ANOMALOUS OSMOSIS WITH GOLD BEATERS SKIN MEMBRANES. CHLORIDE SOLUTIONS IN T H E PRESENCE O F ACIDS AND BASES1 BY F.
E. BARTELL AND
0.
E. MADISON
In our previous studies of the relation of osmose of solutions of electrolytes t o the electrical states of ,the membrane system, we concluded that the nature and magnitude of the resulting osmose was dependent largely upon two factors : ( I ) the electrical orientation of the membrane system, and ( 2 ) the electrical orientation of the capillary wall system. The four conditions responsible for abnormal osmose may be represented by the following diagrams, Fig. I.
Fig.
I
With conditions represented in A and D, an abnormally great positive osmose would be obtained ; while with conditions .represented in B and C, an abnormally low, or even negative, osmose would result. Gold beaters skin in pure water is electro-negative to the water. With dilute salt solutions of univalent cations, the solution side of the membrane system is electro-positive to the other side (case B), which should give as a result a 1 Practically all the data given in this paper had been obtained prior t o December, 1917. Certain minor phases of the investigation as originally planned have not been completed owing t o the fact that both authors entered war service and have not, up to the present time, found it possible to continue the experimental work of this problem. The work is, hbwever, so nearly completed t h a t i t seems desirable to publish the results a t this time.
594
F . E. Bartell and 0. E . Madism
tendency to produce an abnormally low osmose. In our experimental work we have found that this prediction correctly represents the facts. With salt solutions of polyvalent cations as aluminium and thorium, the membrane becomes electro-positive t o the solution. The solution side of the membrane is electro-positive (case D). The resulting osmose should be abnormally positive. The experimental results were entirely in accord with this prediction. It is well known that small amounts of acids or bases play an important r61e in adsorption, and that comparatively small amounts of these substances tend to alter greatly the sign of the charge of any adsorbing materials placed in such solutions. It was our aim in the present investigation t o study the effect of the presence of different concentrations of acids and bases upon the osmose of different salt solutions. If our fundamental hypothesis is correct, we should be able, by altering the sign of the charge of the membrane by having present acids or bases, to greatly alter the osmotic effects of the different salt solutions. For example, those salt solutions which show an abnormally great osmose in neutral solution should be caused to show an abnormally low or even negative osmose when the electrical sign of the system is properly altered by the presence of acid or alkali. Solutions of chlorides of K, Na, Li, Ba, Mg, A1 and Th (the same salts that were used in our earlier investigation) , of 0.05 concentration, were used. Three series of experiments were run in which were used and NaOH solutions of different concentrations. both "OB The acid or alkali was used ( I ) throughout the cell system, (2) on the solutioaside of the membrane with distilled water on the opposite side, and (3) on the side of the membrane opposite to that of the solution. The apparatus and methods used were the same as those described in the previous paper. The results obtained are shown in the following tables.
Anomalous Osmosis
595
TABLEI Concentration of 0.05 M . Solutions of Chlorides in Two-compartment Cells I
Time (hrs.) KC] NaCl
-0
0
2 4
9 20
IO I2
25 28 29 29
6 8
LiCl
BaCI?
ThCL
-0
0
3.5 8.5 I5
5.5 10.5 I9
21
27 31 36
27.5 31
0
‘
Ii
0
42.5 66.5 84 97.5 107
27 42.5 55 62.5 61 61
I12
TABLE2 Acid throughout the Cell System Concentration of Acid 0.0001M . 0.05 M Chlorides in Cells Time (hrs.)
-I
I
0 2
4
6 8
10 12
KCI 0
9.5 16 20
22.5 25 27
NaCl 0
LiCl 0
BaClz
I
MgCla
0
12.5
16
21
29.5 39 42 44 46
27.5 33 34.5 37
1
22.5 36 44.5 49 55.5
ThCla
0
0
0
64
72
I12
90
42 49 40 33 27 24
81 72 56 46
142 I 62 I74 I 82
60
AlCli
TABLE3 Acid throughout the Cell System Concentration of Acid 0.001M . Solutions of Chlorides in Cells
-
Time (hrs.)
K C1
NaCl
LiCl
___-
.o 2
4 6 8
IO I2
BaCl?
0
I7 32 43.5 50 53 55
0
29.5
33 44 54 57 68
AlC13
MgCl? ~
_
ThCla
_
_
0
0
0
0
35 71 91 I08
116 204
105
I4
112
I2
306
100
10.5
380
92
8
71
4.5 3
I I8 I21
414 466
81
I
F . E. Bartell and 0. E . Madison
5 96
TABLE 4 Acid throughout the Cell System Concentration of Acid 0.01 M . 0.05 M Solutions of Chlorides in Cells Time (hrs.)
KC1
NaCl
LiCl
BaC12
MgClz
1
AlCll
ThC14
-I O 2
4 6 8 IO
I2
0
I4 23.5 29 34.5 38 42
0
26.5 35 .38 40 46 48
0
32 51 60.5 62 52 50
TABI
0
49 99 I44 I73 208 227
0
93.5 178 270 336 392 429
0
61 50 40 35 29 23
0 I1
9
7 5 3 3
5
Acid'throughout the Cell System Concentration of Acid 0.1 M . 0.05 M Solutions of Chlorides in Cells Time (hrs.)
KCl
NaCl
LiCl
BaC12
MgClr
AlC13
ThClr
_______ 0 2
4 6 8 IO I2
0
0
3.5 5.5
7.5
7 9 IO IO
IO
16 I9 20.5 22.5
0
9.5 12.5 19 26.5 30 31.5
0
25 44 62 72
81 91
0
26.5 43 63 78 93 105
0
21
36 31 25
21.5 16
0
6.5 5 4 I 0 0
Acid on Solution Side; Distilled Water on Other Side Concentration of Acid 0.0001 M . 0.05 M Solutions of Chlorides in Cells Time (hrs.)
KCl
.NaC1
0 2
0
0
7
8
4 6 8
I1
I7 20
IO I2
I1
I3 I2
9
17.5 I4 9.5
LiCl 0
BaClp 0
29 44 54 66
23 38 37 26 I9
72
I2
10.5
I02
I55
I95
247
242
252
Anomalous Osrnosis
597
TABLE7 Acid on Solution Side; Distilled Water on Other Side Concentration of Acid 0.001 M . 0.05 M Solutions of Chlorides in Cells Time (hrs.) ~
KCl
0 2
0 22
4 6 8
46 58 68 71 74
IO I2
NaCl _ Licl
_
I
AlCh
MgClz
ThCla
BaC1z
0
0
0
0
0
0
31 53 69 76 81
36
52
72
103
49 37
121
21
I35 I44
I3 8
96 196 285 359 429 483
162 291 343 353 347 334
I75 300 350 376 355 330
80
TABLE8 Acid on Solution Side; Distilled Water on Other Side Concentration of Acid 0.01 M . 0.05 M Solutions of Chlorides in Cells Time (hrs.)
KCI
0 2
0 20
4 6 8
37 54 61 67 70
IO I2
NaCl
LiCl
BaCI2
MgClz
0
0
0
25 46 59 67 69 71
75 61 57 43 30 I8
75 163 246 316 380 436
1
AIC13
ThCln
0 I20
240 337 392 432 455
TABLE 9 Acid on Solution Side; Distilled Water on Other Side Concentration of Acid 0.02 M . 0 . 0 5" M Solutions of Chlorides in Cells Time (hrs.) 0 2
4 6 8 IO I2
I I KC'
NaCl 0
25 38 44 54 55 62
LiCl
I
BaClz
MgC1,
AlCl,
ThClr
0
0
0
0
26
63 I33 I90 215 263 287
77 156
98 2 40
51
70 85 99 I09
232
2 80
289 333 274
340 400 445
I
F. E. Bartell and 0. E . Madison.
5 98
TABLEIO Acid on Solution Side; Distilled Water on Other Side Concentration of Acid 0.05 M . 0.05 M Solutions of Chlorides in Cells Time (hrs.)
KCl
NaCl
LiCl
BaClz
AIC13
MgClz
ThClr
--
0 2
4 6
0
0
8
I3 24 36 39 44 48
13.5 16.5 15.5 15.5 15.5
8 IO 12
0
0
0
0
I4 27 37 41 47.5
35 81 I 16 138 I57
43 92 130
IO1
10.5
51
172
216 244 275 306 340
228 2 62 294 324 360
0
I5 1
167 184
Acid on Solution Side; Distilled Water on Other Side Concentration of Acid 0.1M . 0.05 M Solutions of Chlorides in Cells KCI
Time (hrs.) 0
2
4 6 8 IO I2
-I
O
4 7 8.5 IO 10.5 11.5
I
i NaCl 0
9 I5 21
25
28
30
LiCl 0
9.5 I7 23 28 32 35.5
BaClz
MgCL
0
0
25
24 42 62 76 90
44 62 74 86 95
AlCL
II l
' '
IO0
ThCI,
o 54 86 142 I 86 245 282
TABLE1 2 Acid on Solution Side; Distilled Water on Other Side Concentration of Acid 0.2 M . 0.05 M Solutions of Chlorides in Time (hrs.)
KC1
NaCl 0
4 7 I1
12.5 I3 I5
MgCls 0
4 8 12.5 13.5 I7 19
0 IO 20
0 IO 20
30 35 42 46.5
32 38 46.5 52.5
AlCla 0
19.5 39 70 84 107 122
ThCla 0
24
48 88 I 16 132 146
Anomalous Osmosis
599
TABLE13 Acid on One Side; Solution on the Other Side Concentration of Acid 0.0001 M . 0.05 M Solution of Chlorides in Cells Time (hrs.) 0 2
4 '6 8 IO I2
KC1 0
NaCl
LiCl
ThCh
MgClz
0
0
0
9.5 I3 15.5 I7 I8 I8
BaCL
39 56.5 63.5 64 62 59
7.5 I2
14.5 16 I9 22
2.5
I7 I4 IO
7 4
TABLE 14 Acid on One Side; Solution on the Other Side Concentration of Acid 0.001 M . 0.0.5 M Solutions of Chlorides in Cells I
~
Time (hrs.) 0 2
4 6 8 IO I2
KCl
NaCl
LiCl
BaClz
0
0
0
24 42 54 61 64 66
31 53 68 87
76 80 84 64 54 49
I02
114
ThClr
MgCln
0
0 22
67 87 I37
30 29
125
27
26
I IO
2.5
90
TABLE15 Acid on One Side; Solution on the Other Side Concentration of Acid 0.01 M . 0.05 M Solutions of Chlorides in Cells
-
Time (hrs.) 0 2
4 6
8 IO I2
L
KC1 0
28 48 61 69 73 75
NaCl 0
33.5
66
89
LiCl
0
81 92 104
I21
80 72
130
63
106
ThClr
BaClz
0 11.5
12.5 II I1 I1 I1
.
0
0
I47
275 350 43 5 500 525 540
200 222 222 222 222
'
F . E . Bartell and 0. E . Madisout
600
TABLE 16 Acid on One Side; Solution on the Other Side Concentration of Acid 0.1 M . 0.05 M Solutions of Chlorides in Cells ~
~~
Time (hrs.)
KCl
NaCl
~0 2
2 2 2
LiCl
I
0 20
0
4 6
1
0
24
45 54 60 48 45 45
38.5
2
IO I2
2
26
2
26
AlC13
ThClr
I- - - 44 47 47 47
8
BaClz
0
27 30 28
1
0
'
47.5 60 68 68 66 66
0
51 65 71 74 76 75
0 220
310. 340 355 350 350
TABLE 17 Alkali throughout the Cell Concentration of Alkali 0.0001 M . 0.05 M Solutions of Chlorides in Cells I
Time (hrs.) 0 2
0 2
4 6
3
NaCl 0
4 6
4 5 7 9
9
I2
I1
I4
8 IO I2
I
I I
I KCl
LiCl
I
I
1-1
MgC&
0
0
0
5 7
I3 24
I1
29
I5 23 27
I4 17
33 33 33
32 35 35
I8
I I
I BaClz
AlC13
l-
thc14 0 101 I 86
240 262 2 90
310
TABLE I8 Alkali throughout the Cell Concentration of Alkali 0.001M . 0 . 0 5 M Solutions of Chlorides in Time (hrs.) 0 2
4
6 8 IO I2
NaCl
K C1
BaC12
LiCl
MgCIi
AlCls
~0
2.5 4.5
.
0 IO
0 I1
I7
20
7 7.5
22
25 28
9
27
I1
29
25
30 33
0
0
0
7
8
35
9.5
I1
40
9.5 9.5 9.5
I3 I7 16 16
39 39 32 32
10.5 '
thc14
Anomalous Osmosis
60 I
TABLE19 Alkali throughout the Cell Conc. of Alkali 0.01M . 0.05 M Solutions of Chlorides in Cells (hrs.)
1
KC1
I
1
I
NaCl
I
LiCl
I
0
0
0
2
3 4 6 8
3.5
4 6 8
5 7 9 I4 I8
I2
IO I2
'5
TABLE 20 Alkali throughout the Cell Conc. of Alkali 0.1M . 0.05 M Solutions of Chlorides in Cells Time (hrs.)
1
KC1
1
1
NaCl
LiCl 0
0 2
3
4 6
4.5 6
8
7
IO I2
9 IO
T h e Electromotive Force of 0.05 M Chlorides with Nitric Acid and with S o d i u m Hydroxide throughout the .System.In order to study the effect of the presence of acid on the E. M. F. of the neutral salt solutions, and to compare this effect with the effect the acid exercised on the osmose of the same salt solutions, measurements were made of the cell potential of 0.05 M chlorides when different concentrations of nitric acid were used throughout the system. The concentrations of acid used were 0.001M , 0.01M , and 0 . 1 M . A study similar to that made with nitric acid was made with sodium hydroxide. The following tables give only the results obtained when either the acid or alkali was present or - sign indicates throughout the entire system. The the sign of potential on the solution side of the membrane.
+
602
F . E. Bartell aad 0. E . Madisoa W
M
4b l
I
h U
481 I 00 N
2I I
4
2
N
00 IO
!I I
7
* o
y
$ * N
988
+++ 0 0 0
loW 0
IO"
0 0 0
449
:-K
oov,
ggg
+++ 0 0 0
r:
2 2
940 0 0
2
& 0 0 0
Anomalous Osmosis
-
603
Summary of Results Summary of Results.-A summary of the results obtained when acid or alkali are present throughout the cell system is best shown by the curves in Figs. 2 and 3 . From the above data it is shown conclusively that the presence of acid or alkali does have a marked effect upon the osmose of salt solutions. It is also clearly shown that the presence of acid or alkali may alter not only the electrical sign of the capillary wall system but also may alter, or even reverse, the electrical sign of the membrane system. A study of the results obtained brings out the fact that the direction of osmose, as also its magnitude, is closely related to the electrical orientation of the cell system. Although different salt solutions with cations of the same valence do not behave exactly alike under all conditions, they all do show similar effects which may be considered to be characteristic for the solutions of that class. For the purpose of simplifying the analysis of results, we may select the potassium salt as being representative of those with univalent cations, magnesium salt as being representative of those with divalent cations, and thorium salt as being representative of salts with cation with a valence of three and above. Osmosis of Salt Solutions with Acid or Alkali throughout Cell. Potassium Chloride.-The osmose of neutral KC1 sohtion is abnormally small ; its cell system is represented by case B. In the presence of 0.001M acid to 0.01M acid the electrical orientation of the cell system is represented by case D, which is productive of an abnormally high positive osmose. When the system contains acid of 0.1M concentration or greater, the electrical orientation of the system is represented by case C, which is productive of abnormally low or even negative osmose. When the system contains alkali throughout, the membrane is in every case electro-negative and the electrical orientation of the cell system is represented by case B, which is productive of abnormally low, or negative, osmose.
,
604
F. E. Bartell and 0. E. Madison
Anomalous Osmosis
Fig. 3
606
F . E. Bartell and' 0. E . Madison
Magnesium Chloride.-The factors governing the osmose of magnesium chloride are identical with those governing the osmose of potassium chloride. The same explanations given for the results obtained with potassium chloride solutions apply throughout to those obtained with magnesium chloride. Thorium Chloride.-The osmose of neutral thorium chloride solutions is abnormally great and is accounted for by the fact that the electrical orientation of the cell system is represented by case D. An exceedingly small amount of acid present in the cell system lowers the potential of the membrane interface system which, as a result, tends to lower the abnormally great positive osmotic tendency of thorium chloride solutions. A still greater concentration of acid throughout the system (0.1M and above) reverses the electrical orientation of the membrane system giving as a result conditions represented in case C. The resulting osmose now becomes abnormally low or even negative. With a low concentration of alkali (0.0001M ) throughout the system the membrane is still elektro-positive due to the pronounced effects of the quadrivalent cation of the salt solution. The conditions are represented by case D, and an abnormally great positive osmose results. With somewhat higher concentrations of alkali throughout the system, the sign of the membrane material becomes electronegative; the conditions are represented by case B. An abnormally low or negative osmose results. It was mentioned above that the sign of the gold beaters skin membrane to water is electro-negative. The iso-electric point of this membrane is reached with comparatively low concentrations of acid, approximately 0.0001 M . In the presence of different salt solutions with the acid, the iso-electric point comes at a somewhat different concentration with each of the different salts. It is quite likely that the distinct breaks noted in the various curves (Fig. 2), which come a t about 0.0001M acid concentration, may be accounted for
Anomalous Osmosis
607
by the fact that at these points the membrane is near, or is passing through the iso-electric point. It is hardly necessary for the writers to further analyze the results obtained with the various solutions under the different conditions of the above experiments. The same general principles apply throughout. It may be stated that many experiments in addition to those reported in this paper have been carried out in this laboratory during the past eight years in which this investigation has been in progress, and in practically every case the results obtained may be explained when the factors above described are determined and the principles above given are applied. Experiments similar to the above have been carried out with other types of membranes. Considerable work has been done with membranes of collodion; with this material we have been able to vary the diameter of the pore spaces as well as the thickness of the membrane. Both of these factors are important in the consideration of anomalous osmose. I n a subsequent paper we shall attempt to point out the relation of the principles discussed in this paper to colloidal processes, including the swelling of gels and various biological phenomena which, up to the present time, have received n a satisfactory explanation. University of Michigan
