of EnzymaticMMild .cidolysis 3ignin from 2#garcane
,agasse& Cellulose Chem. $echnol.( Gol&66( @=&5( (=ctober ?C4C"( pp&
AAD'A6?( 122@ CD;>'5;:;
Meier( D& V -ai%( =& (4555"& 2tate of the .rt of .pplied -ast <yrolysis of
3ignocell#losic Materials'a Review& %ioresource $echnology( Gol&>:(
@o&4( (.pril 4555"( pp& ;4';;( 122@ C5>C:D?6
Mistri+( R& (?CC6"& . @ew !oncept for the 1nterpretation of Mass 2pectra
,ased on a
!ombination of a -ragmentation Mechanism Database and a !omp#ter
E%pert
2ystem( 1nI Advances in &ass !pectrometry( ,renton( &( Monaghan( K& V
.shcroft( .&(
pp& :?4':?6( Elsevier( 12,@ C'666'D4D?:'A( .msterdam
Mohan( D&( <ittman( !&9& V 2teele( <&/& (?CC>"& <yrolysis of 7oodM,iomass for
,io'oilI .
!ritical Review& Energy # Fuels, Gol&?C( @o&A( (March ?CC>"( pp& :6:O::5(
122@ C::;'
C>?6
@owa+ows+i( D&K& V Kones( M&K& (?CC:"& 9ncatalysed and <otassi#m'!atalysed
<yrolysis of
the !ell'7all !onstit#ents of ,iomass and Their Model !ompo#nds& ".
Anal. Appl.
Pyrolysis( Gol&:A( @o&4( (2eptember ?CC:"( pp& 4?'?D( 122@ C4>D'?A;C
@owa+ows+i( D&K&( ,ridgwater( .&G& V Elliott( D&!& et al& (?C4C"& 3ignin -ast
<yrolysisI
Res#lts from an 1nternational !ollaboration& ". Anal. Appl. Pyrolysis(
Gol&::( @o&4(
(May ?C4C"( pp& DAO;?( 122@ C4>D'?A;C
Kealey( D& V /aines <& K& (?CC?"& Analytical Chemistry( ,1=2 2cientific <#blishers
3td( 12,@ 4'
:D55>'4:5'6( =%ford( 9K
2par+man( =&D& (?CCC"& &ass !pectrometry Desk *eference( lobal Giew <#b(
12,@ C'5>>C:4A'
?'A( <ittsb#rgh( 92.
Tan( F& (?CC5"& !tudy on the Chemical !tructures and $hermochemical 'a,s
of $,o $ypes of
Industrial 'ignin( 2o#th !hina 9niversity of Technology( Doctoral
Dissertation(
#angzho#( !hina
Tan( F&( 7#( 2&,&( V 3o#( R& et al& (?CC5"& Thermogravimetric !haracteristics
and Kinetic
.nalysis of 3ignin /ydrolyzed by Dil#te .cid& "ournal of !outh China
University of
$echnology 9+atural !cience;( Gol&A;( @o&>( (K#ne ?CC5"( pp& ??'?>( 122@
4CCC'D>Dc
7ang( 2&R&( 7ang( K&& V 3i# d& et al& (?CC5"& !omparison of the <yrolysis
,ehavior of
3ignins from Di*erent Tree 2pecies& %iotechnology Advances(
Gol&?;( @o&D(
(2eptember ?CC5"( pp& D>?'D>;( 122@ C;A6'5;DC
7indt( M&( Dietrich( M&( V Kan( /&M& et al& (?CC:"& Micro'pyrolysis of Technical
3ignins in a
@ew Mod#lar Rig and <rod#ct .nalysis by !'M2M-1D and
!L!'
T=-M2M-1D& ". Anal. Appl. Pyrolysis( Gol&:D( @o&4'?( (May ?CC5"( pp& A:'
6>( 122@
C4>D'?A;C
7#( 3&K& (?CCD"& 7as Chromatography Detection &ethod (4
st
edition"( !hemical
1nd#stry <ress(
12,@ 5;:;DC?D>5DA( ,eijing( !hina
7#( 2&,& V .rgyropo#los( D&2& (?CCA"& .n 1mproved Method for 1solating 3ignin
in /igh
Field and <#rity& "ournal of Pulp and Paper !cience( Gol&?5( @=&;( (K#ly
?CCA"( pp& ?AD'
?6C( 122@ C:?>'>??C
7#( 2&,&( ciang( ,&3&( V 3i#( K&F& et al& (?CC:"& <yrolysis !haracteristics of
Technical .l+ali
3ignin& "ournal of %ei6ing Forestry University( Gol&AC( @=&D( (2eptember
?CC:"( pp&
46A'46;( 122@ 4CCC'4D??
Fang( d&( 7#( 2&,&( 3o#( R& V 3v( &K& (?C4C"& .nalysis of 7heat 2traw
3ignin by
Thermogravimetry and <yrolysis'as !hromatographyMMass
2pectrometry& ".
Anal. Appl. Pyrolysis( Gol&:;( @o&4( (Kan#ary ?C4C"( pp& >D'>5( 122@ C4>D'
?A;C
#
Degradation Phenomena o!
'e!orming Catalyst in DI',(CFC
Kimihi+o
2#gi#ra 1saka Prefecture University
College of $echnology, "apan
1. Introduction
1.1 7ac0ground
Recently( energy cons#mption is increasing with the pop#lation growth of
developed co#ntries and developing co#ntries( and an e%ha#sting of petrole#m
reso#rces has become a big problem worldwide& 1n addition( !=
?
( 2=
c
and @=
c
which are to%ic s#bstances emitted when these reso#rces are #sed( ca#se
environmental poll#ting problem s#ch as global warming and acid rain( etc&
-rom these sit#ations( high e8ciency( energy'saving and environmental'
saving power so#rce is needed in recent years( and f#el cell can solve these
problems& Therefore( researching( developing and commercializing on
f#el cell are promoted in many co#ntries& -#el cell is categorized by the
di*erence of its electrolyte and operating temperat#re& 1n this research( we #se
Molten !arbonate -#el !ells (M!-!" which #ses a molten carbonate as the li)#id
electrolyte& M!-! is e%pected as a distrib#ted power station and the !=
?
concentrator &enerally( f#el cell performances are eval#ated by 1'G
performance( cell resistance and gas chromatography( etc& for which f#el cell
only generate by s#pplying f#el gas and o%idant gas to cell& enerally(
altho#gh gas chromatography is #tilized only to detect the gas crossover (it is
gas lea+age phenomenon between two poles thro#gh electrolyte" on f#el cell
development( the performance of reforming catalyst in the anode channel in
operation is eval#ated by gas chromatography on RVD of Direct 1nternal
Reforming'Molten !arbonate -#el !ell (D1R'M!-!"& Moreover( M!-!
installed the segmented electrode is eval#ated abo#t the gas crossover and
the #tility of the segmented electrode by a gas chromatography and the
image meas#rement techni)#e& This chapter introd#ces the #se method of
a gas chromatograph thro#gh the degradation factor of reforming catalyst in
D1R'M!-!&
1.2 8ind o! !uel cell9 po1er generation principle and Issues o! DI',(CFC
-rom above'mentioned( the +ind of f#el cell is decided by the electrolyte
#sed( and the operating temperat#re( the f#el #sed and the system
str#ct#re are decided as shown in Table 4& -or e%ample( altho#gh <hosphoric
.cid -#el !ell (.-!" and <olymer Electrolyte -#el !ell (<E-!" e%ha#st the
prod#ced water to the cathode side( M!-!( 2olid =%ide -#el !ell (2=-!" and
.l+aline -#el !ell (.-!" e%ha#st it to the anode side& Therefore( the system
str#ct#re is different by f#el cell #sed& =n the f#el gas( the high temperat#re
operation type f#el cell s#ch as M!-! and 2=-! can #se vario#s f#els(
beca#se they do not #se an
Applications of Gas Chromatography
electrode catalyst and they can #se != as a f#el& /owever( the low temperat#re
operation type f#el cell s#ch as <.-! and <E-! #se only hydrogen beca#se !=
becomes a catalyst poison( and .-! can only( moreover( p#re hydrogen
beca#se !=
?
ma+es the electrolyte be deteriorated& Therefore( the low
temperat#re operation type f#el cell needs an addition facility s#ch as the
shift convertor&
.-! <.-! M!-! 2=-! <E-!
Electrolyte
<otassi#
m
hydro%id
<hosphori
c acid
Molten
carbonat
e
2tabilize
d
zirconi#
1on'
e%chang
e
membran 1onic
cond#ctor
=/
'
/
X
!=
A
?'
=
?'
/
X
2pecific
resistance
f 4jcm f 4jcm f 4jcm f 4jcm f ?Cjcm
=perating
temperat#re
DC ' 4DCh! 45C '
??Ch!
>CC '
;CCh!
' 4CCCh! :C ' 4?Ch!
!orrosively Medi#m 2trong 2trong non Medi#m
Electrode
catalyst
@ic+elMsilver <latin#m @ot need @ot need <latin#m
-#el
<#re /
?
witho#t !=
?
/
?
(!=
?
conten
tB =K"
/
?
V != /
?
V !=
/
?
(!=
?
content
B =K"
-#el so#rce
,y'
prod#ct
hydrogen
of
electrolytic
ind#stry(
7ater
@at#ral
gas(
3ight oil(
Methano
l
=il(
@at#ral
gas(
Methanol
( !oal
gas
=il(
@at#ral
gas(
Methanol
( !oal
gas
@at#ral
gas(
Methano
l
enerating
e8ciency
>CJ 6C O DCJ 6C O >CJ DC O >DJ 6C O DCJ
Table 4& Kind and feat#re of f#el
cell
,eca#se this st#dy targets M!-!( the power generation principle of M!-! is
shown in -ig&4& The f#el of M!-! is hydrogen obtained by reforming the
nat#ral gas and the coal gasi0cation gas( and !=
?
that stabilizes the molten
salt and steam that prevents the carbon deposition are contained in the f#el
gas& /ydrogen s#pplied to the cell is separated to the proton and the electron
with the anode catalyst (/
?
k ?/
X
X ?e
'
"& This proton and carbonate ion( which
has been transmitted in electrolyte( generate steam and !=
?
with
the electrochemical reaction (?/
X
X !=
A
?'
k /
?
= X !=
?
"&
=n the other hand( o%ygen s#pplied to the cell and electrons transmitted
from e%ternal circ#it react into o%ygen ion with the cathode catalyst (C&D =
?
X
?e
'
k =
?'
"& !arbon dio%ide s#pplied to the cell deli)#esces to the electrolyte on
the cathode electrode( and it becomes carbonate ion as this !=
?
reacts with
o%ygen ion (!=
?
X =
?'
k !=
A
?'
"& /ere( the carbonate ion generated is the
electrolyte( and it moves toward the anode electrode& =verall reaction is an
evol#tion reaction of water&
! 0egradation Phenomena of <eforming Catalyst in 0&<7'CFC
-ig& 4& 2chematic diagram of power generation principle
of M!-!
M!-! has three reforming type to obtain hydrogen from vario#s f#el as shown in
-ig&?& The +inds of reforming type on M!-! are classi0ed into the e%ternal
reforming type( which has the reformer o#tside the cell as shown in -ig&? (a"(
and the internal reforming type( which
-ig& ?& 2chematic diagram of comparison of
reforming type
" Applications of Gas Chromatography
has the reformer inside the cell& Moreover( the internal reforming type is
classified into the indirect reforming type( which sets #p the reformer among
cells as shown in -ig&? (b"( and the direct internal reforming type( which 0lls
the reforming catalyst directly to the anode channel as shown in -ig&? (c"&
.ltho#gh the merits of ER'M!-! (-ig&? (a"" are a simple str#ct#re and the
enlargement of M!-! is easy( the demerits are that a big space re)#ired for
installation and heat s#pply to reformer are necessary& The merits of 11R'M!-!
(-ig&? (b"" can ma+e the system compact by stac+ing the reformer of one every
0ve cells( and can control the cell temperat#re by the endothermic reaction of
the reformer& /owever( as a demerit( the system and the cell str#ct#re of 11R'
M!-! become more comple% than that of ER'M!-!( and the height of 11R'
M!-! stac+ becomes taller than ER'M!-! only by the thic+ness of the
reformer& =n the other hand( beca#se D1R'M!-! (-ig&? (c"" has a reforming
catalyst in the anode channel( the system size of D1R'M!-! is smaller than
that of ER' M!-!( and the cell str#ct#re is simple as well as ER'M!-!&
Moreover( the reforming reaction is promoted from the chemical
e)#ilibri#m val#e beca#se M!-! cons#mes hydrogen to which the
reforming catalyst reforms by the cell reaction& Therefore( the generation
e*iciency of D1R'M!-! is larger than that of ER'M!-! and 11R'M!-!&
,eca#se M!-! #ses the electrolyte of li)#id phase( it has the problem that the
electrolyte decrease as the operating time passes (Tanimoto( K& et al&( 455:"&
/owever( beca#se the reforming catalyst is loaded in the anode gas channel(
the possibility that it is poll#ted by the molten salts of li)#id phase and
vapo#r phase is high as shown in -ig&A& The li)#id phase poll#tion is ca#sed
by which the molten salt lea+ thro#gh the cell component s#ch as separators
and adhere to the catalyst (2#gi#ra et al&( 4555"& The vapo#r phase poll#tion
is ca#sed by which the vaporised electrolyte disperse to the gas channel with
the steam generated by the cell reaction and adhere to the catalyst& The
reforming catalyst is poll#ted by adhering of these molten salts( and the
performance of the reforming catalyst deteriorates
-ig& A& 2chematic diagram of catalyst poll#tion mechanism by molten salts in
D1R'M!-!
# 0egradation Phenomena of <eforming Catalyst in 0&<7'CFC
and D1R'M!-! cannot generate electricity 0nally& Therefore( these poll#tion
phenomena of the reforming catalyst sho#ld be con0rmed by the D1R'M!-!
single cell( and the prevention method of the catalyst poll#tion sho#ld be
proposed&
2. Experimental
2.1 Experimental apparatus and conditions
-ig#re 6 shows the schematic diagram of the e%perimental apparat#s& The heater
plate was set #p in the top and bottom of the D1R'M!-! single cell( and the
cell temperat#re was maintained at >DCh! by which the D1R'M!-! single cell
be blan+eted by the ins#lation #sing the thermo'reg#lator ( EDTl=mron( Kapan"&
The red#ction of the cell contact resistance and the gas sealing in the cell were
carried o#t by compressing the single cell( the heater plates and the ins#lation
by air press& /
?
and !=
?
as anode gases were adj#sted by the mass $ow
controller (A>>ClKo$oc( Kapan" and mi%ed with the mi%er that is contained
glass ball( and were h#midi0ed by passing thro#gh a h#midi0er and being
s#pplied to D1R'M!-!& To prevent the dew formation of the s#pply gas( the piping
between the h#midi0er and the cell was made shorter( and the piping
temperat#re was maintained by a ribbon heater at 4?Ch!& =n the other hand(
air from the compressor and !=
?
as cathode gas were also adj#sted by the
mass $ow controller and mi%ed with the mi%er( and were s#pplied to D1R'M!-!&
!ell voltage was meas#red and recorded by a data logger (DR4AClFo+oga w a
Electric !o& 3td( Kapan"& !ell resistance was meas#red by a milliohm meter with
.! 6 probes (AD>>lT#r#ga Electric !o& 3td( Kapan"&
-ig& 6& 2chematic diagram of e%perimental apparat#s
!% Applications of Gas Chromatography
The D1R'M!-! single cell had 0ve sampling port for meas#ring the gas
composition distrib#tion in the cell as shown in -ig&D( and the sampling gas was
collected by the p#mp thro#gh these ports( and analyzed with the gas
chromatograph ( !':. 1 Tl2himaz# !o&( KapanB the detector was the thermal
cond#ctivity detector"& The locations of each sampling port were A( ?D( DC( ;D
and 5;J against the direction of $ow( respectively& The reforming catalyst
was loaded into the valley of the anode corr#gated c#rrent collector as
shown in -ig&>& /ere( the corr#gated c#rrent collector of anode side was made
of 1nconel steel( and that of cathode side was made of 292A4>3( respectively&
The standard gas condition was called ER modeB anode gas composition was
;?/
?
M4:!=
?
M 4C/
?
= (Gol#me J"( cathode gas composition was ;C.irMAC!=
?
( and
the gas #tilization of both sides was 6CJ( respectively& The standard condition
of D1R'M!-! was called D1R modeB anode gas composition was
?D!/
6
M;D/
?
= (steam carbon ratio is A&C"( and cathode composition was same
as ER mode& The operating atmosphere was C&4M<a& .s shown in -ig A(
general M!-! single cell was composed of anode cell frame (292A4>3"(
anode corr#gated c#rrent collector (1nconel"( anode c#rrent collector (@i"(
anode electrode( matri%( cathode electrode (@i="( cathode
-ig& D& 3ocation of sampling port of anode cell frame in D1R'M!-!
!$ 0egradation Phenomena of <eforming Catalyst in 0&<7'CFC
-ig& >& 2tr#ct#re of corr#gated c#rrent
collector
c#rrent collector (292A4>3"( cathode corr#gated c#rrent collector (292A4>3"
and cathode cell frame (292A4>3"& Table ? shows the specification of each
cell component& .ll cell components s#ch as anode electrode( cathode
electrode( matri% and electrolyte sheet were made by a doctor blade method&
The anode electrode was made of @i'AwtJ.l powder& The cathode electrode
was made of @i powder as a green sheet( and this green sheet was
changed to @i= in the cell while the start #p proced#re& The matri% was made
of 3i.l=
?
& The electrolyte was made of >?3i
?
!=
A
MA:K
?
!=
A
&
.node !athode Matri%
Materials @i'AwtJ.l @i= (in sit#" 3i.l=
?
Thic+ness mmmn C&;D'C&:D C&;D'C&:D C&DC
<orosity mJn DC DD DC
Mean pore diameter mmicronn A 4'6( C&?'C&6 C&4
Table ?& 2peci0cation of cell
components
2.2 Setting o! gas chromatograph
1n f#el cell research( the crossover between anode and cathode thro#gh the
electrolyte and the activation of the reforming catalyst are eval#ated by the gas
analysis& Especially( beca#se !/
6
is reformed to /
?
in the anode channel
of D1R'M!-!( /
?
( !/
6
( != and !=
?
concentration become the inde% of the
catalytic activity& Moreover( beca#se neither @
?
nor =
?
e%ist in the anode gas(
@
?
and =
?
become the inde% of the crossover& To analyse these gases in short
time( the col#mn diverged to two passages( one passage was composed by
C&Dm of the shimalite d 4CCM4:C and 4&Dm of the porapa+ d :CM4CC( and another
passage was composed by ?&Dm of the molec#lar sieve D. >CM:C as shown in
-ig&;& The carrier gas was .rgon gas( the flow rate of the carrier gas was
DCmlMmin( and the inlet press#re was
4?4&>+<a( respectively& The temperat#re of the col#mn( the detector and
the injection temperat#re were 5Ch!( 4CCh! and 4CCh!( respectively& -ig#re :
shows the chromatogram obtained by this col#mn& The pea+ of !=
?
does not
overlap with that of air beca#se air is hardly contained in the anode gas
tho#gh the pea+ of air appears immediately after the analysis beginning&
,eca#se the desorption of != is slow( the analysis time is abo#t ?C
min#tes&
!2 Applications of Gas Chromatography
-ig& ;& 2chematic diagram of the col#mn str#ct#re for
D1R'M!-!
-ig& :& E%ample of chromatogram #sing the col#mn for
D1R'M!-!
2. 3oading method o! re!orming catalyst in the anode channel
The in$#ence of the loading method of the reforming catalyst on the cell
performance is e%amined by fo#r loading methods as shown in -ig&:& /ere( the
reforming catalyst was the commercially available nic+el catalyst (?Dwt
J@iMMg=B Type RK@Rl /aldor Topsoe( Denmar+"( and is 4&?mm=&D&%4&6mm3
of the cylinder type&
a& o-rame sidep means that the reforming catalyst was loaded into only the
frame side of the corr#gated c#rrent collector to +eep away the catalyst
from the electrode that contains the carbonate as shown in -ig&5 (a"&
The catalyst loading density was
6:mgMcm
?
&
!3 0egradation Phenomena of <eforming Catalyst in 0&<7'CFC
b& oElectrode sidep means that the reforming catalyst was loaded into only
the electrode side of the corr#gated c#rrent collector to improve the
reforming rate by ma+ing the reforming reaction adjoin the cell reaction
as shown in -ig&5 (b"& The catalyst loading density was ;:mgMcm
?
&
c& o9pper streamp means that the reforming catalyst was loaded into both
side of the
#pper stream part and the frame side of the downstream part of the
corr#gated c#rrent collector to cool the vicinity of the cathode o#tlet
locally as shown in -ig&5 (c"& The catalyst loading density of the frame
side and the electrode side were >CmgMcm
?
and
ACmgMcm
?
(
respectively&
d& oDownstreamp means that the reforming catalyst was loaded into both
side of the
downstream part and the frame side of the #pper stream part of the
corr#gated c#rrent collector to ca#se the reforming reaction #niformly with
the entire anode electorde as shown in -ig&5 (d"& The catalyst loading
density of the frame side and the electrode side were >CmgMcm
?
and
ACmgMcm
?
( respectively&
-ig& 5& 2chematic diagram of loading method of the reforming catalyst and
loading amo#nt
. 'esults and discussion
.1 Cell per!ormance
-ig#re 4C shows the initial performance comparison between the ER mode (the
reforming catalyst does not wor+" and the D1R mode #nder the downstream
of loading condition& ,eca#se the di*erence of both modes is little( the
reforming catalyst wor+s correctly at the initial period& -ig#re 44 shows the
in$#ence of the loading method of the reforming catalyst on the life
performance& /ere( this res#lt is the cell performance #nder D1R mode& .ltho#gh
all cell voltages are almost same #ntil ACC ho#rs of the operating time( the cell
performances other than the cell of odownstreamp are rapidly
deteriorated& Moreover( the cell performance of odownstreamp is also
deteriorated when the operating time e%ceeds >CC ho#rs& This deteriorating
reason sho#ld be j#dged the catalyst poll#tion originating or the cell
deteriorating originating& Therefore( the deteriorating reason is eval#ated by
comparing of the performance #nder ER mode with that of the oDownstreamp
cell #nder D1R mode as shown in -ig&4?& .ltho#gh the cell performance
#nder ER mode is good( the cell performance #nder D1R mode
!4 Applications of Gas Chromatography
deteriorates grad#ally from 4CC ho#rs to >CC ho#rs of
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!5 0egradation Phenomena of <eforming Catalyst in 0&<7'CFC
operating time( and deteriorates rapidly when the operating time e%ceeds >CC
ho#rs& 1t is a pec#liar problem to D1R'M!-! (Miya+e et al&( 455D"&
$2%%
= 4 = > #?6 4 #?6
! @A
E' mode B 22- 41CC@ 41?- @
$$%%
2 2 2
DI' mode B S4C>.?
$%%%
#%%
"%%
!%% 3oading method o! catalysts
Electrode
%%
% 5% $%% $5% 2%%
Current density :mA4cm
2
<
-ig& 4C& 1nitial 1'G performance of ?DCcm
?
D1R'M!-! single cell
#%%
= 4
=
> #?6 4 #?6
! @A
"%%
S4C>.?
!%%
%%
3oading method o! catalysts
5%%
4%%
% 2%% 4%% %% "%% $%%% $2%%
@perating time :hr<
-ig& 44& 1n$#ence of the loading method of the reforming catalyst on the life
performance
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= 4
=
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2 2 2
DI' mode B S4C>.?
%%
3oading method o! catalysts
Electrode
% 2%% 4%% %% "%% $%%% $2%%
@perating time :hr<
-ig& 4?& !omparison of the cell performance between ER mode and
D1R mode
-ig#re 4A shows comparison of the gas composition change in the cell
according to operating time between o9pper streamp and oDownstreamp&
/ere( these res#lts are that gases that collected at =!G (beca#se the cell
reaction does not occ#r( the ability of the catalyst is p#rely eval#ated&" are
analyzed by gas chromatograph& -rom the res#lt of -ig&4? (a"( beca#se the
hydrogen concentration of o9pper streamp is almost corresponding to the
chemical e)#ilibri#m( the ability of the reforming catalyst is good& /owever( the
hydrogen
= 4 =
> #?6 4 #?6
*"+ Do1nstream
! @A
*a+ =pper stream
! @A
= 4 = > #?6 4 #?6
$%% S4C > .?
E lec tro d e
S4C > .?
Electrode
$%%
"% "%
%
- C-
2 #
4%
2%
2D hr
2D2 hr
.1? hr
/2 hr
- C-
2 #
%
2## hr
#?D hr
4%
.?2 hr
/21 hr
C1# hr
2%
% %
%9% %92 %94 %9 %9" $9% %9% %92 %94 %9 %9" $9%
Fractional distance :,<
Fractional distance :,<
-ig& 4A& as composition change in the cell according to operating time
concentration decreases and the methane concentration increases near the
inlet when the operating time e%ceeds ?5? ho#rs& These concentration changes
become large and progress toward the downstream side at >A? ho#rs of
the operating time& Therefore( the cell performance of o9pper streamp
deteriorates for which the necessary hydrogen content cannot be sec#red by
the catalyst poll#tion&
=n the other hand( altho#gh the hydrogen concentration decreases and
the methane concentration of oDownstreamp increases near the inlet with
the lapse of time( they are corresponding to the chemical e)#ilibri#m in :CJ
region of the entire cell& Moreover( they change rapidly at :46 ho#rs of the
operating time( and this change is corresponding to the drastic descent of
the cell voltage& Therefore( the deterioration factor of the cell of
qDownstreamq is the poll#tion of catalyst loaded into the inlet as well as the
cell of q9pper streamq& .ltho#gh the electrode of the downstream can #se the
hydrogen not #sed for the cell reaction of the hydrogen reformed in the #pper
stream part( the electrode of the #pper stream cannot #se the hydrogen if
the catalyst of the #pper stream cannot ma+e the hydrogen by the catalyst
poll#tion& !onse)#ently( beca#se the electrode of the #pper stream hardly wor+s
when the operating time e%ceeds abo#t >CC ho#rs( the e*ective reaction area
of the electrode decreases and the D1R'M!-! cannot generate electricity 0nally&
.2 Analysis o! the polluted catalyst
These fo#r cells are disassembled to confirm the deterioration factor of D1R'
M!-!( and are observed& Moreover( the poll#ted catalyst collected from the
cell after e%periment ends is analyzed by 1!< for which it con0rm that the
molten salts ma+e the reforming catalyst poll#te& -ig#re 46 shows the s+etch
drawing of anode in each cell disassembled& .ll anode electrodes have
discolo#red from the parabolic and the gray to the blac+ toward the e%its from
the inlet& There was no di*erence of these compositional variations tho#gh
these di*erent colo#rs of electrodes were analyzed by an c'ray str#ct#re
analysis&
-ig& 46& 2+etch drawing of anode in each cell
disassembled
The reforming catalysts were collected according to this discoloration of each
electrode after abo#t 4CCC ho#rs of operating( and the amo#nt of lithi#m and
potassi#m in the catalyst were analyzed by 1!<& -ig#re 4D shows the carbonate
content in the collected catalyst from each cell& /ere( amo#nt of 3i
?
!=
A
and
K
?
!=
A
are converted from the res#lts of lithi#m and potassi#m by 1!<( and the
location n#mber means that it is a catalyst collected from the
3
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2

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2

2%
place shown in the n#mber of the s+etch of the electrode in each 0g#re&
Moreover( r6 and
rD of o9pper streamp and r> and r; of rDownstreamp mean that the catalyst is
collected from the electrode side of the corr#gated c#rrent collector& The frame
of electrode s#ch as r4 of o-rame sidep( rD of oElectrode sidep( r> of o9pper
streamp and rD( r; of oDownstreamp means that the catalyst is collected from
near the wet seal part& Moreover( the colo#rs of the catalysts collected from
each location are corresponding to the colo#r of each electrode& .ltho#gh
the catalysts collected from the wet seal part and the #pper stream part
incl#de m#ch carbonate( the carbonate content of the catalysts collected from
the centre of the cell and the downstream part are comparatively few& The
carbonate content of the catalyst collected from oDownstreamp is fewer than
others& M!-! adopts the wet seal method that prevents the gas lea+age by
forming the li)#id 0lm with the molten salt between the matri% and the
electrode& Therefore( a little molten salt begins to lea+ from the wet seal part into
the cell& Especially( beca#se the wet seal part of the #pper stream is orthogonal
to the gas $ow( the lea+age amo#nt of the molten salts is m#ch& /owever(
beca#se the wet seal part of the cell side is parallel to the gas $ow( the lea+ed
molten salt $ows along the cell frame& The lea+ed molten salt doesn[t(
therefore( penetrate the catalytic layer easily& -rom these res#lts( we #nderstand
that the discoloration of the parabolic in anode is signs where the electrolyte
$ows in the anode channel&
=n the other hand( when the amo#nt of lithi#m is compared with potassi#m( the
amo#nt of potassi#m is m#ch& 1t can g#ess that potassi#m that is more than
this composition is the molten salts of vapo#r phase beca#se the molten salt
of li)#id phase is the same as the composition ratio of the electrolyte
(6;3i
?
!=
A
MDAK
?
!=
A
B wtJ"& Therefore( -ig#re 4D was arranged to the ratio of
the li)#id phase molten salt and the vapo#r phase molten salt as shown in
-ig&4>& The li)#id phase molten salt is more than the vapo#r phase molten salt
in all location( and the vapo#r phase molten salt is distrib#ted in the
entire cell almost
3%
*a+ Frame side
C@
Fuel inlet 3ocation o! catalyst
*"+ Electrode
side
3i C@
Fuel inlet
3%
3ocation o! catalyst
Electrode
3i
2
8 C@
Frame

2
8 C@
2
2
2%

2%

Fuel outlet
$%
Fuel outlet
$%
%
$ 2 3 4
3ocation o! catalyst
3%
%
$ 2 3 4 5
3ocation o! catalyst
3%
*c+ =pper stream
C@
Fuel inlet 3ocation o! catalyst *d+ Do1nstream Fuel inlet 3ocation o! catalyst
Frame Electrode
3i
2
Frame Electrode
3i C@
8 C@
2

2 8 C@
2

2%

Fuel outlet
$%
Fuel outlet
$%
%
$ 2 3 4 5
3ocation o! catalyst
%
$ 2 3 4 5 !
3ocation o! catalyst
-ig& 4D& !arbonate content in the collected catalyst from each cell
5%
/
2
3
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5%
5%
*a+ Frame side
Fuel inlet
3ocation o! catalyst
*"+ Electrode side Fuel inlet
3ocation o! catalyst
5%
3i%uid phase
;apor phase
4%
3%
2%
Fuel outlet
Frame

3i%uid phase
;apor
phase
Fuel outlet
Electrode

4%

3%
2%
$% $%
%
$ 2 3 4
3ocation o! catalyst
%
$ 2 3 4 5
3ocation o! catalyst
*c+ =pper stream
3i%uid
phase ;apor
phase
4%
3%
2%
Fuel inlet
3ocation o! catalyst
Frame Electrode

Fuel outlet
*d+ Do1nstream
3i%uid
phase ;apor
phase
Fuel inlet
Fuel outlet
3ocation o! catalyst
Frame Electrode

4%


3%
2%
$% $%
%
$ 2 3 4 5
3ocation o! catalyst
%
$ 2 3 4 5 !
3ocation o! catalyst
-ig& 4>& Ratio of the li)#id phase molten salt and the vapo#r phase molten
salt in the poll#ted catalyst
#niformly& enerally( as for potassi#m( the deli)#escence is stronger than
lithi#mPs( and the vapo#r partial press#re is also higher& Therefore( we
el#cidate the electrolyte volatile behavio#r in M!-! #sing a vis#alization
techni)#e (2#gi#ra et al&( ?CC:"& The in$#ence of electrolyte lea+age from the
wet seal section on the electrolyte volatile behavio#r is eval#ated by
vis#alizing the wet seal& /ere( beca#se the 3iM@a electrolyte is less volatile
than the 3iMK electrolyte( it is possible to pay attention to the electrolyte
lea+age from the wet seal pa rt by e%cl #d i ng the i nfl #e nce of the
vol ati zi ng phenome n o n i f
D?3i
?
!=
A
M6:@a
?
!=
A
electrolyte is #sed as the electrolyte& The volatilization
phenomenon of the wet seal section is el#cidated by observing a wet seal
section via a vis#alization cell& -ig#re 4; shows the meas#rement image of
the wet seal section in the anode gas channel immediately after operation&
-ig#re 4; (a" shows the meas#rement image #nder =!G conditions( and
-ig#re 4; (b" shows the meas#rement image #nder 4?D m.Mcm
?
of c#rrent
density( respectively& /ere( the electrode is s#pported only on one side beca#se
there is not the s#pport for the cell frame side to observe the wet seal section&
Therefore( this cell #ses the c#rrent collector to prevent the electrode
c#rving& -rom -ig&4; (a"( we can see that volatile matter g#shes from the wet
seal section( which is a part of the anode and cell frame( and this g#sh is
promoted by the increase of the c#rrent density( as shown in -ig&4; (b"& This
g#sh originates beca#se the electrolyte of the wet seal section flows as a mist(
with steam and !=
?
generated in the anode cell reaction& Moreover( this mist
electrolyte volatilizes in the gas( is changed into a powder of @a
?
!=
A
by
reacting with !=
?
( and it f#rthermore becomes a smaller mist by the gas
$ow& 7e #nderstand that the gap of the wet seal part grows when the
elasticity of the corr#gated c#rrent collector decreases by the endothermic
reaction of the catalyst( and the lea+age of the molten salt from this grown gap
is promoted( and the reforming catalyst is poll#ted by this lea+ed molten salt
as shown in -ig&4:& The catalytic activity of the reforming catalyst decreases
by which the speci0c s#rface area
-ig& 4;& Meas#rement image of wet seal part in the anode gas channel
-ig& 4:& Mechanism of the li)#id phase poll#tion of reforming catalyst
decrease by adhering the lea+ed electrolyte to the reforming catalyst& The
electrolyte that adheres to the reforming catalyst cannot be easily removed
beca#se the reforming catalyst
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has a micro pore str#ct#re (2#gi#ra V =hta+e( 455D"& Moreover( the potassi#m in
the lea+ed molten salt easily changes into K=/ with the steam prod#ced by
the cell reaction( and disperses with the prod#ced gas in the catalytic layer&
Therefore( the catalyst poll#tion is divided into the li)#id phase poll#tion and
the vapo#r phase poll#tion& Tho#gh it is di*ic#lt to defend the catalyst from the
vapo#r phase poll#tion( the catalyst can be defended from the li)#id phase
poll#tion for which the catalyst be covered by the material with large
contact angle with the molten salt&
. Pre)ention method o! the li%uid phase pollution
The corr#gated c#rrent collector is plated by nic+el which has large contact
angle with molten salt to defend the catalyst from the li)#id phase poll#tion&
-ig#re 45 shows the effect of @i plating on the cell performance& /ere(
the operating condition is D1R mode (9
f
M9
o%
N;DJMDCJB 2M!NA&C"( and the
catalyst loading method adopted oDownstreamp whose performance was the
best in a c#rrent e%periment& Moreover( @i plating was applied to the corr#gated
c#rrent collector by the electrolytic process( and the thic+ness of @i plating was
abo#t 4CC microns& 1t is clear that the performance of the cell with the
corr#gated c#rrent collector with @i plating is better than that of non plating&
Moreover( the catalyst is collected after abo#t 4CCC ho#rs of operating( and
the carbonate content of the collected catalyst is analysed&
#%%
= 4= >2.64.?6
"%%
! @A
Ei plating
Eon,plating
!%%
%%
5%%
3oading methode o! catalysts
Electrode
4%%
% 2%% 4%% %% "%% $%%% $2%%
@perating time :hr<
-ig& 45& E*ect of @i plating on the cell performance
-ig#re ?C shows the carbonate contents and the ratio of the li)#id phase molten
salt and the vapo#r phase molten salt in the poll#ted catalyst& /ere( (a" and (b"
are the carbonate content
$5
/
2
3
i

C
@

4

C
8

C
@


9

8

C
@
2

:
m
a
s
s
6
<
3
i

C
@


9

8

C
@
:
m
a
s
s
6
<
2

3
i

C
@


9

8

C
@




:
m
a
s
s
6
<
/
2
3
i

C
@

4

C
8

C
@


9

8

C
@
:
m
a
s
s
6
<
2

n the poll#ted catalyst( and (c" and (d" are the ratio of the li)#id phase molten
salt and the vapo#r phase molten salt in the poll#ted catalyst( respectively& 1t is
clear that the carbonate content of the catalyst of the cell frame side by @i
plating decreases from that of non'plating& Therefore( the e*ect of @i plating
on the li)#id phase poll#tion is able to be con0rmed& /owever( the
carbonate content of the catalyst of the electrode side has hardly changed
tho#gh @i plating was applied to the corr#gated c#rrent collector& This
reason is that beca#se the catalyst of the electrode side is faced with the
electrode( the path for the molten salt to reach the catalyst layer is di*erent
from the catalyst of the frame side( and there is a possibility that the catalyst
contacts to the electrode& Therefore( the effect of @i plating on the li)#id
phase poll#tion is small& -rom these res#lts( it is clear that the li)#id phase
poll#tion can be controlled by applying @i plating to the corr#gated c#rrent
collector&
=n the other hand( the ratio of the vapo#r phase poll#tion of most catalysts
in the cell is higher than that of the li)#id phase poll#tion by controlling the
li)#id phase poll#tion& ,eca#se the vapo#r phase poll#tion is ca#sed in the
entire cell( the control of the vapo#r phase poll#tion is not easy li+e the li)#id
phase poll#tion& /owever( we el#cidated that the vapo#r phase poll#tion
originates in volatilizing of the molten salt that lea+s from the wet seal part&
Moreover( beca#se this molten salt lea+age from the wet seal part stops within
one wee+ after the operating temperat#re reaches( we #nderstand that the
catalyst poll#tion does not occ#r if this molten salt lea+age can be controlled
(2#gi#ra et al&( ?C4C"&
$5
*a+ non plating Fuel inlet
3ocation o! catalyst *"+ Ei,plating
$5
Fuel inlet
3ocation o! catalyst
3i C@
Frame Electrode 3i C@ Frame Electrode 2
8 C@
2
8 C@ 2 2
3oading methode o! catalysts
$%
Electrode

3oading methode o! catalysts
Electrode

$%
Fuel outlet
5
Fuel outlet
5
%
$ 2 3 4
%
$ 2 3
Cell !rame side
3ocation o! catalyst
2%
Electrode side Cell !rame side
3ocation o! catalyst
Electrode side
2%
*c+ non plating Fuel inlet
3ocation o! catalyst
*d+ Ei plating
Fuel inlet
3ocation o! catalyst
3i%uid phase
;apor phase
3oading methode o! catalysts
Electrode
$%
Fuel outlet
Frame Electrode

3i%uid phase
;apor phase
3oading methode o! catalysts
Electrode
Fuel outlet
Frame Electrode

$5

$%
5 5
%
$ 2 3 4
%
$ 2 3
Cell !rame side Electrode side Cell !rame side Electrode side
3ocation o! catalyst
3ocation o! catalyst
-ig& ?C& E*ect of @i plating on the poll#tion ratio
#. Conclusion
The catalyst poll#tion in D1R'M!-! was el#cidated from the cell test&
The gas chromatograph is pro0table for the eval#ation of D1R'M!-!& The
degradation factor of D1R'M!-! was the catalyst poll#tion by electrolyte( and
the catalyst poll#tion is classified into the li)#id phase poll#tion and the vapo#r
phase poll#tion& The li)#id phase poll#tion is the lea+ed electrolyte from the wet
seal part( and the lea+ed electrolyte flows with the gas s#pplied along the cell
frame and into the catalyst loading area& The gap of the wet seal part grows
when the elasticity of the cor#gated c#rrent collector decreases by the
endothermic reaction of the catalyst( and the lea+age of the molten salt from this
grown gap is promoted( and the reforming catalyst is poll#ted by this lea+ed
molten salt& The catalystic activity of the refrming catalyst decreases by which
the specific s#rface area decrease by adhering the lea+ed electrolyte to the
reforming catalyst& The electrolyte that adheres to the reforming catalyst
cannot be easily removed beca#se the reforming catalyst has a micro pore
str#ct#re& Therefore( beca#se the li)#id phase poll#tion has to be controlled
physically( the catalyst was covered by the nic+el with large contact angle with
the molten salt& The performance of D1R'M!-! was improved #sing the
corr#gated c#rrent collector with @i plating( which repels molten salts&
-rom the vis#alization e%periment( beca#se the electrolyte that poll#ted the
reforming catalyst dispersed from wet seal section( D1R'M!-! can operate
for long time if the reforming catalyst was protected from the electrolyte
g#sh for ; days from the operation' start& Moreover( tho#gh the most of the
volatile matter of anode side was the electrolyte that g#shed from the wet seal
part( the part of volatile matter was K=/ generated as the water generated by
the cell reaction reacts with the electrolyte( and as the generated K=/ ret#rns
to K
?
!=
A
in the region where the concentration rose by the !=
?
generated
by the cell reaction&
.. 'e!erences
Miya+e( F&B @a+anishi( @&B @a+ajima( T&B 1toh( F&B 2aitoh( T&B 2aiai( .& V Fanar#( /&
(455D"& . st#dy on degradation phenomena of reforming catalyst in D1R'
M!-!( ". Chem. Eng. "pn. Gol&?4 (>"( pp&44C6O44C5
2#gi#ra( K& V =hta+e( K& (455D"& Deterioration of a catalyst[s activity by 3i)#id'
phase M!
poisoning in D1R'M!-!( ". Chem. Eng. "pn. Gol&?4 (>"( pp&44;CO44;:
2#gi#ra( K&B @ar#se( 1& V =hta+e( K& (4555" Deterioration of a catalystPs
activity in direct internal reformingmolten carbonate f#el cells (e*ect of
adsorption of vapo#r'phase
molten carbonate"( ". "pn. !oc. &ech. Eng.( 2er&, >D (>?5"( ppAAC'AA>&
2#gi#ra( K&B @iwata( .&B Fama#chi( M& V Tanimoto( K& (?C4C"& 1n$#ence of the
segmented
electrode #se on electrolyte lea+age in molten carbonate f#el cell( EC!
$ransactions 2
>>? Fuel Cell !eminar # E@position, 5olume A, pp&A:D'A5C
2#gi#ra( K&B 2oga( M&B Fama#chi( M& V Tanimoto( K& (?CC:"& Golatilization
behavio#r of
3iM@a carbonate as an electrolyte in M!-!( EC! $ransactions 2 >>B
Fuel Cell
!eminar # E@position, 5olume /, issue /( pp&ADD'A>4
Tanimoto( K&B Fanagida( M&B Kojima(T&B Tamiya( F&B Mats#moto( /& V Miyaza+i( F&
(455:" 3omg'term operation of small'sized single molten carbonate
f#el cells( ". Po,er sources, ;?( pp;;':?&
.
'ecent Strategies in @rganic 'eactions
CatalyFed "y Phase &rans!er Catalysts and
AnalyFed "y Gas Chromatography
<& .& Give+anand and Maw'3ing
7ang
*
Department of
Environmental Engineering, !afety
and )ealth, )ungkuang University,
!halu District, $aichung,
$ai,an
1. Introduction
The 0eld of catalysis provides chemists with new and powerf#l tools for
the e8cient synthesis of comple% organic molec#les& 1t is s#itable for
carrying o#t chemical and biochemical reactions at a high rate in nat#re as
well as in organic synthesis& !atalysis e%pertPs foresee catalysis among
the most promising 0elds of basic research& This methodology can be
applied to solve many f#ndamental( technological( environmental and social
problems that face h#manity& 1t 0nds application in modern chemical
and petrochemical ind#stries& Reactions involving two s#bstances located in
di*erent phases of a reaction mi%t#re are often inhibited d#e to the reagents
inability to come into contact with each other& 1n s#ch reactions( conventional
techni)#es are environmentally and ind#strially #nattractive& @evertheless
these reactions can be s#ccessf#lly promoted by a pop#lar catalysis
methodology viC., phase'transfer catalysis (<T!" #nder mild operating
conditions (2asson V @e#mann(455;B Mahdavi V Tamami( ?CCDB ,arbasiewicz et
al&( ?CC>B 2harma et al&(
?CC>B Dev#lapelli V 7eng( ?CC5B Fang V <eng( ?C4C"& <hase'transfer
catalysts are being combined with enzymes in biotechnological processes
and with transition metals in s#pramolec#lar chemistry and nano technology
(3ancaster( ?CC?"&
!#rrently( this +ey green approach (Ma+osza( ?CCC" is a powerf#l tool in the
man#fact#re of 0ne chemicals and pharmace#ticals (Fadav V ,isht( ?CC6B Fadav
V ,ad#re?CC:"& 1t has been recognized as a convenient and highly #sef#l
synthetic tool in both academia and ind#stry beca#se of several advantages of
<T! viC., operational simplicity( mild reaction conditions with a)#eo#s media(
s#itability for largescale reactions( etc&( which meet the c#rrent
re)#irement of environmental conscio#sness for practical organic synthesis&
This techni)#e aids in the transfer of an ionic species from either an
a)#eo#s or a solid phase into the organic phase where the chemical
reaction ta+es place& 9ndo#btedly( <T! o*ers many s#bstantial advantages
for the practical e%ec#tion of n#mero#s reactions (7ang V Tseng(
?CC?B Fadav( ?CC6B 7ang V 3ee( ?CC;B 7ang V 3ee( ?CC>B 7ang et& al&( ?CCAB
Give+anand V
,ala+rishnan( ?CC5a( ?CC5b( ?CC5c(
?CC5d( ?CC5e"&
*
!orresponding
.#thor
"4 Applications of Gas Chromatography
/ence( <T! is now well recognized as an inval#able methodology for organic
synthesis from two or more immiscible reactants and its scope and
application are the s#bjects of c#rrent research& !onse)#ently( there is an
#ps#rge of interest in the synthesis of many more s#ch catalysts which wo#ld
be highly advantageo#s and may be employed as a vital tool in organic
syntheses& <hase transfer catalysis will be of c#riosity to anyone wor+ing in
academia and ind#stry that needs an #p'to'date critical analysis and s#mmary
of catalysis research and applications& <resently( ingenio#s new analytical and
process e%perimental techni)#es viz&( #ltraso#nd and microwave irradiation
assisted <T! transformations (Mas#no et al&( ?CCDB 7ang V Rajendran( ?CC>B
7ang V Rajendran( ?CC;a( ?CC;bB 7ang V !hen( ?CC:B& 7ang V !hen( ?C4CB
Give+anand V 7ang( ?C44B Fang V 3in( ?C44B !hatti( et al&(
?CC?B #maste et al&( ?CC6B& 3#o et al&( ?CC6B& !hatti et al&( ?CC6B ,ogdal et al&(
?CCDB /ejchman et al&( ?CC:B ,aelen et al&( ?CC:B 2ah# et al&( ?CC5B .wasthi
et al&( ?CC5B reiner et al&( ?CC5B 7ang V <rasad( ?C4CB -iamegos et& al&( ?C4C"
have become immensely pop#lar in promoting vario#s organic reactions&
!hemical +inetics is the st#dy of the reaction rates of chemical reactions ta+ing
into acco#nt their reaction mechanism& !hemical +inetics is the basis of
catalysisB however( catalysis is not a part of the +inetics& Mastering these
reaction rates has many practical applications( for instance in #nderstanding the
comple% dynamics of the atmosphere( in #nderstanding the intricate interplay
of the chemical reactions that are the basis of life and in designing an
ind#strial process& Moreover( +nowledge of +inetics will be helpf#l in developing
theories that can be #sed to predict the o#tcome and rate of reactions&
@ow a days( +inetic investigation of heterogeneo#s catalytic reactions is an
indispensable step of the theoretical and applied investigations on catalysis& 1t
facilitates in el#cidation of the mechanism of a given heterogeneo#s catalytic
reaction and contrib#tes essentially to the revelation of the catalyst behavior
in the co#rse of its synthesis( #tilization and recycles& Their e%amination
assists in modeling and selection of optimal catalysts and optimization of
catalytic reactors& !onse)#ently( the growth of theory and practice in catalysis is
impla#sible witho#t #nfolding e%tensive +inetic investigations&
!atalytic reactions and reaction +inetics are #s#ally monitored #sing well'
established analytical techni)#es s#ch as gas chromatography (!"& -or
determining the +inetics of any reaction( samples were collected from
organic layer at reg#lar intervals( dil#ted with s#itable solvents and 0nally
injected into ! for analysis& Retention time and area of reactants were
obtained from the chromatograph& 9sing the obtained dataPs( rate constants
were eval#ated from the +inetic plot& Th#s( gas chromatography identi0es
compo#nds by chromatography retention time and thereby( ma+ing the
method a highly acc#rate proced#re and an essential method in the
analysis of organic reactions& The analysis of compo#nds by ! is very fast(
acc#rate and reliable& -#rther small samples can be analyzed with high
resol#tion&
.nionic compo#nds( incl#ding anions of organophosphoric acids( carbo%ylic
acids and phenols in a)#eo#s samples can be directly determined by li)#id
chromatography (3!" or ion chromatography& .lternatively( gas chromatography
(!" analysis after e%traction and derivatization is a very practical option&
enerally( these types of ! proced#res are based on the isolation of anionic
analytes from the a)#eo#s samples followed by p#ri0cation( desiccation(
derivatization and analysis by ! (Mi+ia( et al&( 455;"& !apillary electrophoresis
<ecent Strategies in =rganic <eactions Cataly;ed (y
Phase *ransfer Catalysts and Analy;ed (y Gas Chromatography "5
and ion chromatography identify inorganic anions by retention time or
migration time& @evertheless( a sample contaminated with matri% is often
di*ic#lt to analyze&
.nalysis of inorganic anions in foresenic chemistry (2a+ayanagi( et al&(
?CC>"( iodide anion(3in( et al&( ?CCA"( $avonoids(Fiannis( et al&( ?CC6"(
haloacetic acids in drin+ing waters (!ardador( et al&( ?CC:"( phenolic
metabolites in h#man #rine(,ravo( et al&( ?CCD"( phenols(-iamegos( et al&(
?CC:" etc&( have been carried o#t #sing ! #nder <T! conditions&
1n view of the s#ccess and vitality of ! analysis in <T! assisted organic
reactions( we have proposed to present recent happenings in the 0eld of <T!
and to st#dy its applications to vario#s organic reactions that were monitored
by gas chromatography& -#rther( +inetics of vario#s organic reactions catalyzed
by <T! carried o#t #nder a wide range of e%perimental conditions will be
presented& M#ch of o#r c#rrent e*ort is devoted to e%ploring the +inetic aspects
of the reactions( the role of the catalyst str#ct#re( and in$#ence of e%perimental
parameters& The roles of these species in the overall catalytic organic
reactions are investigated so as to #nderstand whether they are mere
spectators or participate in the reaction and how their presence a*ects the
overall reaction +inetics&
Divided into 0ve sections( the chapter e%plores( 2#z#+i'co#pling( epo%idation( !'
al+ylaion( @'al+ylation and ='al+ylation reactions& /elping readers to better
#nderstand the +inetics of the <T! reactions that are analyzed by !( the
e%amples in the chapter s#bstantiates the development of more e*ective <T!
processes achieved d#ring the last few decades( enabling ind#stry to
embar+ on a safer and more e8cient synthesis of organic compo#nds for the
man#fact#re of a wide array of prod#cts&
2. Phase trans!er catalyst assisted organic reactions !ollo1ed "y gas
chromatography
2.1 E,al0ylation
1mide derivatives are organic compo#nds with n#mero#s applications in biology
(3angm#ir et&al&( 455DB 2ettimo et&al&( 455>"as well as in synthetic (=h+#bo(
et al& 455>" and polymer chemistry(1ijima( et al&( 455D"& ! analysis of <T!
assisted +'al+ylation reactions are well doc#mented (Kan+ovic( et al&( ?CC?B
Mijin( et&al&( ?CC6 V Mijin( et&al&( ?CC:"& 2ynthesis of +' b#tylphthalimide (<TR"
can be achieved by reacting 4'bromob#tane and potassi#m salt of phthalimide
in a li)#id (water"Oli)#id (organic solvent" two'phase medi#m catalyzed by
)#aternary ammoni#m salt& @onetheless( the hydration of potassi#m salt of
phthalimide in a)#eo#s sol#tion is serio#s which res#lts in poor yield&
/erein( we disc#ss the +inetics of synthesis of +'b#tylphthalimide (<TR" (2cheme
4" that was analyzed by ! (7ang( et al&( ?CCD"& The +inetic e%periments were
r#n in an ordinary smooth' wall( three'nec+ed flas+( fitted with an agitator(
refl#% condenser and sampling port& .ll ingredients viC., potassi#m
phthalimide(e%cess agent"( T,., and acetonitrile( were placed in the flas+ and
stirred at :CC rpm for abo#t AC min at ;C
C
! (7ang( et al&( ?CCD"& Meas#red
)#antities of n'bromob#tane (limiting agent" and tol#ene (internal standard" were
then added to reactor& The reaction mi%t#re was stirred at :CC rpm& 2amples of
the organic phase were withdrawn at reg#lar time intervals by stopping the
stirrer for 4D'AC sec s#ch that the organic phase had separated well eno#gh to
get a good sample( then analyzed by ! #sing an internal standard method& The
conditions for the ! analysis are as followsI 2himadz# ! 4;.( KV7
=
" Applications of Gas Chromatography
2cienti0c 1nc&( capillary col#mn (db'4 col#mn"B 4CCJ poly(dimethylsilo%ane"
stationary phaseB
4Dm % C&D?Dm col#mn dimensionB carrier gas( nitrogen (>C mlMmin"B flame
ionization detectorB
injection temperat#reI ?DC
C
! (-ig& 4"& .n ali)#ot of reaction mi%t#re (C&D ml" was
injected and
the retention times for acetonitrile( 4'bromob#tane( tol#ene and +'
b#tylphthalimide are presented in Table 4& The str#ct#re of the prod#ct .
was con0rmed thro#gh ! mass spectroscopy(-ig& ?"( which showed a
molec#lar ion pea+ at ?CA (M
X
"&
,
=
8
*:A:>Chloro(en;ene 8
=
=
!% %C. "%%rpm
:r
1 2

2cheme 4& +'al+ylation of potassi#m salt of phthalimide catalyzed by T,., (7ang(

et al&(
?CCD"&
-ig& 4& ! analysis (temperat#re programming" condition for following @'
.l+ylation of potassi#m salt of phthalimide
<ecent Strategies in =rganic <eactions Cataly;ed (y
Phase *ransfer Catalysts and Analy;ed (y Gas Chromatography "!
/n,r0 No So*ven,1Rea+,an,1
In,erna*
S,andard1Produ+,
Retention
Time
(Min&"
4 .cetonitrile 4&6?
? 4',romob#tane A&CA
A Tol#ene A&DC
6 +'(n'b#tyl"phthalimide 4?&;5
Table 4& Determination of retention time for compo#nds in the @'al+ylation
reaction mi%t#re by ! analysis
-ig& ?& !'M2 analysis of +'(n'
b#tyl"phthalimide
2.1.1 'eaction mechanism and 0inetic model
<T! assisted +'al+ylation of potassi#m salt of phthalimide (<TK" with organic
s#bstrate was carried o#t in a solidOli)#id sol#tion (organic solvent" #nder
phase'transfer catalysis conditions (2cheme 4"&The reaction was carried o#t in
the absence of water so as to avoid hydration& =n comparing the reaction
#nder li)#id (organics solvent"'li)#id (water" phase' transfer catalysis
conditions (33'<T!" with solidOli)#id sol#tion (organic solvent" #nder phase'
transfer catalysis conditions (23'<T!"( the later method is advantageo#s
beca#se reaction rate is greatly enhanced and the yield of the prod#ct is
increased& 1n the beginning of the reaction( the active catalyst +'
(tetrab#tylammoni#m" phthalimide (<Td" is prod#ced from the reaction of <TK(
dissolved in organic solvent( with catalyst d,r& The inorganic salt K,r
precipitated as a solid form from the organic'phase sol#tion& Then( <Td
reacts with organic'phase reactant Rc to prod#ce the desired prod#ct <TR
(2cheme ?"&
=rganic
PTd + Kc
(org" (s"
(org" (org"
(org" (s"
?
PTK
(s"
+ dc
(org"
PTK
(org"
+
dc
(org"
(4"
PTK
(org"
+
dc
(org"
D
4
(org" (org"
(?"
PTd
(org"
+
Kc
(org"

D
?
PTd +
Kc
(A"
PTd
(org"
+
Rc
(org"

=

rg

ani

c s

olv

ent

PTR + dc
(6"
2cheme ?& Mechanism for the +'al+ylation of potassi#m salt of phthalimide
catalyzed by
T,.,&
1n the 2cheme ?( dc
(org"
and Rc
(org"
represent the )#aternary ammoni#m salt in
the organic' phase sol#tion and organic'phase reactant (n'bromob#tane"(
respectively& The s#bscripts oorgp and osp denote the species in organic'
phase and in solid'phase( respectively& The overall reaction is e%pressed asI
PTK
(s"
+
Rc
(org"

=

rg

ani

c s

olv

ent

( d

c
PTR + Kc
(D"
.s shown in e) ?( the reaction is fast and reaches e)#ilibri#m in a short
time& Th#s( the e)#ilibri#m constant K
4
is defined asI
mDE n
org
[
P$0
]
org
(>"
D
4

mP$0n
[
0E
] org
org
.s stated( the inorganic salt Kc precipitates from the organic sol#tion and the
e)#ilibri#m constant K
?
is de0ned asI
D
mDE n
s
[DE ]
org
(;"
The rate e)#ation of the intrinsic reaction is given in E)& (6"I
d
[
P$*
]
org
d
[
*E
]
org

dt dt
k
int
[P$0]
org
[*E
]
org
(:"
where k
int
is the intrinsic rate constant& The material balance for the catalyst
is given byI
[0E ]
org (i
[0E ]
org
+
[P$0]
org
(5"
where mdcn
org(i
is the initial concentration of dc& =n solving E)s& (>"( (;" and (5"( we
obtainI
whe
re f
c
is given as
[P$0]
org
f
c
[0E
]
org (i
(4C"
f
c

4
4
[
DE
]
(44"
4 +
s

D
4
D
?
[P$D
]
org
7e ass#me that the concentrations of mKcn
s
and m<T'Kn
org
are +ept at constant
val#es after the ind#ction period of the reaction& Therefore( as shown in E)&
(4C"( m<Tdn
org
is +ept at a constant val#e& -or this( E)& (;" can be e%pressed asI
d
[
*E
]

org

k
dt
app
[*E
]
org
(4?"
where k
app
is the apparent rate constant of the pse#do 0rst'order rate law&
k
app
k
int
[P$0
]
org
k
int
f
c
[0E ]
org
(i
(4A"
E)& (4?" is
integratedI
ln(4 E "
k
app
t
(46"
where E is the conversion of 4'bromob#tane (Rc"( i&e&
m*En
or
g
E 4
(4D"
m*En
org (
i
where mRcn
org(i
is the initial concentration of Rc in the organic'phase sol#tion&
-rom E)& (46"( it is obvio#s that the reaction follows a pse#do 0rst'order rate
law& ,y plotting 'ln(4 ' E" vers#s t( the apparent rate constant k
app
is
obtained e%perimentally from the slope of the straight line&
1n general( the hydration of potassi#m salt of phthalimide in a)#eo#s sol#tion
is a serio#s problem and meager yield of prod#cts were obtained when the
reaction of potassi#m salt of phthalimide and organic s#bstrate was carried o#t
#nder li)#id (organics solvent"Oli)#id (water" phase'transfer catalysis
conditions (33'<T!"& /ence( in this wor+( phase'transfer catalysis was
s#ccessf#lly employed to synthesize +'al+ylphthalimide (<TR" from the
reaction of potassi#m salt of phthalimide (<TK( as e%cess reagent" with
al+ylating agent (R,r( as limiting reagent" in solidOli)#id phase'transfer catalysis
conditions (23'<T!"& 9nder appropriate conditions( a high yield of the
prod#ct was obtained& The prod#ct was s#ccessf#lly separated and
p#ri0ed from the solidOli)#id phase reaction sol#tion& The +inetic res#lts
show a material balance between reactants and prod#cts( i&e&( the
cons#mption of the amo#nt of reactant (n'bromob#tane" e)#als to the s#m of
the generation of the amo#nt of the prod#ct (+'al+ylphthalimide"& -rom !
analysis (-ig&? and Table 4" and +inetic res#lts( no byprod#cts were
observed d#ring or after the reaction system( indicating that only <TR was
prod#ced from the reactant R,r by phase transfer catalysis conditions&
Therefore( the cons#mption of the reactant e)#als the prod#ction of prod#ct&
The +inetics res#lts obtained from the plot of Oln(4'c" vs& time #sing !
analysis #nder vario#s conditions are disc#ssed in the following sections&
2.1.2 In!luence o! stirring speed
The e*ect of agitation speed on the rate of the reaction #nder standard reaction
conditions were investigated by varying the agitation speed in the range of CO
44CC rpm& -rom the plot of 'ln(4'c" vs& time( the apparent rate constants (k
app
"
were eval#ated (-ig& A"& 1t is clear that
the reaction follows the pse#do 0rst'order rate law& The conversion is
increased with the increase in agitation speed #p to 6CC rpm( b#t there is no
signi0cant improvement in the reaction by f#rther increasing the agitation
speed from 6CC to 4(CCC rpm& This phenomenon indicates the less in$#ence of
the e%ternal mass transfer resistance on the reaction beyond
?CC rpm& Therefore( the agitation speed was set at :CC rpm for st#dying
the reaction
phenomena at which the resistance of mass transfer stays at a constant val#e&
7e observed similar trend in the +inetic st#dy of synthesizing 4'(A'
phenylpropyl"pyrrolidine'?(D'dione #nder solid'li)#id phase'transfer catalytic
conditions (7ang V !hen( ?CC:"&
-ig& A& E*ect of stirring speed on the rate of +'al+ylation of <TKI > mmol of <T'K(
C&; mmol of T,.,( DC m3 of acetonitrile( 6 mmol of n'bromob#tane( C&D g of
tol#ene (internal standard"( ;C
C
!& (Reprinted with permission from 7ang( et al&(
?CCD& !opyright (?C44" Elsevier"&
2.1. E!!ect o! di!!erent catalysts
1n this wor+( eight )#aternary ammoni#m salts viC.( T/.,( T,., T=.,( ,TE.,(
d2=
A
( T/.,( T,., and T=., were #sed to e%amine their reactivity& 1n principle(
there is no #niversal r#le to g#ide in selecting an appropriate phase'transfer
catalyst e%cept that determined from e%periments& The reason is that
di*erent reactions need vario#s catalysts to enhance the rate and to promote
the yields& -rom the plot Oln(4'E" vs time( the rate constants were obtained (-ig &
6"& The order of the reactivities of these oni#m salts isI T/.,s T,.,s T=.,s
,TE., s d2=
A
& TE., and d2=
A
(6'(trial+ylammoni#m" propans#ltan"( which
are more hydrophilic( do not possess high reactivity& T/.,( T,., and T=., of
appropriate hydrophilic and hydrophobic properties e%hibit high reactivity to
obtain high conversion of 4'bromob#tane& -#rther( it is favorable for the
reaction in choosing )#aternary ammoni#m salts of larger carbon n#mbers& The
reason is that the lipophilicity is strong #sing the )#aternary ammoni#m salts
of larger carbon n#mber(7ang V Rajendran( ?CC;b( ?CC;cB 7ang V !hen( ?CC:"&
-ig& 6& . plot of 'ln(4'c" of 4'bromob#tane vs. time with different )#aternary
ammoni#m saltsB 6 mmol of 4'bromob#tane( > mmol of phthalimide potassi#m
salt( DC ml of acetonitrile(
C&; mmol of <T!( C&D g of tol#ene (internal standard"( :CC rpm( ;C
C
!&
(Reprinted with permission from 7ang( et al&( ?CCD& !opyright (?C44"
Elsevier"&
2.2 @,al0ylation
1n this wor+( #ltrasonic irradiation assisted synthesis of
dimetho%ydiphenylmethane (DM=D<M" from the reaction of methanol and
dichlorodiphenylmethane (D!D<M" was s#ccessf#lly carried o#t in a li)#id'li)#id
phase'transfer catalytic (33<T!" reaction (2cheme
A" (7ang V !hen( ?CC5"& /ydrolysis of the +etal prod#ct in acidic sol#tion is
avoided by
carrying o#t the reaction in a basic sol#tion& Two major advantages of
carrying o#t the reaction #nder <T! conditions are i" it enhances the reaction
and increases the yield and ii" also minimizes the by prod#cts&
Cl
Cl
2C2
3
=2
2,=2
P*C
?ltrasound &rr9
2
3
C=
=C2
3
2,Cl 22
2
=
#
. /
2cheme A& 2ynthesis of DM=D<M #nder 33<T! conditions(7ang V
!hen( ?CC5"&
The e*ects of the reaction conditions on the conversion of D!D<M( as well as the
apparent rate constant (k
app,/
" of the first reaction in the organic'phase
sol#tion( were investigated in detail& The prod#ct DM=D<M and the reactants
(D!D<M and ethanol" were all identi0ed by !'M2 and @MR and 1R
spectroscopies& The ! mass spectr#m of 2 showed a pea+ at
-ig& D& !'M2 chromatogram of dimetho%ydiphenylmethane(2"&
m=C ??: (M
X
" (-ig&D" Their concentrations (or contents" were analyzed by ! with
!4;. model instr#ment (2himadz#"& The stationary phase was 4CCJ
poly(dimethylsilo%ane"& The carrier gas was @
?
(AC m3Mmin"& The col#mn was db'
4 type&
2.2.1 'eaction mechanism and 0inetic model
7e believe that methanol 0rst dissolves and reacts with K=/ to prod#ce
potassi#m metho%ide (!/
A
=K or Me=K" in the a)#eo#s sol#tion& Then( !/
A
=K
f#rther reacts with T,., catalyst (d,r" to form tetrab#tylammoni#m
methano%ide (Me=d or d=R"( which is an active organic'sol#ble intermediate&
This active intermediate (Me=d" then reacts with D!D<M thro#gh two
se)#ential reaction steps in the organic phase to prod#ce the desired prod#ct(
dimetho%ydiphenylmethane (DM=D<M"& The reaction mechanism of the overall
reaction is e%pressed in 2cheme 6&
A%ueous Phase
2<=2
@ 2,=2
2<=,
@ 22
2
=
2AB
@
2<=,
2<=,
@
2,B
&nterface
@rganic Phase
AB @ C'=0P'
AB @ 0'=0P'
C
$
A=<
@ 0C0P'
C
2
A=< @ C=0P'
2cheme 6& Mechanism of DM=D<M synthesis #nder 33<T!
conditions&
where R=/( R=K( and d=R represent methanol( potassi#m
metho%ide( and tetrab#tylammoni#m methano%ide( respectivelyB !M=D<M
and DM=D<M are the monochloro's#bstit#ted
(chlorometho%ydiphenylmethane" and dichloro'
s#bstit#ted (dimetho%ydiphenylmethane" prod#cts( respectivelyB and dc is the
)#aternary ammoni#m salt( where c can be either chloride or bromide& k
/
and
k

are the two intrinsic rate constants of the organic'phase reactions&
-or a two'phase phase'transfer catalytic reaction( the rate is #s#ally
determined by fo#r steps( i&e&( (a" the ionic a)#eo#s'phase reaction( (b" the
organic'phase reaction( (c" the mass transfer of species d=R (active
intermediate" from the a)#eo#s phase to the organic phase( and (d" the mass
transfer of species of the regenerated catalyst d,r from the organic phase to
the a)#eo#s phase& The mass transfers of species from the a)#eo#s phase to
the organic phase and vice versa are all fast& The ionic a)#eo#s'phase reaction is
also very fast& Therefore( it is obvio#s that the organic'phase reaction( which is
#s#ally slow( is the rate'determining step& The ionic reaction in a)#eo#s sol#tion
is fast& .lso( Me=d formed from the reaction of potassi#m metho%ide and
tetrab#tylammoni#m bromide (T,.," is an organic'sol#ble compo#nd& The
transfer of Me=d from the a)#eo#s phase to the organic phase is also fast&
Therefore( the two se)#ential reactions in the organic phase are the rate'
determining steps for the whole reaction& -rom the ! spectr#m of the
reaction samples( only DM=D<M prod#ct was observed and no !M=D<M was
observed& This fact indicates that the second reaction is faster than the 0rst
one& -ollowing the ,odenstein steady'state ass#mption( the prod#ction rate of
!M=D<M e)#als the cons#mption rate of !M=D<M in the reaction sol#tion& =nce
!M=D<M is prod#ced( it reacts with d=R very )#ic+ly to prod#ce the 0nal
prod#ct DM=D<M in the second reaction of the organic phase& Th#s( the first
reaction in the
?
organic phase is the rate'determining step& .lso( !M=D<M was not observed&
Th#s( the rate of the change of !M=D<M with respect to time was set to be
zero( as shown in E) 4>& !onse)#ently( the 0rst reaction in the organic phase is
the rate'determining step& Th#s( we have
d [C&1DP& ]
org
C
(4>"
dt
where the s#bscript oorgp denotes the species in the organic sol#tion& The
material balances for D!D<M( !M=D<M( and DM=D<M in the organic'phase
sol#tion are
d
[
DCDP&
]
org

dt
d
[
C&1DP&
]
org
k
4
[DCDP& ]
org
[01*]
org
(4;"

dt
k
4
[DCDP& ]
org
[01*]
org
k
?
mC&1DP& n
org
m01*n
org
d [D&1DP&
]
org
k
?
[01*] [C&1DP&]
dt
org org
(4:"
(45"
!ombining e)s& (4>" and (4:" res#lts in(
[
C&1DP&
]


k
4
k
[
DCDP&
]
(?C"
-rom e)s& (4;"( (45" and (?C"(
we get
org
k
?
org
d
[
DCDP&
]
org
d
[
D&1DP&
]
org

(?4"
dt dt
This res#lt indicates that the cons#mption rate of D!D<M e)#als the
prod#ction rate DM=D<M in the organic phase& @o other byprod#cts were
observed d#ring or after the reaction& Therefore( by integrating the e)#ation
after combining E)s 4;( ?C( and ?4( we have
ln(4 E " k
app
t
(??"
where k
app,/
is the apparent rate constant and E is the conversion of D!D<M( i&e&
[
D&1DP&
]org [
DCDP&
]org (i

[
DCDP&
]org
E
(?A"
[DCDP& ]
org (i
[DCDP& ]
org (i
k
app (4
k
4
[01*
]
org
(?6"
where the s#bscript i represents the initial conditions of the species& The rate at
which the reactant D!D<M is cons#med can be calc#lated from E) 4; and the
rate at which the 0nal prod#ct DM=D<M is prod#ced can be calc#lated from
E) 45& ,y applying the pse#do' steady'state approach( the rate of the 0nal
prod#ct (D!D<M " can be calc#lated from E) 4;&
.s shown in E) ??( it is obvio#s that the reaction follows a pse#do'0rst'order rate
law& The
k
app,/
val#es were obtained by plotting the e%perimental data for 'ln(4 ' E" vs.
time (t"& Th#s(
the reaction rate was calc#lated from E) 4;& 9ne%pected prod#cts were
noticed in the absence of K=/ and phase'transfer catalyst& /owever on the
addition of K=/ and <T!( DM=D<M prod#ct was obtained in a small )#antity&
Therefore to enhance the reaction rate greatly( #ltrasonic irradiation was
employed in the reaction& The +inetics res#lts obtained based on ! analysis
(-ig& >" #nder vario#s conditions is disc#ssed in the following sections&
-ig& >& ! analysis (temperat#re programming" condition for following ='
al+ylation
2.2.2 E!!ect o! ultrasonic po1er and !re%uency
To ascertain the in$#ence of vario#s #ltrasonic fre)#encies on the rate of the
two phase reaction of D!D<M and methanol with same o#tp#t power of
ACC 7( the #ltrasonic fre)#ency was varied in the range of ?C'DC +/z #nder
otherwise similar conditions #sing T,., as the catalyst& The +inetic pro0le of
the reaction is obtained by plotting 'ln(4 ' c" vers#s time (-ig& ;"& -rom these
observed res#lts( it can be inferred that #ltrasonic assisted phase'transfer
catalysis significantly increases the rate of the reaction&
-ig& ;3 E*ect of the #ltrasonic fre)#ency on the conversion of D!D<M& !onditionsI
C&??: g of T,.,( 5C mmol of methanol( ?&;D mmol of D!D<M( 6C m3 of
chlorobenzene( D g of K=/( 4C m3 of water( C&4 g of tol#ene( 6CC rpm( >C h! ACC
7& (Reprinted with permission from 7ang
V !hen( ?CC5& !opyright (?C44" .merican !hemical
2ociety"
7itho#t the application of #ltrasonic power to the reaction sol#tion( the
conversion of D!D<M is low& The reaction follows a pse#do'0rst'order rate
law( and the conversion is increased with higher #ltrasonic fre)#ency(
indicating that #ltrasonic waves enhance the n#cleophilic s#bstit#tion& The
chemical e*ects of the #ltraso#nd can be attrib#ted to intense local conditions
generated by cavitational b#bble dynamics( i&e&( the n#cleation( formation(
disappearance( and coalescence of vapor or gas b#bbles in the #ltrasonic field&
/owever( in the phase'transfer catalytic reaction( rate enhancements are
typically d#e to mechanical e*ects( mainly thro#gh an enhancement of mass
transfer& The #se of sonication techni)#es for chemical synthesis has also
attracted considerable interest in recent years( beca#se they can enhance the
selectivity and reactivity( increase the chemical yields( and shorten the
reaction time& 1n addition( there is no decomposition of phase'transfer catalysts
#nder the e%perimental conditions& 1n this wor+( we fo#nd that the k
app,/
val#es with #ltrasonic conditions (#nconventional method" #nder the present
e%perimental conditions are higher than those of the silent conditions
(conventional method" (7ang V Rajendran( ?CC>B 7ang V
Rajendran( ?CC;b( ?CC;cB 7ang and !hen( ?C4CB Give+anand V 7ang( ?C44"&
2imilar increase in rate constant val#es was observed on varying
#ltrasonic power (-ig& :"& The corresponding k
app,/
val#es are shown in
Table ?&
-ig& :3 E*ect of the #ltrasonic power on the conversion of D!D<M& !onditionsI
C&??: g of T,.,( 5C mmol of methanol( ?&;D mmol of D!D<M( 6C m3 of
chlorobenzene( D g of K=/( 4C m3 of water( C&4 g of tol#ene( 6CC rpm( >C h!( 6C
+/z& (Reprinted with permission from
7ang V !hen( ?CC5& !opyright (?C44"
4*,ra"on!+ Po5er #6$ 4CC ?CC ACC 6CC DCC >CC
k
a&&
#789
.
' )!n
:8
$
6&C ;&4 4C&A 4?&6 46&? 4D&?
a' as chromatographic
analysis
Table ?& E*ect of #ltrasonic power on the apparent rate constants (k
app,/
"
for the phase' transfer catalytic reaction of Me=/ and D!D<M
a
2. C,al0ylation
Recently( the +inetics of monoal+ylation of benzyl cyanide with n'bromopropane
(,<" has been st#died #nder phase transfer catalysis (<T!" conditions #sing
a)#eo#s potassi#m hydro%ide as the base and tetrab#tylammoni#m bromide
as phase transfer reagent #nder
#ltrasonic condition (Give+anand V 7ang( ?C44" (2cheme D"& as
chromatography analyzed reaction was carried o#t at DC
C
! #nder pse#do'
0rst'order conditions by employing n' bromopropane as a limiting reactant and
benzyl cyanide as a e%cess agent (-ig& 5"&
-ig& 5& ! !hromatogram of !'al+ylation of benzyl cyanide& .I4'bromopropane
(Retention time N ?&4D min&"B 12ITol#ene (Retention time N 6&6C min&"B
,I!hlorobenzene (Retention time
N >&45 min&"B !I,enzylcyanide (Retention time N 4?&D? min&"B <rod#ctI ?'
<henylvaleronitrile
(Retention time N 46&AD
min&"&
PhC2
2
C8
2
C
3
2
!
:r
C
,=2 > P*C
5%
o
C>?ltrasound
PhC2+C
3
2
!
-C8
D
2cheme D& .l+ylation of benzyl cyanide #nder <T! assisted #ltrasonic
condition&
The +inetic res#lts indicates a material balance between reactant and
prod#cts( i&e&( the cons#mption of the amo#nt of reactant (,<" e)#als to the
s#m of the generation of the amo#nt of the prod#ct (?'phenylvaleronitrile"
#nder #ltrasonic conditions& Th#s( rate of the decrease of n'bromopropane
is consistent with the rate of prod#ction of ?' phenylvaleronitrile&
<se#do'0rst order +inetics was indicated by the linearity of the plot of ' ln(4'c"
vers#s time& The e*ect of vario#s e%perimental parameters on the rate of the
reaction has been st#diedB based on the e%perimental res#lts( an
interfacial mechanism was proposed& 2imilar <T! assisted !'al+ylation
reactions were analyzed by ! #nder vario#s reaction conditions and an
interfacial mechanism was proposed for these al+ylation
reactions(Give+anand and ,ala+rishnan( ?CC5b( ?CC5c"&
2..1 E!!ect o! organic sol)ents
1n this wor+( cyclohe%anone( chlorobenzene( anisole( benzene( cyclohe%ane( were
chosen as organic solvents to investigate their reactivities& -rom the plot of
'ln(4Wc" vers#s time( the rate constants are obtained& .s shown in Table A( the
dielectric constants(F; for these organic solvents are in the order !yclohe%anone
(F N :&? " s !hlorobenzene (F N D&>" s .nisole (F N
6&A" s ,enzene (F N ?&?:" s !yclohe%ane (F N ?&C?"& The order of the reactivity
of the reactions in these si% organic solvents is !yclohe%anone s
!hlorobenzene s .nisole s ,enzene s !yclohe%ane& The dielectric constants
are #s#ally #sed as the main inde% in choosing an appropriate organic
solvent in a <T! systemB i&e&( the reaction rate increases with increasing
dielectric constant of the organic solvent& .s the dielectric constant val#es
of solvents increases( the activity of the n#cleophilic reagent and also the
distance between the bromide atom and the propyl gro#p is increased&
Therefore( the rate of the reaction increases (7ang and !hen( ?CC5 V 7ang et
al&( ?CC5"&
So*ven,"
C0+*ohe;a
ne
<enzen
e
An!"o*
e
Ch*orobenze
ne
C0+*ohe;ano
ne
F
a
?&C? ?&?: 6&A D&> :&?
k
app
#789
:.
'
)!n
:8
$
?&? ?&5 D&; ;&C 5&:
a'Dielectric constant&
Table A& E*ect of the organic solvents on the apparent rate constants (k
app
"
#nder #ltrasonic conditionI ?4&5A L 4C
'?
mol of benzyl cyanide( 4Cg of K=/( ?C
m3 of /
?
=( C&4 g of internal standard (tol#ene"( ?C m3 of solvent( ?4&5> L 4C
'A
mol of n'bromolpropane( C&A g of T,.,(
>CC rpm( DC h!B #nder #ltraso#nd conditions (DC +/z( ACC 7"& (Reprinted with
permission from Give+anand V 7ang( ?C44& !opyright (?C44" Elsevier"&
2.# SuFu0i cross coupling reaction
2#z#+i cross co#pling reaction (Miya#ra and 2#z#+i( 455DB !orbet and Mignani(
?CC>" has been recognized as a powerf#l and convenient tool for the
carbonOcarbon bond forming
methods in the synthesis of pharmace#tical agents( organic materials( as
well as nat#ral prod#cts(Tomori( et al&( ?CCC V Kertesz et al&( ?CCD"& .s a
conse)#ence( a considerable n#mber of homogeno#s palladi#m catalysts have
been #sed to obtain high yields of desired prod#ct&
. good n#mber of 2#z#+i cross co#pling reaction have been realized in organic
solvents beca#se of the sol#bility of typical reaction components li+e aryl( allyl or
benzyl halides and boronic acids as well as their co#pling prod#cts& 1n
recent times( there has been great interest in developing green chemical
reactions that ma+e carbon'carbon bonds #sing water as a solvent and applying
these reactions in academic and ind#strial lab settings(Devea# V Macdonald(
?CC6B 3i( ?CCDB 3i#( et al&( ?CC>"& /ence researchers started do deal with
the co#pling reaction in a)#eo#s two'phase systems (enet et al&( 455D"
with water'sol#ble palladi#m comple%es as catalysts allowing easy
separation of the water phase which contains the palladi#m catalyst and a
strong base to bind the formed hydrogen halide& 1n s#ch biphasic systems(
phase'transfer reagents were added to promote the transport of the water'
sol#ble palladi#m catalyst to the interface of the reactant& Enhancement e*ect
on the reaction rate was observed depending on the str#ct#re of the added
amphiphiles& Th#s co#pling of broad range of aryl halides with organoboron
compo#nds can be readily promoted by #se of a phase transfer catalyst in a
biphasic solvent system (F&&7ang et al&(
?CC; V 2ah# et al&( ?CC5"& 2peci0cally( this proced#re is e8cient for the cross'
co#pling of aryl halides with electron'withdrawing
s#bstit#ents and sterically
demanding s#bstit#ents(Mi#ra et al&( ?CC;"& The phase'transfer catalyst
system e8ciently promotes the cross'co#pling of electronic variation in the aryl
halides&
<aetzold and =ehme (?CCC" reported the palladi#m'catalysed cross
co#pling of 4' iodoanisole with phenylboronic acid in an a)#eo#s sol#tion of
sodi#m carbonate in the presence of different phase transfer catalysts (2cheme
>"& The co#pling reaction of analyzed by 3! (col#mn /< 4B programI ? min
at DC
C
! then 4C
C
!Mmin #p to ?>C
C
!"& as !hromatography analysis
revealed that on increasing concentration of the <T!( the rate of the reaction
was increased and the formation of byprod#cts was s#ppressed&
B
2=
:
=2
<
<D
< <D
PdCl
2
EPhP+C2
2
-
4
S=
3
,F
2
>C*A:
8a
2
C=
3
<D
<D
1? 11
12 1
2cheme >& <alladi#m'catalyzed cross co#pling of iodoanisole with phenylboronic
acid in the presence of <T!&
Majority of <T!Ps gave yields of s5CJ e%cept cetylammoni#m tetra$#oroborate
(Table 6B entry 4" which inhibits the reaction& The amphiphiles with low
hydrophilic lipophilic balance (Table 6B entries ?( D'5" and short chain
amphiphiles (Table 6B entries 4D and 4>" gave lower activities& @ot only( the
cetyltrimethylammoni#m bromide was favored as phase transfer reagent
(Table 6B entry 4C"( b#t also zwitterionic amphiphiles( e&g&(
al+yldimethylammoni#m propane s#lfonates (Table 6B entries A and 46" are
e%cellent promoters& Dependence of anion was observed by a#thors while
tetraal+ylammoni#m salts were employed as <T!Ps (Table 6B entries A( 6( 4C'46"&
1n addition to yield enhancement( the a#thors also reported that in presence of
<T!( the selectivity increases by the s#ppression of formation of the biphenyl
side prod#ct (8."& -#rther the a#thors e%plored the reaction in presence of
s#pported detergents(<aetzold et al&( ?CC6"&
/n,r
0
PTC Y!e*d #=$
No3
29 M!n3 .29 )!n3
4 !etylammoni#m tetra$#roborate ?C 6;
? <olyo%yethylene(4>"methylester !
4?
;6 5D
A A'Dodecyltrimethylammoni#m propane
s#lfonate
:5 56
6 Dodecyltrimethylammoni#m bromide :6 56
D @'3a#royl'alanine( sodi#m salt :D :5
> @'3a#royl'proline( sodi#m salt :6 :5
; <olyo%yethylene(?C"sorbitanmonola#rate ;: ?>
: <olyo%yethylene(>"la#ryl ether >; ;D
5 <olyo%yethylene(4C"la#ryl ether ;C ;:
4C !etyltrimethylammoni#m bromide 5: 55
44 !etyldimethylammoni#m bromide :5 56
4? !etyltrimethylammoni#m tetra$#oroborate ;; 5?
4A !etyltrimethylammoni#m s#lfate ;: 54
46 A'!etyldimethylammoni#m propane s#lfonate 5C 5:
4D Tetra'n'b#tylammoni#m bromide ;A ::
4> ,enzyltrimethylammoni#m bromide ;C :>
4; @o !atalyst >D :D
Table 6& E*ect of a phase'transfer catalyst in a biphasic solvent system on the
2#z#+i cross' co#pling reactions
The co#pling reaction of iodobenzene and phenylboronic acid occ#rs in a)#eo#s
medi#m in presence of palladi#m comple%es and cali%mnnarenes with good
yields(,a#r et al&( ?CC4"& The in$#ence of water sol#ble macrocycles (-ig&4CB 46'
45" on the 2#z#+i reaction was analyzed by gas chromatography& The +inetic
r#ns of aryl'aryl co#pling reactions were stopped at small levels of
conversion to e%cl#de prod#ct inhibition e*ects and the yields were
determined by !& -or comparison p#rpose( control e%periments were carried
o#t #nder identical conditions witho#t addition of any macrocycle (Table D( entry
5"& The initial yields were fo#nd to be 6 to : times higher compared to the
#ncatalyzed reaction& .#thors attrib#ted the observed increase of initial
yields to balance of binding ability of the host molec#le and phase transfer
properties& 1n order to avoid competition of organic solvent with the starting
materials( apart from iodobenzene no additional organic solvent was
employed in the investigation& =f the two bases compared( !s
?
!=
A
was fo#nd to
be s#perior to diisopropylamine& .ll the cali%arenes were fo#nd to be more
s#perior to G'cyclode%trin& The mono's#bstit#ted caly%m6narene 8>( the
macrocyclic system with lowest sol#bility( was fo#nd to be more active than
other tested macrocyclic systems&
46 4D
4> 4;
-ig& 4C& 2tr#ct#re of vario#s
cali%arenes&
4:(nN6"
45(nN>"
HNPr
(
C"
(
Co
.
No <a"e
4 4: (4C mol J" ?&6 ' '
? 45 (4C mol J" ?&5 ' '
A 45 (?D mol J" ?&> ' '
6 4; (4C mol J" D&: :&4 4&4
D 4; (?D mol J" ;&D
> 4> (4C mol J" ?&? D&D C&4
; 4D (4C mol J" A&> 4?&
;
C&4
: 46 (4C mol J" ?&4 A&6 '
5 ' t4&
C
A&? '
/n,r
0
No3
Ma+ro+0+*e #e%u!v3$ Y!e*d #=$
Table D& 2#z#+i co#pling reaction in presence of di*erent
macrocycles&
2.. Epoxidation
The high'additive'val#e epo%ides are e%tensively #sed in ins#lating materials(
adhesives( coating materials( constr#ction materials and electronic parts& D#e
to growing attraction of <T! assisted epo%idation reactions( we e%amined the
epo%idation of dicyclopentadiene (8?" in presence of sodi#m t#ngstate(
phosphoric acid and hydrogen pero%ide #nder phase transfer catalysis
conditions by gas chromatography(7ang et al&( ?CC6"& /igh conversion of
dicyclopentadiene and a trace amo#nt of by'prod#ct were obtained&
The +inetics of the reaction was carried o#t in a 4DC ml three'nec+ed <yre%
$as+( which permitted agitating the sol#tion( inserting thermometer( ta+ing
samples and adding the feed& Known )#antities of sodi#m t#ngstate and
phosphoric acid were completely dissolved in hydrogen pero%ide a)#eo#s
sol#tion for preparing the active catalyst& The sol#tion was p#t into the reactor(
which was s#bmerged into a well'controlled temperat#re water bath within Y
C&4 u!& Then( meas#red )#antities of .li)#at AA> in chloroform(
dicyclopentadiene in chloroform and biphenyl (internal standard" were introd#ced
to the reactor to start the reaction& 2amples were collected from the organic
layer of the mi%t#re (by stopping the stirring for 4CO4D s each time" at
reg#lar time intervals& The samples were analyzed by gas chromatography
(2himadz#( 4;." for the three prod#ctsB 4(?'epo%y'Aa(6(;(;a'tetrahydro'6(;'
methano'indene ((9"( D(>'epo%y'Aa(6(D(>(;(;a'he%ahydro'6(;'methano'
indene ((8" and
4(?(D(>'diepo%y'octahydro'6(;'methano'indene ((("& as chromatography
(!" mass analysis reveals molec#lar ion pea+s at 46: (M
X
" (-ig& 44a" (
46:(M
X
" (-ig& 44b" and 4>6 (M
X
" (-ig& 44c" for compo#nds (9' (8 and ((
respectively& The ! analyzing conditions wereI
!ol#mnI ACm % C&D?Dmm i&d& capillary col#mn containing 4CCJ
poly(dimethylsilo%ane"
1njection temperat#reI
?DC
C
!
!arrier gasI @
?
at a $ow rate of ?C
m3Mmin
El#tion time of reactant . and prod#cts ,( !( DI A&:?( >&>;( ;&?6(
and 5&6A min( respectively
DetectorI flame ionization detector
(-1D"
-ig& 44& !ontin#ed
-ig& 44& !'M2 analysis of (a" 4(?'epo%y'Aa(6(;(;a'tetrahydro'6(;'methano'
indane((9"( (b"
D(>'epo%y'Aa(6(D(>(;(;a'he%ahydro'6(;'methano'indene((8"B(c" 4(?(D(>'diepo%y'
octahydro'6(;'
methano'indene
((("&
1nitially( from the ion e%change reaction (between hydrogen pero%ide(
phosphoric acid( sodi#m t#ngstate and )#aternary ammoni#m salt in the
a)#eo#s phase"( the active catalyst d
A
v<=
6
m7(="(=
?
"
?
n
6
w was generated& 1n
general( there are eight active o%ygen atoms on each molec#le of the active
catalyst d
A
v<=
6
m7(="(=
?
"
?
n
6
w& @evertheless( we ass#me that each time only
one active o%ygen atom of the active catalyst is cons#med in reacting
with dicyclopentadiene in each reaction step& The remaining seven o%ygen
atoms are no longer active and needed for regeneration( i&e&( the molec#lar
form#la of the catalyst after reaction is ass#med to be d
A
v<=
6
m7(="
(=
?
"
?
n
A
m7(="(=
?
"(="nw& Th#s( three prod#cts( which incl#de the epo%idation of
two single'site do#ble bonds and one two'site do#ble bond of
dicyclopentadiene molec#le( are prod#ced& The reaction mechanism is th#s
proposed as shown in 2cheme ;&
48a /=
"2 = 2 P= 2 GP= E/+=-+= -
F
C
a.$
2 4 @
2 2 @
3 4 3 4 2 2 4 @ "8a=2 @ 42
2
=
A%ueous Phase
A
3
GP=
4
E/+=-+=
2
-
2
F
4 @
32Cl
C
a.2
2 GP= E/+=-+= -
H
@ 3ACl
3 4 2 2 4
Inter!ace
A
3
GP=
4
E/+=-+=
2
-
2
F
4
C
a.3
A GP= E/+=-+= - F E/+=-+= -+=-FH @
2
2
=
2
C
AP/=
3 4 2 2 3
C
$
2
C
AP/
A
3
GP=
4
E/+=-+=
2
-
2
F
4 @
@rganic Phase
1D
A
3
GP=
4
E/+=-+=
2
-
2
F
3
E/+=-+=
2
-+=-FH @
2?
=
A
3
GP=
4
E/+=-+=
2
-
2
F
4
@
C
2
1D
A
3
GP=
4
E/+=-+=
2
-
2
F
4 @
C
3
A
3
GP=
4
E/+=-+=
2
-
2
F
3
E/+=-+=
2
-+=-FH @
=
21
A
3
GP=
4
E/+=-+=
2
-
2
F
3
E/+=-+=
2
-+=-FH
@ =
2?
=
A
3
GP=
4
E/+=-+=
2
-
2
F
4 @
=
21
C
4
A
3
GP=
4
E/+=-+=
2
-
2
F
3
E/+=-+=
2
-+=-FH @
=
22
=
22
=
2cheme ;& Mechanism of dicyclopentadienePs epo%idation #nder <T! conditions&
(Reprinted with permission from 7ang( et al&( ?CC6& !opyright (?C44" Taylor and
-rancis"&
where k
a,/
, k
a,
, and +
a(A
are the three a)#eo#s'phase intrinsic rate constants(
k
/
, k

, k
H
, and k
I
are the fo#r organic'phase intrinsic rate constants and k
0P(
and k
d<7=
are the mass transfer coe*icents of the regenerated catalyst
d
A
v<=
6
m7(="(=
?
"
?
n
A
m7(="(=
?
"(="nw and the active catalyst d
A
v<=
6
m7(="
(=
?
"
?
n
6
w( respectively& Th#s( the entire reaction involves the following stepsI
the ion e%change( the comple% reaction in the
a)#eo#s phase(
formation of the active catalyst at the interface between
two phases(
the epo%idation in the organic
phase( and
the mass transfer of active
catalyst&
Th#s based on the e%perimental res#lt( the conversion follows pse#do 0rst'
order rate law( i&e&(
d [DCPDI ]
org
k
dt
app
[DCPDI
]
org
(?D"
where mD!<D1n
org
is the concentration of dicyclopentadiene in the organic
phase& The s#bscript xxorgPP denotes the characteristics of the species in
the organic phase& 1n the beginning of e%periment( we have
t C ([DCPDI ]
org

[DCPDI ]
org(
i
(?>"
The s#bscript xxiPP denotes the characteristics of the species at the initial
condition& =n solving e)#ations (?D" and (?>"( we have
or
g
ln(4 E " k
app
t
(?;"
where k
app
is the apparent rate constant& c is the conversion of dicyclopentadiene(
i&e&(
mDCPDI n
E 4
(?:"
mDCPDI n
org
(i
.ss#ming that the individ#al organic'phase reaction follows pse#do 0rst'order
rate law( we have
d [DCPDI ]
org

dt
(k
4
+ k
?
"m0P(1n
org
mDCPDI
n
org
(?5"
where md<7=n
org
is the concentration of the active catalyst in the organic phase
d<7= (i&e&( d
A
v<=
6
m7(="(=
?
"
?
n
6
w"&
-or a constant concentration of active catalyst in the organic phase( E) (?:" is
red#ced to
k
app
( k
4
+ k
?
"
[0P(1 ]
org
(AC"
.s shown in the above e)#ation( k
app
represents the s#m of two apparent rate
constants of the two primary reactions( which are indicated in the reaction
mechanism& -rom E) (?;"( the apparent rate constant k
app
can be obtained by a
plot of ' ln(4'c" vers#s time&
2...1 E!!ect o! the amount o! Ali%uat /
.s shown in Table >( the apparent rate constant val#e increases sharply with the
increase in the amo#nt of .li)#at AA> only #pto C&5D%4C
A
mol& @evertheless(
the apparent rate constant does not contin#e to increase when the catalyst
loading e%ceeded C&5D%4C
A
mol& 7e attrib#te the aforesaid fact to limited
)#antity of the active catalyst that is generated #sing a limiting amo#nt of
@a
?
7=
6
and /
A
<=
6
&
enerally( only the active catalyst d
A
v<=
6
m7(="(=
?
"
?
n
6
w promotes the
reaction& The prod#ction of the active catalyst from the reaction of
)#aternary ammoni#m salt( sodi#m t#ngstate( hydrogen pero%ide( and
phosphoric acid ta+es place only in a stoichiometric )#antity& The free
sodi#m t#ngstate( phosphoric acid( )#aternary ammoni#m salt and
hydrogen pero%ide do not enhance the reaction& !onse)#ently( increasing the
amo#nt of .li)#at AA> does not enhance the reaction& 7e observed( the
prod#cts ((9$( ((8$ and ((($ being prod#ced when an appropriate amo#nt of
.li)#at AA> was employed& =n the other hand if a small amo#nt of .li)#at AA>
was #sed( only prod#cts ((9$ and #(8$ were prod#ced&
2...2 E!!ect o! the -
2
@
2
Table ; indicates the e*ect of amo#nt of /
?
=
?
on the rate of the reaction& The
rate decreased with the increase in the vol#me of /
?
=
?
& @onetheless( this
variation is not signi0cant& The foremost ca#se is probably that the o%idation of
dicyclopentadiene by free /
?
=
?
ta+es place when a larger vol#me of /
?
=
?
is
employed& The active catalyst distrib#tes between a)#eo#s and organic
phases( and most of the active catalyst is sol#ble in the organic phase&
Therefore( the active catalyst of a slight portion dissolves in the a)#eo#s phase
by increasing
4&C; C&5D C&;; C&D: C&A5 C&?4 C&C: C
?&55 A&4D A&4D 4&>4 4&54 4&4; C&66 C&4?
4&D; 4&;C 4&;C C&:4 C&5> C&D> C&45 C
C&>5 C&;5 C&;5 C&?C C&6? C&?D C C
4&?6 4&64 4&64 C&DD C&:? C&6C C C
the vol#me of /
?
=
?
& /ence( the concentration of the active catalyst in the
organic phase is slightly decreased by increasing the vol#me of hydrogen
pero%ide& The reaction between the active catalyst and the reactant ta+es
place in the organic phase& Th#s( the reaction rate slightly decreased with
the increase in the vol#me of hydrogen pero%ide d#e to low concentration
of active catalyst in the organic phase(7ang and Rajendran( ?CC;a(b V 7ang
and !hen( ?CC:"&
A)oun, of A*!%ua,
..2
; 89
.
#)o*$

4&?6
k
1,app
; 89
(
#)!n
:8
$
?&;5 k
2,app
; 89
(
#)!n
:8
$
4&D4 k
3,app
; 89
(
#)!n
:8
$
C&>A
k
4,app
; 89
(
#)!n
:8
$
4&44
Table >& 1n$#ence of the amo#nt of catalyst on the conversion of
dicyclopentadiene based on
!
analysis
-o*u)e
of
H
(
O
(
#)L$
>D DD 6D AD ?D
k
1,app
; 89
(
#)!n
:
8
$
4&5; ?&4
A
?&?
>
?&;
4
?&A
;
k
2,app
; 89
(
#)!n
:
8
$
4&?A 4&A
D
4&A
5
4&>
4
4&D
A
k
3,app
; 89
(
#)!n
:
8
$
C&DC C&D
;
C&>
A
C&>
;
C&>
? k
4,app
; 89
(
#)!n
:
8
$
C&5C 4&C
6
4&C
6
4&?
?
4&4
4
a'by !
analysis
Table ;& 1n$#ence of the vol#me of hydrogen pero%ide on the
conversion of dicyclopentadiene
a
<revio#sly( we reported (7ang V /#ang( ?CCA" ! analyzed comparison of
epo%idation conversion of olefins #nder phase transfer catalysis conditions&
The res#lts are shown in Table :& 1n =lefins ((.:.@"( the do#ble bond in the
ring is more easily o%idized than that of the terminal one #sing hydrogen
pero%ide as an o%idant& 7e compared the epo%idation res#lts of olefins
((A"( ((?" V (.8" with those of olefins (.B"( (.2" V (.@"& The res#lts
indicates higher conversion of olefins with do#ble bond in five'carbon( si%'
carbon and eight'carbon rings than that of the aliphatic terminal bond&
7ith minim#m steric hindrance( only two hydrogen atoms appear on the
do#ble bond of the ring& =n the other hand( there is larger steric hindrance for
the do#ble bond of the chain end when #sing the large'sized catalyst
(d
A
v<=
6
m7(="=
6
n
6
w"& D#e to this phenomenon( it is di8c#lt for the o%ygen
atom in the active comple% catalyst to combine with the terminal carbon'
carbon do#ble bond&
.s stated previo#sly( the do#ble bond of the ring can easily be epo%idized&
Therefore( conversion of dicyclopentadiene (8?" is larger than that of the
olefins ((."( V ((>"( which have only one do#ble bond in the ring& Three
different prod#cts were obtained from olefin (8?" for the two do#ble bonds
in the ring& 2ince( si%'carbon ring epo%ide is more stable( conversion of olefin
((A" is higher than olefin ((?"& =n comparing the conversion of olefins ((A"(
((?" V (.9"( we fo#nd that the conversion of 4(D' cyclooctadiene (4CCJ"
was the highest and the conversion of cyclohe%ene (5?J" was the lowest& The
reason for this is
that the si%'carbon ring is the most stable( whereas the eight'carbon ring
is the most #nstable&
The conversion of straight chain compo#nds m(.B"( (.2" V (.@"n was m#ch lower
than those of the above reactants m(8?"( ((." ((>"( ((A"( ((?"( V (.8"n&
!omparing the res#lts of (.B" and (.2"( the conversion of 4'he%ene was larger
than that of 4'octene& enerally( the do#ble bonds of the si%'carbon chain have
more chances to be attac+ed by the active catalyst than those of the :'carbon
chain& 1n the case of (.@"( there are two do#ble bonds on the chain end of 4(;'
octadiene& /owever( epo%idation of 4(;'octadiene gave only one prod#ct
beca#se of the short reaction time& @evertheless .is'epo%y prod#ct was
noticed on e%tending the reaction time&
/n,r0 O*eCn Produ+, Conver"!on
a
4
=
;D
2
2#
=
? 5?
2.
2/
=
A
2?
=
21
5:
1D
=
22
=
6
=
5:
22
2C
D
=
5?
2D ?
>
= = =
1
2

4CC
/
=
; ?D
#
.
=
: 4C
2
=
5 ?C
C
D
a as chromatography (2himadz# ! 5. with -1D #sing 4CCJ
poly(dimethylsilo%ane"( capillary col#mn( ACmyC&D?D mm and nitrogen as the carrier
gas"&
Table :& 2tr#ct#ral in$#ence of different ole0ns on their epo%idation #nder <T!
conditions
(7ang V /#ang( ?CCA" analyzed by !
a
& (Reprinted with permission from 7ang
V /#ang(
?CCA& !opyright (?C44"
2pringer"&
. Conclusions
!#rrent chapter describes recent developments and a perspective in
+inetics of phase transfer catalysis assisted organic reactions analyzed
by as !hromatography& The combination of <T! with sonochemistry can also
be an interesting approach for determining e8cient reaction conditions(
provided that <T! remains stable #nder e%pos#re to #ltra' so#nds& Research
reports from leading laboratories that to#ch on all the themes noted herein and
many others are assembled& The topics are organized by 0ve broad gro#pings(
viC., +' al+yaltion( 1'.l+ylation( C'al+ylation( 2#z#+i co#pling and epo%idation&
The @'al+ylation st#dy reveals that the stirring speed has positive in$#ence on
rate of the reaction only #p to
6CC rpm and the favorable )#aternary ammoni#m salt for the reaction will be the
one with
larger carbon n#mbers& 1n the #ltrasonic irradiation assisted synthesis of
dimetho%ydiphenylmethane( higher the #ltrasonic fre)#enzy and power( higher
will be the
rate constant val#es& !'al+ylation st#dy indicates the in$#ence of dielectric
constant val#es
on the rate of the reaction& !'analyzed 2#z#+i co#pling reactions indicates the
application
of <T! in these reactions& Kinetics of epo%idation of dicyclopentadiene shows that
the rate of
the reaction depends only #pto certain amo#nt of catalyst& @evertheless the
vol#me of
hydrogen pero%ide has a negative in$#ence on the rate of the reaction& Th#s(
<T! approach
leads in establishing gen#inely s#stainable chemical ind#strial processes within
the conte%t
of the forthcoming paradigm shift in worldwide prod#ction of highly val#able
s#bstances&
#. Ac0no1ledgments
7e gratef#lly ac+nowledge s#pport of this wor+ by the @ational 2cience !o#ncil(
Taiwan
(@2!"( #nder several
grants&
.. 'e!erences
.wasthi( 2& Rao .& @&(V anesan( K&& (?CC5"& .n environmental'benign
approach for the synthesis of al+ylthiocyanates& "& !ulfur Chem&( Gol&AC(
@o&D( pp&D4AOD4;( 122@I 4;64'
D55A
,aelen( &G&( Maes( ,& 9& 7& (?CC:"& 2t#dy of the microwave'assisted hydrolysis
of nitriles and esters and the implementation of this system in rapid
microwave'assisted <d' catalyzed amination& $etrahedron, 5ol. >6( @o&?A(
pp&D>C6'D>45( 122@I CC6C'6C?C
,arbasiewicz( M&( Marcinia+( K&( V -edorynzs+i( M& (?CC>"& <hase transfer
al+ylation of arylacetonitriles revisited&$etrahedron 'ett. Gol&6;( @o&?A(
pp&A:;4'A:;6( 122@I CC6C'
6CA
5
,a#r( M&( -ran+( M&( 2chatz( K&( V 2childbach( -& (?CC4"&7ater'sol#ble
caly%mnnarenes as receptor molec#les for non'polar s#bstrates and
inverse phase transfer catalysts&
$etrahedron, Gol&D;( @o&A?( pp&>5:D'>554( 122@I
CC6C'6C?C
,ogdal( D&( 3#+asiewicz( M&( <ielichows+i( K&( V ,ednarz( 2& (?CCD"&
Microwave'assisted
epo%idation of simple al+enes in the presence of hydrogen
pero%ide& !ynth. Commun.(Gol&AD( @o&?A( pp&?5;A'?5:A( 122@I CCA5'
;544
,ravo( R&( !altabiano( 3& M&( -ernandez( !&( 2mith( K& D&( allegos( M&( 7hitehead
Kr&( R& D&(
7eerase+era( &( Restrepo( <&( ,ishop( .& M&( <erez( K& K& ( V @eedham( 3&3&(
,arr( D& ,& (?CCD"& d#anti0cation of phenolic metabolites of
environmental chemicals in h#man #rine #sing gas chromatographyO
tandem mass spectrometry and isotope dil#tion )#anti0cation& "
C)*1&A$17* %., Gol&:?C( @o&?( pp&??5'?A>( 122@I 4D;C'
C?A
?
!ardador( M& K&( 2errano( .&( V allego( M& (?CC:"& 2im#ltaneo#s
li)#idOli)#id microe%tractionMmethylation for the determination of
haloacetic acids in drin+ing waters by headspace gas chromatography& "
C)*1&A$17* A., Gol&4?C5( @o&4'?( pp&>4O>5( 122@I CC?4'5>;A
!hatti( 2&( ,ortol#ssi( M&( 3o#py( .&( ,lais( K& !&( ,ogdal( D&( V Majdo#b( M& (?CC?"&
Efficient
synthesis of polyethers from isosorbide by microwave'assisted
phase transfer catalysis& Eur. Poly. ". Gol&A:( @o&5( pp&4:D4'4:>4( 122@I
CC46'ACD;
!hatti( 2&( ,ortol#ssi( M&( ,ogdal( ,lais( D& K& !&( V 3o#py( .& (?CC6"&
Microwave'assisted polycondensation of aliphatic diols of isosorbide
with aliphatic dis#lphonylesters via phase'transfer catalysis& Eur. Poly.".
Gol&6C( @o&A( pp&D>4'D;;( 122@I CC46'ACD;
!orbet( K& <&( Mignani( & (?CC>"& 2elected patented cross'co#pling reaction
technologies&
Chem. *ev., Gol&4C>( @o&;( pp&?>D4'?;4C( 122@I
CCC5'?>>D
Devea#( .& M&( V Macdonald( T& 3& (?CC6"& <ractical synthesis of biaryl
colchicinoids containing AP(6P'catechol ether'based .'rings via
2#z#+i cross'co#pling with ligandless palladi#m in water&
$etrahedron 'ett., Gol&6D( @o&6( pp&:CA':C;( 122@I CC6C'6CA5
Dev#lapelli( G& &( V 7eng( /&2& (?CC5"& 2ynthesis of cinnamyl acetate by solidO
li)#id phase
transfer catalysisI Kinetic st#dy with a batch reactor Catal. Commun.
Gol&4C( @o&4A ( pp&4>A:'4>6?( 122@I 4D>>';A>;
-iamegos( F& !&( Kefala( .&<&( V 2tali+as( !& D& (?CC:"& 1on'pair single'drop
microe%traction vers#s phase'transfer catalytic e%traction for
the gas chromatographic determination of
phenols as tosylated derivatives& " C)*1&A$17* A., Gol&445C( @o&4'?(
pp&66'D4( 122@I CC?4'5>;A
-iamegos( !&( Karatapanis( .&( V 2tali+as( !& D&( (?C4C"& Microwave'assisted
phase'transfer
catalysis for the rapid one'pot methylation and gas chromatographic
determination of phenolics " C)*1&A$17* A., Gol&4?4;( @o&D( pp&>46'
>?4( 122@I CC?4'5>;A
enet( K&<&( 3in)#ist( .&( ,lart( E&( Mo#ries( G&( 2avignac( M&( V Ga#ltier( M& (455D"&
2#z#+i'
type cross co#pling reactions #sing palladi#m'water sol#ble catalyst&
2ynthesis of
f#nctionalized dienes& $etrahedron 'ett., Gol&A>( @o&5( pp&466A '466>(
122@ I CC6C'
6CA5
reiner( 1&( 2ypase#th( -& D&( r#n( .&( Karsai( E&( V Keglevich( && (?CC5"& The role
of phase
transfer catalysis in the microwave'assisted @'benzylation of amides(
imides and
@'heterocycles& 'ett. 1rg.Chem& Gol&>( @o&;( pp&D?5'DA6( 122@I 4D;C'4;:>
#maste( G& K&( Khan( .& K&( ,hawal( ,& M&( V Deshm#+h( .&R& .& 2& (?CC6"&
Microwave assisted phase transfer catalysisI .n e8cient solvent free
method for the synthesis of cyclopropane derivatives& Ind. ". Chem.,
!ec. %., Gol&6A,( @o&?( pp&6?C'6?A( 122@I
CA;>'6>55
/ejchman( E&( Maciejews+a( D&( V 7ols+a( 1& (?CC:"& Microwave'assisted
synthesis of
derivatives of +hellinone #nder phase'transfer catalytic conditions
&onatshefte fuer
Chemie., Gol&4A5( @o&44( pp&4AA;O4A6:( 122@I CC?>'5?6;
1ijima( T&( 2#z#+i( @&( -#+#da( 7&( V Tomoi( M& (455D"&To#ghening of aromatic
diamine'
c#red epo%y resins by modi0cation with @'
phenylmaleimide'styrene'p' hydro%ystyrene terpolymers& Eur. Polym. ".,
Gol&A4( @o&:( pp&;;D';:A( 122@I CC46'
ACD;
Kan+ovic( G&( Mijin( D&Q&( V <etrovic( 2&D& (?CC?"& .l+ylation of @'
s#bstit#ted ?' phenylacetamidesI ,enzylation of @'(6'
nitrophenyl"'?'phenylacetamide&
".!er..Chem.!oc., Gol&>;( @o&>( pp&A;A'A;5( 122@I CAD?'D4A5
Kertesz( M&( !hoi( !& /&( V Fang( 2& (?CCD"& !onj#gated polymers and
aromaticity& Chem.
*ev., Gol&4CD( @o&4C( pp&A66:'A6:4( 122@I CCC5'?>>D
3ancaster( M& (?CC?"& reen !hemistryI .n 1ntrod#ctory Te%t' Royal 2ociety of
!hemistry( pp 445'4??& 122@I C':D6C6'>?C:
3angm#ir( M& E&( Fang( K& R&( Mo#ssa( .& M&( 3a#ra( R&( V 3ecompte( K& .&
(455D"& @ew naphthopyranone based $#orescent thiol probes&
$etrahedron 'ett., Gol&A>( @o&?A( pp&A5:5 'A55?( 122@I CC6C'6CA5
3i( !&K& (?CCD"& =rganic reactions in a)#eo#s media with a foc#s on carbon'
carbon bond
formationsI . decade #pdate& Chem. *ev., Gol&4CD( @o&:( pp&AC5D'A4>>(
122@I CCC5'
?>>D
3in( -& M&( 7#( /& 2&( Ko#( /& 2&( V 3in( 2& K& (?CCA"& /ighly sensitive analysis of
iodide anion
in seaweed as penta$#oropheno%yethyl derivative by capillary
gas chromatography& ". Agric. Food Chem. Gol&D4( @o&6( pp&:>;':;C(
122@I CC?4':D>4
3i#( 3&( Qhang( F&(V cin( ,& (?CC>"& 2ynthesis of biaryls and polyaryls by ligand'
free s#z#+i reaction in a)#eo#s phase& ". 1rg. Chem., Gol&;4( @o&4C(
pp&A556'A55;( 122@I CC??'
A?>A
3#o( !& 3T( K&( !ai( !&( V dT& 7& (?CC6"& . polymer oni#m acting as phase'transfer
catalyst in halogen'e%change $#orination promoted by microwave& ".
Fluor.Chem., Gol&4?D( @o&D( pp&;C4';C6& 122@I CC??'44A5
Mahdavi& /&( V Tamami( ,&(?CCD"& 2ynthesis of ?'nitroalcohols from
epo%ides #sing
)#aternized amino f#nctionalized cross'lin+ed polyacrylamide as a new
polymeric
phase transfer catalyst& *EAC$ FU+C$ P1'J&, Gol& >6( @o&A(
pp&4;5'4:D(& 122@I 4A:4'D46:
Ma+osza( M& (?CCC"& <hase'transfer catalysis& . general green methodology in
organic synthesis& Pure Appl. Chem., Gol&;?( @o&;( pp&4A55'46CA( 122@I
CCAA'6D6D
Mas#no( M&@&( Fo#ng( D&M&( /oep+er( .&!&( 2+epper( !&K&( V Molins+i( T&-&
(?CCD"&
.ddition of !l
?
!I to (W"'1'Menthyl .crylate #nder 2onicationW<hase'
Transfer
!atalysis& E8cient 2ynthesis of (X"' and (W"'(?'
!hlorocyclopropyl"methanol& ". 1rg. Chem.( Gol&;C( @o&4C( pp&64>?'64>D(
122@I CC??'A?>A
Mijin( D&Q&( Kan+ovic( G&( V <etrovic( 2&D& (?CC6"& .l+ylation of @'
s#bstit#ted ?' phenylacetamidesI ,enzylation of @'(6'
chlorophenyl"'?'phenylacetamide& ".!er..Chem.!oc&( Gol&>5( @o&?( pp&:D'
5?( 122@I CAD?'D4A5
Mijin( D&Q&( <rascevici( M&( V <etrovic( 2&D& (?CC:"& ,enzylation of
@'phenyl'?' phenylacetamide #nder microwave irradiation& ".!er..
Chem. !oc., Gol&;A( @o&4C( pp&56D'5DC( 122@I CAD?'D4A5
Mi+ia( .&( Ts#chihashia( /&( Famanob( /&( V Famashita( M& (455;"&
E%tractive penta$#orobenzylation #sing a polymeric phase'transfer
catalystI a convenient one'step pretreatment for gas
chromatographic analysis of anionic compo#nds& .nal& !him& .cta&(
Gol&AD>( @o&?'A( pp&4>D'4;D(& 122@I CCCA'?>;C
Mi#ra( M&( Koi+e( T&( 1shihara( T&( 2a+amoto( 2&( =+ada( M&( =hta( M&( V
Ts#+amoto( 2&'i&
(?CC;"& =ne{pot preparation of #nsymmetrical biaryls via 2#z#+i !ross{
!o#pling reaction of aryl halide #sing phase{transfer catalyst in a
biphasic solvent system& !yn. Commun., 5ol.A;( @o&D( pp&>>;'>;6( 122@
CCA5';544
Miya#ra( @&( 2#z#+i( .& (455D"& <alladi#m'catalyzed cross'co#pling
reactions of organoboron compo#nds& Chem. *ev., Gol&5D( @o&;(
pp&?6D;'?6:A( 122@I CCC5'?>>D
=h+#bo( M&( @ishim#ra( T& ( Kona( /&( /onma( T&( V Morishima( /& (455>"&
<ractical synthesis of indolopyrrolocarbozoles& $etrahedron( Gol&D?(
@o&?6( pp&:C55':44?( 122@I CC6C'6C?C
<aetzold( E&( V =ehme( && (?CCC"& E8cient two'phase 2#z#+i reaction
catalyzed by
palladi#m comple%es with water'sol#ble phosphine ligands and
detergents as
phase transfer reagents& ". &ol. Catal. A8 Chem. 5ol.4D?( @o& 4'
?( pp&>5';>( 122@I 4A:4'44>5
<aetzold( E&( Kovel( 1&( V =ehme( && (?CC6"& 2#z#+i reactions in a)#eo#s m#lti'
phase systems promoted by s#pported detergents& ". &ol. Catal. A8
Chem. 5ol.?46( @o& ?( pp&?64'
?6;( 122@I 4A:4'
44>5
2ah#( K& ,&( /azra( .&( <aira( <&( 2aha( <&( @as+ar& 2&( <aira( R& ( ,anerjee( 2&(
2ah#( @& <&( ,&Mondal( @&( 3#ger( <&( V 7eber( M& (?CC5"& 2ynthesis of
novel benzo%azocino
)#inolini#ms and )#inolones #nder <T! conditions and their application in
2#z#+i cross co#pling reaction for the constr#ction of polyn#clear
heteroaromatics& $etrahedron( Gol&>D( @o&A6( pp&>564O>565( 122@I CC6C'
6C?C
2a+ayanagi( M&( Famada( F&( 2a+abe( !&( 7atanabe( K&( V /arigaya( F&( (?CC>"&
1denti0cation
of inorganic anions by gas chromatographyMmass spectrometry&
Forensic
!ci& Int&( Gol&4D;( @o&?'A( pp&4A6'46A( 122@I
CA;5'C;A:
2asson( F&( V @e#mann( R&(455;"& )and.ook of Phase $ransfer Catalysis( ,lac+ie
.cademic and
<rofessional (!hapman V /all"( 12,@I C;D46C?D:A(
3ondon&
2ettimo( .&Da&( <rimo0ore( &( 2ettimo( -&Da&( 2imorini( -& ( Motta( !&3a&(
Martinelli( .&( V
,oldrine( E. (455>"& 2ynthesis of pyrrolomA(6'cnpyridine derivatives
possessing an
acid gro#p and their in vitro and in vivo eval#ation as aldose red#ctase
inhibitors&
Eur. ". &ed. Chem., Gol&A4( @o&4( pp&65'D:( 122@I
C??A'D?A6
2harma( <&( K#mar( .&( V 2harma( M& (?CC>"& 2ynthesis of 6'm?'(?'methylprop'4'
enylidene"'
?(A'dihydro'4/'benzimidazole'4'yln'4'napthol via azo gro#p
insertion of
dimethylvinylidenecarbene #nder phase transfers catalysis
conditions& Catal.
Commun. 5ol.;( @o&5( pp& >44'>4;& 122@I
4D>>';A>;&
Tomori( /&( -o%( K& M&( V ,#chwald( 2& 3& (?CCC"& .n improved synthesis of
f#nctionalized biphenyl'based phosphine ligands&". 1rg. Chem., Gol&>D(
@o&4;( pp&DAA6'DA64( 122@I
CC??'
A?>A
Give+anand( <& .&( V ,ala+rishnan( T& (?CC5a"& Kinetics of
dichlorocyclopropanation of vinylcyclohe%ane catalyzed by a new
m#lti'site phase transfer catalyst& Cat. Commun., Gol&4C( @o& D(
pp&>:;'>5?( 122@I4D>>';A>;
Give+anand( <& .&( V ,ala+rishnan( T& (?CC5b"& 2#perior catalytic ef0ciency
of a new
m#ltisite phase transfer catalyst in the !'al+ylation of dimedone O .
+inetic st#dy&
Cat. Commun.( Gol&4C( @o&4C( pp&4A;4'4A;D&
122@I4D>>';A>;
Give+anand( <& .&( V ,ala+rishnan( T& (?CC5c"& 2ynthesis and characterization
of a novel
m#lti'site phase transfer catalyst and a +inetic st#dy of the
intramolec#lar cyclopentanation of indene& Appl. Catal. A8 7en.,
Gol&A>6( @o&4'?( pp&?;'A6& 122@I C5?>':>Cc&
Give+anand( <& .&( V ,ala+rishnan( T& (?CC5d"& !atalytic potential
of a new polymeranchored m#ltisite phase tansfer catalyst in the
dichlorocarbene addition to 1ndene& Catal. 'ett., Gol&4A( @o&A'6( pp&D:;'
D5>( 122@I 4C44'A;?c
Give+anand( <& .&( V ,ala+rishnan( T& (?CC5e"& Eval#ation of catalytic e8ciency
of a triple'
site phase transfer catalyst and the +inetics of dichlorocarbene addition
to D'vinyl'
?'norbornene& Cat. Commun., Gol&4C( @o&4D( pp&45>?'45>>(
122@I4D>>';A>;
Give+anand( <&.&( V 7ang( M& 3& (?C44"& 2onocatalyzed synthesis of ?'
phenylvaleronitrile
#nder controlled reaction conditions O . +inetic st#dy& Ultrason.
!onochem., Gol&4:( @o&D ( pp&4?64O4?6:( 122@I 4ADC'64;;
7ang( M&3&( V Tseng( F&/& (?CC?"& <hase'transfer catalytic reaction of dibromo'o'
%ylene and
4'b#tanol in two'phase sol#tion& ". &ol. Catal. A8 Chem., Gol&4;5( @o&4'
?( pp&4;'?>( 122@D 4A:4'44>5
7ang( M&3&( /sieh( F&M&( V !hang( R&F& (?CCA"& Kinetic st#dy of
dichlorocyclopropanation of 4(;'octadiene #nder phase'transfer
catalysis conditions at high al+aline concentration Ind. Eng. Chem.
*es,. Gol&6?( @o&?C( pp&6;C?'6;C;( 122@I C:::'D::D
7ang( M&3&( V /#ang( T&/& (?CCA"& <hase'transfer catalytic epo%idation of
oleins #nder
li)#id'li)#id biphasic conditions& *eact. Dinet. Catal. 'ett., Gol&;:( @o&?(
pp&?;D'?:C(
122@ I C4AA'
4;A>
7ang( M&3&( /#ang& T&/&( V 7#( 7& T& (?CC6"& Kinetic st#dy of the phase transfer
catalytic
epo%idation of dicyclopentadiene in a two'phase medi#m& Chem. Eng.
Comm., 5ol.
454( @o&4( pp&?;'6>( 122@I
CC5:'>66D
7ang( M&3&( !hen( 7&/&( V 7ang( -& 2& (?CCD"& Kinetic st#dy of
synthesizing @'
b#tylphthalimide #nder solid'li)#id phase'transfer catalysis
conditions ". &ol. Catal. A8 Chem., Gol&?A>( @o&4'?( pp&>D';4( 122@D
4A:4'44>5
7ang( M&3&( V 3ee( Q&-& (?CC>"& Kinetic st#dy of synthesizing bisphenol a dially
ether in a phase transfer catalytic reaction& %ull. Chem. !oc. "pn. Gol&;5(
@o&4( pp&:CO:;( 122@I
CCC5'
?>;A
7ang( M& 3&( V Rajendran( G& (?CC>"& . +inetic st#dy of thioether synthesis #nder
in$#ence of #ltraso#nd assisted phase'transfer catalysis conditions& ".
&ol. Catal. A8 Chem., Gol&?66( @o&4'?( pp&?A;O?6A( 122@D 4A:4'44>5
7ang( M&3&( V 3ee( Q&-& (?CC;"& Reaction of 6(6|'bis(chloromethyl"'4(4|'biphenyl
and phenol
in two'phase medi#m via phase'transfer catalysis ". &ol. Catal. A8 Chem.,
Gol&?>6(
@o&4'?( pp&445'4?;( 122@D
4A:4'44>5
7ang( M& 3&( V Rajendran( G& (?CC;a"& 9ltraso#nd assisted phase'
transfer catalytic epo%idation of 4(;'octadiene ' . +inetic st#dy&
Ultrason. !onochem.( Gol&46( @o&4( pp&6>'D6( 122@I4ADC'64;;&
7ang( M& 3&( V Rajendran( G& (?CC;b"& Kinetics for
dichlorocyclopropanation of 4(;' octadiene #nder the in$#ence of
#ltraso#nd assisted phase'transfer catalysis conditions ". &ol. Catal.
A8 Chem., Gol&?;A( @o&4'?( pp&D'4A( 122@D 4A:4'44>5
7ang( M&3&( V Rajendran G& (?CC;c"& Etho%ylation of p'chloronitrobenzene
#sing phase'
transfer catalysts by #ltraso#nd irradiation O . +inetic st#dy& Ultrason.
!onochem.(
Gol&46( @o&A( pp&A>:OA;6(& 122@I 4ADC'64;;
7ang( M& 3&(V !hen( !& K& (?CC:"& Kinetic 2t#dy of 2ynthesizing 4'(A'
<henylpropyl"'
pyrrolidine'?(D'dione #nder 2olid'3i)#id <hase'Transfer !atalysis& 1rg.
Process *es. Dev.( Gol&4?( @o&6( pp& ;6:O;D6( 122@I 4C:A'>4>C
7ang( M& 3&( !hen( !& K&( V 7ang( -& 2& (?CC5"& Kinetic st#dy of synthesizing 4'
phenyl'A'
propyl ether #nder li)#id'li)#id phase'transfer catalytic conditions&
Chem. Eng. Comm., Gol&45>( @o&D( pp&D;AOD5C( 122@I CC5:'>66D
7ang( M&3&( V !hen( 7&/& (?CC5"& Kinetic st#dy of
synthesizing dimetho%ydiphenylmethane #nder phase'transfer
catalysis and #ltrasonic irradiation& Ind. Eng. Chem. *es., 5ol.6:(
@o&A( pp&4A;>'4A:A( 122@I C:::'D::D
7ang( M& 3&(V !hen( !& K& (?C4C"& Kinetic 2t#dy of 2ynthesizing 4'
(A' <henylpropyl"pyrrolidine'?(D'dione #nder 2olid'3i)#id <hase'Transfer
!atalytic !onditions .ssisted by 9ltrasonic 1rradiation& 1rg. Process *es.
Dev. Gol&46( @o&A( pp&;A;';6D( 122@I 4C:A'>4>C
7ang( M& 3&( V <rasad( &2& (?C4C"& Microwave assisted phase'transfer catalytic
etho%ylation
of p'chloronitrobenzene}. +inetic st#dy& ". $ai,an Inst. Chem. Eng.,
Gol&64( @o&4( pp&:4':D( 122@I 4:;>'4C;C&
7ang( F&&( 9eda( M&( 7ang( c&( /an( Q&( V Mar#o+a( K& (?CC;"& !onvenient
preparation of chiral phase'transfer catalysts with conformationally
0%ed biphenyl core for catalytic asymmetric synthesis of i'
al+yl' and i(i'dial+yl'a'amino acidsI application to the short
asymmetric synthesis of ,1RT'A;;& $etrahedron,Gol& >A( @o&?>(
pp&>C6?'>CDC( 122@I CC6C'6C?C&
Fadav( & D&( V ,isht( <& M& (?CC6"& @ovelties of microwave assisted li)#idO
li)#id phase transfer catalysis in enhancement of rates and
selectivities in al+ylation of phenols #nder mild conditions& Catal.
Commun. Gol&D( @o& ( pp&?D5O?>A( 122@I
4D>>';A>;
Fadav( & D&( (?CC6"& 1nsight into green phase transfer catalysis& $op. Catal.
Gol&?5( @o&A'6(
pp&46D'4>4( 122@I 4C??'DD?:
Fadav( & D&( V ,ad#re( =& G& (?CC:"& 2elective engineering in ='al+ylation of m'
cresol with
benzyl chloride #sing li)#idOli)#idOli)#id phase transfer catalysis. ". &ol.
Catal. A8 Chem. Gol&?::( @o&4'?( pp&AA'64& 122@D 4A:4'44>5
Fang( /&M&( V <eng( &F& (?C4C"& 9ltraso#nd'assisted third'li)#id phase'transfer
catalyzed
esterification of sodi#m salicylate in a contin#o#s two'phase'$ow
reactor&
Ultrason.!onochem., Gol&4;( @o&4( pp&?A5O?6D( 122@I 4ADC'64;;&
Fang( /&M&( V 3in( D&7& (?C44"& Third'li)#id phase'transfer catalyzed
esteri0cation of sodi#m benzoate with novel d#al'site phase'transfer
catalyst #nder #ltrasonic irradiation& Catal. Commun., Gol&46( @o&4(
pp&4C4'4C>& 122@I4D>>';A>;
Fiannis( !& -&( @anos( !& &( Gervoort( K&( V 2tali+as( !& D& (?CC6"& .nalytical
proced#re for the in'vial derivatization}e%traction of phenolic
acids and $avonoids in methanolic and a)#eo#s plant e%tracts
followed by gas chromatography with mass'selective detection& "
C)*1&A$17* A., Gol&4C64( @o&4'?( pp&44O4:( 122@I
CC?4'5>;A
/
P@P and PA- in 7iFerte 3agoon9 &unisia
Trabelsi 2o#ad( ,en .me#r 7alid( Dero#iche
.bde+ader( !hei+h Mohamed and Driss
Mohamed Ridha 'a.oratory of
Environmental Analytical Chemistry, Faculty
of !ciences, %iCerte, :arCouna,
$unisia
1. Introduction
as chromatography is the most recent branch of chromatography and
incl#des all the chromatography processes in which the s#bstance to be
analyzed occ#rs in the gaseo#s or vapor state or can be converted into
s#ch a state& .ltho#gh the 0rst records of gas chromatography go bac+
h#ndreds of years (,ayer( 45D5"( its tr#e history began d#ring 7orld 7ar 11
when a large ind#strial chemical company instit#ted a crash its development
(Tietz( 45;C"& The 0rst p#blished wor+ appeared in the early 45DCzs based on the
s#ccessf#l e%periments by Kames and Martin (45D?"& 1n the years between
45D? and 45D> the early apparat#s came into sight& The s#ccess of gas
chromatography is d#e to its simplicity of operation( high separation power
and speed& 1ts #se involves versatile applications not only to the 0eld of
chemistry b#t also biology( medicine( ind#strial research and control(
environmental health and scienti0c st#dies&
1n the 0eld of environmental control the #se of gas chromatography has
allowed specific separations and meas#rements of to%ic compo#nds on a large
variety of matrices& .mong these hazards( persistent organic poll#tants (<=<s"
are carbon'based organic compo#nds and mi%t#res with to%icity and
environmental persistence that incl#de ind#strial prod#cts and byprod#cts&
<=<s can be transported far from their sites of release by environmental
media to previo#sly pristine locations s#ch as the .rctic& 3ow <=< levels might be
increased by biomagni0cation thro#gh the transmission process in the food
chain& They can be easily acc#m#lated in the organism to levels that can
potentially inj#re h#man health as well as the environment (,irnba#m( 4556B
/ansen( 455:"& There are 4? s#bstances or s#bstance gro#ps prioritized for
global action in the recently signed 2toc+holm !onvention on <ersistent
=rganic <oll#tants( developed #nder the a#spices of the 9nited @ations
Environment <rogramme (9@E<"&
The 4? s#bstances( the xxdirty dozen(PP consist of eight +inds of pesticides(
incl#ding dieldrin( aldrin( endrin( chlordane( heptachlor( DDT( to%aphene(
mire%( two +inds of ind#strial chemicals mpolychlorinated biphenyls (<!,s" and
he%achlorobenzene (/!,"n( and two +inds of byprod#cts (polychlorinated
dibenzof#rans and polychlorinated dibenzo'p'dio%ins" (2toc+holm !onvention
on <ersistent =rganic <oll#tants( ?CC4"& There are fo#r characteristic parameters
(persistence( bioacc#m#lation( to%icity( and long'range environmental
transport"( which can disting#ish <=<s from a m#ltit#de of other organic
chemicals& .ll 4?
$$" Applications of Gas Chromatography
prioritized <=<s or their brea+down prod#cts ran+ high to e%treme on
meas#rements of these parameters& Reprod#ctive( developmental( behavioral(
ne#rological( endocrine( and imm#ne adverse health e*ects on people have
been lin+ed to <=<s& <=< poll#tion has to#ched every region in the world&
M#ch attention is given to <=< contamination problems( and strong action has
been ta+en by most developed and developing nations&
.mong organic poll#tants( polycyclic aromatic hydrocarbons (<./s" are
the most #bi)#ito#s and constit#te a major gro#p of marine environmental
contaminants& <./ show a mar+ed hydrophobic character( resistance to
biodegradation (@e*( 45;5" and adverse e*ects on health (carcinogenic andMor
m#tagenic activity" (2ingh et al&( 455:" and ecosystem (3ong et al&( 455D"& The
carcinogenic properties of some compo#nds( co#pled with the stability of
<./s d#ring their atmospheric and a)#atic transport( and their widespread
occ#rrence have( in recent years( generated interest in st#dying their so#rces(
distrib#tion( transport mechanisms( environmental impact and fate
(,o#lo#bassi V 2aliot( 455A"& Moreover( <./s are )#ic+ly adsorbed onto
s#spended partic#late& These 0ndings prompted 92 E<. to incl#de 4> <./s
within a priority poll#tant list& Therefore( g#idelines were proposed in order to
assist the management of poll#ted sediments (2warz( 4555"& <./s of coastal
sediments are d#e to both anthropogenic and nat#ral so#rces (@R!( 45:D"&
.mong anthropogenic factors( petrogenic and pyrolytic so#rces are the most
important& .ltho#gh somewhat controversial( the aromatisation of cyclic
compo#nds co#ld be a f#rther so#rce of <./s (3a-lamme V /ites( 45;:"&
<erylene is a good e%ample of a <./ s#bstance of biological origin fo#nd in
both marine and freshwater sediments (3a-lamme V /ites(
45;:
"&
.gain( <./s from pyrolytic and petrogenic so#rces e%hibit different chemical
behavio#r and distrib#tion in marine sediments& 1n partic#lar( <./s from pyrolytic
processes are more strongly associated with sediments and m#ch more
resistant to microbial degradation than <./s of petrogenic origin (#stafsson et
al&( 455;"&
The ,izerte lagoon is located in the northernmost part of T#nisia( between
latit#des @hA; C:P and @hA; 4>P and consists of a depression having a
s#rface area of abo#t 4DC +m? and ma%im#m depth of 4? m& This lagoon is
+nown for its geostrategic position since it lin+s the Mediterranean 2ea to an
internal la+e (1ch+e#l"( which is classi0ed as a national par+ and world heritage&
Many decades ago( the lagoon is +nown as a 0shery and a)#ac#lt#re par+
related to the presence of three mytilic#lt#re sectors especially Menzel Kemil
par+ which is the most prod#ctive site& Many years ago( the lagoonPs ban+s
were s#bjected to both #rbanization and ind#strialization& Man#fact#ring
facilities s#ch as iron and steel comple%( the naval constr#ction and tyre
prod#ction( #rban wastewater and open'd#mping'type m#nicipal or ind#strial
solid waste land0lls scattered aro#nd the lagoon co#ld have led to ecological
pert#rbation of this fragile environment&
Two previo#s preliminary st#dies showed that s#per0cial coastal sediments
from ,izerte lagoon were moderately contaminated by <!, (Dero#iche et al&(
?CC6" and <./ (Trabelsi V Driss( ?CCD"& 1n order to perform the c#rrent
contamination stat#s in the st#dy area data compilation and reporting together
with data for <=! contamination are the 0nal steps for a comprehensive s#rvey
of ,izerte lagoon for the levels of organic contaminants( and represent
an attempt to #nderstand the effects of the agric#lt#ral and ind#strial
chemical
/lima
7adi
$$# P=P and PA2 in :i;erte 4agoon. *unisia
poll#tion& .s a res#lt( the following interpretation and disc#ssion will be foc#sed
on the 4D organochlorine pesticides( ?C <!,s and ?C <./s in sediment&
.dditionally( data for combination of m#ltivariate approaches were applied in
order to identify possible inp#t so#rces&
2. (aterials and methods
2.1 Sampling
2ediment samples from ,izerte lagoon were collected in December ?CC4 #sing
a Gan Geen grap& The 0rst top centimetre (DCCg" was placed in an al#mini#m
container and frozen on dry ice( then transferred to the laboratory with no
e%pos#re to light& -ifteen sampling stations in coastal and central areas in the
lagoon are shown in -ig&4&
5hDCP
,izert
e
5hD
D
Mediterranean 2ea
Merazig
7adi
?
44
4
Menzel
.bderahme
n
4C
A;h4CP
Menzel
Kemil
5
Tinja
7adi
A
6
4? 4A 46 4D
:
#eniche
7adi
A;hC
Menzel
,o#rg#iba
N
D
7m
>
;
are+ 7adi
0 2 , ,en /assin 7adi
-ig& 4& 2t#dy area and sampling stations
2.2 Grain siFe and &@C determinations
The fraction of the sediment having a grain size f>A m (siltXclayNpelite" was
determined gravimetrically after wet sieving& . representative s#b'sample was
ta+en for organic carbon (T=!" determination( according to the revised 7al+lyO
,lac+ titration method cond#cted in accordance with cla#se A of ,2 4A;;I <art
A (,21( 455C"& ,rie$y( ?g dried sediments were treated with 4Cm3 of 4&CCC@
potassi#m dichromate followed by the rapid addition of ?C m3 of concentrated
/
?
2=
6
containing C&Dg silver s#lphate( to precipitate chloride ions& 2amples were
allowed to cool #niformly to room temperat#re for ACmin (at ?Ch!"( then the
mi%t#re was dil#ted by ?CCm3 of do#ble'distilled water( and 4Cm3 of
phosphoric acid was added& -inally( the e%tra dichromate was bac+ titrated with
iron (11" s#lphate sol#tion #sing bari#m diphenylamine s#lphonate as an indicator&
2. Instrumental
d#antitative analyses of <./s( <!,s and =!<s in sediments were
accomplished by an .gilent >:5C . gas chromatography (!"& The col#mn #sed
for analysis of <!,s and =!<s was f#sed silica capillary <TE'D (AC m% C&A? Em
thic+ness"& The operating conditions were as followsI 1njector temperat#re
?DCh!B detector ACCh!B oven temperat#reI initial DCh! for ? min(
programmed to 4>Ch! at Dh!Mmin( followed at ?h!Mmin to ?>Ch! for 4C minB
carrier gasI heli#m at a $ow rate (constant $ow" of 4&D m3MminB detector ma+e'
#p gas was nitrogen at a flow rate of >C m3MminB sample injection vol#me ?ElB
injection modeI splitless for 4 min&
<./s separation was accomplished by a /<4 f#sed silica col#mn (ACm length
C&A?mm i&d&(
C&?Dm film thic+ness" and $ame ionisation detector (-1D"& The oven temperat#re
was held at DCh! for 4min( then programmed at ?Ch!Mmin to 4DCh! then at
:h!Mmin to ?:Ch! and held at ?:Ch! for 4D min& The injector was maintained
at ?:Ch! and the detector at ACCh!& /eli#m was #sed as the carrier gas&
2.# Standards
Twenty <./ compo#nds were analysed in this st#dy( incl#ding si%teen 92 E<.
priority <./s (naphthalene (@aph"( acenaphthylene (.ct"( acenaphthene
(.ce"( fl#orene (-l"( phenanthrene (<he"( anthracene (.n"( $#oranthene (-t"(
pyrene (<y"( benzomananthracene (,manan"( chrysene (!hy"(
benzom+n$#oranthene (,m+nft"( benzombn$#oranthene (,mbnft"( benzomanpyrene
(,manpy"( indeno m4(?(A'cdnpyrene (1nd"( dibenzoma(hnanthracene (Dma(hn an" and
benzomghin perylene (,mghinpe" (55J( 2#pelco"( perylene (55J" and three
al+ylatyed <./s [?'methyl'anthracene (55J"( 5'methyl'anthracene (5;J" and 4'
methyl'phenanthrene" (55J"] from Kansen !hemica&
. mi%ed <!, standard reference material (2RM 465A" from the @ational
1nstit#te of 2tandard and Technology (92." was #sed for and containing <!,:(
<!,4:( <!,?:( <!,66( <!,D?( <!,>>( <!,;;( <!,4C4( <!,4CD( <!,44:(
<!,4?>( <!,4?:( <!,4A:( <!,4DA( <!,4;C( <!,4:C( <!,4:;( <!,45D(
<!,?C> and <!,?C5 in 19<.! n#mber&
The standard reference material 2RM ??>4( obtained from @ational 1nstit#te of
standards and Technology( was #sed to )#antify the 4D e%aminated
organochlorine pesticidesI /!,( lindane( /eptachlor( aldrine(
heptachlorepo%yde( o(pP'DDE( cis'chlordane( trans'nonachlor( dieldrine( p(pP'
DDE( o(pP'DDD( p(pP'DDD( o(pP'DDT( p(pP'DDT and mire%&
2.. Analytical procedure
The analytical proced#re #sed for <./s follows the modi0ed method described by
Kelly et al& (?CCC"& ,riefly( ?Cg of dried sediments were e%tracted #sing al+aline
saponi0cation with K=/MMe=/ (?@( 4CCm3"& Digests were filtered and
e%tracted with n'he%ane( and dried over previo#sly roasted @a
?
2=
6
& .fter
s#lph#r removal by activated copper( the sol#tion was red#ced to ?m3 and
dropped into a col#mn (i&d& N 4Cmm"( sl#rry pac+ed with ?g of activated silica
gel >C( then el#ted with a se)#ence of 4Dm3 he%ane (fraction 4'discarded"
and ACm3 of he%aneI dichloromethane (5I4B fraction ?" which contained the
<./s& The el#ate was concentrated to C&Dm3 in a micro'K#derna'Danish
evaporator #nder a gentle stream of nitrogen&
<./s were identi0ed and )#anti0ed by comparison with +nown standards
injected #nder the same conditions& !erti0ed standard reference marine
sediment (E!';( @ational 7ater Research 1nstit#te( !anada" was #sed in the
eval#ation of the analytical method& The mean recovery of certi0ed <./s in the
e%tract was :>J& The detection limit of each <./ has an average of abo#t C&CA
ngg'4 for the sediment samples&
The analytical proced#re of =!<s and <!,s in sediments is a modi0cation of the
method described by Montone et al& (?CC4"& ,rie$y( AC g of dried sediment
were e%tracted with ACC m3 of n'he%ane in a 2o%hlet apparat#s for 4? h&
.ctivated copper treatment and s#lph#ric acid clean'#p proced#res were
employed to remove elemental s#lph#r and other interfering materials& The
sample e%tracts were f#rther p#ri0ed in a col#mn (i&d&N 4C mm"( sl#rry
pac+ed with D g of florisil and then el#ted with a se)#ence of 6C m3
he%ane (fraction contained =!<s" and 6C m3 of he%aneI dichloromethane
(5I4B fraction ?" which contained the <!,s& Each fraction was concentrated to 4
m3 in a micro'K#derna'Danish evaporator #nder a gentle stream of nitrogen&
The whole analytical proced#re was validated by analysing E!'A sediment
reference materials from @ational 7ater Research 1nstit#te (!anada"& The
recoveries of st#died <!,s in the e%tract #sing the same methodology
weres5CJ& The identi0cation of compo#nds was ded#ced from their retention
times and )#antification was based on pea+ area meas#rement as well
comparison with responses of the mi%ed <!,s standard reference material
(2RM
465A
"&
. 'esults and discussion
.1 Sediment characteristics
Di*erent opinions e%ist regarding the relation between <=<s
concentration and characteristics of sediments& 2everal a#thors have
observed that organochlorines and <./ in the sediments are mainly associated
with the organic matter (@e*( 45;5B Knezovich et al&(
45:;B Doong et al&( ?CC?"( and their total content depends on grain size
distrib#tion (3aw V
.ndr#lewicz( 45:AB Doong et al&(
?CC?"&
T=! contents ranged from C&?AJ to ?&5DJ in the st#dy area (Table4"&
=rganic matter contents of sediments appear especially high (s AJ of dry
weight" in the central zone of the lagoon and are relatively low in the peripheral
zones (f4J"& 2ediments from stations 6 and D which are adjacent to area of
Menzel ,o#rg#iba city (abo#t 4CCCCC habitants"( +nown by its big #rban and
ind#strial activities( seem to be especially rich in organic matter (s4&DJ"& This
also seems to be tr#e for the ,izerte and neighbo#ring cities& This 0nding co#ld
be e%plained by the massive discharge (before 455;" of raw m#nicipal
andMor ind#strial wastewater before implantation of wastewater plants in
these cities& The mo#ths of #enniche and are+ wadis are mar+ed by a low
deposit of organic matter (fC&DJ"&
The pelite (fraction of the sediment having a grain size f>A m (siltXclay"" is
given in Table4& The samples from ,izerte lagoon show large variations in
sediments type( from very coarse (D J are f >Am at station 4" to very 0ne
grained (:C J are f >Am in the central zone of the lagoon"& 3ow pelite content
(44J" was also fo#nd in sandy sediments from the eastern part (station 5"& 1n
mo#ths of #enniche( ,en /assin and are+ wadis( the sediments were less
0ne'grained with pelite varying from ?4 to A; J of dry sediment&
The major part of ,izerte lagoon basin is a depocenter of 0ne grey m#d generally
sat#rated with sodi#m ions (sodic clays" having a high cation e%change
capacity e%ceeding 4C me)M4CCg dry sediment (/amdi et al&( ?CC?"& /owever(
a sandy environment( mainly in the so#thern part where coarse sediments are
mi%ed with shell debris( characterizes the near' shoreline conto#r&
The +inetic behavior of hydrophobic organic poll#tants is m#ch in$#enced by
organic carbon contents in sediments and soils (Karic+ho* et al( 45;5"&
=#r st#dy shows that the concentrations of ~DDT and ~<=!( in sediments
from ,izerte lagoon are correlated well with T=! contents (r N C&DDA( p f C&CD"(
which is possibly d#e to the less lipophilic and more volatile nat#re of /!/s
relative to the DDTs&
!orrelation analysis shows negative correlations between total <./s
contentsMT=! contents and the peliteM<./ levels& These res#lts indicate that the
observed distrib#tion of <./s was not governed by sedimentary
characteristics s#ch as T=! contents and the fraction of pelite (grain size
less than >Am"( b#t( it might be d#e to the localised so#rce inp#ts&
/owever( positive and signi0cant #s#al correlations (R
?
NC&;C" were
observed between the sediment contents of fine fraction and those of T=!
contents (Kohnson( 45:>"& 1ndeed this association between 0ne matter and the
organic particles is especially d#e to a common phenomenon in Mediterranean
lagoons called $occ#lation (.loisi et al&( 45;D"&
.2 PA- Composition source identi!ication and ecotoxicological concerns
The distrib#tion of vario#s <./ in the sediments from 4D sampling stations
reveals a wide range of $#ct#ations( as delineated in Table 4&Twenty
individ#al <./s were determined which comprising two to si% ring( with
three al+yl's#bstit#ted homolog#es& Total <./s concentrations ranged from ?C
at station 4D to 665 ngg
'4
dry weight at station
D with a mean average of 4:A ngg'4 dry wt& The lower concentrations were
detected in the middle part of the lagoon and the eastern zone which is
characterized by an agric#lt#ral activity and where several wadis flow directly
into the lagoon& The highest contents are fo#nd at stations 4( ?( 6( D( > and
44 where an intensive #rban andMor ind#strial activities were carried o#t&
!ertain diagnostic ratios have been widely #sed in order to identify and
)#antify the contrib#tion of each so#rces of <./ contamination& The reported
approaches sho#ld be treated with ca#tion&
2tation
s <./ 4 ? A 6 D > ; : 5 4C 44 4? 4A 46 4D
@a
ph
D&6? A A&?
>
A&66 4C&C
?
nd A&A 5&D
6
nd 4?&:
?
>&>5 ?&46 nd @d nd
.ce C&?: C&;; C&:
5
C&:: C&?6 nd A&?
5
6&>
D
C&?; C&66 C&?> C&6? C&5
A
?&D
;
nd
.ct nd nd nd nd 4(6D nd nd nd nd nd nd nd nd @d nd
-l nd nd nd nd ;(: nd nd nd nd nd nd nd nd @d nd
?'me'
.n
C&C: C&4? C&4
:
C&D C&4 C&A? C&4
D
C&C
;
nd C&CD C&4? nd nd @d nd
4'mb'
<he
C&;A 4&:; A nd 4&54 4 &
5:
nd C&A
>
C&A> nd nd nd nd @d nd
5'me'
.n
C&C: C&C5 C&C
:
4&6 C&C> nd nd @d nd nd C&; C&C; nd @d nd
<he AC&:
D
45&5
;
?>&>
4
?;&4 D6&>
6
nd nd @d 4A&5
A
?;&4
5
4A&C
:
?5&5
>
??&;
4
AC&:
4
;&5
5
.n ?&: nd ;&;
?
4A&;
?
AC&>
:
6D&6
:
4>&C
D
?C&>
A
A&65 >&6 4&;D nd nd ?&5 nd
-t 66&? 5>&6
:
nd ;C&C
5
6D&:
>
65&;
;
?C&4
>
A>&;
:
44&?
A
4;&A
6
?>&A
;
??&A
?
4:&5
>
45&C
:
:&>
> <y 54&5
5
>6&A
;
?4&
;
AA&;4;>&C
>
nd nd @d 46&4 5&D4 ?>&:
5
45&D
?
4;&>
;
@d nd
,(a"
an
A:&6
;
>D&>
D
nd nd AA&C
6
nd nd @d nd nd nd 5&;:4>&D
A
;&5
>
nd
!hy ?;&: D?&C
:
nd 46C&5
6
nd A6&>
:
nd @d ;?&;
:
nd 4C>&6
5
44&D
?
4C&6
6
5&?
?
nd
,(b"
ft
A?&A
A
?&6A nd :&;? nd A4&;
6
nd @d nd A6(: 6:&;
;
44&? nd @d A&;>
,(+"
-t
nd nd nd >C&;
A
nd nd nd @d nd nd 6&4> nd nd @d nd
,(a"
py
?C&4
:
D4&>A5&D
>
A>&>
;
AD&D
6
nd 4A&C
A
@d nd 4:&5
>
nd ?C&:
>
nd @d nd
<er C&CD C&CD nd C&C: nd C&>: nd C&C
>
nd nd C&?: C&C5 C&C
;
C&C
>
nd
1nd nd A>&;
D
nd nd 6?&A
4
nd nd @d nd nd nd nd nd @d nd
D(a(h"
an
nd nd nd nd A&44 nd nd @d nd 4A&>
4
nd nd nd @d nd
,(ghi"
pe
nd nd nd nd >&66 nd nd @d nd nd nd nd nd @d nd
Tot
<./
?5D&?
>
6?4&?
A
4CAA5;&5
;
665&?
>
4>6&>
D
DD&5
:
;?&C
5
44>&4
>
464&4
?
?AD&D
>
4?;&:
:
:;&A
4
;?&
>
?C&6
4
=!
(J"
C&A 4&:D 4&5
4
4&:; 4&:; C&:; C&?
A
C&A
>
C&5D C&5 C&:? 4&: ?&> A&? ?&4
<elite
(g"
D&CA 6?&C
6
>6&?
A
::&D
4
D5&5
:
??&;
D
A;&D
:
?4&6
;
44&?
5
?A&4
A
D4&D
>
:>&?
6
54&;
>
5>&6
4
:5&D
;
Table 4& 3evels of <./s (ngg'4 dry wt"( percentage of organic carbon (J=!"
and pelite fraction (g" in s#rface sediments from 4D sampling stations
1n contrast to pyrogenic so#rces( petrogenic so#rces are characterized by <heM.n
ratios4C( -tM<y f4 and ,(a".nM!hyf4 (,#dzins+i et al&( 455;"& =n the other
hand( some <./s( s#ch as perylene come from diagenesis processes of biogenic
prec#rsors (Gen+atesan( 45::"&
Recently( al+ylated <./s also( have been proved #sef#l in petrole#m'related
0ngerprinting by comparing their relative individ#al magnit#des in sediments
(<age et al&( 4555"&
,#dzins+i et al&( (455;" had given attention to distrib#tion of low and high
molec#lar weight <./ (3<./ and /<./s( respectively" as a reliable
tool for discriminating the petrogenicMpyrolytic origin of <./s& The higher
the 3<./sM/<./s ratio( the higher the prevalence of petrogenesis on pyrolytic
origin of <./s&
!oncentrations of <./s are mostly dominated by high molec#lar weight
compo#nd (<./s with 6 to > rings"& The 3<./M/<./s ratios are very low(
from C&C> to 4 and the only congener that is nearly always present is
phenanthrene& This means that probably high temperat#re comb#stion
processes were the predominant so#rce of <./s contamination (!anton and
rimalt( 455?"& This information is con0rmed by the low concentrations of the
al+yl homolog#es (methyl'anthraceneManthracene and methyl'
phenanthreneM phenanthrene"& 1ndeed( close similarities between the
relative distrib#tion of methyl' anthraceneManthracene and methyl'
phenanthreneMphenanthrene ratios for
sample sediments analyzed in the st#dy area were observed b#t less
than #nit val#es of al+yl to parent anthracene and phenanthrene were detected
for all sample sediments&
.dditionally( the <heM.n and -tM<y ratios can be #sed to assess the relative
importance of the so#rces and the e*ect of diagenetic changes (2oclo et al&(
?CCC"& <heM.n ratios span from
A&6D to 44 and -tM<y ratios range from C&?> to ?& -or instance <heM.ns4C and
-tM<yf4( which are characteristics of <./ petrogenic contamination( were
fo#nd only at station 4& -#rthermore( chrysene and ,(a"an derive from
pyrolytic so#rces in ratio that sho#ld be lower than 4 (2oclo et al&( ?CCC"&
Most val#es in o#r samples were closed to 4 or slightly higher& This may be
d#e to some in$#ence from petrogenic contamination or to the
degradation of the less stable ,(a".n&
<erylene( which may be of nat#ral origin( was determined at very lower
concentrations (Table4"& Early st#dies reported diagenetic formation of perylene
from terrestrial prec#rsors in ano%ic conditions (.izenshtat( 45;A"& /owever(
perylene is also prod#ced d#ring pyrolytic processes (Gen+atesan( 45::"& The
low relative ab#ndance of perylene in the st#dy area arg#es for a dominant
pyrolytic origin (Gen+atesan( 45::"&
Distrib#tion of <./s in ,izerte 3agoon sediment reveals general and
moderate contamination& ,ased on the investigation of approaches reported
above o#r res#lts reveal that <./ contamination co#ld be related to #rban
and or ind#strial activities& The data fo#nd indicate that sediments for stations
4( ? and 44 were characterized by pyrogenic <./ contamination when
e%amining the 3<./sM/<./s( methylphenanthreneMphenanthrene(
methylanthraceneManthracene ratios& /owever( <heM.n and -tM<y ratios
reveal <./ petrogenic contamination only at station 4& <./ inp#ts in this area
are most li+ely related to the intensive tra8c of boats and ind#strial activities&
The later station is localised in an area where there are oil re0nery and #sed oil
recycling activities which probably constit#te the main so#rces of contamination
by petrogenic <./s& 2tations ? and 44 are near a base of the T#nisian Military
Marine and a solid waste land0ll& 2tations 6( D and > are located near
Menzel ,o#rg#iba city( where intensive ind#strial activity is carried o#t(
incl#ding the metall#rgic ind#stry( naval constr#ction and tyre prod#ction& 1n
addition( there are several local wastewater discharges in this area&
.dditionally( <./ concentrations for all stations were also plotted #sing a
ternary diagram to investigate combinations of <./s that may have similar
so#rces and modes of inp#ts& The plot reveals two notable gro#ps of stations&
The 0rst incl#des stations 4( ? and 44 which are located in the channel of
navigation of boats& 1n the second gro#p( we disting#ish stations 6( D and >(
which are closed to the #rban and intensive prod#ctive ind#strial zone (city of
Menzel ,o#rg#iba"&
The middle part (4?( 4A( 46 and 4D" of the lagoon shows a clear
tendency of <./ concentration to decrease from west to east part& The
decrease of <./ levels is logically in agreement with the increasing distance
from #rbanised andMor ind#strial area&
8
To assess potential environmental impacts of <./s in sediments( the
concentrations of <./s in sediments can be compared with certain threshold
val#es proposed by the 92 @ational =ceanic and .tmospheric .dministration(
e&g& the e*ects'range low (ER'3" (which is a sediment )#ality g#ideline below
which the chemical concentration in the sediments wo#ld be e%pected to
rarely have adverse biological e*ects" and the e*ect'range medi#m (ER'M" (a
level above which adverse biological e*ects occ#r fre)#ently"&
The concentrations fo#nd for all stations ranged from ?C to 665 ngg'4 dry weight
which are below the ER'3 (6CCC ngg'4" and the ER'M (6DCCC ngg'4"& This range
represents a relatively clean environment&
. Contamination status o! P@Ps
..1 PC7 composition and sources identi!ication and ecotoxicological concerns
The distrib#tion of vario#s <!, in the sediments from 4D sampling stations
reveals that the
<!, ranged from C&:5 to >&>A ngg
'4
(Table ?"& -ig&? shows the geographic
distrib#tion of the
<!, in the whole st#dy area( the contents of total <!, in sediment vary
from a site to another&
= B
r!n
E"
C(C
4C
C
8
?C
:C
88
1
8.
2
6C
8(
/
0
>C
3
>C
,
8>
6C
(
:C
4 ?C
10
= (:.
4CC
C&C = >:2
r!n
E"
C&C
?C 6C >C :C 4CC
r!nE"
-ig& ?& ternary diagram of the distrib#tion of low( mid and high molec#lar
weight <./s
This res#lt re$ects geographic distrib#tion of <!, level of contamination& -or the
coastal sites( the highest <!, concentrations ranged from 6&A5 to >&>A ng g
'4
were detected at northern part covered sites 4( ?( 4C( and 44 and at so#thwest
zone (site D"& 2ediments collected from the other coastal sites are slightly
contaminated (~<!, ranged from C&:5 to ?&D: ng g'4"& Relatively high <!,
concentrations were also fo#nd in samples collected from sites 4?( 4A( 46( and
4D& These stations are located in the central zone of the lagoon and are the
deepest&
2tation
s <!, 4 ? A 6 D > ; : 5 4C 44 4? 4A 46 4D
<!,: C&?
A
C&A
4
C&C
D
C&6
>
C&4
:
C&A
A
C&6
C
C&A
6
C&A
>
C&;
>
C&?
:
C&>
5
C&:
>
4&A
:
C&5
> <!,4: nd nd nd nd nd nd nd nd C&6
:
C&A
4
C&4
5
C&A
;
C&A
4
C&:
C
C&6
D <!,?: C&4
D
C&?
?
nd C&?
6
nd nd C&?
A
C&4
5
C&?
?
C&A
D
C&?
C
C&A
?
C&A
4
C&D
?
C&A
? <!, D? C&4
4
C&6
6
nd C&4
D
nd C&C
;
C&C
5
C&C
;
C&C
:
C&A
?
C&?
?
C&A
>
C&4
A
C&4
C
C&C
: <!, 66 nd C&?
4
nd nd nd C&C
>
nd nd C&4
C
C&4
4
nd C&4
?
C&4
C
C&4
C
C&C
> <!, >> nd C&4
C
C&C
5
nd C&C
A
nd C&C
>
nd C&4
4
C&4
;
C&A
>
C&?
C
C&4
?
C&4
D
C&C
; <!, ;; nd nd nd nd nd nd nd nd C&6
4
C&?
5
C&6
6
C&5
5
C&4
:
C&?
>
C&C
5 <!,
4C4
C&A
?
C&>
6
nd C&4
D
C&4
5
C&C
>
C&C
;
nd C&C
;
C&?
D
C&A
4
C&?
A
C&A
;
C&4
4
nd
<!,
44:
nd C&D
6
C&?
>
C&C
5
C&C
5
nd nd nd C&4
;
C&4
;
C&A
:
C&?
;
C&4
>
C&4
?
C&C
; <!,
4CD
C&4
D
C&?
A
C&4
D
C&C
:
C&C
;
C&C
?
nd nd nd C&C
>
C&4
D
C&C
:
nd C&C
:
nd
<!,
4DA
C&:
C
C&;
A
C&C
5
C&6
C
4&C
5
C&?
A
C&4
C
C&C
:
C&4
C
C&D
4
C&5
4
C&;
:
C&>
?
C&A
;
C&A
6 <!,
4A:
C&5
D
C&:
D
nd C&A
:
4&C
4
C&4
5
C&C
:
C&C
;
nd C&6
C
C&;
?
C&D
:
C&6
C
C&A
?
C&?
D <!,
4?:
C&4
;
C&?
5
nd nd C&4
:
C&C
A
nd nd nd C&C
6
C&C
:
C&C
6
C&C
6
C&C
;
C&C
: <!,
4:;
C&?
?
C&4
D
C&4
4
C&4
?
C&A
>
C&C
;
nd nd C&C
>
C&?
?
C&D
D
C&6
C
C&?
;
C&?
?
C&4
5
<!,
4:C
C&;
C
C&A
6
C&4
5
C&?
A
C&5
6
C&4
D
nd C&C
D
C&?
D
C&6
4
4&4
:
C&;
>
C&D
D
C&?
;
C&?
A <!,
4;C
C&D
C
C&?
C
C&4
?
C&4
D
C&D
;
C&C
;
nd nd C&C
>
C&4
:
C&6
6
C&?
;
C&4
>
C&4
6
C&4
? <!,
45D
C&C
5
C&C
5
nd C&4
C
nd nd C&C
5
C&C
:
nd C&C
D
C&C
5
C&C
6
C&C
A
C&C
?
C&C
? <!,
?C>
nd nd nd nd nd nd nd nd nd C&C
4
C&C
A
C&C
A
C&C
4
nd nd
<!,
?C5
nd nd nd C&C
6
C&C
;
nd nd nd nd C&C
:
C&4
C
C&4
C
C&C
5
C&C
5
C&C
; ~<!, 6&A
5
D&A
6
4&D
4
?&D
:
6&;
;
4&?
5
4&4
?
C&:
5
?&6
:
6&>
:
>&>
A
>&>
?
6&>
5
D&4
A
A&6
C
Table ?& !oncentrations (ngg
'4
( dry weight" of <!,s in s#rface sediments from
4D sampling stations
=#r sediment investigation revealed the general prevalence of lower and mid
molec#lar weight <!,s& The <!, congeners pattern was dominated by bi'
<!,s (4CCJ"( Tri'<!, (<!,?:B :CJ" and tetra'<!, (<!,D?B :>J"& Mid'<!,s
also dominated the <!,s congeners pattern& <!, congeners proportions
consisted of the following distrib#tionI <!,4DA (4CCJ"( <!,4:C (5AJ" and <!,
(4:;( 4;C( 4A:" acco#nting :>J of total <!,s composition& /owever( relatively
moderate percentage of the high chlorinated congeners( s#ch as octa'<!,s
(;AJ"( were fo#nd in this st#dy& 2ediment collected at locations 6( D( >( 46 and
4D contained great proportions of di'( tri'( and tetra'<!,( whereas those from
locations 4( ?( 44( 4C( 5(: and ; had higher proportions of penta'( he%a'( and
hepta'<!,s&
. n#mber of previo#s st#dies have showed the prod#ction of <!,s d#ring
the steel man#fact#ring processes (.lcoc+ et al&( 4555B ,#e+ens et al&(
?CC4"& This is d#e to the presence of <!,s in $y ash generated from
b#rning coal d#ring the iron ore sintering process (,iterna V Go#tsa( ?CCD"&
The later sites (4( ?( 44( 4C( 5( : and ;" are close to some ind#stries
established on the circ#mference of the lagoon (an iron and steel plant( a
cement factory( and a re0nery"&
The h#man pop#lation aro#nd the lagoon is estimated at 4>A(CCC inhabitants
(cens#s of ?CC6" of which appro%imately ;CJ are concentrated in ,izerte town&
The other main important towns bordering the lagoon are Menzel ,o#rg#iba
(which has a naval port and a metal factory"( Menzel .bderrahmen and
Menzel Kemil& The so#rces of #ntreated ind#strial and domestic wastewater of
these cities( which are indicative of the near'so#rce emissions of
-ig& A& 2patial distrib#tion of ~<!,s in s#rface sediment from
,izerte lagoon
<!,s from ind#strial wastewater and domestic sewage( are also( the main
contrib#tors& <!,s are an ind#strial prod#ctB there are no +nown nat#ral
so#rces& .tmospheric depositions( r#no* from the land( and food chain
transport (Morrison et al&( ?CC?B Totten et al&( ?CC>B Davis et al&( ?CC;" have
been regarded as the major so#rces of <!,s in a)#atic environments& 9rban
r#no* from local watersheds is a partic#larly significant pathway for <!, entry
into the lagoon& 2ince <!,s are somewhat volatile and tend to enter the
atmosphere( atmospheric transport and deposition can be important
processes( s#ch as e%change between the water and the atmosphere( and
between the soil and the atmosphere&
. fraction of the <!,s lost by this pathway may ret#rn to the water and land
s#rface via deposition in the watershed and s#bse)#ent r#no*& ,esides( <!,s
have been shown to bioconcentrate signi0cantly in a)#atic organisms
(Morrison et al&( ?CC?"& -o#r open'
d#mping'type m#nicipal or ind#strial solid waste landfills are scattered aro#nd
the lagoonB the 0rst and the biggest one is located on the edge of the canal
near the cement wor+s& The second one( in front of Menzel ,o#rg#iba city
however( the smallest ones and the farthest from the coast receive the garbage
of Menzel Kemil city co#ld escort to an important so#rce of <!,s in the lagoon&
.ltho#gh the observed trends in <!, congener composition was similar in some
sediment sample (i&e& between sites 4? and 4A and between sites 46 and 4D"&
The distrib#tion patterns of <!,s congeners are( in general( di*erent among the
sediments of this st#dy area( which may indicate di*erent inp#t so#rces and
the establishment of correlation between the congener pro0les and the
so#rces is di8c#lt( especially when the distance between the so#rce and the
sampling site is large& 1n addition the #sage of <!,s in T#nisia is not well
established( b#t the #se of <!,s in transformers( electrical( and other ind#stries
is common&
2ediment'bo#nd <!,s can a*ect benthic organisms& To eval#ate the
ecoto%icological aspect of sediment contamination( some p#blished
sediment )#ality g#idelines and to%ic e)#ivalent (7/='TEd" of dio%in'li+e
<!,s congeners were applied in this st#dy& .ltho#gh the g#idelines are limited in
some cases( they provide #sef#l indicators of the e*ects of <!, contamination in
the absence of environmental assessment criteria for <!,s in T#nisia& The e*ect
range low val#e (ER3( ??&; ng g'4 dry weight" s#ggests that <!,s can e%ert
to%ic biological e*ects on a)#atic organisms( while the e*ect range median
val#e (ERM( 4:C ng g'
4 dry weight" indicates the high possibility of <!,s posing detrimental biological
e*ects on
a)#atic organisms (3ong et al&( 455D"& The total <!,s concentrations of the
samples collected for this st#dy do not e%ceed the ERM or ER3 val#es& .s
regards the res#lts obtained for dio%in'li+e <!,s (;;( 4?>( 4CD and 44:" the
concentrations for the <!,;;( 4CD and 44: vary fromfC&C? ngg'4 to C&55 ngg'
4 and only <!,4?> is not detected for all sediment samples& Moreover( in the
lower contaminated sites (; and :" all the st#died dio%in'li+e <!,s were not
fo#nd& The ratios between these levels and those of the total <!,s were
dissimilar in all the locations st#diedB the dio%in'li+e <!,s acco#nted for C'?AJ
of the total <!,s in these samples&
..2 @CPs composition and sources identi!ication and ecotoxicological concerns
1n case of =!<s( only 4C coastal sampling points were considered beca#se
concentrations for the most analysed pesticides were below the detection limit
(fC&C4C" (Table A"& The obtained res#lts showed that /!, and DDT isomers
(DDTXDDEXDDD" were the predominately detected compo#nds in most
stations with concentrations ranged between C&C? to C&4? ngg
'4
and C&?4 to
A&;6 ngg
'4
( respectively& /eptachlor was the second highest with concentration
ranged between C&CA'C&A ngg
'4
whereas( lindane and mire% were detected only
in one station& The other pesticides were not detected in any sample&
The most contaminated stations were ? and A with total pesticides
concentration A&;: ngg'4 and A&6; ngg
'4
( respectively& 2ites > (C&4: ngg
'4
"
and ; (C&?A 4; ngg
'4
" were the less contaminated stations& The other
sites were moderately poll#ted with total pesticides concentration ranged
between C&D> ngg
'4
in station 4C and 4&:A ngg
'4
in station D&
The composition of organochlorines and their metabolities can provide some
information for a better #nderstanding of the origin and transport of
these contaminants in the environment& Microbial degradation of DDT( DDD
and DDE is generally slow( res#lting in
environmental persistence of these compo#nds and DDT may degrade to DDD
with a half' life of a few days #nder certain conditions (arrison et al&( ?CCC"&
DDT can be biodegraded to DDE #nder aerobic condition and to DDD #nder
anaerobic condition (Kalantzi et al&(
?CC4"& !omparing the concentrations of ~DDT and its metabolites( it can
be inferred whether DDTs inp#t are recent or not (<h#ong et al&( 455:"&
The ratio of (DDE X DDD"M~DDT s C&D can be tho#ght to be s#bjected to a
long'term weathering (/ites V Day(
455?B /ong et al&( 4555"& 1n most present samples( DDE and DDD occ#pied the
predominant
percentage& /ere the mean ratio of (DDE X DDD"M~DDT in the sediments from
,izerte
lagoon was C&:D( which indicated that the degradation occ#rred signi0cantly&
/owever( the DDT (incl#ding o(p'P and p(pP'" in the sediment of site A occ#pied
abo#t DCJ& The high levels of ~DDT and high percentage of DDT might d#e
to intensification of the agric#lt#ral activities in areas s#rro#nding the lagoon&
1n general( potential so#rces of =!<s poll#tion in the st#dy area can beI the #se
of these pesticides in the past in agric#lt#ral area s#rro#nding the lagoon(
domestic sewage and atmospheric transport&
2tation
s
=!<s 4 ? A 6 D > ; : 5 4C
/!, C&CA C&C? C&4C C&C5 C&C> C&CA C&C? C&C5 C&4? C&4?
3indane nd nd nd nd nd C&C5 nd nd nd nd
/eptachlor C&?; C&CA C&C> nd nd C&C> nd C&A> C&46 C&C>
o(pP'DDT C&CD C&6: C&?5 nd C&A? nd nd nd C&CA nd
p(pP'DDT nd C&:D 4&AA nd C&4; nd nd nd nd nd
o(pP'DDE nd C&C> C&4D C&46 C&4A nd nd C&4A C&?? nd
p(pP'DDE C&46 C&4: C&6A C&A; C&?4 nd nd nd C&4> C&4A
o(pP'DDD C&AA C&55 C&6: C&A: C&6C nd C&?4 C&65 C&6: C&AD
p(pP'DDD C&C5 4&4; C&>C C&C: C&D4 nd nd nd C&C? nd
~DDT C&>4 A&;A A&?: C&5; 4&;6 C C&?4 C&>? C&54 C&6:
~=!<s C&54 A&;: A&66 4&C> 4&: C&4: C&?A 4&C; 4&4; C&>>
Table A& !oncentrations (ngg
'4
( dry weight" of =!<s in s#rface sediments from
4C sampling stations
#. Conclusion
1n ,izerte lagoon( T#nisian area economically very important( sediments appear
moderately poll#ted& The contamination level appears rather low compared to
those fo#nd in other ecosystems&
=n the basis of this st#dy( we can concl#de that the lagoon is s#bject to intensive
ind#strial activities& There are fo#r main zones of anthropogenic in$#enceI 1n
zone 4 are sit#ated oil re0neries( food and ceramic ind#stries& 1n zone ? are
located cements( treatment of metals (copercraft( asbestos" and sprin+ling
beverage factories& 1n zone A are ceramic and metall#rgy activities& 1n
zone 6 are present metall#rgy activities (-e( Qn( !d( 2n( /g"( naval
constr#ctions and tire prod#ctions&
,eca#se T#nisia has a long Mediterranean coast of cr#cial economical interest( it
is obvio#s that a larger spatio'temporal <=< monitoring has to be planned(
incl#ding harbo#r areas&
This is the condition to have an eval#ation of the act#al organic poll#tants
contamination of the T#nisian marine environment&
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