Aug., 1916
T H E JOCR-VAL O F IYDC‘STRIAL A n T D E-VGISEERISG CHEMISTRI’
13-Vanilla extract is decidedly improved b y aging. T h e period of t h e aging should be at, least one vear and should be carried out a t room temoerature (60 t o 70’’ F.) and in unpainted, porous, wooden barrels. B I B L I 0 G RX P H P
A. L. Winton and Ll. Silverman, “Analysis of Vanilla E x t r a c t , ” J . A m . Chem. Soc., 24, 1129. S. Iserman, “Chemistry and Character of Constituents of Vanilla.” Western Druggist, 1910, 358. Adolph Henning, “Commerce of Vanilla and Vanillin,” N e v c k ’ s Report. 1898, 105. G. hl. Beringer, “Commercial Varieties of Vanilla,” A m . J . Pharm., m a , 289. J . C . Sawer, “Commercial T-anilla,” A m . J . Pharm.. 1881, 345. From Pharm. J . S Tvans..1880-81, i i 3 . F. Tiemann and W. Haarmann, “Composition of Katural Vanilla,” Ber., 9, 128i. Jaillet, “Culture e t Preparation de la Vanille,” Rip. d . Pharm., 1880, 3 5 7 , 411. W.H . Hess and A. B. Prescott, “Coumarin a n d Vanillin, Their Separation, Estimation and Identification in Commercial Flavoring Extracts,” J . Am. Chem. Soc., 21, 256. Karl Dieterrich, “Detection of Vanillin in Resins,” Phaum. Zentralhalle, 37, 424; Ahs., J . Chem. Soc., 1897, 610. A. L . Winton and E. M . Bailey. “Determination of Vanillin. Coumarin and ilcetanilide in Vanilla Extract,” J . A m . Chem. SOC.,27, 719. Otto Folin and W. Denis, “ B Iiew Colorimetric Method for t h e Determination of Vanillin in Flavoring Extracts,” THIS JOURNAL, 4 (1912), 670. Oscar E . Harder, “Standard Solution of Vanillin for t h e Folin Method,” THISJOURKAL,6 (1913). 619. W. H. Hess, “Distinction of T r u e Extracts of Vanilla from Liquid Preparations of Vanillin,” J . A m . Chem. Soc., 21, 719. A , L. Winton and C. I. Lott, “Distinction of Vanilla Extract and I t s Imitations,” U. S. Dept. of Agr., Bureau of Chemistry, Bull. 132, 109. H . H . Rusby, “Distribution. Habitat, Cultivation and Curing of Vanilla,” M e v c k ’ s Report, 1898, 74, 105. J. Hanus, “Drying Vanilla with Calcium Chloride,” Z.Xahv.-Genussm.. 1900, 531; Abs., J . Chem. Soc., 1900 [ I I ] , 7 7 3 . J. Hanus, “Estimation of Vanillin,” 2. Nahu.-Genussm., 1906, 585 ; Abs., J . Chem. Soc., 1906 [II], 133. J. Hanus, “Estimation of Vanillin in t h e Presence of Piperonalriehyde,” 2.Nahr.-Genussm.. 1900, 657; .4bs., J . Chem. Soc., 1901 [II],2015 A. Moulin, “Estimation of Vanillin in Vanilla,” Bull. soc. ckim.. 29 (1903j, 278; Abs., J . Ch-m. .Soc., 1903,457. Ferd. Tiemann and W. Haarmann, “Estimation of Vanillin in Vanilla,” Ber.. 8, 1115; Ahs., J . Chem. Soc., 1876, 112. Paul Welmans, “Estimation of Vanillin,” Pharm. Z.,1898, 634: Ahs., J . Chem. Soc., 78 (1900), 327. “Eruptions Caused b y Handling Vanilla,” Pharm. J . , 1908, 626. Y. Kotake, “ F a t e of Vanillin in t h e Animal Body,” Z . physiol. Chem., 46 (1905), 320. “Flavoring Extracts,” U. S. Dept. oE Agr., Bureau of Chemistry,
Bull. 66. S. E. Jelliff, “Microscopical Characters of Vanilla,” M e r c k ‘ s Report, 1898, 75. H . H . Sawyer, ”Parasites Infecting Vanilla Beans,” Amev. Dvug., 1896; Chem. Record, 1896. H . Lecomte, “Formation of the Perfume of Vanilla,” Compt. rend.. 133 (1901), 745; Abs., J . Chem. Soc., 1902,40. “Poisonous Character of Vanilla,” Amer. Drug., 1884. “Poisonous Effects of Vanilla.” Amer. Dvug., 1884. From Boston M e d . and Surg. Journal. A. v . Humboldt, “Reise in die Aequinoctialgegeden des Xeuen Continents,’’ Stuttgart, 3 (1861-621, 235. Walter Busse, “Tahiti Vanilla Bean,” Schimmel’s Report. October, 1909, 142. Jean Pongnet, “Action of Ultraviolet Light on Green Vanilla Pods,” Compt. rend., 152 (1911), 1184; Abs., J . Chem. Soc., 1911, 5 2 8 . E. H . Edwards, “Vanilla Cultivation in Ceylon,” Chem. CS Drug., 1900. W. Krebs, “Vanilla Cultivation and Collection,” Phavm. Cenlralb., 1896,487, 507, 517. C . H . Dietz, “Vanilla Cultivation, Curing and Preparation.” d n z e v . Drug., 1899,99. J. C. Sawer, “Vanilla Curing, Different Methods of.” Pharm. Jour.,
1901. Walter Busse, “Vanilla in German E a s t Africa,” ilpoth. Z t g . , 1898, 894. Dr. King, “Vanilla Cultivation in India,” A m . J . Pharm.. 1877, 38. From Pharm. Jour. S Tvans., 1876. “Vanilla Cultivation in Mexico.” Pharm. Jour. S Trans., 1893, 266. C. E . Hires, “Vanilla Cultivation in Mexico,” A m . J . Pharm., 1893,571. “Vanilla Cultivation in Mexico,” Muller’s Reisen, A m . J . Pharm., 1866, 3 8 .
709
J. H . H a r t , “Vanilla Planifolia,” Bull. of Misc. Information, Royal Bota$~~o“,“f~r, of Vanilla Planifolia and Its Constituents,,, Pharm 2. fuer Russland.. a i (1871) , , John
Uri
Lloyd,
“Vanilla
Planifolia,”
Monographic
Description,
West. Drua., 1897, 548. Essential Oil R . 0. Brooks, “Vanilla Resins.” A mevican Pevfumev Review, November, 1908, 167 Kuhl. “Vanilla, Sources and Properties,” Apoth. Ztg.. 61, i72. Devaux, “T‘anilla and its Culture,” A m . J . Pharm., 1847, 31i. Walter Busse. “Vanille,” 1899, 113 pp., 2 cuts. (German.) John C. Sawer, “Vanilla,” in “Odorographia,” 1902, 143 t o 174. John R.Jackson, “I‘anilla,” A m . J . Pharm., 1876, 317. From Pharm. Joziv. CS? Tvans., M a y 8, 1875. Bentley and Trienen, “Vanilla,” Medicinal Planls, 1880, No. 2 i 2 . “Vanilla Pods, Method of Preserving,” Amer. Drug., 1892. J. Behrens, “Vanillin in Vanilla,” Tuopecpjanzer. 1899, 299; J . Chem. Soc., 78 (1900), 679 V. Coblentz, “ T h e Chemistry of Vanillin,” M e r c k ’ s Report, 1898, i 5 , 104 Vv’allace LIawbey, “Vanilla Beans,” Minutes of the Flavoring Extract Manufacturers’ h?sociation, 1914; .4m. Perfumer 6- Essential Oil Review, 8, 242; lbid., 9, 8. Bernard H. Smith, “Vanilla Extracts, Storing and Aging,” Minutes of the Flavoring Extract Manufacturers’ Assoc., 1914, 42. Heinrich Walbaum, “Composition of Tahiti T’anilla,” “Festschrift Otto Wallach,” 1909, g . 649. Abs., J . Chem. SOC.,1910, 235. R . 4 . Kuever, “Vanilla,” I c e C?eam Jour.. February, 1916, 26. A L. Winton and E. H. Berry, “ T h e Chemical Composition of Authentic Vanilla Extracts, Together with Analytical Methods and Limits of Constants,” U. S. Dept.. of hgr., Bureau of Chemistry, Bzdl. 162, p. 146. A. L. Winton, 4. R.Albright and E. H. Berry, “ T h e Acidity and Ash of Vanilla Extracts.” THIS J O U R N A L , 7 (1915j. 516. 666 MAIKSTREET
EASTROCHESTER. SEW YORK
RELATIVE OIL YIELD OF FLORIDA ORANGES Ry
S
C HOOD
Received April 22, 1916
I n connection ivith experiments carried on t o determine the commercial possibilities in the manufacture of orange oil from Florida cull oranges, it seemed advisable t o determine how early in t h e shipping season t h e oil was present in commercial quantities, and also t o secure some d a t a on t h e relative oil yield of different varieties and from various localities. I n the fall of 191j a series of tests was made beginning a t the opening of t h e shipping season of t h e early varieties and extending until well into the season for all except the very late varieties. The writer is indebted t o SIr. M . G. Mastin of t h e Bureau of Chemistry for the material used in this study. VARIETIES SELECTED
T h e Parson Brown was selected as being t h e principal commercial early variety, and although mature enough t o ship a t the time t h e experiments were begun, yet t h e color was bright green. At the close of the work this variety was well colored. Another variety of yery early maturity is t h e Ilsworth Early; and on November 12th it was fully mature and beginning t o show a slight yellow color. The Homasassa was taken as t h e t y p e of the early mid-season orange, and on t h e date of t h e first tests was still green in color, although fairly well matured. The Pineapple being one of the leading mid-season varieties, was taken as t h e t y p e of this group, and samples from three widely separate localities were secured. These were still immature and green in color when t h e experiment began. Since the common seedlings are still extensively grown in Florida, and there are wide differences in the fruit, samples were taken from eight
710
2”E
J O U R N A L O F I , V D C S T R I A L A N D E.ATGIlYEERIJG C H E M I S T R Y TABLEI---PERCENTAGES
VARIETY Parson Brown Ilsworth Early Homasassa Jaffa Carlton Seedless Pineapple Seedlings
LOCALITY Lake Weir Windermere Florence Pilla Palatka Palatka Windermere Kew Smyrna Palatka Florence Villa Plant Citv 1,alCelanci Tampa
Valencia
Geneva Florence \7illa Oakland Tyindermere Manatee
OF OIL I N
...
7-13
....
14-20 0.35
....
21-27
....
Dec. 4 0.50
....
.
. . .
0.43 0.51 0,40
0.49
0.24 0.35
........
0.58 0.25
0.38 0.32
0.44 0.36
0.50
. . . . . . . .
0.31
.... 0.37
0.35
0.46 0.43
....
0.38
.
5-11
12-18
. . . . . . . . 0.40 0.51
0.36 0.50
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.42 .,. . 0.30 .,., 0.41 0.41 0:13 . . . . 0.14 .... 0.14 . . . . 0.15 .... 0.17 . . . . . . . 0.30 . . . . . . . . . . . 0 . 3 0 0 . 3 2 0.35 0.32 0.35 0.41 . . . . . . . . . . . . . . . . 0,37 .... 0.39 0.25 . . . . 0.2: . . . . 0.2; . . . . 0.36 0.21 . . . . 0.1, . . . . 0.14 . . . . . . . . . . . . 0.16 . . . . 0.14 . . . . . . . . 0 27 .... 0.11 .... 0.25 . . . . . . . . 0 34 ... 0.32 . . . . 0.25 . . . . 0.41 .... 0.40 .... @;35 . . . . . . . . 0.36 . . . . 0.44 . . . . . . . . 0.41 ... 0 47 . . . 0.46 . . . . . . .
localities. O n November Ist, all of these were livid green in color, b u t a t t h e close of the tests they were mature and n~ellcolored. Since the Valencias do not mature until the latter part of the winter, t h e tests were not continued on this variety t o maturity. Most of the samples of this variety were only partially grown a t t h e beginning of t h e tests, and a t the close were of full size, b u t still very immature and green in color. Each series of samples was gathered from t h e same tree a t intervals of one t o two weeks from Sovember 1st t o December 18th. M l? T H OD S
Each sample consisted of 1 2 oranges picked from t h e tree set apart for these tests. Usually I t o 3 days elapsed between t h e date of picking and t h e date of the tests. The oranges were peeled with a knife and care was taken t o remove all of t h e peel without cutting t h e pulp cells. Care was also taken t o prevent breaking of t h e strip of peel and consequent loss of oil. T h e fresh peel was then finely ground in a food chopper and t h e ground material distilled with water in a Remington still. The colorless oil secured was taken as t h e total oil content. Since this oil consisted almost entirely of limonene. it does not represent the actual oil content of t h e peel. b u t t h e loss of the oxygenated constituents would be fairly constant in each sample, and this method may be used as a relative means of the total oil determination. The percentages, Table I! were calculated on both t h e weight of the peel and the weight of t h e fresh fruit. I t will be noted from Table I t h a t in the case of most samples there was a considerable increase in oil content as maturity advanced, b u t t h a t there is a high percentage of oil in the peel of t h e fruit sometime prior t o the change in color. This is especially marked in t h e case of t h e Valencias. I t will also be noted t h a t there is a very viide difference in the oil content of t h e same variety from different iocalities. From this preliminary investigation it is not possible t o determine whether this variation is due t o soil and climatic conditions, or t o t h e degree of care which t h e trees have received. From the appearance of t h e fruit as received. however: it is beliexTed the latter is t h e case. Especially in t h e case of seedlings this difference was marked, and fruit showing by its form and texture t h a t the trees were highly fertilized and
PERCEXTAGES Nov. Kov. 1-6 7-13 2 74 . . . 2.51 . . 2.63 . . . 2.44 . . . 2.13 .... 2.47 1.00 .... , . 1.42 . . . . 2.00 2.02 . 1.70 .... 1.55 . . 1.00 0.92 . . 1 91 2.53
0.35
0 53
2:46
..,.
0.24 0.41
.
... . . . . . . ...
NO.8
FLORIDA OR.4NGES
PERCEKTACES CALCULATED o w WEIGHT OF FRUIT Nov. Nov. Nov. Nov. Nov. 28 Dec. Dec. 1-6 0.41
T70l. 8 ,
.... ....
.
2.58 220 2.47
.
.
CALCULATED O N W s l G H T OF PEEL Nov. Xov. Kov. 28 Dec. Dec. 14-20 21-27 Dec. 4 5-11 12-18 2.05 . . . . 3.18 . . . ... 1.52 . . . . 2,3s 1 .b, 2.56 2.00 3.26 2.94 2.67 . . . . . . . . 1.62 ... .... . . . . . . . . 1.74 .... .... .... 1.78 .... 2.42 2 24 1.14 1.20 .... . . . . 0.99 ,, , . ,. 1.83 .,.. 1.88 2.30 1.95 2.21 1 :84 . , . . 2.27 2,ii 1.05 . . . . . . . 2.18 . . 1.34 .., 0.83 . . . . 0.88 . . . . . . . . 1.43 1.45 . . . ... 1.91 . . . . 1.52 . . . 2 : 5 1 .... 2.74 ... . . . . . . . 2.15 2.40 . . 2.50 ... 2.68 2.50 1 . 9 5 2.60 2.00 3.04 . . . 2.76 .... . . . . 2.00 . . . . . . . . i.4i 2.10 . . . . 2.38 . . . 2.27
well cared for. showed a higher oil content. There was a marked drop in oil content in most samples during t h e two weeks from November 14th t o 27th. During this period there was an excessive rainfall throughout t h e entire state. Table I 1 gives t h e rainfall records of the Weather Bureau in the localities where samples were secured during t h e period of these experiments. T.4BLE 11-RAINFALL
IN
INCHES
IN
LOCALITIES WHERE ORANGE SAMPLES
WERE GATHERED
Kames in Parentheses are Weather Bureau Stations Nearest t o where Orange Samples were Taken iSov. Nov. Nov. iYov. 28 Dec. 7-13 1 6 2 0 21-27 Dec. 4 5-11 0.26 Lake Weir (Lynn). . . . . . . . . . . . . . 1.93 0.16 Windermere (Clermont). . . . . 0 . 0 3 3.46 0.11 0.10 1.82 .... 0.58 FlorenceVilla (Lucerne Park) . . , . Palatka (Satsuma Heights). . 0 . 0 4 0.67 0.10 0.05 .... New S m y r n a . , . . . . . . . . . . . . 0 . I O 2.34 . . . 0.01 Plant C i t y . . . . . . . . . . . . . . . . . . . . 3 . 1 5 . . . . 0.20 0.30 .,.. Lakeland. . . . . . . . . . . . . . . . . . . . . 2.18 .... 0.12 . . . . 0.30 T a m p a . . . . . . . . . . . . . . . . . . . . . . . 2.89 0.. 09 .... Ozona (Tarpon Springs). . . . . . . . 3.77 0.63 0.65 Orlando. . . . . . . . . . . . . . . . . . . . . . . 2.22 . . . . 0.02 0.05 , . . 3.59 .... 0.15 Wauchula (Fort Meade), . . . . . . . ..,. .... Geneva (Sanford). . . . . . . . . 0 . 0 8 1.85 0.14 0.11 Oakland (Clermont) . . . . . . . 0 03 3.46 ... 1.10 0 . 1 0 0 .26 Manatee . . . . . . . . . . . . . . . . . . . . . . 7.67 0.66
Place Dec. 12-18 0 26
0 09
0 20
0 26
I n some cases no observations are available from t h e places where the samples were taken. and the records of the nearest observer are given. It will be noted t h a t this decrease in oil content immediately follows t h e period of rainfall. and t h a t where the rains extended over a longer period, the oil content was retarded in its increase. EFFECT O F RUST UITE
I t has long been believed t h a t the typical brown coloring of the orange skin known as “russet” following t h e presence of large numbers of the rust mite, Eriophyes oleioorous Ashm., is due t o the puncturing of the oil cells. I n order t o determine if this insect injury decreased the oil yield of t h e fruit, tests were made on the fruit of the same tree a t two stages of maturity. The f i r s t test was made on Sovember 26th while t h e fruit was immature and the second on January z j t h after the oranges had reached full maturity. Each sample consisted of 1 2 bright and 1 2 russet fruit. The results are gi\Ten in Table 111. TABLE111-011. YIELD OF
RUSSET A X D
BRIGHTFRUITOF SAME TREE J A N U A R Y 25 Peel Fruit Peel 1.25 0.40 2.26 0.40 2.68 0.60
~ - O V E Y I B E R 26
PEK CENT OIL I N :
Fruit
Bright F r u i t , , , . , , , , , , . . , . , 0 . 2 0 Russet F r u i t . . . . . . . . . . . . . . . . . 0 . 1 0
These results indicate t h a t early i n t h e season there is a lower oil content on the fruit infected b y rust mite,
Aug., 1916
T H E J O I ’ R N A L O F I N D U S T R I A L ISD E N G I N E E R I N G C H E M I S T R I ‘
b u t as t h e orange matures B normal a m o u n t of oil is formed. T h e results secured in t h e commercial tests on large lots of bright a n d russet fruit also indicate t h a t an equal amount of oil may be secured from each kind of fruit. CONCLUSIOSS
These preliminary results show t h a t there is a wide variation in t h e oil yield of Florida oranges under different climatic and cultural conditions, a n d t h a t ‘the question of variety is likely t o have.some bearing on t h e commercial production of orange oil. The oil content has not reached its maximum until. t h e oranges are fully mature, b u t t h e oil is present in commercial quantities before t h e f r u i t are ready for harvest. T h e occurrence of heavy rainfall during t h e season of harvest will cause a considerable decrease i n t h e oil content. The presence of rust mite does not decrease t h e percentage yield of oil of t h e mature fruit, b u t may show some effect early in t h e season. BUPBIU 01 PLANTI N D U S ~ Y WISHING~ON .
A NUMERICAL EXPRESSION FOR COLOR AS
TEE m
j i l
t h e object of which is t o blend t h e light. The a m o u n t of light reflecled through t h e left-hand aperture is controlled by a shutter actuated b y a long levcr (C) t h a t moves over a scale ( I ) ) so divided into 1 0 0 divisions or parts t h a t at zero rebding t h e sliding shutter is entirely closed a n d at 100 divisions is wide open. By means of a t h u m b screw ( E ) t h e second aperture m a y be adjusted b u t through much narrower limits. T h e base of t h e eye-piece t u b e is equippcd with a sliding carrier (F) in which are mountcd red, green, a n d blue color screens, as well as one of colorless glass. T h e light under which t h e tests are made is received through a south window covered with tracing cloth, I n using t h e instrument two magnesia blocks are first placed directly beneath t h e reflecting mirror a n d in f r o n t of a vertical mirror (GI. The lever operating t h e s h u t t e r is set at roo, t o give full opening of t h e left aperture, and t h e right-hand aperture adjusted by t h e t h u m b screw until t h e two halves of t h e field are of uniform intensity. This adjustment made, t h e mag-
GIVEN BY
s TINT PHOTOMETER
Ry O m KRSSSI A N Y G. C. MCNAIIGHTONI
Received May 27. 1916
The matter of a numerical expression of a definite shade of color is one on which various investigators have expended considerable energy with varying del grees of success. In almost countless phases of commercial a n d experimental work i t is extremely desirable t h a t there be a means b y which a n exact shade of color may be communicated t o others or so recorded t h a t this shade may be matched or referred t o when t h e original is not available. One readily comprehends t h e importance a n d practicability of an instrument which would give an accurate reading of color. So far as t h e authors know, there are b u t two instruments on t h e market, which would appear t o he practicable from a scientific a n d a possible mill standpoint, for measuring t h e depth of color of either liquids or solids. These instruments are known as t h e Ives T i n t Photometer a n d Colorimeter. T h e t i n t photometer, being t h e more simple instrument, was used in these experiments. The original purpose of t h e experiments following was, ( I ) t o determine if color indications as shown b y t h e Ives t i n t photometer could be employed as a means of measuring t h e progress of beating, a n d ( 2 ) t o observe t h e relation between t h e numerical expressions for depth of color as read from t h e instrument and t h e relation of t h e shades as noted b y t h e eye. The t i n t photometer (Fig. I ) consists essentially of a form of telescope into which light from t w o sources is reflected, b y means of a mirror ( A ) , into two apertures, a n d focused b y a special lens into two semicircular fields. Each semicircle is uniformly illuminated by passing t h e light from t h e apertures, or slits, through a rotating wheel ( B ) mounted with lens, I
l o charge. Section 01 Pulp and Paper. Enginrcr in Poresf Products.
PIC.
I
nesia block on t h e right is removed a n d t h e paper ( H ) Using each of t h e color screens successively (i. e . , red, green, a n d blue) t h e a m o u n t of light entering t h e left aperture is decreased until i t is of t h e same intensity as t h a t entering t h e right aperture from t h e paper sample, or until t h e two halves of t h e field appear of one luminosity. The position of t h e lever when this matched condition of fields is obtained with each screen indicates numerically t h e proportion in which red, green, a n d blue light are reflected by t h e paper under test. F o r example, t h e white standards show 100 p a r t s each of red, green, a n d blue, while a certain sample of a n undyed sulfite p i p e r gives readings of 7 j parts red, 7 1 parts green, a n d 67 p a r t s blue. The sum of t h e three colors in t h e case of t h e white standard is 3 0 0 , while in t h e case of t h e paper it is b u t 2 1 j. For purposes of convenience it has been assumed t h a t in t h e latter case there exists a darkening effect of 8j parts of black (in 300). This factor of “parts black” which
to be tested is substituted.
