Dec., 1911 49. 50. 50. 51.
52. 52. 53. 53. 53. 54. 54.
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 H E M I S T R Y .
Ingersoll and Littleton, Physic. Rev., 31, 489. (a) Matignon, Compt. r e n d , [22] 131, 891. ( b ) Muthmann and Baur, Liebig’s Annalen, 326, 281. Matipnon, Compf. rend., [21]431, 837. ( e )Didier, Compt. rend., 100, 1461 (1885). ( b ) Muthmann and Stutzel. Ber. d . chem. Ces., 32. 3413 (1889). (a) 2.Elekfrochen., 14, 549 (1908). ( b ) Fattinger. Chem. Z / g . , 33, 1113 (1909). ( c ) C.R.Behm, Ibid., 361, 367 (1910). (a) Fattinger, Ibid.,34, 469 (1910). ( b ) Samter, Ibid., 34, 52 (1910).
v,
ON THE DENSITY OF SILICATE MIXTURES. By EDWINWARDTILLOTSON. JR.
897
Winkelmann.
Modified
2.3 3.3 3.8
2.3 4.1 4.0
SiOn................................. CaO ................................. MgO .................................
The densities of the several calcium-magnesium silicates computed with the aid of the modified factors are given in the last column of Table I and shown graphically in line I (Fig. I ) . They show a far more satisfactory agreement with the observed densities, and since the errors throughout the entire series are less than one-half of one per cent., the densities assumed for the oxides in the glass may be considered t o be nearly correct.
,
Received October 20, 1911.
-It has been shown b y Winkelmann and SchottI t h a t the densities of a glass may be calculated, with a rough degree of accuracy, from its chemical composition. The method depends upon the supposition t h a t the several glass-forming oxides have densities which are always the same, for a particular oxide, in whatever combination it occurs. On this assumption, b y addition of the partial volumes of the oxides, the densities of the glasses were calculated, according t o the following equation, (I)
a, -
21
a* a3 IO0 ++=--, a2
23
s
where S is the density of the glass, a,, a 2 , u3 are the percentages of the oxides, and zl,z,, z 3 are the densities of the oxides in the glass. That this assumption is not entirely fulfilled is shown in the original article b y the values of the densities for twenty-nine glasses calculated by this method. However, the average variation of I I / ~ per cent., between the observed and calculated values does not militate against the methods value where extreme accuracy is not required. I n order that the factors used b y Winkelmann might be checked against the more recent and accurate work in pure silicates, they were employed in calculating the densities of a series of calcium and magnesium metasilicates, described b y Larsen,= two series of lithium-barium and lithium-calcium metasilicates, described b y Wallace,3 and some mixed feldspars prepared by Day and Allen.4 The observed and calculated densities of the calcium-magnesium silicates are given in Table I. It is evident from these figures t h a t Winkelmann’s factors gave a fair value for the density of magnesium silicate, but a false value for calcium silicate. This is shown graphically in Line I1 (Fig. I ) . The observed density of calcium silicate is greater than t h a t of magnesium silicate while the hypothetical, calculated, density of calcium silicate is less. New factors for CaO and MgO were then calculated from the values of the observed densities. Following are the two sets of factors which were employed:
TABLE1.--CaOSi03-MgSiOs. CaSiOs, CaO, per cent. per cent. 100 48.20 95 45.80 85.26 41.09 74 35.70 64 30.84 60 28.92 53.64 25.85 40 19.28 30 14.46 10 4.82 5 2.41 0 0.00
-
Obs.1 2.904 2.899 2.891 2.881 2.872 2.859 2.854 2.834 2.821 2.780 2.777 2.758
Density. I
Calc.2 2.698 2.700 2.701 2.706 2.709 2.711 2.713 2.718 2.722 2.730 2.733 2.735
Calc.3 2.920 2.910 2.897 2.879 2.863 2.855 2.848 2.829 2.815 2,787 2.780 2.773
When these factors were used for calculating the densities of some of the Jena glasses, the results were, in general, more satisfactory than those obtained with Winkelmann’s factors. The following examples show the observed and calculated densities of several of these glasses.4
------
Density.
NO.
3. . . . . . . . . . . . . . . . 6,. . . . . . . . . . . . . . . 10... . . . . . . . . . . . . . 34,. . . . . . . . . . . . . . .
Obs. 2.424 2.585 2.518 2.378
Calc.2 2.42 2.52 2.51 2.34
Error.2 Error.3 Calc.3 Per cent. Per cent. 2.424 0.2 0.0 2.543 2.5 1.6 2.545 0.3 1 .o 2.350 1.6 1.2 _ .
Average, 1.15
__ 0.95
The observed and calculated densities of the lithiumbarium metasilicates and the lithium-calcium metasilicates are given in Tables I1 and I11 respectively and all shown graphically in Fig. 2. I n his original communication Winkelmann gave no factor for lithium oxide, consequently the value employed in TABLEII.-Li,SiOs-BaSiOa. Density. BaSiOa. Li20. Per cent. Per cent. 0
10 20 30 40 50 60 70 80 90
100 Winkelmann. An%. d Pkys. und Chem., 49, 401 (1893);Winkelmann and Schott, Ibid.,61, 697 (1894); ’‘ Jena Glass and I t s Industrial Applications,” Hovestadt (English edition), p. 148. 2 A m . J . Sci.. 28, 263 (1909). 2.anorg. Chem., 63, 1 (1909). Bull. 31, Carnegie Institute of Washington.
SiOn, MgO, per cent. per cent. 00.00 51.80 2.01 52.19 5.91 53.00 10.43 53.87 14.43 54.73 16.04 55.04 18.59 55.56 .24.06 56.66 28.07 57.47 36.09 59.09 38.10 59.49 40.10 59.90
33.30 29.97 26.64 23.31 19.98 16.65 13.32 9.99 6.66 3.33 0.00
BaO. Per cent.
SiO2. Per cent.
00.00 7.18 14.36 21.53 28.71 35.89 43.06 50.24 57.42 64.60 71.78
66.70 62.85 59.00 55.16 51.31 47.46 43.62 39.77 35.92 32.07 28.22
Larsen, A m . J . Sci.. 2 8 , 263 (1909).
* Using Winkelmann’s factors.
Using modified factors. Winkelmann and Schott. Loc. cit. 6 Wallace, 2.anorg. Chem., 63, 1 (1909).
3 4
-
7 -
Observed.5
Calc.3
2.61 2.70 2.80 2.91 3.17 3.38 3S O 3.77 4.02 4.19 4.44
2.63 2.74 2.87 3 .OO 3.14 3.31 3.48 3.69 3.91 4.16 4.44
T H E J O U R N A L OF I N D U S T R I A L A N D EL\’GINEERING
898
CHEMISTRY.
Dec., 1911
2.92 2.91 2.90 2.89 2.88 2.87 2.86 2.85 2.84 2.83 2.82 2.81
>: 2.80
v
‘8 a
2.79 2.78 2.77
‘
2.76 2.75 2.74 2.73 2 . 2.71 2.70
Cas03 00
90 10
80 20
70 30
60 50 40 30 40 50 60 70 I. Densities observed (dots) and calculated (line) 11. Densities calculated from Winkelmann’s factors. Fig. 1.
TABLE III.-LizSi03-CaSiOa. Density. CaO. SiOz. CaSiOa. LizO. Per cent. Per ceut. Per cent. Per cent. 0 33.30 00.00 66.70 10 65.21 29.97 4 82 20 9.64 63.72 26.64 30 23.31 14.46 62.23 40 19.98 19.28 60.74 16.65 24.10 59.25 50 60 28.92 57.76 13.32 70 56.27 9.99 33.74 54.78 80 6.66 38.56 53.29 3.33 43.38 90 0.00 48.20 51.80 100
.
Obs.’ 2.61 2.64 2.69 2.72 2.76 2.80 2.80 2.84 2.85 2.88 2.91
Calc.2 2.63 2.63 2.645 2.655 2.66 2.665 2.67 2.68 2.69 2.69 2.70
-
Calc.3 2.63 2.65 2.69 2.71 2.74 2.77 2.80 2.83 2.85 2.88 2.92
20 80
10 90
00 MgSjOa
these calculations is new so far as the writer is aware. The factors used in computing these densities are as follows: Winkelmann. Si0z . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3 BaO . . . . . .. . . . . . . . . . , . . . . . . . . . .. . . . . . 7.0 CaO. ................................ 3.3 LinO .................................
...
Modified. 2.3 7.0 4.1 3.7
I n the case of the lithium-barium series, Winkelmann’s factor for BaO was found t o give good results, 1 2
3
Wallace, 2.aaorg. Chem.. 63, 1 (1909). Using Winkelmann’s factors. Using modified factors.
Dec., 1911
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 H E M I S T R Y .
900
T H E J O U R L V A L OF I N D U S T R I A L A N D ENGINEERIJ\~G C H E M I S T R Y .
The value of the de‘nsity of aluminum oxide, employed in these calculations, was checked against two Jena glasses‘ which contain large percentages of A1,0,. The results are as follows: NO. Observed. 4 ........... 2.480 9 . . . 2.588
Calc.2 2.60 2.69
Calc3 2.471 2.612
Error.2 Per cent. 4.8 3.9
__
Average, 4.35
Emor.3 Per cent. 0.3 0.9
0.6
I n both cases the use of the new factors gives more accurate values for the densities. These new factors present some interesting variations from those originally proposed. From the following table, which shows the old and new factors a n d the densities of the pure oxides, it appears, as Winkelmann observed, t h a t the oxides in general show a higher density in the glass than in the uncombined condition. Winkelmann. Modified. 3.3 4.1 C a O . .. . . . . . . . . . . . . . . . . . . . . . . 3.8 4.0 MgO.. ....................... ....................... 4,l 2.75 Lis0 ......... 3.7
Density of pure oxide. 3.3164 3.6146 3.855 2.1028
Especial attention should be called to* the condensation of lithium oxide w’hich amounts to a seventyfive per cent. increase in density. Aluminum oxide appears t o be a n exception t o this generalization and shows a n expansion of 40 per cent. Although deductions may not be drawn from these figures, they appear t o indicate a peculiar molecular condition, perhaps association, in the aluminum oxide, which is not characteristic of the other oxides in question. Although these differences are interesting and suggestive, they are not truly indicative of real differences, since the method b y which they are obtained Only the oxides rests upon incomplete assumptions. are considered and no account is taken either of the compounds which are present or of their constitution. That this is a n important item in any theoretical relationship between the chemical composition of a substance and its density, or any other physical property, is well known in the case of organic compounds, and, even among the silicates, polymorphic forms7 of the same chemical composition, but of different density, have been described. A knowledge of the different compounds which exist, together with knowledge of the compounds which are stable a t the temperature a t which the glass may be formed, will aid materially in solving the numerical relationship between the chemical composition of a glass and its density. Until such information is a t hand resort must be had t o empirical factors which represent not the true density, but the true density plus or minus a n element which is characteristic of the nature of the compound which is formed. Since, in all the pos1
Winkelmann and Schott. Lac. cil.
* Using Winkelmann’s factors.
Using modified factors. D a y and Shepherd, A m . J . Sci., [4] 22, 265 (1906). Larsen, Ibid.,[4] 28, 273 (1909). 6 Van Nostrand’s Chemical Annual. 7 “The Lime-silica Series of Minerals,” Day and Shepherd, J.A m . Chem. Soc., 28, 1089 (1906). “Minerals of the Composition Mg.SiOa;A Case of Tetramorphism.” Allen, Wright and Clement, A m . J.Sci.. [4] 22, 385 (1906). 3
5
Dec.,
1911
sible mixtures of glass-forming oxides, the field in which glasses are formed is rather limited, the constitution of the more common glasses is more or less similar, and it therefore becomes possible t o find factors which hold t o a limited degree. SUMMARY.
The density of some pure and mixed silicates have been calculated, using the method and factors suggested by Winkelmann and Schott, with unsatisfactory results. 2. New factors have been derived, which appear t o be more satisfactory. These are CaO 4.1,MgO 4.0 and A1,0, 2 . 7 5 . 3 . A factor has been derived for lithium oxide, Li,O 3 . 7 . 4. Although the method is not theoretically correct, it is capable of giving, for large variety of glasses, results which are not more than one or one and onehalf per cent. in error. I.
DEPARTMENT OF INDUSTRIAL RESEARCH, UNIVERSITY O F KANSAS. LAWRENCE.
T H E DETERMINATION O F VOLATILE MATTER IN COAL. B Y S . W. PARR. Received October 6, 1911.
The variable results obtained in volatile matter determinations on coal have been ascribed t o ( a ) mechanical loss and ( b ) t o different forms of decomposition as a result of varying methods of applying heat. With lignites, as shown b y Somermeier,’ the first-named difficulty is especially pronounced; but we find also in this laboratory t h a t there are numerous coals of the Illinois type which suffer mechanical loss t o a n appreciable extent when subjected t o the usual method for volatile matter determination. This is evident from the sparks t h a t frequently accompany the discharge of the volatile matter and seems also t o be indicated b y Table 11, which gives values for ash as derived from the coke resulting from the official method of determining the volatile matter (column B) as compared with the ash as derived b y the official method. I n any study, therefore, of the effect of varying temperatures, it is essential t h a t variations due to mechanical loss be first eliminated before conclusions can be safely drawn as t o the effect of varying degrees of heat. Moreover, the method employed must admit of the application of the maximum of heat in the minimum space of time in order t h a t variations due t o different sorts of decomposition may be brought within a narrow range. This precludes, of course, the application of a slow preliminary heating as suggested for lignites, at least with Illinois coals. I n our experiments it has seemed well t o bear in mind certain other sources of variation. First on account of the great avidity of freshly mined coal for oxygen, i t is possible t h a t this element, mechanically held or absorbed by the finely ground material, accentuates or adds t o the normal content of oxygen
*J
A m Chem S o c , 28, 1003 (1906).
.
