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tested out in pure culture, and the fact t h a t B . coli writer desires also t o thank Dr. V. C. Vaughan and Dr. can go through t h e ozonizing wells has been proven F. G. Novy, of the University of Michigan, and Mr. beyond a doubt. Gardner S. Williams for their many helpful suggesAs an explanation of t h e negative efficiency of the tions. DEPARTMENT O F MEDICINE AND SURGERY ozone considered alone, I might state t h a t the bottom UNIVERSITY OF MICHIGAN ANN ARBOR of t h e third well of each unit is lower t h a n t h e height of water in t h e pumping when full. Consequently, these third wells are flooded with basin water, and as STUDIES ON THE ABSORPTION OF WATER BY BUILDING BRICK this is open and located near a railroad, it is liable By HERMANN W. MAHR t o receive more or less contamination. This is the Received July 2, 1914 explanation advanced b y some; b u t each day, during The absorption of water b y building brick has probt h e entire time t h a t the writer was taking samples, ably been given more attention t h a n all the other propt h e water in the basin was low, and consequently no basin water could get back into these wells. It would erties of this important construction material. We seem t h a t they would gradually sterilize themselves are, however, still in doubt as t o t h e best method of if t h e ozone were present in large enough quantities conducting the test for absorptive power. Attempts t o have a n y beneficial action on t h e water in them, t o explain the significance of the amount of water taken b u t samples taken after ten hours' continual opera- up and the relation of this value t o t h e strength of t h e tion, during which time no basin water could get material have been unavailing. Howard' has preinto these wells, showed no improvement in the ozon- sented papers pointing out t h e indefiniteness of t h e term absorption as applied t o brick. I n spite of this ized water. Another explanation of this negative efficiency, confusion, t h e absorption requirement is regarded as of advanced b y Dr. F. G. Novy, professor of bacteriology importance in judging quality, apparently because of in t h e University of Michigan, is as follows: a micro- a well-grounded belief t h a t future investigations would scopical particle of organic matter may contain several open up this dark continent. Some experimenters have attempted t o evolve abbacteria and still appear as one colony and be counted sorption test methods which give total porosity, and as an individual. Now this ozonized air tears through t h e water under several pounds pressure, and it is t h e standard method of The American Society for probable t h a t some of these particles of organic matter, Testing Materials, proposed in 1913, has this object containing germs, are broken into several sections in view. It has been pointed out by several authorities, and give several colonies, whereas they all showed among them J . C . Jones,2 t h a t no constant relation exists between the absorptive power and porosity of as one colony in t h e raw or filtered water. bricks. We are, therefore, forced t o conclude t h a t t h e I n t h e summer of 1 9 1 2 a large dam was built just two are distinct properties having some small dependabove t h e former intake of t h e water company. As ence on one another. Investigations of absorption t h e manager of this company wished t o be absolutely of water have been mainly from t h e exterior of t h e sure of t h e quality of the water supplied t o t h e city, brick, and these have failed t o answer many queries. t h e use of hypochlorite of lime was begun. Plate Necessarily the structure of t h e brick holds these counts of t h e t a p water in t h e city are made every day secrets. a n d t h e amount of lime is varied t o suit t h e requireT o investigate the structure of bricks as revealed ments. At t h e present time t h e intake is above this b y t h e absorption test and t h e significance of the latter, dam, a n d as t h e water is backed up for nearly two miles, a very good settling basin is formed. This a s t u d y of these materials was undertaken. The water contains considerable organic matter and t h e bricks employed were of different degrees of 'burning amount of hypochlorite used is rather high, from I O and were submitted b y Hudson River and New Jersey t o 16 Ibs. per million gallons. The percentage of manufacturers. Previous t o immersion they were available chlorine in this averages about 331/3 per dried for 2 4 hours a t 110' C. They were then subcent, t h u s making the available chlorine used come t o jected t o absorption tests, either t h e 48 hours' total a n average of about 0 . j part per million. Even with immersion or t h e boiling test proposed b y a committee this comparatively high amount of hypochlorite, of The American Society for Testing Materials in t h e germ count in t h e service water will average 1 9 1 3 . ~The immersion liquid was a 2 per cent solution more t h a n j o per cc. However, t h e colon bacillus is of potassium ferrocyanide. At t h e close of t h e test superficial moisture was removed and weights deterrarely found. Now chlorine is much more soluble in water t h a n is mined. The bricks were then split across (or lengthozone, and gram for gram is as strong, if not a stronger, wise), into sections, b y means of a brick chisel. T h e disinfecting agent. Consequently, t h e fallacy of t r y - surfaces t h u s obtained were treated with a j per cent ing t o purify a water with 0 . 2 2 7 part per million of solution of ferric chloride. When the section was dried ozone, when the water is comparatively rich in organic t h e zones and channels of penetration by t h e liquid matter, and when 0 . j part per million of available were colored blue. The two surfaces from t h e same chlorine does not give ideal results, must be plain t o fracture showed markings in practically all instances 1 National Brick Manufacturers' Association, Buffalo Meeting, Februall. 1909. The writer wishes t o t h a n k Dr. A. K. Hale, of t h e ary 51, Trans. Amer. Cer. Sac., 9. Ann Arbor Water Co., for his many favors. The a Proc. Amer. SOL.f o r Testing Materials. 13 (1913), 287.
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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 I I E M I S T R Y
t h e same. This indicated t h a t t h e coioring was definite and characteristic of the penetration a t t h a t place, and not due t o flowing of the absorbed solution on the fractured surfaces or other chance phenomena, I n some cases splintering of the brick a t the surfaces, due t o t h e operation of cutting, gave colorings and zones somewhat different on the two adjoining surfaces. The procedure just outlined gave well-defined pictures of the penetrated sections; the coloring was, however, not deep and did not contrast as sharply with the unpenetrated parts as when the following treatment was employed. After cutting, the sections were placed in an oven a t iioO C . and dried one-half to one hour. The potassium ferrocyanide was t h u s concentrated on
801
Percentage by weight absorption in 2 % . Percentage absorption in water. bv weizhi
potsrsiium ferrocyamde 301uti0n
21.3 15.2 27.0 16.2 16.1
Percentage by -eightabsorption in 2% Sample 42- 1 42-13 44-21 44-31
Percentage absorption p a t a r i i ~ mferrocyanide in water. by weight S0I"tiD" 18.1 18.2 11.0 11.3 14.1 12.4 14.7
14.5
T h e results were illuminating and revealed the structure considerably better than breaking the nn-
3
1
4-
2
5
the surface of t h e penetrated Darts. r h e v were thcn dipped into the ferric chloride solution, dricd and washed well. The washing removed t h e escess of salts and intensified the marking. This method' was adopted for the treatment of the bricks hereafter described. T h e amount oi absorption in 2 per cent potassium ferrocyanide was practically the same for both the 48 hours immersion and boiling tests as when pure water was uscd. This will he seen from the following tables: Mr. Gilbert Kigg ( J , S o r . Chim. l n d . . $3. 619-June 30, 1914) hna described a method, somewhat 4mi:ar in princinle io the above, which lic used in studying fire-brick. Ills m e t h d consisted 1ii allow in^ colored zelafin rolutiorrs io Penetrate the refractories, and had !or it$ object the revealing of t h e method and ! o m in which fire~brickwould be penetrated j
very recently
by molten Elas.
treated brick and visual examination are able to. Some of the grosser defects and variations in composition are shown by t h e latter, b u t t h e method in question showed vitrified and soft portions which are indistinguishable in the untreated brick. Some of the results illustrative of the penetration into various types of bricks were photographically reproduced. The photographs fall f a r short of presenting the finer lines and areas of penetration, because of the irregularity of t h e fractured surfaces and contrasts poorly suited for photographing. Fig. I represents opposite surfaces from the same fracture, t h e sections being in the position of having
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T H E JOURNAL OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
been folded open. This shows t h e great similarity of t h e markings obtained on such surfaces. Fig. z is a photograph of a soft absorbent brick subjected t o t h e treatment. The absorption was 18.2 per cent in forty-eight hours total immersion. The penetration was complete a t this point. At other places i t was not as thorough. Fig. 3 shows t h e manner in which a hard, vitreous brick absorbed t h e liquid. This absorption was only 6.5 per cent. The liquid entered into small channels and soft absorbent zones. T h e method in which t h e liquid penetrated a brick with a hard vitreous core is shown in Fig. 4. The penetration was even in character t o t h e core. This brick absorbed 12.4 per cent. Some of these nonabsorbent cores extended t h e entire length of t h e brick and their presence on t h e outside surface was shown by t h e treatment. Fig. j , a photograph of t h e end surface of t h e preceding brick, shows a n instance of this. A brick, with a large black core, which has been subjected t o t h e absorption test, is shown in Fig. 6. This brick took up only 4.1 per cent. The core, while un-
SAXPLE 40-12.. . 40-22.. 41-31,. 42- l.... 42-13.. 43- 1 . 44-24.. . 44-31. . . . 45- 1. . . . 45-23. . .
. .. .. .. ... . .
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way they had been penetrated, the exception being soft absorbent bricks which were penetrated evenly and apparently t o t h e same extent by both methods of treatment. Half bricks containing vitreous cores were penetrated only t o t h e core as a result of t h e 48 hours immersion, while the cores were more or less permeated with liquid b y t h e boiling operation. I n Fig. 7 t h e lower section is from a half b r h k which was totally immersed for 48 hours. The upper is a section from t h e other half of t h e same brick, subjected t o the boiling test. They both contained the same core, b u t i t was penetrated b y the liquid as a result of boiling. The absorption b y the latter treatment was 1 2 . 1 per cent against 4.1 per cent in t h e half immersed a t ordinary temperature. The results of t h e experiments lead t o several conclusions regarding t h e methods in which liquids penetrate building brick. The manner of penetration is primarily governed b y t h e type and structure of the brick. T h e following generalities have resulted from t h e studies made: I-Soft, uniform, absorbent bricks t a k e u p water uniformly and distribute it evenly t o 'all parts of their
TABLE111-EXPERIMENTSON ACCURACY OF WATERABSORPTION TESTS 48 HOURSTOTAL IMMERSION AT ROOMTEMPERATURE AMERICAN SOCIETY FOR TESTING MATERIALS BOILING METHOD Percenta e moisture absorbed Deviations from mean E'ercentage moisture absorbed Deviations from mean Test Test Test Test Test Test Test Test AVERTest %st Test Test Test Test AVER1 2 3 MEAN 1 2 3 AGE 1 4 2 3 MEAN 1 2 3 4 AGE 0.42 0.17 0.59 0.39 19.67 19.08 19.71 19.61 19.52 0.52 18.14 18.39 19.15 18.56 17.09 16.33 17.28 17.09 16.95 0.14 0.00 0.00 0.00 0.00 15.94 15.94 15.94 15.94 0.11 0.23 0.11 0.15 13.77 15.00 14.42 12.88 12.54 12.88 12.77 14.40 0.63 0.06 0.00 0.06 0.06 20.98 19.46 21.23 20:86 20.63 18.05 15.99 15.93 15.99 0.35 14.11 12.97 14.11 13.87 13.77 10.78 9.44 10.35 10.19 0.35 0.59 0.75 0.16 0.50 19.23 17.78 19.54 18.65 18.80 17.05 16.93 16.55 16.84 0.43 0.21 0.09 0.29 0.20 14.45 14.38 15.67 15.38 14.97 0.52 0.31 0.34 0.02 0.22 12.85 13.50 13.14 13.16 0.54 0.41 0.24 0.18 0.27 15.94 14.75 15.28 15.65 15.40 14.44 13.79 13.85 14.03 25.64 24.95 26.42 25.91 25.73 0.09 0.21 0.03 0.24 0.16 21.38 21.20 20.93 21.17 0.09 0.18 0.09 0.12 14.80 13.87 16.08 16.57 15.33 12.73 12.46 12.73 12.64 0.53
Average deviation from the mean for method... .
. . .. . . . . . . . .
_ .
0.21
penetrated, appears t o be quite soft. The brick is apparently one which while having a very low absorption, has also low mechanical strength. I n order t o compare t h e effect of t h e penetration b y t h e boiling test and by t h e forty-eight hours total immersion, we proceeded as follows: A number of bricks were cut into halGes and t h e large openings in t h e fractured surfaces stopped with p u t t y . These faces were then given two coats of shellac varnish, each coating followed b y a baking a t 110' C . A coat of good spar varnish and another baking completed t h e treatment, which was designed t o prevent absorption through any b u t the natural external surfaces of t h e brick. One-half of each brick was then subjected t o t h e boiling test. of t h e American Society for Testing Materials, in potassium ferrocyanide solution, and t h e other half t o t h e 48 hours total immersion in the same medium. The halves absorbed approximately the same amounts as t h e whole brick did when subjected t o t h e same test. Since the ends of the brick may differ in absorptive capacity, exact agreement with results obtained on t h e whole brick is not t o be expected. The half which was boiled showed t h e usual increase in absorption percentage over the other half which was immersed for 48 hours. After treatment with ferric chloride t h e halves of t h e same brick showed considerable differences in the
......
t...................................................
0.51
structure. This is true for both t h e 48 hours total immersion and t h e boiling tests. z-Hard, vitrified bricks are penetrated only through channels and small absorbent zones b y t h e 48 hours immersion. The boiling test opens up more of t h e channels, b u t no large sections of bricks of this class are uniformly penetrated. 3-Bricks containing hard vitrified cores are penetrated t o t h e latter when merely immersed. These cores are well defined and t h e penetration apparently takes place naturally t o t h e core. Boiling forces t h e water into these cores t o a greater or less extent. 4-An important reason for t h e lack of definite relation between t h e absorption and porosity is t h e existence in some bricks of highly porous cores which are impenetrable in t h e ordinary immersion test. The absorption test has, therefore, many points of view from which i t should be regarded and interpreted. 5-The 48 hours total immersion test fails t o penet r a t e hard cores and apparently gives results which are more indicative of the natural absorptive capacity t h a n t h e boiling test. The assumption t h a t t h e 48 hours total immersion is a measure of the true natural absorption value has been borne out by another set of experiments. A number of bricks were three times subjected t o t h e 48 hours t o t a l immersion test, and the same bricks were likewise subjected to t h e boiling test of The American Society for Testing Materials a number of times. T h e
'
Oct., 1914
T H E J O U R X A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRE7
results are given in Table 111. I n relation t o these tests i t may be cited t h a t Douty and Beebel have found t h a t no change in t h e absorption value was caused b y repeated dryings and immersions. T h e mean results for each brick by each method were then calculated. Similarly t h e deviation of each result from t h e mean absorption for the brick by each method was obtained. The latter are given in t h e columns marked "Deviations from mean." The average deviation from t h e mean for each brick is also listed under the preceding heading. The average of t h e latter for all the bricks is a measure of t h e accuracy with which t h e test can be carried out. The average deviation for t h e 48 hours immersion is 0 . 2 1 per cent and for t h e boiling test 0.51 per cent, The balance used for weighing t h e bricks was accurate t o a gram. The cons t a n t error due t o weighing is, therefore, about 0.06 per cent and is t h e same for both methods. With t h e same instruments and care, results more t h a n twice as concordant may be obtained b y t h e 48 hours total immersion test t h a n b y t h e boiling test. The former being more accurate and uniform in indications is better adapted for contractual testing. The 48 hours total immersion test a t ordinary temperatures gives absorption values which uniformly and readily approach t h e same figure. This is apparently a substantiation of t h e theory t h a t t h e absorption by this method is t h a t natural and characteristic of the brick. STANDARD TESTINGLABORATORY B O A R DOF ESTIMATE A N D APPORTIONMENT NEW YORKCITY
ISOPRENE FROM COMMERCIAL TURPENTINES By CHAS: H. HERTYAND J. 0. G R A H A X Received July 27, 1914
I n connection with t h e studies of rubber made b y polymerization of isoprene, Harries and Gottlob3 described a method for t h e preparation of isoprene from spirits of turpentine b y means of t h e "isoprene lamp." I n this method t h e spirits of turpentine is boiled in a flask, in which, just below t h e neck, is suspended a n electrically heated platinum wire coiled somewhat like t h e filament of a tantalum incandescent bulb. A part of t h e vapors are decomposed as they pass upward across t h e heated wire. The flask is attached t o an upright condenser maintained at a temperature of 50" C., for condensing t h e unchanged vapors of spirits of turpentine. The upright condenser is connected with a n inclined condenser fed with t a p water and this in t u r n is connected with a receiver surrounded b y a freezing mixture. The crude product collected in this receiver is fractionated and t h e isoprene collected as t h e fraction boiling between 35" and 37" C. With this apparatus, Harries and Gottlob obtained a yield of only I per cent of isoprene from commercial pinene as against 30 t o j o per cent from commercial limonene. They, therefore, concluded t h a t t h e yield of isoprene from spirits of turpentine is due chiefly t o t h e presence of dipentene (limonene). Proc. Amer. SOC.f o r Testing MaLeuials, 11, i i 0 . 2 Presented a t the 48th Meeting of t h e American Chemical Society, Rochester.. SeDtember 8-12. 1913. . 8 Ann., 383, 228. 1
803
I n view of t h e general interest in the production of rubber from isoprene, i t seemed desirable t o extend these studies t o commercial products closely related t o spirits of turpentine and t o test further t h e point mentioned above as t o t h e origin of t h e isoprene from spirits of turpentine. Accordingly, studies have been made using commercial spirits of turpentine, fractions of t h e same, pine oil, t h e volatile oil of Pinus serotina (pond pine) and refined spruce pine turpentine. The apparatus used closely resembled t h a t of Harries and Gottlob, short-circuiting of t h e sections of red hot platinum wire being prevented b y winding t h e wire on a pipe stem triangular prism. A constant current of 2.25 amperes maintained a n even temperature of the wires a t a red glow. The flask containing t h e turpentine was heated by means of a bath of cottonseed oil containing a thermometer. The receiving vessel in t h e freezing mixture, salt and ice, was a small sulfurous acid condenser. The crude products were refined by distillation through a Hempel column filled with glass beads. The yield of pure isoprene in each of t h e experiments which follow represents the fraction collected between 3 j " and 37 " C. SPIRITS O F TURPENTINE
cc. of spirits of turpentine were boiled in t h e isoprene lamp until condensation ceased in the inclined condenser. At two-hour intervals the crude product was removed from t h e receiver and fractionated. Following this experiment, similar experiments were conducted with zoo cc. fractions of spirits of turpentine obtained b y fractionation b y means of a Young's still head. The first fraction was collected between 155' and 156' C., the pinene fraction; t h e second, between 1 6 9 " and 1 7 5 " C.; t h e third fraction from 1 7 5 ' C., up. These two last fractions should include the dipentene content of the original spirits of turpentine. The heating of the two last fractions was continued only two hours, as after t h a t time no further condensation could be observed in t h e inclined condenser. The results of t h e three experiments are shown in Table I. 200
TABLE I
--
Volume of Time distillate of TemperPer cent heating ature of Crude Refined of Substance used Hrs. oil bath Cc. Cc. isoprene 6.5 3.25 2 17.5' 17 Spirits of turpentine., 3.5 1.75 2 185' 8 1.0 0.50 Totals..
. ... . . . . ..
6 2
-
.. . .
175'
-
37 10
Fraction 155°-1560.. . 2
. ..
17.50
_ _ ,
...
180: 185
4
2i 56! 3.25
...
-
-
io3 --
11.0 6 5
5.50 3.00 2.50
103
2.00
4
Totals.. . . , . . . . 8 Fraction 169°-1750... . . 2 Fraction l i S 0 + .... , . . . 2
Volume of residue in heating flask Cc.
-1 16 1 0
0.50 ~
8.00 0.50 0 00
. .. ... ...
...
so
192 195
From t h e direct proof thus obtained it is evident t h a t the yield of isoprene from spirits of turpentine is due t o pinene, rather. t h a n t o dipentene as claimed by Harries and Gottlob. T H E V O L A T I L E OIL O F P I N U S S E R O T I S A
This substance has been studied b y Herty and Dickson' and was found t o be particularly rich in 1
J . A m . Chem. SOC.,30, 872.
