application book fastgc
DESCRIPTION
ChromatographyTRANSCRIPT
-
Chro
matog
raph
yVolu
me2
Appli
catio
n Boo
kFa
st GC
/GCM
S
-
Fast
GC an
d GC/
MS us
ing na
rrow-
bore
colum
ns:
Princ
iples
and A
pplic
ation
s
Prof.
Luigi
Mon
dello
,Univ
ersit
y of M
essin
a,Ita
lyDr
.Han
s-Ulri
ch B
aier,S
himad
zu D
eutsc
hland
Gmb
H,Ge
rman
y
Appli
catio
n Boo
kFa
st GC
/GCM
S
-
App
licat
ion
Boo
k Ch
rom
atog
raph
y Vo
lum
e 2
Fast
GC/
GCM
S
Publ
ishe
r:Sh
imad
zu D
euts
chla
nd G
mbH
Alb
ert-
Hah
n-St
r. 6-
10
4726
9 D
uisb
urg,
Ger
man
yTe
leph
one:
+49
(0) 2
03 7
687-
0Te
lefa
x:
+49
(0) 2
03 7
6662
5Em
ail:
shim
adzu
@sh
imad
zu.d
eIn
tern
et:
ww
w.s
him
adzu
.de
Edito
rial
Tea
m:
Prof
. Lui
gi M
onde
llo, U
nive
rsity
of M
essi
na, I
taly
Dr.
Han
s-U
lrich
Bai
er, S
him
adzu
Deu
tsch
land
Gm
bH,
Ger
man
y
Des
ign
and
Prod
uctio
n:M
E W
erbe
agen
tur G
WA
D
sse
ldor
f
C
opyr
ight
:Sh
imad
zu D
euts
chla
nd G
mbH
, Dui
sbur
g.
Repr
int,
in w
hole
or i
n pa
rt, i
s su
bjec
t to
the
perm
issi
on o
f the
edi
toria
l offi
ce.
Win
dow
s is
a T
rade
mar
k of
Mic
roso
ft Co
rpor
atio
n.
-
I. II. III.
IV.
V. VI.
VII.
VIII. IX.
Conte
nt
Ove
rvie
w7
Bas
ics
of s
epar
atio
n in
fast
GC
111.
Col
umn
and
stat
iona
ry p
hase
2. L
engt
h an
d pe
ak re
solu
tion
3. In
ner d
iam
eter
and
pea
k re
solu
tion
4. F
ilm th
ickn
ess
and
peak
reso
lutio
n5.
Typ
e of
car
rier g
as a
nd a
vera
ge li
near
vel
ocity
6. G
C ha
rdw
are
requ
irem
ents
Inje
ctio
n re
quir
emen
ts in
fast
GC
15
Det
ecto
r re
quir
emen
ts in
fast
GC
191.
Con
vent
iona
l det
ecto
rs2.
Mas
s sp
ectr
omet
ric d
etec
tor (
quad
rupo
le M
S)
App
licat
ions
in fo
od a
naly
sis
231.
Org
anop
hosp
horo
us p
estic
ides
in fo
od m
atric
es
(GC-
FPD
, GC-
FTD
, GC/
MS)
2. T
he a
naly
sis
of o
rgan
ochl
orin
e pe
stic
ides
in fo
od m
atric
es
usin
g G
C-EC
D a
nd N
CI G
C/M
S.
3. A
naly
sis
of b
utte
r fat
ty a
cid
met
hyl e
ster
s (G
C-FI
D)
App
licat
ion
in th
e pe
troc
hem
ical
fiel
d31
Kero
sene
ana
lysi
s (G
C-FI
D)
App
licat
ions
in th
e fie
lds
of fl
avor
s &
frag
ranc
es32
1. P
oten
tial a
llerg
ens
in p
erfu
mes
2.
Qua
lity
cont
rol o
f fla
vors
(GC-
FID
)
App
licat
ion
in th
e en
viro
nmen
tal f
ield
37PC
B a
naly
sis
with
GC-
ECD
det
ectio
n
Sum
mar
y39
-
Chro
mat
ogra
phy
Volu
me
2I.
OVE
RVIE
W
8
as c
hrom
atog
raph
y is
a w
ell-
esta
blis
hed
tech
niqu
e, e
mpl
oyed
in m
any
appl
icat
iona
l fie
lds
such
as e
nvir
onm
enta
l, fo
od, p
etro
-ch
emic
al a
nd p
harm
aceu
tica
lan
alys
is [
1].
The
cap
illar
y co
lum
ns u
sed
may
have
sol
id f
illin
gs (
PL
OT
colu
mns
) or
a li
quid
film
as
a st
atio
nary
pha
se. T
he la
tter
are
empl
oyed
in g
as li
quid
chr
oma-
togr
aphy
(G
LC
), w
hich
is t
hesu
bjec
t of
the
pre
sent
boo
klet
. In
GL
C, a
naly
te s
epar
atio
n is
achi
eved
by
mea
ns o
f a
dyna
mic
ther
mal
equ
ilibr
ium
bet
wee
n th
est
atio
nary
pha
se (
liqui
d) a
ndm
obile
pha
se (
gas)
. The
dim
en-
sion
s of
the
col
umns
em
ploy
ed,
whi
ch v
ary
depe
ndin
g on
the
appl
icat
ion,
gen
eral
ly r
ange
fro
min
ner
diam
eter
s be
twee
n 0.
25 t
o0.
53 m
m a
nd le
ngth
s fr
om 2
5 to
60 m
. The
film
thi
ckne
ss s
elec
t-ed
, dep
ende
nt o
n th
e bo
iling
poin
ts o
f th
e an
alyt
es, u
sual
lyra
nges
fro
m 0
.25
to 1
m
(in
som
e ca
ses
up t
o 3
m o
r ev
enm
ore)
.
Now
aday
s in
dai
ly r
outi
ne w
ork,
apar
t fr
om in
crea
sed
anal
ytic
alse
nsit
ivit
y, d
eman
ds a
re a
lso
mad
e on
the
eff
icie
ncy
in t
erm
sof
spe
ed o
f th
e la
bora
tory
equ
ip-
men
t. R
egar
ding
the
rap
idit
y of
anal
ysis
, tw
o as
pect
s ne
ed t
o be
cons
ider
ed:
1. T
he c
osts
in te
rms
of ti
me
requ
ired
, for
exa
mpl
e in
qua
lity
cont
rol a
naly
sis
2. T
he e
ffici
ency
of t
he a
naly
tical
equi
pmen
t em
ploy
ed
It is
wel
l kno
wn
that
ana
lyti
cal
tim
e co
sts
may
be
very
hig
h in
stan
dard
GC
app
licat
ions
. In
the
last
few
yea
rs, f
ast
GC
met
hods
have
bee
n sh
own
to b
e su
itab
lefo
r ro
utin
e la
bora
tory
wor
k. I
nth
is r
espe
ct, t
he e
mpl
oym
ent
ofna
rrow
-bor
e co
lum
ns is
of
par-
ticu
lar
inte
rest
[2
-5].
The
se a
naly
tica
l too
ls e
nabl
e a
cons
ider
able
red
ucti
on o
f an
aly-
ses
tim
es w
hile
pea
k re
solu
tion
ises
sent
ially
mai
ntai
ned.
Ano
ther
appr
oach
wor
thy
of m
enti
on is
the
use
of m
ulti
capi
llary
col
umns
[6-8
] w
ith
mor
e th
an 9
00 c
apil-
lary
tub
es w
ith
inne
r di
amet
ers
of a
bout
40
m.
The
pre
sent
ove
rvie
w is
foc
usse
don
the
use
of
narr
ow-b
ore
colu
mns
in f
ast
gas
chro
mat
ogra
-ph
y. A
s m
enti
oned
, thi
s ty
pe o
fap
proa
ch e
nabl
es s
ubst
anti
alre
duct
ions
in G
C r
un-t
imes
wit
hout
com
prom
isin
g th
e ch
ro-
mat
ogra
phic
res
olut
ion.
An
exam
ple
of t
he v
alid
ity
ofth
is a
ppro
ach
is il
lust
rate
d in
Fig
ure
I.1
(low
er c
hrom
atog
ram
)
whi
ch r
epor
ts a
fas
t G
C a
naly
sis
(RT
X-5
10
m, 0
.1 m
m I
D, 0
.4
mfi
lm t
hick
ness
) on
a c
apill
ary
col-
umn
test
mix
ture
(G
rob
test
mix
-tu
re, M
ache
rey
und
Nag
el).
The
cond
itio
ns w
ere
as f
ollo
ws:
inje
c-ti
on m
ode:
spl
it (
200
:1),
ave
rage
linea
r ca
rrie
r ga
s ve
loci
ty: 1
20cm
/s (
502
kPa,
H2)
, tem
pera
ture
prog
ram
: fro
m 1
40
C a
t 60
C/m
in t
o 28
0 C
. A c
onve
ntio
n-al
app
licat
ion
(DB
5 3
0 m
, 0.2
5m
m I
D, 0
.25
m f
ilm t
hick
ness
)on
the
sam
e m
atri
x is
als
o sh
own
in t
he d
iagr
am (
uppe
r ch
ro-
mat
ogra
m).
As
appa
rent
, the
degr
ee o
f se
para
tion
is e
ven
bet-
ter
in t
he f
ast
GC
app
licat
ion
whi
le a
spe
ed g
ain
of a
ppro
xi-
mat
ely
8 ti
mes
is a
ttai
ned.
How
ever
, the
GC
har
dwar
e ha
sto
mee
t so
me
requ
irem
ents
inor
der
to e
nabl
e th
e ef
fici
ent
use
of n
arro
w-b
ore
colu
mns
. In
the
follo
win
g ch
apte
rs, g
ener
al a
ndfu
ndam
enta
l iss
ues
rela
tive
to
fast
gas
chr
omat
ogra
phy
are
dis-
cuss
ed (
inje
ctio
n sy
stem
s, c
apil-
lary
col
umns
, car
rier
gas
and
dete
ctor
cha
ract
eris
tics
).
All
the
chro
mat
ogra
ms
show
nw
ere
reco
rded
wit
h a
Shim
adzu
GC
-201
0 or
GC
MS-
QP
2010
wit
h an
AO
C-2
0i a
utoi
njec
tor
and
GC
solu
tion
or
GC
MSs
olu-
tion
sof
twar
e fo
r da
ta e
labo
ra-
tion
.
G
-
9
Chro
mat
ogra
phy
Volu
me
2I.
OVE
RVIE
W
6.0
7.0
8.0
9.0
Min
utes
35 1
10.0
11.0
12.0
13.0
14.0
15.0
x 10
6
12
34
5
67
8
9
0.25
0.50
0.75
1.00 M
inut
es
24 0
1.25
1.50
1.75
x 10
4
FWH
M =
0.4
8s
12
3
45
6
78
9
FWH
M =
3s
6
Figu
re I.
1:
Top:
Chro
mat
ogra
m re
cord
ed w
ith a
Gro
b te
st m
ixtu
re u
sing
a D
B5
30 m
,0.
25 m
m, 0
.25
m c
olum
n.B
otto
m:C
hrom
atog
ram
reco
rded
w
ith th
e G
rob
test
mix
ture
usi
ng a
RTX-
5 10
m, 0
.1 m
m, 0
.4
m c
olum
n.
Peak
iden
tific
atio
n:1)
n-D
ecan
e2)
n-O
ctan
ole
3) n
-Und
ecan
e4)
2.6
-Dim
ethy
lphe
nole
5) 2
.6-D
imet
hyla
nilin
e6)
Dec
ane
acid
met
hyl e
ster
7)
Und
ecan
e ac
id m
ethy
l est
er8)
Dic
yclo
hexy
lam
ine
9) D
odec
ane
acid
met
hyl e
ster
-
N =
16
wb
t R2
Bot
h th
e po
lari
ty a
nd t
he b
oilin
gpo
ints
of
the
sam
ple
anal
ytes
mus
t be
con
side
red
duri
ng t
hese
lect
ion
of a
spe
cifi
c st
atio
nary
phas
e m
ater
ial.
Now
aday
s, s
ever
-al
pha
se m
ater
ials
are
ava
ilabl
efo
r ty
pica
l fas
t G
C a
pplic
atio
ns.
An
impo
rtan
t is
sue
in f
ast
GC
rega
rds
the
narr
ow-b
ore
colu
mn
Chro
mat
ogra
phy
Volu
me
2
1.Co
lumn a
nd st
ation
ary ph
ase
II. B
ASI
CS O
F SE
PARA
TIO
N I
N F
AST
GC
12
sam
ple
capa
city
, whi
ch is
con
sid-
erab
ly lo
wer
tha
n w
ith
conv
en-
tion
al c
apill
arie
s (t
his
aspe
ct w
illbe
dis
cuss
ed la
ter)
.
Apa
rt f
rom
the
cho
ice
of t
he s
ta-
tion
ary
phas
e, o
ther
impo
rtan
tco
lum
n pa
ram
eter
s to
be
opti
mi-
zed
are
leng
th, i
nter
nal d
iam
eter
and
film
thi
ckne
ss.
The
num
ber
of t
heor
etic
al p
la-
tes
Nof
a c
olum
n is
a m
easu
re o
fit
s se
para
tion
eff
icie
ncy
and
isde
fine
d as
[9]
:
2.Le
ngth
and p
eak r
esolu
tion
R =
4
E N
a
a
1
k 2
k 2 +
1
k =
,
t Mt Ra
=
=
k 1k 2t R
1
t R2
L =
col
umn
leng
thN
=
H
ET
PL
R
E L
R =
_1 2
[wa +
wb]
i t
whe
re w
bis
the
bas
e pe
ak w
idth
and
t Ris
the
ret
enti
on t
ime.
Pea
kre
solu
tion
is o
f pa
rtic
ular
inte
rest
as t
he m
ain
aim
is t
o re
duce
the
anal
ysis
tim
e w
hile
mai
ntai
ning
the
colu
mn
reso
lvin
g po
wer
(F
ig-
ure
II.2
). T
he r
esol
utio
n be
twee
ntw
o pe
aks
is d
efin
ed a
s:
Res
olut
ion
(R)
on t
he o
ther
han
dde
pend
s on
the
cap
acit
y fa
ctor
kan
d th
e pl
ate
num
ber
Nin
the
follo
win
g eq
uati
on [
9]:
Wa
Wb
Dt
Figu
re II
.1: P
eak
reso
lutio
n pa
ram
eter
s fo
r tw
o su
bseq
uent
pea
ks in
a
chro
mat
ogra
m
wit
h k
2=
cap
acit
y fa
ctor
of
the
mor
e re
tain
ed s
olut
e an
d a
= s
epar
atio
n fa
ctor
:
whe
re t
Mis
the
tim
e re
quir
ed f
oran
unr
etai
ned
anal
yte
to p
ass
thro
ugh
the
colu
mn
(gen
eral
lyre
ferr
ed t
o as
dea
d ti
me)
. The
rela
tion
ship
bet
wee
n th
e le
ngth
of t
he c
olum
n, N
and
heig
ht o
f a
theo
reti
cal p
late
(H
ET
P)
is a
sfo
llow
s:
thus
the
res
olut
ion
is p
ropo
r-ti
onal
to
the
squa
re r
oot
of t
heco
lum
n le
ngth
:
Con
sequ
entl
y, d
oubl
ing
the
col-
umn
leng
th a
chie
ves
a ga
in o
fre
solu
tion
of
a fa
ctor
of
only
1.41
. The
refo
re t
ypic
al c
olum
nle
ngth
s in
fas
t G
C a
re w
ithi
n th
e10
-15
m r
ange
.
Co
lum
n le
ngth
for
fast
GC:
10
-15
m
1 2 3
4 5
-
b
d I 4d
fK
D =
k
b
13
Chro
mat
ogra
phy
Volu
me
2II
. BA
SICS
OF
SEPA
RATI
ON
IN
FA
ST G
C
In g
ener
al, t
he c
hrom
atog
raph
icpe
ak w
idth
incr
ease
s w
ith
the
rete
ntio
n ti
me
due
to r
esis
tanc
eto
mas
s tr
ansf
er in
the
mob
ilean
d st
atio
nary
pha
se c
ontr
ibu-
tion
s. T
he in
flue
nce
of t
he in
ner
diam
eter
wit
h re
spec
t to
the
th
eore
tica
l pla
te n
umbe
r is
now
cons
ider
ed. T
he b
asic
equ
atio
nfo
r th
e re
tent
ion
of a
sub
stan
ce
is [
9]:
The
line
ar r
elat
ions
hip
betw
een
peak
res
olut
ion
and
stat
iona
ryph
ase
thic
knes
s re
quir
es t
he la
t-te
r to
be
as t
hin
as p
ossi
ble
infa
st G
C.
On
the
othe
r ha
nd, i
t sh
ould
als
obe
sui
ted
to t
he b
oilin
g po
ints
of
the
anal
ytes
(se
e al
so b
). S
ince
the
colu
mn
sam
ple
capa
city
als
ode
crea
ses
wit
h th
e fi
lm t
hick
ness
(les
s am
ount
of
stat
iona
ry p
hase
),th
e sp
lit r
atio
nee
ds t
o be
adj
ust-
ed d
epen
ding
on
the
conc
entr
a-ti
on o
f th
e sa
mpl
e. H
igh
split
rati
os e
nsur
e th
at t
he s
ampl
e is
3.Inn
er di
amete
r and
peak
reso
lution
4.Fil
m thi
ckne
ss an
d pea
k res
olutio
n
HE
TP
min
pro
p d
I
whe
re:
d I,d
f=
inne
r di
amet
er/f
ilmth
ickn
ess
of t
he c
olum
n K
D=
dis
trib
utio
n co
nsta
ntb
= p
hase
rat
io
The
dis
trib
utio
n co
effi
cien
t K
Dis
dep
ende
nt o
n th
e te
mpe
ratu
rean
d th
e ph
ysic
al a
nd c
hem
ical
prop
erti
es o
f th
e an
alyt
es a
ndst
atio
nary
pha
se. T
he r
eten
tion
tim
e is
the
refo
re d
eter
min
ed b
yth
e in
ner
diam
eter
, film
thi
ckne
ssan
d le
ngth
of
the
colu
mn
for
fixe
d m
ater
ial p
rope
rtie
s. F
orty
pica
l inn
er d
iam
eter
s an
d fi
lmth
ickn
esse
s su
ch a
s 0.
25 m
m a
nd
0.25
m
, the
pha
se r
atio
is e
qual
to a
ppro
xim
atel
y 25
0. T
his
is a
typi
cal p
hase
rat
io v
alue
for
am
ediu
m b
oilin
g po
int
anal
yte
rang
e. I
n ge
nera
l, th
is p
aram
eter
is u
sed
by t
he a
naly
st t
o m
ake
afi
rst
sele
ctio
n of
the
col
umn
dim
ensi
on f
or a
giv
en d
istr
ibu-
tion
of
anal
yte
boili
ng p
oint
s.C
olum
n m
anuf
actu
rers
usu
ally
offe
r sc
hem
atic
tab
les
in t
heir
cata
logu
es g
ivin
g an
ove
rvie
w o
fty
pica
l bva
lues
for
dif
fere
ntap
plic
atio
ns. T
he v
alue
for
bty
p-ic
ally
var
ies
betw
een
50 (
colu
mns
wit
h th
ick
film
s fo
r vo
lati
les)
and
530
(wid
e-bo
re c
olum
ns, h
igh
boile
rs).
For
fur
ther
elu
cida
tion
, the
so
calle
d va
n D
eem
ter
curv
es [
9]w
ill b
e di
scus
sed
in t
he f
ollo
win
gch
apte
r w
here
HE
TP
val
ues
for
diff
eren
t ca
pilla
ry c
olum
ns a
repl
otte
d ve
rsus
the
ave
rage
line
arca
rrie
r ga
s ve
loci
ty [
u].
Wit
h re
gard
to
the
expe
rim
enta
lcu
rves
, the
HE
TP
val
ues
are
deri
ved
from
the
pea
k w
idth
s(e
q. 1
and
4)
and
are
plot
ted
as a
func
tion
of
the
aver
age
linea
rve
loci
ty o
f th
e ca
rrie
r ga
s.
A t
ypic
al c
urve
is s
how
n in
Fig
-
ure
II.2
for
2 c
olum
ns o
f di
ffer
-in
g in
ner
diam
eter
[10
]. T
he p
late
heig
ht is
cha
ract
eriz
ed b
y a
min
i-m
um v
alue
(H
ET
Pm
in)
at t
heop
tim
um li
near
vel
ocit
y [9
].
Bot
h co
lum
ns h
ave
a b
valu
e of
appr
oxim
atel
y 25
0. F
or c
olum
nsw
ith
such
a h
igh
phas
e ra
tio
val-
ue, t
he r
esis
tanc
e to
mas
s tr
ansf
erin
the
sta
tion
ary
phas
e ca
n be
negl
ecte
d an
d H
ET
Pm
inca
nth
eref
ore
be a
ppro
xim
ated
to
the
colu
mn
ID [
10]:
Ave
rage
Lin
ear V
eloc
ity (c
m/s
ec)
Conv
entio
nal a
nd U
ltra
Fast
Van
Dee
mte
r Cur
ves
C16
: 0 F
AM
E
isot
herm
al (1
50
C)
0.0
050
100
150
200
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
HETP(mm)
30 m
x 0
.25
mm
i.d.
0.2
5 m
film
10 m
x 0
.10
mm
i.d.
0.1
0 m
film
Figu
re II
.2: V
an D
eem
ter c
urve
s [1
0] fo
r 0.2
5 m
m a
nd 0
.1 m
m ID
col
umns
. Th
e ph
ase
ratio
is 2
50 in
bot
h ca
ses.
tran
sfer
red
rapi
dly
from
the
gl
ass
inse
rt t
o th
e co
lum
n (s
eeII
I. I
njec
tion
).
As
a co
nclu
sion
, a t
ypic
al f
ilmth
ickn
ess
in f
ast
GC
of
0.1
m(d
I=
0.1
mm
, b=
250
) is
use
d.
In s
peci
fic
case
s of
hig
hly
vola
-ti
le c
ompo
unds
film
thi
ckne
sses
of u
p to
0.4
m
(b
= 6
2.5
for
0.1
mm
dI)
may
be
used
.
Co
lum
ns in
fast
GC:
fil
m th
ickn
esse
s ar
e ty
pica
lly
0.1
m (
0.4
mm
)
As
seen
fro
m e
quat
ion
7 an
d F
ig-
ure
II.2
the
min
imum
the
oret
ical
plat
e he
ight
dec
reas
es li
near
lyw
ith
the
capi
llary
col
umn
inne
rdi
amet
er. F
urth
erm
ore,
the
asce
ndin
g pa
rt o
f th
e cu
rves
ris
esm
ore
grad
ually
, ena
blin
g th
eap
plic
atio
n of
hig
her
than
opt
i-m
um v
eloc
itie
s w
ith
littl
e lo
ss in
term
s of
res
olvi
ng p
ower
. To
conc
lude
, the
inne
r di
amet
er o
fsu
itab
le c
olum
ns f
or f
ast
GC
are
:
Co
lum
ns fo
r fa
st G
C:
inne
r di
amet
er
0.15
mm
6
7
-
Chro
mat
ogra
phy
Volu
me
2II
. BA
SICS
OF
SEPA
RATI
ON
IN
FA
ST G
C
14In f
ast
GC
app
licat
ions
, par
ticu
-la
r at
tent
ion
mus
t be
pai
d to
the
type
of
carr
ier
gas
used
. The
Van
Dee
mte
r cu
rves
hav
e di
ffer
ent
min
ima
for
diff
eren
t ga
s ty
pes
[9].
Thi
s fa
ctor
is s
how
n in
det
ail
in F
igur
e II
.3.
As
can
be s
een,
the
min
imum
HE
TP
for
the
hyd
roge
n cu
rve
isat
tain
ed a
t a
high
er a
vera
ge li
near
velo
city
whe
n co
mpa
red
to o
ther
carr
ier
gas
type
s. I
n ad
diti
on, t
heas
cend
ing
part
of
the
curv
e ri
ses
mor
e gr
adua
lly f
or t
he h
ydro
gen
curv
e. T
he d
ata
illus
trat
ed in
F
igur
e II
.3 w
ere
deri
ved
from
a0.
25 m
m I
D c
olum
n. I
n th
e ca
seof
sm
alle
r in
ner
diam
eter
s, a
sal
read
y re
ferr
ed t
o, t
he a
scen
ding
part
ris
es e
ven
mor
e gr
adua
lly a
sm
enti
oned
in s
ecti
on 3
.
5.Ty
pe of
carri
er ga
s and
avera
ge lin
ear v
elocit
y
The
afo
rem
enti
oned
issu
es h
ave
dire
ct c
onse
quen
ces
on G
C in
stru
-m
enta
tion
req
uire
men
ts s
uch
as in
ject
ion
syst
em, c
arri
er g
as p
neu-
mat
ics,
col
umn
oven
hea
ting
/coo
ling
and
dete
ctio
n. T
hese
asp
ects
are
sum
mar
ized
as
follo
ws:
GC
inst
rum
ent r
equi
rem
ents
fa
st in
ject
ion
35
auto
inje
ctor
, rap
id in
ject
ion,
hig
hsp
lit r
atio
s (s
ee c
hapt
er I
II.)
re
duce
d in
tern
al d
iam
eter
35
larg
e he
ad p
ress
ure,
hig
h m
axi-
mum
ope
rati
onal
hea
d pr
essu
re(u
p to
970
kP
a)
te
mpe
ratu
re p
rogr
am
35
aver
age
linea
r ca
rrie
r ga
s ve
loci
tysh
ould
be
cons
tant
ove
r th
een
tire
ana
lysi
s (t
he c
onst
ant
lin-
ear
velo
city
mod
e re
quir
es a
pres
sure
pro
gram
)
hi
gh s
epar
atio
n ef
fici
ency
35
linea
r te
mpe
ratu
re r
amps
are
high
er c
ompa
red
to s
tand
ard
GC
[70
C/m
in li
near
and
hig
her
(bal
listi
c)]
6.GC
hardw
are re
quire
ments
In m
ost
appl
icat
ions
, a li
near
tem
pera
ture
pro
gram
is e
mpl
oy-
ed r
athe
r th
an is
othe
rmal
ana
ly-
sis.
Und
er is
obar
ic c
ondi
tion
s,40
2060
N2
HET
P (m
m)
[u] c
m/s
HET
P
[u] c
urve
for C
17 a
t 175
C
with
k =
4.9
5
Capi
llary
col
umn:
OV-
101
25 m
, 0.2
5 m
m ID
. 0.4
m
film
0.4
0.8
80
He H2
Figu
re II
.3: V
an D
eem
ter c
urve
s m
easu
red
usin
g di
ffere
nt c
arrie
r gas
es
(Shi
mad
zu C
orpo
ratio
n, K
yoto
, Jap
an)
aver
age
linea
r ve
loci
ty d
ecre
ases
wit
h in
crea
sing
tem
pera
ture
s [9
].T
his
is d
ue t
o th
e fa
ct t
hat
the
gas
visc
osit
y in
crea
ses
linea
rly
hi
gh f
inal
tem
pera
ture
35
fast
coo
ling
of t
he G
C o
ven
(2 m
in f
rom
280
C
to
100
C)
hi
gh c
once
ntra
tion
ran
ge3
5hi
gh s
plit
rat
ios
shou
ld b
e av
aila
ble
(tot
al f
low
of
up t
o12
00 m
L/m
in)
sh
arp
peak
s in
fas
t G
C3
5hi
gh s
ampl
ing
rate
s an
d lo
w
filt
er t
ime
cons
tant
s (2
50 H
z,
4 m
s-co
nven
tion
al d
etec
tors
)
The
data
in b
rack
ets
refe
r to
spe
cific
atio
ns o
f the
GC-
2010
.
In t
he e
xam
ple
illus
trat
ed in
Fig
ure
I.1
(see
pag
e 9)
, a 1
20 c
m/s
ave
r-ag
e lin
ear
velo
city
was
app
lied.
In
orde
r to
obt
ain
this
vel
ocit
y an
in
itia
l pre
ssur
e of
502
kP
a w
as r
equi
red
at t
he in
itia
l tem
pera
ture
of
140
C. T
he g
as c
hrom
atog
raph
mai
ntai
ns t
he a
vera
ge li
near
vel
ocit
yco
nsta
nt o
ver
the
tem
pera
ture
pro
gram
(60
C
/min
up
to 2
80
C).
Thi
s is
ach
ieve
d by
the
app
licat
ion
of a
pre
ssur
e pr
ogra
m a
utom
a-ti
cally
cal
cula
ted
by t
he G
C s
oftw
are,
and
lead
s to
a f
inal
pre
ssur
e of
660
kP
a at
280
C
. The
coo
ling
tim
e fo
r th
is a
naly
sis
is b
elow
2
min
utes
and
the
cyc
le t
ime
is u
nder
4 m
inut
es.
wit
h te
mpe
ratu
re. H
ence
, the
sepa
rati
on e
ffic
ienc
y is
red
uced
as t
he t
empe
ratu
re in
crea
ses
(the
opti
mum
vel
ocit
y is
gen
eral
lyse
lect
ed f
or t
he in
itia
l tem
pera
-tu
re)
and
the
anal
ysis
tim
e is
als
opr
olon
ged
whe
n co
mpa
red
toco
nsta
nt v
eloc
ity
cond
itio
ns.
Con
sequ
entl
y, t
he g
as c
hrom
ato-
grap
h sh
ould
hav
e an
aut
omat
icpr
essu
re r
egul
ator
in o
rder
to
keep
the
ave
rage
line
ar v
eloc
ity
cons
tant
ove
r th
e en
tire
tem
pera
-tu
re p
rogr
am. T
his
issu
e le
ads
dire
ctly
to
fast
GC
har
dwar
ere
quir
emen
ts.
-
Chro
mat
ogra
phy
Volu
me
2II
I. IN
JECT
ION
REQ
UIR
EMEN
TS I
N F
AST
GC
16
As
can
be o
bser
ved
in F
igur
e I.
1(s
ee p
age
9), t
he p
eak
wid
ths
atha
lf h
eigh
t (F
WH
M)
are
belo
w0.
5 s,
muc
h le
ss if
com
pare
d to
conv
enti
onal
GC
(ab
out
3 s)
.T
he p
eak
wid
th is
aff
ecte
d by
the
tim
e ne
eded
to
tran
sfer
the
sam
-pl
e, v
apor
ized
in t
he g
lass
inse
rt,
onto
the
col
umn.
The
sam
ple
tran
sfer
mus
t be
fas
t en
ough
(mov
emen
t of
syr
inge
plu
nger
,pu
rge
spee
d of
the
gla
ss in
sert
).
In t
he c
ase
of a
rel
ativ
ely
slow
sam
ple
tran
sfer
rat
e (s
uch
as in
split
less
inje
ctio
n, s
ee F
igur
eII
I.1)
, thi
s re
sult
s in
an
init
ial
sam
ple
band
bro
aden
ing
on t
hefi
rst
part
of
the
colu
mn
[11]
, w
hich
has
a c
onsi
dera
ble
effe
cton
the
who
le s
epar
atio
n ef
fici
en-
cy. T
he w
ell-
know
n so
lven
tef
fect
indi
cate
d by
Gro
b [1
1] is
not
appl
icab
le a
s th
e co
lum
n in
-it
ial t
empe
ratu
re h
as t
o be
set
belo
w t
he s
olve
nt b
oilin
g po
int,
mak
ing
the
anal
ysis
tim
e lo
nger
,an
d in
add
itio
n th
e fi
lm t
hick
ness
is v
ery
smal
l. T
his
requ
ires
tha
tth
e gl
ass
inse
rt is
not
ove
rloa
ded
wit
h va
por
afte
r liq
uid
inje
ctio
n[1
1].
The
sha
rpne
ss o
f th
e pe
aks
isal
so a
ffec
ted.
For
exa
mpl
e, a
1
L n
-hex
ane
inje
ctio
n in
to a
Injec
tion r
equir
emen
ts in
fast G
Csp
lit/s
plit
less
inje
ctor
res
ults
in a
vapo
r vo
lum
e of
abo
ut 1
75
L a
t28
0 C
and
a h
ead
pres
sure
of
100
kPa.
In
the
case
of
acet
one
as s
olve
nt t
he v
apor
vol
ume
unde
r th
e sa
me
cond
itio
ns is
abou
t 31
0 L
. Typ
ical
gla
ss in
sert
volu
mes
on
the
othe
r ha
nd a
rew
ithi
n 1-
2 m
L.
Whe
neve
r sp
litle
ss in
ject
ion
isap
plie
d in
fas
t G
C, a
red
uced
volu
me
glas
s in
sert
and
hig
hpr
essu
re in
ject
ion
are
requ
ired
.In
gen
eral
, sam
ple
tran
sfer
has
apr
ofou
nd in
flue
nce
on p
eak
shap
e an
d ne
eds
to b
e op
tim
ized
:
Sam
ples
with
a h
igh
conc
entr
a-tio
n: h
igh
split
rat
io
At
low
con
cent
rati
on r
ange
s (l
owsp
lit r
atio
or
split
less
inje
ctio
n):
1. U
se o
f gl
ass
inse
rt w
ith
smal
lin
ner
diam
eter
to
enha
nce
purg
ing
wit
h ca
rrie
r ga
s.2.
In
the
case
of
split
less
inje
c-ti
on: h
igh
pres
sure
inje
ctio
n.
1. G
lass
inse
rt
Fig
ure
III.
2 sh
ows
the
effe
ct
of g
lass
inse
rt d
imen
sion
s on
peak
wid
th. H
ere
the
Gro
b te
stm
ix w
as a
naly
zed
wit
h a
stan
-
0.5
1.0
1.5
n-Decane
Gla
ss in
sert
with
sm
all
inne
r dia
met
er
Stan
dard
gla
ss in
sert
2.0
2.5
3.0
3.5
4.0
Dodecane acid methyl ester
Dicyclohexylamine
Undecane acid methyl ester
Decane acid methyl ester
Dimethylaniline
Dimethylphenolen-Undecane
n-Octanole
Min
utes
Figu
re II
I.2: C
hrom
atog
ram
s re
lativ
e to
a G
rob
test
mix
ture
.To
p:re
duce
d ID
(inn
er d
iam
eter
) gla
ss in
sert
= 1
mm
.B
otto
m:s
tand
ard
glas
s in
sert
, 4 m
m ID
.
Figu
re II
I.1: S
chem
atic
of a
split
/spl
itles
s in
ject
or (S
PL-1
7):
Fc: c
arrie
r gas
, Fs:
spl
it flo
w,
Fl: F
low
thro
ugh
glas
s in
sert
Fc
Fs
Split
ting
poin
t
Fl
Gla
ss in
sert
Carr
ier
Purg
e
Split
Colu
mn
flow
-
17
Chro
mat
ogra
phy
Volu
me
2II
I. IN
JECT
ION
REQ
UIR
EMEN
TS I
N F
AST
GC
dard
gla
ss in
sert
(4
mm
inne
rdi
amet
er
bot
tom
) an
d a
glas
sin
sert
wit
h a
1 m
m I
D (
top)
. All
othe
r pa
ram
eter
s re
mai
ned
unch
ange
d. I
n pa
rtic
ular
, the
peak
wid
ths
of t
he le
ss r
etai
ned
vola
tile
com
pone
nts
wer
e na
r-ro
wer
whe
n th
e gl
ass
inse
rtdi
men
sion
was
red
uced
. The
effe
ct o
f pu
rgin
g, w
hich
was
mor
e ef
fect
ive
for
the
redu
ced
IDgl
ass
inse
rt, i
s cl
earl
y de
mon
-st
rate
d. T
he s
plit
rat
io w
as 4
0:1
in b
oth
case
s. F
or in
crea
sed
split
rati
os t
he p
eak
wid
ths
wer
e al
sona
rrow
er w
hen
usin
g th
e st
an-
dard
gla
ss in
sert
.
In t
he c
hrom
atog
ram
illu
stra
ted
in F
igur
e I.
1 (s
ee p
age
9), a
200
:1sp
lit r
atio
was
sel
ecte
d. F
or p
eak
no 1
, the
pea
k w
idth
mea
sure
dw
ith
the
stan
dard
gla
ss in
sert
was
FW
HM
= 0
.42
s (s
plit
rat
io20
0:1
) in
con
tras
t to
1.5
6 s
inF
igur
e II
I.2
bo
ttom
(sp
lit r
atio
40:1
).
2. H
igh
pres
sure
inje
ctio
n
As
disc
usse
d in
cha
pter
II
(sec
-ti
on 5
), t
he c
arri
er g
as a
vera
gelin
ear
velo
city
has
a g
reat
infl
u-en
ce o
n th
e co
lum
n se
para
tion
effi
cien
cy. T
he a
pplie
d he
ad p
res-
sure
is t
here
fore
of
grea
t im
por-
tanc
e af
ter
sam
ple
tran
sfer
to
the
colu
mn.
In
this
res
pect
, it
is p
os-
sibl
e to
app
ly a
n in
crea
sed
pres
-su
re ju
st f
or s
ampl
e tr
ansf
er (
typ-
ical
ly f
or 3
0 s
to 1
min
). A
fter
this
per
iod
the
pres
sure
isdr
oppe
d au
tom
atic
ally
to
the
anal
ytic
al p
ress
ure
to e
nsur
e pe
akre
solu
tion
. Thi
s op
erat
ion
mod
e
is d
efin
ed a
s hi
gh p
ress
ure
inje
c-ti
on. O
bvio
usly
, the
pur
ging
of
the
glas
s in
sert
is in
crea
sed
whe
nco
mpa
red
to s
tand
ard
cond
itio
ns.
In c
hapt
er V
(se
ctio
n 1)
, whe
rean
alys
is o
f or
gano
phos
phor
ous
pest
icid
es is
dis
cuss
ed, h
igh
pres
-su
re in
ject
ion
(600
kP
a) w
asap
plie
d in
com
bina
tion
wit
h a
split
less
inje
ctio
n te
chni
que
inor
der
to o
ptim
ize
peak
sha
pes.
3. S
ampl
e ca
paci
ty o
f cap
illar
yco
lum
ns
The
max
imum
am
ount
of
sam
ple
whi
ch m
ay b
e in
trod
uced
ont
o a
capi
llary
col
umn
wit
hout
ove
r-lo
adin
g is
low
er f
or n
arro
w-b
ore
colu
mns
. Whe
n ex
cess
ive
sam
ple
amou
nts
are
inje
cted
ont
o a
cap-
illar
y, p
eak
fron
ting
eff
ects
are
obse
rved
[9]
. The
gen
erat
ion
ofas
ymm
etri
c pe
aks
may
obv
ious
lyle
ad t
o a
subs
tant
ial l
oss
in r
eso-
luti
on. C
onse
quen
tly,
the
inje
ct-
ed s
ampl
e am
ount
mus
t be
bel
owa
thre
shol
d va
lue,
as
may
be
obse
rved
in F
igur
e II
I.3
[10]
.H
ere
the
plat
e nu
mbe
r (c
alcu
lat-
ed f
rom
the
pea
k w
idth
acc
ord-
ing
to e
q. 1
) an
d he
nce
sepa
rati
onef
fici
ency
is p
lott
ed a
s a
func
tion
of s
ampl
e am
ount
for
tw
oco
lum
ns o
f di
ffer
ent
inte
rnal
diam
eter
. It
can
be s
een
that
for
stan
dard
col
umns
(0.
25 m
m I
D)
up t
o 50
ng
solu
te q
uant
itie
s m
aybe
inje
cted
wit
h lit
tle
or n
o lo
ssof
sep
arat
ion
effi
cien
cy. F
or a
narr
ow-b
ore
colu
mn
wit
h a
0.1
mm
ID
, ana
lyte
am
ount
s of
up
to1
ng m
ay b
e in
ject
ed w
itho
ut lo
s-in
g se
para
tion
eff
icie
ncy.
Am
ount
inje
cted
(ng)
0.1
1.0
10.0
60708090100
Plat
e N
umbe
r X 1
000
25 m
x 0
.25
mm
i.d.
0.2
5 m
film
thic
knes
s
10 m
x 0
.10
mm
i.d.
0.1
0 m
film
thic
knes
s
100.
01,
000.
0
Figu
re II
I.3: N
umbe
r of t
heor
etic
al p
late
s as
a fu
nctio
n of
sam
ple
amou
nt fo
r tw
o di
ffere
nt c
olum
ns
-
Chro
mat
ogra
phy
Volu
me
2IV
. DET
ECTO
R RE
QU
IREM
ENTS
IN
FA
ST G
C
20
Filter
time
cons
tant a
nd sa
mplin
g freq
uenc
y
1.Co
nven
tiona
l dete
ctors
Sign
al h
eigh
t = 6
3.2
%
Tim
e
Sign
al
Figu
re IV
.1: D
efin
ition
of f
ilter
tim
e co
nsta
nt t
0.03
00.
031
0.03
2
uV (x
10,
000)
Min
utes
0.0
0.5
1.0
1.5
2.0
0.03
30.
034
0.03
50.
036
4 m
s
20 m
s
50 m
s
100
ms
200
ms
Filte
r tim
e co
nsta
nt
Figu
re IV
.2: F
ID s
igna
l of c
hlor
odec
ane.
The
filte
r tim
e co
nsta
nt t
was
cha
nged
from
4 to
200
ms.
The
sam
plin
g fr
eque
ncy
was
250
Hz
in a
ll ca
ses.
In t
his
sect
ion,
con
vent
iona
lde
tect
ors
such
as
the
flam
e io
n-iz
atio
n de
tect
or (
FID
), e
lect
ron
capt
ure
dete
ctor
(E
CD
), f
lam
eph
otom
etri
c de
tect
or (
FP
D)
and
flam
e th
erm
ioni
c de
tect
or (
FT
Dor
NP
D)
are
disc
usse
d.
Mas
s sp
ectr
omet
ric
dete
ctio
n is
desc
ribe
d in
the
nex
t se
ctio
n.
As
men
tion
ed, t
ypic
al f
ast
GC
peak
wid
ths
are
0.5
s or
less
. T
he d
etec
tion
sys
tem
mus
t m
eet
a se
ries
of
requ
irem
ents
in o
rder
to m
aint
ain
the
peak
wid
th a
tco
lum
n ou
tlet
. In
this
sec
tion
the
requ
irem
ents
for
FID
are
dis
-cu
ssed
, but
the
pri
ncip
les
are
valid
for
all
of t
he c
onve
ntio
nal
GC
det
ecto
rs. I
n ge
nera
l, de
tec-
tor
peak
bro
aden
ing
may
be
caus
ed b
y tw
o fa
ctor
s. F
irst
ly,
the
poss
ible
pre
senc
e of
dea
dvo
lum
es in
the
sam
ple
path
.M
oder
n G
C d
etec
tors
are
gen
er-
ally
cha
ract
eriz
ed b
y lo
w d
ead
volu
mes
. Fur
ther
mor
e, m
ake-
upga
s is
em
ploy
ed t
o op
tim
ize
peak
shap
es t
hrou
gh a
n ad
diti
onal
flow
(ty
pica
lly 3
0 m
L/m
in).
For
mas
s fl
ow d
epen
dent
det
ecto
rs
(FID
, FP
D, F
TD
) th
is f
eatu
reen
hanc
es s
ensi
tivi
ty [
9].
In m
oder
n G
C, t
he d
etec
tor
sig-
nal i
s di
gita
lized
in t
he d
etec
tor
elec
tron
ics
and
the
A/D
con
vert
-er
pas
ses
digi
tal d
ata
to t
he P
C.
Due
to
the
pres
ence
of
RC
chai
n-co
ntai
ning
cir
cuit
s, a
nysi
gnal
am
plif
ier
has
a ce
rtai
nre
spon
se t
ime
wit
h th
e pr
esen
ceof
som
e sm
ooth
ing
effe
ct. T
his
shou
ld n
ot in
flue
nce
the
peak
wid
th w
hich
is d
eter
min
ed b
yth
e ch
rom
atog
raph
ic p
roce
ss
prio
r to
the
det
ecto
r (i
njec
tion
syst
em, c
olum
n). T
he p
aram
eter
of d
etec
tor
elec
tron
ics
rega
rdin
gth
e re
spon
se t
ime
is u
sual
lyre
ferr
ed t
o as
filt
er t
ime
cons
tant
(FT
C)
[12]
. The
ele
ctro
nic
dete
c-to
r si
gnal
am
plif
ier
cann
ot f
ollo
wa
sign
al in
an
infi
nite
ly f
ast
way
.It
nee
ds a
cer
tain
tim
e to
fol
low
rapi
d si
gnal
cha
nges
. In
Fig
ure
IV.1
thi
s pa
ram
eter
is v
isua
lized
grap
hica
lly [
12].
A t
heor
etic
alst
ep in
crea
se o
f si
gnal
is s
how
nhe
re a
nd t
he r
espo
nse
of d
etec
tor
ampl
ifie
rs in
dica
tes
that
it f
ol-
low
s th
e si
gnal
wit
h so
me
tim
e
dela
y (1
-1/e
t ). T
he t
ime
inte
rval
whi
ch t
he d
etec
tor
elec
tron
ics
need
s to
rea
ch t
he (
1-1/
e) f
rac-
tion
of
such
a s
tep
sign
al is
defi
ned
as f
ilter
tim
e co
nsta
nt.
Thi
s pa
ram
eter
sho
uld
bese
lect
able
[12
] to
geth
er w
ith
the
num
ber
of d
ata
poin
ts r
ecor
ded
acro
ss a
pea
k. I
n an
exp
erim
ent,
the
infl
uenc
e of
thi
s pa
ram
eter
on r
eal p
eak
shap
es w
as m
eas-
ured
. The
eff
ects
of
the
inje
ctio
nsy
stem
and
col
umn
on b
and
broa
deni
ng w
ere
redu
ced
as f
ol-
low
s:
1. A
0.1
mm
ID g
lass
inse
rt a
nd a
0.2
L in
ject
ion
volu
me
of ju
ston
e co
mpo
und
(chl
orod
ecan
e)w
ith a
hig
h sp
lit r
atio
(600
:1).
2. U
se o
f a 1
m c
olum
n w
ith a
0.
1 m
m ID
and
0.1
m
film
th
ickn
ess;
isot
herm
al a
naly
sis
at 2
00
C.3.
Det
ecto
r m
ake-
up g
as fl
ow o
f 60
mL/
min
.
Chl
orod
ecan
e w
as d
ilute
d in
met
hano
l. F
igur
e IV
.2 s
how
s th
ech
loro
deca
ne p
eak
whi
ch e
lute
sat
0.0
332
min
und
er is
othe
rmal
cond
itio
ns. T
he f
ilter
tim
e co
n-st
ant
tw
as v
arie
d fr
om 4
ms
to20
0 m
s. I
t ca
n be
cle
arly
obs
er-
Filte
r tim
e t
-
21
Chro
mat
ogra
phy
Volu
me
2IV
. DET
ECTO
R RE
QU
IREM
ENTS
IN
FA
ST G
C
2.Ma
ss sp
ectro
metri
c dete
ctor (
quad
rupole
MS)
0.2
0.4
0.6
0.8
1.0
1.2
1.4
Filte
r tim
e co
nsta
nt t
1.6
1.8
2.0
2.2
2.4
2.6
0.2
0.4
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
2.4
2.6
Figu
re IV
.3: C
hrom
atog
ram
s re
lativ
e to
a k
eros
ene
sam
ple
reco
rded
at a
filte
r tim
e co
nsta
nt t
of 1
00 m
s an
d 10
ms
resp
ectiv
ely
5 m
s10
ms
Normalized SN ratio
Tim
e co
nsta
nt
0
0.2
0.4
0.6
0.81
1.2
20 m
s50
ms
100
ms
200
ms
500
ms
1 s
2 s
4 m
s
Hal
f wid
th 1
0 s
Hal
f wid
th 1
s
Hal
f wid
th 0
.1 s
Figu
re IV
.4: S
igna
l-to-
nois
e ra
tio a
s a
func
tion
of th
e fil
ter t
ime
cons
tant
and
for d
iffer
ent p
eak
wid
ths
(sou
rce:
GC-
2010
ope
ratio
n m
anua
l)
ved
that
incr
ease
s in
the
filt
erti
me
cons
tant
aff
ects
bot
h th
epe
ak r
eten
tion
tim
e an
d sh
ape
aspr
edic
ted
from
the
ory
[12]
. The
full
wid
th a
t ha
lf m
axim
um f
or a
tva
lue
of 2
00 m
s (a
sta
ndar
dpa
ram
eter
in m
any
GC
sys
tem
s)is
abo
ut 3
s, w
here
as f
or a
tva
lue
of 4
ms
the
FW
HM
val
ue is
abou
t 40
ms.
The
eff
ect
of t
he
filt
er t
ime
cons
tant
on
peak
shap
e ob
viou
sly
has
a dr
asti
cef
fect
on
reso
luti
on a
s sh
own
inF
igur
e IV
.3. T
he f
igur
e ill
ustr
ates
two
kero
sene
ver
y fa
st G
C c
hro-
mat
ogra
ms
wit
h ap
plie
d fi
lter
tim
e co
nsta
nts
of 1
00 a
nd 1
0 m
sre
spec
tive
ly. T
he im
prov
emen
t in
term
s of
pea
k re
solu
tion
is e
vi-
dent
in t
he 1
0 m
s F
TC
ana
lysi
s.T
his
expe
rim
ent
show
s th
eim
port
ance
of
dete
ctor
par
amet
erop
tim
izat
ion
in t
erm
s of
pea
kre
solu
tion
. In
addi
tion
, the
FT
Cha
s a
cons
ider
able
infl
uenc
e on
the
sign
al-t
o-no
ise
rati
o (S
/N).
Fig
ure
IV.4
sho
ws
the
norm
al-
ized
sig
nal-
to-n
oise
rat
io a
s a
func
tion
of
the
filt
er t
ime
con-
stan
t. T
hese
cur
ves
are
plot
ted
for
diff
eren
t pe
ak w
idth
s. F
or a
peak
wid
th o
f 0.
1 s
the
opti
mum
filt
er t
ime
cons
tant
is 2
0 m
s w
ith
rega
rd t
o th
e S/
N r
atio
. The
opti
mum
FT
C v
alue
und
er s
uch
cond
itio
ns is
als
o de
pend
ent
onth
e sa
mpl
e co
ncen
trat
ion
and
rang
es b
etw
een
4 an
d 20
ms.
A f
urth
er e
lect
roni
c pa
ram
eter
of
impo
rtan
ce is
the
sam
plin
g ra
teor
, in
othe
r w
ords
, the
num
ber
ofda
ta p
oint
s ac
quir
ed p
er s
econ
dw
hich
are
tra
nsfe
rred
fro
m t
heA
/D c
onve
rter
to
the
PC
. The
num
ber
of p
oint
s m
ust
be s
uffi
-ci
ent
for
the
prop
er r
econ
stru
c-ti
on o
f a
Gau
ssia
n pe
ak (
min
i-m
um 1
0 to
15
data
poi
nts)
. If
the
num
ber
of d
ata
poin
ts is
too
low
,da
ta r
epro
duci
bilit
y is
red
uced
.T
he f
ilter
tim
e co
nsta
nt a
nd t
hesa
mpl
ing
freq
uenc
y pa
ram
eter
sne
cess
ary
for
the
rang
e of
pea
kw
idth
s ob
serv
ed in
gas
chr
o-m
atog
raph
y w
ere
sum
mar
ized
by
J.V
. Hin
shaw
[12
]. T
he la
tter
repo
rted
tha
t fo
r pe
ak w
idth
sbe
twee
n 0.
1 an
d 0.
5 s
the
filt
erti
me
cons
tant
and
sam
plin
g ra
tesh
ould
be
abou
t 10
ms
and
20 t
o10
0 H
z re
spec
tive
ly.
Min
utes
Min
utes
The
mos
t co
mm
on m
ass
spec
tro-
met
ric
dete
ctor
use
d in
gas
chr
o-m
atog
raph
y is
the
qua
drup
ole
MS.
Wit
h re
gard
to
fast
GC
/MS
anal
ysis
, the
MS
dete
ctor
obv
i-ou
sly
need
s to
be
fast
eno
ugh
for
the
rapi
d el
utin
g an
alyt
e ba
nds.
For
iden
tifi
cati
on p
urpo
ses,
G
C/M
S ap
plic
atio
ns a
re c
arri
ed
out
in t
he f
ull s
can
mod
e in
orde
r to
per
form
a M
S lib
rary
sear
ch. I
n th
is o
pera
tion
mod
e,ev
ery
data
poi
nt c
orre
spon
ds t
o a
com
plet
e m
ass
spec
trum
ove
r th
em
ass
rang
e se
lect
ed (
scan
).
Aft
er p
eak
assi
gnm
ent,
the
SIM
mod
e (s
elec
ted
ion
mon
itor
ing)
may
be
used
in o
rder
to
incr
ease
the
anal
ytic
al s
ensi
tivi
ty.
In o
rder
to
atta
in t
his
data
, tw
opa
ram
eter
s of
the
GC
/MS
hard
-w
are
mus
t be
con
side
red:
fir
stly
,th
e m
ass
rang
e se
lect
ed b
y th
ean
alys
t m
ust
cove
r al
l the
ana
lyte
ion
frag
men
ts in
ord
er t
o D
-
Chro
mat
ogra
phy
Volu
me
2IV
. DET
ECTO
R RE
QU
IREM
ENTS
IN
FA
ST G
C
22
3.87
3.88
3.89
3.90
3.91
3.92
3.93
3.94
3.95
3.96
3.97
3.98
6,08
6,27
13.
922
TIC*
1.00
Min
utes
m/z
R.Ti
me:
3.9
21 (S
can#
: 302
6)
m/z
R.Ti
me:
3.9
22 (S
can#
: 302
7)
Figu
re IV
.5: D
efin
ition
of s
can
spee
d, in
ter-
scan
del
ay a
nd s
ampl
ing
freq
uenc
y fo
r a q
uadr
upol
e M
S
100
4080
120
160
200
240
280
100
4080
120
160
200
240
280
Scan
N
m1
Inte
rval
l I:
1/I =
sam
plin
g fr
eque
ncy
Inte
r-sc
an ti
me
RF s
etup
m2
Scan
N +
1
2.4
min
.2.
52.
4m
in.
2.5
Lina
lool
61,3
07,1
1061
,307
,110
TIC
TIC
2.4
min
.2.
5
61,3
07,1
10TI
C
2060
100
140
180
m/z
Wile
ySI
= 9
7
2060
100
140
180
m/z
Wile
ySI
= 9
8
2060
100
140
180
m/z
Wile
ySI
= 9
7
Figu
re IV
.6: L
inal
ool p
eak
gene
rate
d by
a na
rrow
-bor
e co
lum
n (F
WH
M 0
.6 s
)an
d th
e sp
ectr
a re
cord
ed a
t the
beg
in-
ning
, ape
x an
d en
d of
the
peak
afte
rba
ckgr
ound
sub
trac
tion.
Spe
ctra
sim
i-la
ritie
s ar
e 94
, 96,
94
usin
g th
e W
iley
MS
libra
ry.
perf
orm
a li
brar
y se
arch
for
com
-po
nent
iden
tifi
cati
on (
scan
). I
nth
is c
ase,
the
sca
n sp
eed
shou
ldbe
hig
h en
ough
so
that
the
rel
a-ti
ve in
tens
itie
s of
the
fra
gmen
tsdo
not
cha
nge
sign
ific
antl
y fr
ompo
int
to p
oint
acr
oss
a na
rrow
peak
. In
this
res
pect
, a lo
w s
can
spee
d w
ould
res
ult
in lo
w q
ualit
ylib
rary
mat
ches
. Sec
ondl
y, t
hesa
mpl
ing
freq
uenc
y, w
hich
cor
-re
spon
ds t
o th
e nu
mbe
r of
sca
ns(o
r th
e nu
mbe
r of
SIM
dat
apo
ints
) pe
r se
cond
, is,
as
afor
e-m
enti
oned
, a f
unda
men
tal p
ara-
met
er. F
ast
GC
/MS
appl
icat
ions
requ
ire
a hi
gh q
uadr
upol
e sc
anra
te (
up t
o 10
,000
am
u/s)
and
, in
addi
tion
, a lo
w in
ter-
scan
dea
dti
me
(res
et t
ime
of t
he e
lect
ro-
nics
) so
tha
t th
e sa
mpl
ing
rate
m
ay b
e su
ffic
ient
ly h
igh
(up
to50
Hz/
100H
z in
sca
n/SI
M m
odes
for
the
GC
MS-
QP
2010
). T
his
situ
atio
n is
sho
wn
in F
igur
e IV
.5.
The
tru
e sc
anni
ng s
peed
of
the
quad
rupo
le is
cal
cula
ted
by t
hesc
an r
ange
div
ided
by
the
inte
rval
tim
e m
inus
the
RF
set
up t
ime
whi
ch r
ange
s fr
om 5
to
10 m
s fo
r th
e G
CM
S-Q
P20
10. I
n F
ig-
ure
IV.6
thi
s is
dem
onst
rate
d by
expe
rim
enta
l dat
a. A
lina
lool
peak
was
sca
nned
wit
h a
20 H
zsc
anni
ng f
requ
ency
and
a s
elec
t-ed
mas
s ra
nge
of 3
0 to
350
am
u.T
he a
naly
sis
was
car
ried
out
wit
ha
SPB
5 10
m, 0
.1 m
m, 0
.1
m c
ol-
umn.
The
pea
k w
idth
at
half
heig
ht is
abo
ut 0
.6 s
and
abo
ut1.
2 s
at t
he b
ase
resu
ltin
g in
24
dat
a po
ints
acr
oss
the
peak
.A
s ca
n be
see
n, t
he q
ualit
y of
the
spec
tra
in t
hree
poi
nts
acro
ss t
hech
rom
atog
raph
ic p
eak
is g
ood
(a W
iley
libra
ry s
earc
h w
as p
er-
form
ed).
The
spe
ctra
sim
ilari
ties
,94
, 96,
94,
indi
cate
tha
t th
ere
isno
ske
win
g.
-
Chro
mat
ogra
phy
Volu
me
2V.
APP
LICA
TIO
NS
IN F
OO
D A
NA
LYSI
S
24
1.Or
gano
phos
phoro
us pe
sticid
es in
food
matr
ices
Org
anop
hosp
horo
us p
esti
-ci
des
(OP
Ps)
are
wid
ely
used
in a
gric
ultu
re
in o
rder
to
prot
ect
a br
oad
rang
eof
pro
duct
s. U
nfor
tuna
tely
, the
pres
ence
of
thes
e to
xic
com
poun
dsis
oft
en d
etec
ted
in f
oods
.
The
max
imum
allo
wab
le c
once
n-tr
atio
ns o
f O
PP
s in
foo
ds is
,
3.00
5
Min
utes
Tric
hlor
phon
1.75
1.50
1.25
1.00
0.75
0.50
0.25
0.00
2.00
1015
20
RTX-
5: 1
0 m
, 0.1
mm
, 0.4
m
RTX-
35: 3
0 m
, 0.2
5 m
m, 0
.5
m
Phos
pham
idon
(E)
Azi
npho
s - M
eEt
hion
Fent
hion
Phos
pham
idon
(Z)
Carb
ophe
noth
ion
Prof
enop
hos
Met
hida
thio
n
Tolc
loph
os -
Me
Dis
ulfo
ton
Dio
xath
ion
3.00
1.50
1.25
1.00
0.75
0.50
0.25
0.00
1
4
Min
utes
68
1.75
2.00
2.25
2.50
2.75
11
10
9
8
7
6
5
4
3
2
13
uV (x
1,0
00.0
00)
Figu
re V
.1: T
op:c
onve
ntio
nal G
C ch
rom
atog
ram
of o
rgan
opho
spho
rous
pes
ticid
e st
anda
rds
in a
tom
ato
extr
act.
Conc
entr
atio
ns v
ary
bew
een
125
and
1,00
0 pg
. Bot
tom
:fas
t GC
orga
noph
osph
orou
s pe
stic
ide
anal
ysis
car
ried
out w
ith a
RTX-
5 : 1
0 m
, 0.1
mm
, 0.4
m
col
umn.
Peak
iden
tific
atio
n:1.
Dic
hlor
phos
, 2. T
richl
orph
on, 3
. Dio
xath
ion,
4. P
hosp
ham
idon
(E),
5. D
isul
foto
n, 6
. Pho
spha
mid
on (Z
), 7.
Tol
clop
hos
met
hyl,
8. F
enth
ion,
9. M
ethi
dath
ion,
10.
Pro
feno
phos
, 11.
Eth
ion,
12.
Car
boph
enot
hion
, 13.
Azi
noph
os m
ethy
l
how
ever
, str
ictl
y co
ntro
lled
[13]
.In
Ger
man
y, t
he w
ell-
know
nD
FG
S19
(D
euts
che
For
schu
ngs-
gem
eins
chaf
t) is
em
ploy
ed f
orth
e de
term
inat
ion
of t
race
s of
thes
e su
bsta
nces
in f
oods
. Thi
sSt
anda
rd is
als
o pr
esen
t in
Eur
o-pe
an r
egul
atio
ns a
s D
IN E
N15
28-3
, DIN
EN
123
93-2
. In
addi
tion
, the
se m
etho
ds d
efin
e
the
proc
edur
e fo
r th
e de
term
ina-
tion
of
orga
noch
lori
ne, n
itro
gen-
cont
aini
ng a
nd o
ther
typ
es o
f pe
s-ti
cide
s. T
he p
roce
dure
ste
ps a
rem
ainl
y: 1
. ext
ract
ion
and
part
itio
n,2.
gel
per
mea
tion
chr
omat
ogra
phy,
3. m
ini s
ilica
gel c
hrom
atog
raph
yan
d 4.
ana
lysi
s w
ith
GC
-FT
D,
GC
-FP
D o
r G
C/M
S.
A c
hrom
atog
ram
rel
ativ
e to
an
OP
P-s
pike
d (a
mou
nt r
ange
betw
een
125
and
1,00
0 pg
) to
ma-
to m
atri
x is
sho
wn
in F
igur
e V
.1.
The
col
umn
used
was
a R
TX
-35
30 m
, 0.2
5 m
m, 0
.5
m. T
he f
ig-
ure
also
sho
ws
the
resu
ltob
tain
ed w
ith
a R
TX
-5 (
5 %
phen
yl),
10
m, 0
.1 m
m, 0
.4
mco
lum
n un
der
fast
GC
con
di-
tion
s [1
4] (
tem
pera
ture
pro
gram
from
100
C
(1
min
) at
80
C/
min
to
220
C a
t 10
C
/min
to
240
C a
t 50
C
/min
to
320
C;
carr
ier
gas:
H2
(120
cm
/s).
The
inje
ctio
n vo
lum
e w
as 2
L
in t
hesp
litle
ss m
ode.
In
orde
r to
incr
ease
the
sam
ple
tran
sfer
spee
d (s
ee a
bove
) a
600
kPa
high
pres
sure
inje
ctio
n w
as a
pplie
dfo
r 1
min
ute.
The
pea
k w
idth
s(F
WH
M)
are
appr
oxim
atel
y 3
sin
the
sta
ndar
d an
alys
is a
nd,
belo
w, 0
.5 s
in t
he c
hrom
atog
ram
obta
ined
wit
h th
e na
rrow
-bor
eco
lum
n. A
s th
e ar
ea in
gen
eral
isde
term
ined
by
the
sam
ple
amou
nt w
hich
was
not
cha
nged
(bot
h ru
ns w
ere
carr
ied
out
inth
e sp
litle
ss m
ode)
the
sig
nal-
to-
nois
e ra
tio
was
hig
her
in t
he f
ast
GC
exp
erim
ent.
The
ret
enti
onti
me
of a
zino
phos
met
hyl w
as 2
2m
inut
es in
the
sta
ndar
d an
alys
isan
d 9
min
utes
in t
he f
ast
resu
lt.
A c
hrom
atog
ram
der
ived
fro
m a
blac
k te
a an
alys
is is
sho
wn
inF
igur
e V
.2. T
he a
naly
tica
l res
ult
indi
cate
d a
cont
amin
atio
n of
diox
athi
on (
225.
2 pg
), p
hos-
pham
idon
(67
.1 p
g), d
isul
foto
n(2
17 p
g), d
ichl
orph
os (
243
pg),
ethi
on (
145.
1 pg
) an
d az
inop
hos
met
hyl (
244.
8 pg
).
The
lim
it o
f de
tect
ion
in a
fas
tG
C a
pplic
atio
n m
ay b
e de
rive
d,fo
r ex
ampl
e, f
rom
the
res