"COPY" 29*12*59o
Research & Developnent Establishment,
Brit i sh-Ameri can Tobacco CoAtd.,
Southampton.
Report No. RD-15 - R
JjtLe s Progress Report No.1 s SWKE GROUP
Authort D.G.Felton
Issued by% H.D.Anderson
Original Distributions
Copy No*7
8
9
10
11
12
13
14
Copy No.e.e****.*
Date of Issues 6.3.57.
D.S.F.Hobson Esq.,
Sir Charles Ellis
File 46D
T,,M*Wad* Jnr. Esq.
File 46B
master
Le.Hinsholwood Esq.,
UbrM
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"ODPY" 29o 12o 59.
SMOKE GROUP
Proaress Revort No.1
le INTRODUCrION
The following report covers work accomplished by
the Smoke Group
up to March lst, 1957.
The broad strategy adopted and the outline of the
basic programme
has been dealt with in other documents.
The following progress report is therefore
subdivided into the
constituent parts of the programme.
2. BORSTAL ASSAY
2.1 Ec[uinment
A Hilger Nedium Quartz spectrograph has been
Installed and the
ancillary optical equipment necessary for
fluorescence spectrography has
been tested In various arrangements in order to
determine that which gives
the greatest degree of sensitivity amsistent with
even Illumination of
the spectrograph alit.
A modified recording microphotometer has recently
been received
from Hilger and Watts. Installation of this has
been hold up until the
"A" Laboratory was completed and is still delayed
because Hilger's omitted
to enclose directions and a circuit diagram for
the power pack. When this
instrument is installed a certain amount of
orientation work will be
necessary to check plate calibrations and the
characteristic curves of
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Photographic emulsions. The detailed procedure to
be adopted in the final
assay plate remains to be checked.
2.2. Materials
Samples of pure BORSrAL have been prepared from
cammercial
material and have been charact*rised by the
ultra-violet absorption spectrum.
This spectrum will then serve as a base line for
the assay of standard solutions
from time to time.
2.3 Limits of Detection
Using serial dilutions of BORSrAL, the lowest
limits of
detectability using fluorescence spectrography
have been determined. Two
criteria of detectability may be *mployeds
a) The concentration at WUch the throe main bands
(at 403, 408
and 427 mg) in the BORSTAL fluorescence spectrum
are visible
on the photographic plate.
b) The concentration at which the strongest band
only (at 403 m1l)
Is visible.
Initially-, using Ilford HP3 plates, developed in
ID-11
developer, the limits of detection have been shown
to be 0.05Pg/ml.
(criterion a) and 0.025 Wml. (criterion b). Ywry
recently, a faster
emulsion has been studied using a vigorous
developer* This has lowered
the limit of detection fivefolds using Ilford HPS
plates, developed in
PFP developer, the limits of detection are now
0.01 or 0.005 p9/61.
respectively for the same two criteria.. This will
in future be tho
standard technique for detection. Such sensitivity
is unnecessarily high
for assay measurements and it may prove
advantageous from the point of view
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of emulsion grain size to revert to HP3 plates
developed in fine-grain
developer (e.g. Microphen) for the final assay
plates of an experiment.
It has already boon found that then the nor*
sensitive plates
are used for fluorescence spectrography of
elgaretto tar fractions, the
background fluorescence is grossly over exposed
when the usual 0-minute
exposure Is given. The exposure has therefore been
reduced to 3 minutes
with a consequent gain In the speed of working.
2.4 Experimental Results
2.4 (1) A preliminary run on 500 cigarettes was
carried out.
BORSTAL was detected in the chromatographic
fractions of the neutral
portion of the smoke condensate and those
fractions exhibiting the
characteristic fluorescence spectrum were combined
and refractionated.
The final DDRSrAL concentrate was then assayed by
comparison between
standard solutions of BORSrAL and aliquots of the
unknown to which had
been added standard aliquots of BORSTAL. The
estimation of DDRSTAL
concentration in the unknown was carried out
visually, perforce, and
yielded an estimated content of 7 jig BORSUL from
= cigarettes. This
estimation will be repeated on the microphotometer
when this Is fully
operational and for this purpose a step-wedge
calibration was Included
on each assay plate.
2.4 (2) The foregoing experiment was follow-*d by
a 'Fronts and
Backs" experiment. The smoke from the initial 26
mu of cigarettes was
collected separately from that from the a-cond 26
m. portions and the
cigarettes were discarded at a butt length of 20
m. These two moke
samples were processed separately to yield the
respective neutral fractions.
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At this stage the experiment was interrupted,
owing to the
disorgaikisation of the laboratory consequent upon
the move to "A* Factory,
The two samples of tar were stored at &C in the
dark for about a month
and during this time it Is possible that
deterioration of the samples may
have occurred. For this reason, reliance cannot be
placed on the eventual
results as typical examples.
The first fractionation of tar from "Fronts" did
not reveal
BORSrAL in the first 32 fractions (it was expected
to appear from Fraction 17
onwards, or thereabouts). The column was therefore
abandoned and the tar
sample recovered for refractionation; but
meanwhile the final fractions
(33-40) were examined and very faint indications
of the presence of BORSTAL
were obtained. This anomalous behaviour may be
explicable in terms of the
temperature of develppment. In the original
laboratory on "B* Floor, the
temperature of the darkroom was generally about
680F and no special
precautions were necessary. It was now noted that
in the "A" Factory
darkroom the temperature was 58-OF; this would
make a difference of
50-100% in development speed and may account for
the failure to detect
threshold concentrations of BORSTAL. This point
has now been attended to
by the installation of a heater in the darkroom.
The fractionation of
"Fronts-tar' will be repeated at once.
Meanvihile, the fractionation of tar from "Backs*
is in progress.
BORSUL has been detected in Fractions 19-38
inclusive and these have been
bulked for refractionation. The more sensitive
means of detection have
been employed here for the first time.
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2.5 Future Work
When this initial "Fronts and Backs* experiment is
completed,
three more such assay$ are planned to check the
degree of replication
attainable. This is especially necessary as the
initial experiment may
be of doubtful reliability because of possible
"aging" effects on the
tar, as noted earlier. This and other extensions
of future work are
outl ined in the proprosed Programme for the
ensuing throe to four months.
3. QUALITATIVE ANALYSIS OF THE AROMATIC POLYCYCLIC
HYDROCARBONS
The experimental procedure for the Qualitative
Analysis may be
outlined as (1) Separation of the neutral
fraction, (2) Chromatographic
fractionation of the neutral fraction, and (3)
Identification of the
Constituents thereby separated.
3.1 Separation of the Neutral Fraction
The separation of the neutral fraction from the
acidic and
basic moieties present is carried out by one of
the two mothodst-
(a) alkali/acid washing
(b) ion exchange resins
Several comparisons of the two methods war* made,
and for the
purpose of this analysis, (b) was chosen, since it
gives a cleaner neutral
tar and is less time consuming.
The resin method involves passing a solution of
the tar through
a column of Zoo-Carb 225 (in the H + ion cycle) in
series with another
containing Do-Acidito FF (in the OH - Ion cycle).
After passage, the
columns are regenerated for further use, or elut*d
for the acidic* and basics
and then regenerated.
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~.2 Detection and Identification
The methods used for the detection and
identification of the
Polycyclic hydrocarbons are (a) paper
chromatography and (b) measurement
Of ultra-violet absorption spectra.
To standardise the methods and provido reference
compounds, a
number of hydrocarbons were obtained (anthracene,
chrysene, phenanthrenet
pyrene, perylene, fluaranthene, econsphthyleno,
n&phthaceneg coronenep
fluorene, 1,2,5,6-dibenzenthracene,
1,2-benzahthraisene, and 20-sethyl
cholanthrone). These have been purified by either
sublimation or
chromatography on alumina, and crystallisation.
The purified compounds
were then used to standardise the paper
chromatography teghnique, employLng
such variations as pre-saturation of paper,
equilibrium times and
developing solvents.
3.3 Exnertmental Results
Early experiments indicated that aging of the
condensed tar may
cause variations in the chemical composition.
Therefore, a fairly
comprehensive qualitative study of the composition
of the neutral fraction
of tar produced in the autosmoker (i.e. by
electrostatic precipitation)
is being made. This qualitative picture will
provide the basis on which
any compositional variation produced by varying
conditions of smoking,
collection etc., may be sompared.
250 cigarettes were mokod, tar collected and this
neutral fraction
freed from acidic/basic moieties. Alumina
chromatography of the neutral tar
gave 10 main fractions, 7 of which have been
rechromatographed on alumina.
The collected sub-fractions were examined on paper
ghromatography. Mhere
more than one fluorescent zone showed, further
separation has been carried out.
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The ultra-violet spectra measurements have been
made an the sub-fractions
showing only one, apparent fluorescent zone.
Results (to date) - A crystalline solid has been
Isolated
Wiich, on Infra-Red Analysis, was shown to be a
saturated aliphatic
hydrocarbon.
The followihg compounds are also thought to be
presento
naphthalene
acenaphthene
phenanthrene
anthracene
pyrene
fluoranthene,
1,2-benzanthracene
4 o PHYSICAL STUDIES
4.1 Temnerature Measurements of Cioaretto Goals
Early experiments carried out at Uverpool were
restricted by
shortage of thermocouples, but showed that maximum
temperatures were
remarkably independent of cigarette conditionsp
*.go moisture content,
packing density*
Later work using the Flik galvanometer with
photographic
recording using a low-speed camera required the
provision of an anti-
vibration mounting to eliminate large amplitude
vibrations to which the
then laboratory was subjected. This work forms the
subject of a separate
report by A.W.Cronshaw. The work may be summarised
briefly as followat-
4.1 (1) No effects complicated the interpretation
of the results
a) Conduction of heat along the thermocouple
leads,
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b) Phasing of puff relative to thermocouple
location
in the cigarette.
Factor (a) could be minimised by using very thin
thermocouples.
Factor (b) was less easy to evaluatel by using
measurements, of the
advance of the coal along the cigarette during and
between puffs, It was
possible to deduce roughly the distribution of
temperature along a
cigarette at any one Instant in time.
4 o1 (2) An attempt was made to provide
photographic evidence which
would enable accurate measurement of the advance
of the coal along the
cigarette to be made. Rapid sequence photography
during and between puffs
was tried but with only limited success, using a
Robot II camera.
Difficulties arose through the limited number of
frames which could be
taken and by the failure an occasions to
photograph the beginning and end
of a puff accurately. A more suitable cameras such
as the Shackman
Auto-camera Mark III, is required.
4.1 (3) With the installation of the Medium Quartz
Spectrograph
(Para. 2.1) there was insufficient working space
In the darkroom to permit
the photographic recording of temperatures to
continue and this work has
therefore been in abeyance until now, when
separate darkrooms are available.
The completion of the above project is scheduled
for the immediate future.
4.2 TemDerature Measurements on Cloarette Smoke
The temperature of smoke dram Into the mouth was
measured using
the on*-mit smoking machine. This temperature was
found to increase,
rapidly with increase in the puff-volume and also
with reduction in the
butt length. This work was undertaken to check an
Idea that these factors
may be of importance in the preparation of tar
samples.
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5* MISCEIMEOUS APPARATUS AND SERVICES
5.1 Molins Automatic Individual Cicarette Weiaher
This instrument, which is used for selocting
cigarettes on a
basis of might, has been modified by the provision
of now selector
pieces which enable cigarettes to be selected
within a range of + 20 mg*
on foxmul& weight, i.e. + 2% approx.
5.2 Draw Resistance Amaratus
This has been constructed In the laboratory and is
used for
the secondary selection of weight-selected
cigarettes, an a basis of draw
resistance. This Is done by measuring the pressure
drop across a cigarette
when a constant air flow is passing as measured by
& capillary flow motor.
5.3 Humiditv Cabinet
A Gallonkamp, Humidity Cabinet for the storage of
cigarettes
before and after selection has been installed. It
required modification
in order to maintain an R.H. of 55% at 260C.,
conditions very near to
ambient vmrage conditions. The modification
consists in the provision
of facilities for the pumping of air through
drying columns of silica gel
before enttry Into the oven. Preliminary
exptriments yielded data enabling
final design requirements to be estimated and the
modification Is in hand,
but has not yet been completed. It will require to
be tested over a period
of some weeks before success can be claimed.
5.4 Hilaer Uvisook Photoelectric SvectroDhotmeter
This has been Installed and has been such used for
the
detozmination of ultra-violet absorption spectra
of chromatographic fractions
and of pare compounds (see especially para. 3).
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5.5 I-T.Co. Autdamoker
This is used for the production of cigarette tars
under standard
conditions of smoking. It has r*quired maintenance
from time to time,
e.g. replacement of E.H.T. unit, replacement
of.leat spring, Tufnol brake
adjustment, and periodic cleaning of valves eic.v
5.6 Solvents
A programs for the production of purified
solvents, e.g..
petrol, benzene and acetone, which are used In
large quantities In
the chromatographic fractionations, has been
established under the
responsibility of a technician.
6. PERSONNEL
Four laboratory technicians have bean trained in
particular
aspects of the work involved to the state where
they can perform the
routine operations with the minimum of close
supervision.
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BATCo document for Province of British Columbia 12
November 1999