Nov., 1915
T E E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
been a d d e d . When a sample of t h e original oil t o which 8 per cent of linseed oil h a d been a d d e d was examined, i t s s p e c t r u m showed only a yellow b a n d ; 8 . 5 per cent of linseed oil was t h e n a d d e d t o t h e original sample a n d t h e observation m a d e ; t h e I < t u r n i n g p o i n t ” was now reached, shown b y t h e characteristic red b a n d appearing o n t h e upper side of t h e spectrum. Subtracting t h e a m o u n t a d d e d , 8 . j per cent, f r o m t h e a r b i t r a r y figure I j.5 per cent, it is evident t h a t t h e sample in question contained 7 per cent adulteration. a-Another sample t a k e n from a rejected s h i p m e n t , when first observed i n t h e cell, showed a s p e c t r u m which was deficient in t h e red. It vias therefore t h o u g h t t o contain a b o u t I O per cent adulteration. When 6 per cent of linseed oil was added t o this s a m ple, t h e s p e c t r u m appeared only a s a yellow b a n d , a n d when 6 . 5 per cent of a d u l t e r a n t was added t o t h e sample in question t h e red appeared o n t h e upper side of t h e spectrum. Subtracting 6 . j from I j .5 t h e adulteration m-as shown t o be 9 per cent. 3-Another sample, t a k e n from a rejected shipment, when examined b y this method, showed a n adulteration of 7 . j per cent, a n d a sample marked questionable b y t h e chemist of a large varnish works, showed a n adulteration of 4 . j per cent. T h e sample of pure Chinese wood oil used b y t h e American Society for Testing Materials, a n d reported o n a s a n exceptional oil, required a n addition of I 7 . o per cent linseed oil before t h e “ t u r n i n g p o i n t ” occurred; hence i n examining t h e four adulterated samples of this oil, which were used b y t h e society in t h e work for 1915,it was deemed advisable, for sake of comparison, t o use t h e figure I 7 . o as well as t h e a r b i t r a r y figure of I j. j. Table I V gives t h e results in b o t h cases: TABLE IV Per cent adulteration found by using as “turning point” 1 7 . 0 per cent 15.5 per cent 2.................... 5.25 3.75 3 . . . . . . . . . . .. . . . . . . . . 10.50 9.00 3.5 4.................... 5.0 .j. . . . . . . . . . . . . . . . . . . . 10.0 a.5
957
of detection in Chinese wood oil a t t h e present time i n t h i s ’ l a b o r a t o r y . If t h e a t t e m p t is successful t h e accuracy for adulterations with other oils will be increased, since t h e only other oil which causes t h e “ t u r n i n g p o i n t ” t o t a k e place a s high a s I 7 . o per cent adulteration is perilla oil, which is used only occasionally a s a n a d u l t e r a n t of wood oil. T h e detection of sesame b y t h e Baudouin t e s t a n d t h e detection of cottonseed oil b y t h e various methods as described in Lewkowitsch. would eliminate most of t h e oils which affect t h e t u r n i n g point as low a s 14.j per cent. T h e remaining oils affect t h e t u r n i n g point within such a close range of each other t h a t t h e a r b i t r a r y figure assumed a s t h e turning point would be very close t o t h e t r u e value. T h e writer believes t h a t concentration of t h e adulterating oils b y t h e light break method described b y Ware and Schumann’ m a y facilitate t h e detection of those oils readily identified. Another factor which must be t a k e n i n t o consideration is t h e fact t h a t t h e prism itself has a dispersive power a n d if i t s dispersion is t o o large t h e anomalous dispersion of Chinese wood oil will be counteracted. Also, prisms, t h o u g h having a dispersion low enough t o b e used in this method, m a y v a r y from each other, so t h a t i n using a n i n s t r u m e n t of this t y p e one m u s t first calibrate his prism before making determinations. This is readily done b y finding t h e “ t u r n i n g points’’ brought a b o u t b y t h e addition of different oils t o Chinese wood oil. T h e f a t t y acids of Chinese wood oil also show anomalous dispersion. This fact gives promise of interesting information when studied in connection with other f a t t y acids. RESEARCH LABORATORY ACME WHITELEADA X D COLORWORKS DETROIT, MICHIGAN
SAMPLE No.
If these samples h a d been examined without h a v ing t h e pure oil t h e last column would h a v e been considered as t h e percentage t o which t h e Chinese wood oil h a d been adulterated. SUMAIIARY O F R E S U L T S
If t h e adulterating oil is known, very accurate results can be obtained b y this method, otherwise t h e accuracy is limited t o I . z j per cent either way from t h e t r u e value, owing t o t h e fact t h a t t h e t u r n i n g point varies between t h e limits of 1 4 . j t o 1 7 . 0 per cent a n d t h e a r b i t r a r y value of I j . j is not correct. If, however, t h e oil with which t h e Chinese wood oil is adulterated can be determined, t h e accuracy is t h e r e b y increased. Lewkowitsch,’ in commenting on tallow seed oil; says: “ T h e most characteristic property of t h i s oil is t h a t i t r o t a t e s t h e plane of polarized light t o t h e left, viz., 6’ 4 j ‘ in a zoo m m . t u b e i n a Laurent polarimeter, corresponding t o -29.9 saccharimeter degrees. T h e optical activity is confirmed by Nash.” This is being investigated as a means 1
“Chemical Technology and Analysis of Oils, F a t s a n d Waxes,” Vol.
11, p . 70.
COMPOSITION OF WOOD TURPENTINE B y MAXWELL ADAXS Received June 14, 1915
Because of t h e shortage in t h e supply of “ g u m ” t u r p e n t i n e , a n d t h e enormous wood waste of our lumber mills during t h e past t e n years, m a n y methods for t h e extraction of t u r p e n t i n e from wood h a v e been proposed. T h e economics of s t e a m , solvent, alkali digestion, oil b a t h , destructive distillation, under b o t h increased a n d diminished pressure processes have been given thorough consideration, b u t very little a t t e n tion has been accorded t h e composition of t h e turpentine obtained b y these different procedures. Alt h o u g h t h e products obtained b y these various methods differ widely a s t o color, odor a n d physical cons t a n t s , without a n y a t t e m p t at standardization, t h e y have all been classed together. T h e result has been t h a t a strong prejudice has arisen against a n y product sold under t h e n a m e of wood turpentine. T h e physical properties of wood turpentine obtained, presumably, from long leaf or C u b a n pine, h a v e been THISJ O U R N A L ,
6 (1914), 806. This work was in part done in Prof. Wallach’s laboratory a t Gottingen. Germany, and supported by the Adams Fund of the Nevada Agricultural Experiment Station. 1 2
958
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
worked o u t b y Hawley,l F. W. Richardson a n d J. E. F. Whitaker,2 M a r ~ i l l e , Parry.4 ~ Others have published methods for t h e analysis of different kinds of turpentine, b u t for t h e most p a r t these workers h a v e been concerned with t h e identification of adulterants, or with physical constants; little a t t e m p t has been made t o identify or separate t h e different terpenes present, a n d i n n o case observed has wood turpentine obtained f r o m a n y variety of Western pine been investigated. T h e present investigation was undertaken for t h e purpose of determining t h e physical properties a n d identifying t h e various terpenes present i n t h e wood turpentine prepared from pine growing in t h e weste r n p a r t of t h e United States. T h e “ g u m ” turpentines of t h e varieties chosen have previously been examined b y S c h ~ r g e r . ~ Samples of wood from Western yellow pine ( P i n u s ponderosa), obtained from trees growing i n t h e neighborhood of Independence Lake, Cal., Jeffrey pine ( P i n u s j e j r e y i ) from trees growing o n t h e E a s t e r n slope of M o u n t Rose a n d near Galena Creek, Nev., a n d f r o m single leaf n u t pine (Pinus monophylla) growing on t h e western slope of t h e mountains between Steamboat Springs a n d Virginia C i t y , Nevada, were collected. E a c h sample was distilled under diminished pressure i n a retort, a r o u n d which circulated hot oil, according t o t h e method described b y Adams a n d Hiltom6 T h e distillate from t h e wood was separated roughly i n t o three fractions: ( I ) t h a t which comes over below 160°, ( 2 ) t h e distillate between 160 a n d 2 2 0 , a n d ( 3 ) t h a t driven over above 220’. I n most of t h e following experiments only t h e first fraction was used. T h e second fraction contained considerable quantities of decomposition products, which could be removed only b y alternate t r e a t m e n t s with sulfuric acid a n d caustic soda, together with s t e a m distillation. Since t r e a t m e n t with these chemicals might affect t h e chemical composition of t h e oil, t h e second a n d t h i r d fractions were discarded. This procedure has doubtless slightly increased t h e percentage of t h e lower boiling terpenes over t h a t which would be found i n ordinary crude wood turpentine. S I N G L E LEAF N U T P I N E
A sample of wood turpentine obtained from t h e distillation of t h e wood of single leaf n u t pine, according t o t h e above method, when redistilled with steam, h a d t h e following physical constants: d160 0.9702, T Z D I ~ O 1.4771, ( ~ ~ 2 0 + 0 2 1 . Ij. T h e oil was colorless a n d h a d a very characteristic aromatic odor. A s a m ple of t h e oil was dried over fused potassium carbona t e , distilled a t a pressure of I j m m . a n d separated i n t o three portions: I-B. p. 5-60‘, consisted of 77.9 per cent of the original oil and had the following properties: d15 0.8691, ~ Z D ~ S O1.4693, +29.76 11-B. p. 6-80’, consisted of 7.6 per cent of the original oil and had the following constants: d150.8721,~ D I S O1.4777, +11.78 (YDZOO
CYDZDO
Eighth I n t . Congr. APPlied Chem., 1912, and Forest Service. Bull. 106. J . SOC.Chem. I n d . , 80, 115. 8 Bull. SOC. chim., 2, 762. 4 Chem. and Drugg., 81, 5 2 . 5 THISJOURNAL, 6 (1913),971, and U. S. Forest Service, Bull. 119. 6 I b i d . , 6 (1914).378. 1
2
Vol. 7 , No.
11
111-B. p. 8-135 ’, consisted of 9.2 per cent of the original oil and had the following constants: d15 0.8982, T Z D I ~ O 1.4856 There mas a residue left i n t h e distilling flask consisting of j per cent of t h e original oil. E a c h fraction decolorized a n alkaline solution of permanganate a n d absorbed bromine readily, b u t none gave a test with sodium bisulfite or semicarbizide for aldehydes or ketones. a-PINEXE-FrOm Fraction I. when distilled over sodium, there was obtained a material with a boiling point of I j j-156’) which when dissolved in acetic acid a n d t r e a t e d with amyl nitrite a n d hydrochloric acid gave crystals of pinene nitrosochloride. After dissolving i n chloroform a n d reprecipitating with methyl alcohol t h e crystals melted a t 103 ”. T h e nitro1 piperidene, prepared in t h e usual manner1 from t h e nitrosochloride melted a t I 18 O. T h e above results prove t h e presence of d-a-pinene. b-PIr\.ENE-Fraction 11, after several redistillations over sodium, yielded 15 per cent, or about one per cent of t h e original oil, which boiled a t 167’; 3 . 7 grams of this oil were added t o 4 . 9 grams of potassium permanganate, a n d 1 . 8 grams of sodium hydroxide dissolved in 11 grams of water a n d crushed ice. T h e mixture was agitated on a shaking machine for 6 hours, according t o t h e method of Wallach.’ As t h e ice melted t h e temperature was allowed t o rise t o t h a t of t h e room. T h e hydrocarbons n o t acted upon were driven off with steam a n d t h e solution remaining in t h e retort was filtered from t h e oxide of manganese a n d t h e filtrate evaporated, while a constant s t r e a m of carbon dioxide was conducted through t h e solution. Crystals of sodium nopinate separated when t h e solution cooled. T h e yield, however, was so small t h a t a n a t t e m p t t o prepare t h e nopinic acid in sufficient q u a n t i t y for complete identification failed. CADIxEsE-The t h i r d fraction, tvhich was light yellow in color, when heated a t atmospheric pressure began t o boil at 170’ b u t t u r n e d brown, indicating some decomposition. A second portion was therefore distilled a t 15 mm. pressure a n d separated i n t o t w o portions. T h e lower boiling fraction was tested for ’ limonene a n d phellandrene without positive results. T h e higher boiling fraction, after distilling over sodium, thereby removing considerable t a r , boiled without a n y apparent decomposition at 2 0 5 - 2 1 jo. This fraction, t h u s purified, was dissolved i n four p a r t s of glacial acetic acid, cooled in brine a n d ice, a n d s a t u r a t e d with d r y hydrogen chloride. A heavy brown liquid separated, which when placed i n a n open dish evolved considerable gas a n d quickly solidified. This solid was dissolved in acetic acid a n d allowed t o s t a n d f o r 1 2 hours. A good yield of white crystals separated, which melted a t I I 7 O , t h u s establishing t h e presence of cadinene. These results, when compared with those of Schorger* on t h e volatile oil obtained from t h e oleoresin, indicate t h a t wood turpentine obtained from this species is almost identical i n both physical properties a n d chemical composition with t h e pure “ g u m ” spirits. 1
Ann., 866, 288.
2 LOC.
Cil.
.
N o v . , 1915
T H E J 0 C R ; V A L O F I , T U C S T R I A L ALVD E S G I S E E R I ; V G C H E M I S T R Y J E F F R E Y PI K E
In t h e following experiments on t h e volatile oil Erom Jeffrey pine especial care was t a k e n t o identify the wood used, because t h e differentiation between Piizus j e f i e y i a n d Piitus po?idevosa is very close, a n d some confusion has arisen on this account. Sadtler’ reports having obtained heptane from Piizzrs p o n d e r o s a . This error probably arose from a confusion of Yellow pine with Jeffrey pine. Sudwirth2 says in writing of Jeffrey pine: “Some specialists consider it a variety of Piiziis p o i i d c v o s n , which it resembles so closely in its habits and soil a n d climate requirements t h a t from t h e foresters’ point of view there appears t o be no practical reason for distinguishing t h e two.’’ Jepson3 says, “ T h e Jeffrey pine which merges insensibly into t h e Yellow pine is in its typical form found at high elevations ranging from 6000 t o 9000 feet. B y some writers this variety is regarded as a species. While t h e typical form is clearly t o be recognized i t is t o be said, on t h e contrary, t h a t Jeffrey pine not only passes over into Yellow pine, b u t t h a t t h e transition forms in t h e intermediate region are quite a s numerous a n d occupy a s extensive a n area as the t r u e Jeffrey pine itself.” In the publications of t h e United States Forest Service4 similar ideas are expressed as follows: “ T h e Jeffrey pine bears very close resemblance t o western yellow pine a n d some authorities regard it simply a s a variety.” Because of t h e distinct chemical difference in t h e volatile oils obtained from t h e moods of these trees, a s shown b y t h e following analyses, [here is good evidence for t h e contention t h a t Yellow a n d Jeffrey- Pine are distinct species; at least there is a definite chemical method for distinguishing between t h e m . I t wouid be interesting in this connection t o examine chemically t h e volatile oil from a specimen which t h e botanist considers a transition form. A sample of wood turpentine obtained from distilling carefully selected wood from a well identified Jeffrey pine tree, mas distilled under diminished pressure. T h e distillate t h u s obtained was steam-distilled, the resulting volatile oil dried over potassium carbonate a n d separated into four fractions b y distilling a t a pressure of 1 5 mm.: Fraction I Boiling p o i n t . , . . . . . . , . . . 25-30’ Per cent o b t a i n e d . . . . . . . . . 74
I1 30-35O 13
I11 35-65’ 6
I\‘
Residue
65-125’ 4
3
T h e first three fractions distil without decomposition a t ordinary pressure. T h e y were combined a n d distilled over sodium a n d a portion, consisting of about 9 0 per cent of t h e entire volatile oil, was obThis tained which distilled between 99 a n d 1 0 0 .5’. distillate gal-e no test for t h e double bond with von Beyer’s reagent, neither would it absorb bromine. When added t o amyl nitrite in acetic hydrochloric acid solution it gave no test for pinene. T h e physical 1
A m Jour. Pharm., 51, 176.
2
“Trees of the Pacific Slope.” “The Silva of California,” p . 80. Silvica Leaflet, p 21.
3
959
properties n-ere d160 0 . 6877, nD200,I . 3890, optically inactive. These tests prove t h a t t h e volatile oil from Jeffrey pine wood contains from 90 t o 95 per cent of normal heptane. T h e fourth fraction was redistilled at diminished pressure a n d separated into t w o parts. The lower boiling fraction was distilled over sodium a n d tested for limonene a n d dipentene. It absorbed t h e calculated a m o u n t of bromine t o form the tetrabromide, butr cystais mere not obtained from t h e oil. T h e higher boiling fraction gave a precipitate with sodium bisulfite, which would indicate the presence of citronellal, b u t t h e small a m o u n t of t h e material available prevented malting confirmatory tests. S E L L O I V PIPI-E
A sample of volatile oil obtained from Yellow pine, according t o t h e method already described, was clear, water-white, a n d had t h e odor which is characteristic of Yellow pine wood. I t s specific gravity a t 15’ was 0.8626, index of refraction I . 4;27, specific rotation -13.15. On distilling 500 grams of t h e oil, using a Norton a n d Otto distilling t u b e , a n d a t a barometric pressure of 642 mm., the following results were obtained: FRACTIOXAL DISTILLATIONO F Temp. C. 156-158 159.9 161.2 162.1 163.0
;::::
176.7 169.8
ii;::
Residue
THE VOLATILE OIL OBTAINICD F R O M THE WOODOF Pinus ponderosa Specific Index of re- Specific roDistillate Observed Cumulative aravitv, 1 5 O fraction. 15O tation. 20” 4.72 4.72 0.8467 1.4621 -15.14 9.39 14.11 0 8525 1.4710 -14.48 9.20 25.32 0,8546 1.4731 -14.57 9.99 33.32 0 8552 1.4732 -13.68 1 ,4738 10.08 43.40 0.8559 -12.15 1,4740 9.51 52.91 0.8562 -11.89 1.4744 -11.04 9.65 62.56 0.8590 9.95 72.51 1.4745 -10.56 0 8603 6.958 79.47 1.4752 -10.97 0.8633 7.86‘ 87.35 1.4913 -14.12 0.8733 9.36 97.71 0,9246 1.5038 -17.22 2.3
When t h e above table is compared with a similar one prepared b y Schorger’ on “ g u m ” spirits, i t will be noted t h a t the wood turpentine contains more of t h e low boiling a n d less of t h e high boiling fractions t h a n t h a t obtained from the oleoresin of western pine. This difference is perhaps due t o t h e fact t h a t wood turpentine was obtained from t h e first fraction of t h e wood distillate a n d t h a t t h e barometric pressure was abnormally low. A second analysis, which was made upon a smaller b u t a more representative sample of Yellow pine wood distillate, a n d which contained all t h e volatile oil given off u p t o t h e temperature a t which t h e wood began t o decompose, gave t h e following results : Fraction I Distilling t e m p e r a t u r e . . . . . . . . . 156-164’ Per cent distillate.. , . . . . . . . . . , 8.7
I1 164-172’ 72.5
I11 172-180° 16.4
Residue 2.4
Fraction I of t h e oil when tested for a-pinene readily yielded nitropiperidine which melted a t I 18 ’. Fraction 11, when oxidized with potassium permanganate according t o t h e method previously described, gave a n a b u n d a n t yield of crystals of nopinic acid, which melted a t 1 2 j o . Fraction 111 gave crystals of limonene tetrabromide when treated with bromine. c 0 h-cL u SI 0NS T h e presence of practically every constituent of t h e 1
U. S. Forest Service, Bull. 119, 12.
T H E J O U R N A L OF I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y
960
volatile oil of t h e oleoresin has been identified i n t h e wood turpentine of t h e three varieties of wood under examination. T h e physical properties a n d t h e percentage composition do not always agree, yet t h e y coincide a s closely as could be reasonably expected, w h e n we consider t h e inaccuracies of some of t h e
SOME IMPROVED ELECTRICAL LABORATORY APPARATUS B y CHAS. MORRISJOHNSON Received July 23, 1915
I-QUICK
HEATING
ELECTRIC F U R S A C E F O R
THE
DE-
T E R M I N A T I O N OF CARBOX I N S T E E L , ETC., WITH T R A I X
T h e t r a i n (Fig. I) consists o f : ( I ) a mercury t u b e t o detect leaks a n d stoppages; ( 2 ) a s a f e t y j a r containing a I : I solution of KOH; (3) a tower filled loosely with a plug of glass wool followed with anhydrous calcium chloride, a layer of soda lime a n d another
11
methods available. T h e results t h u s far obtained justify t h e conclusion t h a t t h e volatile oil obtained from distilling wood under diminished pressure is similar t o t h a t obtained from t h e oleoresin of t h e same species of tree. CHEMICAL LABORATORY, UNIVERSITY OF NSVADA R E N O ,NEVADA
LABORATORY AND PLANT
1
Vol. 7, No.
I
placeable heating element, a n d a supporting s t a n d . T h e furnace will heat from t h e cold t o 1000' C. in 20 t o 2 j minutes with a current consumption of 3 t o 4 amperes. I t can be cooled rapidly, if desired, b y lifting off t h e t o p half of t h e split muffle. T h e writer has supplanted for some t i m e i n this laboratory, a n d in another laboratory under his direction, all of t h e t y p e introduced b y h i m in 1908~with t h i s new t y p e shown i n Fig. I. This t y p e of electric furnace can be built i n a n y length of heating surface with coils connected in parallel. T h e t y p e shown i n Fig. I is 1 3 inches long b y 35/32
FIG.I
plug of t h e wool; (4) a j a r of short pieces of stick caustic potash with a plug of glass wool a t t h e t o p a n d a t t h e b o t t o m ; ( 5 ) a clay a n d rubber connector doing a w a y with rubber stoppers a t t h e charging e n d ; (6) t h e vitrified clay combustion t u b e with t h e tapered outlet doing away with t h e rubber stopper at t h i s point also; (8) is t h e j a r of granulated zinc t o stop acid a n d sulfur; (9) is a j a r of phosphoric acid powder a n d ( I O ) is t h e bulb for absorbing a n d weighing t h e C O S . This t r a i n was designed b y t h e writer, being a simplification of his t r a i n described i n J . A m . Chem. SOC.,M a y , 1908. T h e writer has now used t h e tapered clay combustion t u b e s for over t w o years for t h e determination of carbon i n steel, etc., a n d has been using t h e m for some months for oxygen determinations also. T h e new split muffle t y p e of furnace was designed a b o u t a year ago. I t is of most simple construction, consisting of a split muffle of kieselguhr, a coil of nichrome wire embedded in a l u n d u m cement a s a re-
inches 0. D. a n d 1 1 ~ / I. ~ ~ D. T h e writer built t h e same t y p e for organic work 18 inches long. B y using three rheostats a long furnace can be made t o heat t o three different temperatures a t once or i t can be heated in one p a r t if desired. T h e furnace presents a bright n e a t appearance with i t s white muffle; new heating elements can b e kept i n stock a n d quickly p u t i n place in case of a burn-out as there are no screws or powdered heat insulation t o bother with. I n case t h e muffle becomes soiled i t can be p u t in a muffle furnace a n d heated t o a red heat for a b o u t 2 0 minutes when i t becomes.as white as new. T h e simple construction makes t h e furnace a very inexpensive one. By using a split insulation muffle of j 5 / s inches 0. D. a n d 2 5 / 3 2 I. D., t h e writer obtained a furnace of this t y p e which is developing 1020' C. with a current consumption of only 2 . 7 amperes. This furnace has been i n daily service in this laboratory for several months. 1
J . Am. Chem. Sac., 80 (1908). 773.
