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
Feb., 1919
A STUDY OF THE FATTY ACIDS OBTAINED FROM VARNISH OILS AND FROM VARNISHES [PAPER NO. I ] B y W.
T. PEARCE
Received June 15, 1918
This work was undertaken with the object of finding methods for estimating China wood and other oils t h a t are being substituted for linseed in oil varnishes. It was stated eight years ago t h a t a part of the above problem would be taken up by the Bureau of Standards, but inasmuch as nothing had been reported a n d as i t was of such importance t o the development of a reliable system of varnish analysis, we decided i t must be included in t h e program of varnish investigations begun in this laboratory in June 1917. We report here a p a r t of t h e work we have in progress. T h e linseed oil used was the raw oil boiled 2 hrs. a t 200' C. with t h e oxides of lead a n d manganese. T h e China wood oil used was clear and possessed a golden yellow color. . The soy bean oil was light and clear, a n d the menhaden and cottonseed were light clear oi1s.l The acid mixtures were in most cases obtained b y making up mixtures of t h e desired oils, saponiEying with alcoholic caustic potash, extracting t h e liberated acids with ether, a n d drying t h e solvent-free acids a t 110' C. I n other designated cases we used the f a t t y acids obtained from varnishes of known composition by Boughton's method.2
I21
Menhaden, I O O per cent, gave a small brown residue which in no way resembled the China wood jelly. Composition of t h e Mixtures from which t h e Acids were made Per cent Linseed, 100. . . . . . . . . . . . . . . . . . . . Menhaden, 100. . . . . . . . . . . . . . . . . Soy bean, 1 0 0 . . . . . . . . . . . . . . . . . . . Cottonseed, 100.. . . . . . . . . . . . . . . . China wood, 100
................ ............. { .............
1 1
China wood, 50 Linseed, 50 China wood 33l/3 Linseed, 662/3 China wood, 20 Linseed, 80 China wood, 10 Linseed, 90 China wood, 5 Linseed, 95 China wood, 50 Menhaden, 50 $ ~ ~ ~ ~ ~
{ .............{
} .............
JELLY
FORMED
N o t any Not any Not any Not a n y Large amount-1 in. in 6 tube Large amount--'/n in. in 6 tube Fair amount--'/a in. in 6 tube Small amount--'/E in. in 6 tube Very small amount
] . . . . . . . . . . . Not any in. ] '. { Fairt u bamount--'/a e } ............. ~ ~ d & Very O small amount
5/s
test-
X s/s testX
S/R
test-
X
'/E
test-
in 6 X
S/R
test-
~,
' '
' ' ''
' ' '
' '
i............. { { i
China wood, 40 Menhaden, 30 Linseed, 30 China wood, 20 Soy bean, 40 Menhaden, 40
X
.............
Good amount--'/a tube
in. in 6 X s/s test-
Small amount--'/s tube
in. in 6 X s/j~test-
F a t t y acids from a varnish containing East India copal, rosin, a n d a n oil mixture made up of 2 ; per cent China wood, 2 5 per cent menhaden, a n d 50 per cent linseed gave a fair amount of jelly, about '/FJ in. in 6 X 3 / 4 test-tube. One containing roiin a n d China wood oil alone gave results previously found for 100 per cent China wood; a n d one containing Sierra Leone copal and linseed gave t h e negative test. PHYSICAL CHARACTERISTIC3
I N D I C E S OF R E F R A C T I O K
T h e following readings were obtained: Composition of Mixtures from which t h e Acids were made Per cent Linseed, 100..
....................
Readings Calc. t o 20' C. 1.4666
Difference
....
~ ~ ? ~ $ o 9% o d ,.................
1.4707
+0.0041
China Good, Linseed 90
1.4775
+0.0109
1.4824
+O.OlSS
1.4895
+O .0229
Linseed, China wood, 80 2o Linseed China dOod, 50 5o
] ] ................. ] .................
1 .................
These were repeated several times a n d fair checks were obtained in t h e cases where t h e acids came from the oils direct, b u t where they came from varnishes t h e values were not in good agreement. Readings were taken on mixtures of t h e other oils with linseed b u t the change in reading with t h e increase of the adulterating oil was too small t o be of a n y value.
P e r cent Linseed, 100. Soy bean, 100. Cottonseed, 100. Menhaden, 100.. China wood, 100.. China wood, 50 Linseed, 50 China wood, 20 Linseed, 80
These oils were obtained from Toch Brothers. E. W.Boughton, Bureau of Standards, Technical Paper 65. 8 Proceedings of the Sezrenth International Congress of Applied Chemistry, Sec. 1, p. 96. 1 2
xlor of oil large p a r t is s..L'd; characteristic odor A small p a r t is solid; no odor detected
1 ............... { A
] ............... { ~~~~a~~''p$~o ] ............... Solid; fishy odor large p a r t is solid; odor of China China wood. 50 ...............{ A wood Soy bean, 50 small p a r t is solid; no odor de...............{ A tected g;eyf(j 20 ] A small p a r t is solid; no odor dep&;n-~~~,'," ] ...............{ tected ACKNOWLEDGXENT
T h e writer wishes t o express his thanks t o Dr. E. F. Ladd who not only suggested t h e work, but gave advice and encouragement while it was in progress. CHEMICAL LABORATORY NORTHDAKOTA AGRICULTURAL COLLEGE N. D. AGRICULTURAL COLLEGE,
JELLY TEST
This was carried out as given by Boughton,3 except t h a t the fatty acids were used instead of t h e oils and t h e time of heating was increased t o 2 hrs. A 5 g. sample was used in each test. The results obtained b y using acids from the oils direct are found in table near t o p of next column. Mixtures of soy bean and China wood a n d cottonseed a n d China wood gave just as good results as linseed a n d China wood, while mixtures of linseed a n d soy bean and linseed a n d cottonseed gave no jelly.
PHYSICAL CHAdACTERISlICS
................... Liquid .................. Liquid ................ Liquid ............... Solid; fishy odor .............. Solid; chara,teristic
.
THEFORMATION OF AMMONIA AND AMINES IN CANNED SARDINES DURING STORAGE By F. C. WEBER AND J. B. WILSON Received June 17, 1918
I n the investigations conducted in the sardine industry of Maine b y this laboratory during the seasons of 1913 t o 1916, numerous determinations of ammonia were made in following t h e degree of spoilage of t h e fish. I n this phase of the work, two methods of determining ammonia, namely, titrating a n d nesslerizing t h e volatile alkaline material, were employed.
I 2 2
T H E JOLiRLVAL O F 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
The methods used were as follows: NESSLERIZING1-Weigh out three I-g. samples and transfer to large test-tubes, or small Kjeldahl flasks, with 2 0 to zj cc. of water. Add 3 cc. of I O per cent solution of potassium carbonate, 3 cc. of 15 per cent solution of potassium oxalate, and a little heavy cylinder oil. Pass a strong current of air through this mixture for 4 hrs. Collect the ammonia in 5 cc. of N/2o sulfuric acid contained in a IOO cc. volumetric flask. After aerating, dilute the contents of the flask to the I O O cc. mark. Transfer a 25 cc. aliquot portion to a IOO cc. volumetric flask and dilute nearly to the mark. After adding z cc. of Nessler solution and making to volume, compare the density of the color of the solution in a Duboscq colorimeter with that of a known standard. TITRATIoN1-The same procedure as above was followed to the point of dilution of the contents of the IOO cc. flask. After aeration, the excess of acid was titrated with N / j o alkali, using methyl red as the indicator. The results are calculated to milligrams of nitrogen per IOO grams of material. In fish and fish products, the results by the titration method constitute the total volatile nitrogen (ammonia and amines) and are here considered as such. In order to obtain a sufficient quantity of total volatile nitrogen on which to make a separation of the ammonia and amines, thirty 3-8. samples were aspirated, using the procedure described for the titration method. SEPARATION OF AMMONIA AND AaiINgs2--T!nite the distillates obtained by the preceding method in a large dish, make distinctly acid, and evaporate until the volume is about 400 CC. Wash into a 500 cc. graduated flask and cool. If the total volatile nitrogen exceeds a strength equivalent to 30 cc. N/IO in amount, make up to 500 cc. and transfer a portion equivalent to 20-30 cc. of N/IO to another joo cc. flask. If the amount of total volatile nitrogen is less than the equivalent of 2 0 cc. N/IO add enough of a standard solution of ammonia to raise the content to that point. Add to the liquid in the joo cc. graduated flask I O cc. of a solution made by mixing equal parts of 2 0 per cent sodium hydroxide and 30 per Cent sodium carbonate. Fill to the mark with water. Now add 0.1 g. of yellow mercuric oxide for each cc. of N / r o acid to which the total volatile nitrogen present in the solution is equivalent. Stopper tightly, cover with a black cloth to exclude light, and shake I hr. Allow to stand 12 hrs., or over night, to permit the oxide of mercury to settle. Separate from the mercuric oxide by forcing the liquid through a tube containing a little absorbent cotton, using a moderate blast. Discard the first 20-30 cc. Distil zoo cc. of the filtrate in duplicate into standardized acid. The amount of acid required is equivalent to the nitrogen present as amines. The total volatile nitrogen minus the amine nitrogen equals ammonia nitrogen. Express the quantities as milligrams of nitrogen per IOO g. of sample. The separation and estimation of t h e alkylaniines composing t h e “amine” fraction of t h e total volatile nitrogen were made according t o our own m e t h ~ d . ~ I n t h e analysis of experimental packs of sardines made from fresh fish and from fish which had been allowed t o stand for 24 hrs., it was found t h a t the. results b y t h e titration method were enormously higher, amounting in some instances t o nearly twice t h e amount obtained by the nesslerizing method. From t h e nature of the product and t h e well-known fact t h a t a m k e s are formed in the decomposition of fish, fish brine 1 Adapted from methods of Folin, Macallum, and Farmer, J. B i d . Chem , I I (1912), 500, 523. 2 Adopted from method of Erdmann, J . Bid. Chem , 8 (1910), 41. 3 “A Method for the Separation and Quantitative Determination of the Lower Alkylamines in the Presence of Ammonia,” J . Biol. Chem , (21 35 (1918), 385.
Vol.
11,
No.
2
being a source of trimethylamine, these substances were naturally regarded as being t h e cause of t h e discrepancy. This difference in the values for ammonia, as determined b y these two methods, was noted in other instances where analyses were made at t h e time of packing and after t h e same packs had stood. A change evidently takes place in t h e packed goods on standing, with t h e liberation of substances having a n alkaline reaction (amines) and which are determined as ammonia by t h e titration method. Unfortunately t h e method of determining ammonia by nesslerizing is not reliable in t h e presence of amines. The difference in t h e values, determined b y t h e methods employed for ammonia, while giving some indication of t h e amount of amines present, is not even sufficiently accurate t o warrant regarding it as a n approximate measure of t h e amine content. I n packs of fresh and 2q-hr.-old fish (sampled a short time after packing) the average of two determinations calculated t o a water- and fat-free basis, expressed as milligrams of ammoniacal nitrogen per 100 g., was: Nesslerizinx Fresh fish, not in pickle.. . . . , . . , , . . . . . 1 0 7 . 8 24-hr.-old fish, not in pickle.. . . . . . . . . . 121. 7
. ..
Titration 147.6 189.6
After these packs had stood for 19 mos. t h e total volatile nitrogen, which was separated into ammonia and amine nitrogen, was again determined on samples of t h e pack made from t h e fresh fish. The following results, expressed as milligrams of nitrogen per IOO g. on a moisture- and fat-free basis, were obtained: Total Volatile Ammonia Amine Nitrogen by Nitrogen by Nitrogen by Titration Difference Separation Fish ‘/z hr. in pickle’. .. , 271.8 49.5 222.3 Fish: 1 hr. in pickle. .. 239.4 43.7 195.7 Fish, 1 1 / 2 hrs. in pickle ... . 223.0 34.2 188. a
. . . ..
1 T h e pickle employed was approximately a saturated solution of common salt.
T h e values for total volatile nitrogen in this tabulation correspond t o t h e results shown b y t h e titration method above. The total volatile nitrogen b y t h e titration method, on samples of these particular packs when they were 7 mos. old, amounted t o 203.1, 206.1, and 204.5 mg. of nitrogen per IOO g., respectively. These results indicate t h a t upon standing t h e packed sardines show a marked increase in t h e quantity of total volatile nitrogen contained, t h e greater part of which is in t h e form of amines. On extracting a little more t h a n a kilogram of t h e sardines from this pack with I’/* liters of 50 per cent alcohol, 2 8 0 mg. of total volatile nitrogen were obtained b y t h e titration method a n d 189 mg. by t h e nesslerization method. About 1.5 t o 2 . 0 g . of a white crystalline material having a strong ammoniacal odor and very deliquescent was obtained when this alcoholic extract was evaporated after making acid with hydrochloric acid. There was a considerable loss of total volatile nitrogen during t h e evaporation; nevertheless determinations of total amines on t h e residue obtained showed t h a t 62.46 per cent of t h e alkaline material present was in t h e form of amines. The following results were obtained on samples of sardines from commercial packs which had been kept a t a practically uniform temperature and which were 2 , 4, and 6 yrs. old a t t h e time the determinations were made.
'Fe b . ,
I 9x 9
T H E J O U R A V d L O F IAVL?L7STRIALA N D E N G I N E E R I X G C H E M I S T R Y
TABLEI-DETERMINATIOXO F AMIMONIA AND AMINES I N No. Water Years Per Description . Packed cent 533A Best grade. Packed i p 1912. Good 55.88 533A1 appearance on opening c a n s . . , , , . 54.15 533B Poorer grade. Packed in 1912. Very 57.08 533B1 good appearanceon opening cans. 55.40 Packed,in 1910. Poor appearance on 50.01 533C 53361 opening cans... , , , , , , , , , , , , , , , . , ,. 533D Packed.in 1908. Poor appearance on 57.75 533D31 opening cans . . . .... 1 Determinations made on 3.0-g. samples. 2 Determinations
SAIMPLE S O .
1 11 1
.
.............
{ { { 2 { 2
...
COMMERCIAL P A C K S O F S A R D I N E S A F T E R
LONGP E R I O D S
123
OF STORAGE
Total Alkaline Volatile Material' Fat Mg. Nitrogen (N) per 100 g. Mg. Nitrogen (N)2 Percentage Per TitraDifferper 100 g. of Total cent tion Nessler ence Total Ammonia Amines Ammonia Amines 29.3 46.9 20.1 26.8 42.9 57.1 20.73 46.6 17.3 23.4 46.6 15.6 31.0 33.5 66.5 21.76 40.8 17.4 24.9 44.7 17.8 26.9 39.8 60.2 18.73 39.6 14.7 20.95 43.1 18.9 24.2 37.7 5.0 32.7 13.3 86.7 33.60 33.8 14.0 19.8 37.2 5.9 31.2 15.9 84.1 .. 45.9 6.4 39.5 13.9 86.1 21.94 60.6 14.9 45.7 51.1 8.6 42.5 16.8 83.2 ... .. .. ., 69.3 .. Lost ,, .. and separations made on 50.0-g. samples.
...
Determinations of ammonia b y t h e titration and nesslerizing methods were made on 3-8. samples. The volatile alkaline material for the separation of ammonia and amines was obtained in these determinations from 50-8. samples, in duplicate, using t h e same proportional amount of I O per cent carbonate of soda a n d ~j per cent potassium oxalate as used in t h e ordinary determination of ammonia. I n addition, about 11,"~ g. of potassium fluoride were added t o t h e flasks containing t h e samples t o prevent decomposition during t h e time of aspiration, which was carried on for 5 hrs. The volatile material, ammonia and amines, was carried into an excess of N / I O acid. At the end of t h e operation t h e excess of acid was titrated, a n d t h e total alkaline material determined. Duplicates agreed closely, t h e results being taken as the total number of milligrams of volatile alkaline nitrogen per IOO g. of material. The separation of ammonia and amines was made on t h e total volatile alkaline material obtained b y combining t h e portions from t h e two 50-8. samples. T h e results b y t h e titration method on t h e 3-5. samples, which is the ordinary method of determination, agree b u t fairly well with t h e amounts obtained on t h e 50-8. samples as here used. It was found t h a t t h e jo-g. samples continued t o give off a small amount of ammonia, even after air had been passed through them foi a period of 5 hrs. All t h e alkaline material was obtained from t h e 3-8. samples in 3 t o 4 hrs. of aspiration. I n later work a sufficient number of 3-8. samples were taken for t h e determination t o obtain an amount of alkaline material on which this separation could be made. The difference between t h e amounts of ammonia obtained b y t h e titration and nesslerizing methods is again shown t o be very great, although in some instances it agrees fairly well with the amount of amines actually determined. The determinations indicate t h a t a change in t h e relative amount of ammonia a n d amines occurs, t h e degree depending on t h e time t h e fish remain in t h e cans. The total amount of alkaline material appears t o be quite constant in t h e 2- and 4-yr.-old goods, b u t has noticeably increased in t h e 6-yr.-old pack. The quantity of ammonia, both in t h e actual amount obtained and in t h e percentage of t h e tot a l volatile nitrogen, decreases, while t h e increase in t h e percentage amount of amines corresponds directly t o the age of t h e goods. Eliminating one determination, which shows a very low ammonia content on t h e 2-yr.old packs, t h e average percentage amount of ammonia of t h e total is 38.7, while t h e three determinations on t h e 4- and 6-yr.-old packs show only 15.5 per cent of
..
..
t h e total alkaline material as ammonia, with t h e corresponding increase of from 61.3 t o 8 4 . j per cent, respectively, in nitrogen as amines. An experiment was conducted t o ascertain whether these changes in the canned fish could be followed during shorter periods of standing. A pack of a little more t h a n half a case of quarter oil cans was made from fresh fish which had been only a short time in brine. After t h e fish were steam cooked and dried, under ordinary commercial conditions, t h e heads were removed, t h e portion used for packing ground in a meat chopper, and t h e whole thoroughly mixed in a large pan, a representative sample (534A, Table 11) being taken for analysis. T h e ground meat was t h e n packed in t h e cans which were sealed and processed for 1 ~ / 4 hrs. a t 2 1 2 O F. Samples (534B) were taken from several cans directly after they had been processed. Other samples were taken from this pack after i t had stood a t room temperature for I, 2 , 3, 4, 6, 18, and 36 mos. Water, f a t , and t h e total alkaline material were determined, and t h e separation of a m monia a n d amines was made. T h e results for t h e total alkaline volatile material, reported in Table 11, were obtained b y t h e titration method which was here employed for t h e determination of ammonia, using 3-8. samples. Also in this experiment for t h e separation of ammonia a n d amines, 50-8. samples were used, with t h e exception of the determinations after t h e 4-mo. period of standing, when thirty 3-8. samples were employed. The total volatile alkaline material obtained was combined t o make an amount sufficient for t h e separation. The ground fish meat, after steaming a n d drying, and before being packed, contained 13.3 mg. of total volatile alkaline material per I O O g. of meat, of which 7.4 mg., or 55.6 per cent, was present in t h e form of ammonia, and j.9 mg., or 44.4 per cent, i n t h e form of amines. After being processed in the cans for 1 3 / ~ hrs. a t 2 1 2 ' F. t h e total volatile alkaline material per I O O g. of this meat had increased t o 39.7 mg., of which 63.6 per cent was present as ammonia and 36.4 per cent in t h e form of amines. During t h e processing, therefore, an increase in t h e amount of ammonia, with a corresponding decrease in the amount of amines, occurs. There is an increase in t h e actual amounts of both the ammonia and amines. Standing produces a gradual increase in t h e amount of total alkaline material obtained from t h e meat, due t o t h e formation of alkylamines, t h e ammonia content remaining fairly constant, with t h e exception of a decrease in t h e pack a t t h e 6-mo. period of standing. The results, expressed in percentage of t h e total
T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
Vol.
11,
NO. 2
TABLE 11-CHEMICAL CHANGES,ON STANDING, IN GROUNDWHOLEFISH STORED AT ORDINARY ROOMTEMPERATURE Packed in quarter oil cans, processed 1S/a hrs. a t 212’ F. Total Alkaline Volatile Material Mg. Nitrogen (N) Mg. Volatile NitroPercentage Time Water F a t per 100 g. gen (N) per 100 g. of Total SAMPLE Packed Per Per Titration AmmoAmmoDescription Months cent cent Method Total nia Amines nia Amines No. 5348 Ground fish meat before packing in c a n s . . . . . . . . . . . . 0 67.01 9.07 14.0 13.3 7.4 5.9 55.6 44.4 0 65.75 9.13 30.3 39.7 25.3 14.4 63.6 36.4 534B Ground fish meat after packing and processing. . . . . . 1 65.85 9.02 42.0 46.8 27.2 19.6 58.1 41.9 534C Ground fish meat after packing and standing.. . . . . . . 2 67.00 8.7% 47.8 47.3 22.6 24.7 47.8 52.2 534D Ground fish meat after packing and s t a n d i n g . , . . , , , . 3 66.40 8.69 52.5 53.1 24.2 28.9 45.6 54.4 5343 Ground fish meat after packing and standing.. 4 66.64 8.18 55.0 54.3(a) 25.8 28.4 47.7 52.3 534F Ground fish meat after packing and standing.. 6 66.25 9.23 55.6 55.6 a ) 19.1 36.5 34.3 65.7 5340 Ground fish meat a f t e r packing and standing.. 64.79 9.93 69.0 69.01~) 35.8 33.2 51.9 48.1 534H Ground fish meat after packing and standing.. . . . . . . 18 534K Ground fish meat after packing and standing, normal cans .......................................... 36 78.9(a) 41.3 37.6 52.4 47.6 534K Ground $sh, meat after packing and standing, swell cans, springers”. 36 ... 82.4(a) 44.0 38.4 53.4 46.4 ( a ) These determinations were made on the combined volatile alkaline nitrogen obtained from thirty 3-g. samples.
...... ...... ......
...
.............................
volatile alkaline material, point more clearly t o a reduction in the quantity of ammonia, with a corresponding increase in the relative amount of amines, up t o and including the 6-mo. period of standing. T h e figures show t h a t this ammonia decreased from 63.6 per cent in the wesh processed meat t o 34.3 per cent after standing 6 mos., while t h e amines increased f r o m 36.4 per cent in t h e fresh processed goods t o 65.7 per cent. The same determinations were made on samples of this pack after it had stood 18 and 36 mos. A t the end of t h e 36-mo. period of storage, analysis was also made of the contents of a few cans which were just beginning t o swell (“springers”). The total volatile material continued t o increase in t h e case of t h e cans stored for 18 and 36 mos. A more marked increase over the amount found a t the end of 6 mos. occurred during t h e first 18 mos. t h a n during the last year and a half. The incipient swell cans contained b u t a slightly greater quantity of volatile alkaline material t h a n the normal cans. The separation of ammonia and amines in t h e volatile alkaline material gave, in all three cases, results quite different from those obtained a t the earlier periods of examination, particularly those of the 6-mo. period. After standing 18 and 36 mos. the volatile alkaline material was composed of practically equal parts of ammonia and amines. Table I11 gives t h e results of the analysis of different packs of sardines, showing t h e influence of time a n d temperature of storage on t h e formation of ammonia a n d amines. P a r t of these packs were stored for different lengths of time a t ordinary room temperature and a t a temperature of 33O F., j u s t above freezing. The fish used t o prepare Packs 599, 600, and 601 were d r y salted when taken from the water a t the rate of sack of salt per hogshead (1000lbs. of fish), T h e fish had been in the salt for the periods of time indicated in t h e table. Pack 603 consisted of fish which were surrounded with a n ice a n d salt mixture during transportation, a n d a t no time in contact with salt or pickle. T h e fish composing Pack 604 were “feedy” fish from Grand Manan, N. B. They were gorged with feed which did not have the appearance of shrimp. The fish were sheam cooked, dried, packed, without being eviscerated, in one-quarter cans, and processed for hrs. in a boiling water bath. T h e packs were prepared from fish which varied greatly in preliminary treatment, in regard t o “feedy” condition and length of time in salt. As soon as the processed cans were
... ...
...
...
cool, samples were prepared and analyzed. The remainder of the packs was placed in shooks and stored for future examinations. At the time t h e analyses were made, the viscera of some of the fish were separated from the meat and determinations were made upon the whole fish, as taken from the can, upon the meat of t h e fish, and on the viscera and contents. As seen by the results, these variations in the preliminary treatment of t h e fish and their condition had no connection with the formation of ammonia or amines during the time of storage. Except for slight variations in the results of the analyses of the whole fish as removed from the can, the fish meat alone, and t h e viscera and contents, there is no indication t h a t greater changes took place in either of these portions of t h e fish. The quantity of total volatile alkaline material gradually increased in amount during storage a t ordinary temperatures in all three of the divisions made for analysis, but when stored a t a temperature of 33’ F. the formation of total volatile alkaline substances was greatly retarded. The relative quantities of ammonia and amines composing t h e total volatile alkaline material change during storage. After processing, the results indicate t h a t practically two-thirds of the total alkaline nitro-. gen consists of ammonia a n d one-third of amines. After storage these proportions have changed, t h e volatile alkaline material consisting of about equal parts of ammonia and amine nitrogen. Storage a t low temperature, while causing a decrease in the total quantity of ammonia and amines apparently does not affect t h e relative amounts. The quantity of ammonia a n d amines in t h e storage samples is also about equally divided. I n Table IV1 are given t h e quantities of monamine, diamine, and triamine composing the fraction of t h e total volatile alkaline material designated as t o t a l amines in Table 111. The method for this determination was not available a t the time the first examination of these packs were made, consequently t h e d a t a f o r t h e separation of t h e total amine fraction into i t s different constituents are given only for the longer periods of storage. It is seen t h a t by far the largest part of the volatile alkaline. material, consisting of amines, exists in t h e form of triamine in canned sardines stored for t h e lengths of time indicated. 1
385.
For the method of determination see J . B i d . Chcm., 121 35 (1918)-
Feb., 1919 cn P W
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 n E M I S T R Y m
m
cn
P 0
&
3
3
m 0 0
Y
.. .. .. .. .. . .. .. .. .. .. .. .. .. .. .. .. ..
. . . . . . .............. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. ..
.. .. .. .. .. .. . . . . . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. / :: :: :: :: ' ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... / .. .. .. .. .. .. ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... .............................. i . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . :...... ........................ : ~. .. .. .. .. .. .. .. .. .. .. .. .. . . . .. .. .. .. .. .. .. . . . :. .. . . p; .......................... Pa.--.
~
I . . . . . . I t
c
UmWw
??"P E; NWolO
t m
W-
N NP
W e
0
W P
I
%%e: &&LL N
W
N
W
N
"v: ? PI" ? " : P mo -u m W W
-
wP: ? c"? p w : w(n 0 olm m w b
-
. N . . . .. .0 0. W. -.. .. .w .NVI.. . .. . 0 .," . .. O O N . . o m . . 00 C U . .
.. ..
molmol
mvlcn
ololcn
L ;POL : owow
OF?: cnffiol. W P U
O W U .
wu w0W uN0mU0.:.:
- c c N
N r N
N r r
u m m u . -wm
r ow mmu
m
.. ..
.. .. .. .. .. ..
P m P w
mlpw
W r N W
Nmu
mcw uwol
V N W p : ."Ou: I"??: :
..
.* ..
.. .. .. .. .. ..
..
..
N
Ncnol
N
W
*
. :.
P OIPW
wr-2
- W
"7: m P N
W
N
wa : :
-
U
N?:
N
w: .w:
N m -
W
N
vr :
( r , N
7:?:: W
N
07:N::
..m .--.. . ... ... ...
-0..
;ow:
.-. . .
.-w-.m. .. . .. ... .-. . .. : m.. . c- N
??:: Ne
"
: : ?c nPNI : :
..b
: : i:: : ;o::
N
: c": : : r
.
..
Pol P O
N?: N . .
w . . r?: w:: m o W
Y: m
.. ..
cnol
:
IP olcncn
w oom
-
::
..
P
..
N
N +a
wcnm W
N
0:f"
v)w N U
?Po: -4-
I
c*:: W
..
.. .. .. .. .. .. . ...... :
7 : : : .-: : : PP :. :. : : b:: :: N r w . . P . .
..
..
.. .. .. .. .. .. : ......
? : : :!-:: : ? : : : : :. :. N eo.. .e.. . N . . . .
..
-
W NUN
: ? :: : : U
.
.
P
*
mmm.
& &bo&
m ol+m
P
0..
N N W
vlcw
w??:
m wcnm W
N
w;o
P
-0:
N N
.Nm: \oP
Pol
my:
.. .. o. l.P . r w c U.
o l u * m
N
w
r
(nul
W?: w w
?: W
wm :
U . . P .
I
P
w
c
n
: " : : 0'
-w : : w
?:: w
c?
V
::
i"::
e 1 W
IPP
P":
c n m . wm : : .-: u .
"?Pa: :
.. ..
03
m
pop: P : :
da VIP(* .. .. .. .. .. .. ? "??: :
.. .. .. .. .. ..
? ??? : w p r : ??PO: cnool\o
:
oom
? NN?: :
w
.. .. .. .. ..
~ W I P
-am.
e m -
.. .. .. .. .. .. ...... .. .. .. .. .. ..
PAW.
N -e-
vi
.. .. .. .. .. ..
-
olcnvl wm ?pop' :: . 01
C
w: r: ": v l m -
": :
c n w
P: 0 : : w ololcn
?PI": N-m.
m0-
NUN
-
:
.-0 .- : : UPol.. 0-w
126
,
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 C H E M I S T R Y
The results for triamine do not indicate a difference in amount for t h e separations of t h e canned fish as made for analysis. I n respect t o t h e different portions of t h e fish analyzed, there does not appear t o be any uniform increase or decrease in t h e amount of triamine in relation t o t h e different periods or temperatures of storage. Monamine and diamine are present in very small amounts and about equal quantities at the end of 1 5 and 1 8 mos. At the end of 32 mos. of storage no monamine was found, while t h e amount of diamine had increased, in some instances being double or more t h a n double t h e quantities found at ~j mos. The temperature of storage apparently has no influence on t h e quantities of q o n a m i n e and diamine found.
11,
No.
2
relation t o t h e keeping qualities of sardines in respect t o t h e appearance, softness, or texture of t h e fish. It is noted, however, t h a t when cans of t h e long standing commercial packs were opened, t h e fish constituting t h e 4- and 6-yr.-old goods were decidedly soft. These contained t h e largest amounts of amines. Other work has shown t h a t t h e quantity of ammonia and amines in t h e canned sardines has a decided bearing upon t h e detinning of t h e interior of t h e cans. ANIMALPHYSIOLOGICAL CHEMICAL LABORATORY BUREAUOF CHEMISTRY, u. DEPARTMENT O F AGRICULTURE WASHINGTON, D. C.
s.
FUMIGATION WITH FORMALDEHYDE1-A FOR THE PERMANGANATE-FORMALIN
SUBSTITUTE METHOD
By DAVIDWILBURHORN Received May 8, 1918
COKCLUSIONS
The d a t a collected in the analyses of old packs of sardines and of t h e experimental packs under known conditions of storage show t h a t marked changes in t h e quantities and relative amounts of ammonia and amines take place in t h e canned fish on standing. I n the case of packs composed of ground meat, these changes could be detected a t I mo. intervals, and amount, in t h e first few months, t o an increase of approximately 5 mg. of alkylamines per I O O g. of material per month. Directly after processing, the volatile alkaline material obtained by t h e method of determination contains practically two-thirds ammonia and one-third alkylamines. During storage a t room temperature t h e proportions appear t o change slowly, until after a long period of standing t h e total alkaline material is about equally divided between t h e ammonia and amines. When stored a t a temperature just above freezing the total quantity of volatile alkaline material produced is much less t h a n t h a t produced when stored at ordinary temperatures. Table I11 shows t h a t t h e samples stored above a freezing temperature for 32 mo. contained in most cases less volatile alkaline material t h a n was found in t h e sardines held a t room temperature for a period of I j mo. The relative amount of ammonia and amines formed a t t h e lower temperature of storage remains t h e same as t h a t composing t h e total volatile alkaline material formed while t h e sardines were standing a t room temperature. The amines composing this volatile alkaline material consisted in most part of triamine which amounted t o practically 80.0 per cent of t h e total. Monamine and diamine are also present during t h e earlier periods of storage (I j and 18 mo.) b u t in much smaller quantities. At t h e end of t h e 32-mo. storage period no monamine was found, b u t t h e diamine had increased 50.0 per cent and over in some instances. The difference in’the rate of formation of ammonia and amines a t a lower temperature of storage and a t room temperature suggests t h a t these changes may be caused in some instances b y bacterial growth. Anaerobic, spore-bearing, gas-forming bacteria which have been found associated with these fish produce both ammonia and amines when grown on media containing fish protein. whether the quantities Of ammonia It is and amines in t h e canned product have .any direct
Vol.
The object of this paper is t o explain, defend, and justify t h e use of bleaching powder and formalin in t h e fumigation of rooms. The common method using permanganate has become prohibitively expensive since the war began. The dichromate method uses an unstable and corrosive acid mixture of formalin and is chemically of low efficiency. The bleaching powder method will be shown in this paper t o be to-day t h e cheapest and best available method for t h e fumigation of rooms. I n t h e past t h e main difficulty in dealing with new methods proposed for fumigations has been t o learn how much formaldehyde gas actually was evolved* and how t h e proposed methods compared with t h e welltried permanganate method. I n this paper t h e method using bleaching powder is compared quantitatively with t h e permanganate method and with t h e dichromate methods, and a simple apparatus and procedure are described whereby t h e yield of formaldehyde gas in any wet method may be determined. The present state of knowledge with respect t o just how much formaldehyde gas must be set free in a room t o get satisfactory germicidal action may be fairly gathered from t h e very different quantities recommended b y several authorities, and brought together in t h e following table: TABLEI-YIELDS
OF
FORMALDEHYDE GAS BY SEVERAL FUMIGATION
METHODS in Which Liquid Formalin Is Used FormalFormalin FormalFormaldehyde used for Chemical dehyde dehyde in t h e air CHAR1000 efficiency of gas gas of the room cu. f t . ACTERISTIC methods given off a t 68’ F. VolumeCHEIIICAL Cc. Grams Cu. ft. Per cent Per cent Permaneanatez 5nn 17 5 75 n 7 in n 3111 ~ e r m a n i a n a t i a : : : : 296 35;6 42.3 1.20 0.120 Dichromate4.. . . 473 13.9 26.5 0.75 0.075 Alum and lime6., 177 10.0 14.0 0.28 0.028 B-Methods in Which Solid Paraform Is Used Formaldehyde Paraform Chemical FormalFormalin the air used for efficiency dehyde gas dehyde gas of the room 1000 cu. f t . of methods given off a t 68” F. VolumeGrams Per cent Grams Cu. f t . Per cent 283: 45.0 122.2 3.49 0.350 25 45.0 10.8 0.31 0.030 45.0 12.9 0 37 0.037 308 A-Methods
.
The calculations for this table were made f r o m the most reliable d a t a available and upon t h e assumption 1 Abstract of a paper presented before Section C, American Association for the Advancement of Science, Pittsburgh, December 29, 1917. * Numbers refer t o corresponding numbers in “References,” p . 129.
