scholarly journals THE ORIGIN OF THE POTENTIAL DIFFERENCES RESPONSIBLE FOR ANOMALOUS OSMOSIS

1921 ◽  
Vol 4 (2) ◽  
pp. 213-226 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Salt Solution ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Neutral Salt ◽  
Hydrogen Ion Concentration ◽  
Hno3 Solution ◽  
Donnan Equilibrium ◽  
Double Origin ◽  
Concentration Cells ◽  
As If

1. Collodion bags coated with gelatin on the inside were filled with a M/256 solution of neutral salt (e.g., NaCl, CaCl2, CeCl3, or Na2SO4) made up in various concentrations of HNO3 (varying from N/50,000 to N/100). Each collodion bag was put into an HNO3 solution of the same concentration as that inside the bag but containing no salt. In this case water diffuses from the outside solution (containing no salt) into the inside solution (containing the salt) with a relative initial velocity which can be expressed by the following rules: (a) Water diffuses into the salt solution as if the particles of water were negatively charged and as if they were attracted by the cation and repelled by the anion of the salt with a force increasing with the valency of the ion. (b) The initial rate of the diffusion of water is a minimum at the hydrogen ion concentration of about N/50,000 HCl (pH 4.7, which is the point at which gelatin is not ionized), rises with increasing hydrogen ion concentration until it reaches a maximum and then diminishes again with a further rise in the initial hydrogen ion concentration. 2. The potential differences between the salt solution and the outside solution (originally free from salt) were measured after the diffusion had been going on for 1 hour; and when these values were plotted as ordinates over the original pH as abscissae, the curves obtained were found to be similar to the osmotic rate curves. This confirms the view expressed by Girard) Bernstein, Bartell, and Freundlich that these cases of anomalous osmosis are in reality cases of electrical endosmose where the driving force is a P.D. between the opposite sides of the membrane. 3. The question arose as to the origin of these P. D. and it was found that the P.D. has apparently a double origin. Certain features of the P.D. curve, such as the rise and fall with varying pH, seem to be the consequence of a Donnan equilibrium which leads to some of the free HNO3 being forced from the solution containing salt into the outside solution containing no (or less) salt. This difference of the concentration of HNO3, on the opposite sides of the membrane leads to a P.D. which in conformity with Nernst's theory of concentration cells should be equal to 58 x (pH inside minus pH outside) millivolts at 18°C. The curves of the values of (pH inside minus pH outside) when plotted as ordinates over the original pH as abscissae lead to curves resembling those for the P. D. in regard to location of minimum and maximum. 4. A second source of the P.D. seems to be diffusion potentials, which exist even if no membranes are present and which seem to be responsible for the fact that the rate of diffusion of negatively charged water into the salt solution increases with the valency of the cation and diminishes with the valency of the anion of the salt. 5. The experiments suggest the possibility that the establishment of a Donnan equilibrium between membrane and solution is one of the factors determining the Helmholtzian electrical double layer, at least in the conditions of our experiments.

scholarly journals ELECTRICAL CHARGES OF COLLOIDAL PARTICLES AND ANOMALOUS OSMOSIS

1922 ◽  
Vol 4 (4) ◽  
pp. 463-486 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Isoelectric Point ◽  
Salt Solution ◽  
Electrical Transport ◽  
Colloidal Particles ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Trivalent Cation ◽  
Hydrogen Ion Concentration ◽  
Donnan Equilibrium ◽  
Positively Charged

1. It has been shown in previous publications that when solutions of different concentrations of salts are separated by collodion-gelatin membranes from water, electrical forces participate in addition to osmotic forces in the transport of water from the side of the water to that of the solution. When the hydrogen ion concentration of the salt solution and of the water on the other side of the membrane is the same and if both are on the acid side of the isoelectric point of gelatin (e.g. pH 3.0), the electrical transport of water increases with the valency of the cation and inversely with the valency of the anion of the salt in solution. Moreover, the electrical transport of water increases at first with increasing concentration of the solution until a maximum is reached at a concentration of about M/32, when upon further increase of the concentration of the salt solution the transport diminishes until a concentration of about M/4 is reached, when a second rise begins, which is exclusively or preeminently the expression of osmotic forces and therefore needs no further discussion. 2. It is shown that the increase in the height of the transport curves with increase in the valency of the cation and inversely with the increase in the valency of the anion is due to the influence of the salt on the P.D. (E) across the membrane, the positive charge of the solution increasing in the same way with the valency of the ions mentioned. This effect on the P.D. increases with increasing concentration of the solution and is partly, if not essentially, the result of diffusion potentials. 3. The drop in the transport curves is, however, due to the influence of the salts on the P.D. (ϵ) between the liquid inside the pores of the gelatin membrane and the gelatin walls of the pores. According to the Donnan equilibrium the liquid inside the pores must be negatively charged at pH 3.0 and this charge is diminished the higher the concentration of the salt. Since the electrical transport is in proportion to the product of E x ϵ and since the augmenting action of the salt on E begins at lower concentrations than the depressing action on ϵ, it follows that the electrical transport of water must at first rise with increasing concentration of the salt and then drop. 4. If the Donnan equilibrium is the sole cause for the P.D. (ϵ) between solid gelatin and watery solution the transport of water through collodion-gelatin membranes from water to salt solution should be determined purely by osmotic forces when water, gelatin, and salt solution have the hydrogen ion concentration of the isoelectric point of gelatin (pH = 4.7). It is shown that this is practically the case when solutions of LiCl, NaCl, KCl, MgCl2, CaCl2, BaCl2, Na2SO4, MgSO4 are separated by collodion-gelatin membranes from water; that, however, when the salt has a trivalent (or tetravalent?) cation or a tetravalent anion a P.D. between solid isoelectric gelatin and water is produced in which the wall assumes the sign of charge of the polyvalent ion. 5. It is suggested that the salts with trivalent cation, e.g. Ce(NO3)3, form loose compounds with isoelectric gelatin which dissociate electrolytically into positively charged complex gelatin-Ce ions and negatively charged NO3 ions, and that the salts of Na4Fe(CN)6 form loose compounds with isoelectric gelatin which dissociate electrolytically into negatively charged complex gelatin-Fe(CN)6 ions and positively charged Na ions. The Donnan equilibrium resulting from this ionization would in that case be the cause of the charge of the membrane.

scholarly journals DONNAN EQUILIBRIUM AND THE PHYSICAL PROPERTIES OF PROTEINS

1921 ◽  
Vol 3 (5) ◽  
pp. 667-690 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Osmotic Pressure ◽  
Chloride Solution ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Neutral Salt ◽  
Hydrogen Ion Concentration ◽  
Monovalent Anion ◽  
Donnan Equilibrium ◽  
The Difference ◽  
Fair Degree

1. It is shown that a neutral salt depresses the potential difference which exists at the point of equilibrium between a gelatin chloride solution contained in a collodion bag and an outside aqueous solution (without gelatin). The depressing effect of a neutral salt on the P.D. is similar to the depression of the osmotic pressure of the gelatin chloride solution by the same salt. 2. It is shown that this depression of the P.D. by the salt can be calculated with a fair degree of accuracy on the basis of Nernst's logarithmic formula on the assumption that the P.D. which exists at the point of equilibrium is due to the difference of the hydrogen ion concentration on the opposite sides of the membrane. 3. Since this difference of hydrogen ion concentration on both sides of the membrane is due to Donnan's membrane equilibrium this latter equilibrium must be the cause of the P.D. 4. A definite P.D. exists also between a solid block of gelatin chloride and the surrounding aqueous solution at the point of equilibrium and this P.D. is depressed in a similar way as the swelling of the gelatin chloride by the addition of neutral salts. It is shown that the P.D. can be calculated from the difference in the hydrogen ion concentration inside and outside the block of gelatin at equilibrium. 5. The influence of the hydrogen ion concentration on the P.D. of a gelatin chloride solution is similar to that of the hydrogen ion concentration on the osmotic pressure, swelling, and viscosity of gelatin solutions, and the same is true for the influence of the valency of the anion with which the gelatin is in combination. It is shown that in all these cases the P.D. which exists at equilibrium can be calculated with a fair degree of accuracy from the difference of the pH inside and outside the gelatin solution on the basis of Nernst's logarithmic formula by assuming that the difference in the concentration of hydrogen ions on both sides of the membrane determines the P.D. 6. The P.D. which exists at the boundary of a gelatin chloride solution and water at the point of equilibrium can also be calculated with a fair degree of accuracy by Nernst's logarithmic formula from the value pCl outside minus pCl inside. This proves that the equation x2 = y ( y + z) is the correct expression for the Donnan membrane equilibrium when solutions of protein-acid salts with monovalent anion are separated by a collodion membrane from water. In this equation x is the concentration of the H ion (and the monovalent anion) in the water, y the concentration of the H ion and the monovalent anion of the free acid in the gelatin solution, and z the concentration of the anion in combination with the protein. 7. The similarity between the variation of P.D. and the variation of the osmotic pressure, swelling, and viscosity of gelatin, and the fact that the Donnan equilibrium determines the variation in P.D. raise the question whether or not the variations of the osmotic pressure, swelling, and viscosity are also determined by the Donnan equilibrium.

scholarly journals CATAPHORETIC CHARGES OF COLLODION PARTICLES AND ANOMALOUS OSMOSIS THROUGH COLLODION MEMBRANES FREE FROM PROTEIN

1922 ◽  
Vol 5 (1) ◽  
pp. 89-107 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Salt Solution ◽  
Electrical Transport ◽  
Pure Water ◽  
Diffusion Potential ◽  
Ion Concentration ◽  
High Concentration ◽  
Hydrogen Ion Concentration ◽  
Osmotic Effect ◽  
Diffusion Potentials ◽  
As If

1. It had been shown in previous papers that when a salt solution is separated from pure water by a collodion membrane, water diffuses through the membrane as if it were positively charged and as if it were attracted by the anion of the salt in solution and repelled by the cation with a force increasing with the valency. In this paper, measurements of the P.D. across the membrane (E) are given, showing that when an electrical effect is added to the purely osmotic effect of the salt solution in the transport of water from the side of pure water to the solution, the latter possesses a considerable negative charge which increases with increasing valency of the anion of the salt and diminishes with increasing valency of the cation. It is also shown that a similar valency effect exists in the diffusion potentials between salt solutions and pure water without the interposition of a membrane. 2. This makes it probable that the driving force for the electrical transport of water from the side of pure water into solution is primarily a diffusion potential. 3. It is shown that the hydrogen ion concentration of the solution affects the transport curves and the diffusion potentials in a similar way. 4. It is shown, however, that the diffusion potential without interposition of the membrane differs in a definite sense from the P.D. across the membrane and that therefore the P.D. across the membrane (E) is a modified diffusion potential. 5. Measurements of the P.D. between collodion particles and aqueous solutions (ϵ) were made by the method of cataphoresis, which prove that water in contact with collodion particles free from protein practically always assumes a positive charge (except in the presence of salts with trivalent and probably tetravalent cations of a sufficiently high concentration). 6. It is shown that an electrical transport of water from the side of water into the solution is always superposed upon the osmotic transport when the sign of charge of the solution in the potential across the membrane (E) is opposite to that of the water in the P.D. between collodion particle and water (ϵ); supporting the theoretical deductions made by Bartell. 7. It is shown that the product of the P.D. across the membrane (E) into the cataphoretic P.D. between collodion particles and aqueous solution (ϵ) accounts in general semiquantitatively for that part of the transport of water into the solution which is due to the electrical forces responsible for anomalous osmosis.

scholarly journals ON THE INFLUENCE OF AGGREGATES ON THE MEMBRANE POTENTIALS AND THE OSMOTIC PRESSURE OF PROTEIN SOLUTIONS

1922 ◽  
Vol 4 (6) ◽  
pp. 769-776 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Membrane Potential ◽  
Hydrostatic Pressure ◽  
Osmotic Pressure ◽  
Membrane Potentials ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Gelatin Solution ◽  
True Solution ◽  
Hydrogen Ion Concentration ◽  
Donnan Equilibrium

1. It is shown that when part of the gelatin in a solution of gelatin chloride is replaced by particles of powdered gelatin (without change of pH) the membrane potential of the solution is influenced comparatively little. 2. A measurement of the hydrogen ion concentration of the gelatin chloride solution and the outside aqueous solution with which the gelatin solution is in osmotic equilibrium, shows that the membrane potential can be calculated from this difference of hydrogen ion concentration with an accuracy of half a millivolt. This proves that the membrane potential is due to the establishment of a membrane equilibrium and that the powdered particles participate in this membrane equilibrium. 3. It is shown that a Donnan equilibrium is established between powdered particles of gelatin chloride and not too strong a solution of gelatin chloride. This is due to the fact that the powdered gelatin particles may be considered as a solid solution of gelatin with a higher concentration than that of the weak gelatin solution in which they are suspended. It follows from the theory of membrane equilibria that this difference in concentration of protein ions must give rise to potential differences between the solid particles and the weaker gelatin solution. 4. The writer had shown previously that when the gelatin in a solution of gelatin chloride is replaced by powdered gelatin (without a change in pH), the osmotic pressure of the solution is lowered the more the more dissolved gelatin is replaced by powdered gelatin. It is therefore obvious that the powdered particles of gelatin do not participate in the osmotic pressure of the solution in spite of the fact that they participate in the establishment of the Donnan equilibrium and in the membrane potentials. 5. This paradoxical phenomenon finds its explanation in the fact that as a consequence of the participation of each particle in the Donnan equilibrium, a special osmotic pressure is set up in each individual particle of powdered gelatin which leads to a swelling of that particle, and this osmotic pressure is measured by the increase in the cohesion pressure of the powdered particles required to balance the osmotic pressure inside each particle. 6. In a mixture of protein in solution and powdered protein (or protein micellæ) we have therefore two kinds of osmotic pressure, the hydrostatic pressure of the protein which is in true solution, and the cohesion pressure of the aggregates. Since only the former is noticeable in the hydrostatic pressure which serves as a measure of the osmotic pressure of a solution, it is clear why the osmotic pressure of a protein solution must be diminished when part of the protein in true solution is replaced by aggregates.

Di Brom Thymol Sulhpone Phthalein as a Reagent for Determining the Hydrogen Ion Concentration of Living Cells

1922 ◽  
Vol 12 (4) ◽  
pp. 781-784 ◽  
Author(s):  
W. R. G. Atkins
Keyword(s):  
Sea Water ◽  
Living Cells ◽  
Marine Organisms ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Toxic Action ◽  
Thymol Blue ◽  
Neutral Salt ◽  
Dilute Solution ◽  
Hydrogen Ion Concentration

1. Brom thymol blue may be used in dilute solution for ascertaining the hydrogen ion concentration of certain marine organisms. It penetrates slowly, but the stained portions remain actively motile, so its toxic action does not appear to be great at the dilutions found serviceable.2. The animals studied gave values from pH6·2 to about pH7·5, though possibly the more alkaline end of the range may be pathological. About pH0·2 should be subtracted from these figures for neutral salt error. The sea water used was initially at pH8·2, corrected.

Intracellular hydrogen ion changes and potassium movement

1963 ◽  
Vol 204 (5) ◽  
pp. 765-770 ◽  
Author(s):  
E. B. Brown ◽  
Bernard Goott
Keyword(s):  
Extracellular Fluid ◽  
Plasma Potassium ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Reverse Direction ◽  
Acid Base ◽  
Hydrogen Ion Concentration ◽  
Donnan Equilibrium ◽  
Extracellular Compartment ◽  
Direction Of Movement

Intracellular hydrogen ion concentration was determined on skeletal muscle by the DMO technique in dogs subjected to various acid-base alterations. The data verified the fact that a given alteration in Pco2 produces a larger hydrogen ion change in intracellular fluid than in extracellular fluid. In spite of this, however, the ratio (See PDF) decreased. On the basis of this change in ratio, the Donnan equilibrium would predict that potassium would move from intracellular to extracellular compartment and not in the reverse direction as had been assumed previously. Using the change in plasma potassium as the criterion of direction of movement of potassium between intracellular and extracellular fluids, the movement of potassium produced by any of the acid-base alterations which were studied was usually that which would be predicted by the Donnan equilibrium.

scholarly journals AMPHOTERIC COLLOIDS

1918 ◽  
Vol 1 (1) ◽  
pp. 39-60 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Physical Properties ◽  
Osmotic Pressure ◽  
Isoelectric Point ◽  
Alkali Treatment ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Neutral Salt ◽  
Sharp Drop ◽  
Hydrogen Ion Concentration ◽  
Alkaline Side

1. It has been shown in this paper that while non-ionized gelatin may exist in gelatin solutions on both sides of the isoelectric point (which lies for gelatin at a hydrogen ion concentration of CH = 2.10–5 or pH = 4.7), gelatin, when it ionizes, can only exist as an anion on the less acid side of its isoelectric point (pH > 4.7), as a cation only on the more acid side of its isoelectric point (pH < 4.7). At the isoelectric point gelatin can dissociate practically neither as anion nor as cation. 2. When gelatin has been transformed into sodium gelatinate by treating it for some time with M/32 NaOH, and when it is subsequently treated with HCl, the gelatin shows on the more acid side of the isoelectric point effects of the acid treatment only; while the effects of the alkali treatment disappear completely, showing that the negative gelatin ions formed by the previous treatment with alkali can no longer exist in a solution with a pH < 4.7. When gelatin is first treated with acid and afterwards with alkali on the alkaline side of the isoelectric point only the effects of the alkali treatment are noticeable. 3. On the acid side of the isoelectric point amphoteric electrolytes can only combine with the anions of neutral salts, on the less acid side of their isoelectric point only with cations; and at the isoelectric point neither with the anion nor cation of a neutral salt. This harmonizes with the statement made in the first paragraph, and the experimental results on the effect of neutral salts on gelatin published in the writer's previous papers. 4. The reason for this influence of the hydrogen ion concentration on the stability of the two forms of ionization possible for an amphoteric electrolyte is at present unknown. We might think of the possibility of changes in the configuration or constitution of the gelatin molecule whereby ionized gelatin can exist only as an anion on the alkaline side and as a cation on the acid side of its isoelectric point. 5. The literature of colloid chemistry contains numerous statements which if true would mean that the anions of neutral salts act on gelatin on the alkaline side of the isoelectric point, e.g. the alleged effect of the Hofmeister series of anions on the swelling and osmotic pressure of common gelatin in neutral solutions, and the statement that both ions of a neutral salt influence a protein simultaneously. The writer has shown in previous publications that these statements are contrary to fact and based on erroneous methods of work. Our present paper shows that these claims of colloid chemists are also theoretically impossible. 6. In addition to other physical properties the conductivity of gelatin previously treated with acids has been investigated and plotted, and it was found that this conductivity is a minimum in the region of the isoelectric point, thus confirming the conclusion that gelatin can apparently not exist in ionized condition at that point. The conductivity rises on either side of the isoelectric point, but not symmetrically for reasons given in the paper. It is shown that the curves for osmotic pressure, viscosity, swelling, and alcohol number run parallel to the curve of the conductivity of gelatin when the gelatin has been treated with acid, supporting the view that these physical properties are in this case mainly or exclusively a function of the degree of ionization of the gelatin or gelatin salt formed. It is pointed out, however, that certain constitutional factors, e.g. the valency of the ion in combination with the gelatin, may alter the physical properties of the gelatin (osmotic pressure, etc.) without apparently altering its conductivity. This point is still under investigation and will be further discussed in a following publication. 7. It is shown that the isoelectric point of an amphoteric electrolyte is not only a point where the physical properties of an ampholyte experience a sharp drop and become a minimum, but that it is also a turning point for the mode of chemical reactions of the ampholyte. It may turn out that this chemical influence of the isoelectric point upon life phenomena overshadows its physical influence. 8. These experiments suggest that the theory of amphoteric colloids is in its general features identical with the theory of inorganic hydroxides (e.g. aluminum hydroxide), whose behavior is adequately understood on the basis of the laws of general chemistry.

scholarly journals HYDROGEN-ION CONCENTRATION RELATIONS IN A THREE-SALT SOLUTION

Soil Science ◽  
1921 ◽  
Vol 11 (5) ◽  
pp. 325-352 ◽  
Author(s):  
HENRY F. A. MEIER ◽  
CLIFTON E. HALSTEAD
Keyword(s):  
Salt Solution ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Hydrogen Ion Concentration
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