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
864
To take 5 cc. of oil in a “cassia” flask, oxidize with whatever permanganate the flask will hold, and report, without more ado, the volume of unoxidized oil as cineol, is not what I have advised, nor is i t sufficient to ensure useful or reliable results. The examination of the cineol isolated is indispensable, not only for the purpose of detecting any unoxidizable substances, as camphor or paraffins, but also as a check on the completeness of the oxidation; for it not infrequently happens that a n apparently satisfactory oxidation is yet incomplete, owing to some unnoticed irregularities in conditions or manipulation. But it is always possible t o ascertain this, in the manner suggested, and unless this is done the results are inevitably uncertain and devoid of meaning. Umney’ states: “We have shown quite recently that this process is of little value for eucalyptus oils.” This alleged demonstration has, however escaped me, unless he refers to Bennett’s experiments, in which case, I admit, the conclusion would appear t o be well’founded. But if, in a well conducted oxidation, 7 0 per cent of reasonably pure cineol has been isolated, I consider it safe t o assume that the oil in question contains really a t least that amount, for, in the present state of our knowledge, the formation of cineol by oxidation of any other constituent of the oil, must be regarded as improbable. Hence, I maintain t h a t the method, properly executed, cannot give results higher than the truth. It is possible, of course, in a hasty assay, t h a t a 7 0 per cent oil may yield 80 per cent or even 90 per cent of unoxidized product, but examination of the latter will immediately show its impurity, and incidentally the necessity of more careful repetition of the operation. But such results, due to faulty manipulation, should not be held up to the prejudice of the method, any more than in the case of a titration, where one has used an insufficient amount of the reagent. As regards a second criticism,Z that with oils low in cineol a loss occurs by oxidation of the cineol itself, especially in the presence of terpineol, I am quite ready to admit the possibility thereof, as the oxidation of cineol by excess of strong permanganate is a well known reaction. But what interests us here is the relative stability of cineol, and I have endeavored to show, and still hold, that it is possible so to conduct the reaction, that practically all of the oil except the cineol is oxidized with little, if any, loss of the latter. For oils containing less than 50 per cent cineol, however, the method is not to be recommended, as the large amount of reagent and time required make it tedious and impracticable. The increasing alkalinity of the solution also tends to cause a loss of cineol. But as such oils are in general inadmissible for pharmaceutical use, the difficulty is not serious. Modifications of the method have been tried, in the hope of simplifying the procedure, or shortening the time, but no decided improvement has resulted. An acid permanganate solution reacts very quickly, but the results are less uniform. The mixture of permanganate and magnesic sulfate (used to ensure neutrality) is so slow in its action as t o be impracticable. We have found, however, that it is not necessary t o keep the assay very cold, except in the first stages of the oxidation. As the reaction diminishes in vigor, the operation may be conducted at the ordinary temperature without apparent loss of accuracy. As regards the other methods suggested for the determination of cineol, the phosphoric acid and resorcinol processes are, in my experience, of little use in the presence of camphor or terpineol, and i t is exactly these compounds which it is most important to detect. FRANCIS D. DODGE
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LABORATORY OF THE DODGEAND OLCOTT Co. BAYONNE, N. J., July 13, 1914 1
LOC.cit.
2
Schimmel and Co., LOC.cit.
Vol. 6 , No.
IO
THE PRESENT STATUS OF THE GLASS BOTTLE INDUSTRY IN THE UNITED STATES The glass bottle and hollowware industries of the United States have undergone important changes during the last bottle “ season,” and both the automatic and semi-automatic bottle machines have been improved and more widely adopted since the last report on these industries.’ When one considers that the manufacture of glass bottles by the use of machinery has been practiced only twenty years, the status, of the mechanical blower is indeed remarkable. It was in 1882 that Phillip Arbogast was granted a patent wherein the method of prepressing a blank in a mold and then transferring it to another mold to be blown into finished form was claimed. This basic patent was sold t o D. C. Ripley, a flint glass manufacturer of Pittsburgh, Pa., and the process was first put into operation in the early nineties in the manufacture of small wide-mouth ware. It was employed in the production of fruit jars in 1896 and about five years later was first used in the manufacture of narrow-mouth bottles. Automatic machines came into use in 1904. At the present time 172 machines of this type are installed, an increase over last year of 2 1 ; a list of these installations follows: LOCATION AND NUMBER O F AUTOMATIC MACHINES INSTALLED American Bottle Co., Newark, Ohio.. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 This company manufactures beer, malt and water bottles. 210 gross of pint beer bottles and 165 gross of quart beer bottles are produced in 24 hours. American Bottle Co., Streator, I l l . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24 17 six-arm machines are installed. Each machine produces 140 gross of quart beer bottles and 170 gross of pint beer bottles in 24 hours. 7 tenarm machines, each of which will make 150 gross of quarts or 230 gross of pints in 24 hours, make up the remainder of the equipment. 11 Ball Brothers, Muncie, I n d . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . This firm manufactures fruit jars. 14 Charles Boldt Glass Co., Cincinnati, Ohio.. . . . . . . . . . . . . . . . . . . . . . . . . All kinds of liquor ware. 4 Dominion Glass Co., Montreal, C a n a d a . . . . . . . . . . . . . . . . . . . . . . . . . . . . General line. 4 Dominion Glass Co., Hamilton, Ontario.. . . . . . . . . . . . . . . . . . . . . . . . . . . General line. 3 Dominion Glass Co., Wallaceburg, Ontario., . . . . . . . . . . . . . . . . . . . . . . . Beer bottles and flasks. 1 Dominion Glass Co., Redcliffe, Alberta. . . . . . . . . . . . . . . . . . . . . . . . . . . . . Beer bottles. 1I Hazel-Atlas Company, Washington, Pa.. . . . . . . . . . . . . . . . . . . . . . . . . General line. 3 Hazel-Atlas Company, Clarksburg, W. V a . . . . . . . . . . . . . . . . . . . . . . . . . . General line. 3 Heinz Company, Sharpsburg. P a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Condiment wares. 22 Illinois Glass Co., Aiton, I l l . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Liquor, prescription and packers’ wares. Total number of machines to be installed, 24. 5 Illinois Glass Co., Gas City, I n d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . General line of prescription and liquor ware. 2 Northwestern Company, Toledo, Ohio,. . . . . . . . . . . . . . . . . . . . . . . . . . . . Catsup and brandy bottles. 1 Owens Automatic Bottle Co., Toledo, Ohio.. ........................ Experimental plant. Owens Bottle Co. Fairmont W V a . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 Liquor, cats;p and grape-;uice bottles. The 12 machines installed are all of the ten-arm type. The output is as follows: 4-ounce grape-juice bottles 360 gross in 24 hours; 9-ouncecatsup bottles, 220 gross in 24 hours; 16-oun;e grape-juice bottles, 195-200 gross in 24 hours. 5 Owens Eastern Bottle Co., Clarksville, W. V a . . ..................... Oval, round, square and flat prescription bottles, panels and other small ware. 4 Thatcher-Baldwin Company, Elmira, N. Y.. ....................... Milk jars. 4 Thatcher-Baldwin Company, Streator, Ill. ......................... Milk jars. Each of the machines installed turns out about 100 gross of quart or 130 gross of pint milk bottles in 24 hours. 4 Thatcher-Baldwin Company, Kane, P a . . . . . . . . . . . . . . . . . . . . . . . . . . . . Milk jars. Each machine produces 7 5 gross of quarts, 90 gross of pints, or 100 gross of 1/2 pints in 24 hours. 7 Whitney Glass Co., Glassboro, N. J . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Medicine bottles.
The small ware output of the Owens machine is as follows: */2-ounce round prescriptions, 60 per minute; I -ounce round prescriptions, 5 2 per minute; 2-ounce round prescriptions, 48 per minute; 4-ounce round prescriptions, 40 per minute; 8-ounce round prescriptions, 36 per minute; I 6-ounce round prescriptions, 28 per minute; and gz-ounce round prescriptions, 1 8 per 1 See Hamor, THISJOURNAL, 6, 951. On the glasses from which bottles are made, see Hamor, A m . Druggist, 62, 29; THISJOURNAL, 6 , 509.
T H E J O U R N A L O F I N D U S T R I A L A N D EiVGIAVEERING C H E M I S T R Y
OCt., 1914
minute. These data apply to practically all round, oval, French square, oblong and flat bottles. Panels from 4 ounces up are made a t the rate of 38 per minute. During the season 1g13-’14 there was not only a n increase in the number of automatic machines in operation, but an improvement in their mechanical equipment. The six-arm machine was changed to one of ten and, in some instances, to fifteen arms, thus increasing greatly the number of bottles produced. However, so far the Owens interests do not have a monopoly of the bottle industry, for the hand-operated machines and the semi-automatic contrivances still offer competition. But the time is rapidly approaching when the automatic machine will replace all other types as well as the hand blower: during the past year, several hand-blown ware manufacturers stated that unless some further concession was made in wages, they would install machines for producing narrow-mouth bottles, practically the only line now manufactured by hand. The season was also productive of a number of improvements in increasing the efficiency of the semi-automatic machines. Manufacturers are of the opinion that the work of one man only, the gatherer, is necessary in operating semi-automatic machines, and most of the improvements were directed towards reducing the number of men employed. The three-shift system is becoming more generally adopted, for it has been shown t h a t continuous production procured in this way is a great factor in helping to keep pace with the production of the automatic machines. STANDARD BOTTLE CAPACITY
Ever since the introduction of automatic machines, the operators of hand-blown ware factories and officers of the Glass Bottle Blowers’ Association have been much exercised by state legislation requiring exactness in the capacity of containers of all descriptions. By the old hand method it has always been impossible to produce bottles of exactly uniform capacity, this being evidenced by a provision in the wage scale which allowed variations below and above a given capacity. With the machine every bottle is of exactly the same capacity. Accordingly, while the disposition of state and municipal authorities t o require exactness in bottle capacities has been strenuously opposed by the hand blowers, machine operators have been rather inclined t o lend support to the formulation and enforcement of these statutes and ordinances. A convention of the sealers of the United States was held in Washington during May of this year, a t which ones in attendance urged that no enactments discriminatory t o the interests of the hand blowers be adopted. New specifications in accordance with the laws now in force in certain of the states were presented by officials of the Glass Bottle Blowers’ Association, and i t is reported t h a t they are regarded as reasonable in the matter of tolerance by certain of the authorities. FOREIGN COMPETITION
Germany, France and Austria-Hungary were the leading exporters of bottles to the United States during the fiscal year ending June 30th. The values of the imports of bottles follow: Value of bottles empty or filled Germany. . . . . . . . . . . . . . . $204,883 Austria-Hungary . . . . . . . . 143,086 France . . . . . . . . . . . . . . . . . 277,439 United Kingdom, . . . . . . . 77,485 Belgium. . . . . . . . . . . . . . . . 439
SOURCE
Value of bottles cut or ornamented $332,809 299.978 115,232 107,416 141,436
W. A. HAMOR N E W KENSINGTON, PA September 1. 1914
THE HYDROCARBONS OF UTAH-A CORRECTION Our attention has been called t o certain inaccuracies in the above paper.’ According t o Messrs. Richardson and Forrest,Z
86 j
“ I t is stated that Trinidad asphalt, supplied by the New York Testing Laboratory, contains 60.36 per cent of bitumen. This is a t least 4 per cent out of the way. It is stated that it contains 3.94 per cent of organic matter insoluble in CS2. In view of my (Richardson) investigations on ‘ The Proximate Composition and Physical Structure of Trinidad Asphalt’ published in Vol. 6 of the Proceedings of the American Society for Testing Materials, 1906, page 509, this is, of course, quite incorrect. It is, in reality, water of hydration in the clay which is lost on ignition on the detkrmination of the mineral matter. The authors say that Bermudez and Trinidad have a tarry odor, than which nothing could be more absurd. The percentage of bitumen in the specimen of Bermudez furnished the authors by the N. Y. Testing Laboratory is stated as 90.93. It must have been considerably higher than that. The ultimate composition of the samples of the various bitumens, as given, are entirely wrong. The authors have evidently attempted t o make a combustion on the material in its ordinary form, and not on the pure extracted bitumen. The percentage of sulfur, determined by the Eschka method is, of course, too low. They do not seem to be aware that the nitrogen in bitumens cannot be determined by a modified Kjeldahl method.” It seems t h a t we were mistaken in the kind of materials furnished under the names Refined Trinidad Lake Asphalt, Refined Bermudez Lake Asphalt, and Gilsonite, for we believed t h a t they were “pure” and not merely “purified commercial products which, however, were not free from all extraneous substances * * * *.” Samples of the hydrocarbons under discussion were re-analyzed by one of us (T. B. B.) and by the New York Testing Laboratory with the following results:
s.Y .T.L.
Trinidad R . A.
Bitumen soluble in CSn.. . . . . . . . . . . . . 56.9YG Mineral matter. . . . . . . . . . . . . . . . . . . . 3 5 . 6 Fixed carbon . . . . . . . . . . . . . . .. . . . . . . 1 2 . 0 T . B. B. Bitumen soluble in C S z . . . . . . . . . . . . . 5 J . 5 Mineral matter. . . . . . . . . . . . .. . . . . . . 3 5 . T Fixed carbon., . . . . . . . . . . . . .. . . . . . . . . . .
pi. Y
. T.L
Gilsonite
Bitumen soluble in CSI . . . . . . . . . . . . . . . . . Mineral m a t t e r . . . . . . . . . . . . . . . . . . . . . . . . Fixed carbon . . . . . . . . . . . . . . . . . . . . . . 13.6CG
Bermudez R. A.
Tabbyite
92.5% 5.1 12.9
94.7%
92.3 5.3
....
4.8
9.2
....
....
....
Wurzelite No. 1
Wurzelite No. 2
...
...
... ...
7.8%
7.5%
Our errors in Bitumen soluble in CS2 were due t o our not igniting the filtrates in order t o detemine the insoluble matter t h a t passed through the asbestos filtering medium. What we reported originally as Fixed Carbon were in reality the nonvolatile residues, minus ash, left from the fractional distillations, as shown in our Table IV.’ Through a n oversight a n explanation of this was omitted. When determined according t o the standard method for the proximate analysis of coal* very much lower results are obtained, as indicated above. The “Organic Matter insol. in CS2” we obtained by difference. We were not acquainted with the article by Mr. Richardson, in which he points out the importance of the water of hydration in the clay. All ultimate analyses reported were made on the original materials furnished us, and not on purified samples specially prepared for the purpose. The modified Eschka method is used extensively in the west for sulfur, arsenic, molybdenum, vanadium and other determinations, and has been found to be very accurate, even with relatively volatile substances like certain coals and vegetable matter. Concordant analyses were obtained in all determinations reported. The last statement applies also t o the nitrogen results.
1
THISJOURNAL, 6 (1913), 9i3.
1
2
Private communication.
2
LOC.til., 976. Jour. iimer. Chem. Soi., 2 1 (1899), 1116.
