STUDIES ON ELECTROKINETIC POTENTIALS. VI11 Ion Antagonism* B Y HENRY B. BULL AND R O S S AIKEX GOHTNER
Historical It has long been recognized by biologists that electroiytes which are individually toxic to cell life are no longer toxic when present in the proper ratios with certain other electrolytes. That this is true has been demonstrated by Loeb,’ Szuck,2Berger13Lillie14and others. Osterhout5 has shown the existence of ion antagonism between NaCl and CaClz by studying the electrical conductance of Laminaria tissue in the presence of XaC1 and CaCh solutions. With KaCl the conductivity of the tissue was increased; with CaClz it was decreased. When the salts were present in the ratio of I O O molecules of XaC1 to I of CaC12the conductance of tissue indicated increasing permeability. Keuschloss6 reports a marked ion antagonism in the effect on the surface tension of lecithin sols. The alkalies, alkali earths, and aluminum increase the surface tension of lecithin sols to a maximum. This maximum is considerably depressed upon the addition of another electrolyte. He reports that a maximum effect is secured when the ratio of uni-univalent cation mixture is I : I , uni-bivalent z o : ~and , uni-trivalent I O O : I . An exception is encountered with Na and K which have their maximum effects in a ratio of N a to K of I :zo or K to K a of I :zo. Freundlich and Scholz’ believe that the ion antagonism encountered in sols in the test tube is closely related to the biological action of electrolytes. I t is also their belief that purely electrical influences of pronounced ion antagonism cannot be produced; for ionic antagonism a hydration influence is always necessary. Tlieisers~gJoJ1has done considerable work on ion antagonism in colloidal systems. He does not agree with Freundlich and Scholz that emphasis should be placed on the hydration influences but maintains rather that the electrical effects play the major role. He seems to feel that there are two factors which influence the precipitating power of a mixture of electrolytes on a colloidal system. These are: ( I ) the effect of each precipitating ion on the adsorption of the other and ( 2 ) the stabilizing action of the ion having the same charge as the colloidal particles. Weiser compares the cell membrane to a copper ferrocyanide membrane. He thinks that the membrane consists of myriads of
* From the Division of Agricultural Biochemistry, University of Minnesota. Published with the approval of the Director, as Paper No. 970, Journal Series, Minnesota AgriculturaI Experiment Station. This paper is taken from Part I1 of a thesis presented by Mr. H. B. Bull to the Graduate School of the University of Minnesota in partial fulfilment of the requirements for the degree of Doctor of Philosophy, June, 1930.
STVDIES IN ELECTROKINETIC POTESTIALS
j01
small particles which adsorb water strongly, forming a true colloidal system which is capable of reversible coagulation, and that all the work on the effect of electrolyte mixtures on colloidal systems should apply. Clowes” worked on the problem of emulsion inversion as influenced by different ions. He concludes that the mono-valent cations, in general, favor the oil-in-water emulsion and that di- and tri-valent cations favor the waterin-oil emulsion. There appears to be a marked antagonism between S a and Ca, both in respect to the type of emulsion and their effect upon the interfacial tension of oil-water. NaCl was found to increase the interfacial tension between olive oil and a solution of S a O H or K a oleate or a mixture of both. CaC12 in the presence of Ca(OH)? was found to increase the interfacial tension. Here again an ion antagonism was found when the ratio of Ca to Na was I to 100. Clowes suggests that the cell membrane is also an emulsion which is capable of inversion, and depending on whether or not we have Ca or Na we get an oil-in-water emulsion which is permeable or a water-in-oil which is impermeable to water-soluble materials. At the proper concentrations S a and Ca ions antagonize each other, and we have an inversion point at which neither type of emulsion predominates. Harkins and Zollmanl3 repeated the work of Clowes in so far as the ion effects upon interfacial tension of oil-water systems are concerned, and using exact physico-chemical technic demonstrated a marked lowering of interfacial tension in pure solutions of KaC1, an increased interfacial tension in pure solutions of CaC12, and an ion antagonism between Na and Ca so that no changes in interfacial tension occurred in the proper mixtures of NaCl and CaC12. Simms14reports the effect of neutral salts on the pH of a glycine solution. He finds an ion antagonism between NaCl and KC1; KaC1 and MgC12;NaCl and CaCl?;CaC12and MgC12. The fact that ion antagonism was observed in a non-colloidal system is very suggestive.
Experimental The apparatus and technic were identical with those of our previous paperIs and involved only slight modifications from those used by Martin and Gortner16 which in turn were a modification of Briggs’” methods. Salt
NaaSOa Na2HP04 NaHC03 KaC1 KC1 CaCL MgClz
Equivalent ratio 0.5
3.0 30 .o 89 ’ 5 4.3 3.4 2.6
Milli-equivalents per liter
Mg per liter
0.0075
0.0450
0.53 8.06
0.4500 I .3428 0.0645
31 .go 78.49 4.81
0.0510
3.75
0.0390
3.96
702
HENRY B. BULL AND ROSS AIKEN GORTNER
The dilute physiological salt solution was made up to contain the salts in the same ionic ratios as in blood plasma. The dilutions were made from the stock solutions shown on the preceding page. The cation concentration of the dilute physiological salt solution in the streaming cell was increased progressively until 0 . 2 x 10-3 X was reached. At this point sufficient RIgClz was added to make the solution 0.0; X IO-^ S in respect to Mg and in addition to the amount of Mg already in solution. This solution was streamed through the diaphragm, then sufficient CaCh
I
01
0
0.4
0.1
Concentration
in
Normalit7
0 .a
0.b
x
io'
FIQ.I Showing the effect of KC1 and CaCL and of mixtures of these salts on HK./P.
was added to the solution to make it 0.05 X IO-^ &' in respect to Ca in addition to that already in solution. The same technic was employed with the K and X a in the ratio of ZO:I and also with the Na and Ca in the ratio of I O O : I , as with the dilute physiological salt solution. The data are given in Tables I to XIF' and Figs. I through 9. The concentration is always expressed in terms of the total cation equivalency. As with all the results reported in this paper, the individual datum is the average of six determinations, three made while streaming the liquid in one direction and three in the reverse direction. For comparative purposes the data for each curve are multiplied by an appropriate factor SO that the value of HK,/P for zero salt concentration is reduced to IO
X IO-^.
STUDIES IN ELECTROKINETIC POTENTI.4LS
703
-15.
4 01
0
0.4
0.2
Concentration
in
Norrnalirr
0.b
x
!
IO’
FIG.2 Showing the effect of NaCl and KC1 and of mixtures of these salts on HK,/P.
1q
k
?$ s
0
HENRY B. BULL AND ROSS AIKEN GORTNER
704
-0 0
0.2
Concentration
0.4
0.C
a8
in Norrnalitv x I #
FIG.4 Showing the effect of MgCL and KC1 and of mixtures of these d t s on HKJP.
0
STUDIES I N ELECTROKINETIC POTENTIALS
-If
5
0.
a 0
0. I
Concentration
0.2
as
i n N o r m a l i i Y x 18 FIG.7
Showing the effect of MgClz and CaCL upon the r-potential in a dilute physiological salt solution.
HENRY B. BGLL AND ROSS AIKEN GORTNER
0
4
8
12
D
ConcenTraTion in Normalirv x IO' FIG.8
Showing the effect of the addition of NaCl to KCI in the ratio of I to 2 0 on the electrical potential at a cellulose-aqueous interface.
"'1 0
4
Concenrrerion
8
le
in Norrnalirr x IO'
D
FIG.9 Showing the effect of the addition of CaClz to NaCl in the molecular ratio of I to IOO on the electrical potential at a cellulose-aqueous interface.
STUDIES IN ELECTROKINETIC POTENTIALS
707
TABLE I
Data for MgClz Concentration MgC1z 0
.oo
Pressure cm. Hg
61.3 78.1 i5.5
o
IO
0.20
X IO-^
X IO-^
0.4 X
IO-^
66.3 80.9
-11.1
74.5 81.7
73.9
-11.;
75.7
Average HKJP =
-I
-
58.9
51.2 80.6 78.5
60.5 80.9 79.5
0.8
x
10-3
jo.1 80.6 76.5
1.6 X
IO&
57.2 79.6 78.3 Average HKJP = - I j .48 X
81.9 80.7
-15.5 -15.5
-15.5 -15.5 -15.5
-10. j
8.j2
I
-15,3 IO+
-11.4 -11.1
-10.7
.os x
10-5
-
8.84
- 9.95 80.6 - 9.42 - 9.76 78.9 - 9.45 Average HKJP = - 9 . 3 2 X IO-^ - 8.83 63 .o - 8.72 81.4 - 8.60 79.3 Average HKJP = - 8.50 X
-
6.90
8.0; - 8.50 - 8.21
10-5
61.8
81.3 78.1 Average HK,/P = -6.75
-
-
6.94 6.68
2.69
X
5.10
-
6.75 6 . j ~
IO-$
- 3.10 - 2.71
66.9
81.1 Average HK,/P = - 2.62 X 2
-
.oo
10-j
HENRY B. BULL AND ROSS AIKEN GORTNER
TABLE I1 Data for CaClz Concentration CaClz
Pressure
%x
105
77.2 72
.o
69.5
IO-^
63.5 i4.9
X IO-^
53.8 76.9 82 , 3
0.1X
0.2
0.4
X IO-^
80.3 82 . 8 75.5
0.8
x
10-8
59 . o 78.2 83.5
1 . 6 X IO-^
70.5 79.0 82.3
P
em. Hg
cm. Hg 0.00
Hr, x
Pressure
10s
-13.7 68.3 -13.4 -13.8 72.9 - 13.6 -14.0 Average HK,/P = - 13 . 7 X IO-^ -10.5 -10.4
51.8 -11.6 73.7 -10.5 78.4 -10. j Average HKJP = - I O ,7 X IO-^
- 9.80
57.9
-10.1
- 9'45 76.9 - 9.4 - 9.20 82.9 - 9.3 Average HK,/P = - 9 . j j X IO-^ - 9.2 - 9'3 - 9.2 Average HKJP
=
52.2
-10.8
73.1 80.4
-
-9.55 X
9.5 9.2
IO-$
-10.0 66 . o - 9.5 - 8.9 80.2 - 8.5 - 8.0 82.9 - 8.4 Average HKJP = - 8 . 9 0 X IO-^
-
9.0 67.8 - 8.8 80.3 - 8.7 76.4 Average HK,/P = -8.87
- 9'5 - 8.6 - 8.6 X
IO+
STUDIES IN ELECTROKINETIC POTENTIALS
709
TABLE I11 Concentration
KCI
Preasure cm. Hg
0 .oo
0.05X
IO-^
Data for KCI x 103 P -13 . o
78.4
-12.6
51.6 83 . o 78.2
Average HKJP =
- I2
77.4
-11.;
-12.4 -12.5
4 X IO-^
-13.8 80.6 -13.8 77.2 -13.6 Average HK,/P = 13 , 8 x
-13.8 -13.8
-
0.10 X
0.20X
IO-^
48.7 82 .2 76.1
IO-^
103
cm. Hg
51.9
82.4 76.0
7x
Pressure
-15.1
59.1
- 14.3
77.4
-14.3 Average HK./'P
=
Io-5
84.4 14.01x
-
-12.4 -14.1 -14.2 10-5
-13.7
63.3
- 14.3
82.4
81.2
-12.7
50.3
- 1 2 .jo
66.8 71.4
- 12.4
82.9
-12.95 - 13 .40
-13.1
-14.2 -13.9 78.2 --I4,4 Average HKJP = - 13.9X IO-^ 0 . 4 X IO&
0 . 8 X IO-^
41.6
76.7 83.3
-13.5 72.2 Average HK,/P = - I 2 .9x
10-5
-11.75
53.2
-13.7
- 12.3
76.8 68.
-12.6 -13.4
-12.2
Average HKJP =
- I2 , 8 X
IO-5
HENRY B. BULL AND ROSS AIKEN GORTNER
710
TABLE IV Data for NaCl Concentration NaCl
Pressure
x
105
0.00
71.9 75.1
78.9
0.05
X IO-^
0.10X
IO-^
70.3 78.5 73.9
72.9 75.7 79.7
%X
Preasure
cm. Hg
P
cm. Hg
-
-10.23 - 9.90
75.9 79.1
-10.02
72 .o
Average HKJP =
- 9 .90X
- 1 2 .80 69.7 -12.34 74.7 -12.4j 78.6 Average HKJP = - I 2 .6X
74.1 76.5 -13.70 73.5 Average HKJP = - 14.I
-12.84 -12.50
- 12.58 IO+
-13.90 -13.85
-14.30 -14.40 -1j.jO
x
72.9 75.9 -13.7 79.2 Average HK,/P = - 13.75 x
0.8X IO-^
69.5 74.7 78.3
61. j 70.I
10-5
77.7
73.2 76.9 80.2 -13.5 Average HK./P = - 13.30x
67.8 74.8 80.5
IO-;
-13.0 -13.1 10-6
-11.6 -11.6
82.1 =
- I I .95 X
-10.02
75.2
-10.20
79.2 82.3
-10.2j
Average HKJP
-13.3
71.7 75.7
-12.3j
Average HnJP 1.6X IO-^
-13.8 -13.6 -13.6
-13.4 -13.4
-12.40 - I 2 .4j
=
9.85 9.70 9.jO
IO-&
-14.0 -13.8
0.4X IO-^
105
- IO.90 X
-11.2
IO+
-11.6 -11.6 -11.8 IO+
STUDIES IN ELECTROKINETIC POTENTIALS
TABLE V D a t a for MgCh a n d CaC12 in Concentration MgCL CaCL
Preasure
Hr, P x
I :I
105
cm. Hg 0.00
0.00
73.3 71
.4
77.4
0.05
X IO+S0.05 X I O - ~ N
72.7
81.3 76.3
x IO-~S 0.1 X IO+X
0.1
0.2
X 1o-T
0.2
x IO-~N
53.4 63.4 66.7
68.3 74.4 69.9
ratio Pressure
H.. P x
105
cm. Hg
-12.45 71.6 -12.20 80.7 -12.26 74 .o Average HKJP = - I 2 . 2
-11.82 -12.20
- 12.40 x IO-^
-10.6
62.2
-11.0
-
74.6
- 9'9
9.9
9.7 AverageH~JP=
-10.22
-
9.16 59.5 9.20 74.0 - 9.25 70.8 Average HKJP = -9.32
-
7.26 7.85 - 7.62
70 ' 7 76.7 70.0
x
10-5
- 9.70 - 9,32 - 9.25
x
IO+
- 6.85
-
7.50
- 7.62
h v e r a g e H ~ , / P= -7.45 X IO-^ 0.4 X IO-~S 0.4 X
0.8 X I O - ~ X 0.8 X
1 0 - W
10-T
54.9 69.1 82.8
75.3 79.7 82 . o
- 5.20 - 5.95
62.1 70.6
- 4.37
-
5.72
-
6.12 84.0 - 5'42 Average HKJP = - 5.46 X I O +
- 3.38
-
4.83
56.8 82.4
-
4
-
j ,IO
85
- 5.12 78.2 - 5.06 A v e r a g e H ~ J P = -4.72 X IO-5
HENRY B. BULL AND ROSS AIKEN GORTNER
712
TABLE VI Data for Mixture of MgClz and KCl in Equivalent Ratio of Concentration MgCh KCI 0.00
0.00
Preasure cm. Hg 52
.o
69.9 82.3
0.05
X
0.10X
0.2
X
10-V
IO-~N
0.05
X IO-^?; 64.I 79.1 76 . o
0.10X IO-%
56.8 69.2 79.6
IO-~N 0.20 X I O - ~ N 49.6 78.8 83.I
0.40 X
IO-~N0.40X IO-W
60.7 78.5 81.3
0.80 X IO-3N 0.80 X I O - ~ N 59.I 81.9 77.1
5
P
s
x
Io6
Preasure cm. Hg
I :I
.+
HK
*OS
61.9 -12.30 69.4 - '3.37 -13.18 81.8 -13.75 Average HKJP = - 13.2 X IO-^ -13.20
- 13.35
-11.8
45.9 -10.2 66.3 -11.7 -12.4 81.2 - 12.3 Average HK,/P = - I 1.8X IO+ -12.3
62.2 -11.5 81.4 -11.6 82.3 - 12.3 -11.9 Average HK,/P = - I I . 7 X IO-& -11.1
-11.8
-
64.7 - 8,jo 78.2 -10.3c -10.50 81.9 -10.60 Average HKJP = - 10.0X IO--^ 9.80 -10.40
-
- 7.94 - 9 .oo - 9.IO 9.15 75.2 Average HKJP = - 8.86X IO-&
9 .oo 9 .oo
65.9 80.3
78.2 - 7.20 5.95 7.60 82.7 - 7.60 8.45 75.1 - 8.05 Average HK,/P = - 7.48x IO-5
-
STUDIES IN ELECTROKINETIC POTENTIhLS
713
TABLE VI1 Data for Mixture of CaClz and KC1 in Equivalent Ratio of Concentration CaC12 KC1
Pressure
E PI r s x
105
cm. Hg 0.00
0.05
X 1o-T
0.00
0.Oj
Pressure
0.2
X
IO-3K
0.1X
IO-~N0 . 2 X 10-~r\’
105
82 . G 86.7
-
77.2
-11.10
81.4
-11.10
86 .o
76.4 9.05 Average HK,/P = - 10.1 X IO-^
X IO-W 7 5 . 6 80.5 85 .o
IO-~K
%x
cm. Hg
-11.10
9.10
9.12
-11.3
80.2
-11.42
-11.2
84.7 75.1
-11.97
.o
-11
Average HK,/P = 0.1X
I :I
-I I .4
-11.50
x
10-5
78.8
-IO.
18
81 . I
-10. I2
82.1
-10.05
-10
86.6
-10.03
86.2 72.8
- I O . 50 S v e r a g e H ~ J P= -10.15 X IO+
68.5
-
9.77
79.8
-
9.22
77.7
-10.00
85.6
-
9.60
85.2
-10.22
7 2 .O
-10.17
I3
AverageH~Jf = -9.83 X IO-^ 0.4 X
I O - ~ N 0.4 X
1o-W
85.8 81 .o 73.4
-
7.73 - 7‘70 - 7’85 Average HKJP =
- 7.76 X
IO-^
TABLE VI11 Data for Mixture of NaCl and MgCL in Equivalent Ratio of Concentration NaCl h4gCL
Preaaure
E
P
a
x
105
0.00
72.7 79.6 85.5
H.. x P
103
cm. Hg
cm. Hg 0.00
Pressure
I :I
-11.20
-11.34 -11.38
81 .o 84.1 87.4
Average HK./P =
-10.00
-
9.95
-10.32
- 10.7 x
10-6
HENRY B. BULL AND ROSS AIKEN GORTNER
714
TABLE VI11 (Continued) Data for Mixture of NaCl and MgC12 in Equivalent Ratio of Concentration NaCl MgCL 0.05
X IO-3N
0.05
X
Pressure
H.. x P
Io5
IO-~S 71.9
-10.25
79.9 85.1
-10.22
-10.28
Pressure
81.8 84.0 76.8
AverageHK,/P = X IO-~N
0.1
0.1
X
IO-%
X IO-~S 0.2 X 10-3N
0.2
0.4 X IO+S0.4 X I O - ~ N
0.8 X
10-W
74.8 80.9 84.8
-10.22
- 9.75 - 9.75
74.9 81.2 -10.00 86.1 Average HK./P = -9.75
X IO-~X
0.05
-
9.60 9 . 6 ~ - 9 . 6 ~
x
10-5
-
- 8.12
8 0 .j 86.0
- 8.23 84.1 - 7.96 - 8.26 88.5 - 7.82 Average HKJP = -8.07 X IO-^
-
80.6
Pressure
8.90 - 8.86 - 9.20 x IO-^
- 8.05
80.6 - 6.62 86 .o - 7.02 75.6 - 6.90 AverageH~,/P = -6.55 X 10-j 6.27 6.30 6.25
1Ir. x P
105
cm. Hg
0.05
-10.27
- I O .oo x 10-5
74.0
TABLE IX Data for Mixture of NaCl and CaClz in Equivalent Ratio of
0.00
105
P -10.28
- 9.15 81.8 - 9.07 87 . o - 9.15 77.7 Average HKJP = - 9.05
79.7 86.I
0.00
HKg x
82.5 86.8
79.1
0.8 X IO-3S 7 2 . 4
Concentration NaCl CaC12
I :I
Pre&sure
I :I
x
105
cm. Hg
66.1
- 9.90
76.5 79.3
- 9.75 - 9.90 74.8 - 9.65 Average HK./P = -9.86 X IO-^
x IO-3hT5 8 . 4 68.9 73.7
63.5
-10.00
70.0
-10.35 -10.23
51.5
63.8 -10.20 70.9 AverageHx,/P = -9.72
-10.00
- 9'48 - 9.02 - 9.10 X IO-^
715
STUDIES IN ELECTXOKINETIC POTENTIALS
TABLE IX (Continued) Data for Mixture of NaCl and CaCL in Equivalent Ratio of Concentration SaCl CaCL 0.1
0.2
X
X
1o-Y
IO-%
0.1
0.2
x
1o-T
X IO-~N
Pressure
HI +x
Io6
Pressure
69.5
- 9.72 68.3 - 9.70 AverageH~JP = -9.71 X IO+
67.8
-
58.1
- 8.33
66.9 7 5 .O 78.2
9.75 9.62
8.35
48. I 73.7
62.8
70.7
-
- 8.5 7
- 7'75
75 .o 79.8
-
69.1
7.90
7.80
ilverage HKJP = - 7.1 5 0.8
x
10-3s
105
-
Average HK,/P =
0.8 X IO-3N
2x
41 . I 60.9
69.9
0.4 X IO-~X 0.4 X IO-^^
I :I
70.9
- 6.13
76.9 80.3
-
77.3
-
-
X
9.84 9.65
8.65 8.76 8.78
10-j
-
6.67
-
5'64
7.20
x 10-5 -
6.10 81.4 - 6.15 60.5 AverageH~JP = -6.24 X
6.07 6.33 6.63
10-5
TABLE X Data for Mixture of NaCi and KC1 in Equivalent Ratio of Concentration NaCl KCl
Pressure
3x
105
cm. Hg 0.00
0.00
IO-~X
0.05
H.. x P
10s
cm. Hg
59.9
-12.3
i7.5
78.8 -11.9 81.1 -12.3 Average HK./P = - I I .8 X 10-5
78.3
0.05 X
Pressure
I :I
48.9
-10.7
-11.9
-11.8
X IO-~S 61.7
-14.7
53.4
-14.6
78.9 82.8
-14.8 -14.6
82.1 79.2
-15.1
Average HK,/P =
- 14.8
-14.9 X IO-^
HENRY B. BULL AND ROSS AIKEN GORTNER
7’6
TABLE X (Continued) Data for Mixture of NaCl and KCl in Equivalent Ratio of Concentration KCI NaCl 0.10X 10-W
0.10X
X P
HX8
Pressure
io-3N 62 . 5 78.1 82.3
105
I :I
Preeaure
-14 5
59.1 77.5
-14.6
71.2
-14.5
H ; x -
103
-13.4 -14.6 -16.5
A v e r a g e H ~ ~ , ’=P -14.7 X IO-^ 0.20 X IO-%
0.20
x
78.0 80.0
IO-%
-12.90 54.4 - 13 .os 81 .o - 13 .oo 81.4 AverageH~JP = -13.03
77.6
0.4X IO-W
0.40X
78.8 82.8
0.8 X IO-3N
0.8 X I O - ~ N
X IO-^
- 13.oo 54.1 - 12.30 - 12.80 78.6 - 12.90 -12.85 81.2 -12.60 Average HK,/P = - 12.72 x IO-^
52.2
IO-3N
-10.90 -12.90 - 13.30
- 8.55 - 9.98 - 9.70 AverageHK./P
65 .4 81.2 81.8
54.2 - 7.20 82 . o - 9.95 84.2 -10.25 = -9.27 X IO-^
TABLE XI Summary of Ion Antagonism Data HKJP X IO^ Concentration in Cation Equiv.
MgC12
CaCL
- 15.48
- 13 . i o
0 . 1 0X IO+
-11.05
-10.70
X IO-^ 0.40X IO-^
- 9.32 - 8.50 - 6.76 - 2.62
- 9.55 - 9.55 - 8.90 - 8.87
0.00 0.05
X IO-^
0.20
o .80 X IO-^ I .60 X IO-^
MgClz CaCL 0.00
X 0.10X 0.20 X o .40X 0.80X 1.60X 0.05
IO-^ IO-^ IO-^
IO-^ IO-^ IO-^
Mlg;?
MgCL NaCl
KCI
NaCl
-12.4 - 13.8 -14.01 -13.9
- 9.90 -12.60
- 14. IO -13.75 - 13.30
-12.9
-12.8 -13.6
-11.95 -10.90 CsCh KC1
CaCL NaCl
-9.86
KC1 NaCl
-12.2
-13.20
-10.70
-10.10
-10.2
-11.80
-10.22
-11.40 -9.72 -14.80
-
9.32
-
9.75 - 1 0 . 1 5 7 . 4 5 -10.00 - 9.05 - 9.83 5.46 - 8.86 - 8.07 - 7 . 7 6 4.72 - 7.48 - 6.55 -11.70
-11.80
-9.71 -14.70 -8.57 -13.03 -7.15
-6.24
-12.72
-
9.27
STUDIES IN ELECTROKINETIC POTENTIALS
717
TABLE XI1 Data for Dilute Physiological Salt Mixture Cation concentra- Preeaure tion X 1 0 3 cm. Hg 0. o
HIP
82.7
H/P
Pressure em. Hg
82 . 5
-3,911
-3.860
84.9 -3.904 84.8 86.8 -3.934 86.2 Average H / P = -3.900 HKJP = -9.75 X IO-^ 0.oj
0.10
77.6 81.6
-3.279 73.3 -3.290 78.3 -3,303 83 . 8 84.9 Average H I P = -3.312 HKJP = - 1 2 . 5 7 x -3.060
82.5
84.1 -3.049 86.1 -3 , 0 7 2 AverageHjP = -3.08 HKJP = 0.20
0.20*
Average H,'P = 0.20**
85 . o 86.2
-3.094 -3.091
-15.172
x
-I
-I
-1 ,187 -1.186 - I .163 ,205 HKJP
81. 7 84.7
88.5 Average H;P =
* plus 0.05 X 10-3 N MgCL * * plus 0.05 X IO-^ S MgC12 and
IO-5
-3,I 16
,629 83.6 ,625 85.1 - I ,618 86.8 ,6148 HKJP = -13.29 x
87.1
-3.342 -3.339 -3.323
83.9
75.5 -2.304 82.4 80.o -2.287 84.6 85.2 -2.300 86.2 AverageH,/P = - 2.305 HKJP = - 1 5 . 8 j X
81.o 83.35
-3.879 -3.915
IO+
-2.326 - 2 ,304 - 2 ,302 IO&
-I
-I . j90
-1
- I ,603 -1.624
0.Oj
X
IO@
IO-$
- I ,205
73 .O
78.5
-1
,223
83.9
-I
,269
= -IO
K CaC12
x
IO-$
HENRY B. BULL AND ROSS AIKEN GORTNER
718
TABLE XI11 Data for Mixture of NaCl and KCl in the Equivalent Ratio of Concentration
Pressure cm. Hg
48.6 65.1 73.7 Average H / P = -6.6306
0.0
0 . 1 X IO-^ KCI
58.3 69.6 78.3 Average H / P = - 3 . 7 9 6
0 . 3 X IO-^ KC1
62.5 73.7 80.1 AverageH/P = -1.8653
0 . 6 X IO-^ KCl
65.1 66 .o
Average H / P = I
.o X IO-^ KC1
Series
I
-I
X IO-^ KCl Series 2
.099
61.9 72.5 77.7 66.5 76.5 80.7
.o X
.OS
IO-^ KC1
X IO-^ NaCl
HKJP =
AverageH/P =
-0.j522
65.9 73.9 79.7 -17.06 x
-0.5573
10-6
-3.707 -3.758 -3.792 10-6
-0.5469 -0.6165 -0.5424 -0,5452
HKJP =
-12.715
10-5
x
64.8 71.5 80.1 70.5 76.4 81.8 HK./P = - 1 3 . 1 8 X
-0.5698 -0,5758 -0,5674 -0.5848 -0.5832 -0.5821
HK,/P
=
-1.781 -1.744 -1.753
-1.107 -1.123 -1.122
- 0.6060 -0.6232 -0.5897 -0.5120 -0.5160 -0,493 1
62.7 70.6 78 .o 66.4 74.6 80.1
- 0.5448
-0.5200 -0.5165 -0,5539 -0.5317 -0.5263
79.3 60.7 70.3 77.3
-6.661 -6.639 -6.637
63.7 73.4 80.7 HK,/P = -17.65 X IO-^
-0.5555
71.2
66.5 73.5 79.7 .93 X
-2.008 -1.953 -1.953
HK,/P =
20
H/P
70.8 77.7 81.6 HK,/P = - 1 8 . 3 8 x
72.1
62.3
-Ij
I
Pressure cm. Hg
-3.927 -3.829 -3.767
63 . o
78.4 71.3 77.1 81 . 7 AverageH/P = -0.5731 I
-6,759 -6.589 -6.499
-1.105 - I ,038
AverageH/P = -0.5577 I .o
H/P
66.4 7 5 .o 81.2 67.9 75.6 80.4 -12.75 x
10-6
-0.6327 -0.6573 - 0 . 6 0 54 -0,5957
- 0.6020 -0.5806 IO+
-0,5195 -0.5066 - 0.4987 -0.5301 -0,5555 -0,5534 10-5
STCDIES I N ELECTROKINETIC POTENTIALS
TABLE
719
XIT’
Data for Mixture of S a C l and CaClz in Molecular Ratio of Concentration 0.0
0 . 1X
H/P
Pressure cm. Hg
71.9 78.1 76.2 Average H/P = - 6 . 6 9 4
10-3NaCl
75.4 79.3 82.7 AverageH/P = - 3 . 6 3 4
0 . 3 X 10-3IiaCl
71.7 77.I 82.3
Average H / P =
-2.2
I
x
173
.o X
IiaC1
70.1 75.7 80.1 68 .o 74.7 79.4 Average H / P = -0.6953
10-3
NaCl
63.1 73 ’ 1 80.6 84 .o 74.6 81.7 Average H / P = -0.6510
10-3
o .oz X IO-^ CaC12
-7.065 -6.888 -6.797
66.0 75.4 80.7 H K ~ , ’= P -14.95 X IO-^
-3.872 -3.883 -3.863
74.5
78.7 83.2 HK,,~P= -17.116 X IO-^ 67.3 76.9 81.3 HKJP = - 1 8 . 4 9 X
-I.
187
-I.
168 ,133
68.1 76.3 -1 80.9 HKJP = -15.979 X
-0.6704 -0.6472 -0.6367 -0.7058 -0.6827 -0.7052
HKJP =
-3.369 -3.437 -3.383
10-5 - I . 167 -1.186 - I . 162
10-5
69.7 74.1 78.4 65.9 74,s
81 . o HKJP = - 1 3 . 6 3 X IO-^
-0.6814 -0.6429 -0,5955 - 0.6666 -0.6300 -0.6609
-6.636 -6.446 -6.332
-2.184 - 2 ,197 -2.195
-2.243 -2.205
58.1 68.5 78.5 AverageH/P = -1.1671
.o
H/P
-2.280
0 . 6 X 1o-~IiaC1
I
I:IOO
Pressure cm. Hg
-0,7317 -0.7422 -0.7716 -0.7132 -0.6711 -0.6666
69.5 - 0,6906 76.2 -0.6692 80.5 -0.6708 70.5 -0,6241 76.1 -0.6438 81.7 -0.636; -12.317 X IO-^
HENRY B. BULL AND ROSB AIKEN GORTNER
Discussion The results show, in general, an averaged effect of the individual salts in a mixed salt solution upon the surface potential. Thus the curve for KC1 and KaC1 is clearly simply a component curve of the individual curves for KCl and NaCl. There is a slight suggestion of antagonism between CaC12 and MgC12 below a concentration of 0.2 X IO+, but it is very doubtful if the results are clear enough to warrant one considering that this is a case of ion antagonism. I n any event, it is certainly very slight. Other than this, somewhat doubtful case, we may state definitely that in the concentrations investigated there are no ion antagonistic effects on the surface potential. The results with dilute physiological salt solution indicate clearly the absence of ion antagonism between MgClz and CaC12, as influencing the electrokinetic potential. I n interpreting these results it is to be remembered that the concentrations used are very much less than those usually employed in observing ion antagonism in biological systems. These low concentrations were necessarily employed since the specific conductivity becomes large in more concentrated solutions and thus invalidates streaming potential measurements. summary
The surface potential a t a cellulose-aqueous solution interface has been measured for solutions of KaC1, KCl, CaC12, MgC12, NaCl with KCl, NaCl with CaC12, IC’aCl with MgCl,, KC1 wit,h CaC12, KCl with MgC12, and CaClz with LLlgC12 up to a total cation normality of 0.8 x 10-3. 2. With the possible exception of CaClz and MgC12 the results obtained for the mixtures of the salts are more or le& an average of the results obtained for the salts separately. 3. There is no antagonism between MgC12 and CaC12 in a 0 . 2 x IO+ N diluted physiological salt solution. 4. There is no antagonism, as affecting the electrokinetic potential, between KCl and KaC1 in the ratio of Z O : I , or between NaC1 and CaCL in the molecular ratio of IOO:I. I.
Literature Cited J. Loeb: “Artificial Parthenogenesis and Fertilization,” (1913). * J. Sziick: Experimentelle Beitrage zu einer Theorie der antagonigtischen Ionenwirkungen, Jahr. Bot., 52, 85-142(1913). 3 Eva Berger: Unterschiedliche Wirkungen gleicher Ionen und Ionengemische auf verschiedene Tierarten, Pfliigers’ Archiv, 223, 1-39(1929). Ralph S. Lillie, The Relation of Ions to Ciliary Movement, Am. J. Physiol., 10, 419443 (1904). 6 W. J. V. Osterhout: “Injury, Recovery, and Death, in Relation to Conductivity and Permeability” (1922). 6 S. M. Neuschloss: Untersuchungen iiber antagonistische Wirkungen zwischen Ionen gleicher Ladung, Kolloid-Z., 27, 292-306 (1920). H. Freundlich and P. Scholz: Cber die Flockung durch Elektrolytgemische, Kolloidchem. Beihefte, 16,267-284 (1922).
STUDIES IN ELECTROKINETIC POTENTIALS 8 Q
721
H. B. Weiser: Adsorption by Precipitates. VI., J. Phys. Chem., 28, 232-244 (1924). H. B. Weiser: The rlntagonistic Action of Ions in the Neutralization of Sols, J. Phys.
Chem., 30, 20-33 (1926). 10 H. B. Weiser: The Antagonistic Actions of Ions in the Neutralization of Sols II., J. Phys. Chem., 30, 1527-1537 (1926). H. B. Weiser: Ionic Antagonism in Colloid Systems, Colloid Symposium Monograph, 42 354-373 (1926).
1% G. H. A. Clowes: Protoplasmic E uilibrium. I. Action of Antagonistic Electrolytes on Emulsions and Living Cells, J. Phys. %hem., 20, 407-451 (1916). W. D. Harkins and H. Zollman: Interfacial Tension and Emulsification. I. The Effect of Bases, Salts, and Acids upon the Interfacial Tension between Aqueous Sodium Oleate Solutions and Benzene. 11. Extremely Small Interfacial Tensions Produced by Solutes, J. Am. Chem. SOC.,48, 69-80 (1926). 14 H . S.Simms: Chemical Antagonism of Ions. IV. Effect of Salt Mixtures on Glycine Activit,y, J. Gen. Physiol., 12, 783-792 (1929). H. B. Bull and R. A. Gortner: Studies on Electrokinetic Potentials. VI. Electrical Phenomena at Interfaces, Eighth Colloid Symposium Annual, J. Phys. Chem., 35, January issue ( 1 9 3 1 ) . W. McK. Martin and R. A. Gortner: Studies on Electrokinetic Potentials, V. Interfacial Energy and the Molecular Structure of Organic Compounds. I. Electrokinetic Potentials a t Cellulose-Organic Liquid Interfaces, J. Phys. Chem., 34, 1509-1 539 (1930). I'D. R. Briggs: The Determination of the I-Potential on Cellulose-A Method, J. Phys. Chem., 32, 641-675 (1928).
