386
0. F. TOWER.
tests is very small. The influence of the nature of the hot surfaces, like porcelain or glass, is so great as to warrant the assumption that the decomposition takes place almost altogether on the impact of the ammonia molecule against the solid surface. With a rough surface a larger proportion of impinging molecules are decomposed than with a smooth surface. Experimentally, it has been found that ammonia gas in contact with a hot glass tube may be decomposed only slightly, while a t the same temperature in contact with an equal extent of porcelain, the decomposition may be fifty times as great. It follows as a conclusion that in the destructive distillation of coal, the decomposition of ammonia map be prevented by keeping the temperature low, and by lessening, so far as possible, the time which the red-hot gases remain in contact with rough substances like coke or the fire-clay retort. The introduction of blue water-gas into the retorts, as in the Lewes process, should, by rapidly sweeping out the gases, lessen the ammonia decomposition. The high yield of ammonia in the Mond gas producer map be assigned to the combination of lower temperature and rapid withdrawal of the gases. CHEMICAL L A B O R A T O R Y , 1-XIVERSITY Or l f I C H I G A K
NOTE ON T H E CONSTITUTION OF CERTAIN ORGANIC SALTS OF NICKEL A N D COBALT A S THEY EXIST IN AQUEOUS SOLUTION. BY 0 . F. TOWER. Received January 28, 1905.
IN A former paper1 it was shown that the nickel and cobalt salts of succinic, malic and tartaric acids exist in a polymerized state in aqueous solution, and that this polymerized condition becomes more noticeable the more hydroxyl groups are present in the molecule; that is, the tartrates are more polymerized than the malates, and these latter than the succinates. These facts were brought out by means of measurements of the electrical conductivity and determinations of the depression of the freezing-point of solutions of these salts. An extension of these determinations2 to the salts of malonic and tartronic acids showed 1 2
This Journal, 24, 1012 LOG. c i f , ,pp. 1020-1022.
(1902).
ORGANIC SALTS OF NICKEL AND COBALT.
387
that the salts of the latter were no more polymerized than those of the former, that is, that the hydroxyl group in this case apparently did not increase polymerization of the molecules. It was, however, stated a t the time that this was probably an exceptional case, as the lowest members of many of the organic series exhibit peculiar behavior. To throw further light on this subject, I have recently extended these investigations to the salts of the glutaric acid series. The nickel, cobalt, and magnesium salts of glutaric, a-hydroxyglutaric, and trihydroxyglutaric acids have been prepared and their conductivity and freezing-points determined. The first of these acids was a preparation of Merck, the second of Gerhardt, and the last was made by myself from arabinose, according to the method of Ki1iani.l The yield of trihydroxyglutaric acid was small, but after crystallizing from alcohol enough was obtained to prepare the three salts in sufficient quantity to make one complete series of determinations. The solutions were prepared in the manner detailed in the paper already referred to, and almost all of the phenomena mentioned there were observed here. All of the solutions, except that of magnesium trihydroxyglutarate, which seemed to be exceptionally soluble, were practically saturated. The analyses of the solutions and the details of the measurements were likewise the same as before. The conductivity of the water used in preparing the solutions was I .8 x IO^. This was subtracted from the conductivity of the solutions. The molecular conductivity, M , of the salts is shown in Table I ; v represents the number of liters in which a gram-molecule of the salt was dissolved.
V
33. I5 2 x 3 3 . I5 4 x 3 3 . I5 8x33.I5 16X33.15 3 2 x 3 3 . I5 6 4 x 3 3 . I5 1
TABLEI. NICKELGLUTARATE. M V 84.7 34.47 99.3 2 x34.47 115.9 4x34.47 129.9 8X34.47 142 * 7 16 x 34.47 154.5 32 x 3 4 . 4 7 165.6 6 4 X 34.47
Be?. d. chem. Gcs., ai, 3007 (1888).
M 91.3 106.4 122.3 135.4 147. I 157.7 167.8
0.
F. TOWER.
MAGNESIUMGLUTAKATE. 21
sI
22.80
87.5
2X22.80 4X22.80 8 X22.80 16X22.80 32X22.80 64 X 2 2 . 8 0
96.7 107.7 119.4 130.4 140.7 149.2
7J
23.48 2X23.48 4 x 23.48 8 X23.48 16 X23.48 3 2 X 23.48 64 X 23. 48
Z'
31.38 2X31.38 4X31.38 8X31.38 16X31.38 32x31.38 64X31.38
M 25.56 ~ X z jj 6. 4X2j.j 6 8 X25.56 16X25.56 32x25.j 6 6 4 X 25.56
COBALTHYDROXYGLCTARATE. -21 V 67.1 81.6 97.6 110.0
12j.3 138.8 1j0.6
24.16 2X24.16 4X24.16 8Xq.16 16X24.16 32X24.16 64X24.16
COBALTGLUTARATE. M 7J 90.7
104.j 118.6 132.8 146.7
158. j 1;o.o
29. 70 2x29.70 4x29.70 8X29.70 1 6 x 2 9 . 70 32 x 29.70 64X29.70
86.8 97.6
108.6 119.5 131, I 141.8 152.4
-11 66.6
81 .o 95.3 109.9 123. I
137.5 1j1.1
11f 86.7 101.3
114.7 129.3
143.7 155.4 165.3
NICKELHYDROXYGLUTARATE. V
33.31 2x33.31 4x33.31 8x33.31 16X33.31 32x33.31 64 x 33.31
V
21.54 2 X Z I .54 4X21.54 8X21.54 16 X 21.54 32x21.54 64X21.54
iVI 71.3 87.3 102.8 121.8 138.8 156.2 168.9
J
30.41 2 x30.41 4X30.4' 8 X30.41 16 X 30.41 32x30.41 6 4 X 30.41
MAGNESIUMHYDROXYGLUTARATE. 31 7, 8j. I 98.6 113.2 127.7 139.5 151.3 161 .o
23.32 2x23.32 4x23.32 8X23.32 16X23.32 32 x 23.32 64 >*: 2 3.3 2
ill 71.4 86.6 101.9 116.6 132.2 147.0 161.2
;M
88.4 101.9 115.5 127.6
'39.4
150.7 160.6
389
ORGANIC SALTS OF NICKEL A N D COBALT.
MAGNESIUMTRIHYNICKEL TRIEYDROXYGLU-~-COBALT TRIHYDROXYTARATE.
39.13 2 x 3 9 . '3 4 x 3 9 . I3 8 x 3 9 . I3 16X39.13 32X39.13 64X39.13
DROXYCLUTARATE.
CLUTARATE.
M
V
53.0 62.8 72.4 82.6 92.1 101.6 111.6
M
V
42. I 4 2X42.14 4X42.14 8X42.14 16X42.14 32X42.14 64X42.14
M
V
51.6 62.9 74.7 89. I 100.6 116.0 131.6
10.600 2X10.600 4X10.600 8X10.600 16X10.600 32X10.600 64X10.600 1:28X10.600
38.8 47.8 57.8 70.3 84.0 99.0 114.9 130.7
From these results, interpolations have been made graphically for the dilutions, v = 16, 32, etc. These interpolated values are given in Table 11. In cases where the conductivity was determined in duplicate, only the averages are given in the table. TABLE11. MOLECULARCONDUCTIVITY
OF
GLUTARATES.
u.
Nickel.
Cobalt.
16 32 64
87.0
89.5 103.4 117.6 131.9 145.9 157.6 168.3
I28 2 56 512
1024 2048
..
..
102. I
117.8 131.5 143.9 155.3 165.9
MOLECULARCONDUCTIVITY u.
16 32 64 I 28 2 56 512 1024 2048
OF
Cobalt.
71.6 87. I 102.4 119.0 134.6 151.7 165.4
72.9 87.5 101.7 116.3 130.5 143.7 155.6
MOLECULARCONDUCTIVITY V.
Nickel.
....
16 32 64 I 28 2 56
.... 50. I 60.0 69.5 79.3
OF
81.8 91.0 101.4
112.7 124. I 135.3 145.1 154.5
HYDROXYCLUTARATES.
Nickel.
....
Magnesium.
Magnesium.
80.0 93.7 107.7 121. I
TRIHYDROXYGLUTARATES. Cobalt.
....
47.0 58.5 69.8 83.0
Magnesium.
43.6 52.0
64.0 78.2 92.9
0.
390 3.
512
1024 2048
F. TOWER.
Kickel.
Cobalt.
89.2 99.1 108.8
96.8
Magnesium.
108.0
110.j
124.0
125. j
140.2
Although the conductivity of the cobalt and nickel salts is, in general, somewhat greater than the conductivity of the corresponding salts of malic and tartaric acids, still the conductivity seems to decrease as the number of hydroxyl groups increases in a manner quite similar to that of the succinic acid series. The depression of the freezing-point for different solutions of these salts is given in Table 111, together with the apparent molecular weights calculated from them. TABLE111. NICKEL GLUT.4RATE. 3.101. wt. = 1S9. Substance in IOO cc. Grams.
Depression.
0.5508 0.5476 0.2754 0 . 2 738 0.1377 0.1369
0.IZIO
0.
I08
0.065 0.059 0.033 0.031
;MAGNESIUM
COBALT GLUTAFATE. Mol. wt. = :sg.
Apparent mol. wt.
84 94 78 86
-/ /
82
GLUTARATE.
Mol. wt. = 154. 0.6j69 0.1270 0.6038 0.114 0.5077 0.100 0.3019 0.064 0.2538 0.055 0.1510 0.033
99 98 94 Si 85 85
Substance i n roo cc. Grams.
0.636j 0.6144 0.3183 0.30j2 0 . I 592 0 . I 536
Depression.
0.119~ 0.118
0.063
0.061 0.038 0.032
Apparent mol. wt.
99 96 94 93 78 89
NICKEL HYDROXYGLUTARATE. Mol. wt. = 205. 0.6733 0.108~ 0.6147 0 . io6 0.3367 0.058 0.3024 0.054 0.1864 0.030 0.1512 0.029
115 107 107 10.5
104 98
COBALTHYDROXYGLUTARATE. MAGNESIUM HYDROXYGLUTARATE. Mol. wt. = 205. 1101. wt. = 170. 0.8734 0.8487 0 * 4367 0.4244 0.2184 0.2122
0.148' 0 . '47 0.077 0.075 0.043 0.041
109 I08 103
105 94 96
0.7907 0.7304 0.3954 0.3652 0 . I977 0.1826
0.164' 0.141
89 96
0.083 0.074 0.044
9' 83
0.042
80
58
RADIOACTIVITY AS AN ATOMIC PROPERTY.
39 I
NICKELTRIHYDROXYGLUTARATE. COBALT HYDROXYGLUTARATE. Mol. wt. = 237. 3101. Wt. = 237. 0.6050 0.080' 140 0.5625 0.0j2' 145 0.3025 0.042 317 0.2813 0.037 141 0.025 112 0.1407 0.021 124 0.I 513
MAGNESIUMTRIHYDROXYGLUTARATE. Mol. wt. = 202. 0.293' 0.9544 0.154 0.4772 0.092 I . 9087
I21 I
IS 96
When we compare the apparent molecular weight with the molecular weight calculated on the basis of the simple formula in the above table there appears to be but little evidence of polymerization. In the case of the tartrates of nickel and cobalt, apparent molecular weights were obtained which exceeded the calculated molecular weights, and this was the reason for postulating polymerization in those cases. Since, however, the trihydroxyglutarates yield somewhat higher apparent molecular weights than the other glutarates and also molecular conductivities, it can be said that, if there is any tendency toward polymerization of these salts, it is strongest when the maximum number of hydroxyl groups are present in the molecule. It may, however, be stated that the tendency toward polymerization shown by the cobalt and nickel salts of malates and tartrates apparently grows no stronger with similar salts of the higher hydroxy-acids of this series. WESTERN RESERVE USIVERSITY, Januaty, 1905.
[CONTRIBUTION FROM T H E
KENT CHEMICAL
LABORATORY O F T H E U N I -
VERSITY O F CHICAGO.]
RADIOACTIVITY A S AN ATOMIC PROPERTY. BY HERBERT N . McCoy. Received February 18, 1905.
IT IS now generally considered that the radioactivity of any element is independent of its form of chemical combination, that, in fact, radioactivity is a property of the atom rather than of the molecule. There is already much evidence in favor of this view. Thus it is well established that the rate of decay of activity of temporarily radioactive products is wholly independent of all
