IA'DUSTIZIAL A N D EXL;(;INEElZINGCIIEMISTRY
7 22
Vol. 20, No. 7
Figure 3, which represents a transverse section of a portion of a large ray in white oak after treatment with 72 per cent sulfuric acid to reniovo the cellulose. The lignified middlelarnella network encloses a certain amount of cell matcrialzo which in the living wood WBS incorporated in the protoplasm characterizing this type01 cell. It is clenr that the secondary cdlulose wall has completely disappeared. With these facts in mind, attention is called to Figures 4 and 5 , which depict transverse sections of ray tissue and fiber-tracheids, respe~.bively. I n the ray the niiddle lamella is X o r c T h e fiber-tracheids r r e vertical element$ of the and occur for the inoit part in the summer-wood portion of the annani ring, The spring wood eonsistsof iarye vessel^ ac.companicd by thin-walled vertical woody elements (tracheids). Rays and loogitudinai parenchyma arc common to both spring and summer wood. rued
noticeably thicker than in the fiber-tracheid tissue, while thereverseis true in the secondary u-all,which is thinnest in the ray. The smaller Piavre ,%Transverse Section of White quantitative differencesbetween rays and total F i ~ u r e +Tanqmtial Section of Oak Taken fhrouah tho Summerwood W h i t e Oak Shouing a Portion of a ~ o o din the Australian she-oak are entirclv The thick-walled cellsaie hbcr-tracheids. Larae Wood Ray Cntreated. x 400 reasonable, since the secondary walk of the rays (Figure 1) approach more nearly the photomaph. " X 400 thickness of the walls in t.he vertical woody Correlation of Minute Structure and Microchemical eleni~nts. In tlsii study the microscopic evidence is in Tests with Quantitative Data linnn~iny with the quantitative results and suggests that microclics~iicdmethods may he entirely trust,worthy proFigure 2 depicts a trail rse section (t~ngeniial vided reazents are chosen which will react in an underof tlie wood) of a portion of a wood ray in the Aust,raliaii standable "manner. I n t.his instance the dierences in eelluslie-oak. It is evident that many of the cell cavities are lose nix1 lignin content of rays and wood may be correlated occluded with ail opaque substance which appears dark red rvit,li (1) thickness of the middle lamella, 12) width of the undcr the niicroscope. This substance is widespread througli- secondary cell wall, ( 3 )the ray volume of the mood. wit the ~vooil;it is foiind abundantly in ressels, fiber tracheids, Acknowledgment rcr1,ical parenehynia, and r:tys, and explains the high yield of henzenoalcohol ext.ract,ivefrom this wood. Our thanks are due to L. E. Partelow for making the sketch HitterBshomd that in wood the middle lamella, or eontrd layer, of the cell u~nllis lignin, and it 11% also been deinon- io Figure 1 and to t,he Department of Wood Technology of itratcdn that the secondary cell rvall in the hardwoods is the Xew York State College of Forestry for the use of their egiiipnient. principiilly cellulose. This is indicated snicrocliemically in * I n n . Eao. CIIEM.. 17, 1191 (1925). I liarlow, N . Y.State Coil orertry, Tech. Pzb. 1 4 (1928)
Occurrence of Pinite in Redwood' E. C. Sherrard and E. F. Kurth U. S . P O K B S ~PXODUCIS L ~ B u R ~ T o x YPonnsr , SBxvrcB, MADISON,U~IS.
P I S I T E , mon~~niet~liylcyclohexan~iexol, CaII,OCH,(O€I),, was discovered by RerthelotZ in Pilaus lambertinna in 1856. It has also been isolated as sennitea from senna leayes. as matezite4 from tlie juice of Mateza roritina, and from the mother liquorss resulting from the cryst.allization of coniferin. Wileye and Combes7 have aided in identifying these various compounds as pinite. I lie present writers have secured it in varying amount,s from the aqueous extract of different saniples of redwood
,.
Received March27, 1928. Preseeied before t l i e Division of Ceiltilore Chemistry at Lhe 75th Meeting oi the dnreiicaii Chemival S o c i e t y ~ n r i l 16 to 19. 1028. a A n n . chim 9hys.. I31 46. 7 6 (1856). 1 Uragendorli and Kubly, Z . Chern.. 1 8 6 4 411. 4 Giraid, ComPl. r o d 77, 996 (1873); 110, 81 (1290). n Tiemhnn. liaarmann, Be,.. 7,609 (1874). J . A m . C:helli. Soi., 13, 22s (1891). 1 Cornpi. r e n d . . 110, 46 (1890).
lo This remnant of the original nrotoplasm does not appreciably afiect tlie w m t i t a l i v e resuits, since the nitrogen content of w m d is probably less than 0.3 per cent [Schwalbe, "Chemie der Cdluiose;' p, 439 (1918)j.
heartwood (Sequoia sempervirens). The gums and other water-soluble materials in the green wood rendered its isolation difficult so that the best yields were obtained from airdried material. It was isolated in the following manner: The aqueous solution obtained by extraot.ing sawdust of &dried heartwood with cold water was concentrated t o a thick sirup under reduced pressure. It was then taken up with three to four volumes of ethyl alcol~oland was set aside to allow crystals to form. Several days were required for coniplete crystallization. Ai't.er the impure crystals had been filtered by suction, they were dissolved in a smsll quantity of water. The resulting solution was quite dark, but the color was reduced by repeated filtering. Following this decolorization tlie solution in turn was evapora1,ed to a sirupy consistency on the st.eam b:ith, dissolved i11 one volume of alcohol, and filtered to remove the impurities thrown out by the alcohol. The alcoholic content of the filtrate was then incrertsed to about 70 to 75 per cent of the total volume and the whole set aside in a cool place to crystallize. White rhombic-hemihedral crystals, which adhered very tenaciously to the sides of the beaker, separated out. They
INDUSTRIAL AND ENGINEERING CHEMISTRY
July, 1928
were dried on a porous plate and were recrystallized from hot alcohol. A constant melting point of 185" C. was finally obtained. The crystals had the same degree of sweetness as cane sugar, and did not reduce Fehling's solution. Analysis gave the following results: = $65.4 FOWND Per cen CHsO C €I
15.67 43.22 7.40
CALCD. FOR PINITE Per cent 15.9 43.27 7.27
Acetylation with acetic anhydride and anhydrous sodium
723
acetate and subsequent hydrolysis showed the presence of five hydroxyl groups. I n addition to pinite the writers have isolated a new from the cold-water extract of the heartcyclose, C~H~607, wood of redwood. The two are found together, although when one is found in considerable quantity the other is always present in a smaller amount. The new compound is extremely sweet, has a melting point of 234" C., and sublimes with little or no decomposition. The writers advance the tentative formula CJ3s(OH)6CH20CH3, methoxy mytilit, and suggest the name "sequoiite." A report on the experimental work in confirmation of this formula will appear a t an early date.
Volatility of Nicotine',' W. R. Harlan and R. M . Hixon DEPARTMENT OF CHEMISTRY, IOWASTATECOLLEGE, AMES,IA.
0 quantitative data are available upon vapor concentrations obtained either from pure nicotine or from dusts impregnated with nicotine. I n the course of investigations involving the volatility of nicotine from dusts using various materials as a carrier, the vapor concentration over the pure liquid was desired in order to find the limiting value for nicotine vapor over any dust carrier. Accordingly, the concentration of nicotine in the vapor phase has been determined a t 25", 30°,35", and 40" C. by the air-bubbling method, this range including temperatures usually met in fumigation. The vapor concentrations of nicotine over a 2.97 per cent nicotine-hydrated lime dust and a 2.99 per cent nicotine-bentonite dust a t 35" C. are also reported. The apparatus used was free from rubber connections, it having been shown in a previous paper3 that rubber adsorbed nicotine to a considerable extent.
N
Concentrations of Nicotine over the Liquid
Measured quantities of dry air were saturated with nicotine vapor by bubbling the air through pure nicotine contained in a Mohr-Geissler potash bulb and an 8-inch (20-cm.) test tube tightly packed with glass wool containing nicotine in the bottom. It was necessary to pass the air saturated with nicotine through the test tube packed with glass wool in order to eliminate the spray which passed over from the MohrGeissler bulb. The nicotine vapor was adsorbed by washing the gases in a series of bubblers containing 2 N sulfuric acid. Analysis was made by precipitating the solution with silicotungstic acid, igniting, and weighing the residue according to the A. 0. A. C. methods. The quantities of air passed through the nicotine were measured with a calibrated flowmeter. The air was passed through a t rates varying from 5 to 10 liters per hour, constant results being obtained showing that equilibrium had been attained. Temperature control was maintained to * 0.5" C. by an air thermostat. From the weight of nicotine obtained and the volume of air passed over, the concentrations of nicotine vapor were calculated in milligrams per 10 liters of air and also in parts of nicotine per million of air, assuming the ideal gas law for 1 Received April 30, 1928. These studies were made possible through a fellowship maintained by the Tobacco By-products and Chemical Corporation a t Iowa State College. * Harlan and Hixon, Iowa State College, J . Sci., in press.
nicotine vapor. The barometric pressure was 740 mm. These data are reported in Table I. Table I-Vapor Concentrations of Nicotine AIR PASSED NICOTINE TEMPERATURE OVER NICOTINE OBTAINED CONCENTRATION Liters Gram M g . / l O 1. air P. 9 . m. c. 1.84 28.525 60 0.01106 1.76 27.3 0,01056 25 60 2.73 43.00.01635 60 30 2.66 41,90.01596 30 60 4.17 0.01250 35 30 66.84.11 0.01232 35 30 65.95.74 40 94.3 0.01723 30 6.04 40 99.2 0.01812 30
The vapor pressure may be approximately calculated from the data in Table I, but for practical purposes the concentration as given in the table is more convenient for this type of work. Concentrations of Nicotine in Vapor Phase over Hydrated Lime and Bentonite Dusts
The apparatus consisted of a humidity control, mixing bottle, and flowmeters, to regulate the volume of air, being essentially the apparatus described by Hixon and Drake.4 The dusts were made with hydrated lime and bentonite as carriers. These materials were sieved, that portion being used which passed a 100-mesh and was retained by a 200mesh sieve. The size of particles of a carrier undoubtedly influences the rate of attainment of equilibrium of the vapor phase, but should not influence the value of this equilibrium. Pure nicotine was used for preparation of the dusts, analyses showing 2.97 per cent nicotine in the hydrated lime dust and 2.99 per cent nicotine in the bentonite dust. Measured quantities of air were passed over a sufficient quantity (20 to 30 grams) of the dust in the mixing machine to give equilibrium conditions. The rates a t which air was passed over the dust varied from 5 to 10 liters per hour. KO consistent variation in results was obtained a t the different rates, indicating that the vapor phase was in equilibrium with the nicotine in the dust. The data on the nicotine-lime dust are given in Table 11. Concentrations 2.97 Per C e n t of Nicotine-Hydrated Lime Dust at 35O C. NICOTINE CONCENTRATION OVER DWST OBTAINED Mg./lO 1. air P. P. m . LifWS Gram 3.28 52.5 60 0.01971 3.13 50.1 0,00940 30 3.42 54.8 0,00892 0.01025 30 2.97 47.6 30
Table 11-Vapor h.0.
1 2 3 4
*
4
AIR PASSED
Iowa State College, J . Sci., 1, 373 (1927).
