THE SOLUBILITY OF THE CHLORIDE, THE BROMIDE, AND THE IODIDE OF LEAD, IN WATER, AT TEMPERATURES FROM Oo UPWARD. BY D. M.
LICHTY.
Received March 5,
190).
THEsolubility of lead chloride at 25", as given by von Ende: is 38.8 milligram-molecules or 10.678grams per liter of solution, and therefore somewhat higher in 1000grams,of water. Ditte2 gives the solubility in 1000 grams of water as 8 grams at o", 11.8at 20°, 17 at 40°, 2 1 at 55", and 31 at 80". The solubility was found to be higher at 20' than von Ende found it at 25". According to Bell,3 the solubility at 16.5" is 9,503 grams4 in 1000 of water, while the solubility at the same temperature based on Ditte's results is about 11 grams in 1000 of water. T h e data on the s d u bility of the bromide and the iodide being even less satisfactory, the writer undertook to determine the Solubility of these three salts at different temperatures from 0" upward. The purity of the salts used is attested by the results of analysis given later. Very pure water, such as is used in electric conductivity work, was employed. T h e saturated solutions were prepared by making approximately saturated solutions at a higher temperature (generally by IO') than the one at which the solubility was to be determined, and then placing these solutions in a bath at the desired temperature for about six hours. T h e considerable quantity of larger crystals which always formed over the smaller crystals left undissolved in the bottom of the flask, served to show that the solutions had really been supersaturated with respect to the temperature of measurement, The flasks used for making the solutions had a capacity of 2j0 cc. and were immersed to the lip in the bath and stoppered. From these, calibrated glass-stoppered flasks (capacity 100 CC.) which were brought to the working temperature by weighing and immersing in the bath, were filled to a point slightly above the mark by means of a siphon and rubber bulb. After a few minutes,
.
Zfschr. a n o c . Chem a6, 134 ( r y a r ) . Compt. Rend., 9 2 , 718: 3 Chem. News. 1 6 , @ 4 A saturated solution of lead chloride contains o.gq14 per cent. of the salt at 16.5". is the substance of Bell's statement. 9
470
D. M. LICHTY.
the solutions mere carefully brought to the mark by means of a pipette. The flasks and their contents were then rapidly brought to the temperature of the r m m , dried and weighed, after which the solutions were transferred to weighed platinum dishes, evaporated and then dried at 180" for several hours. The evaporation proved ver). tedious, oiving to the fact that on the surface of the solutions there collected a very thin film of crystals through which burst gas bubbles rising from the bottom of the dishes, thus causing a small amount of the salt to be thrown out, which could be prevented only by ver!. frequent stirring until the solutions were froin one-half to three-fourths evaporated. The measuring flasks were calibrated either at 20' or 2j0,andat all other temperatures corrections were made for either expansion or contraction. Each weight of solution was reduced to weight i l l uaci~o,while the weight of the salt was not, the correction amounting at most to only 0.2 milligram. The data were reduced to solubility in grams and milligram-molecules per liter of solution antl to grams and milligram-molecules per 100 grams of water. The densities compared with water at lo C. I\ cre also calculate(!. The flasks chosen for measuring the solutions had necks of such diameter that a laigth of I O mni. had a capacity of about 0.6 gram of \I ater at 2 j 0 or 6 milligrams pcr 0.1 nim,, so that the meniscus could be adjusted to i.IO milligrams or I part in 10,000for rvater, ant1 to a but slightly larger quantity for the solutions, ivhose densities did not differ much from the density of water. [:elow 1j " the temperatures ivere maintained within less than o.I', for d j " and j j " to about o.I', for 65" and 80" within o.L', antl for 95' within 0 . 3 O , the correct temperature being cletermined by means of a standardized instrument, Ivhose oo and 100' points had not measurably altered siiice the standardizing. XNALVSIS OF S.u,Ts. G rani.
Lead chloride taken. ..................... 0.3848 Silver chloride obtained .................. 0.3970 Silver chloride calculated. ................0.3971 Lead bromide t a k e n . . .................... 0.446s Silver bromide obtained .................. 0.457'2 Silver bromide calculated. ................ 0.4576 Lead iodide taken.. ..................... 0.2462 Silver iodide obtained.. ................. 0.2507 Silver iodide calculated. .................. 0.2510
SOLUBILITY OF T H E CHLORIDE, ETC.,I N W A T E R .
TABLEI.-sOLUBItITS
O F LEAD CHLORIDE IN MILLIGRAM-MOLECULES.
Temper. Milligram-molecule per ature. 100 cc. solution. 00
00
Go 15O
25O 25O
39 35O
45O 45O 55O 55O
65O 65O 800 800
95O 95O 10002
2.428 2.415 3.266 3.264 3.878 3.887 4.734 4.732 5.5% 5.578 6.484 6.488 7.498 7.482 9.I49 9.152 10.931 10.922
...
.... ....
2.421
3.265
....
3.882' 4.733
.... 5.579 .... 6.486 .... 7.490 .... 9.150 ....
10.926 11.52
TABLEII.-sOLUBILITY Temperature. 00
00
15O 15O
2S0 25O
35O 35O
45O 45O 55O 55O
65O 65O 800
8.812
800
8.826 11.387 11.386
95O
95O 1w04
....
.... ....
1.241 1.987
....
2.
646s
.... .... 4.705 .... 5.73' .... 6.859 .... 8.819 ....
3.577
11.386 12.40
Von Ende, 38.8 per liter. 2 By extrapolation, see Fig. I . :Von Ende, 26.18per liter. 4 By extrapolation, see Fig. I.
1
Milligram-molecule per 100 grams water.
2.428 2.415 3.273 3.271 3.905 3.901 4.768 4.766 5.646 5.642 6.553 6.594 7.655 7.647 9.439 9.440 11.395 11.393
....
OF LEAD
Milligram-molecule per 100 cc. of solution. I , 242
1.241 1.990 1.985 2.648 2.644 3.589 3.566 4.704 4.706 5.743 5.719 6.870 6.849
471
....
I. 00666
2.421
I ,00665
3.272
....
3.903 4.767
.... 5 644 .... 6.573 .... 7.651 .... 9.439 .... *
1.00693
....
I .00725
11.394
1.00598 1.00417 1.00429 1.00206 1.00195 0.99938 0.99928 0.99465 0.99484 0.98962 0.9892I
....
1.00600
.... ....
I .00423
I.00200
.... .... 0.99474 ....
0.99933
0.98941
....
12.01
BROMIDEIN
....
I. 00695 1.00691 1.00726 1.00724
....
I,00665
I .00602
MILLIGRAM-MOLECULES.
Milligram-molecule per 100 grams of water.
1.242 1.241 1.991 1.988 2.658 2.652 3.615 3492 4.758 4.763 5.840 5.814 7.027 7.006 9.'07 9.120 11.890 11.8go
Density referred to water at 0".
Density referred to water at oo.
....
I .00435
1.241
....
1.989
....
2.655
3.603
.... 4.760 .... 5.827
....
7.016
.... ....
9.113 11.890
12.94
1.00431
1.00433
1.00525
1.00536 I .00617 1.00599 I .00587 I .00609 1.00601 1.00586 1.00449 1.00461 I.00284 1.00281 1.00000
1.oooo7 0.99948 0.99945
....
1.00530
....
I. d o 8
1.00598
.... .... 1.00455 .... 1.00282 .... I
.m593
1.oooo3
.... ....
0.99946
472
D. fir. LICHTY.
TABLEIII.-~OLUBII,ITE' Temperature. 00
00
I5O
IS0 25O 25 O
35 35O 45 O 45 O
55O 65 65O 80' Bo0 95 O 95O 'I
IN
MILLIGRAM-MOLECULES.
Milligram-molecule per 100 grams of water.
....
0.096
....
0.096 0.096 0.1.72
0.096
0.733
0.134
0.165'
....
0.166 0.r6j 0.225
0.133 0.166
0.225
0.224
0.227
0.226
0.827
2 0002
....
LEAD IODIDE
0.096 0.096 0.132 0. I34 0.166 0.165 0.224 0.3'3 0.312 0.374 0.374 0.465 0.464 0.636 0.639 0.829
55O
OF
Milligram-molecule per 100 cc. of solution.
....
....
....
....
....
....
0.316
....
0.312
0.315
0.315
0.374
0.380 0. 3s2
0.381
.... ....
....
0.4i4
....
0.473
....
0.473 0.6jj 0.657 0.860
0.828
0.858
0.464
....
0.637
0.895
.
.
.
....
0.656
....
0.859 0.927
I
El0
Density referred to water at oO. 7.000j7
1.00055 0.99982 0.99984 0.99801 0,99795 0.99498 0.99518 0.99 0.99 49 0.98729 0.987 17 0.98264 0.9S272 0.9iJ50 0.97454 0.96689 0.96730
'
....
....
1.0~056
....
0.99983
....
0.99798
....
0.99505
....
0.99'53
....
0.95723 0.9826s
....
0.97452 0.96709
....
1
A comparison of the data in the three foregoing tables will a t once show that the solubility curves based on milligram-molecules in IOO cc. of solution and those based on milligram-molecules in 100 grams of water will be similar, the latter turning a little iar1
Voti Ende, I j 9 per liter By extrapolation, see F I I~
SOLUBILITY OF THE CHLORIDE, ETC., I N WATER.
473
ther away from the temperature axis than the former; it was consequently deemed sufficient to draw the curves for the former. Either the data or the curves show that at the lower temperatures the molecular solubility of the bromide is less than that of the chloride, but that the solubility of the former increases more rapidly with the temperature than does that of the latter, and that the solubilities are the same between 80" and 95". The C U N ~ S show that the temperature of common solubility is 88.5" and the solubility IO. I 5 milligram-molecules. The solubility of the iodide is decidedly less than that of either of the other salts, not reaching, even at IOO", the same value as that of the bromide at 0".
d Fig. 2 .
T H O M A S B . OSBORNE A N D I S A A C F. H A R R I S .
474
TABLEIV.--SOI.UBILITY
BY Bromide.
Chloride. ~-------7-h
WEIGHT.
----
Iodide. I7
Temper- Grams in 100 Grams in 100 Grams i n 100 Grams in 100 Grams i t 1 100 Grams in 100 cc. solution. grams water cc. solution. grams water. cc. solution. grams water. ature. 0'
1 5 ~ 2j6
35' 45' jjo
65" 80" 95' 100"
0.6728 0.~70 1.0786 1.3'5 1.5498 1.8019 2.081o 2.5420 3.035s 3.208
0.6728 o.gogo
1.0842 1.3244 1.5673 1.8263 2.1265 2.6224
3.16j4 3.342
0.4554 0.7285 0.9701 1.3124 1.7259 2.1024 2.5161 3.2350 4.1767 4.550
0.4554 0.7305 0.9744 1.3220 1.7457 2.1376 2.5736 3,3430 4.3613 4.751
0.0442 0.0613 0.0762 0.1035
0.0442 0.o613 0.0764
0.1440
0.1453 0.1755 0.2183
0.1042
0.1726 0.2140
0.2937 0.3814
0,3023
0.3960 0.436
0.420
At 0" the solubility of the chloride by weight is about one and one-half times that of the bromide; a t 35', their solubilities are practically equal and at 95" that of the chloride is about threefourths of that of the bromide. DPI'ARTMEKT
O F G E K E R A I . C H E M I S T R Y . CSIVERSITY
01'
MICHIGAN,ANN A R B O R ,MICII., .March, 1903.
T H E CARBOHYDRATE GROUP IN T H E PROTEIN I1OLECULE.' B Y THO.MA~ 1%.O S B ~ R NA N I~ D
IS.ZAC 1:. H A R R I S .
ReceiveGI i'clirunry s j , ~ p o j ,
IT HAS been known for some time that certain complex substances found in animal organisms, when decomposed with acids, yielded protein and carbohydrate bodies, together with other products. These substances, known as mucins, mucoids, chondroproteids, nucleins, hyalogen substances, etc., are generally regarded as conipounds in which the protein is united with some other complex organic group of which this carbohydrate is a part. Although several investigators long ago suggested the possible presence of a carbohydrate group in the protein molecule proper, no evidence of weight supported this view m t i l Pavy.? by hydrolyzing coagulated ovalbumin, obtained a solution from which he prepared an osazoiie with a melting-poiiit near that of glucosazone. In consequence of this discovery. I'avy concluded that his investigations brought "the extensive group of proteids of both the animal and vegetable kingdonis of nature into the class of glucosides." This announcement of l'avx's let1 t o numerous iiivcstigations '
By extrapolation, see Fig, 2 . From the laboratory o f the Conuecticut Agricultural Experimew Statiou. a " Physiology of t h e Carbohydrates." 1
3
