1180
INDUSTRIAL A X D ENGINEERING CHEiMISTRY
tained with articles sprayed with petroleum naphtha solutions. Furniture, rugs, and hangings were treated in mothinfested homes to determine the effectiveness of the various ways of using the cinchona alkaloids as moth repellents. The conclusion drawn from a number of tests of this nature was that the cinchona alkaloids or their compounds in either water or petroleum naphtha solution are commercially suitable for treating materials by immersion in or by spraying with the solution. Since this conclusion was drawn over a year ago, more than 4000 gallons of cinchona alkaloid solutions have been applied to articles of wearing apparel, furniture, etc., under commercial conditions in the dry-cleaning plants of members of the Mundatechnical Society. hfany of the articles treated were moth-infested when received. They were all guaranteed to be mothproofed and free from moths after treatment. Not one complaint has been made by any of the many owners of the articles treated. Four thousand gallons of the solution are sufficient to treat 160,000 pounds of wool. feathers, or fur. The plants in which the work was
Vol. 19, No. 10
done are located in eight large cities of the eastern, southern, and midwestern parts of the United States, and this successful and extensive use of the process in several sections of the country indicates its adaptability in the dry-cleaning industry. The utility of the process in other fields is apparent. As a spraying solution for household use the value of high flashpoint petroleum naphtha solutions of the cinchona alkaloids is obvious. The process can readily be made applicable for meeting the mothproofing requirements of a wide range of wool, feather, and fur industries, inasmuch as some of the many compounds and derivatives of the cinchona alkaloids are soluble and therefore usable in almost any solvent desired. The process can be readily adapted to treating upholstering materials, felts, blankets, comforts, mattresses, suitings, etc. For the past year the process has been successfully applied commercially in the dry-cleaning and dyeing industry. The process will be made available to other interested branches of technology just as soon as commercialization plans are concluded.
Possible Use of Shale Oil, as a Wood Preservative’ Toxicity of Pyridine and Quinoline to Fomes annosus By Arthur M . Sowder SCHOOL OF FORESTRY, UNIVERSITY OF IDAHO, Moscow, IDAHO
The toxicities of pyridine and quinoline have been oils contain from 1.855 to ACH year t h e wood determined by the Petri dish and sawdust methods. 1.501 per cent total nitrogen. preservation industry The results indicate that pyridine can play no imWeiss4 has shown that a becomes of greater important part in influencing the availability of shale oil concentration of 0.10 per Cent portance, owing to the ecoas a wood preservative. The toxicity of quinoline to quinoline in nutrient agar is nomic conditions caused by wood-destroying fungi compares favorably with the toxic to Penicillium. The the steadily increasing prices toxicities of creosol, phenol, and mercuric chloride. toxicity of quinoline apparof structural timber due to the If shale oil contains from 2.43 to 3.06 per cent quinoline, e n t 1y compares favorably threatened shortage of this there is reason to believe that it will inhibit the growth with pure phenol, creosol, and material. Close utilization of wood-destroying fungi when injected into wood at mercuric chloride. No data is a n aid in alleviating a future the rate of 12 pounds of oil per cubic foot of wood. dealing with the toxicity of wood famine and wood prespyridine to wood-destroying ervation is one way to effect fungi are known to the writer. this closer utilization. Pyridine6r6is a colorless, mobile liquid, having a characWood preservatives are substances injected into wood through various processes to prevent or inhibit the destruc- teristic penetrating odor and the empirical formula CsH5N. tion of the wood by decay or by infestations of marine borers, It is readily soluble in water in all proportions, basic to litwhite ants, beetles, etc. For general use a good preservative mus, has a specific gravity of 0.9779, and boils at 115” C. should be cheap, available, efficient, easily handled, and not Quinoline, having the empirical formula C ~ H T Nis, sparingly injurious to the mechanical properties of wood or increase soluble in water but readily soluble in alcohol and ether. its inflammability to too high a degree. Since the shale oil It is dark brown in color and has a penetrating odor and industry seems to have vast possibilities, the question arises burning taste. The specific gravity of quinoline is 1.081 and as to whether or not this oil fulfils the requirements of a wood i t boils at 239’ C. Both pyridine and quinoline are found in coal-tar creosotes and stand somewhat in the same relation preservative. Oil-bearing shales occur in various parts of the United to each other as do phenol and naphthalene. States in enormous quantities, but the largest deposits are Methods found in the Rocky Mountain states. It is estimated2 that Colorado alone has enough shale to produce 58 billion barrels There are two common methods’ of determining the effecof oil. Data showing the composition of shale oils are rela- tiveness of a wood preservative-(1) actual service of treated tively meager, but according to Franks3 shale oil, especially timber, and (2) laboratory tests. Service tests, although that obtained from Colorado, contains relatively large amounts always desirable, are often impractical as they frequently of nitrogen and some of this nitrogen a t least possibly occurs require from 10 to 15 years to get the final results. Labin the form of pyridine and quinoline. The exact amounts oratory tests, on the other hand, permit the determination of pyridine and quinoline present in shale oil are not known, of the relative toxicity to wood-destroying fungi within a but Franks’ analyses show that the crude Colorado shale J . Soc. Chem. Ind., 30, 1348 (1911).
E
4
1 2
a
Received May 31, 1927. Alderson, “The Shale Oil Industry,” 1920. Quart. Cola School Mtnes, 16, 1 (1921).
6 6
7
Lunge, “Coal Tar and Ammonia,” Gurney & Jackson, London, 1900. Sudborough, “Organic Chemistry.” Richards, Proc. A m . Wood Preservers’ dssocn., 19, 127 (19231.
October, 1927
IXDUSTRIAL AND ENGINEERING CHEMISTRY
1181
very short time. The expense also is very much less. The culture has been used in all the toxicity tests conducted a t methods used are those ordinarily followed in toxicity studies. the Forest Products Laboratory. Strain B was obtained In applying laboratory tests the preservative is either mixed from sporophores on Pinus virginiana collected by George with nutrient agar or sawdust and then inoculated with a G. Hedgcock. Miss Richards reports that strain B is much pure culture of the desired fungus. The former, or Petri more susceptible to poison than strain A . dish method, is in most common use. I n the present invesResults tigation the toxicities of pyridine and quinoline were determined by both the Petri dish method and by the sawdust The results obtained by the Petri dish method are giveii method. in Table I. The percentage concentrations were calculated PETRIDISH i\lETHoD-The nutrient agar used has the on a volume basis. After the final results were taken from following composition: Trommers’ malt extract 25 grams. the plates the inocula on the plates in which all growth was bacto-agar 15 grams, and distilled water to make 1000 cc. inhibited were transferred to nutrient agar slants in order The bacto-agar and about 900 cc. of distilled water were to determine whether or not the fungus was merely inhibited heated in an autoclave for about 40 minutes to melt the agar from growing or act,ually killed. These data are recorded and then the malt extract and hot distilled water were added in the column headed “Recovery.” to make up 1000 cc. While still in the melted condition varying amounts of T a b l e I-Toxicity of P y r i d iNn ue tar ni edn tQAugi naor l i n e t o F o m e a annosus o n STRAINA STRAINB the nutrient agar were pipetted into 250-cc. Erlenmeyer TOXIC ReReflasks, the quantity depending on the concentration of pyridine MATERIAL CONCN. Remarks covery Remarks covery P e r cent and quinoline desired, but a t least 25 cc. of the final mixture Very good growth Very good growth are needed for each Petri dish. For the lower concentrations Very good growth Very good growth Very good growth Very good growth the pyridine and quinoline were added to 200-cc. amounts Very good growth Very good growth of the nutrient agar, while for the higher concentrations 100-cc. Good growth Good growth Good growth Good growth portions of nutrient agar were used. Fair growth Fair growth Slight growth Slight growth Prior to adding the pyridine and quinoline the flasks conToxic concentrationa Yes Toxic concentration@Yes taining the nutrient agar were sterilized by steaming for 30 No growth Yes No growth Yes N o growth Yes No growth Yes minutes on three consecutive days in an Arnold cooker. While No growth Y e s No growth NO No growth S O No growth No still in the melted condition pyridine and quinoline were Excellent growth Excellent growth added in sufficient amounts to make the desired concentraVery good growth Very good growth Very good growth Very good growth tions, care being taken not to contaminate the culture medium. Yery good growth Very good growth The flasks and contents were then well shaken and the mixGood growth Good growth Fair growth Fair growth ture was poured into sterile Petri dishes under sterile conToxic concentrationa Yes Toxic concentration” Yes No growth Yes No growth Yes ditions. Duplicate plates of each concentration were preNo growth No growth Yes No pared. No growth Yes No growth No Excellent growth Excellent growth After cooling, the plates were inoculated with Fomes annoa The toxic concentration is defined a s the minimum percentage of pyrisus in the usual manner and the plates placed under a bell dine a n d quinoline which will completely inhibit the growth of Fomes jar and incubated a t room temperature for 22 days in the annosus. case of pyridine and for 30 days in the case of quinoline. The data obtained from the sawdust cultures are recorded SAWDUST METHOD-An amount of air-dried sawdust equiv- in Table 11. The percentage concentrations are calculated alent to 5.000 grams of oven-dried western yellow pine saw- on a weight basis-i. e., the ratio of the weight of pyridine dust was placed in each of several small Erlenmeyer flasks. and quinoline each added to the 5 grams of western yellow To each of these flasks 10 cc. of distilled water were added pine sawdust (moisture-free) . and the culture flasks then sterilized by heating a t 15 pounds P y r i d i n e a n d Q u i n o l i n e to Pomes a n n o a z s on (70 grams per sq. cm.) pressure in an autoclave for 20 minutes. T a b l e 11-Toxicity of W e s t e r n Yellow P i n e S a w d u s t The pyridine and quinoiine were not added directly to TOXICMATERIAL CONCENTRATION REMARKS the sawdust, as it wa6 believed that this procedure would Per cent Pyridine 0.98 Good growth result in an uneven distribution of the material. Conse1.47 Fair growth quently, the desired amounts of pyridine and quinoline were 1.95 Slight growth 2.45 Toxic concentration added to 10 cc. of sterile distilled water and this solution or 2.93 N o growth 3.42 No growth mixture was then added to the sterilized sawdust prepared 3.91 No growth as stated above. 4.40 N o growth No growth 4.89 After the addition of the pyridine or quinoline, as the case Control Excellent growth might be, to the sawdust the flasks and contents were shaken Quinoline 0.54 Good growth 0.81 Fair growth in order further to facilitate a uniform distribution of the 1.08 Toxic concentration 1 . 6 2 No growth toxic material in the sawdust. The culture flasks were then 2.18 h‘o growth allowed to stand for 24 hours before inoculation. Inocu. 2.70 No growth 3.24 N o growth lation was made in the usual manner. The cotton plugs of 3.78 No growth 4.32 No growth the flasks were covered with tin foil to prevent excessive Contro! Excellent grvwth volatilization. The efficacy of this covering is demonstrated by the fact that practically no odor of either pyridine or quinTable I shows the toxic concentration of pyridine and oline could be detected in the incubator in which the cultures quinoline when added to standard malt agar to be 1.20 and were placed. The incubator was maintained a t 28” C. and 0.07 per cent: respectively. I n the pyridine series, strain A the final results taken after 7 days. of Fomes annosus was not killed until the concentration reached The cultures of Fomes annosus used in this work were ob- 1.40 per cent. Strain B was killed when the concentration tained from Miss C. Audrey Richards, Forest Products Lab- reached 1.35 per cent. I n the case of the quinoline series oratory, Madison, \Tis. Strain A , according to Miss Rich- strain A recovered even when the highest concentrations were ards, was obtained from fungous tissue collected in a Pennsyl- used. Strain B did not recover when the concentration of vania coal mine in May, 1910, by C. J. Humphrey. This quinoline reached 0.09 per cent.
INDUSTRIAL A N D ENGINEERING CHEMISTRY
1182
Table I1 shows the toxic concentration of pyridine and quinoline when added to western yellow pine sawdust to be 2.45 and 1.08 per cent, respectively. It is evident that pyridine is much less toxic to Fomes annosus than quinoline. Owing to the low boiling point of pyridine, its high volatility, and low toxicity, it is obvious that this particular substance can play no important part in influencing the preservative properties of shale oil. Quinoline, on the other hand, owing to its high boiling point, low degree of volatility, and high toxicity, will undoubtedly influence the toxicity of shale oil to a high degree. Concentration Necessary
The question arises as to how high a percentage of quinoline shale oil must contain when used as a wood preservative
Vol. 19,No. 10
to inhibit the growth of wood-destroying fungi. Assuming quinoline to be the only toxic substance in shale oil and assuming an injection of 12 pounds of shale oil per cubic foot of wood, the shale oil must contain the percentages of quinoline shown in Table I11 when used as a preservative for different woods. The woods selected are those commonly given preservative treatment in the western United States. Table 111-Concentrations of Quinoline in Shale Oil Necessary to Inhibit G r o w t h of Wood-Destroyin$ Fungi INJECTION OF CONCN.OB WEIGHTPER SHALEOIL PER QUINOLINE SPECIESOB WOOD CUBICFOOT CUBICFOOT WOOD NECESSARY Pounds Pounds Per cent Western yellow pine 28 12 2.52 Lodgepole pine 28 12 2.52 Douglas fir 34 12 3.06 White fir 27 12 2.43
Water-Softening as Practiced at Oberlin, Ohio’ By W. H. Chapin OBERLINCOLLEGE, OBERLIN,OHIO
Gause and Nature of Hardness
H E soil in n o r t h e r n Ohio consists of glacial drift, and 80 contains considerable amounts of limes t o n e , gypsum, and magnesite, with Some magnesium s u l f a t e and perhaps slight amounts of the chlorides and nitrates of these same elements. As the rain water runs over this soil, or filters through it, it dissolves some of these compounds. Limestone is only very slightly soluble in pure water, but, in the presence of carbon dioxide (carbonic acid) quite appreciable amounts go into solution in the form of the bicarbonate. Magnesite is more soluble in water, and may dissolve as it is, but owing to the ever-present carbon dioxide from the air and the soil it is sure to be found in solution as the bicarhonate. The other substances mentioned dissolve, as they - .are without action of the carbon dioxide. The salts of calcium and magnesium form insoluble compounds with soap; and so when soap is added a curdling or precipitation occurs, and no lather will be formed until all these salts are precipitated. Water containing these salts is therefore termed “hard.” Natural waters contain other substances in solution, such as sodium chloride or sodium carbonate, but these substances do not ordinarily cause a ‘coagulation of soap. A water might in rare cases contain free acids-sulfuric, for example-and would be classed as “hard,” because the free acid would decompose the soap and thus precipitate the free fatty acid. Since the carbon dioxide is an active agent in bringing certain hardening constituents into solution, it is sometimes spoken of as if it still existed as such in the water. That which exists in the form of carbonates is called “fixed” or “bound,” that in the form of bicarbonates as “half-bound,” and that which is not attached as “free.” A water containing “free” carbon dioxide cannot a t the same time contain carbonates (“fixed” carbon dioxide), but bicarbonates (“halfbound” carbon dioxide) may be present. When a hard water is boiled the bicarbonates are changed into normal carbonates-that is, free and half-bound carbon
T
1
Received June 16, 1927.
d i o x i d e are expelled. The calcium c a r b o n a t e t h u s formed, being nearly insoluble, is mostly precipitated. M a g n e s i u m carbonate, because of its greater solubility, is not thus precipitated, but i s f u r t h e r changed into a more insoluble basic carbonate and is precipitated in this f o r m . H a r d n e s s thus removed by boiling is called “temporary” hardness. The sulfates of calcium and magnesium are not changed by boiling, and so the hardness due to their presence is called “permanent hardness.” When water containing these substances is evaporated in a steam boiler to the point of saturation, a hard deposit forms on the boiler plate or flues. For this reason the salts producing permanent hardness are often called “incrustants.” The term “non-carbonate hardness” is also used.
At the Oberlin softening plant much trouble has always been experienced with after-precipitation. After the plant had been in operation for twenty years the city mains had become SO badly incrusted as to make cleaning necessary. To obviate further difficulty in this line provision is now made for storing the treated water for ehirty days before it enters the mains. This has almost completely stopped the after-Precipitation, and has given the added advantage of making filtration unnecessary.
Manner of Indicating Hardness
Hardness is now almost universally stated as “parts per million” and in terms of calcium carbonate. An older method of stating hardness was in “grains per gallon.” One U. S. gallon of water weighs 8.33 pounds or 58,300 grains. Hence 1 grain per gallon equals 1part in 58,300, or about 17 p. p. m. The hardness in water does not actually occur entirely, if at all, in the form of calcium carbonate, as stated. This does not cause any inaccuracy, however, since the effect is the same, whether stated in terms of the actual compounds or of an equivalent amount of calcium carbonate. This method of stating hardness has the advantage of uniformity and ease of calculation. Variation in Hardness
Natural waters vary widely in hardness. The supply a t Oberlin averages about 270 p. p. m. The same is true of the Columbus supply (Scioto River). Waters in a region where the soil is of granitic or schistose origin are soft, as in parts of New England and in eastern Canada. The water of the Great Lakes is softer than that of our local streams, because much of it comes from Canadian soil of granitic origin. The hardness of Lake Erie water averages about 100 p. p. m.
