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 41 I S T R Y
1302
taining an appreciable amount of gum will begin to deposit this gum, and such deposits are heavier from a rich mixture than from a lean one. The carbon deposits in the combustion chamber are somewhat, but not much greater with gumbearing fuels a t low intake temperatures, but the well-known tendency to lower carbon deposits with higher head temDeratures could readily be invoked to remcdy this diffickty. The use of low manifold temperatures calls for more volatile gasolines. The question of gum tolerance is significant chiefly because of the steady demand for fuels of better antiknock value; these can be supplied by cracking, but the products are usually difficult to refine to permanently low gum content values. Fortunately antiknock value usually improves somewhat as a gasoline is made more volatile. The present work duggests that by lowering intake manifold temperatures, volatile gasolines of moderate gum content might perhaps be used without serious trouble from gum deposits. Such a possibility should be considered in its relation to the applica-tion of high antiknock cracked gasolines. ~~
Vol. 24, No. 11
ACKNOWLEDGMENT The authors wish to acknowledge their indebtedness to E. lLIartin and p. Ridenour for valuable assistance rendered in carrying out the experimental work described in this publication,
c.
w.
LITERATURE CITED (1)
Brown, G. G., Dept. Eng. Research, Univ. Mich., Research Bull. 14, 173 (1930).
Cooke, M. B., Bur. Mines, Rept. Investigations 2686 (1925). (3) Livingstone, C. J., Marley, S. P., and Gruse, TV. A , IND.ENQ. CHEM.,18, 502 (1926). (4) Livingstone, C. J., Marley, S. P., and Gruse, TT. A., J . SOC. Automotive Eng., 20, 688 (1927). (5) Marley, S. P., Livingstone, C. J., and Gruse, W. A , Ibid., 18, (2)
607 11926). Ibid., 24, 598 (1929). (6) Mock,'F. C.'.
(7) Vilkas, Peter, and O'Neill, L. P., Oil Gas J., 28, No. 26, 4 8 (1929). (8) Voorhees, V., and Eisinger, J. O., J. SOC.Automotive Eng., 24, 590 (1929).
RECEIVED June 9, 1932.
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Chemical Studies of Sulfite Waste Liquor Pollution of Sea Water H. K. BENSON, University of Washington, Seattle, Wash.
T
The chemical composition of sea water containThe values thus reported are a t by conv a r i a n c e with the results obwaste liquor in sea water ing sulfite waste liquor is notably and its quantitative estitained by analytical m e t h o d s centrations of one part of liquor in 1200 qf sea commonly employed in pollution mation has been discussed in a .tlumberofpublishedarticles. By water* There is no evidence that subte liquor studies. It is therefore of inoomparison with an unpolluted permanently accumulates in sea water, and in terest to examine the value of Oakland Bay (subject to pollufion) the results do chemical c o n s t a n t s obtained reference sampling station in the the belief that the sea water is polfrom known concentrations of same locality, it has been shown not waste liquor in the sea water thatthe biochemical Oxygen luted to any detectable degree. which enters Oakland Bay; secdemand is useful for measuring small amounts of sulfite liquor. Precipitated lignin is readily oxidized by POand, the on such constants The objection to this dete&inatassium permanganate. of ska water when large quantities of s u l f i t e l i q u o r are distion is that it is equally sensitive to sewage and other usual polluting agents. Still more sensitive charged into it; and third, their values in samples of the sea is a modification (3) of the permanganate method for oxygen water itself after equilibrium had been attained in Oakland consumed. Thompson and Bonnar have also proposed (12)the Bay, after the lapse of a year or longer. measurement of the buffering capacity of sea water as a means OF WASTE af detection of sulfite liquor. This property of sea water is, CHEMICALVALUESOF FIXEDCONCENTRATIONS LIQUOR chowever, affected by photosynthesis and land drainage, in The equipment available for this study consisted of a numaddition to trade wastes. I n higher concentrations such as one part of waste liquor in a thousand parts of sea water, a ber of troughs similar to those used in fish culture experiments. much larger range (2) of determinations, such as color, pH, Water is pumped twice each day about one-half hour before buffer capacity, sulfate ratio, dissolved oxygen, and oxygen high tide a t a point marking the entrance of Hammersley Inlet to Oakland Bay. It is stored in wooden tanks of 10,000 consumed, are available. I n a study of the effects of pulp-mill pollution on oysters by gallons capacity. It flows from them by gravity into a dismeans of well-known biological methods ( 8 ) ,it was found that tributor box maintained a t constant level by means of a float concentrations of one part of sulfite liquor per thousand parts valve, and thence into a header for distribution to the troughs. of sea water or greater kill oysters within less than a month. The pollution mixture was made up in barrels with cold tapped I n this same study an attempt is made to apply the results of digester liquor, of specific gravity 1.051 and with total sulfite the laboratory experiments to oyster beds in an arm of Puget content of 0.75 per cent. These barrels were sealed and conSound, known as Oakland Bay, on which a pulp mill is lo- tained a S/einch (0.95-cm.) Pyrex glass tube extending from cated. The authors claim that no chemical means can be re- the bottom of the barrel to the level of the pollution mixture lied upon to demonstrate the presence or absence of lignin in a small wooden bucket used for the purpose of securing (which largely comprises the waste liquor of the pulp mill), a constant head to facilitate regulation of the flow of and that the concentration of waste liquor attainable in Oak- pollution t o the troughs. The head in this bucket was kept land Bay when equilibrium is reached may be computed from constant to within 0.25 inch (0.6 cm.). About 2 inches ( 5 em.) below the level of the polluting mixture in the bucket, observations on the currents and other physical data. HE d e t e c t i o n of sulfite
November, 1932
INDUSTRIAL
AND ENGINEERING CHEMISTRY
another 3/&ch (0.95-em.) glass tube was inserted to carry the pollution to the troughs. The trough end of this tube was drawn to a nipple to give exactly the right flow with the head under which it was operating. The outlets were calibrated to produce a flow of 131 cc. per minute of straight sea water in trough 1 as the control, the same quantity of polluted sea water containing one part of digester liquor in 1200 parts of sea water in trough 2, and of polluted sea water (one part in 10,000) in trough 3. To insure thorough mixing, the troughs were baffled. The wooden containers were painted on the inside with Ravenite paint, the pump coated with white DUCO, and connecting parts were of Pyrex glass or rubber. The analytical values obtained are given in Table I.
is swept a n a y by the tidal current is also apparent in the sample taken one hour after the dumping of the liquor. OAKLAND BAYVILUES The chemical values of Oakland Bay water are given in Table 111. Although the mill was running somewhat intermittently a t this time, the sampling comes ne11 nithin the equilibrium period claimed. For comparison, the values obtained from a station in the same locality but free from pulpmill pollution are given, as are also the average of the \ allies gix en in Table I for a hnown concentration of one part in 1200. TABLEIII BCFFER
STUDIES OF TROUGH CONCENTRATIONS~ D 4 T E TABLE I. CHEMICAL DIECOLORO X Y PH, BUFFER S O L V E D 20(PT GEN TROUGH LACA- CHLO- OXY- DAY STAND-CONDATE KO, TEMP. MOTTEPACITY R I D E S G E N B. 0. D. A R D ) B U M E D
2 3 1 2 3 1 2 3
1/29/31 2/2/31
1
2/6/31
0
2 3
11.3 10.7 10.7 8.4 8.5 8.5 8.0 8.0 8.0 10.0 10.8 10 0
Mg./
mMH+/ M g . / liter lifer
c. 1
1/22/31
7.7 7.0 7.7 7.5 6.9 7.4 7.9 7.4 7.7 7 9 7.3 7.8
1.93 1.81 1.87 1.22 1.11 1.13 1.77 1.69 1 77 1.81 1.66 1.81
liter
15690 15630 15700 8970 8970 8970 13860 13760 13870 15020 14890 15020
8.36 5.35 8.06 8.56 5.41 8.26 9.89 7.48 9.40 8.18 6.98 7.72
AVO./ liter at
A V O . /
80°C. P . P. m. M e r 0.51 8 2.58 23.60 25 48.09 3.60 12 5.40 2.36 37 10.80 41.60 40 65.85 6.03 37 12.51 1.65 23 5.62 40.50 38 69.48 5.43 25 20.87 1 06 11 4.73 38.45 30 67.13 4 27 14 15.83
Analyses made b y B. T. n'iniecki under author's direction.
Owing to the variables in different samples of sea water and of digester liquor over a period of three weeks, it cannot be expected that the net change will be constant. Yet t,he order of magnitude is unmistakable. If the average of the four sets be taken (excepting trough 3, taken for color) it may be said that the addition of one part of waste liquor to 1200 parts of sea water has reduced the pH 0.6 point, the buffer capacity 0.11 mMH+ per liter, the dissolved oxygen 2.7 mg. per liter; and increased the b. 0.d. 34.6 mg. per liter, the color 17 parts, and the oxygen consumed 57.2 mg. per liter. Results of much the same order (except color) are obtained in similar concentrations of sulfite liquor in stabilized sea wat,er ( 2 ) .
TABLE11. CHEMICAL STUDIES TIhlE
P. hl.
DEPTHT E Y P .
Ft. 2.03 2.03 3.23 2.23 2.28 335 3.35
0.5 22
2 21 0.5 0.5 20
OC. 8.2 8.2 8.3 8.3 8.6 8.1 8.3
PH
7.9 8.1 7.1 7.9 6.1 7.9 8.0
OF
LIQUORSPREAD
BCFFER DISEF- CHLO- SOLVED
OXYGEN
RIDE
SUYED
FECI.
mMH+/ liter
Mg./
1.69 1.74
13730 15340 14060 14980 12400 13320 13640
1.48
1.66 1.29 1.69 1.69
liter
B. 0. D. ( Z O L O R MQ./ M Q . / liter liter p . p . m.
OXYGEN
8.11 7.96 7.77 7.53 2.19 z.86 ,.13
1.22 1.16 30.15 7.47 Lozt 0.,8 0.12
cos-
16 3.70 9 4.09 90 177.6 38 36.5 2fjt 1036.3 5.0 24 6 58
--
Although digester liquor is heavier than sea water, the blowpit liquor is diluted with wash water and is discharged a t a higher temperature. Hence the surface samples of sea water are characterized by greater changes in the chemical constants than the bottom samples. This is notably true of the sample taken a t 228. The rapidity with which the discharged liquor
PH
C4PACITl
2/2/31 2/9/31 2/11/31 2/13/31 4/28/31
1 /99/21-, --, - -
2/6/31 5
7.9 7.9 7.5 7.7 8.1
1.68 1.74 1.75
7.2
1 56
O A K L ~ YBDk Y
V4LUE3a
DIS-
oXUGE\
CHLO-S O L V E D
m-EET'/
RIDE
OXYGENB
%! '22
14080 7.59 15500 7.77 14800 7.09 1.81 14060 7.15 1.93 15028 11.45 13310
6 30
CON-
0 D
LOC~TION
COLORSUMED
2:
P p m M 17ter I0 / 20 12 11 12 13
1.34 1.79 2.41 2 41 2.32 36 03
33
OaklandBay OaklandBay OaklandBay OaklandBay PugetSound
4 98 4.29 5.12 4.73 2.15 62.6
A v . for concentration 1:1200.
Analyses made by R. T Winiecki
It is evident that although Oakland Bay shows the effect of pollution, the extent is very much less than that obtained when one part of waste liquor is added to 1200 parts of incoming sea water. BIOCHEhIICAL OXYGEN DEVAKDSTUDIES IS OAKLAND BAY AND PUGET SOUND In Table IV is given a comparison of biochemical oxygen demand values obtained from Oakland Bay water with the sea water from unpolluted stations in Puget Sound. Those footnoted are located in an adjoining bay where oyster beds are also located, but a t some distance from the source of pollution. OXYGEN DEMAXD STUDIEB IN TABLE IT. BIOCHEMICAL OAKLASDBAYAND PUGETROUND DATE
OAKLAND BAY ~ O - D A I3 T 0.D h T 25' c. Mo./Ziter
1/28/28 5/27,'28 1/20/29 4/20/29 5/23/29 7/20/29 8/1/29 11/17/29 12/14/29
CHEMICAL STVDY OF SPREAD OF WASTELIQUOR IN SEAWATER For the purpose of showing the effect of waste liquor on chemical constants, samples were taken a t the disposal tanks prior to, during, and after liquor discharge in Hammersley lnlet. For this purpose the sampling boat was anchored in the tidal stream below the outlets of the storage tanks. The liquor dumping began a t 2:Oi P. M. and was complete a t 2:32 P. 11. The analytical results are given in Table I1
1303
a
I n Oyster Bay.
Av.
2.88 2.78 2.71 2.01 1.53 1.65 2.54 1.53 2.66 2.25
PCGET SOUND
~ O - D A YR. AT 25'
0. D
c.
Mo./Ziter " , 1.03 1.73 0.22 2.31 1.85 2.15 2 . 4fja 1.44a 2.04O 1.80
d period of more than one year had elapsed since pulp-mill pollution began and equilibrium should, therefore, have been attained. The differences are, however, not of sufficient magnitude to warrant the belief that the addition of waste liquor is cumulative and that it constitutes a permanent addition to sea n-ater. Whether the oxidation products are residues which still may be toxic to oysters, or are of the same nature as those obtained by biologic oxidation of sewage and organic matter, has not been investigated. It is of interest, therefore, to consider analogies which have been studied in greater detail. CHEMICAL OXIDATIOX OF LIGSIN Although lignin under aerobic conditions is considered highly resistant to decay and natural decomposition, it is, nevertheless, subject to ready change chemically. It is readily oxidized by potassium permanganate, as is shown by the results taken from a study made by Pivertz and Grant (11) on the consumption of permanganate by mixtures of pure cellulose and lignin. The latter had been separated by the 72
I N D U S T R I A 1, A N D E N G I N E E R I N G C H E M I S T R Y
1304
per cent sulfuric acid method. Two-gram samples were treated with 500 cc. of 0.1 N potassium permanganate for 2 hours a t 25” C. The consumption of permanganate was found to be directly proportional to the lignin added: LIQNIN IN
SlVPLE
0.1 N KMnOd
CONSUMED
cc.
As has been previously pointed out (S), the reaction of potassium permaiiganate with vanillin and sucrose is from 84 to 99 per cent complete, the end products being carbon dioxide and water From the sirnilarity of substances present in digester liquor, i t is believed that thr osygen consumption method is a very complete measurement of the organic components of sulfite liquor, including lignin itself. BIOLOGICAL OXIDATION OF LIGNIN The decomposition of lignin by microorganisms is a matter that requires fuller investigation. Althoupli analyses (5, 10) of decn\ ed wood show that the sample of decayed wood contained a hiptier percentage of lignin than the sound wood, the recent worh of Phillips, Weihe, and Smith (9), of Boruff and Buswell ( h ) , and of Campbell (6)on the action of soil microorganisms on lignified plant materials indicate very conclusively that the loss of lignin was as great as that of cellulose
Vol. 24, No. 11
and pentosans, and in some instances greater. Franz Fischer (7) has presented evidence of the biological oxidation of coal and even of hydrocarbons such as methane into carbon dioxide and water. The well-known oxygen demand of sulfite waste liquor and of lignin precipitated from waste liquor by the Howard process indicates its susceptibility t,o breakdown by organisms naturally occurring in sea water. The general purifying action of both the soil and the sea are very much alike, and would warrant the belief that lignin is subject to the same biological reactions as other organic constituents of land drainage and pollution. The assumption, therefore, that a t the end of a year it is still present in sea water in unchanged form or even as oxidation products does not seem reasonable. LITERATURE CITED (1) Benson, Puper Trade J.,90, 69 (1930). (2) Benson and Benson, IND.ESG. CHEM.,Anal. Ed., 4, 200 (1932). (3) Benaon and Hicks. Ibid., 3, 30 (1931). (4) Borufi and Buswell. IND. EXQ.C‘BEX., 22, 931 (1930). (5, Bray and Andrcwa, I h i d . , 16, 137-9 (1824). (6) Caniphell, Biochem.J.,24, 1235 (1930). (7) Fiachcr. Proc. 3rd Intern. Conf. Bituminous Coal, 1931, 809-19. (8) Hopkins, Galstoff, and McMillin, Bur. Fisheries, Bull. 6, 15961 (1931). (9) Phillips, Weihe, and Smith, Soil Sci.. 30, 383-90 (1930). (10) Schaalbe and Ekenstam, CelZuloaechem., 8, 13-15 (1927). (11) Sivertz and Grant, Proc. Tech. Assoc. Pulp Puper Ind., Fob.. 1932. (12) Thompson and Bonnar, IND.ENG. CHEM.,Anal. Ed., 3, 393 (1931). RECEIVED May 23, 1932. Prewnted before the Division of Water, Eewage. m d Sanitation Chemistry at the 83rd Meeting of the American Chemical Society, New Orleans, La., hlarch 28 t o April 1, 1932
Shopright and International Convention OSCARA. GEIER, 274 Madison Ave., New York, N. Y.
U
NITED STATES inventors and owners of United States patent applications frequently wish to protect their inventions in foreibm countries only after the examination in the Patent Office in Washington has shown that the invention is really novel and that there is a t least a good chance of obtaining United States Letters Patent. They are perhaps aware that the provisions of the International Convention, to which most of the important countries of the world belong, give them a period of twelve months in which to deride whether foreign protection is desirable and in what countries it should be sought. I t is probably known also that, according to the terms of this Convention, nothing which transpires during these first twelve months from the date of the filing of the first patent application can invalidate their patents in foreign countries in the event that the foreign applications are filed during such period. The general idea about the International Convention is that the inventor or owner is fully protected in his rights during this twelvemonth period, as far as a particular invention is concerned. However, this idea is incorrect, and many inventors and manufacturers have lost valuable rights by not examining the stipulation of this Convention with more care. Article 4 of the International Convention reads as follows: “(n) He Tho has properly tiled a patent, a petty patent, a design patent or a trade-mark aj)plicstion in one of the Cnnvention countrieq . . . will enjoy the right o f prior’itg for filing in other countries provided, honever, that the rights of the third parties will be maintained.
( b ) Consequently, a suhsequent fi!ing in one of the ot,her countries of the Union . . . will not Le invalidated by events taking place in the interval. . .”
It has been found that the wording of this article is somewhat obscure and indefinite, and, therefore, practically every country has a different conception of its interpretation. It seems to be definitely established, however. that the sole purpose of this article is to protect an applicant filing under the International Convention and to secure his rights to a patent which would otherwise be voided. It is expressly stipulated in the article that rights of third parties will not be affected by any actions that the applicant mag take. The question as to what these rights of third parties actually are is differently defined in practically every country subscribing to the Convention. An important question, to which there is no answer in the text of the Convention, refers to the rights of a tliird prrson who has reduced an invention to practice in a foreign country during the period of time between the date of filing the first application and the date of filing of an application under the Convention in that foreign country. In some countries this person has no rights whatsoever. Should he file a patent application, he is considered as the junior applicant and the application is refused. Should he begin to manufacture the invention and to sell it to others, the patentee, who filed under the Convention, is able to stop him from continuing to do so as soon as a patent is granted.
