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 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 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 ELECTRIFICATION OF WATER AND OSMOTIC PRESSURE

1919 ◽  
Vol 2 (1) ◽  
pp. 87-106 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Osmotic Pressure ◽  
Salt Water ◽  
Pure Water ◽  
Preceding Paper ◽  
Ion Concentration ◽  
Hydrogen Ions ◽  
Hydrogen Ion Concentration ◽  
Positively Charged ◽  
As If ◽  
Charged Water

1. Amphoteric electrolytes form salts with both acids and alkalies. It is shown for two amphoteric electrolytes, Al(OH)3 and gelatin, that in the presence of an acid salt water diffuses through a collodion membrane into a solution of these substances as if its particles were negatively charged, while water diffuses into solutions of these electrolytes, when they exist as monovalent or bivalent metal salts, as if the particles of water were positively charged. The turning point for the sign of the electrification of water seems to be near or to coincide with the isoelectric point of these two ampholytes which is a hydrogen ion concentration of about 2 x 10–5 N for gelatin and about 10–7 for Al(OH)3. 2. In conformity with the rules given in a preceding paper the apparently positively charged water diffuses with less rapidity through a collodion membrane into a solution of Ca and Ba gelatinate than into a solution of Li, Na, K, or NH4 gelatinate of the same concentration of gelatin and of hydrogen ions. Apparently negatively charged water diffuses also with less rapidity through a collodion membrane into a solution of gelatin sulfate than into a solution of gelatin chloride or nitrate of the same concentration of gelatin and of hydrogen ions. 3. If we define osmotic pressure as that additional pressure upon the solution required to cause as many molecules of water to diffuse from solution to the pure water as diffuse simultaneously in the opposite direction through the membrane, it follows that the osmotic pressure cannot depend only on the concentration of the solute but must depend also on the electrostatic effects of the ions present and that the influence of ions on the osmotic pressure must be the same as that on the initial velocity of diffusion. This assumption was put to a test in experiments with gelatin salts for which a collodion membrane is strictly semipermeable and the tests confirmed the expectation.

Ionic Equilibria and pH

2009 ◽  
Author(s):  
Christopher O. Oriakhi
Keyword(s):  
Pure Water ◽  
Weak Acid ◽  
Hydrogen Ion ◽  
Ion Concentration ◽  
Hydrogen Ions ◽  
Hydrogen Ion Concentration ◽  
M 10 ◽  
Ionic Equilibria ◽  
Hydrated Protons ◽  
Dilute Aqueous Solution

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.

Comparative Study of Additives Effectiveness on Portable Water Mist System

2012 ◽  
Vol 610-613 ◽  
pp. 2501-2505
Author(s):  
Zhi Hao Sun ◽  
Jun Cheng Jiang ◽  
Lin Qiao
Keyword(s):  
Salt Solution ◽  
Fire Suppression ◽  
Pure Water ◽  
Surfactant Solution ◽  
Water Mist ◽  
High Concentration ◽  
Fire Control ◽  
Additive Solution ◽  
In Fire ◽  
Physical And Chemical

Extinguishing performance of portable water mist system was studied in this paper, considering the effects of additive addition and its type. The experimental results were statistically processed and numerically analysed by mathematical software. The results demonstrated that water mist with additive solution can extinguish pool fire efficiently due to physical and chemical mechanisms. The salt solution produces better fire control result than surfactant solution at low concentration, whereas the surfactant solution brings the better one at high concentration. Furthermore, the salt solution and surfactant solution have similar fire expansion behaviours to pure water in fire suppression with portable water mist system. The study, based on the application of the portable water mist system with additives, revealed that the system performed well on fire suppression and could be useful on movable fire control.

scholarly journals ELECTRICAL CHARGES OF COLLOIDAL PARTICLES AND ANOMALOUS OSMOSIS

1922 ◽  
Vol 4 (5) ◽  
pp. 621-627 ◽  
Author(s):  
Jacques Loeb
Keyword(s):  
Isoelectric Point ◽  
Salt Solution ◽  
Colloidal Particles ◽  
Pure Water ◽  
Gelatin Film ◽  
Diffusion Potential ◽  
Relative Mobility ◽  
Adsorption Theory ◽  
Direct Measurements

1. When solutions of KCl, NaCl, or LiCl are separated from water without salt by a collodion-gelatin membrane and when the pH of both salt solution and water are on the acid side of the isoelectric point of gelatin, water diffuses from the side of pure water into the salt solution at a rate increasing inversely with the radius of the cations. 2. The adsorption theory would lead us to assume that this influence of the cations is due to an increase of the P.D. between the liquid and the membrane inside the pores of the gelatin film of the membrane, but direct measurements of this P.D. contradict such an assumption, since they show that the influence of the three salts on this P.D. is identical at pH 3.0. 3. It is found, however, that the P.D. across the membrane is affected in a similar way by the three cations as is the transport of water through the membrane. 4. This P.D. across the membrane varies inversely as the relative mobility of the three cations which suggests that the influence of the three cations on the diffusion of liquid through the membrane is partly if not essentially due to a diffusion potential.

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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