SEPTEMBER, 1939
INDUSTRIAL AND ENGINEERING CHEMISTRY
may be obtained the grams of nitrocellulose which will dissolve in any solvent-toluene mixture to form 100 cc. of base lacquer a t any given viscosity within the determined range. Figure 2A shows the relations as they exist a t the low solids content corresponding to a viscosity of 40 seconds, B shows the conditions existing a t 50-second viscosity, and C those a t 60 seconds. Finally, on the high solids side of the viscosity range, D shows the relations a t 70 seconds. The influence of the solids content upon the slope and relative positions of the curves for the various esters is illustrated most strikingly by a comparison of A and D. From Figure 1, curves for any viscosity within the given range other than those shown may be established. With these curves it becomes a simple matter to calculate the relative value of the solvent strengths of the solvents a t any desired viscosity. The method was covered in detail in the preceding paper (2) and consists in assigning a cost value to the solvents and to the diluent, calculating on this basis the costs of the amount of several different solvent-toluene mixtures necessary t o dissolve 100 grams of nitrocellulose with each of the eight solvents. Curves are drawn for solvent and diluent cost against nitrocellulose content, and from these curves the mixture of minimum cost for each solvent is determined. At this point the mixture of minimum cost for any one of the eight solvents may be chosen as a standard, and the values of the other solvents a t the same nitrocellulose content calculated accordingly; to make the evaluation still more complete, the value of each solvent may be calculated on the basis of the most economical mixture of all the other solvents. Obviously, the comparison of the cost values is of greatest practical use with solvents or solvent mixtures which have
1121
comparable evaporation rates and similar film-laying characteristics, or in cases where a change of these properties in one direction or the other is definitely desirable. The CVP has been used to evaluate, in addition to the esters covered in this paper, other acetates and propionates, several ketones, ether-alcohols, and miscellaneous solvents. Although toluene is the only hydrocarbon for which data have been presented, other commonly used diluents have been compared in formulas containing the solvents described here. Several commercially used petroleum hydrocarbons of both the aromatic and aliphatic types have been included. Lack of space prevents a complete description of these data, and the results will be reported in future communications. Dry nitrocotton has been used in the evaluations summarized above to conform with usual practice. However, comparable data are being obtained with commercial, alcohol-wet nitrocellulose. Further studies now under way demonstrate the utility of the CVP, not only for measuring the activating effect of various alcohols, but also for comparing in a practical way the influence of alcohol concentration on solvent activation. These investigations confirm the wide applicability of the constant viscosity procedure and will be described later with the other applications of this method.
Literature Cited (1) Gardner, H. A., “Physical and Chemical Examinations of Paints, Varnishes, Lacquers and Colors,” 8th ed., p. 585
(1937).
(2) Ware and Teeters, IND. ENQ.CHEM., 31, 738 (1939). PR~SH~NTIUD before the Division of Paint and Varnish Chemistry at the 96th Meeting of the American Chemical Society, Milwaukee, Wis.
Acidic Constituents of Bone Oil MAX F. ROY AND GEORGE HOLMES RICHTER The Rice Institute, Houston, Texas
A
LTHOUGH numerous studies have been made of the basic and indifferent portions of bone oil, there has been little mention of the acidic compounds present other than the reported isolation of phenol by Weidel and Ciamician (3). The purpose of this study was to investigate further the constituents of the acid fraction of bone oil. I n so far as possible the methods of modern qualitative organic analysis were followed in which the oil was treated as a very complex mixture. Preliminary experiments showed that extraction with immiscible solvents was impractical owing to the troublesome emulsions that formed. Therefore the crude oil was purified somewhat by the removal of the nonvolatile matter by distillation. This distilled oil was extracted with water, dilute acid, and dilute alkali. In this manner the constituents of the distillate were separated into the following groups: watersoluble compounds, 7.7 per cent by weight; organic bases, 22.6; organic acids, 2.9; indifferent compounds (i. e., substances not appreciably soluble in water and neither basic nor acidic), 66.8. The acidic fraction was found to contain phenol, o-cresol, m-cresol, p-cresol, 1,3,5-xylenol, and probably 1,4,3-xylenol. Some pyrrole was also found in this fraction; its presence was due to its solubility in water.
Sixty liters (51.2 kg.) of the crude oil were distilled to give 48 liters (41.5 kg.) of a clear yellow-brown oil and a water layer of 1.5 liters. The temperatures of distillation ranged from 80’ to 270 C. The residue was a black viscous tar which solidified on cooling. During the distillation small quantities of a white solid material collected in the condenser; it consisted of ammonium carbonate with smaller amounts of ammonium sulfide and cyanide. Four-liter portions of the distilled oil were extracted six times with 1-liter portions of water. In this operation the weight of the oil diminished 3.2 kg. or 7.7 per cent. Four-liter portions of the oil thus extracted were again extracted with 1-liter portions of 5 er cent hydrochloric acid until the extract was acid to Congo Reland then washed once with 0.5 liter of water. The weight of the oil decreased 9.4 kg , which indicated 22.6 per cent of organic bases. Four-liter portions of the remaining oil were then extracted with 1 liter of 5 per cent sodium hydroxide solution which was sufficient t o remove all the organic acids. The loss in the weight of the oil was 1.2 kg., representing 2.9 per cent of acidic constituents. After being washed with water, the residue from the extractions weighed 27.7 kg. This represents 66.8 per cent of indifferent compounds. O
Isolation of Acidic Constituents The alkaline extract was acidified with sulfuric acid and extracted with ether. The removal of the ether left a residue of 847 grams of crude acidic compounds, which was then put
INDUSTRIAL AND ENGINEERING CHEMISTRY
1122
through the systematic fractional distillation. Eleven fractions were finally obtained with the following characteristics: Fraction" I I1 I11 IV V
VI VI1
VI11 IX X XI a
b
Boiling Point OC. Mm. U p t o 128 760 128-131 760 131-182 760 50- 91 31 91- 93 31 93- 95 31 95- 98 31 98-106 31 106-108 31 108-111 31 111-116 31 116-126 31
{
1
Weight Grams 2 60 11 198 35 31 30 134 30 10 10
M. P. "C.
djg
.. .. ..
... ... ...
33 17.6 15.3 17.6 19.8
1.065 1.053 1.042 1.033 1.026
.. ....
... ... ...
Mol. Wt.b
94.5 98.3 102 108 109 109 119 120
Residue, 260 grams; loss on distillation, 36 grams.
BY the Rast method.
FRACTION I had a marked odor of mercaptans and gave a precipitate with mercuric chloride that did not melt sharply. FRACTION 11. Although this fraction had a strong odor of mercaptans it was suspected to be almost completely pyrrole. It was washed several times with 10 per cent potassium hydroxide to remove mercaptans and any true acidic compounds. The remaining oil was distilled (boiling point, 130131" C.). The distilled material was easily polymerized to a red solid by mineral acids and when heated with solid potassium hydroxide gave a potassium salt which was readily hydrolyzed to the original material by water. This substance was assumed to be pyrrole without further characterization. FRACTION IV had a distinctly phenolic odor and was partially solid a t room temperature. Its boiling point a t 760 mm. was 182-184" C. and its density (d::) 1.065. The aryloxyacetic acid derivative melted a t 95-96" C. and had a neutral equivalent of 152. These properties agree well with those of phenol. This was further confirmed by conversion into tribromophenol, melting a t 91-92" C., and picric acid, melting a t 121" c. FRACTION VI had a boiling point of 189-192" C. a t 760 mm., and a density (d::) of 1.042. The aryloxyacetic acid derivative melted at 152-153" C. and had a neutral equivalent of 165.4. This fraction was therefore concluded to be mainly o-cresol. FRACTION VI11 boiled a t 201-202" C. a t 760mm.; its density (d::) was 1.026. It was suspected that this fraction contained both m- and p-cresols. Fifteen grams of this fraction were heated with 10 grams of anhydrous oxalic acid for one hour to give a clear solution. Crystals of p-cresyl ester of oxalic acid separated on cooling ( 2 ) . They were removed by filtration and washed with benzene. The ester was hydrolyzed by being heated with dilute hydrochloric acid for one hour. An oil of phenolic character separated during this process which was found to boil from 200-202" C. Its aryloxyacetic acid derivative melted a t 136-137 " C. and had a neutral equivalent of 165.6. It was concluded to be p-cresol. The filtrate and benzene washings from the above mentioned ester were evaporated to leave a residue which was distilled (boiling point, 200-202" C.). This material was evidently a mixture, inasmuch as its aryloxyacetic acid derivative melted over the range 120-130" C. This melting point did not change on repeated recrystallization. However, 1 cc. of the material was heated a t 100" C. with 20 cc. of concentrated nitric acid and 20 cc. of concentrated sulfuric acid for one hour. On dilution with water, yellow needles of trinitro-m-cresol (melting a t 106-106.5" C.) separated from the solution. FRACTIONS X AND XI. The boiling points and molecular weights of these fractions indicated that they probably consisted of one or more of the xylenols. However, since the boiling points of the six isomeric xylenols ranged from 212225" C. and coincided for several isomers, a clean-cut separation by distillation was not to be expected.
VOL. 31, NO. 9
The aryloxyacetic acid derivative of fraction X melted from 109-112" C. After three recrystallizations it had a neutral equivalent of 173. This is evidently a mixture and is in better agreement with 1,4,3-xylenol than any of the other isomers. The aryloxyacetic acid of fraction XI1 melted from 8588" C. and had a neutral equivalent of 182. This is in good agreement with the constants for 1,3,5-xylenol derivative (1). FRACTIONS 111, V, VII, and IX were not investigated inasmuch as they were regarded as intermediate fractions.
Acknowledgment The authors wish to express their appreciation to the Consolidated Chemical Industries, Inc., of Houston, for the generous supply of material.
Literature Cited (1) Meyer, "Nachweiss und Bestimmung der organischen Verbindungen," p. 241,Berlin, Julius Springer, 1933. (2) Riitgers, German Patents 137,584 and 141,421 (1901). (3) Weidel and Ciamician, Ber., 13,65 (1880).
Setting of Cement under High Gas Pressure JUDSON SWEARINGEN
The University of Texas, Austin, Texas
S
EVERAL observations in high-pressure gas wells have indicated that the cement may not be setting when saturated with gas a t extreme pressures. For instance, the mud blown from gas wells during the cleaning period often has the characteristic taste of cement. To be sure, this may have been cement that was too diluted by the mud or water to set. I n one case where two strata separated by 4 feet of hard formation were tested separately, there was an indication that the cement was not holding. I n two wells used for injecting gas in repressuring operations, the casing head, commonly known as the "Christmas tree," rose more than was expected. These findings prompted us to investigate the setting properties of cement under bottom-hole conditions and saturated a t that pressure with wet natural gas. Two comparative tests were made at a pressure of 3100 pounds per square inch and 180" F. on a well-known brand of slow-setting cement. The mold inside the bomb was 2 inches inside diameter and 6 inches long but was only two thirds full of cement slurry. This allowed room for shaking and saturating the cement slurry with the gas while it was under pressure before it was left in an upright position to set. A similar test specimen from the same batch was allowed to set in the same thermostatic bath but a t atmospheric pressure. The results are as follows: Setting Time
Water :Cement Ratio
Hours
Gal./sack
48 96
5.5 5.5
Compressive Breaking Strength
Gas-aatd.
sample Lb. p e r 4410 4831
sq.
Blank in. 3973 5140
These are close enough to be considered checks. Hence the obvious conclusion is that wet gas does not affect the setting of portland cement, even a t 3100 pounds per square inch and 180" F. The author wishes to thank John F. Camp for his financial assistance in conducting this work.
