Bab.

19241 THOMSON-“SOME NOTES ON BENZINE SOAPS” 45

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many people worked for the larger part of the Only a very small quantity of methylated
day under conditions in which sunlight was alcohol can be dissolved in petroleum without
totally excluded. separation taking place a t ordinary tempera-
Mr. F. W. Lake asked whether the artificial tures; about 0.5 cc. per litre being the maxi-
daylight lamp was suitable for general illumina- mum when using the above grades of petroleum
tion of a dyehouse, and the Lecturer replied and alcohol. It was found that by ordinary
t,hat the Macbeth lamp was not intended for observation a mixture might seem perfectly
general illumination. clear, yet, after standing several hours, separa-
tion had taken place, and the simplest method
found for quickly detecting this separa-
tion was t o examine the mixture after it had
SCOTTISH SECTION been violently shaken in a stoppered clear-glass
cylinder by the light from a north window
glazed with rippled glass, allowing the shadow
Meeting held on 2nd November 1923, a t the of a black bar to fall across the cylinder. When
works of Messrs. J. Pullar & Sons, Ltd., Perth, separation was taking place i t was possible by
Mr. JAMES CRA4WFORT) in the chair. moving the cylinder up and down t o notice
a peculiar appearance in the liquid just below
Some Notes on Benzine Soaps . the shadow of the bar-an appearance rather
R. G. THOMSON difficult t o describe-a sort of silvery band on
the edge of the shadow. Microscopical examina-
When employing petroleum in cleaning and tion of a drop of the liquid was not found to be
dyeing operations, one of the first difficulties a practicable method of determining whether
met with is due to the comparatively small separation had taken place, as when near
range of substances soluble in or miscible with separation point the mixture was very sensitive
i t which would be of service in the operations of to changes of temperature and t o the presence
dyeing and cleaning; and it was with a view of of moisture in the air.
investigating what was possible under works)
conditions that the research from which these Preliminary trials showed that soaps made
notes are taken was initiated. with oleic acid were most serviceable for this
purpose. If any considerable quantity of hard
All materials used in the investigation were fatty acids was present there was always trouble
such as could be easily obtained in quantity and on account of the insolubility of the hard soaps
a t such cost as would not make the processes formed, consequently a very high grade of
impossibly expensive, and eventually the work commercial oleic acid was used, containing only
practically narrowed itself down to an in- very small quantity of hard fats and which
vestigation into thr 1)rpopertics of soaps in showed 98.5 per cent. fatty acid. Ammonia
solution in petroleum. 0.88 sp. gr. was used as the alkali of the soap,
The petroleum used 1s a s an urcliiiary trade and a quantity of neutral soap was prepared.
spirit of 0.772 sp. gr., understood to be a Borneo
petroleuni. I t was ustd as receivcd from the This soap was only sparingly soluble in
refiners, a large stock bring put aside to serve petroleum on account of the water introduced
all through the trials. Thc reason for this will hy the aqueous ammonia. Various anhydrous
be shown Iitttlr. soaps were prepared but, except when a con-
siderable quantity of free oleic acid was present,
Solvent naphtha is iiiuch tnorc suitable for these soaps were not very suitable, as they
the purpose than petrolwm, hut it has several tended, on standing, t o gelatirlise in the petr-
serious disadvantages, amongst which may be oleum. One method which gave fairly satis-
mentioned its unpleasant cbffect upon the skin factory results was t o prepare the soap with
and the toxic properties of its vappour. alcohol saturated with ammonia gas. The water
Next to water, the solvent which it is most introduced by aqueous ammonia was thus
desirable to be able to introduce into petroleum avoided. Another method of rather limited
is alcohol, both on account of its valuable application was t o saturate the petroleum itself
solvent powers and because of its fairly reason- with ammonia gas and add the oleic acid to
able cost. this. All measurements were made by volume.
Absolute alcohol is miscible in all proportions An addition of soap t o the petroleum required
with petroleum, and were it possible to use it, the also an addition of alcohol to ensure complete
introduction of many substances into petroleum solution, and the minimum amount of alcohol
would be easy ; but the cost of absolute alcohol required for each proportion of soap was
is so exceedingly high that its use on a practical determined. This was termed “clearance
scale is impossible. The most suitable substitute amount,” and it waa found best to incorporate
is industrial met hylated :LIcohol, which is this amount of alcohol with each quantity of
obtainable at ihbout 66” O.P., containing about soap before its addition t o the petroleum,
92 per cent,. alcohol by weight. This was the otherwise proper solution of the soap in the
spirit used throughout the trials. petroleum was slow and doubtful, except when
 46 THOMSON-“SOME NOTES ON BENZINE SOAPS” :Neb. 1024
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using soaps having a fair proportion of free water available as solvent for dyestuffs &c. in
oleic acid. I n all the results given the percentage order t o produce full shade.
of soap added is stated as its oleic acid content. The investigation proved that the amounts
The maximum amount of industrial methyl- of water which could be added did not bear
xted spirit which could be added to petroleum a direct relationship to the proportions of
cont,aining definite proportions of soaps was alcohol and soap in the mixtures.
determined by mixing one litre of petroleum in a By adding a certain percentage of neutral
clear glass-stoppered cylinder with the deter- soap. to the petroleum, a certain amount of
mined amount of soap and adding alcohol in alcohol is rendered soluble therein, and by
small quant,ities a t a time with vigorous shaking ; increasing or decreasing the amount of soap,
observing carefully after each addition whether therc is a corresponding iiicreasc or decrease in
there werc any signs of separation. The amount the amount of alcohol which can be dissolved.
of a,lcohol added before first signs of mistiness Also when using soaps containing free oleic
were observed was taken as the maximum acid or free ammonia, the amount of alcohol
addition possible a t that temperature. dissolved i s proportional to the amount of
A t this. point strange irregularities were real soap present, but when water is added to the
noticed and only after much investigation were already formed petroleum-soap-alcohol mixture,
they found to be due to very slight alterations the addition of a certain quantity of oleic acid
of temperature. Of course, ordinary pre- as neutral soap enables a certain amount of
cautions had been taken to ensure a normal alcohol and water to be added, yet when the
working temperature, but near the saturation same amount of oleic acid not fully neutralised
point the mixture is exceedingly sensitive. is added, the amount of alcohol and water
Once the maximum amount of alcohol has been which can be added is greater. This is best
added t o a petroleum soap solution, should the shown by t,he chart.
temperature be lowered slightly so as to cause OF WATERAND
AMOUNTS OF METRYLATI~D
SP~IT
separation, the separated globules, although WHICH C A N B E ADDIED TO PETROLEUM SOLU-
only in the form of a fine mist, do not readily TIONS OF SOAP.
redissolve on again raising the temperature to
normal, but: require prolonged vigorous mixing lb

or else elevation of the temperature above the 5

normal for a short time.

The amount of alcohol which soaps having 13

either an excess of oleic acid or of ammonia I1

I1
enabled t o be added to the petroleum mixture
bore a distinct relationship to the amount of ;10
true soap present when working with small ;9

percentages. The proportion, however, rises a t ;@

Ul
an increasing ratio until a point is reached when, 6
by t,he addition of a certain amount of soap, any 5
quantity of alcohol may be added without 4
separation taking place. 3

Yererntngr
l8f sllllp.
. Cv. A l r t i I ~ t ~ tl l i w h ~ i l
prr litre.
’1

1 . . . . . . . . . . . . 33 10 00 Jo 40 Po M 70 10 90 100 110 110 a30 IM 150 100 1111 180 190 2 0 0

2 . . . . . . . . . . . . 66 C.C. McTnYLITCD SCIR~T

R . . . . . . . . . . . . 100 ?u‘oTE-‘l‘lre flgures in brackets ,give t.he amount of

4 . . . . . . . . . . . . 134 oleic acid or uf ammonia added to the soap.
6 . . . . . . . . . . . . 170
6 . . . . . . . . . . . . 212
The following table shows in the second
7 ............ 264
column the amount of water added t o the
Having determined the “clearance amounts’.’ mixture (allowing for t.he proport,ion added as
and “maximum addit,ions” of alcohol, the part of the mcthylated alcohol) when using
amount of water which could be added to neutral and acid soap respectively, and in the
petroleum-soap-alcohol mixtures was next deter- third column the calculated amount,s hased
mined, as it is very necessary to know how much upon the 1 per cent,. result-
water may be used as solvent for substances Oleic ,Arid. s El”L’HAL SUAP.
insoluble in alcohol and in petroleum, yet which 11. Tll.
’i . . . . . . . . . 4.2 ... --
i t is desirable to introduce into petroleum. This 2 . . . . . . . . . 8.2 ... 8.4
determination gives also a measure of the amount 3 . . . . . . . . . 12.5 ... 12.6
of dampness a petroleum bath may contain in 4 . . . . . . . . . 17.5 ... 18.8
6 . . . . . . . . . 22.0 ... 21.0
cleaning operations, for it is well known that a
dry soap has not nearly the same cleansing power
in petroleum as one which introduces a definite
proportion of water. I n the so-called “Dry 2 . . . . . . . . . 9.6 ... 7.0
Dyeing,” too, it is a n advantage to have some 3 . . . . . . . . . 17.0 ... 10.6
 This must be kept in mind when making up Meeting held a t the College of Technology,
these mixtures on a practical scale and allow- Salford, Manchester, on 9th November 1923,
mces made for possible absorption of moisture, Mr. J. W. MCMYN in the chair.

the various petroleums ha,d changed difkrently ; these they claim ortho-ether groups, and in the
some showed higher figures after storage, but second halogen substituted para-toluidides or