Vapor Phase Analysis of Tobacco Smoke - Legacy Tobacco ...

Vapor Phase Analysis of Tobacco Smoke 

Tobacco Science 9 : 102 (1965) 

J. R. Newsome, V . Norman and C . H. Keith= 

Research Department 

Uggett and Myers Tobacco Company 

Durham, Norhh Carolina, USA 

~ 

Introduction 

The smoke stream issuing from 

burning tobacco products contains, 

in addition to the billions of visible 

smoke particles, a highly complex 

mixture of atmospheric gases and 

volatile combustion products. In the 

case of cigarette smoke this gaseous 

mixture represents 90 to 95 per cent 

of the mass of the effluent stream 

and contains a large number of components 

of widely differing volatilities 

which are present in widely differing 

concentrations . Over 95 per 

cent of the mixture comprises seven 

major components, nitrogen, oxygen, 

carbon dioxide and monoxide, bydrogen, 

argon, and methane and has 

been extensively studied both as to 

overall quantityand variations in 

quantity within a burning cigarette 

~(15, 17, 19, 20) . A considerable anay 

of components makes up the balance 

of the mixture, and many oi these 

have been identified and estimated 

(7, 19, 20, 21, 22) . 

The complexity of the vaporous 

mixture, and the extremely minute 

concentrations of the minor components 

when combined with the rapidly 

changing character of the mixture 

due to chemical and physical 

inter-action of it with the condensed 

smoke particles- make its analysis 

rather difficult . Previous studies have 

generally involved the IoNc temperature 

condensation of smoke vapors 

from a number of cigarettes and the 

extensive fractionation of the condensate 

. Such techniques in addition 

to being time consuming generally 

permit the partial loss of some components 

through imperfect collection, 

volatilization during fractionation, 

or through chemical interaction 

of the condensed vapors . Also the 

results obtained by such methods are 

quite dependent on the collection 

system employed, as this frequently 

alters the partition of the less volatile 

components between the vapor 

and the particulate phases . 

BASIC SMp9NG SYSTEM 

The recent increase of interest in 

the gas phase of cigarette smoke has 

made it desirable to develop a rapid 

and quantitative analytical sy stem 

for its minor gaseous components . 

Many of these materials have long 

been known to be of physiological 

significance in concentrations far in 

excess of their reported levels in tobacco 

smoke, and have variously been 

classified as irritating, anaesthetic, 

or toxic vapors . In their minute concentrations 

in tobacco smoke, their 

chief contribution has been towards 

imparting the indefinite physiological 

sensations of "bite" and "sting" 

to the taste of the smoke . Recently 

Kensler and Battista (13) demon- 

' Pruewsod +n part ot tir ScJtN Natiana/ Mert- 

'np of tAe A'r.rsitan CAemice7 Sansty, Nem Yor#. 

, SrD1e'~ber 1i-17, 1963 awd e : tAr 17th 

Tubaece Che+,.i.rt.' Reseurch C`w ./s.rxr, Srpee,~.- 

ber II-15, 1V61, ,n Montrraf, Q„ebre, Canads . 

address : Crlm,rsr Fibrrs Qa . . CLorlour, 

A: C. Fi9ure 1 . Basic Smoking System 

(Tobacco Science 102) 

http://legacy.library.ucsf.edu/tid/pvl86a00/pdf 

PM3006662914

strated a more specific effect in their 

finding that the vapor phase of cigarette 

smoke can inhibit the action 

of mammalian ciliated tissue, and 

thereby interfere with the ability of 

the lung and trachea to eliminate 

foreign matter (6) . They also have 

found that gaseous smoke constituents 

such as hydrogen cyanide, ammonia, 

acrolein, and formaldehyde 

inhibit ciliary motion at concentrations 

approaching those found in 

ordinary cigarette smoke . A companion 

development has been the introduction 

of a considerable variety 

of adsorbent bearing filters which 

serve to selectively reduce the levels 

of a number of the components of 

the gas phase . 

To fulfill this need for a suitable 

gas phase analytical system, this paper 

describes a system for quantitatively 

collecting smoke samples, and 

applying a variety of colorimetric, 

electrometric, and chromatographic 

+ techniques to the unfractionated 

sample . As an illustration of the 

utility of the system, comparative 

data on eighty gaseous components 

issuing from three different types 

of cigarettes are presented . It is 

thought that these techniques would 

also be of use in studies of other 

complex vapor systems. 

6perimental 

1 . Smoking dnd Sample CoIkction 

System . 

A simple smoking system which 

allows the quantitative collection and 

subsequent rapid analysis of the 

gaseous phase of a single puff of 

smoke is illustrated in Figure 1- 

The components are the cigarette 

under study, a particulate smoke 

filter, a flow limiting orifice, and 

an evacuated flask which provides 

the source of suction to withdraw 

the puff and also wholly contain 

the vapor sample. In the modification 

illustrated in Figure 1, the 

flask contains 10 ml of an absorbing 

solution appropriate to the component 

under study. In operation the 

flask is evacuated by an external 

pump, and the puff is taken by turning 

the three-way stopcock to connect 

the orifice, filter, and the previously 

lighted cigarette to the flask, 

Following the puff the sample of 

smoke vapors in the flask are transferred 

to the absorbing solution by 

manual shaking . The puff characteristics 

are controlled by the free voIume 

of the flask (ea . 45 ml with 10 

ml of absorbing solution), the vacuum 

drawn on the flask (27 in Hg), 

and the hole diameter of the orifice 

(0.508 mm) . These parameters are 

found to provide a normal human 

puff volume of 40 ml with an appropriate 

velocity distribution during 

the two second duration of the puff . 

The particulate filter (Cambridge 

CM-113 glass fiber filter) provides a 

crude separation of the particulate 

and vaporous smoke, and can be discarded 

if a total smoke sample is 

desired. Since the division of materials 

effected by such filters is generally 

becoming empirically defined 

as the division between particulate 

and gaseous tobacco smoke, and 

since the vaporous components of 

pharmacological interest pass 

through such filters, they have been 

used throughout these experiments . 

No . of 

C atoms 

in 

Compound molecule 

Table 1 . Ffome response data, compared to n•hexane 

1 x 10° maies n-hexane-5415 integrator counts . 

FunctConal 

group 

Change in 

response, 

No . of C 

atoms 

l:ffective No . of C 

a4oms in molecu(e 

Exp. iterature (3) 

Ethane 2 . . . +0 .03 :1 .03 1 .98 

Propene 3 -0 .07 2 .93 2.88 

Butane 4 . . . -0 .09 3 .91 

Isoprene (2-methyl•1,3-butadiene) 5 0-00 5 .00 

Benzene 6 +0.12 6 .12 6 .00 

A cetonihlle 2 C~V 1 .35 

Acnlonitrile 3 CM*I -0.73 2 .47 

Propionilrile 3 C~\ -0 .64 2 .36 

Isabutvronitrile 4 CnnN -0 .64 3 .36 

Furan 4 cyc1 . ether, CGO- -0 .99 3 .01 2.97•, 2 .9• 

Methylfuran 5 cyc1. ether, C-O- -1 .12 3 .88 

Methylacetate 3 C-O-C -1 .27 1 .73 

0 

0 

Ethal acetate 4 

// 

C-O--C -1 .28 2 .72 2.49 

Acetone 3 C-O -0.85 2.15 2.00, 1 .8 

2-Butanone 4 C-O -0.91 3 .09 3.16 

2-Pentanone 5 C-O -1 .02 3 .98 

3.3-Butanedione 4 Two, C-O -1 .87 2.13 

:+cetaldehvde 2 C-O -1 .07 0 .93 

Propionaldehyde 3 C-O -1 .2 1 .88 

Isobutyraldehyde 4 C-O -1 .22 2 .78 2 .83 

\4ethanol 

1 C-OH -0 .26 0 .74 0 .75 

• DieiAyl etMr 

(Tobacco Science X0s) 


PM3006662915

PARTICULATE I VACUUM 

FtLTER PUMP 

CRITICAL 

FLOW 

ORIFICE 

• 

MDOIFICATION FOR CMROMATOGRAPHIC USE 

CIGARETTE 

~ 

PARTCULATE 

FILTER 

TO COLUMN AND 

ChWOMATOGRAPH 

-SMQ 

MODIFICATION FOR SEQUENTIAL PUFFING 

TIMER 

• 

~ / -~~3-WAr sOLENOD VALVE 

'f VAODUM PUMP 

CRITICAL 

FLOW I 

ORIFlCE sMOKE 

COLLECTION 

FLASg 

Figure 2 . Modifications of the Basic Smoking System 

It is realized that many of the vapors, 

particularly those of lesser 

volatility, are partitioned between 

the condensed particles and the gaseous 

phase, and that some may be 

absorbed by the filter pad, so that 

larger amounts may be present in 

the total smoke stream than are in- 

•dicated by these measurements of 

the "vapor" phase . 

Since any individual collection 

flask is designed to take and retain 

enly one puff, eight or more flasks 

are used in smoking one cigarette 

at one minute puff intervals . The 

flasks are generally connected to a 

common vacuum manifold and the 

orifice, filter, and cigarette are 

switched from flask to flask between 

puffs . Each individual puff 

can thus be analyzed and averages 

obtained over the whole cigarette . 

A middle puff, such as the fourth 

or the fifth can be considered tc be 

representative of the whole cigarette 

since the burning cone is by 

then completely established and air 

dilution through paper and filtration 

by the tobacco column have 

reached an approximately . average 

value. The HC\ data in Table 3 

\TRAPS •• 

are typical of the variation of 

smoke gas phase components as a 

function of puff number . 

Two modifications of the basic 

smoking system of Figure I are 

illustrated in Figure 2 . That schematically 

represented at the top 

of the figure is an adaptation for 

gas chromatographic analyses . By 

replacement of the three-way stopcoek 

with a timer operated solenoid 

valve and the use of a manual six 

port linear calve (llicrotek or 

equivalent), a portion of the initially 

evacuated smoke collection 

space can be utilized as a chromatographic 

sample loop . This loop, 

which is filled with smoke vapors 

during the puffing process . is subsequently 

switched by the six port 

valve into the carrier gas stream 

so that a 20 ml sample is rapidly 

and directly introduced onto the 

chromatographic column . 

A second modification useful for 

obtaining samples of specific components 

from repetitive puffs on 

one or more cigarettes is also illustrated 

in Figure 2. In this syste[n 

each puff is taken by a smoke 

collection flask which is re-evac- 

uated prior to the next putf. Th 

gases removed from the flask dur• 

ing the re-evacuation process are 

collected in fritted bubble traps 

placed betn•een the collection flask 

and the vacuum pump . By having 

these traps external to the puffing 

mechanism, the trapping system 

can be as extensive as desired without 

deleterious effect on the smoking 

parameters . 

2 . Ckemicat Analytical Techniques . 

A number of physiologically active 

smoke vapors have been estimated 

by colorimetric and electrometric 

techniques which are summarized 

as follows : 

a. Hydrogen Cyanide . 

Utilizing the basic smoking syFtem 

or the second modification with 

0.1 \- \aOH as an absorbing reagent 

. HC\ can be estimated in the 

presence of other smoke vapors 

either by the electrometric method 

of Baker and lforrison (2) or the 

colorimetric method of :lfurty and 

Viswanathan (16) . In the eIectrometric 

method the peak electrolysis 

current generated in an Ag-Pt cell 

by smoke solutions (1-6 puffs per 50 

ml 0.1 N \aOH) is directly compared 

with that obtained from 

known SCV solutions with a cyanide 

ion concentration equivalent to 10 

to 30 itg HCN per 50 inl . The electrode 

system consists of 18 inches 

of 18 gauge silver wire and 10 

inches of 20 gauge platinum wire 

coiled on glass supports and separated 

bc two cm in the magnetically 

stirr+-d electrolyte solution . The currentis 

read on a galvanometer (sensitivity 

0 .0016 rafmm, resistance 

A500'.i) shunted with a variable resistance 

of five to 25 ohms . Since 

the electrolysis current is linearly 

proportional to the cyanide ion concentration, 

simple ratios of the current 

readings of known and unknown 

cyanide solutions are sufficient 

for calculation of the unknown 

cyanide concentration . Of the 

acidic gases found in tobacco smoke 

vapors . onl .- H,5 is found to appreciably 

interfere in this measurement, 

and its concentration is sufficiently 

low in smoke so that its 

effect may be neglected . 

b . Hydrogen Sulfide . 

The hydrogen sulfide content of 

tobacco smoke was determined by 

the meth>-lene blue colorimetric 

method (10) . With the basic single 

puff smoking flasks, an absorbing 

solution consisting of 15 ml of one 

per cent zinc acetate in water and 

0 .5 ml of 10 per cent aqueous haOH 

is injected by means of a hypodermic 

syringe into each puffing flask . After 

collection and absorption of a 

puff of smoke gases. 2 .5 ml of 0 .1 

(Tobacco Science I0¢) 


PM3006662916

per cent N.A'-dimethyl-p-phenclene 

8iamine chloride in 1 :1 HCl and 0 .5 

ml of 0 .2 .11 aqueous FeCI„ are added 

to the absorbing solution . After 

complete color development within 

2 hours the solution is transfered 

and made up to 25 ml volume and 

its absorbance determined at 665 mlx 

against a reagent blank . Compari- 

=on of these with known sulfide solutions 

yielded the level of H,S in 

smoke gases in micrograms per puff . 

Possible interfering materials, including 

heavy metals, oxidizing sub- 

:tances and other sulfide reactants 

present in smoke gases . were inve=tigated 

and found to be present 

in inFufficient quantities in smoke 

rn seriously interfere with the 

measurement of H,S . 

Alternatively, the second modification 

of the basic smoking system 

can he used for estimating the H,S 

coming from a whole cigarette rather 

than from individual puffs . In 

. zuch experiments, the rolumes of 

the various reagents are increased 

fivefold . 

c . Nitrogen Oxides 

The Saltzman (23) procedure ultilizing 

Griess-Ilosvay reagent was 

found to be satisfactory for estimating 

the nitric oxide and nitrogen 

dioxide in cigarette smoke . 10 ml of 

an aquecus absorbing solution containing 

20 mg of ?t"-(1-napthcl)- 

ethylene diamine dih y drochloride . 

five g of sulfanilic acid, and 140 ml 

of glacial acetic acid per liter was 

contacted with individual puffs of 

smoke vapors in the collection flasks . 

After one hour for oxidation of NO 

to \O : and for complete color de- 

N elopment . the NO and \O, concentrations 

w ere estimated by the 

amounts of pink azo dye formed, as 

measured by the optical density of 

` the reaction mixture at 550 mµ . 

Other experiments (14, 18) have 

! 

. 

Material 

Ketones : 

acetone 

2-butanone 

butenone 

2,3-butanedione 

3-methyl-2-butanone 

2-pentanone 

3-pentanone 

Esters : 

methyl formate 

eth,vl formate 

methyl acetate 

isopropvl formate 

vinyl acetate 

ethyl acetate 

Cyclic Ethers : 

furan 4 .8 

2-methylfuran 5 .8 

tetrahydrofuran t.race 

2.5-dimethvlfuran 4 .9 

Nitriles : 

hydrogen cyanide 32 

acrylonitrile 1.5 

acetonitrile 18 

methacrylonitrile 0 .4 

propionitrile 2 .8 

isobutyronitrile 1 .0 

crotononitrile 0.4 

Miscellaneous : 

nitric oxide 30 

methyl chloride 19 

hydrogen sulBde 3 .4 

ammonia' 12 

thiophene 0 .1 

Table 2. (Continued) 

• Totnl of nrnmonveal rorayauMt det, . .n:ns61, by the 

.c~.~~nl .nt n,tcrnu*nn.r °f nmtwwfu. 

ysis . 

d. Ammoniacal Compounds 

Compounds in tobacco smoke that 

yield the ammonium ion in an acidic 

solution can be conveniently estimated 

by the colorimetric ?ieriee 

aaehvd-{3, 11, 24) applied to smoke 

gas samples trapped in 0 .02 N H2- 

SO, . The basic smoking system containing 

10 ml of acid solution per 

puffing flask was utilized . The H. 

SO, trapping solutions from each 

flask were subsequently heated for 

i hour at 90-100' to expel interfering 

acidic gases and acetone . After 

cooling to 25°, addition of \essler's 

reagent . and dilution to 25 ml, the 

optical density at 450 m/, was measured 

. Comparison of these observed 

absorbances with those of known 

(\H,) :SO, solutions provided a 

Yield in micrograms per 40 ml puff 

No Acetate Combined Acetate 

Filter Filter Adsorbent Filter 

42 39 13 

10 9.4 2 .3 

3 .7 .3.5 0 .9 

15 15 3 .9 

1.0 1.0 0 .2 

2.3 1.9 0 .5 

0.5 0.5 0 .2 

3.6 3.5 1 .2 

0.5 0.5 0 .2 

1.7 1.6 0 .5 

0.6 0.5 0.1 

0.5 0.5 0.2 

1.0 1.0 0.3 

4.3 1 .7 

5.4 1 .5 

trace 0 .0 

4.5 1 .0 

29 11 

1.3 0 .4 

15 5 .8 

0.4 0 .1 

2.5 0.7 

0.9 0 .2 

0.4 0.1 

35 41 

24 22 

3.1 1 .3 

13 7 .6 

0.1 trace 

h-errte. 

;rovedwrr, srt+s :nd n.r tAt 

measure of the ammonical compound 

content of smoke . This method does 

not differentiate between ammonium 

compounds and free ammonia . 

Hydrogen sulfide and acetone are 

found to interfere with the determination 

of the ammoniutn ion 

through formation of colloidal products 

with Nessler's reagent . The extensive 

heating step is found to eliminate 

these materials from the absorbing 

solution, and thus avoid their 

interference . 

e . >iirrmatd®hvd .- 

Formaldehyde in cigarette smoke 

can most conveniently be estimated 

by the cly,omotropic aai,d . method 

(1, 25) and alternately and less conveniently 

by Schryver's method (12) . 

Utilizing the basic puffing flasks, 

five ml of 0 .1 per cent aqueous chromotropic 

acid solution (1,3-dibydroxynaphthalene-3,6-disulfonic 

acid) is utilized as an absorbing solution 

. After smoking and absorption 

of the smoke gases the solution 

is transferred to a 50 ml volumetric 

flask and 43 ml of concentrated 

11,SO, is added . Color development is 

essentially immediate due to the heat 

of reaction of sulfuric acid and 

water. Subsequently on cooling the 

solution is made up to 50 ml with 

water and the optical density measured 

at 580, 500 and 600 mµ, the 

short and long wavelength values being 

for the purpose of providing a 

base line correction for the formaldehyde-chromotropic 

acid peak, thus 

eliminating acrolein interference . 

The amount of formaldehyde is calculated 

by comparison of the absorbance 

of smoke solutions with that 

of known formaldehyde solutions . 

A variety of known smoke components 

including unsaturated and 

aromatic hydrocarbons, nitric oxide, 

aldehydes, ketones, phenols and 

alcohols were tested for possible 

interference with the formaldehyde 

reaction . In general . unsaturated 

hydrocarbons and acrolein w ere 

found to interfere, but the utilization 

of the aqueous collection system 

and the base line correction essentially 

eliminated these effects . It 

sras found that the particulate 

smoke collected on Cambridge filter 

pads adsorbed appreciable quantities 

of formaldehyde, so that it was necessary 

to use a fresh pad for each 

individual puff . 

Because of the possible lack of 

specificity of the chromotropic acid 

method for formaldehyde, additional 

estimations were made by Schn1 er's 

method (12) which involves the formation 

of an intense magenta coloration 

by the reaction of formaldehyde 

phenylhydrazone with potassium ferrieyanide 

. Smoke gases were collected 

in 10 ml of 1 per cent aqueous 

phenylhydrazine hydrochloride solution 

. Subsequently this solution was 

diluted with water to 50 ml and a 10 

ml aliquot of this was combined with 

one ml of freshly prepared 5 per cent 

K,Fe(C\ )s in water and four ml 

of 31 .5 per cent HCI in water . The 

reaction mixture was diluted to 25 

ml and its absorbence determined at 

525 mµ within 10 minutes . Comparable 

results were obtained with both 

methods. 

3 . Chromatogra.phic Teclentqlses 

Most of organic materials in cigarette 

smoke vapors are most concenientlc 

estimated by gas-liquid 

chromatngraphic techniques . R hile 



PM3006662918

other workera such as Grob (7) have 

auccessfully employed capillary columna 

for tobacco smoke analysis, 

this work was confined to small 

diameter packed columns to improve 

the quantitative aspects of these 

analyses. A Microtek GC 2500R chromatograph 

equipped with linear temperature 

programming, a disc integrator, 

and dual flame ionization 

detectors was utilized in this work . 

The dual detector feature was, however, 

not utilized since the columns 

employed had negligible "bleed" 

aver the temperature range of interest 

. Helium dried over 5A molecular 

sieve was employed as a carrier gas . 

The packed columns were all constructed 

from ?S" stainless steel tubing 

coiled in a helix . They were 

packed under 75 pounds helium pressure 

with mechanical vibration . The 

liquid phase was generally applied as 

• a water or methylene chloride solution 

to the substrate, after which the 

solvent was removed in a rotary 

evaporator . Three major column systems 

were utilized, one being for low 

molecular weight hydrocarbons and 

the other ta-o for larger hydrocarbons 

and oxygenated smoke components- 

These were as follows : 

Column I . 

Highly polar column for hydrocarbons 

. 

To adequately resolve the complex 

mixture of hydrocarbons in smoke, 

a composite column consisting of a 

25 foot section containing 18 per cent 

fl,/3-ocydipropionitrile on 100-120 

mesh Alcoa F-20 alumina followed by 

a second 25 foot section packed with 

22 per cent bis-2-(2-methoxyethoxy) 

ethyl ether and three per cent hexadecane 

on 100-120 mesh C22 firebrick 

. The alumina section was operated 

ated at 0° and the second section at 

25° . A third section consisting of 

five feet of tubing packed with 60-80 

mesh firebrick coated with 25 per 

cent mercuric perchlorate was utilized 

in some of the measurements 

and was inserted by means of a valve 

system between the first two sections 

. The third section was used to 

remove all the unsaturated hydrocarbons 

from the mixture without 

affecting the saturated components 

and thus resolve a number of overlapping 

peaks (5) . Helium at 100 psi 

gave a flow of 30 ml per minute 

through this series of columns . Preparative 

purging with hetium at elevated 

temperatures was necessary 

before use of this composite column . 

Column 11 . 

First polar column for aromatic 

hydrocarbons and oxygenated components 

. 

The more polar vaporous mixture 

of aromatic hydrocarbons and low 

C0WhT1 I 

a. 

TME, MIN. 

27520 

Figure 3 . Chromotogram of gas phase smoke hydrocarbons, showing removaL of unsoturated 

compounds with mercuric perchlorate . 

Compounds for Figure 3 . 

s 

14 15 

1 . methane 19 . propyne 

22 ethene 20 . 1-pentene 

3 . ethylene 21 . 1 .2-butcdienn 

4 . propane 22 . 2-methyl-l-buten e 

5 . propene 23 . trans-2-pentene 

6 . 2-methylpropone 24 . cis-2-penfene 

7. acetylenn 25 . cyclopentone 

B . butane 26 . unknown 

9 . propudiene 27 . 2-methy I-2-bute ne 

10 . 1-butene 28 . 2-methylpentane 

11 . 2-methylpropene 29 . 1,4-pentodiene 

12. trans-2-burens 30 . 3-metby4pentonw 

13, cis-2-butene 31 . hexone 

14. 2-methylbutene 32 . 4-m ethy (-1-pe nte n* 

15 . penrane 33, ryclupentene 

16 . 3-m e th y l-1-b u f e n e 34 . 4-methylB-pentene (cis- } trons-} 

17 . 1,3-butadiene 3S . 2-methy I-1,3 .butadiene 

18 , methyl chloride 36. methylcyclopentene 

molecular weight materials containing 

oxygen and nitrogen was partially 

resolved by on~ column and completely 

resolved by two columns . The 

first of these consisted of a 60 foot 

column packed with 100-120 m-n 

C22 firebrick coated with 25 per cent 

licon Polar 50 FIB280X . Operating 

conditions were holding at 25° for 

60 minutes, programming 1' per 

minute to 70°, and holding at 70° 

until completion of the chromatogram 

. A carrier gas pressure of 110 

psi gave an exit flow of 40 mlJmin . 

and the column was purged with 

helium at 1000 for 48 hours before 

use . 

Column III . 

Second polar column for aromab 

ics and oxygenated components . 

This consisted of a two component 

column connected in series. The first 

section of 35 ft contained 100-120 

mesh C22 firebrick coated aith 20 

per cent 1,2,3-tris-(2-cyanoethoay) 

32 

wo 

propane- The second section, 25 ft 

long, contained the packing of column 

II . The operating and preparations 

conditions were the same as 

for column II except that the initial 

hold at 25' was for 45 minutes instead 

of one hour . 

It was found that methanol, a vaporous 

component of cigarette 

smoke . w as eluted with considerable 

tailing from both columns II and III, 

which interfered with several following 

peaks . This interference was 

removed by inserting a small six 

inch precolumn containing one per 

cent boric acid on 100-120 mesh C22 

support operated at 25° (8) . With 

this precolumn methanol was quantitatively 

removed from the mixture, 

thus allowing the estimation of the 

succeeding peaks . Methanol ia turn 

was estimated by the difference between 

chromatograms with and without 

the precolumn. Methyl- and di- 



PM3006662919

• TIME . MIN . 

Fi9ure 4 . Chrometeg :em of gos phase smoke hydrocarbons aid oxygenoted components . 

. 

Compounds for Figure 4 

1 . acetoldehyde 21 . ethyl acetate 

2 . 2-methyl-1, 3-butadiene 22 . 2-butanone 

3 . trers-1,3-pentadiene 23 . butenone 

4 . cyclopenaene 24 . ocetonitrile 

5 . cis-1,3-pentodiene 25 . ocrylonitrile 

6- methyl formate 26 . isovalercldehyde 

7 . propionoldehyde 27 . 2,3-butaneidione 

8 . furon 28 . benzene 

9 . acetone 29 . 3-methyl-2-buto none 

10 . ethyl formote 30. methacrylonitrile 

11 . ecrolein 31 . propionitrile 

12 . isobutyroldehyde 32 . isabutyronitrile 

13 . methyl ocelote 33 . 2,5-dimethyfforan 

14 . pivaloldehyde 

34. 2-pentonone 

35 . 3 .pentanone 

15 . iaopropyl formate 

36. vcleraldehyde 

16 . methocrolein 

37 . thiophene 

17 . 2-methylfvron 

38 . crotonoldehyde 

18 . butyrotdehyde 39 . 2-methylvoleraldehyde 

19 . tetrnhydrofuran :0 . crotononitrile 

20 . vinyl acetate 41 . toluene 

methylfuran were also found to be 

partially removed by this precolumn, 

so that chromatograms with it in 

place were used onl y to estimate 

those materials subject to methanol 

interference . 

Smoke samples of 20 ml, obtained 

with the chromatographic modification 

of the basic smoking system, 

were sub ;ect to analysis . -lluisture 

and temperature equilibrated cigarettes 

(7-t`F, 60 per cent RH) were 

smoked and an average fourth puff 

was chromatographed when 57 to 

60 mm of the cigarette remained . 

The data reported herein, are the 

average of eight to 10 such measurements 

. 

Calibrations were made using a 

20 ml sample loop fitted with an injection 

port so that calibration mixtures 

could be injected at atmospheric 

pressure . Calibration standards 

were mixed in a one liter flask 

to which was attached a second 

smaller, about 25 ml, flask . The two 

containers l-ere connected through 

a stopcock and both were fitted with 

injection ports that were sealed with 

rubber septums. With the larger 

flask evacuated . microgram quantities 

of the pure compound -ere injected 

into the smaller flask which 

uas maintained at atmospheric pres- 

sure. The stopcock connecting the 

two containers was then opened, and 

a h .-podermic syringe needle was inserted 

throuRh the injection port of 

the smaller flask in order to permit 

air to enter the flask and flush the 

sample into the larger container . For 

higher boiling materials the flask 

was heated before flushing. Final 

mixing was attained by adding several 

pieces of teflon to the one liter 

flask and shaling- Samples prepared 

in this manaer were found to deteriorate 

rapidly since most of the 

materials were readily adsorbed by 

the rubber septums_ The simplicity 

of the method, however, permitted 

almost instantaneous mixing and 

sampling. The reproducibility of this 

method was found to be better than 

=2 per cent . The highest purity 

gases and liquids were utilized as 

obtained or, if impure, were fractionated 

prior to use . 

Resulis and Discussions 

1 . Idenfi,8cation and Estimation of 

ConEpoitFntS. 

For the components estimated by 

non-chromatographic methods, the 

apecificity of the individual techniques 

and the frequent use of alternate 

methods are sufficient to provide 

a reasonable assurance that the results 

are in fact a measure of the 

particular components•under study . 

For the chromatographically estimated 

components, the identification= 

can only be considered as tenta- 

(Tobacco Science 108, 


PM3006662920

tire. and are based on the retention 

tir:ies of the individual materials on 

di''erent column packings and on a 

comparison of this work with that of 

others- For the hydrocarbons listed 

in Table 2. Osborne et al. (19) and 

Philippe et al . (20, 21, 22), have provided 

sufficient evidence of the presence 

of most of these materials in 

cigarette smoke . Since our hydrocarbon 

column (column I) was essentially 

that used subsequently by 

Philippe (21) with the same elution 

order of hydrocarbons . the identity 

of these materials is fairly rx-ell established 

. For the oxygenated components 

analyzed with columns II and 

III . the considerable alteration of 

elution times between these packings 

and the comparison of these data 

with those of Irby and Harlow (9) 

and Grob (7) allows a tentative assignment 

of these materials . Figures 

3 and 4 show the chromatographic 

tracings obtained with columns 

I . II, and III with and without 

the additional mercuric perchlorate 

and boric acid columns . 

These illustrate the degree of separation 

achieved . In Figure 3, the 

thorough scavenging effect of the 

mercuric perchlorate for unsaturated 

hydrocarbons is clearly 

shown . u-hich allows the resolution 

of all but one of the overlapping 

peaks . 

Considerably greater mixing of 

components is apparent in Figure 

4. where eight to 10 overlapping 

peaks are evident in the two chromatograms. 

The considerably different 

polarities of these two columns 

resulted in a pronounced change in 

retention times for a number of 

components, thus allowing an interchange 

of partners in the mixed 

peaks . It w as thus possible to resolve 

each mixture by means of difference 

calculations . 

Calibration data using individual 

components and mixtures thereof 

were obtained for estimation of the 

amounts of each material . As has 

been reported previously (1), each 

class of compound was found to exhibit 

a linearly increasing flame 

ionization detector response with increasing 

numbers of carbon atoms 

in the molecule . The difference between 

classes of compounds which 

are primarily dependent on the nalure 

of the functional groups present 

can be expressed in terms of an efieetice 

number of carbon atoms 

(\c) . For hydrocarbons Kc is es- 

,entially equal to the number of 

carbon atoms, while for materials 

containing carbon-oxygen bonds, the 

effectire number is generally one unit 

less than the actual number. Table 

1 summarizes some of our calibration 

data in terms of this quantity, 

which is measured relative to n-hexane, 

and compares these with values 

reported in the literature (4) . 

The general agreement between 

Ve values computed from our calibration 

data and those reported in 

the literature is useful in that it 

provides a check on our calibration 

procedures . Although calibration 

data were obtained for most of the 

compounds reported herein, the 

linearity of the flame response for 

homologous series was occasionally 

used to estimate minor members of 

such a series and provided a further 

check on the individual calibrations . 

2 . Analysis of Cigarette Smoke . 

To demonstrate the utiliri- of these 

methods, comparative data an three 

different types of cigarettes were 

obtained . These iiere chosen to demonstrate 

the effect of cigarette filters 

on this array of minor gaseous smoke 

components . All three cigarettes bad 

the same tobacco column, which consisted 

of a commercial blend of the 

major types of cigarette to'naccos . 

The first sample, labelled "no filter," 

is representative of an 85mm unfiltered 

cigarette . The second . labelled 

"acetate filter," is also 85 mm 

long and is equipped with a I6 mm 

cellulose acetate filter, and is found 

to be quite similar to most ordinary 

commercial filter cigarettes in its 

smoke and gas filtration properties . 

The third 85 mm cigarette, labelled 

"combined acetate adsorbent filter," 

is equipped with a 20 mm combination 

filter consisting of two outer 

sections of cellulose acetate surrounding 

a five to six mm cavity 

filled with 100 to 120 milligrams of 

a specially impregnated granulated 

charcoal adsorbent . 

The yields of minor gaseous components 

obtained from these cigarettes 

are given in Table 2. As is 

apparent from this table tobacco 

smoke contains a highly complex 

mixture of gaseous materials . As 

noted by Philippe et oi . (21) the array 

of hydrocarbons approximates 

that of thermally cracked gasoline . 

The composition of the whole mixture 

suggests a combination of a randomized 

series of pyrolytic reactions 

which would form a large number of 

individual components and some destructive 

and non-destructive distillations 

which w ould generate the 

greater than expected amounts of 

such materials and 2 .3-butanedione . 

2A striking feature of these data is 

the capacity of the adsorbent bea' 

ing filter to remove apprecia 1rb 

quantities of the less volatile gaseous 

constituents of tobacco smoke . 

Materials boiling above -40° to -10° 

are appreciably extracted from the 

smoke stream by the adsorbent and 

removals of up to 85 per cent are 

achieved for some of the less volatile 

materials . Although the contact 

time between the flowing smoke 

stream and the charcoal is only of 

Table 3 . Variation of the deliver/ of hydrogen cyanide and 

formaldehyde during the smoking process. 

Combined acetate-adsorbent filtered cigarettes 

1 . H.-drogen ccanide (pg 40 ml puff ) 

Ci _arette • puff \ o . 

1 2 3 -i 5 6 T 3 Average(2-8) 

1 6 .5 4 .8 7 .7 9 .9 9 .5 7.9 10 .7 12 .5 9 .0 

2 10.3 7.6 12 .0 S .7 10 .2 15 .0 12 .3 14.2 11 .4 

3 3 .0 4 .2 6 .7 7 .5 9 .2 8 .^ 13 .0 14.0 S .6 

4 J .4 7.0 9 .7 13 .2 5A 12 .4 20 .6 17.6 12 .7 

5 6.4 -4.8 10 .- 10 .6 8 .7 8 .3 16.2 18.3 11 .1 

AVERAGE 5.9 5.7 9 .°_ 100 9 .2 10 .0 14 .6 16.4 10 .6 

S.D. 2 .9 1 .5 2 .4 2 .2 0 .7 3.6 3 .9 2.6 1 .7 

2. Formaldehyde (pg ;-f0 ml puff) 

Ciqarette'puff \o . 

1 2 3 -1 5 6 7 8 Acerage(2-8) 

1 7 .0 -.9 1 .1 1 .7 2 .4 1 .S 1 .2 2 2 1 .7 

2 5.9 3.3 1 .3 2 .0 2 .0 1 .3 1 .9 1.5 2 .0 

3 10 .4 4.1 2 .8 3 .3 4 .3 3 .4 4 .5 3.6 3 .7 

4 5.9 2.0 2 .0 2 .2 2 .0 1 .0 2 .1 2.7 2 .0 

5 3 .2 3 .2 3 .0 2 . 8 2 .7 2 .6 3 .9 4.7 3 .3 

AVERAGE 7.5 3 .1 2 .0 2 .5 2 .4 2 .0 2 .7 2.9 2 .5 

S.D. 1 .9 0.3 0 .9 0 .2 1 .1 1 .0 1 .4 1.2 0 .9 

(TobnC4o Science 109) 


PM3006662921

the order of 0 .1 second or less, the 

extensive pore structure provides a 

considerable adsorption capacity . It 

is estimated that the charcoal has a 

5000 fold greater surface area than 

the cellulose acetate filter, a factor 

which allows appreciable condensation 

and capture of smoke components 

which are essentially unaffected 

by passage through ordinary acetate 

filters . 

The concentration of gases that 

are not affected by filters is generally 

slightly higher in filtered cigarette 

smoke . This is probably the 

composite effect of the fixed volume 

puff and gas diffusion through cigarette 

paper. Since the smoking machine 

takes a fixed volume puff, the 

volume previously occupied by the 

adsorbed smoke components is made 

up by the less readily adsorbed gas 

phase components which are usually 

the very low boiling gases . The loss 

of gases by diffusion through cigarette 

rette paper has been found to be a 

significant factor for gases such as 

hydrogen and methane (17)•and 

since in a filter cigarette the paper 

area available for diffusion is considerably 

reduced, the concentration 

of such gases would be expected to 

be somewhat higher . 

Since many of the irritating materials 

in smoke are in the proper 

volatility range for removal by adsorbent 

filters, such filters have been 

found to enhance the "smoothness" 

of the smoke . Some of these irritants 

. such as hydrogen cyanide, ammonia 

. acrolein and formaldehyde, 

are ciliary depressants and thus 

smoke passed through such an 

adsorbent filter is considerably less 

inhibitory to mammalian ciliary 

activity (13) . 

Since the smoking technique deacribed 

herein is primarily an individual 

puff technique, it is possible to 

study the variation of the composition 

of the gaseous phase from puff to puff 

as the cigarette is consumed . As an 

example of this type of measurement 

. Table 3 illustrates the variations 

found for two irritating components, 

hydrogen cyanide and formaldeh}-de 

. Although considerable 

variation between measurements is 

evident, there appears to be a general 

trend towards slightly increasing 

yield of these materials as the 

cigarette is consumed . This behavior 

is consistent with a decreasing 

air dilution through the paper 

wrapper, but is not so marked as to 

indicate a breakdown of the adsorption 

capacity of the filter . 

Summary 

A combination of a relatively simple 

smoking technique and a variety 

of electrometric, colorimetric and 

chromatographic analyses has been 

utilized to investigate some of the 

minor gaseous components of cigarette 

smoke . Eighty different materials 

have been isolated and estimated . 

Literature Cited 

1 . Altschuller, A . P ., D . L . Miller, 

and S . F . Sleva, Determination 

of Formaldehyde in Gas 3iiztures 

by the Chromotropic Acid 

Method . Anal. Chem . 33 : 621- 

625, 1961 . 

2 . Baker, B . B . and J . D . Morrison, 

Determination of \ficrogram 

Quantities of Fluoride and Cyanide 

by lfeasurement of Current 

from Spontaneous Electrolysis . 

Anal . Cl:e>n . 27 : 1306-1307, 1955 . 

3 . Bradford, J, A ., E . S . Harlow, 

W . R. Harlan and H . R . Hanmer, 

Nature of Cigarette Smoke . 

Volatile Bases and Acids. Ind . 

Eng. Chetn . 29 : 46-50, 1937 . 

4. Brenner, N ., J . E . Callen and 1f . 

D . 1Ceiss, editors, Gas CArovn.atography, 

1st Ed ., Chapt . 18 

and Chapt. 19, Academic Press, 

New York. 1962. 

5 . Brenner, N ., J. E . Callen . and 

M . D . Weiss . editors, ibid ., Chapt . 

28 . 

6 . Falk, H . L . and P . Kotin, Symposium 

on Chemical Carcinogenesis 

. III . Chemistry, Host Entrland 

Metabolic Fate of Carcinogens 

. Clin . Plw.rmacol . 4 : 88-103, 

1963 . 

7. Grob, K., Zur Gaschromatographie 

des Cigarettenrauches . 1 . 

Teil . Eine Methode zur Routineanalyse 

der Gas-Dampf-Phase . 

Beitr. TabakJorsch. 1 (7) : 285- 

290, 1962 . 

2 . Tei1 . Verfeinerte Trennung 

mit Hilfe von Kapillarkolonnen . 

Beitr. Tobakforsch . 1 (9) : 315- 

323, 1962. 

8 . Ikeda, R . >f ., D . E . Simmons and 

J . D . Grossman, Removal of --Ucohols 

from Complex Mixtures 

During Gas Chromatography . 

Anal . Chem . 36 ; 2188-2189, 1964 . 

9 . Irby, R . M ., Jr ., and E . S . Harlo 

.c, Cigarette Smoke . I . Determination 

of Certain Vapor Constituents 

. Tobacco Sci . 3 : 52-56, 

1959 . 

10 . Jacobs, M. B ., The Analytical 

Che»e.istry of Industriai Poisora, 

Hazards and Sofvents, 2nd_ Ed ., 

p . 326, Interscience, New York, 

1948 . 

11 . Jacobs, M. B ., ibid ., p . 364 . 

12. Jacobs, 1f . B ., ibid., p . 673. 

13 . Kensler, C. J . and S . P . Battista, 

Components of Cigarette Smoke 

with Ciliary-Depressant Activity 

. Their Selective Removal by 

Filters Containing Activated 

Charcoal Granules . Netv Eng. J. 

]fed. 269 : 1161-1166, 1963 . 

14 . Levins . P . L . . and D . Koch, Arthur 

D . Little, Inc ., Cambridge, 

.llass ., Unpublished data, 1964 . 

15 . Mumpower . R . C . . J . S . Lewis 

and G . P . Touey, Determination 

of Carbon ?fonoxide in Cigarette 

Smoke by Gas Chromatography . 

Tobacco Sci . 6 : 142-145, 1962 . 

16 . _'kIurty . G . V . L. N . and T . S . 

Viswananthan, Determination of 

Traces of Cyanide . .4wa.t . Chirn . 

.4cfa 25 : 293-295, 1961 . 

17. Newsome, J . R . and C . 11 . Keith, 

Variation of the Gas Phase Composition 

Within a Burning Cigarette 

. Tobacco Sci 9 : 30-34, 1965 . 

18. Norman, V . and C . H, Keith . 

Nitrogen Oxides in Tobacco 

Smoke. Nature 205 : 915-916, 

1965 . 

19 . Osborne . J . S . . S. Adamek and 

3f . E . Hobbs, Some Components 

of Gas Phase of Cigarette 

Smoke . Anal . Chem. . 28 : 211-215, 

1956 . 

20 . Philippe . R . J . and M . E . Hobbs, 

Some Components of the Gas 

Phase of Cigarette Smoke . Anai . 

Chem . 28 : 2002-2006, 1966 . 

21 . Philippe . R . J ., H. :lioore, R. G. 

Honeycutt and J . Tf . Ruth . Some 

H}-drocarbons of the Gas Phase 

of Cigarette Smoke . Anat . Chem . 

36 : 8n9-866, 1964 . 

22, Philippe . R. J., Unpublished 

data, 1964 . 

23 . Saltzman. B . E ., Colorimetric 

-IIicrodetermination of Nitrogen 

Dioxide in the Atmosphere. Anal. 

Chene . 26 : 1949-1955, 1954_ 

2-4 . Thompson . J. F . and G . R . Morrison 

. Determination of Organic 

Nitrogen . Control of Variables 

in the Use \essler's Reagent . 

Anal . Chnn . 23 : 1153-1158, 1951 . 

25 . West, P. R' . and B . Sen, Spectrophotometric 

Determination of 

Traces of Formaldehyde . Z . Anal. 

Cltetn . 153 : 177-183, 1956 . 



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