INDUSTRIAL AND ENGINEERING CHEMISTRY
April, 1929
required to complete gasification after the preliminary liquefaction. If liquefaction has been very pronounced, as in the case of addition of filter paper, casein, or oils, it will take longer for the gasification to be completed. The retarding effect of liquefaction on subsequent gasification might be due to the unfavorable conditions produced in the reaction of the medium on the gasifying organisms. Where liquefaction was induced by the addition of substances like filter paper, casein, and oils, the reaction of the mixtures had reached the alkaline range long before gasification started. It is possible, however, that the initial lower reactions caused
325
by these substances had a pronounced retarding effect on the gasifying bacteria from which they did not recover for a long time. Conclusions
The data presented show that there is a loss of carbon and nitrogen on drying liquid from digesting sewage solids mixtures, and that the greater the liquefaction the greater is this loss. The loss from this source may be as high as 25 per cent of the total solids. The apparent anomaly of low gas yields with high volatile reduction may be explained on this basis.
Terpenes and Terpene Alcohols' I-Vapor
Pressure-Temperature Relationships 0. A. Pickett and J. M. Peterson
HERCULES EXPERIMENTAL STATION, HERCULES POWDERCo., KENVIL,N. J.
I
K T H E course of development of plant processes for mak-
ing the desired component separations of the various naval stores products from pine stumps, many data of a physico-chemical nature have been obtained in this laboratory. Since the literature in general is relatively poor in data on these materials, i t has been deemed advisable to present certain of them in a series of papers of which this is the first. Method
The method used in determining the vapor pressure-temperature data herein reported was a modification2 of that of &msay and Young.3 This modified method is susceptible Received October 11, 1928. Pickett, I N D . END.CHEM.,Anal. Ed., 1, 36 (January 15, 1929). a Ramsay and Young, J . Chem. SOL, 47, 45 (1885). 1
2
Table I-Vapor
--PINENE Mm. 21.2 4.0 22.0 4.3 22.2 4.8 22.5 6.0 54.7 22.8 55.3 24.0 55.5 24.8 77.4 58.8 77.5 59.3 77.7 59.7 77.9 60.2 78.6 61.9 78.7 62.2 79.3 63.9 79.6 64.8 101.1 147.2 102.8 155.7 103.2 157.5 103.5 159.3 103.7 160.3 103.8 160.9 131.2 391.5 132.3 401.0 132.4 404.0 132.5 404.3 132.7 405.7 132.9 407.1 133.0 410.7 133.1 411.5 133.2 412.5 134.9 428.5 135.4 432.1 138.5 478.0 138.8 482.0 139.8 494.0 140.1 501.0 140.5 506.0 141.2 516.0 141.3 520.0 141.9 528.0 147.0 604.0 148.0 623.0
c.
...
.
I
.
...
...
@-PINENE
c.
Mm.
24.3 24.5 24.7 24.8 25.0 26.4 53.5 54.0 54.4 54.6 55.0 68.7 68.9 69.1 70.9 94.7 95.1 95.7 96.0 96.2 96.5 105.8 106.0 106.4 106.9 107.1 107.6 108.2 131.2 131.6 131.7 131.9 132.1 132.6 132.9 133.6 133.9 154.7 154.9 155.2 156.2 158.0 158.1
3.4 3.6 3.9 3.0 4.6 4.9 17.9 18.3 18.5 18.9 19.4 35.1 36.4 36.5 39.3 103.8 106.7 109.4 110.3 110.8 111.8 156.2
...
...
...
157.5
159.8 162.5 163.6 164.5 168.9 356.5 359.5 358.6 362.5 366.7 371.9 375.0 379.7 381.0 688.5 691.0 693.5 711.5 752.0 767.0
... ,..
...
of a high degree of accuracy, although some of the data presented may have an error of as much as 0.5 per cent, with an average accuracy probably within 0.2 per cent. Since most of the samples tested were only of good technical grades, the extra time and effort necessary for higher accuracy was not thought justifiable. Materials Used
Samples of the materials used were from either pIant or Semi-plant lots. Boiling ranges On the Samples used were made according to A. S.T. M. turpentine specifications, and the figures given are for temperatures a t which 5 per Cent and 95 per cent had distilled over. Specific gravities were determined in calibrated pycnometers a t 15.6"C. The refractive index for each was determined a t 20' C. using diffused day-
Pressure--TemperatureData on Terpenes and Terpene Alcohols (Pressures for Hg a t 25' C.) DIPENTENE TERPINOLENE FENCHYL ALCOHOL c. Mm. O c. Mm. O c. Mm. 21.1 1.5 40.5 1.2 59.1 2.5 21.2 45.5 1.6 63.6 4.2 3.5 11.5 58.2 55.7 64.4 6.5 3.9 56.2 12.3 59.7 71.1 7.5 5.3 78.5 29.8 63.3 72.1 8.4 5.6 78.9 30.1 83.0 22.5 73.0 5.9 79.0 30.3 83.5 74.0 23.6 6.5 79.7 31.7 84.0 24.8 77.1 7.9 80.2 32.2 84.1 78.1 25.3 8.8 SO. 5 32.5 63.4 107,6 108.5 36.6 81.8 34.8 63.7 107.7 38.1 108.9 81.9 35.0 108.5 68.6 109.0 37.7 82.0 36.5 108.6 69.0 137.6 119.6 82.6 36.7 108.7 74.1 138.0 122.5 82.9 38.5 108.8 74.5 138.2 128.0 51.4 90.0 131.2 167.1 148.2 339.3 91.2 52.1 131.4 168.1 149.2 344.9 92.1 54.2 131.8 151.0 168.5 355,2 93.5 57.9 132.1 152.0 169.1 358.9 98.9 70.5 133.5 161.4 704.0 195.5 101.6 78.5 133.6 161.6 724.3 196.9 102.1 79.5 133.9 198.6 162.8 747.0 102.5 81.1 157.8 198.8 343.8 751.3 102.7 82.4 158.2 357.0 199.2 759.3 103.2 83.1 164.1 414.3 ... ... 103.6 84.7 175.9 559.6 ... ... 105.7 91.8 176.0 571.3 ... ... 108.0 99.5 176.4 579.2 ... ... 109.0 178.0 103.5 602.2 ... .. 109.5 178.2 105.4 609.0 ... , . . 130.1 178.5 218.5 619.0 ... ... 131.5 228.0 178.8 622.3 ... ... 132.5 235.0 178.9 623.9 ... ... 133.3 240.0 ... ... ... , . . 134.0 247.0 ... ... ... ... 134.1 250.3 ... ... ... ... 161.9 560.0 ... ... . . . ... 166.4 631.5 ... ... ... ... 166.9 643.5 ... ... ... ... 167.2 648.5 ... ... ... ... 167.5 650.5 ... ... . . . ... 167.9 655.5 ... ... ... ... 168.8 667.5 ... ... ... ... 169.1 670.5 ... ... ... . .. 169.2 683.5 ... ... ... ... 170.3 695.5 ... ... ... ...
a-TERPINEOL a
c.
Mm.
83.8 89.9 90.6 94.7 100.0 100.7 105.8 106.6 107,3 107.9 108.2 108.6 108.7 119.1 119.9 140.9 141.6 142.3 172.0 173.3 174.0 174.5 177.6 178.0 178.3 178.8 208.4 209.5 209.6 209.7 216.9 216.5
5.9 8.1 8.6 9.6 12.6 12.7 18.6 19.2 20.1 20.6 20.7 21.0 21.2 29.1 29.7 72.6 74.6 73.7 207.2 216.5 220.4 223.0 246.0 249.5 251.9 255.8 597.1 612.0 614.5 617.8 747.5 749.5
...
...
... ... ... ...
... ... ...
... ... ... ... ... ...
... ... ... ... ... ... ...
...
... ... ...
...
...
INDUSTRIAL A N D ENGINEERING CHE-WISTRY
326
Vol. 21, KO.4
light, and the optical rotation was that observed in a 100mm. tube a t room temperature (18-28” C.) using sodium light. SAMPLE
BOILING RANGE SPECIFIC REFRACTIVE OPTICAL .570 9570 GRAVITY INDEX ROTATION
c.
c.
a-Pinene &Pinene0 Dipentene Terpinolene
155 160.2 174 187
158 163.8 178 189.7
Fenchyl alcohol
200
201.3
a-Terpineol
218
219
0.8625 0.8677 0.8481 0.8744
1.4560 1,4709 1.4743 1.4809
+26.50
+- 1 14. 7. 21
-2 2; 2,
~
( 4 I . Y - L.J
a 1,
0.94 (350 C.) 0.961 (15.6’ C . ) b (m. p. 35’ C.)
1.4626
1.0 (200 C.)
1.4789 (25’ C.)a
0.19 (10% in alc.)
Distilled from gum turpentine. Supercooled.
Experimental
In using the modified Ramsay and Young method for obtaining vapor pressure data on these materials, special precautions had to be taken against contamination from two main sources. One of theee was possible dissolving of foreign matter from the rubber stopper through which the thermometers passed by condensing vapors of the material under test. This source of error was avoided by raising the top of the vapor pressure tube higher above the constant temperature bath. For high-temperature points a wet cloth was wrapped just below the stopper to condense any vapors rising above the mouth of the condenser return tube. The other
source of error was from possible solution by the sample of stopcock grease from the funnel used t o introduce the sample into the vapor pressure apparatus. This was prevented by substituting some of the sample itself for stopcock lubricant. Then, to prevent the thin samples from leaking away under vacuum, an excess of sample was made to flood continuously the outside contact edges of the stopcock. The flooding liquid WRS held in place on absorbent cotton. Details for making the tests are described under Manipulation Details in the previous paper.2 The results are presented in Table I and Figure 1.
The Additive Quality of Oil Absorption’ J. T. Baldwin SANDURA COMPANY, IFC., PAULSBORO. PU’. J.
Determinations of the oil absorption of pigment flocculating or deflocculating I L absorption is genermixtures show that in general oil absorption is additive. action of the liquids4 The ally expressed as the The graph of oil absorption against pigment pergreater the flocculation the number of cubic centicentages in a mixture of pigments is a straight line. greater the liquid absorption, meters of oil or other liquid A slight exception to this is found in mixtures containsince the larger the pigment required to s a t u r a t e 100 ing active pigments such as red lead or zinc oxide. If aggregates the larger is the grams of pigment or filler, and oil absorption is additive, oil absorption is dependent p o r e v o l u m e . Grohn5 has is generally determined by the emphasized the importance Gardner-Coleman methodU2 essentially on the specific surface of the pigment and the interfacial tension or affinity between the pigment of the affinity between the The term “oil absorption’’ and the oil. pigment and the oil, not only h a s been used b o t h a s a in regard t o oil absorption, specific term denoting the absorption of oil, and as a general term denoting the absorp- but also in regard to the character of the paint.5 Blom6 has shown that for mixtures of chrome oxyhydrate tion of any liquid. I n order to avoid confusion, the terms “oil absorption,” “water absorption,” “benzene absorption,” green with barytes or blanc fixe the graph of oil absorption etc., will be used according to the liquid absorbed, and the against the percentage composition of the pigment mixture is a straight line. This means that oil absorption is additive; term “liquid absorption” will be used in the general sense. Gardner2 considers oil absorption to be relative to the spe- that is, the oil absorption of a mixture of pigments is equal to cific surface of the pigment. The fact that the oil absorption the sum of the oil absorptions of the individual quantities of barytes is 13 while that of blanc fixe is 19 shows that the of each pigment. For a binary mixture: specific surface is an important factor. Klumpp3 advances 0, = A 0 a Bob (1) the opinion that oil absorption corresponds with the pore vol- where 0, = oil absorption of mixture A = per cent of pigment A in mixture ume of the closest packing of the pigment after removal of B = per cent of pigment B in mixture the absorbed air. “Pore volume” may be defined as the total 0, = oil absorption of pigment A volume of voids. Klumpp determines the water absorption o b = oil absorption of pigment B of blanc fixe as 110, and the paraffin oil absorption as 200. Such differences in liquid absorption he explains as due to the This fact implies that oil absorption is not dependent on the pore volume, for the pore volume of a mixture of two powders 1 Presented before the Division of Paint and Varnish Chemistry at is seldom equal to the sum of the pore volumes of the two
0
~~
+
the 76th Meeting of the American Chemlcal Society, Swampscott, Mass., September 10 to 14, 1928. * P a i n t Mfrs. Assocn. U. S., Cwc. 86 (1919). I Klumpp, Farben-Zfg., 32, 2306 (1927).
4
5 6
Klumpp, Farben-Zrg., 33, 1044 (1928). Grohn, Ibid.,33, 1660 (1928). Blom, I b i d . . 33, 1970 (1928).
