Change in Specific Gravity of Essential Oils and Perfumes with

Change in Specific Gravity of Essential Oils and Perfumes with Temperature .... The Camp Fire is the deadliest and most destructive wildfire in Califo...
8 downloads 0 Views 527KB Size
Download PDF
CHANGE IN SPECIFIC GRAVITY O F

Essential Oils and rertumes WITH TEMPERATURE L. W. BOSART The Procter & Gamble Company, Ivorydale, Ohio

specific gravities found, but many of the results are so widely different that they are omitted here. Schreiner and Downer found a mean variation in the specific gravity of 0.00064 per degree, which they considered satisfactory to use in calculating results from 25" to 15" C. to meet the requirements of the U. S. Pharmacopeia then in force. Considering that their maximum temperature was 25", this was no doubt satisfactory for this particular purpose since they estimated the maximum error in specific gravity would be 0.0018. Their value of 0.00064 when calculated for 15"/15" to 25"/15'C. becomes 0.00084. The average found in this work for 15"/15" to 35"/15" on the same oils is 0.00081. The agreement is only moderately close. Schimmel & Company (5)state that they found differences of 0.0007 to 0.0008 per degree based on water a t 15" C., but their published work points to greater differences. Later (6) they published specific gravity tests on about forty perfume oils a t 15"/15" and 25"/25" C., and gave a table showing their results. From these results the variations per degree based on water a t 15" may be calculated. This calculation has been made by the author, and the results are recorded in Table I together with the values here determined for the same oils in so far as determinations on these oils have been made. The present results are in fairly close agreement. For the sake of simplicity only the variations per degree are given in this

Determinations of the specific gravities of a large number of perfumes were made and recorded. A table shows the correction to be made per degree of temperature for each of these perfumes. The perfumes may be tested for specific gravity at the room temperature, and by applying the correction, the specific gravity at 15" C . , based on water at 15" C . , is obtained. ENERALLY the specific gravities of essential oils and other liquid perfumes are obtainedat 15°C.basedonwater a t 15"C., with a plummet balance. This offers some difficulty, especially in hot summer weather when the room temperature is frequently as high as 35" C. or even higher. Obviously if we had a factor that could be applied for the variation of the specific gravity of perfumes with the temperature, we could make the tests a t the temperature prevailing a t the time and correct to 15" C. If the perfumes all had the same coefficient of expansion, this would be a simple matter since the same correction per 1" C. could be made in each instance. But since this is not the case, it becomes necessary to determine the coefficient of expansion of each separate perfume and apply the correction. This work was therefore undertaken to find the proper correction for each of the more commonly used perfumes.

TABLE I. VARIATIONS PER IN SPECIFIC GRAVITY

1"

c.

Variation per 1" C. Based oN n Water at 16' Calcd. by author Detd. by from Sohimmel's tests author

Literature In 1885 Lyons (3) made determinations on the coefficient of expansion of various liquids, among them a few essential oils, Since these are not in very close agreement with the values found in the course of this work, they are not given here. Schimmel & Company (4)in 1887made determinations on about forty essential oils a t lo", 15", and 20" C. and gave the change per degree between 10" and 15", 15" and 20°, and 10" and 20'. These, likewise, are not considered to be in sufficiently close agreement and are not given here. The changes per degree were for a range between 10" and 20", which would not be very useful in any case. Schreiner and Downer (7) made determinations of the change per degree on thirty-two essential oils a t 15", 20', and 26" C., in most cases on two different samples. Their ,ecific gravity determinations are based on water at the same ,emperature, and therefore the changes per degree have to be -!calculated to bring them to the same basis as those here obmed. The variations per degree agree in some cases with che author's or with those obtained in 1906 by Schimmel I% Company (6) when the latter have been calculated from the 867

Anise oil Benzaldehyde Bitter almond oil Cajeput oil Caraway oil Cassia oil Chenopodium oil Cinnamic aldehyde Clove oil Copaiba oil Coriander oil Cubeb oil Erigeron oil Eucalyptol Eucalyptus oil Eugenol Fennel oil Hedeoma oil (Am. pennyroyal) Juniper-berry oil Lavender oil Lemon oil Mustard oil Nutmeg oil Peppermint oil Pimenta oil Rosemary oil Safrol Sandalwood oil Sassafras oil Savin oil Spearmint oil Sweet-orange oil Thyme oil Turpentine oil Turpentine oil, rectified Wintergreen oil: From Betula lenta L. From Gaultheria procumbens L. Artificial

0.00080

0.00091 0.00090 0,00083 0.00076 0.00084

0.00083

0.00078

0,00086

0.00073 0.00085

0.00082 0.00089 0.00089

.....

0.00078

0.00081

.....

0.00080 0.00085

.....

.....

..... .....

0.00074

0.00080 0.00086 0.00082

o.ooos8 0.00082

0.00079

0.00080

O.OOOS6 0.00075 0.00101 0.00083 0.00073 0.00089 0,00084 0.00092 0.00067 0.00089 0.00077 0.00081 0,00074 0.00079 0.00084 0.00083 0.00100

0.00100 0.00103

.....

0.00084 0,00087

.....

0.00078 ,.... 0,00082 0.00077 0

:ooasz

0.00076 ..... 0,00081 0.00089 0.00070 0,00087

.....

0,00079 0.00078 0.00079

.....

..... .....

0.00099 0.00098

.

INDUSTRIAL AND ENGINEERING CHEMISTRY

868

VOL. 28, NO. 7

TABLE11. SPECIFIC GRAVITIES AND VARIATIONS IN SPECIFIC GRAVITY PER 1" C. 15O/15O C. Acetophenone a-4myl cinnamic rtldehyde 4 m y l salicylate Anisaldehyde (aubepine) Benaaldehyde Bensyl acetate Bornyl acetate Bromostyrene Carvacrol Cinnamic aldehyde Citral Citronellal Citronellol p-Cresyl acetate: No. 1

No. 2

Averaxe p-Cymene Diethyl phthalate Diphenyl oxide Eugenol Geraniol, pure Geraniol, technical Geranyl acetate Hvdr oxvoitronellal Idnone Isoeugenol Limonene Linrtloal from bois de roae Linal 1 acetate: 9 2 6 , No. 1 92%, No. 2 Extra Average Methyl anthranilate Methyl b e n ~ o a t e : No. 1 No. 2 Average Methyl phenyl acetate: No. 1 No. 2 Average Methyl salicylate Oils: Almond, bitter, genuine, free from prussic acid Anise, star, U. 8. P.

E:gamot

extra fine Bois de rdse, Brazilian Cade from Juniperus oxycedrus

Camphor:

Brown Light-colored gp. gr. 0.95 to 0.97 Average Cananga Caraway, U. S. P. Cassia:

No. 1 No. 2

Average Cedarwood

1.05429 1.05343

.....

0.86715 1.12366

.....

1.07173 0.87497 0.88575 0.91905 0.92597 0.93517 1.09134 0.85393 0.87355

Specific GraTrity 3So/l5O C. 25"/15" C 1.01604 0.95581 1.04023 1.11049 1.03224 1,04272 0.97294 1,38699 0.96837 1.04033 0.87764 0.85154 0.85534

.

.. .. ..... ..... ..... 1,07142 ..... ..... ..... 0.91051 .....

..... ..... ..... .....

15-26' C.

......

:......

0 000853

...... ......

0.000928 0.001147 0.000759

...... ...... ......

......

0,'86ii7 1.10680 1,06289 1.05434 0.86081 0.87110 0.90210 0.91065 0.92002 1.07394 0.83828 0.85707

......

0.000841

...... ......

...... ...... 0.000831

1,16406

1.15534

0.000887

1.09487 1,09384

..... .....

1.07581 1,07485

1.07218 1.07238

..... .....

1.05366 1.05384

..... ..... .....

1,03284 0,97276 0,95489 0,86788 0.88014 0.97248

1.18957 1.05064 0.98925 n....... 071~8 0.88414 0.89651 0.98733 1,00146 1.01919 0,97369 0:94074 0.91156 1.06120 1.06440

.....

0.95206

1.16988

.....

0.88835

..... ..... ..... .....

..... ..... ..... .....

table and not the specific gravities. Schimmel & Company's work was not done for the purpose of finding the variation per degree but to show the relationship between the specific gravities a t 15"/15" and 25"/25" because the then new U. s. Pharmacopeia used the temperature 25"/25". They were not interested in the variations per degree and did not trouble to calculate them. Gildermeister and Hoffmann (I), taking into account that Schimmel & Company (6) found a variation of 0.0007 to 0.0008 per degree based on water at 15" C., state that the mean variation for essential oils is 0.00075. This figure is probably too low since the average variation for the essential oils here tested is 0.00078, and for the essential oils, synthetics, and isolates taken together is 0.00081. Schreiner and Downer's figure of 0.00084 (recalculated), on the other hand, is too high. In any case it would be unsatisfactory to take an average figure obtained from a variety of oils and apply it to any particular oil, all the more so when there is a difference of opinion as to what that figure should be. Irk (9)gives a table showing results on a number of oils tested a t 15"/15" and 20"/15" C. by several observers. Results for such a narrow temperature range would be of little value except for the fact, as shown later, that the variation is the same for each degree, a t least up to a temperature of

0.98592 1.00240 0.95767

0: 000i695 0.000708 0.0007325 0.0008475 0.000766 0.0007575 0.000870 0.000783 0.000824

:

1,17293

.....

...... ...... ......

0 000i54

0,000844

.....

0.000794 0.0008430

0.000853

...... ......

......

......

0,000872

... ...... ..... ......

...... ......

......

0.000816

.....

.......

...... ......

...... ......

0.91646 0.89559 0.93893

.....

...... ......

......

0.0007565 0.0008025 0.0007955 0.000817 0.0006955 0.000928 0.0009245

0.92478

.....

o:OOiiis 0,000755 ......

1.03573 1.03494

0.93322 0.91239 0.95574

..... .. .. .. .. ..

Variation per 1' C.26-35' C. 16-35' C. 0.000865 ....... ...... 0.0007605 0.0008455 O.OO0838 0.0008510 ...... 0.00892 0.0009235 0,000919 0.0011425 0.000860

0.0008375 0,000840 0.0008405

.......

0,0008795 0.000953 0.0009495

.....

0.00093 0.00079 0.00084 0.00085 0.00087 0.00071 0.00073 0.00085 0.00077 0.00076 0.00087 0.00078 0.00082

.....

0,00084 0.00088

.....

0.00095

..... .....

.......

0.00093 0.00098

...... ...... ......

0.0008905 0.0008245

......

0.0007425

0.00089 0.00082 0.00085 0.00081 0.00081 0.00074

0.000821

0.0009845

n. .. 0008545 ..~ ~. . ~

0.000813 0.0008135

0.000777 0.0008395 0.000801

.......

0.92596 0.89604

...... ...... ......

0.000739 0.000776

1.04514 1.04802

...... ......

...... ......

0.000803 0.000819

0.93791

0.00086 0.00114 0.00076 0.00080 0.00080 0.00082 0.00070

0.000926 0.000927

...... ...... ......

...... ......

0,00085 0.00089 0.00092

...... ...... ......

.....

.....

Value to use 0.00087 0.00076 0.00085

...... ......

.......

0.000707

.... .

.

I

.

.

0,00081 0.00074 0,00078

.....

0.00081 0.00071

3.5" C. However, some of the values given agree so poorly with those recorded in this paper that they are not given here.

Experimental Procedure An attempt was made to select the most commonly used perfumes, fully realizing that many perfumers may make considerable use of some not given here and that a few of those given may not necessarily be widely used. Specific gravity was first determined a t 15" based on water at 15" C. as unity, then a t 35" likewise based on water a t 15" as unity. On a number of perfumes the specific gravity was also determined a t 25"/15" to discover whether there was any appreciable difference in the rate of expansion from 15" to 25" as compared with 15" to 35". In no case was any appreciable difference noted (Table 11). The variation per degree is so uniform that the same correction may be safely used even if the temperature exceeds 35",as it may occasionally on very warm days. In Table I1 the various perfumes tested are recorded together with their specific gravities and the variation in specific gravity per 1" C. The last column, taken in conjunction with Table 111, gives the data for practical use. Table 111 gives the variation per 1" C. on some additional perfumes tested by

JULY, 1936

INDUSTRIAL AND ENGINEERING CHEMISTRY

869

TABLE11. SPECIFIC GRAVITIES AND VARIATIONSIN SPECIFICGRAVITY PER 1' C. (Continued) 15'/15' Citronella, Ceylon: No. 1 No. 2 No. 3 No. 4 Average Citronella, Java: No. No. 1 .... No. 2 No. 3 No. 4 Average Clove Eucalyptus globulus 70 to 80% Geranium African, African ektra fine Geranium Bourbon Bourboh Ho Lavender: 38/42'% Barreme, No. 1 No. 2 Average Lemon Lemongrass Linaloe Mace Mirbane (nitrobenzene) Orange, sweet Origanum Palmarosa Patchouli Pennyroyal Peppermint: No. 1 No. 2 Average Petitgrain Pine Rosemary Sandalwood East Indian Sassafras, a;tificial Spearmint S p k e (oil lavender aspic) ansy Thyme Vetivert: Bourbon, No. 1 Bourbon, No. 2 Average Wintergreen, southern, from Gaultheria procumbens Ylang-ylang Orange terpenes Phenyl ethyl acetate:

No. 1 No. 2

Average Phenyl ethyl alcohol Phenyl methyl carbinyl acetate (styrallyl acetate) Phenyl propyl alcohol Rhodinol Safrol Terpineol Terpinyl acetate

Specific Gravity-25'/15'C.

C.

..... .....

0.89924 0.89742 0.89750 0.90060

...... ...... ......

.....

1.03285 0.89763 0.88561 0.87654 0.87119

...... ...... ...... ......

..... .....

0.87259 0.88529

.....

0.88906 0.90164

..... .....

.....

0.85684 0,90822 0.88143 0.91112 1.20940 0.84993 0.96526 0.88751 0.96749 0.93969

0.90020

..... .....

..... .....

.....

.....

.....

0.84145 0.89234 0.86489 0.89479 1.18974 0.83438 0.95002 0.87282 0.95288 0.92415 0.91499 0.89813

0.93020 0.91343

.....

..... ..... .....

0.89317 0.93704 0.90170 0.97759 1.07263 0.92760 0.90944 0,92375 0.93140

..... .....

.....

0.87690 0.92124 0.88545 0.96366 1.05519 0.91180 0.89301 0.90770 0.91569

.....

.....

.....

0.97722 0.99503

1.18813 0.92637 0.84750

.....

.....

1.16837 0.91183 0.83199

.....

.....

1.02072 1.02072

. . I . .

1.00962

0.99156 1.00917

.....

1.03867 1.03879

.....

:

1 02450

.....

1.03196 1.00590 0.87836 1.10644 0.93840 0.96604

C.

0.87992 0.87468 0.87815 0.87915

..... ..... ..... .....

.....

15-25'

......

.....

1.04991 0.91442 0,90082 0.89182 0.88770

C

0.88292 0.88150 0.88115 0.88428

..... .....

0.89840 0.89355 0.89664 0.89752

35'/15'

.....

..... .....

.....

1.01362 0.99132 0.86417 1.08861 0.92279 0.94963

...... ...... ...... ......

......

......

Variation per 1' C. 25-35' C. 15-35' C.

...... ......

...... ......

.. ......

...... ......

...... ...... ...... ......

.......

0.00081

..... ..... ..... .....

0.0009185

0: 000ssi

0.00093 0.00084 0.00085

0.0008255

0.00076 0.00076 0.00083

0.0008395 0.000764 0.0007605

0.000802

0.000785

0.0007695 0.00079 0.000827 0.000983 0.0008165

...... ...... ...... ......

0.0007775 0.0007620 0.0007345 0.0007305 0.000777

......

......

......

...... ...... ......

...... ...... ......

......

...... ...... ...... ......

...... ...... ...... ......

...... ......

......

......

0.00073 0.00078

..... .....

.......

......

0.000727 0.000988

......

0 06082 0.00077 0.00079 0.00083 0.00082 0.00098 0.00078 0.00076 0.00073

0.0007605 0.000765 0.0008135 0.000790 0.008125 0.0006965 0.000872 0.000790 0.0008215 0.0008025 0.0007855

...... ...... ...... ...... ...... ...... ......

:

.......

...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ...... ......

....

0.0008235 0.000818

0.00076 0.00081 0.00079 0.00081 0.00070 0.00087 0.00079 0.00082 0.00080 0.00079

.....

0.0007165 0.000707

0.0007755

......

..... ..... .....

0.000924 0.0009245 0.0009435

...... ......

......

.....

0.000816 0.000796 0.0008175 0.000816

...... ...... ...... ......

......

-

Value to use

0.0008925 0.0009035

:

0 00071

'

0,00099 0.00073 0.00078

..... .....

.......

0.00090 0.00074

0.000917 0.0007095 0.000729

0.00092 0.00073 0.00071 0.00089 0.00078 0.00082

0.000744

0.0008915 0.0007805 0.0008205

samples, no doubt indicating difference in purity, but the change per 1 'C. was the same in every case. When practicable, fresh perfumes and perfumes of high purity were used. Acetophenone could not be determined readily a t 15" C. on account of its rather high solidifying point. It was therefore tested a t 25'/15' and 35'/15', and the variation calTABLE111. VARIATION PER ' 1 C. ON SOMEPERFUMES TESTED culated from these results. Diphenyl oxide was handled in BY SCHIMMEL & COMPANY the same manner. Calcd. Variation Calcd. Variation Pycnometers of about 50 cc. capacity were used for the deper 1' C. Base$ per 1" C. Based terminations of the specific gravities, instead of a plummet on Water a t 15 Perfume on Water a t 15O Perfume balance, for the sake of both accuracy and speed. The pycEucalyptol 0.00086 Oil fennel 0.00082 Oil cajeput 0.00083 Oil mustard 0.00101 nometers filled with the perfumes were immersed in a water Oil copaiba 0.00073 Oil pimeuta 0.00089 Oil coriander 0.00085 Oil savin 0.00077 bath kept a t the desired temperature * 0.1' C. for a t least Oil cubeb 0.00074 Oil sweet birch 0.00100 30 minutes. Oil erigeron 0.00080 Oil turpentine 0.00084 All tests made before 1906 may be classed as unsatisfactory. ~ ~ _ _ _ ~ ~ Schimmel & Company's results reported in 1906 were not published for the purpose of establishing the variation per Notes degree of temperature, but their specific gravity determinaThe most surprising result was in the difference between tions a t 15'/15' and 25'/25' C. are considered satisfactory, Ceylon and Java citronella oil. Four different samples of and the author therefore calculated the variations for the each of these oils were therefore tested. difference from 15"/15' and 25'/15' from their results and Tests were made on three samples of linalyl acetate. gives them as acceptable values. These variations do not There was a wide variation in the specific gravities of these differ from those found here by more than 0.00003 on the

Schimmel & Company in 1906 a t 15'/15' and 25'/25' C. From these determinations the author has calculated the variation from 15"/15' to 25"/15O C. and considers the results satisfactory for use, considering that the agreement of their results with his as shown in Table I is close.

~

INDUSTRIAL AND ENGINEERING CHEMISTRY

850

twenty-three perfumes tested in both laboratories except in the case of sweet-orange where the difference is 0.00004 and artificial wintergreen where the difference is 0.00005. No allowance was made for the coefficient of expansion of the glass in the pycnometers. This should make a difference of about 0.0005 in the specific gravity at the maximum temperature of 35”. In determining the specific gravity with a plummet balance a t the same temperature, however, this error would be exactly compensated, assuming that the glass of the plummet and that of the pycnometer have the same coefficient of expansion.

VOL. 28, NO. 7

Literature Cited and Hoffmann, “Volatile Oils,” 3rd German ed., Vol. I, p. 702 (1913); 2nd English ed., Vol. I, p. 559 (1928). (2) Irk, K,, p h a r m . Zentraihalle, 55, 831 (1914). (3) Lyons, Proc. ~ i c hPharm. . A S S O C . , 1885, 203. (4) Sohimme1 & Co., Report, April, 1887, p. 45; Pharm. Arch., 4, (1)

Gildermeister

167 (1901). ( 5 ) Schimmel co., Report, Oct., 1905, p. 87, (6) I b i d , , ~ ~ ~1906, i lp. ,71. (7) Schreiner and Downer, Pharm. Arch., 4, 167 (1901). ~

R~CEIVE .4pril D 16, 1936.

Compressibility of BUTANE-AIR MIXTURES below One Atmosphere F. W. JESSEN AND J. H. LIGHTFOOT Humble Oil & Refining C o m p a n y , Houston, Texas

+

TO R E S E R V O I R

ro

The method employed in this investigation was essentially that of Guye and Batuecas (6). Since the apparatus and method have been fully described elsewhere ( 5 ) , only a brief outline is presented here. Figure 1illustrates the apparatus.

VACUUM

The gas chamber consisted of three glass bulbs of approximately 220-cc. capacity each, connected with I-mm. capillary tubing. The volume of the gas chamber was varied by filling the lower and middle bulb, respectively, with mercury. The gas under consideration was admitted t o volume I until the pressure was approximately one-third atmosphere. The mercury in the manometer was brought to the reference point and the mercury column height read. The data were completed by reading the mercury column height with the gas subsequently occupying volume I1 and then volume 111. The volume of the separate bulbs and “nuisance” volume (the volume of the capillary tubing and small volume to the reference point) were obtained by calibration with triple-distilled mercury. The results (in cc.) are as follows:

’HERMOM iEATER

;TI R R E R

Bulb 1 Bulbs 1 and 2

I

FIGURE1. DIAGRAM OF APPARATUS

@T

HE use of readily liquefiable gases for fuel, light, and domestic purposes has led to an ever-increasing demand for commercia1 butane and propane. Recently a number of municipal gas systems which use a mixture of butane and air have been installed. A knowledge of the compressibility of such a gas mixture is of importance in the design and operation of plants that use this type of fuel supply. The purpose of this investigation was to determine the pressure-volumetemperature relations of gaseous mixtures of air and butane a t pressures below one atmosphere. The literature records no compressibility measurements for butane-air mixtures. For air (1 A) = 1.00061 at 0” C. and one atmosphere (6). Lebeau ( 7 ) and Oudinoff (8) report a value of (1 A) = 1.0437 for n-butane at 0 ” C. and one atmosphere. Beckers (2) found that for n-butane ( p u ) = ~ ~0.997013; ~ Felsing and Jessen (4) obtained a value of (1 A) = 1.04212 a t 0’ C. and one atmosphere. Batuecas ( 1 ) has calculated (1 A) = 1.0419 from the data of Seibert and Burrell (9).

+

+

+

+

220.1372 438.8484

Bulbs 1, 2, and 3 “Nuisance” volume

665.8070 1.9694

The temperature of the water bath surrounding the gas chamber was maintained at 30” C. =t0.01’ by means of supersensitive thermoregulator and relay. A temperature correction of the “nuisance” volume was made for any variation in room temperature compared to that of the bath. All pressure measurements were observed by means of an absolute manometer, the mercury column heights being read to 0.03 mm. with a sensitive cathetometer. Proper correction for the meniscus was made. A 3-liter, round-bottom flask served as a mixing chamber and reservoir for the gases under consideration. The flask was first evacuated and then filled with one gaseous component until the partial pressure was that required for a definite mole per cent mixture. The other gaseous component was then allowed to fill the flask until the pressure reached atmospheric. To test the method of obtaining mixtures of definite mole percentages,

The compressibility of n-butane-air mixtures and of n-butane was determined at 30” C. I t is shown that the additive rule for determining the compressibility of gas mixtures at low pressure does not hold for butane and air, the maximum deviation being 23 per cent. Thevariation of the compressibility coefficient of nbutane with temperature is presented.