scholarly journals SOME CONSEQUENCES OF THE THEORY OF MEMBRANE EQUILIBRIA

1925 ◽  
Vol 9 (1) ◽  
pp. 97-109 ◽  
Author(s):  
David I. Hitchcock

In applying Donnan's theory of membrane equilibria to systems where the non-diffusible ion is furnished by a weak acid, base, or ampholyte, certain new relations have been derived. Equations have been deduced which give the ion ratio and the apparent osmotic pressure as functions of the concentration and ionization constant of the weak electrolyte, and of the hydrogen ion concentration in its solution. The conditions for maximum values of these two properties have been formulated. It is pointed out that the progressive addition of acid to a system containing a non-diffusible weak base should not cause the value of the membrane potential to rise, pass through a maximum, and fall, but should only cause it to diminish. It is shown that the theory predicts slight differences in the effect of salts on the ion ratio in such systems, the effect increasing with the valence of the cation.

1922 ◽  
Vol 4 (6) ◽  
pp. 769-776 ◽  
Author(s):  
Jacques Loeb

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.


(1) Long chain carboxylic acids dissolved in benzene show regular changes in interfacial tension against aqueous "buffered" solutions as the hydrion concentration of these is altered. A fall in interfacial tension starts at p h 5·5 and extends over the range of 4·0 p h 9·3 approximately, tending to vanish at this point. The curve is not identical with a dissociation curve, though it extends over the same range of p h . For a given p h the results are identical for phosphate and glycine "buffered" solutions, and for all acids investigated, except capric acid(C 10 ), which shows an abnormality for phosphate. (2) Hexadecylamine shows similar changes, in the opposite sense between approximately the same p h range, which follow the dissociation curve of a weak base rather closely


2020 ◽  
pp. 2182-2198
Author(s):  
Julian Seifter

The normal pH of human extracellular fluid is maintained within the range of 7.35 to 7.45. The four main types of acid–base disorders can be defined by the relationship between the three variables, pH, Pco2, and HCO3 –. Respiratory disturbances begin with an increase or decrease in pulmonary carbon dioxide clearance which—through a shift in the equilibrium between CO2, H2O, and HCO3 –—favours a decreased hydrogen ion concentration (respiratory alkalosis) or an increased hydrogen ion concentration (respiratory acidosis) respectively. Metabolic acidosis may result when hydrogen ions are added with a nonbicarbonate anion, A−, in the form of HA, in which case bicarbonate is consumed, or when bicarbonate is removed as the sodium or potassium salt, increasing hydrogen ion concentration. Metabolic alkalosis is caused by removal of hydrogen ions or addition of bicarbonate. Laboratory tests usually performed in pursuit of diagnosis, aside from arterial blood gas analysis, include a basic metabolic profile with electrolytes (sodium, potassium, chloride, bicarbonate), blood urea nitrogen, and creatinine. Calculation of the serum anion gap, which is determined by subtracting the sum of chloride and bicarbonate from the serum sodium concentration, is useful. The normal value is 10 to 12 mEq/litre. An elevated value is diagnostic of metabolic acidosis, helpful in the differential diagnosis of the specific metabolic acidosis, and useful in determining the presence of a mixed metabolic disturbance. Acid–base disorders can be associated with (1) transport processes across epithelial cells lining transcellular spaces in the kidney, gastrointestinal tract, and skin; (2) transport of acid anions from intracellular to extracellular spaces—anion gap acidosis; and (3) intake.


1921 ◽  
Vol 3 (3) ◽  
pp. 391-414 ◽  
Author(s):  
Jacques Loeb

1. Ions with the opposite sign of charge as that of a protein ion diminish the swelling, osmotic pressure, and viscosity of the protein. Ions with the same sign of charge as the protein ion (with the exception of H and OH ions) seem to have no effect on these properties as long as the concentrations of electrolytes used are not too high. 2. The relative depressing effect of different ions on the physical properties of proteins is a function only of the valency and sign of charge of the ion, ions of the same sign of charge and the same valency having practically the same depressing effect on gelatin solutions of the same pH while the depressing effect increases rapidly with an increase in the valency of the ion. 3. The Hofmeister series of ions are the result of an error due to the failure to notice the influence of the addition of a salt upon the hydrogen ion concentration of the protein solution. As a consequence of this failure, effects caused by a variation in the hydrogen ion concentration of the solution were erroneously attributed to differences in the nature of the ions of the salts used. 4. It is not safe to draw conclusions concerning specific effects of ions on the swelling, osmotic pressure, or viscosity of gelatin when the concentration of electrolytes in the solution exceeds M/16, since at that concentration the values of these properties are near the minimum characteristic of the isoelectric point.


Author(s):  
Christopher O. Oriakhi

Water is a weak acid. At 25°C, pure water ionizes to form a hydrogen ion and a hydroxide ion: H2O ⇋ H+ + OH− Hydration of the proton (hydrogen ion) to form hydroxonium ion is ignored here for simplicity. This equilibrium lies mainly to the left; that is, the ionization happens only to a slight extent. We know that 1 L of pure water contains 55.6 mol. Of this, only 10−7 mol actually ionizes into equal amounts of [H+] and [OH−], i.e., [H+] = [OH−] = 10−7M Because these concentrations are equal, pure water is neither acidic nor basic. A solution is acidic if it contains more hydrogen ions than hydroxide ions. Similarly, a solution is basic if it contains more hydroxide ions than hydrogen ions. Acidity is defined as the concentration of hydrated protons (hydrogen ions); basicity is the concentration of hydroxide ions. Pure water ionizes at 25°C to produce 10−7 M of [H+] and 10−7 M of [OH−]. The product Kw = [H+]×[OH−] = 10−7 M×10−7 M= 10−14 M is known as the ionic product of water. Note that this is simply the equilibrium expression for the dissociation of water. This equation holds for any dilute aqueous solution of acid, base, and salt. The pH of a solution is defined as the negative logarithm of the molar concentration of hydrogen ions. The lower the pH, the greater the acidity of the solution. Mathematically: pH=−log10[ H+] or −log10[H3O+] This can also be written as: pH = log10 1/[H+] or log10 1/[H3O+] Taking the antilogarithm of both sides and rearranging gives: [H+] = 10−pH This equation can be used to calculate the hydrogen ion concentration when the pH of the solution is known.


1963 ◽  
Vol 204 (5) ◽  
pp. 765-770 ◽  
Author(s):  
E. B. Brown ◽  
Bernard Goott

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.


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