A Table for Ebulliometers For Use with Alcoholic Liquids Containing Solid Matter R . F. LOVE, Alcohol Tax Unit Laboratory, Bureau of Internal Revenue, San Francisco, Calif.
and although it had not been certified bv the National Bureau of Standards, it agreed very closely with the Taylor instrument. In a third ebulliometer, water was kept boiling continuously to detect any change in boiling point during the periodp of testing. Before each series of tests, the ebulliometers were cleaned by boiling with a strong solution of alkali to remove the film of solid matter which collects inside the boiler after only a few tests are made and which causes bumping. Solutions containing more than 10 grams per 100 ml. of sucrose were not used because of the tendency of liquids of high-solid content to bump. Such liquids are best analyzed by diluting the samples. Even after thorough washing of the boiler, the first boilin point of water was usually different from the succeeding ones; &ere fore the boiling point of water was obtained by boiling successive portions of water until several duplicate results were obtained. The boiler was then thoroughly rinsed with the alcoholic liquid to be tested, but in spite of that fact, the boiling point of the solution was affected by the previous presence of water and the first reading had to be discarded, as it was usually high, corresponding to a percentage of alcohol which was too low.
T
HE ebulliometer is used in many industrial plants such as wineries, breweries, and distilleries for rapid determination of the alcohol content of wine, beer, mash, and distilled liquors. The tables or scales which accompany the ebulliometers are constructed for liquids containing either no solid matter or one rather definite quantity of solids such as would be found in beer or light wine. Since the variety of alcoholic liquids which the ebulliometer may be called upon to analyze is rather large and may cover solid contents of considerable range, a table which takes into account such solid matter may be of value. To obtain data with which to construct such a table, mixtures of 192-proof ttlcohol, sucrose, and distilled water were prepared containing approximately 1, 3, 5, 7, 9, and 11 per cent of alcohol by volume accurately determined by a pycnometcr, and 0, 2, 4, 6 , 8 , and 10 grams of sucrose er 100 ml.-a total of 36 solutions. Dilutions were made with a Euret and a volumetric flask which were checked against each other, and the liquids were measured at 20' C . Each solution was tested, simultaneously, in a Juerst and a Salleron ebulliometer. The thermometer used with the Juerst was manufnctured by the Taylor Instrument Company, was graduated the stirne as the Juerst thermometers, and was certified by the National Bureau of Standards. The thermometer used with the Salleron was the one furnished with the ebulliometer,
The boiling point of each solution was determined at least six times with each ebulliometer. T h e readings were made by observing the thermometers every 15 seconds from the time boiling started until the mercury remained constant during several observations. The point at which the mercury was
TABLE 1. BOILINGPOINT DIFFERENCES, JUERST EBULLIOMETER Alcohol
of Sucrose per 100 M1. of Solution-
-Grams 0
2
0.95 2.68 4.20 5.60 6.83 7.96
0.92 2.68 4.23 5.65 6.91 8.02
4
6
8
10
0.89 2.69 4.22 5.66 6.92 8.12
0.86 2.72 4.25 5.71 7.02 8.19
0.83 2.07 4.27 5.73 7.07 8.17
0.82 2.70 4.30 5.76 7.12 8.27
Sucrose Qranzs/100 ml. 0
%
I"
0.9585 2.8755 4.7925 6.7095 8.6265 10.5435
0
0 0
0
0
2 2 2 2 2 2 4 4 4 4 4 4 6 6 6 6 6 6 8
TABLE 11. ADJUSTED RESULTSUSEDIN CONSTRUCTING A TABLE, JUERST EBULLIOMETER Alcohol
-Grams
of Sucrose per 100 MI. of Solution4 6 8
0
2
0.95 2.68 4.20 5.00 6.82 7.96
0.92 2.68 4.22 5.63 6.88 8.02
10
% 0.9585 2.8755 4.7925 6.7005 8.6365 10.5435 ~~~~
0.89 2.68 4.24 5.66 6.94 8.08
0.86 2.68 4.26 5.69 7.00 8.14
0.83 2.68 4.28 5.72 7.06 8.20
0.80 2.68 4.30 5.75 7.12 8.26
~
SALLERON TABLB 111. BOILINGPOINTDIFFERENCES, EBULLIOMETER Alcohol % ._ 0,0585 2.8755 4.7025 6.7005 8.6255 10.5435
-Grams
of Sucrose per 100 M1. of Solution4 6 8
0
2
0.94 2.68 4.20 5.60 6.84 7.96
0.92 2.68 4.23 5.65 6.90 8.02
0.89 2.69 4.26 5.66 6.92 8.09
0.88 2.70 4.29 5.71 6.96 8.16
0.85 2.70 4.31 5.77 7.06 8.17
TABLE v. READINGS WITH JUERST EBULLIUMETER
8 8
10
8 8
0.84 2.70 4.35 5.81 7.10 8.26
8
10 10 10 10 10 10
Alcohol % by volume 0.9585 2,8755 4.7925 6.7085 8.6265 10.5435 0.9585 2.8755 4.7925 6.7095 8,6265 10,5435 0.9585 2.8755 4.7925 6.7095 8.6265 10.5435 0.9585 2.8755 4.7925 6.7095 8.6265 10.5435 0.9585 2.8755 4.7025 6.7095 8.6265 10.5435 0.9585 2.8755 4.7925 6.7095 8.6265 10.5435
Boiling Point Difference Found
High
Low
Variation
0.95 2.68 4.20 5.61 6.83 7.08 0.92 2.68 4.23 5.65 6.91 8.04 0.89 2.69 4.22 5.66 6.92 8.12 0.86 2.72 4.26 5.71 7.02 8.19 0.83 2.67 4.27 5.73 7.07 8.17 0.82 2.70 4.30 5.76 7.12 8.27
0.95 2.69 4.22 5.63 6.85 7.99 0.93 2.69 4.24 5.68 6.93 8.05 0.89 2.70 4.25 5.70 6.93 8.14 0.87 2.73 4.27 5.74 7.04 8.21 0.84 2.70 4.30 5.76 7.11 8.18 0.84 2.71 4.32 5.78 7.15 8.29
0.94 2.67 4.19 5.69 6.82 7.97 0.92 2.67 4.22 5.62 6.87 8.03 0.90 2.67 4.20 5.63 6.90 8.10 0.85 2.70 4.22 5.68 7.00 8.18 0.82 2.63 4.23 5.71 7.03 8.13 0.81 2.68 4.26 5.73 7.10 8.24
0.01 0.02 0.03 0.04 0.03 0.02 0.01 0.02 0.02 0.06 0.06 0.02 0.01 0.03 0.05 0.07 0.05 0.04 0.02 0.03 0.05 0.06 0.04 0.03 0.02 0.07 0.07 0.05 0.08 0.05 0.03 0.03 0.06 0.05 0.05 0.05
TABLE IV. ADJUSTED RESULTS,SALLERON EBULLIOMETER Alcohol
-Grams 0
2
of Sucrose per 100 M1. of Solution4
6
8
10
0.90 2.69 4.26 5.68 6.94 8.07
0.88 2.69 4.29 5.72 6.99 8.13
0.86 2.69 4.32 5.76 7.04 8.19
0.84 2.69 4.35 5.80 7.09 8.25
TABLE VI. FORMULAS FOR CALCULATING EBULLIOMETER TABLE (Figures in first column represent grams of sucrose 0.0300421 0 2 1 = 0.984602 0.02088sZ 2 1 / = 1.006182 0.00907~2 4 1,03436s 2/= 0.00072~2 6 2 / = 1.05861s 0.008172z 8 Y E 1.08209s 0.02054~2 10 Y = 1.115772
% 0.9585 2.8755 4.7025 6.7005 8.6255 10.5435
0.94 2.69 4.20 5.60 6.84 7.95
0.92 2.69 4.23 5.64 6.89 8.01
++ ++-
548
per 100 ml. of solution)
++ 0.00158~s 0.0021 9x8 0.002912~ ++ 0.00348~s ++ 0.00402~8 0.00484~8
OCTOBER 15, 1939
ANALYTICAL EDITION
stationary for the longest period was recorded and the total of such readings averaged. Readings were estimated to hundredths of a degree on each thermometer. Results obtained, in boiling point differences, are shown in Table I for the Juerst and in Table I11 for the Salleron. Since these figures were slightly irregular, they were adjusted so that when plotted, smooth curves would be obtained. Table I1 shows the adjusted results used for constructing the table for
549
the Juerst ehulliometer. The adjusted results for the Salleron, shown in Table IV, were so nearly like the corresponding ones for the Juerst that one table was considered satisfactory for both ebulliometers. Table V shows the highest and lowest readings obtained for each solution and proves that consistent results can be obtained by using care in all of the manipulations. The variations in individual readings on the Salleron thermometer were larger than those on the Juerst because the
TABLE VII. TABLE TO ACCOMPANYEBULLIOMETER (Per cent of alcohol by volume corresponding to differences in boiling points for quantities of sucrose between 0 and 10 grams per 100 ml.) Boiling Boiling Point -Grams of Sucrose per 100 M1. of SolutionPoint -Grams of Sucrose per 100 MI. of Solution2 0 Difference 4 6 8 Differenoe 10 2 0 4 6 8 10 Per cent by volume Per cent b y volume -0.15 .. 0.0 3.95 4.45 4.43 4.42 4.41 4.40 4.39 -0.10 .. 0101 0 04 4.00 4.50 4.52 4.4s 4.46 4.47 4.45 -0.05 0:0 0103 0.06 0.09 4.05 4.57 4.59 4.55 0.0 4.53 4.52 0:0 0:02 0.05 4.51 0.11 0.14 0.08 4.10 4.63 4.61 4 65 4.59 4.58 4.57 0.05 0.05 0.07 0.10 0.13 0.16 0.19 4.15 4.70 4 72 4.68 4.66 4.64 4.63 0.10 0.10 0.12 0.15 0.21 0.18 0.24 4.20 4.76 4.78 4.74 4.72 4.70 4.68 0.15 0.15 0.17 0.19 0.25 0.22 0.28 4 25 4.83 4.85 4.81 4.78 4.76 4.74 0.20 0.20 0.22 0.24 0.30 0.33 0.27 4 30 4.80 4.91 4.87 4.84 4.82 4.80 0.25 0.25 0.27 0.29 0.35 0.32 0 38 4.96 4 35 4 98 4.93 4.90 4.88 4.86 0.30 0.30 0.32 0.34 0.40 0.37 0 43 4 40 5.02 5.04 4.99 4.96 4.94 4.92 0.35 0.35 0.39 0.44 0.37 0.41 0.47 4 45 5.08 5.11 5.05 5.02 5.00 4.98 0.40 0.40 0.44 0.42 0.49 0.46 0.52 4 50 5.15 5.18 5.12 5.09 5.06 5.04 0.45 0.49 0 45 0.47 0.54 0.51 0.57 4 55 5.22 5 25 5.19 5.16 5.13 5.10 0.50 0.54 0.50 0.52 0.59 0.56 0.62 4 60 5.28 5.32 5.25 5.22 5.19 5.16 0.55 0.59 0.55 0.57 0.64 0.61 4 65 0.67 5.34 5.31 5.38 5.28 5.25 5.22 0.60 0.64 0.62 0.60 0.69 0.66 0 72 5.41 4 70 5.38 5.45 5.35 5.32 5.29 0 65 0.65 0.69 0.67 0.73 0.71 4.75 0.76 5.48 5.45 5.52 5.41 5.38 5.35 0.70 0.70 0.74 0.72 0.78 0.76 4.80 0 81 5.55 5.52 5.59 5.48 5.46 5.42 0 75 0.76 0.80 0.78 0.84 0.82 4.85 0 86 5.62 5.69 5.66 5.52 5.55 5.48 0.80 0.85 0.81 0.83 0.89 0.87 0.91 4 90 5 69 5.73 5.66 5.58 5.62 5.54 0 85 0.86 0 no 0.88 0.94 0.92 4.05 0.96 5.76 5.73 5.80 5.65 5.69 5.61 0 90 0.91 0.92 0.94 0.9s 0.96 1.00 5.00 5.83 5.79 5.87 5.71 5.75 5.67 0.05 0.97 0.96 0.99 1.03 1.01 1.05 5.05 5.94 5.90 1.00 5.86 5.82 1.02 1.04 5.78 1.03 5.74 1.08 1.06 1.10 5.10 6 01 5.96 5.92 5.84 5.88 5.80 1.05 1.07 1.08 1.09 1.11 1.13 1.15 5.15 6.03 5.99 6.08 5.91 5.95 5.87 1.10 1.12 1.14 1.13 1.16 1.18 1.20 5.20 6.15 6.10 6.06 6.01 5.97 5.93 1.15 1.17 1.19 1.18 1.21 1.23 1.25 5.25 6.22 6.17 6.13 6.04 6.08 6.00 1.20 1.22 1.23 1.24 1.26 1.2s 1.30 5.30 6.25 6.30 6.20 6.11 6.15 6.06 1.25 1.29 1.30 1.28 1.32 1.34 1.36 5.35 6 32 6.37 6.27 6.22 6.17 6.12 1.30 1.34 1.35 1.33 1.37 1.39 1.41 5.40 6.44 6 39 6.34 6.29 6.24 6.19 1.35 1.41 1.39 1.40 1.43 1.45 5.45 1.47 6.52 6.46 6.41 6.36 6.31 6.26 1.40 1.44 1.46 1.45 1.48 1.50 5.50 1.52 6.59 6.53 6.48 6.43 6.38 6.33 1.45 1.52 1.51 1.50 1.54 1.56 5.55 1.58 6.66 6.60 6.55 6.49 6.44 6.39 1.50 1.57 1.55 1.56 1.59 1.61 5.60 1.63 6.73 6.67 6.62 6.56 6.51 6.45 1.55 1.63 1.61 1.62 1.65 1.67 5.65 1.89 6.81 6.74 6.69 6.63 6.57 6.51 1.60 1.68 1.66 1.72 1.67 1.70 5.70 1.74 6.88 6.81 6.76 6.70 6.64 6.58 1.65 1.72 1.74 1.73 1.78 1.76 5.75 1.80 6.95 6.88 6.83 6.77 6.71 6.55 1.70 1.80 1.77 1.78 1.84 1.82 5.80 1.86 7.03 6.96 6.90 6.84 6.78 6.72 1.75 1.86 1.84 1.83 1.92 1.00 1.88 5.85 7.04 7.11 6.08 6.92 6.86 6.80 1.80 1.01 1.89 1.88 1.05 1.93 1.97 5.90 7.11 7.18 7.05 6.99 6.93 6.87 1.85 1.94 1.97 1.95 2.01 1.99 2.03 5.95 7.18 7.25 7.12 7.06 7.00 6.93 1.90 1.99 2.02 2.00 2.06 2.04 2.08 6.00 7.26 7.33 7.19 7.13 7.07 7.00 1.95 2.05 2.08 2.06 2.12 2.10 2.14 2.00 6.05 7.40 7.33 7.26 2.13 2.10 2.11 7.20 7.13 2.17 2.15 7.06 2.19 6.10 7.41 7.34 7.48 7.27 7.20 7.13 2.05 2.16 2. I9 2.17 2.21 2.23 6.15 2.25 7.48 7.55 7.41 7.34 7.27 7.20 2.10 2.21 2.24 2.22 2.26 2.28 6.20 2.30 7.56 7.63 7.49 7.42 7.35 7.28 2.15 2.30 2.28 2.27 2.32 2.34 6.25 2.36 7.64 7.56 7.71 7.42 7.49 7.35 2.20 2.36 2.34 2.33 2.38 2.39 2 41 6.30 7.72 7.64 7.79 7.50 7.57 7.43 2.25 2.42 2.40 2.39 2.44 2.45 6.35 2 47 7.80 7.87 7.72 7.57 7.65 7.50 2.30 2.47 2.45 2.44 2.49 2.50 6.40 2.52 7.87 7.94 7.79 7.64 7.72 7.57 2.35 2.62 2.50 2.50 2.54 2.55 6.45 2.57 7.05 8.02 7.87 7.72 7.80 7.65 2.40 2.58 2.56 2.56 2.59 2.60 6.50 2.62 8.03 8.10 7.95 7.79 7.87 7.72 2.45 2.62 2.64 2.62 2.65 2.66 2.68 6.55 8.10 8.18 8.02 7.86 7.94 7.79 2.50 2.69 2.67 2.67 2.71 2.70 6.60 2.73 8.18 8.26 8.10 7.94 8.02 7.86 2.55 2.75 2.73 2.73 2.76 2.77 6.65 2.79 8.26 8.34 8.18 8.02 8.10 7.94 2.60 2.81 2.79 2.79 2.82 2.83 6.70 2.85 8.34 8.42 8.26 8.10 8.18 8.02 2.65 2 87 2.85 2.85 2.88 2.89 6.75 2.91 8.42 8.60 8.34 8.17 8.26 8.09 2.70 2.01 2.93 2.91 2.94 2.95 6.80 2.97 8.49 8.58 8.41 8.24 8.33 8.16 2.75 2.97 2.97 2.98 2.99 3.01 3.03 6.85 8.49 8.57 8.66 8.31 8.40 8.13 2.80 3.04 3.03 3.03 3.05 3.07 3.08 6.90 8.65 8.74 8.57 8.39 8.48 8.31 2.85 3.10 3.09 3.09 3.12 3.11 3.13 6.95 8.73 8.82 8.65 8.47 8.56 8.38 2.90 3.15 3.15 3.15 3.16 3.17 3.18 7.00 8.82 8.91 8.73 8.55 8.64 8.46 2.95 3.21 3.21 3.21 3.21 3.22 3.23 3.00 7.05 3.27 8.99 8.90 3.27 3.27 8.81 8.72 8.63 3.27 3.28 8.54 3.29 7.10 9.07 8.98 8.89 8.80 8.71 8.62 3.05 3.33 3.33 3.33 3.33 3.84 3.35 7.15 9.06 9.15 8.97 8.86 8.79 8.70 3.10 3.39 3.39 3.39 3.39 3.40 3.41 7.20 9.23 9.14 9.05 8.96 8.87 8.78 3.15 3.45 3.45 3.45 3.46 3.45 3.47 7.25 9.31 9.22 9.13 9.04 8.95 8.86 3.20 3.51 3.50 3.50 3.50 3.51 7.30 3 52 . 9.40 9.31 9.22 9.12 9.03 8.94 3.25 3.57 3.56 3.56 3.56 3.57 3.58 7.35 9.48 9.39 9.30 9.20 9.11 9.01 3.30 3.63 3.62 3.62 3.62 3 63 3.64 7.40 9.57 9.48 9.38 9.28 9.19 9.09 3.35 3.69 3.68 6.68 3.68 3.69 3.69 7.45 9.65 9.56 9.46 9.36 9.27 9.17 3.40 3.75 3.74 3.74 3.74 3.74 3.74 7.50 9.74 9 65 9.55 9.45 9.36 9.26 3.45 3.81 3.80 3.80 3.80 3.80 3.80 7.55 9.82 9.73 9.63 9.53 9.44 9.34 3.50 3.87 3.86 3.86 3.86 3.86 3.86 7.60 9.91 9.81 9.71 9.61 9.52 9.42 3.55 3.94 3.93 3.93 3.92 3.92 3.92 7.65 9.90 IO.00 9.80 9.70 9.61 9.51 3.60 4.00 3.99 3.99 3.98 3.98 3.98 7.70 9.99 10.09 9.89 9.70 9.79 9.60 3.65 4.06 4.05 4.05 4.04 4.04 4.04 7.75 10.18 10.08 9.98 9.88 9.78 9.68 3.70 4.13 4.12 4.12 4.11 4.10 4.10 7.80 10.26 10.16 10.06 9.96 9.86 9.76 3.75 4.20 4.19 4.18 4.16 4.17 4.16 7.85 10.35 10.25 10.15 9.95 10.05 9.84 3.80 4.26 4.25 4.24 4.22 4.23 4.22 7.90 10.44 10.34 10.24 IO.03 10.14 9.92 3.85 4.32 4.30 4.31 4.28 4.29 4.27 10.42 7.95 10.52 10.32 10.11 10.22 LO. 00 3.90 4.39 4.37 4.36 4.34 4.35 4.33 8.00 10.61 10.51 10.40 10.19 10.30 LO.09
..
VOL. 11, NO. 10 the Juerst table a t boiling point difference 5.00 and from 6.20 to 7.75. A correction table (1) to be used for beer and beverages having a real extract (solids) of from 3 to 12 per cent gives a factor to be added to the alcohol found, according to the amount of solids present. It agrees exactly with Table VI1 a t 5.66 per cent alcohol, for t h e various percentages of sucrose, but it cannot be used for liquids containing other percentages of alcohol.
Literature Cited (1) E i m e r a n d A m e n d , Bull. 600, p. 6. (2) U. 8. Internal Revenue Regulations, 7, Table
VII.
(3) Ibid., Table VIII.
FIGURE1
A Modified Jones Reductor scale divisions of the Salleron are smaller and consequently more difficult to read. A formula was obtained for each series of solutions containing the same quantity of sucrose, by use of the equation y = ax bxZ cx3,in which y is the difference between boiling points, x is the per cent of alcohol by volume, and a, b, and c are constants whose values were calculated from the experimental data, by the method of least squares. These formulas are shown in Table VI. By their use Table VI1 was constructed, showing per cent of alcohol by volume, for each 0.05 degree difference between boiling points, from 0 to 8, for solutions containing 0,2,4,6,8,and 10 grams of sucrose per 100 ml. This table may be used with any ebulliometer whose thermometer is based on the Centigrade scale. Using boiling point differences as ordinates and percentage of alcohol as abscissas, the author plotted a curve for each quantity of sucrose used. These curves are shown in Figure 1. The column of Table VI1 for solutions containing no sucrose agrees very well with the table which accompanies the Lefco ebulliometer (3) except a t one point. When the boiling point differences in the Lefco table are plotted against percentages of alcohol, they form a smooth curve, except for the boiling point differences 4.00 to 6.00, where they form a straight line. Evidently the interpolations at that part of the table were made by proportion rather than by use of a formula. Almost exactly the same discrepancy is noticed a t the corresponding part of the Juerst table (2). At boiling point difference 6.20, Table VI1 and the Juerst table again begin to separate and a t 7.75, the highest point on the Juerst scale, the discrepancy is 0.07 per cent alcohol. Repeated attempts to check the Juerst table a t its upper limit were unsuccessful. Table VI1 agrees very well with the Lefco table a t its upper limit. It is concluded that there is a small error in the Lefco table a t boiling point difference 5.00 and in
+ +
W. A. TAEBEL, University of Illinois, Urbana, Ill.
T
HE Jones reductor is a convenient apparatus for effecting the reduction of certain compounds. Its efficiency in certain cases, however, is governed by the rate at which the solution containing the substance to be reduced flows through the reductor. A definite rate of flow through a Jones reductor equipped with an ordinary stopcock can be obtained only by trial and error; furthermore, duplicate rates are practically impossible. The modified Jones reductor herein described enables one to obtain a definite and constant rate of flow. This may be accomplished by fitting the delivery tube of the reductor with replaceable ground-glass capillary tubes of varioussized orifices. The tip of the delivery tube is first expanded to form the female joint. A 15-cm. (6-inch) length of capillary tubing, possessing an inside diameter of 1.5 mm. and an outside diameter approximately equal to that of the delivery tube of the reductor, is heated at one end until the orifice is barely closed. The capillary tube is then heated at a point 5 cm. ( 2 inches) from the closed end and drawn out until it possesses a taper simulating that of the female cone. The male cone is obtained by cutting the tubing at the constriction. Three or four male cones should be made and ground into the delivery tube of the reductor, care being taken not t o grind too long on any one cone before grinding in the next. In this way all the cones are gradually ground to the same size and may be used interchangeably in the reductor. The closed tips of the cones are then ground down on a piece of plate glass until each cone possesses the desired orifice size. In this way cones delivering approximately 20, 50, 100, or any desired number of milliliters er minute may be obtained. The volume delivered must be getermined by trial. If too large a volume is delivered, the orifice may be closed slightly by reheating the tip.
