T H E J O L'RNAL O F I N D L ' 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
Dec., I913
TABLE IV
so2
Percentage of samples
P a r t s per million
I
1907
1908
1912
0.00
7.45 11.70 7.45 9.56 7.45 5.85 2.66 2.66 2.12 3.72 5.32 4.25
20.22
1909 1911 1910 1'0.45 17.46 7.45 100.78 9.09 7.84 26.35 20.0.00 5.23 22,85 10.64 300.00 10.47 11.11 9.50 40- 50 3.15 7.84 4.76 9.56 50- 60 3.93 3.1; 7.84 5.32 60- 70 3.93 0.95 6.92 2 62 70- 80 2.36 7.19 0.63 5.32 80- 90 3.93 4.57 0.63 2.12 90- 100 1.57 1.95 0.63 1.60 loo-- 150 1 0 . 2 3 3.90 0,63 11.17 150- 200 9.45 0.31 5.23 3.i2 200.- 250 4.72 2.62 1.26 3.20 4.iX 250- 300 6.30 2.62 2.22 1.60 0.53 300- 350 5.51 0.95 1.06 1.06 1.95 350- 400 2.36 1.95 1.26 0.00 0.53 400- 450 3.15 0.00 1.58 1.60 1.06 450- 500 3.15 0.95 0.00 0.65 2.66 500- 600 3.15 2.62 0.63 2.12 1.611 600- 700 6.30 1.31 0.63 1.60 3.i2 0.31 700- 800 3.93 0.53 1.06 1.31 0.00 800- 900 3.93 0.65 1.06 2.66 9oo-inoo I .5i 0.00 1.60 0.00 1.31 0.31 100C-1500 11.81 3.26 3.i2 3.20 1500-2000 2.36 2.66 n 53 0.63 0.65 2000-2500 0 . 78 1.06 0.00 0.00 0.65 1.31 2500-3000 0.i 8 0.53 1 .60 0.31 3000-3500 0.78 0.65 0.00 0.53 0.00 0.52 0.00 3500-4000 0.00 0.00 0.00 Above 4000 0.00 0.00 0 . 6 5( a ) 0 . 0 0 0.00 ( a ) Contained 0 . i 4 1 0 per cent, or 7410 parts per million. 0-
10 20 30 40
7.86 4.49 4.49 0.00 1.12 4.49 2.24 1.12 2.24 15.73 14.60 3.36 3.36 2.24 0.00 2.24 1.12 1.12 2.24 0.00 1.12 1.12 3.36 0.00 0.00 0.00 0.00 0.00 0.00
TABLEV
SO'
Percentage of samples
Parts per million 010 0- 20 0- 30 0- 40 0- 50 0- 60 0- io 0- 80 0- 90 0- 100 loo- 150 100- 200 100- 250 100- 300 100- 350 100- 400 100- 450 ion- 500 500- 600 500- 700 500- 800 500- 900 500-1 000 1000-1500 1000-2000 1000-2500 inon-3ono inno-35on 1000-4000 IOOc-4OOO
+
1907
1908
1909
1910
1911
1912
0.00 0.78 0.i8 0.i8 3.93 7.86 11.79 14.15 18.08 19.65 10.23 19.68 24.40 30.70 36.21 38.57 41.72 44.87 3.15 9.45 13.38 17.31 18.88 11.81 14.17 14.95 15.73 16.51 16.51 16.51
i.45 19,15 26.60 36.16 43.61 49.46 52.12 54.78 5 6 , YO 60,62 5.32 9.57 14.35 15.95 li.01 ii.ni 18.61 18.61 2.12 5.84 6.90 9.56 11.16 3.72 6.38 i.44 9.04 9.04 9.57 9.57
10.45 18.29 23.52 34.63 42.47 50.31 52.93 60.12 64.69 66.64 3.90 9.13 11.75 14.37 16,32 18.2i 18.27 18.92 2.62 3.93 5.24 5.89 i.20 3.26 3 .9 1 4.56
7.45 16.54 27.18 35.62 45.19 50.51 57.43 62.75 64.87 66,47 11.17 14.89 18.09 18.62 19.68 20.21 21.27 23.93 1.60 3.20 3.i.3 4.i9 4.79 3.20 3 , 73 3 . 73 4.26 4.79 4.79 4.79
17.46 43.81 66.66 7:. 13 81.89 85.06 86.01 86,64 87,24 87.90 0.63 0.94 2.20 4.42 5.37 6.63 8.21 9.16 0.63 1.26 1.5i 1. S i 1.57 0.31 0.94 0.94 1.25 1.25 1.25 1.25
20.22 28,08 32.57 37.06 37.06 38.18 42.67 44.91 46.03 48.2i 15.73 30.33 33.69 3i.05 39.29 39.29 41.53 42.65 1.12 3.36 3.36 4 .48 5.60 3.36 3.36 3.36 3.36 3.36 3.36 3.36
5.87 6.52 6.52 7,li
The results show t h a t t h e 1907 samples contained t h e largest a m o u n t of SOz, only 19.6j per cent of t h e samples containing less t h a n IOO p a r t s per million a n d 3 j . 3 9 per cent above 500 parts per million. T h e 1908 samples show 60.62 per cent of t h e samples below IOO parts per million a n d 2 0 . ~ 3 per cent above j o o p a r t s per million. T h e 1909 a n d 1910 samples are quite similar throughout. I n 1911 t h e analyses show 87.90 per cent of t h e samples with less t h a n I O O p a r t s per million a n d only 2 . j j per cent above j o o p a r t s
987
per million. T h e 1912 samples contained more SO2 t h a n t h e 1911 samples, this being due t o t h e fact t h a t a large number of t h e 1912 samples, 42.6j per cent, contained from I O O t o 500 parts per million. Comparatively few samples contained less t h a n I O parts per million. A number of t h e samples containing less t h a n I O p a r t s per million were found t o contain hydrogen peroxide evidently added t o destroy
so,.
I n this connection, t h e results obtained on t h e two samples of gelatin prepared in the laboratory are significant. These samples contained 189 a n d 199 parts per milion of SO?, respectively, whereas t h e air-dried "stock" from which t h e y were prepared contained only 6 parts per million. Two more samples of gelatin prepared in t h e laboratory from fresh calf bones, purchased in a butcher shop, contained 2 3 a n d 78 parts per million. I n this case t h e jelly was also dried on glass plates in a current of air from a n electric fan. It is, therefore, not surprising t h a t even excessive amounts of S O z m a y b e found in gelatin prepared from selected stock. I n t h e manufacture of gelatin, t h e t h i n gelatin solutions are concentrated t o t h e desired consistency so t h a t gelatinization will t a k e place on cooling. T h e jelly is t h e n sliced a n d dried in a continuous current of a.ir a t 8 j t o 9 j o F. If t h e factory is situated in a manufacturing district, where much coal is burned, i t is t o be expected t h a t t h e SOz absorbed b y t h e gelatin would be greater t h a n in t h e case of gelatin manufactured in outlying districts. Naturally, t h e selection of t h e stock is also import a n t , since it m a y contain considerable amounts of S O z . Thirty-six samples of stock examined in 1908, 1909 a n d 1910 gave t h e following results: Sulfur dioxide P a r t s per million Maximum. . , . . . . . . . . 1695 Minimum., . . . . . . . . . . . 9 ~
Average . . . , . . . .
407
I n conclusion, I wish t o acknowledge m y indebtedness t o m y assistant, hlr. E. S. Liebscher, for his painstaking work in carrying out a considerable p a r t of t h e analyses and experiments. LEDERLE LABORATORIES 39-41 WSST 3 8 T ~STREET NEW Y O R K
EXPERIMENTAL DATA ON THE DETERMINATION OF SACCHARIN IN FOODS WITH A MODIFICATION OF SCHMIDT'S METHODS By HALSEYDURAND Received October 13, 1913
A recent ruling of t h e Board of Health of t h e Dep a r t m e n t of Health of S e w York City prohibited t h e use of saccharin in foods a n d drinks (see Section 68, Sanitary Code). The enforcement of this law required t h e examination of a large number of samples of various foodstuffs a n d soft drinks in which violations were expected. A method for t h e detection of saccharin w a s sought which could be done positively and with as much speed as possible. A review of t h e literature gave five methods, as follows:
988
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
I. TASTETEsT.-The aqueous solution of t h e sample is acidified a n d shaken out with ether. T h e ethereal layer separated a n d evaporated t o dryness a n d a small portion of t h e residue applied t o t h e tongue. An extremely sweet taste followed by a bitter taste indicates saccharin. 11. BORNSTEIK’S TIXT.-(Z. anal. Chem., 27, s. 165). Aqueous solution is shaken as above a n d t h e ether residue heated with resorcin a n d a few drops of concent r a t e d sulfuric acid, till t h e mass begins t o swell. Cool. Repeat heating a n d cooling several times. Cool, dilute with water a n d neutralize with sodium hydrate. Red-green fluorescence indicates presence of saccharin. 111. KASTLE’ST E S T . - - ( B ~ . 26, Hyg. Lab., U. S. P u b . Health & Mar. Hosp. Serv.) T h e ether residue is treated with a few drops of a mixture of j cc. of phenol and 3 cc. of pure concentrated sulfuric C. acid. It is t h e n heated for j minutes t o 16-170’ a n d t h e mass dissolved in water a n d made alkaline with sodium hydrate. -4 dark purplish red or pink indicates t h e presence of saccharin. IV. SCHMIDT’S TEsT.-(Rep. Anal. Chem., 30.) Residue from ether extraction is heated in a porcelain dish with about I gram sodium hydrate for one-half hour a t 250’ C. i n air oven or linseed oil bath. This converts saccharin t o sodium salicylate. T h e melt is dissolved in water, acidified with hydrochloric acid a n d shaken with ether. Evaporate ether, t a k e up residue with water a n d a d d dilute ferric chloride solution. A violet color indicates t h e presence of saccharin. T h e absence of salicylic acid must first be ascertained before applying this method. If salicylic acid is prese n t t h e ether residue is treated with dilute hydrochloric acid a n d bromine water added in excess. T h e liquid is well shaken a n d filtered. T h e salicylic acid is completely removed as a bromine derivative. T h e filtrate is made strongly alkaline a n d evaporated a n d heated as above. By this means t h e false saccharin frequently found in wines a n d giving faint reactions for saccharin is also eliminated. ALLEN’STEsT.--(Allen’s Corn. Organ. Anal., 2, Pt. 3, p. 38.) T h e ether residue is rendered alkaline with sodium hydrate a n d ashed. T h e ash is t a k e n up with water made acid with hydrochloric acid a n d tested with barium chloride or sulfur. The presence of sulfur indicates saccharin. This test, a little potassium nitrate being added during ignition, is also used for t h e quantitative determination of saccharin, t h e barium sulfate being weighed a n d t h e weight x 0.783 = saccharin. This quantitative method was not tried a s t h e presence of saccharin is sufficient ground for prosecution. TEST1.-The taste test was tried a n d found t o be very satisfactory, t h e absence of t h e sweet t a s t e being a good indication in most cases of t h e absence of saccharin. However, t h e possibility of other substances producing t h e sweet taste, a n d also of t h e sweet taste being masked b y bitter substances in t h e residue, made i t necessary t o have some f u r t h e r test a s confirmation. TESTI1 was tried a n d gave good reactions. It
v.
Vol. j, No.
12
was found, however, t h a t a large number of organic compounds give t h e same reaction a s saccharin, so this method was discarded. TESTI11 was tried a n d excellent results were obtained when pure saccharin was used. When ether residues obtained from shaking out aqueous solutions of foods a n d drinks were treated with t h e phenol-sulfuric acid mixture and neutralized with sodium hydrate t h e characteristic color did not appear. T h e failure of this reaction is evidently due t o t h e presence of small amounts of impurity in t h e residue. Efforts were made t o obtain the pure phenol compound from t h e aqueous solution after treating the residue with phenol-sulfuric acid mixture, by shaking out with amyl alcohol a n d isobutyl alcohol a n d treating t h e separated alcohol solutions with sodium hydrate, without results. TESTI V (Schmidt’s) was tried repeatedly by t h e laboratory force using t h e various modifications a s suggested b y different authorities. Invariably t h e ether residue, obtained b y shaking out t h e acidified aqueous solution of t h e mass after heating, gave a benzoic acid reaction on addition of dilute ferric chloride solution. It was found also t h a t t h e saccharin in t h e original ether residue was converted into benzoic acid when treated with saturated sodium hydrate solution a n d allowed t o s t a n d over night a t room temperature. Excellent results were obtained in this way a n d this method was adopted b y this laboratory a s a confirmatory test t o be used with t h e taste test. This method while giving good results required t o o long a time for its completion. METHOD ADOPTED
T h e writer has recently succeeded in obtaining t h e salicylic acid b y Schmidt’s method ( I V ) both in pure saccharin a n d in ether residues containing saccharin, b y proceeding as follows: One hundred cc. of a n ‘aqueous solution of t h e sample t o be examined for saccharin are acidified with phosphoric acid a n d shaken out with ether in t h e usual manner. T h e separated ether is filtered through double folded filter papers, t o remove moisture, into a nickel dish of convenient size a n d evaporated t o dryness. After ascertaining t h e absence of salicylic, (see description of Schmidt’s method) , the residue is treated with about I cc. of saturated sodium hydrate solution, allowing t h e alkali t o come in contact with t h e entire residue. Place t h e dish on a piece of asbestos board about 3 mm. in thickness, heat for 8-10 minutes over a Bunsen flame, cool, take up with water, acidify with hydrochloric acid, a n d shake out with ether. Evaporate ether, t o which a small amount of ammonium hydrate has been added, in a glass dish on water b a t h , t a k e up residue with a little water and test with dilute ferric chloride for salicy’ic acid. This method gave very satisfactory results requiring about three-quarters of an hour. The writer has further simplified a n d shortened t h e time required for t h e method a n d also eliminated t h e possibility of t h e sublimation of the salicylic acid on t h e water b a t h by omitting theitreatment of t h e final ether residue with ammonium
Dec., 1913
T H E J O U R N A L OF I N D U S T R I A L AND ENGINEERING CHEMISTRY
hydrate a n d i t s evaporation t o dryness. T h e ether residue, after separation, is poured into a t e s t t u b e a n d a b o u t j cm. of water containing a small amount of ferric chloride a r e added. T h e t e s t t u b e is t h e n shaken vigorously a n d t h e ether a n d water layers allowed t o separate. T h e presence of salicylic acid is indicated b y a violet coloration of t h e water layer. CHEMICAL LABORATORY, DEPARTMBNT O F HEALTH N E W YORKCITY
BOUKLON CUBES By
F. C. COOK‘
Received September 13, 1913
INTRODUCTION
Bouillon cubes consist of a large a m o u n t of common salt mixed with varying amounts of meat a n d plant extract, a small per cent of fat, a n d a little condiment. Some of t h e products sold under t h e name “bouillon cubes” contain b u t a small per cent of meat stock o r extractives, a n d are not entitled t o t h e t e r m “bouillon” unless i t is modified. T h e y are extensively advertised as capable of making a stimulating a n d appetizing hot drink simply b y being dissolved in hot water. T h e y have, therefore, a legitim a t e place among Aur dietary accessories. Several brands of these cubes have appeared on t h e TABLEI - h i A L Y S I S
* Sample
No. 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986
Brand Behrend Oxo Steero Burnham Sunbeam Armour Morris Standard Liggitt Knorr
Solids Per cent 96.60 95.06 96.05 96.87 95.73 96.05 96.77 95.81 96.00 95.44
Organic material Per cent 22.86 25.31 28.41 41.94 45.23 26.48 33.00 21.76 21.91 26.24
of t h e Association of Official Agricultural Chemists,‘ total creatinin b y t h e Benedict-Myers2 autoclave method, a n d precipitation with alcohol in hydrochloric acid solution was carried out according t o Rippetoe’s method,3 which is as follows: Rippetoe’s Method.-Transfer I O cc. of a n aqueous solution containing z grams of t h e sample t o a zoo cc. glass-stoppered measuring cylinder, a d d I. z cc. of 1 2 per cent hydrochloric acid, mix a n d a d d absolute alcohol t o t h e zoo cc. mark, shake a n d let s t a n d several hours a t 2 0 t o 2 j o C , If necessary make t o mark, filter, a n d determine total nitrogen i n I O O cc. of filtrate. T h e acidity figures were obtained b y titrating one g r a m of t h e sample dissolved in roo cc. of water with twentieth-normal sodium hydroxide, using phenolphthalein as indicator. The results obtained on t h e t e n samples of cubes analyzed are given in Tables I a n d 11. The water content of t h e cubes examined was under j per cent a n d t h e ether extract figures varied from I t o 4. j 8 per cent. These last figures represent t h e amount of fat added t o these cubes during t h e process of manufacture. T h e ash, which is largely sodium chloride, varied from 50 t o 74 per cent. il large amount of sodium chloride is necessary t o give a salty taste t o t h e cup of water in which t h e cube is d:ssoloed, a n d
OF BOUILLONCUBES-ORIGINAL
Ether extract Per cent
Per cent
1.93 3.10 1.20 1.00 1.44 0.96 3.79 4.19 4.58 4.57
73.74 69.75 67.64 54.93 50.50 69.57 63.77 74.05 74.09 69.20
Ash
American market i n t h e past five years, most of t h e m manufactured in this country, a n d some imported from Germany. M a n y are wrapped in tin foil, while others are wrapped in paraffin paper, a n d occasionally a brand of cubes is found in both foil a n d paper. As t h e moisture content is low a n d a large a m o u n t of salt is present, t h e y will keep indefinitely, although certain makes t e n d t o lose their form during warm weather. The bouillon cubes which are reported in this paper were collected on t h e New York market in 1 9 1 2 . M E T H O D S O F ANALYSIS
T h e samples were prepared for analysis b y grinding fifteen t o t w e n t y cubes in a mortar as thoroughly as possible a n d placing t h e composite paste in small screw-cap jars. T h e solids were obtained b y drying t o constant weight in v a c u o a t 6 j 0 C. T h e ash, sodium chloride, phosphoric acid (P*O,), nitrogen, a n d ether extract were determined b y t h e methods 1 Physiological Chemist, Animal Physiological Chemistry Laboratory, Bureau of Chemistry.
989
Total chlorine a s sodium chloride Per cent i2.13 65.00 62.15 52.90 49.26 67.44 59.17 72.22 71.98 65,OO
BASIS
Acidity (cc. trventiethTotal normal phosphoric sodium acid (PzOs) hydroxid Per cent per 1 gram) 1.02 1.51 1.83 0.58 0.54 0.62 1.69 0.48 0.41 1.55
6.20 6.50 9.15 6.10 7.30 6.00 9.68 5.01 4.75 7.40
h‘itrogen precipitated b y absolute alcohol in Total hydrochloric nitrogen acid Per cent Per cent 2.19 2.97 3.62 2.11 2.36 2.79 3.67 2.09 2.11 3.20
0.13 0.86 0.76 0.05 0.02 0.17 0.56 0.07 0.05 0.91
Total creatinin Per cent 0.84 1.07 1.67 0.88 0.92 1.07 1.07 0.50 0.49 1.38
t o furnish body t o t h e cube. Sudendorf4 analyzed 18 samples of cubes bought on t h e market a t H a m burg, Germany, a n d t w o samples prepared in his TABLE 11-ANALYSIS
Sample NO.
1977 1978 1979 1980 1981 1982 1983 1984 1985 1986
Brand Behrend oxo Steero Burnham Sunbeam Armour Morris Standard Liggitt Knorr
OF
BOUILLONCUBES-WATER, FAT, A N D ASH-FREE BASIS
Phosphoric acid (PzOs) Per cent 4.86 6.80 6.73 1.41 1.23 2.43 5.78 2.73 2.37 7.14
Total nitrogen Per cent 10.50 13.37 13.30 5.03 5.39 10.94 12.57 11.88 12. IS 14.75
Ratio of Total creatinin creatinin to Per cent total nitrogen 1 : 2.6 4.01 1 : 2.8 4.82 1 : 2.2 6.14 1 : 2.4 2.10 1 : 2.6 2.10 1 : 2.6 4.10 1 : 2.2 5.82 1 : 4.2 2.84 1 : 4.3 2.83 1 : 2.3 6.36
laboratory. T h e latter contained sufficient salt t o give a satisfactory taste t o t h e cup of bouillon. T h e 1
3
4
Bull. 107, Rev., Bureau of Chemistry, U. S. Dept. Agr. Am. J . Phys., 18, 397 (1907). Private communication. 2. Nahr. Genussm., Z3, 577 (1912).
