REPQ1r1* OF THE TASK FORCE
ON THE GAS VIASE OF THE CIGAR1~11'P. SHOXE
CORESTA Conference - Y,01,`TREUX - Septerber
P3-27, 1974
0
I INTRODUCTION THE GAS PHASE OF CIGARETTE SMOKE
1.1 - Definition - Prepggion
1.2 - Problems of Aging - Conservation
1.3 - brawbac)~s and Advantages of Determinations
on the Gas Phase
1.4 kethods of DeterminatioYi Used
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IM-RODUCTION : THE GAS PHASE OF CIGAIRUM'E'
I.1 - Definition - Proparation:
:-.L-cJ9aKettc s.-ock6' J-- ;,n acronol it it;
th-c-c-tical17 FO--~ULIC
to distinguish a gas phase and a particulate
phase. In prar-tice,
the problem of the separation of the two phases is
less simple:
any screen capable of retaining particle& larger
than a certain
a hig-1, PTOT_Ortio7i -of pan=
with the gases and vapours. Furtherrore, as puffs
succeed one
another, the filter become:. partially blocked so
that, durinU an
"L,pli:aLiun, certain st--mi-vulaLilu pru6ucLs
~UqLc~lvud 2W the
condensate will pass through the filter, whereas
(which is more
troublesome in gas phase determinations) c ertain
volatile products
could be dissolved by the condensate. The great
complexity of the
equilibria involved means that the gas phase is
defined empirically
and rather arbitrarily as being "that which
passes" through a glass
fibre filter of well defined mesh size, known as a
Cambridge filter,
placed immediately behind the smoked cigarette.
Tobacco moisture
content# the -conditions of. temperature and
moisture obtaining in.
the-smokinq room, the type of _Mtoking machitie
and how it it
adjusted should also, naturally. -be carefully
defined. This
a priorf-definition of the srDke phase is to be
the subject of
an ISO standard, and what we refer to as the "gas
phase" 'in the
following article is the fraction of smoke
separated according to
this standard.
L. 2 _Problems of Agifiq ConserVationj__
Most of,the compounds found in the gas phase which
are of
interest in determinations arereactive compounds
(NO acrolein,
H2 S, HCN):. it is therefore de.%irable tp, carry
out determinations
1 :: ~b~ e~_
-injection in Gq or,:by non-dispersive
spectrometry) or to convert
. ~'_ - - .- - I _. -, , _t'', --able' id4i & I
~0-
~em very qu) o -in 0
Y
'xequire.no' pr'dcatti6ris, -exc
n (CO - 'C02) apt, - for - tk"
"Jmterial~ of the container in which they are'
stored. Furthermorei.
the, metal portions-of the
app4rat%is~'.Vi~l.c*!talyse' the. reactions
Th
p~f a, <jky6n product.trore
effj.ci=tly,,:.cauk;in9 i~ to,4isappear. e
articles GROB. -(2) an~ SCHONHERR et al (41)
deal_with the
on"
lems, of
prob gas ph"i dfazia~~&ti
The dr&wb.aokis are'p
rincipally me
146 -the mixture of. g0s. and. yapours knj*n es t
e
-.gas ~hase".co"tanf_ for a gkven type of
cigarette?-:._ Proviaed
that, the- precautions roq4ti qd in 1 1. 1 area:
taken, thii answer is.
1 ?n .. A
ihsar-ar 4cv- -two cigAvetteit 6f Vic, ~Sa4 -type
-axo - -
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Percentage Of ULL, comp'Jilunt. CA th'! Wtal nwukv
J,;,1--1irq iaiLc, the
gas.phaE--e is not kn(A..,n, dett.:rmination in
the .Jkls 11.6!;C, is of
little intoru:;t. With respQct to this protAcm,
for example,
reference may be madr: to the artic-lo,_ by WALTZ
1. HAUSERMIM (5)
and WILLIAtj,1011 & ALLY1,1! (6). This is why we
have restricted our
study to compounds which arc sufficiontllk
volatile for it to be-
a.it.ui.it;-J LhaL 1,r pcrtioriL of thcm exi=t in
th~, ciass r , ,
hne
although definite indications do not always exi9t
as to their
distributicii in the two phases.
7 he adv:tntagcs -are r~f n mnrp prActical nnture!
- the relative simplicity of this mixture of
volatilia-
pxuduct:~,, whiLa, CCU!-. not con'Lain i:cztnous
product= (a great
advantage for colorimetric analysis and gas
chromatography, where
there is no short term threat to the columns);
owing to this "cleanliness", the possibility of
analysing ."native" products (with a time lag
which may not be more
than a few seconds for analysis of one puff,.
which reduces the risks
of destroying the corpotuid)..and of using
spectrometric. or. colori-
metric methods without excessive absorption.-
To sum ups although the gas pha" is not smoke, in
the
case of important compounds, its analysis makes it
possible to
obtain:
in certain cases, a value which can be taken as
being identical to that of the whole smoke (CO,
410, H2 S)
in other cases,.an indicative value.(but which
has.
the 'virtue. of existing) which enablesi
comparisons to be'made between different
treatments', manufacturing -pethodp -_Iftizturg~s
of tobaccos, etc.,
exact information to'be,obtaiiw4pri the
QZMQMtr_*t_;LM Qf Srvc!lrt0i_,rb -LO 1qP -mir
_M, ' ' _-Iq~,t, __ysr -
~which.can be important in thecase of studies on
absorbent filte~a.,.
which -aLftect compounGs i
The ~Ualitative composition of the, gas phase Was
been dealt.
with firs ,t~ by WYNDER HOMANit J7) ; theyi ` irf.
greatet ~ devAi I - by
MZ~IMOR.$T & SCHUtZ. (1~, 1~his royiew. only q"ls
wtth the mthods
for determixiing. some -of tbe- major components
smoke ~re';ent in
them gas ~]~h ase~ in their tot~4~ty, or in' large
proportions, with
1 ;0~. further inf,6rmation o)v- chroaktographic
-determiaatij,~ns of thp.
as phase,, taken,, as a vhole. It is.there fore,,,
-in a.w
ay a thorough
re J 3Y which, s it deals with -.A ver1r much
larger . ndmber of,
compomde' -~60 ch6ic*`;6,f`.refeLzeAc1efi. Fojr
each
had M be~.Umited i&
compouad Studied, -We shall t".,to give.an.idea.
of all ~t;be methoog.
yropo~ad and thote tftiCk appear to~be-the moats
intaxesting-at,preunt.-
erml
[on 11sociz
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(dispui:.;ivu oi: iic)n-1ir~por.J,?r 3)q UV) r ti
nativt~ compound.
F%dvnntaqeR: rapidity and simplicity; secondary
reactiras
roducr!d.
Drnwbackr-i: risks of interferences cn the
selected wavelengths;
.difficu_Lt to autamatt`_
Colorimetrx on an addition compound.
Advantnqas: autemation ponsible (at least for
cieasurement))
can eliminate seconnary redctlons vhich woulL,
consume the
compound to be determined.
Drawback: risk of.int.-rferences whicb are
sometimes uncontroll-
able.
Gas chromat,M2L3~y - on conventional column
- on capillary colu=
with various detectors (thermal conductivity,
flame ionization,
flame photometry, thermionic, electrolytic
conductivity, etc;.~.
Advantages: "visualisation" of the mixture,
therefore relative
specificity, "pecially with -specific detectors
(flame photo-
metry, thermionic or electrolytic tonductivity);
generally
speaking, good reproducibility.
Drawbacks: the difficulty of knovring whether a
peak is not
composite (except- wheh a coupled.nass
ppectrometer is
-available) ; the necessity of manually measuring
pcaks, or
using an integrator (postly) I special experience
for
capillary columns.
4 Ej!FS!o njS.21 et- -p6~entiometry)
_E~~L _nttods (selective electrod
of-.measurement...
7-
De~MbMkq t -,-difficult.. _tp. ax~tq!wte; may,
furthermore, r
a preliminary- reaction which can taxid a(;e,xtain
'wt6vnt. of....time-
PRINCIPAL CC)MObims, bow Drrrmim) 'ju 5r.,.J, GAS-
PHASE OF CIGARETTESMOXE
11. 1 - Carbon, Monoxiaer CO -(B.P. 1.- 5 0c) 4-
_:E~ L, VIG thk &dtQ~Qit:ia In
Q..D.VoAuctm to de'timl 4_
it. is,~stable' -h i#y reactej .,intier, a.enL
In the, gas. phase a
conditiong,'. Iwd -is a.'perugment-9".. ftt
certain-precautions. should
to'4Void by. di-ffu,-i?,)n wh" the gas -phase. is
-stored
pxior'to datermitafion 'T.~Vw &,1Ji9FFMANN-. (10)
11(
)RTO
GUERIN flOji_ the'-best contaihers-W4ox tt be
-blags made from
chloii~O or---rletathene". (Pblythene/pow
nn~l rubber,',,44-
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cout,L,nt of' Mtrofje,
.11 or belinjil). Failinq this, Co j.,.-,ty IAa
Vx0duced by thc actiLn of ,;ulphuric, acid on
formic iciel
[cf. KRUSZYMA-1 & (17)].
Two types of methods compete for deter-ninationz
a) Chromatcgraphic mc-thods:
-------------------
Taking into account the high concentration of CO
in smoke
(about 50,00U ppm., or.5%), the detector is a
thermal conductiv:Ltv
detector (katharomcter?. KLIMISCH & I-IFTSSNER
(15) in a recent
in-.-c-sLigation nevertheless use flame.
ionisation detection, after
reduction of CO to wethane Cl.'4 on a nickel
catalyst. The increased
sensitivity thus obtained does not appear useful
for determinations
on "native" smoke (even puff by puf f) . but can
become so for
detcrminatio-s on atmospheric samples, or-for
physiol-ogical studies
on CO.'
Conventional columns, 1/4 or 1/8 inch in diameter,
are used.
Analysis can take from I minute to I hour,
depending on the
temperature of analysis, length of the column,..
and the type of
adsorbent Isolid) used as packing, which'may he:
- silica gel:-
As CO is not separated from atmospheric gases, as
opposed-,,,
to C02, a.smiAll amount of iodic acid anhydride,
which oxidises, Co
to C02 # is placed in the. middla of the. column,
which perrhits the
permanent gases, CO and C02, to be finally
:separated. The fact
that the analysis only lasts for 2 minutes, and
the strength of the
isubstrate , are two very positive elements- of
this method [WATANABE
-A aMBASHI-i2l); .cf. also BRUNNDIANN.& HOFFMAIM
(10); DONZEL (12-)].-
The 1265 nand Ag. cartri4ge_should probably.'be
replaced every 200. to
300 determinations..
6 psctilied by- MORLE __Ualt _-d=ation GL.
analysiaj.- 3 m"Wes J
for CO,,8 minVtes-for CO and C02, with temperature
progimimed-it W-
to 100%j thim by. KLIXISH (~fi) : duration
qf~4na~ysis, leep, thani
rainik . _whi,~ n'
-h. Maj"es, it poosible to m~ the 'C;0 ~n,
each_puf~
of"tbe,same ciga~rett,~.
'It iffiouid- be- 4th
not at it is only necessaryto
carry,,
out su6h-'rapid analyses for-fundamental studies
on eigarette
-in eadxalt, yield'per-,4iqare~t' ed in, thl-6
e is_s~udii 1
case,.. the' analysis'~hould bp "i6ker-than.
tmoking out h
ab 10 mi utes)
_pliclatio"11
doulof the - Swokilic
of the measurement are reql4red.
_advlant.ale of catho'njwlecurar-bieves 6%;tr
zqqlite
T
he
Molwular. sieves is -Ithekt- ~1~by are. not
9"Siti~e to, M'0'3~stair~ (and
therefore do not riecessitate... desiccation of
ihe gai phase) As the*
.:column is. nqt.. very' fragile, marry analyses
can' be.-c fected (abput .
.,1,000) without regeheration
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typo 13 X: cf. Y-LI111SCII F, !,Eir;SW.~T Q 5)
v1)0
det(.-rmirie C114 and CO in the form of U1,,
!:-1rcc .-,*.-.;:oqenation,
in less than 2 minutesi AYRES M use-, tv.-7,
colurim.- in rarall~J,
the zoolite. colu!fai boing u,3ed for the
separation C,.T CO from
perm,ment ga,.;c-G after absorption of, Co-~ on
soda Wuratic_n
about 15 minutes for permanont gases, Ic!,s for CO
'Ionu) .
The sensitivity u:1 zeolitez to waLei~ rezults in
most authors vigorously drying thn gas phase Oeith
I'U W10 4) 2 for
examp) e) , ancl the 11'q11 C02 retention level
nec3snitatc-s very
strong heating [cf-, MUF & KUHN (20)
cation eychuige resin;
A cation exchange resin (Mterlito)- in the M form,
reduced with hydrogent. Ct. 110V1'014 & GULi-LIN
(14). Aa!alysis iLa~cs
less than 4 minutes. The manufacture of adsorbent
nay pose
problenis (notably, reproducibility of Rf from one
batch to another).
it should be noted that a method using-porous
-reLin
(Poxapak with teiaperatuim programming from -70%
[MOPIE & SLaAN
(1-9)), has beon given up by its authors in favour
of a methed Dn.-
a carbon sieve [14ORIE (18)), as the'apparatus is
cheape r and results
are more easily reproducible.
I?) Non-cUspersive IR spectrometry method:.
----------------------------- -
Although. a non-dispersive IR apparatus costs
about the same
as a chromatograph a few laboratories now use them
for dcter_--~ininq
CO, probably because of its specificity [which
-necessitates two
0
analysers. if CO -and.C 2 are both to be
det-erminedl cf. IKIILLIA14S
& BELK-(22)).
The-method is simple and analysis very rapid
Ut-enables the
'ing
evol-11ti on of Co concentration in' the smoke to
bc followed, Out
own to
w'ho are kn
one puff cf.-. WILLIAM-& Br~LK (22) keqnXe
'
this methbd (AYTMS (9) ~GAISCH' U 3) att-
s4tialied with it, tven
It 1.t- is slltg~htaql
Fin&lly, an, automatie. method tor oeter".
lnilri4- C6 J:~irr,bj, Pt~ f~
a tar :the ~m'oke, from ~2O.ckgarettes has bee4i
.0011~cted Isboked
=
Itanebusly In line)-is-deseribed-'by COLLINS 4
WILLIAMS (11)
S.
11. 1- 14itrogen Oxides M (D.P. C11 1402 (a. P.
+21-3*6)
Routifte determination of'nitrous Qxida N;&
Immti6ned. fibrz'
"
t. I is
PHILIPPE BACKn-Y, (12) -c
ciample, i~re" kiot arried outs
x~j -"xi-p - -an& not -sasi 1y -.'ox"Uuab1 e
under. Aibiu
-comp9nent of, h~qhe:r.nitrocjen oX4_dds'1
-Nitric oxidd-'M, tl)e major,
(N6 '00 + N in 'native vmMe .RORMAN. gkiTn Q0)_;,
i PAWTFF~V;R. V
X ()2
WILT I +J-partis iy oxidises. fairly
9 EEHOMM. '(2 4).1 AMS i BEM (37
_-quiclcly to aitrogqa.~.Grolkide NO r:,wbiant
conditions
2 $maq
(24)1. arf:R
[EMMEMMM & SEE110FER sLoM. &,rz. (34 14117 in ti-
v
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sulp Ude jh10R14hN & VINOW (31)), and
methanf!thiol [21.0AN & XTyr
I . . !.:r,
(34)). it woula- tlierefore ho c1c.:A.rable tc,
havo a LT-Ithod Which
does not suffer from interferences zuid pormits
almoct instantolic-ous
analyGis after one cigarette Is swoked, or,
bettor, after eacit ptiff.
Uje mout satisfacLc.-Ly veUicZ for NO,_'Lrom UIL!
Point of. ViLAr: 0"'
rapidity and specificity (allowing for thc
regligibIL- amounts of
N02 in native ctrckc) would doubtless be the
1.uiiintF;rr_-nce producod
by the reaction 1-10, + 0 3 --) NO, + 0 2*
Unfortunately, the apparatus
indibpensable for this mc-thod Is coutly (ziliout
$10,000).
Gas phase chromatography is c~nly usc_(l for smohe
by TIORT011
et al. A28), iO-zo use a 1/4 inch column. pachc_,d
with 29t Pennealt 22.1
and 4% KOH on "Gas-Chrom R" 80-100 mesh, and an
electrolytic con-
ductivity detector. Their results agree
"reasonably well" with
those obtained by line specttometry.
All the other methods-described-consist of:
a) either immediately determining the nitroge n
oxides in the "native" gas phase
b) or -cohtadtintj them immt~dirttely- Vith- a
reacft-rit
having more rapid kinetics than the-.o.ther smoke
components In
their.'reaction with M..
The methods of type ~j used in Dractice are.
Non-dispersivo IR spectrometry: KLLIAMS & BELK
(37).
A study'Df -the possible interf4ur-ences shows
that, apart from.
ethylene-, isoprene and acetaldehyde, the
conponents of the gas
phase are.not very-troublesome, and that errors in
meaGurements- of
NO -due tq .'t ing-that of the above 3 -coL,
~he# pmsenpe. iqclud npounds)
r_,thc-4 abo. t 6%.'
are no.g;eate u
dcz"i4ed--!~y UrXM? C -.6
S (36) 22 7-25mg: alter the C*vdbridge Mter, the
smoke
b. -i Iroug I reduce$
4 ~t It I- r ox spec3-a.L act vaireu,,:cgroon
thi;t interfe~renae's duo 'tq.. tl~e 4ther
components qf Ithe' gap-phase)
can be'used for'xoutine analysis [AYRES (23)] -and
permits measurements,
re ted 3 times 'in'. 40 minutet, poff by,puff.-
Tho. only 'two dr a-.Z a ck s-
to the r.Qthod" (a Rart~fr on-the :pr.iL-e of
t4e,app~-ratuss,.,which, i.s "in
fairly q."aral.,usel .#ret'.. rather =Tlicated
ca1vulattons --(to takd...
'intp 'ac ibio,`o*f the.volume of the mh~~imment
cell.--vol
count .the za
io_ JroM
nce.. Of abbut 0 e 0
of puff, arvd the. _dis-appearA th N th&. U
cc- 2
,betw n above all, the necesstty of it-
typuz .-of..
zom
to - an
pos-41t.ih disappearance .6,f. 4. -s..ubst tiA.1.
poytion of,the, NO
URPANIC-4 SUTIT)
n
lb~~,Metho e b) actually,,used tkrei,,
_2 s of typ
-Sele.ctivin.:*1eotrq0q ior, .,nt t~rate__Iorks
of. 40, -to - 16,
Zoj atjT., -V LOAN A
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snoke before i~160. I!-,.,!Y ha-,-o t-ho
advant.p.,'of only requiring
cheap aFjjLratuEi in yvnural u~.u,. ajid could
d~~W.)ULL;L~ly bc &a%Loajav.(-d
fairly ca~;Ily.
The only specific rothod pulb.-,slied for W i% to
C~,nnplex
it with fcrrou-q sul-,hatn FeCO (coluurad complex
with /\taa~: = 445rx..)
4
Ly bLR1-U:.Mi_7j';rt & SjZriloi~Ek (24), who
'"i,t*1k711:',L iL~. iu!.Live
standard error to be less than 4t.
Most authors use the SALTZMAN mnthod (33) for
dotcx-xininc
1 :02: NO therofore be o%idiscd to h"02 assuming
thz~t, during; the
tinic necct:~_ary, the unoridi!~cd 1,70 does noL
X---act urith
of the cfar. phase., which is not certain (31)
(34). As in thu
technique uzing a-sc:lective electrode, the cjas
phase is collectcd
in a vacuur. flask containing a sufficient amount
of reagent. In
about 2 hc~=s- the o7~yegen of the teintroduvo~d
2tir Oxidis-~t NO -to
which is convotted into 140 2 - (a mechanism which
is not well under-
stood and ia certainly complex)k NO 2- diazotices
sulfaftilic ac4d
and the diazo couples with arr aromatic amine,
usually N(z,~-naphtyl)-
ethylene diamine, to give a -~~auve-pink compound
max = 54Snm)
stable for longer than 24 hours. The method has
many drawbPckL,: 7
questionzble zeproducibility;_ doubtful value (and
apparently
variable u-ith the corcentraticn of NOO of the
coefficient ' to bc
used.to pass from molar concentrations in'nitrite
ion NO 2
(generally u&ed for calibrating for reasons of
convenience) to the
concentrat'on of oxide, N02; slow kinetics for
the-, formation of
the dye.. To improve the method (for mixtiLres
other than cicarette
smoke) it has.,been suggested:. to idd an axsenite
AsO2-, whl6i
collects the OH radicals formed by the reaction NO
M - in a
basic. aqueous medium (and'vihich interferes with
this formaLol
by producing V03' ions) JCHOVIN & VELAUNNY, (26)
or, i ng nitrate,,as &-standard, using
nste4a of us-i
[FISHER BEMWELL .127)
a mixture having a: -knovin NO or, N02 content
BULTEZ (25)1;
-,NO .can be oiiaised toJ40* ~iith'6zon_e_ JFT~MR
& BEMUX-IL
~e3f' RIJA;z nag, tbViNosh, -
2"
--,a filtor inpregna d with bichroXnate Cr-267.
-'IKURODA, (29) 1, chroln-c
oxide'CrO3, or. por~paganat~e ,K:4nc;
4,
finally, 0. rf!~IER -9 LL,, by add ing
according t
or~c 13 -to almost,
It b a-.Id H 0 tp- the ac -at, it,.~i possible,.
3
113 '(k'P' to
c=pletely.el mi je
a the interferences due to ammonia N
-25
i ed" t~e wi
S is', s~bsti~ntial Y' W-iv,rov
te9dency for -1-aboratofies mi .shin%-to' make
i'Aar~"-MMber 6f.''-A'.
ur nis wi Uh x0au"Eill
J
zi. 3 - Acroloin '+5-2*5 C) t.
MRDIN't J44) affirm4tiqn. tb at there ivi no
loss a the - Carbr
f acivlcdn ow idc '
302056895
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Th" fol)uwiriq m~-thncis ari-
Gan
1-;,_-d convcntionul CC,)IWrs but, un(l,-r
certain conditions, it- ia very difficutt. Lo
separate acrolcl.1) fl-011%
furwui (AY),.';S (39); TF~TA & (,16)1 , E,xcept
lor cl*yot),,:rMAl 01rc-
mato'll'aphy I I
0,61)111 & WERIN Lr3pp~-ng Or th2 qn-, p~~-se is
achit!ved on the colt=n at -75*(,; :~naly!Js tinu
is about J." hr. At
pre,>CTIL. mvto. or 01c '-ALoratori~-, v.-hirh
--terrviro- acroleii, direcilv.
by Cr urc, glass capillary colur;r~s, like AkTI10
& KOCH. (3B). in a neti.od
adapted from GROB (43). For suck, a rnethcd, it is
naturally n,!Ce~~Szlry
to- have a good technique for manufactur.,rig
capillary and to
ready to acccpL that analysi o44 L"
W 5 ShOlaj~i Taku quite a 1 . .1 Ifie k 1.1
the range of aO to 60 rainute,-) to bring out tiic
1,E--aks or aii. titti
ComponeliLs Of the gar; phase (it is obvjo~Jily
Possible to te-mPer"Alu-
programine iiiorc rapi,11y in-ordcr to clute thf-.
hiVI-.-r hoilina
without attempting to recover them, but this
procedure may rapiQlly
degrade the column).
Anotht,~r problem is the length or time si4.okc is
kept w-.3re.
being injected: injection of one puff (Iro,
A -a one cigarette or From
several smoked ~;inultau~o'usly) appears to b---
more reliable than
amalgamating the gas phase of a whole cigarette
althou-
gh, according
to GROB (2), a stainlez~L- steel - tcflon syringe
hardly denatures the
10 as phase at- all. When a -single puff is
injected the problem rrisk:s
of the mpber of tbc ruff, so that it is
representative of-the Niholc
of the smoke from the cigarette (the anUysis takes
too long fl.')' -LZI,n
..pufr to be analysed zuccessively). A
reasonable-solution would seen
to be.the us-e of a certain nwtbur of cigarett-jes
smoked s-I'multancausly,
Vith one or two pufft'"displace=nt between their,
the injection -hcirZ.
done on a fraction of the mixture of all thei~r
gas phases. But 'this
system poses a problem of the smoking machine, and
perhaps also 'or
the mixing chamber before. ,the injectionAsee
11-6).
Colorimetr ic method usin'9 resorcinol 'accotding
t1o
COHEN L ALTEuznul T~677--
Thd g4s.phase
is coI4 trappe6 iz'.the..rcaqent solvent,
(ethanol) in the da:rk. This method has the..
drawback of belhg difficv4t'
to pcrfectj~~anOf -vning t'b,-ic reagents (corro,s
ive inercury chl oride,
trichloidcet I'c a~.Id) -3S -ddt-
thc...trApping.so 1~~on.,are not.recovereq,
ntmrally cf.. DQM~EC L.
~(4
Gas phase chronata9taphy of the addition compounds
Z)r acrdlcir..'
-on ot lab--liea cyst
& a a iti I
CiLike
by electrophoresis and two-di'mensional paten
lircmatoqrALphy peritit a
determination of acrolelzi,-and 6f-many othee
com?ou:hd!~i.
t 1
_b) For adding-to.an alXyl hio JUSTA f, JOIGIV
(468. 9-~s'
phase may be, trapped on.. a water-iinprf, gnat ed
chro=norb
ciindi ti,o'nr. in vkiich it appears that
a-crolcin does not bave, a ..fcndekY_.
to-. be_dlaitroycd. -,. A;oLa~ ;vpA~ :04'_q tion
products obtained
C~ ~,OUA4 with an,.:aqtivated doubte boM.-
other c=poundn ofttti Oa' lie Vreai4y facili-t4ted
cozqpai-eq'wittj~~:
t~e- St, ati
Artinq prddWt's. owinq To, be r. , V_a 1y 'large
increase irk _tht~
mass. Conveqtianal coluOis c= t~us~'by'.x~skd. tnd
c
bromatography. lastjn
sL for
rbr abo~i ten ininixia':' -ttctiolein'at,~ in
the.order of' 1/2 ..hovr fori all
the vis.iL dravbar;k or nec-L
-ile Products. 14s irethod has the -s~Ai txt ing
oii with^kinctics which are q%_Ai.t(:: di'M t, to
a clzl ~Xnd -
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tbat tho motliou of clirc,rotoqvaphy on
Porapa]~ describcd by Mon], & ',;LOAjj (45) boon
abandoned by
its authors (for rvasons of' hoinogenicity of.
batchen of the Foroucs
Substrate) for a method using capillary columns.
IIA-Eydrocien cyanide HC7N (B.P. - 26"C)
Hydrogen cyanide is distributed in variz-03.u
proportions
(not-hi-t.- f4-.-n,lina on the tyucs of Lobaccol.
bctwcc~n t1le Qa.-5 J:.hase
and particulate pha5a (which retains ;&S Au 501,
according to anthors)
Ho%-.,cvcr, the sare mcthods of trapping can be
used for total crnnoke
or the gas r)hase (the only difference being. the
presence or absence
of a Cara)ridgc filter behind-the cigarette) and
the mothods
clescxibed here are valid in both-cases.
Trapping is done either on a solid adsorbent:
ascarite (or
any asbestos containing soda) [COLLINS-et al.
(50), KUHN & BPAUN (52).
REIF (55)] or silica gel behind a Cambridge filter
[COLLINS et al.
(51) ] (both - filters _' are connected for the
determination of HCM, the
silica gel only being reserved for the
determination of volatile
aldehydes)-, or in -a scrubber containing -an'
aqueuos caustic soda
solx)tion [Areruo & Kom (47), AyRrs (48)).
Determination is then effected by three principal
types of.
methods,.
Colorimetric methods:
They use:
either a bromination of the cyanide ion in an
HC1 medium (the excess'o.f bromine is destroyed by
arsen,ic oxide
As'0 or an arsenite As033-), follbwed',...by a
coloured reaction in..-
2 3
a,,pyiUine medium with benzidino [ARTHO.axocH
(47)],-p-pheinylene.
d1 vanine faccording to MIT, .4 111GSON (49),
AYRES (48), M%M-.- (54)]
z BAAUff__(5T)
-bk in 4LA -"ttow.&Let 'tet~,od -e.- --the
cyanide ion with,,chloramine T in a basic buffer,
sol-vition, followed
by a coloured reaction with methylphenyL
pyrazolone i4 the presence.
of ftrid1re [COLLINS et 150) 1. - Acetaldehyde
and-hydrogen
sulphide, which Tnight Interkere, do-n .ot appear
to'be 'a hin~rqnce
at the le'vel s at which. they exist In swke-.,
Al 1 the se me tho4s , . and. ~ pdrti cularly the.
last, qtve o
acceptable. rdaults 6n the lovdl
of'repro~uc,.ibility,,Provi..di*ng the..
same conditions of..trappiag and smoking, are
aLways respected
-Zit v0t=tuTo'- eoiit6rt-_~-haV,1-'h itrrkcd
iTtfluendd
on IICN-yield).
anide -ions.. selpctive [VICKROY &.GAUNT (!~7)
_!12ctrod
REIr 059)1
This meth9d has - tho aU*q0tagi~, ot s;mplicity.
and, for
i -the-
laboratories possesging a PH motor, only
necastitates buy nq
302056897
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It 1,L! jj,~tu6 that', iqua!:L Flow t'.L:
auLh,.;i:,- of thc two
publications, jim-ntionciLl, whc; consid,,r the
mnthod to be natisfacto~-J,
other laboratoric2 ITESTA (56), M01,11" (54)]
9A-vu it up aftcr
several trials, as they obtained valu:-.s too far
removed from those
obtained with colorimatry, and/or a.~; it was
insufficiently
reproducible. Furthermore, this iac.,thod requires
fairly frequent
cnl-ibr=:1-1 ons.
Potent3ometric -mathod [MATTUM (53)
This method uses the roaction of silver icns Ag +
with
cyanide ions CN ; it necessitates a pH meter, a
qla.-Sti Qlcctrode
and a silver electrode, but does not require
calibration and,
according to its author, gives rise to no
interference, as the
precipitation potential has a fairly specific
value. 1t further
permits hydrogen sulphide to be determined
simultaneously
(cf. 6 11. 5). But it is prebably not easy to
automate.
11.5 Sulphur compound-, H2S (B.P. -.-60-1*Cj, COS
(B.P. - -550-2oC)l
CS,2 .(B.P. = +4r*-5*C) , and S02 (B. P. = -.1
Oo-C)
As these compounft may plky a part in the taste
and the
toxicity (SO of smoke it could b e an advantage to
have simple
methods for 9.termining them. There may be
mentioned:
-.For His alone:
The HATTINA method (53),.already mentioned and
criticised with respect to HCN;
A method using the coloured reaction :(absorption
at 665nm) of H2 S (trapped in a2-5M soda solutiorf
dontainitfg 0-5%
zinc. acetate) witli p-alnino- N,N~dimethylanilina
sulphate (in aqueous
HC1, :!solution) 'and. ferric chloride [AYRES_
(58) J.*. impregnation, of
-the Cambrid4e filterwith citric acid.is
recoTmended to avold_.any
A sulphide icm selective electrode method [MORIE
whi6h,bds tli~, d'dv-W' L't'd"' ~7-611r, giv&a4
-.r4bd r"uItz--- (aboti 2. -minttes-) c
agas phase solutions (trapped.14 a I H. NaOH
solVt16n *n the.1presence-
of. 0-01 14 ascQrbate' hs, ant4okidawt). 1
For
A GC rpethod on a conventicnal, column packed w1th
tpecksl,,
4,6a 111ORTON. .-,&MERIN (59)). Th
silica; yith Ila~'e phoiomptxy-dotaq e
authors: i4commond A tefloh smakiny circuit iristo
ad of --a sta&y)leiFs-
stee-1 one, which . appe4va.,to catalyse
:a..dastructiqn. _-.9f . HS *. (probably.
.-in - 4, seconds. They ~klso-note -a substantial
increase tn the-mean
MQ1e6uXarVeight..9f *fulphi# prodlictS after:
phase-.has btenl-'
stored for .1.0 -seconds An a, taflon 1pop (and g-
fortlori in atainle",
steelY. These last remarks prove
Xhat.&~terminition is fairly.
--en native smoke
difficult c. Oen
-covor i for all thaso e'SOW Iata
o) cczapounds there
N
j., -
302056898
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For overall. cc,:7~parison of tho strjoke from
several. cigaretter',
it may be a;i advantage to obtain thu values for a
certain number
of their csmponontn in letis than one hour. In the
prenent state
of the tecr:niques, ~.UC: On d LQnVCnti0ra1 C011=1
does nut
permit uufficiently r-,atirfactory separations c_~
the products~
even in the gas pha5e, although it is a very
nimple mixture
ccm-Dared vlth total smoke. On the other hand,
according to
Mil (43), Viie use v.' ciApil3ary colurns rermi.LS
a scmi-q--ant-itativ~
descripticn of the gas phase (values of
concentrations of about
ten or twenty prod-u--ts in about I hour and with
a maximun error CE
about 20%). Criticism in the g!is phase axe
naturally justified here by the large number of
products having a
relatively high.boiling point (110' for toluene)
among the cumpctmds
determined, which poses the problem of their
distribution betv Pn
the gas and particulate phase-;. If it suffices to
consider such
a "determination" as an empirical description of
an arbitrary, bubb
reproducible, fraction of smoke, interesting
indications can be
obtained for studies of filters, of now
manufacturing techniques,
for instance. Technically speaking, this method
necessitates
sufficient expeiience working with qlass capillary
columns.-
A noteworthy qualitative application of the nethod
has
recently been described by ARTHO.& KOCH (61).
"Quantitative" adaptations of GROB's technique are
used in a
certain number of laboratories-. REIF 165) ;
DONZEL & TESTA (62),
vho.now determine It products and who now use a
smdking machine
with 4 synchronous pisttns to ptoduce- a -"mean"
gas phase; GAISCH
(63) determined 14 products; HJERN ct al. (64),
t.-house pressure
'programming which furthe.r.-improves separation
as~ yell, as temperature
proqram~dnq from -70"C.
ad'vantagts and drawbaak.s
ikethod,
able to Judge it -as a fun~ction of local.
requirq~tents_- (frequency of
1*11 ---CONCLUSION
Although it is always desii~ble to have ret6urse
to sever4l.-
for- a determination one checkingthe othe.'q,in
-case of doubt it is
.9 ften dcoavanient,, ebpecially ~,hen a
laboratory starts a new.,. determinat ton,.
and,to
-to -have an 'h
of -each
idea of,,.t e
,atlons -Alth . 9h this
d"=An accuracy desired, apparatus availr,.bke) 60
#,ay be ~-rafth**,- 4~,- am -effort-. ha's'
I~Rwl..!Qado Make.-it ~fts-. compkete'_
and~objective ai,~ossible. .-It has shown that" :
although,- satis , A(;wx
miathodr quic)~, adcu.
e*ist for zAte and..x1eliable detti~9~6ation of CO
..and
HCN, p~oqrass still ficeds to -be madc-t and
opnditions. spqcifiet
V2 S and aciolein. , We have. not,:1=ntioned
light. unzaturated hy~droc~arhor5,
hir i.9 -an ideal component pf the gaa7phaae (B.P.
~amonq ~h h~ethyle"
as far as -we know caily-'=e vacent.caso of
determination Aby IRf hais been
3).1
irj~ 27th TCRC (October 197 Z
302056899
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GENFRAT-ITES MP, LA P!Tf--ST~ C*-A71;',USr 0111
CAS PHASE
(1) 11. rLFF.T.-HURST & Ch. S011111-TZ, Beitr.
T-1hakfornch, 1968, 4 (3), 90-123
(2) K. GROB, Beitr. Tabakforsch, '1965, 3 (4), 24
3-250
(3) M- SE1,05, Joint conferen'ce CORESTA-TCRC -
Williamsburg, Oct. 22-26,
MI~NARRR,
(4)
1 ~'72
11.
H-j- Ki-IMUSCH 111AI !~cilr. 1~-73' 7 fl)
T6-23
(5) P. WALTZ & H. JlAkERVIANII, 13citr.
Tabakfornch, 1965, 1 (3), 10-193
(6) J.T. WILLIAMS074 & D.R.ALLMAN, Bcitr.
Tabakforsch, 196G, 3 (9), 59U-596
M.-F-L. =4DER & D. HOFFMANN, Tobacco and Tobacco
stnoke;Academic Press,
1967, P. 43V,-453
OXYDE DE' CARBONE / CARBON MONOXIDE
C.I. AYRES (non publik) (not published)
(9) C.I. AYRES (non publi,6) (not published).
(10) K.D. BRUIaiEVAM4 & D.' HOFMUM, J. Chromatogr.
Sci., 1974, 12 (2), 70-75
(11) P.F.. COLLINS J.P. WILLIAMS, Beitr.
Tabakforach, 1973, 7 (2), 67-72
(12) M..DONZEL, Antales dix tabac Sect. 1. 1973,
115 45-57
'(13) It. GAISCH (non Publi6) / (not. published)
(14) D. HORTON & .0 k. GUERIN
X-.r 1971L.
(15) H-3 KLIHISCU T.. 14EXSSIIER, Bei tr.
Tabakforsch 1972, 6 (5),' 216-21.q
(16 11--T, TL114fSCH,- -Ou~mt-
-I tA nd, C i
and zmlpz~-fillcd inhalation
chambers. 27th TCRC,. Winston-Salem, A
Oct 3.5, 1973
(17) A.J..'1RUSZYNSK1 A,. HENRIKSEN,,, 13eitr..
Tabakforsch, 1969 5 (1), 9-12
(18) G~.P. KO~IE, Tob.'.Scf., 1973; 125-12G-
("i 9L) G.P. NORIE & C.H. SLOAN,
Zeitr..-labakforsch, 1972-, j (4),
178--181
1 .-2
(20) H. RP.IF & H.., MIN,, Fachl'. Xitte!14
Austria Tabakwerke A-.G., 19,73, -2
_4 239-251'
(221 H. VkAVARR- KOBAVI, Nippon -Senbai rqsha Chuo
Tcnkyusho Kenk
YU&
Hoko*u' I
9,65, n0 107, 177-180
Chem. Abstr., 196 .4~. I 11 186n-r-
'-VILLIAMS BELK, Beit'. Va~akforsch, 1972, 6
(.22). T.P. r (5),: 219 -~l 5
OXYD86 D OA7,07T, ~N ITROGE R 0X11tS
L
302056900
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(:>6) P. C110"111: & C.-1*'LA11VAY, C.R. Acad.
Sci. (Pari.), Ser. C, 197,11, P7,11,
137- 140
(27) G.L~. Cl-'HER & D.U. Anal. Chem., 1972,, 44
(6), 863-F6b
(Pb) A.D. PIMTON, GUERIN, J.H. STUELY A.S. M-EUX,
27th TCRC, Wjj,~iton
Salem, Oct. 3 5, 1973
pyo (Oc,.,
(29) D. KURGDA, Kaqaku to Yoc -ika), 19,70, 44
(9), 467-471
Chem. Abntr., 1971, 74 (22), 119(113 h-
(30) V. I-10?*tu & C..". KEITH, Nature, 1965, 205
(4974), 915-916
(31) V. 110R,"-'J1 & R.P. V1115011, 21st: TCFC,
Durlirim, Oct. 20-21, 1967
(32) X.J. PHILIPPS & E.j. iIA(-,K,,F.Y, Tob. Sci.,
1959, 3, 139-143
(33) H.E. SALTZMAN, Anal.. Chen., 1954, 26,
1949-1955
(3 p') r. 14. ';:.nrx J.F:. KIEFER, Tob.-Sci-,
1961J, 13, 180-182
35) C-11. SL0.Q-'.' G.P. 14ORIE, Tob. Sci., 1974,
18, 101-102
(36) J.E. URBANIC & R.F. SUTT, 23rd TCRC,
Philadelphia, Oct. 22-24, 1969
(37) T.B. WILLTA14S & C.W. DEUt 27ih TCRC, Vinston
Salem, Oct. 3-5, 1973
ACPOLETNE ACROLEIN
(38) A. ARTH-0 R. YOCII, Trav. Chim.-alim.-Hyg.,
1969t 60 (5), 379-388
.(S9) C.T.- AYRPS (non publiC-) / (not 'published)
-
(40) COHEN & ALTSCHULER, Arial, Ghem. 1961, 33 -
(6 726
J41) H. DONZEL, Arm. SEITA-DrE, Sec.t. 1, 1969t Z,
p. 125
(42) (non publi6)' / knot publisht;d)
(2) K. GROB, Beitr. Tabakforsch,..19.65, 3 (4)..
~41-250
(43)
403-408
Ki GROB, Beitr. TabakforsalL, 1966 .(r A
-413al A-D- HTITON Guggnuj T-Oh. 19 71 4 P- .2
c'-oo
'IMP ?7
-,(45) G-,'P. MORIE & C.M. $LOAF, Beitr.
-Talmkformch. 1,972, 6 (4), 178-181
A. TFSTA &,.C. -TPlc, ~n. SETTA-DEE, Sect. '1-
197a, 10 ''.67-81
ACIDE CYAPITTYDRIOUF" ityr)Rormi CYANIDE
~RTPO ~Ae Tzabat 9 5!~ -5 5e-153
.(48) r,,, I -ANT Xnp-t pul?lishe
r's' (.nw P4~1 '0 d).
(49)' a 1'964, .471-479 'et 621-631.
S. BARK .4 H.G. HIG5011, Talant
(59) ,
12
-P. H. S~IZJ'l & WILLIANS.j Tob. Sci., -1970,. 14#
7-15
51
'NS,
eftr. -TabakforsCh, 1-9'-i~' .
N.M. WUX & -3.F,. W1LLLQZ,.'-D
P-T- CML.l
.
.
302056901
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I. I ItT & n . III? Al I; Fitc It I. V, It vii) -
/,,j 7 tria Tal 1970, 11 , 1 '11-1 M
(5-.3) C.F. 11AMM, It-, Tob. Sui., 1972, IG, 113
(54) G.P. 1-10111r, (11011 PUbUO / (r'Ot
PUbli'Aled)
(55) fl. RNIF, Ilachl. flitteil. Au-stria
Tabakvcj,ke, 1972, 13., 220-224
(56) A. TESTA (non publi6) / (riot published)
(57) D.G. VICKROY & G.L. GAUNT, Jr., Tob. Sci.,
1972, 16, 22-25
COMPO!~I-19 S0113"PES /SULFUR CO'M[1011-71!~
(58) C.I. AYRMS (non publi6) / (not published)
(59).A.D. HORTON & M.R. GUFRIN, J.A.0-A.C., 1974,
90, 63
(53) C.F. MAWINA, Jr, Tob. Sci., 1972, 16, 113
(60) G.P. MORIE, Tob. Sci., 1971, -15, 107
PHASE GAZEUSE TOTALE /-'~.IPOLF GAS PHASE
(61) A. ARTHO & R. MC-11, Ann.. SEITA-DEE,. Sect.
'1, 1973, 11, 37-43
(62) 14. DONZEL & A. TMTA, Ann. SEITA-DEE, Sect.
1, 196.9, 7. 157-166
(63) H. CAISH (non publi6) (not Oublished)
~43). K. GROB, .13eitr.. Tabakfor-qch, 1966, 1
(G), 403
(64) L. 11JERN & Coll. (non~.publid) (not
published)
(65), H.
_RnIF, -published)
(norr publ-iA-) -pot
-77.77
%
302056902
BATCo document for Province of British Columbia 19
April 1999