j16
s
.
’
T H E J O U R M d L O F I A V D 1 7 S T R I A LA 9 D E N G I N E E R I N G C H E M I S T R Y
free lime, using phenolphthalein as an indicator. Preferably t h e sample should s t a n d for about 30 min. with a slight excess of acid a n d be tested again for free lime, inasmuch as t h e free lime in t h e sediment does n o t combine very rapidly with t h e acid. T h e effluent resulting from t h e liming process may contain such a n excessive q u a n t i t y of lime sediment a s ‘to make complete initial neutralization extremely ,difficult. My experience with these particular efAuents is t h a t t h e y do not lend themselves t o biochemical demand determinations readily by either t h e saltpeter or t h e dilution method. When employing t h e dilution method adsorption of t h e methylene blue takes place in t h e majority of cases even in t h e higher dilutions. I n a mixed t a n n e r y waste, however, suspended lime is ordinarily not present in quantities sufficient t o interfere with t h e reliability of either mode of procedure. -4s a rule, t h e bacterial content is high, making unnecessary t h e seeding of t h e waste with sewage after neutralization. However, in order t o insure t h e presence of sewage bacteria, t h e waste may be seeded after neutralization by t h e addition of one cubic centimeter of domestic sewage or polluted river water for each 8-oz. bottle containing t,he waste. T h e wash water resulting from t h e chemical tanning process is likely t o be acid. If i t is desired t o test this waste separately, i t becomes necessary t o neutralize with sodium bicarbonate a n d t o seed with sewage. Although t h e t a n n e r y wastes are often strongly colored t h e dilutions required in employing t h e dilution method are as a rule so great t h a t t h e y do not interfere with t h e observations of t h e decolorization of t h e methylene blue. T h e dilution method has been found t o check well with t h e saltpeter method when employed on combined t a n n e r y waste with t h e precautions mentioned The average of 2 4 days’ results showed t h e dilution method not quite 3 per cent higher. Considering t h e unavoidable working errors involved b y either method, this is a n excellent check. T h e t o t a l oxygen demand varied appreciably during t h e da.y, namely, from 4 0 0 t o 1000 p. p. m. The oxygen consumption in t h e first 24 hrs. was about 7 per cent a n d in t h e first j d a y s 6 0 per cent of t h e total. As y e t , I have not encountered other germicidal .or antiseptic t r a d e wastes, although such waste can undoubtedly be found in t h e gas works industry. .Offhand, I should say t h a t in such waste t h e dilution m e t h o d will be preferably employed t o offset t h e germi,tidal effect, a n d t h e dilution method would probably b e desirable when determining t h e oxygen demand of a ,disinfected sewage. Cases are rare where a sewage .or waste contains germicides other t h a n free lime or f r e e acid in quantities sufficient t o interfere with t h e application of t h e saltpeter method. If free lime or free acid is present in a n y waste, t h e procedure t o be t r i e d should be t h e one which is described. Finally, I may say a f e w words t o clear up certain misconceptions regarding t h e meaning of t h e t e r m oxygen demand. As determined, t h e oxygen is entirely supplied b y t h e nitrate. But this does not mean t h a t t h e oxygen demand so determined will have t o
1‘01. 7 , XO. 6
come from t h e available oxygen in t h e stream into which t h e sewage is discharged. On t h e contrary, while most of t h e oxygen may be derived from t h e stream, t h e rest may come from t h e air b y absorption or from t h e plankton. N o definite rule can be given, for each p a r ticular case is a m a t t e r of individual study. Whether a11 of t h e oxygen must be supplied from t h e stream or n o t . t h e saltpeter method affords a reliable a n d simple comparison of t h e strength of a sewage or waste from t h e deoxygenating standpoint. This a n d t h e amount of settling suspended matter are t h e items most interesting t o the sanitary engineer or chemist. Of less value are t h e routine chemical determination of t h e constituents usually looked for in sewage. T h e great advantage of the saltpeter method lies in the fact t h a t t h e oxygen consumption can be determined after a n y desired interval in a much more reliable a n d comparable manner t h a n can be accomplished by methods involving fresh water dilutions. T o t h e sanitary engineer this is a m a t t e r of great importance. The method h a s also been employed by me for t h e past year t o determine t h e efficiency of sewage purification devices a n d t h e degree of pollution of rivers. For t h e l a t t e r purpose, somewhat different technique is required,’ t h e discussion of which is not within t h e scope of this paper. THES A N I T A R Y DISTRICTOF CHICAGO 700 KARPENBUILDING, CHICAGO
THE ACIDITY AND ASH OF VANILLA EXTRACT B y A L WINTON,A. R. ALBRIGHTAND E H. BERRK Received January 23, 1915
I n a paper entitled “ T h e Chemical Composition of Authentic Vanilla Extracts. together with Analytical 5Iethods a n d Limits of Constants,”2 Winton and Berry tabulate analyses of 7 7 extracts prepared in t h e laboratory from different varieties, grades a n d lengths of vanilla beans a n d 18 extracts employing different menstrua. T h e determinations made were vanillin, normal lead number, color value of t h e extract a n d of t h e lead filtrate and t h e color insoluble in amyl alcohol. I n addition t o t h e extracts made b y t h e direct t r e a t ment of t h e beans with t h e menstruum, second extracts were prepared from t h e residues a n d separately analyzed. Since this paper was published it occurred t o us t h a t determinations of acidity a n d ash, a s well as t h e solubility a n d alkalinity of t h e ash, would be of value in t h e examination of suspected samples. It is indeed surprising t h a t such simple determinations should have been overlooked in t h e search for means of distinguishing genuine from imitation extracts especially when ash a n d ash constants have been regarded of such importance in t h e analysis of fruit products a n d various other classes of foods. T h e ash values would appear t o be useful on t h e one hand because t h e common ingredients of imitation extracts, namely, vanillin, coumarin, sugar, glycerine and alcohol, are practically free from ash a n d o n t h e other h a n d because t h e use of alkali in t h e manufact u r e of extracts from beans would not only increase A m . J Pub Heallh, May, 1916 Proceedings of the Assn. of Official Agricultural Chemists for 191 1, U S. Dept of Agric., Bureau of Chemistry, Bull. 162, 146-158 1 Lederer,
2
June, r g ~ j
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
t h e a m o u n t of ash b u t change t h e values for solubility a n d alkalinity. X marked degree of acidity, due chiefly t o organic acids dissolved from t h e beans a n d in lesser degree t o n a t u r a l vanillin, is a characteristic of genuine vanilla extract, whereas low t o t a l acidity or low acidity n o t vanillin is indicative of adulteration. Fortunately, t h e extracts prepared a n d analyzed b y Winton a n d Berry, excepting those made from t h e residues which seemed u n i m p o r t a n t , h a d been preserved a n d opportunity was found b y one of us (E. H. B.) during t h e present year for t h e supplementary determinations n a m e d . Check analyses were made b y M r . C. K . Glycart, of t h e Chicago laboratory. T h e work o n t h e acidity of vanillin was carried o u t by one of us (A,R. A , ) a t Washington. THE ACIDITY O F V A N I L L I S
T h e f a c t t h a t vanillin combines with alkalies has long been known a n d compounds with sodium, barium, magnesium, zinc, lead a n d other metals are described i n t h e literature.' If t h e acid hydrogen of vanillin were completely replaceable b y metals it might be calculated from i t s formula t h a t one g r a m of vanillin should neutralize 6 j . 8 cc. of N/IOalkali; this replacement is, however, n o t complete as is evidenced b y t h e analytical figures given i n Table I . While one g r a m of vanillin is sometimes present in I O O cc. of imitation extract, t h e a v erage q u a n t i t y in t h a t volume of U. S. P. vanilla ext r a c t found b y Winton a n d Berry is from 0 . 1 1 t o 0.31 gram, equivalent t o from 7 . 2 t o 2 0 . 4 cc. of N I 1 o alkali. F r o m these figures i t is evident t h a t t h e acidity of genuine vanilla extract of s t a n d a r d strength is due in appreciable p a r t t o vanillin a n d t h a t t h e distinction between genuine a n d imitation extracts is one of degree rather t h a n t h e presence of acidity in one a n d i t s absence i n t h e other. I n order t o determine b y actual experiment t h e acidity of vanillin a n d whether other ingredients of extracts influence t h e results, solutions of different a m o u n t s of vanillin with a n d without t h e addition of sugar, glycerine a n d caramel were dissol\Ted i n I O cc. of 60 per cent alcohol diluted t o 2 0 0 cc. with mater a n d t i t r a t e d with N / r o sodium hydroxide solution, using phenolphthalein as indicator T w o different lots of vanillin were used, one made b y Merck. melting at 78.4' C., a n d t h e other b y t h e Verona Chemical Co., known as "Vera Vanillin," melting a t 78.0' C . T h e results appear i n Table I.
51;
f o r one g r a m 63 instead of 6 j . 8 cc. of ~ V / I O alkali; furthermore, t h a t i t is not influenced b y sugar, glycerine a n d caramel. It should be noted t h a t while t h e n a t u r a l color present in I O cc. of genuine vanilla extract does n o t interfere with t h e titration after dilution t o 2 0 0 cc., t h e caramel i n imitations m a y be present in sufficient a m o u n t t o render t h e e n d point indistinct. This fact is more of a n advantage t h a n a disadvantage as i t furnishes evidence of t h e presence of caramel in addition t o t h a t obtained b y t h e usual tests. We have found t h a t t h e vanillin i n a n imitation ext r a c t m a y be fairly accurately determined by t h e tit r a t i o n of t h e ether solution of vanillin a n d coumarin obtained b y shaking o u t t h e lead filtrate as in t h e Hess a n d Prescott method; furthermore, t h a t t h e supern a t a n t e t h e r solution after this titration m a y be evapWhen, orated for t h e determination of coumarin. however, t h e extract contains organic acids, as is t r u e of genuine vanilla extract, t h e titration gives high results due t o t h e solubility in ether of t h e acetic acid liberated from t h e lead acetate in t h e precipitation of t h e organic acids of t h e extract. Experiments are now in progress with t h e view of overcoming this error. M E T H O D S O F D E T E R M I N I K G A C I D I T Y . I S D ASH T O T A L ACIDITY-Dilute IO C C . Of t h e extract t o 2 0 0 cc. a n d t i t r a t e with N/IOalkali, using phenolphthalein a s indicator. Calculate t o I O O cc. of extract b y multiplying t h e n u m b e r of cc. obtained in t h e titration by t e n . VANILLIN ACIDITI.-?rfUltiply t h e percentage of vanillin b y 6j.8, t h u s obtaining t h e cc. of N / I O alkali corresponding t o t h e vanillin i n I O O cc. of t h e extract. A C I D I T Y O T H E R T H A S vasILLIs-subtract t h e vanillin acidity from t h e t o t a l acidity. T O T A L ASH-Evaporate I O cc. of t h e extract in a platinum dish a n d b u r n below redness. SOLUBILITY A N D ALKALINITY O F A S H - - F O ~ ~ OtW he method of t h e A. 0. A . C. for saccharine products,' except t h a t all t h e results should be calculated t o grams per I O O cc. of t h e extract. ACIDITY AND
4 S H IN
U. S. P . V A N I L L A E X T R A C T
T h e results of determinations of acidity a n d ash. also of solubility a n d alkalinity of ash appear in Table 11. These supplement t h e d a t a previously reported b y Winton a n d Berry2 who determined vanillin. normal lead number a n d color values. For reasons explained b y these authors t h e abnormal figures obtained on t h e extracts of Ceylon beans are not included i n t h e maximum, minimum a n d average of all varieties. ACIDITY-It is remarkable t h a t t h e range in total TABLE I-.%CIDITY O F v A S I L L I h WITH 4 S D W I T H O U T S U G A R , GLYCERINE acidity (30 t o j Z cc. N,'Io N a O H per I O O cc.) is less ASD C A R A M E LRESULTSI S TERMS OF Cc \ - / I O NAOH SVBSTASCES ADDED t h a n of t h e acidity corrected for vanillin (14t o 4 2 c c . ) . NaOH Extracts having a high acidity usually have low vanillin Vanillin 2 g 2cc Theory Mg. S o n e sugar glycerine Caramel requirement content a n d vice versa, suggesting a physiological reMerck's. , . 100 6.3 6.3 6.3 6.5(a) 6.58 35 2.2 2.2 2 2 ... 2.30 lation between t h e two. Xotwithstanding t h e wider IO 0.6 0.6 0.6 .. 0.66 "\'era'' . . . . . 100 6.3 6.3 6.3 ... 6.58 range of t h e acidity other t h a n vanillin, this figure will 35 2.2 2 2 2 2 .. 2.30 doubtless be of t h e greater value in judging imitation ( a ) Indistinct end point extracts i n which t h e acidity is largely -or entirely due F r o m t h e figures obtained, i t appears t h a t t h e acidity t o synthetic vanillin. of commercial vanillin b y actual titration, using phenolT h e acidity other t h a n vanillin, as a rule, bears a phthalein, is slightly lower t h a n t h e theoretical, being 1 U. S. Dept. of Agr., Bur. of Chem., Bull. 107, rev.. 68 and 69 7
--
,
Tiemann and Haarmann, Bey., 7 (1874), 614.
2 LOC.
Cil.
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
518
TABLE11-ACIDITY, ASH AND ALKALINITYOF ASH OF VANILLA EXTRACT (TINCTUREOF VANILLA,U. S. P.) MADE I N Acidity of extract Acidity of extract Alkalinity of a s h Cc. N/10 alkali ASH per 100 cc. G r a m per 100 cc.
+.g
-'&
Ba
K i n d a n d quality of bean 1 Mexican: 1st.. . , , 2 3 2nd . . . . . . . . , . . . .. , 4 5 . 6 3rd
cn
7
,
.
........
i
9 3 r d (. d_i t s ) . . . . . 10 4 t h . . . . . . . . . . . . . .. 11 5 t h . . . , . .. . . .. I
1-
. ...
. .. . .. ... ... .. . . ... .. .. .
'I
13 C u t s ....... . . . . Maximum. . Minimum. . ,. . AVERAGE. , 14 Bourbon: 1 s t . . 15 16 17 2 n d . . . . . . . . . . . . . 18 19 20 3rd ....... . . . . . . . . 21 22 23 3 r d (splits).. . . . . . 24 4 t h . . . . . . . . . . . . . . 25 26 27 5 t h . . . . . . . . . . . . . . 28 29 Maximum. . Minimum. .. . . AVERAGE.. . . 3 0 Seychelles: 1st.. . 31 32 . 33 3 r d . . . . . . . . 34 35 36 4 t h ..... . .. . . . .. 37 38 Maximum. . .. . Minimum. .. .. Av ER A GE . . . 39 Madagascar: 2 n d . 40 41 42 3 r d . . . . . . . . . . . . . . 43 44 45 4 t h ... . . , . . 46 47 Maximum. ... . . . . . Minimum. . . . . . . . , AVERAGE.. . . . . .
..
.
.
1 .Es >8 *Y' 2a v 0 W $ 5 +
12 12 13 13 12 12 13 11 10 13 10
27 23 22 27 29 30 28 27 29 30 22
0.258 0.25 1 0.316 0.309 0.299 0.301 0.307 0.293 0.305 0.316 0.25 1
15 27 15 29 12 34 13 32 13 3 4 10 35 20 25 16 28 16 28 20 35 10 26
0.220 0.242 0.264 0.300 0.326 0.325 0.313 0.253 0.313 0.326 0.220 0.284
.. . .. .. .. . . . . . .. 39 42 44 46 . 45
. . . . . ..
.
3
47 45 45 44 44 47 42 45
0.297 0.326 0.297 0.354 0.347 0.378 0.346 0.392 0.387 0.398 0.422 0.385 0.422 0.297
0.359
11 29 0.317
ia
* a
2 G 0.279 0.338
0.263 0.274 0.265 0.335 0.348 0.373 0.329 0.287 0.336 0.314 0.328 0.317 0.333 0.35 1 0.310 0.313 0.373 0.263
35 40 41 42 41 38 39 42 35
$2 e,
H W 0 43 11 32 37 1 0 27 42 11 31 42 11 31 48 11 37 45 12 33 50 12 38 47 13 34 50 12 3 8 49 12 37 48 10 38 52 10 42 46 10 36 52 13 42 42 10 27 46 11 35 38 13 25 41 13 28 41 12 29 42 10 32 46 13 33 51 14 37 36 14 22 39 13 26 48 11 37 40 12 28 38 10 28 37 9 28 38 8 30 37 9 28 35 10 25 35 10 25 51 14 38 35 8 22
. . . .. .. .. .. . . . . 40 39 . . 35
......
2,
55
Cc. N / 1 0 acid per 100 cc.
W
$2
2.e
a i 0.293 0.243 0,050
14 31
0.239
a
0.027 0.036 0.045 0.036 0.060 0.054 0.051 0.045 0.045 0.060 0.027 0.045
'& r/i
9
8 8
7 8 9 10 12 12 11 12 13 9 13 7
10 9 9 9 11 11 13 11 11 16 11 14 17 18 10 13 14 18 9
13 9 9 15 14 11 12 10 11 17 17 9
C'
8 11 10 14 13 12 11 11 14
8 11
closer relation t o both t h e normal lead number a n d t h e a m o u n t of t o t a l ash. For example, t h e highest acidity was obtained in sample No. 1 2 which was one of t h e highest in normal lead number a n d t o t a l ash, while t h e lowest acidity was obtained in sample No. 5 7 which was t h e lowest in normal lead number a n d one of t h e lowest i n ash. ASH-The range of t o t a l ash ( 0 . 2 2 0 t o 0,432 gram per I O O cc.) is greater t h a n t h a t of t h e t o t a l acidity b u t less t h a n t h a t of t h e acidity other t h a n vanillin. T h e relation between ash a n d normal lead number is more striking t h a n between either of these a n d t h e acidity. T h e highest ash a n d normal lead number were obtained in t h e same sample ( N o . 54), while t h e lowest was found in sample No. 39 with a lead number only a trifle above t h e minimum. SOLUBILITY OF ASH-AS a rule over 8 0 per cent of t h e t o t a l ash was soluble in water. A L K A L I N I T Y O F ASH-The figures for t h e t o t a l ash ranged from 30 t o 54 cc. a n d for t h e soluble ash from 2 2 t o 4 0 cc. of N / I O N a O H per I O O cc. of extract. It is a remarkable coincidence t h a t t h e ranges of al-
48 49 50 51 52 53 54 55 56 57 58 59
c
Kind andquality of bean Comores: lst(u) .... 41 39
-c
.
3rd ( a ) . . . . . . . . . . . 4 1 41 41 4th(u).. . . .. , 41
. . . . . 40 39 lst(b). . . . . . . . . . . . . 34 42 2nd ( b ) . . . . . . . . . . . . 43 60 4 t h ( b ) . . . . . . . . . , . . . 47 61 l s t ( c ) . . . . . . . . . , . . . 3 6 62 3rd(c). . . . . . . . . , . . 37 63 4th(c). . . . . . . . . , , . 40 M a x i m u m . . . .. , . 47 M i n i m u m . . . . . , . . 34
..
, ,
, ,
,
. .., , , 40 AVERAGE..
6 4 S. Amer.: 1st ..... . 65 2nd , .. , , . , 66 S p l i t s . . . . . . . . . . . . Maximum.. . .. . . . Minimum.. . , . . , , AVERAGE.. . ... . 67 Ceylon: 1st ...... . . 68 69 Maximum.. . . . , Minimum.. . . . , , AVERAGE.. . ... , 70 Java: 4 t h . . . . , . , , 71 72 Maximum.. , . . . . , , Minimum.. . , , , . , A V E R A G E .. .. . , . 73 T a h i t i : . . . . . . . . . . . 74 AVERAGE.. . .. . .
........
.
..
.
52 44 50 52 44
62
P
.
8
8 10 20 14 16 8 13 13 10 20
8 12 37 32 36 37 32
0.305 0.344 0.327 0.344 0.305
0.251 0.248 0.274 0.289 0.279 0.285 0.357 0.332 0.299 0.198 0.232 0.182 0.326 0.217 0.270 0.320 0.357 0.182 0.272 0.261 0.295 0.273 0.295 0.261
Alkalinity of a s h Cc. N / l O acid per 100 cc.
1
B* -P $. .9 0.059 0.054 0.063 0.059 0.068 0.081 0.075 0.079 0.075 0.037 0.048 0.047 0.074 0.048 0.045 0.059 0.081 0.037
. 31
75 Vanillons. . . . . . . . . . 38 T o n k a beans: 5 76 Angostura: Prime.. . .' 5 77 Bloaters.. . . . AVERAGE. . . 5
.... .. .
26 23
0.288 0.221
15 33 0.311
:: 9
0.044 0.049 0.054 0.054 0.044
38 39 42 42 38
26 27 30 30 26
40 as
12 12 12 12 12
ia
0.364 0.313 0.386 0.386 0.313
0.060 0.048 0.057 0.060 0.048 0.354 0.055 0.299 0.050 0.250 0.044 0.246 0.044 0.299 0.050 0.246 0.044 0.265 0.046
49 43 56 56 43
37 33 44 44 33 38
12 10 12 12 10
11
49 40 RR 4.1 38 42 37 30
38 33
11 7
5 5 4 5 4 5 15 16 14 15 14
48 52 45 48 33 30
i : 33 22
11 12 13 13 16 17 15 16 17 9 12 13 16 10 12
14
14 35 0.325 0.276 0.049
0.349 0.294 0.290 0.349 0.290
31 30 33 33 33 34 38 38 34 24 28 22 38 23 28
45 31
34 33 49 49 33
30 36 34 37 30
42 42 46 46 49 51 53 54 51 33 40 35 54 33 40
0.061
49
. . .. . . 39 . 52 45
.
12 11 11 12 11 10
15 12 14 15 12
LABORATORY
Y +
Y
:;
;2 2
A1
THE
ASH G r a m per 100 cc.
*: E'y1
-i
5
0.059 0.246 0.05 1 0.283 0.043 0.260 0.037 0.299 0.055 0.290 0.057 0.3 17 0.061 0.285 0.061 0.321 0.071 0.323 0.064 0.332 0.066 0.349 0.073 0.327 0,058 0.349 0.073 0.246 0.037 0.301 0.058 0.220 0.043 0.227 0.047 0.221 0.044 0.275 0.060 0.291 0.057 0.319 0.054 0.282 0.047 0.232 0.055 0.263 0.073 0.256 0.058 0.263 0.065 0.248 0.069 0.253 0.080 0.298 0.053 0.252 0.058 0.248 0.065 0.319 0.080 0.220 0.043 0.269 0.068 0.214 0.044 0.213 0.038 0.261 0.055 0.256 0.053 0.241 0.058 0.244 0.057 0.262 0.045 0.249 0.044 0.249 0.056 0.262 0.058 0.213 0.038 0.193 0.206 0.219 0.264 0.266 0.271 0.262 0.208 0.268 0.271 0.193
Cc. N/10 alkali per 100 cc.
Vol. 7, No. 6
49
31
38
7
31 34 29 23
11 7 8 8 7
33 26
7
7 7 7
24 0.254 0.214
0.249 0.179
0.039 0.042 0.q40
4
34
0.263
0.214
0.048
38
30
7
0 0 0
5 5 5
0.132 0.163
0.122 0.156
0.010 0.007 0.008
15 16
12 14
3 2
15
13
2
40 22
18 7
0.147 0.139
ALL ANALYSES( d ) M a x i m u m ..... . . .. 52
20
42
0.432
7
14
0.220
0.357 0.179
0.081
M i n i m u m ..... , . , , 30
0.027
54 30
12 30 0.319
0.265
0.054
42 30 12
. . . . . . 42
AVERAGE.,
( a ) Pomoni, Anjouan.
( b ) Comoro. lon vanilla, Vanillons. a n d T o n k a beans.
(c) Mayotte.
( d ) Excluding Cey-
kalinity of t o t a l ash a n d of t o t a l acidity of t h e extract are practically identical. ACIDITY AND ASH I N EXTRACTS NADE WITH D I F F E R E N T MENSTRUA
T h e results are given in Table I11 a n d like those in A N D ALKALINITY OF ASH OF VANILLAEXTRACT PREPARED WITH DIFFERENT MENSTRUAIN THE LABORATORY Alkalinity of a s h Acidity of extract Cc. N/10 alkali ASH Cc. N / 1 0 acid ner 100 cc. Gram Der 100 cc. Der 100 cc.
TABLE111-ACIDITY, ASH
BEANS: 54 6 0 None 6 0 Sugar-U. S. P. 5 4 53 6 0 Glycerin 54 35 None 53 35 Sugar 35 Glycerin 52 BOURBONBEANS: 47 6 0 None 6 0 Sugar-U. S. P. 46 45 6 0 Glycerin 45 35 None 45 35 Sugar 44 3.5 Glvcerin TAHITI- BEANS: 29 60 None S. P. 30 60 Sugar-U. 27 60 Glycerin 22 35 N o n e 24 35 Sugar 23 35 Glycerin
MEXICAN
0,046 0.061 0.063 0.098 0.100 0.106
49 47 50 65 63 66
39 37 39 47 45 47
10 10 11 18 18. 19
0.355 0.341 0.348 0.414 0.388 0.405
0.294 0.061 0.282 0.059 0 . 2 8 2 0.066 0 , 3 1 9 0.095 0.303 0.085 0.310 0 . 0 9 5
42 45 43 52 51 49
28 32 27 30 34 29
14 13 16 22 17 20
0.225 0.221 0.226 0.234 0.227 0.244
0.198 0.178 0.182 0.189 0.173 0.190
0.027 0.043 0.044 0.045 0.054 0.054
30 30
24 23
6
31 32 33
22 22 23
12 12 10 11 11 11
42 0 , 4 0 9 42 0 . 3 9 1 43 0.386 43 0 . 5 0 7 42 '0.481 41 0 . 5 0 8
12 12 13 11 11 12
35 34 32 34 34 32
7 7
22 23
7 6
20
6 6
~~
16 18 17
0.363 0.330 0.323 0.409 0.381 0.402
30 22
7
8 9 10 l@
J u n e , 1915
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
Table I1 should be compared with t h e analyses reported b y m i n t o n a n d Berry.‘ T h e influence of sugar or glycerine in t h e menstruum on t h e a m o u n t of acidity a n d ash extracted was hardly appreciable. Decreasing t h e strength of t h e alcohol increased t h e amount of ash a n d diminished t h e acidity. S U M S IA R Y
I-The following ranges in acidity a n d in ash values were found in 7 7 U . S. P. extracts made i n t h e laboratory from different varieties, grades a n d lengths of vanilla beans: TOTAL ACIDITY:
30 t o 52 cc. N/10 alkali per 100 cc. ACIDITYOTHER THAN VANILLIN: 14 t o 42 cc. “10 alkali per 100 cc. TOTAL ASH: 0.220 t o 0.432 gram per 100 cc. SOLUBLE ASH: 0.179 t o 0.357 gram per 100 cc. OF TOTAL ASH: 30 t o 54 CC; N/10 acid per 100 CC. ALKALINITY ALKALINITY OF SOLUBLE ASH: 22 to 40 cc. hr/10 acid per 100 cc.
11-Practically t h e same values were obtained with a n d without t h e use of sugar or glycerine in t h e menstruum. 111-Diminishing t h e strength of alcohol in t h e mens t r u u m tended t o increase t h e ash values a n d diminish t h e acidity. IV-The possibility of developing a method of determining vanillin based on t h e acidity is suggested. BUREAUOF CHEMISTRY,WASHIBGTON, D. C.
A MODIFICATION O F WICHMANN’S M E T H O D F O R THE DETECTION OF SMALL AMOUNTS O F COUMARIN, PARTICULARLY I N FACTITIOUS VANELA* EXTRACTS B y J. R . DEAN Received April 9, 1915
..
T h e essential part of t h e Wichmann method for t h e detection of coumarin in vanilla extracts is t h e conversion of t h e coumarin, in t h e residue obtained b y evaporating t h e distillate from a vanilla extract t o dryness, into salicylic acid b y fusion with potassium hydroxide a n d testing for salicylic acid with ferric chloride. Saccharin a n d salicylic acid interfere completely with this test. T h e following modification of TVichmann’s method has been found t o be as useful as t h e original, is much less troublesome a n d is not interfered with by either salicylic acid or saccharin. Render a de-alcoholized portion of t h e extract alkaline with j cc. of ammonia (use of t h e residue after a n alcohol determination is recommended) a n d extract with I 5 cc. of ether.3 Iranillin, salicylic acid and saccharin are insoluble in ether in t h e presence of ammonia while coumarin is readily dissolved. Transfer t h e ether t o a nickel or porcelain crucible a n d evaporate on t h e steam b“ath or hot plate. Add five drops of a j o per cent solution of potassium hydroxide a n d , after carefully drying, fuse a t t h e lowest possible temperature, care being t a k e n t o avoid any blackening. Dissolve t h e mass i n a few cc. of water, render acid with dilute sulfuric acid a n d transfer t o a test tube. Add j cc. of 1
Lac.
’ “A
Cil.
Method for t h e Detection of Small Amounts of Coumarin. Particularly in Factitious Vanilla Extracts,” by H. J. Wichmann. Circular 96, U. S. Dept. of Agr., Bureau of Chemistry. Hess a n d Prescott, J. A . C. S., 28 (1899), 256.
519
chloroform t o dissolve o u t t h e salicylic acid produced i n t h e fusion a n d shake t h e t u b e vigorously. Xllow t h e chloroform t o separate a n d remove i t with a small pipette extended t o t h e b o t t o m of t h e tube. Transfer t h e chloroform t o a second test tube, filtering through a small plug of cotton. Add I or z cc. of water, containing a drop or t w o of ferric chloride solution, t o t h e chloroform a n d shake a s before. T h e presence of coumarin is indicated b y t h e formation of t h e purple color of ferric salicylate. TABLEOF R ~ S U L T S SAMPLES Extract of vanilla plus A’othing 25 mg. salicylic acid 25 mg. saccharin 1 mg. coumarin 2 . 5 mg. coumarin 5 mg. coumarin 5 mg. coumarin 25 mg. salicylic acid 25 mg. saccharin 25 mg. coumarin
No. of samples Results 4 Negative 4 Negative 4 h’egative 4 Positive 4 Positive 4 Positive
1\
Depth of purple color
Light purple Strong purple Deep purple
4
Positive
Deep purple
4
Positive
Very deep purple
I t does not seem possible t o employ t h e above reaction i n a n accurate quantitative method for coumarin t h a t would be a n y shorter or better t h a n t h e extraction method now employed. By experience, however, one can learn t o form a very good idea of t h e a m o u n t of coumarin present b y t h e depth of color obtained. Attention is called t o t h e f a c t t h a t coumarin would interfere with Durand’sl test for saccharin as both coumarin a n d saccharin yield salicylic acid when fused with either potassium or sodium hydroxide. It is possible t o eliminate t h e saccharin, as stated above, b u t as coumarin is of such a n inert nature chemically, i t s removal is far less easy-an extraction b y means of a n immiscible solvent in t h e presence of a n alkali being t h e method generally used. Coumarin a n d saccharin are very likely t o be f o u n d together in food products, especially in soft drinks of a cheap nature where coumarin has been used in place of, or with, vanilla or vanillin. I n using Durand’s test for saccharin i t would be necessary t o remove t h e coumarin b y rendering t h e substance alkaline a n d extracting as above. After t h e complete removal of t h e coumarin, t h e sample under e x a m h a t i o n could be rendered acid a n d tested for saccharin as in Durand’s method. 520 CHURCHSTREET,ANH ARBOR,MICHIGAN
STUDIES I N SYNTHETIC DRUG ANALYSIS 111-ESTIMATION O F CAFFEINE AND ANTIPYRIN I N
ADWXTURE By
a‘.0. EMERYA N D
S. PALKIN Received March 20, 1915
T h e first recorded a t t e m p t s looking t o t h e quantitative separation of these t w o drugs were apparently made by J . J . Hofman,2 who, taking advantage of t h e tendency of antipyrin t o yield with mercury salts difficultly soluble products, subjected t h e caffeineantipyrin mixture t o t h e action of mercuric nitrate, thereby precipitating t h e antipyrin as t h e molecular compound CllHl2N20.Hg(N03)2. After separating t h e precipitate b y filtration, t h e caffeine was isolated from a n aliquot of t h e filtrate by extraction with chloroform a n d estimated as pure caffeine. The weight of t h e 1
Halsey Durand, THISJOURNAL, 6 (1913), 987.
2
Pharm. Weekblad, No. 49 (1894).
,
I
