摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13. H. HARTLEY AND H. R. RMKES 393 THE MOBILITIES OF THE ELEMENTARY IONS IN METHYL ALCOHOL. By H.HARTLEY and H. R. RAKES. Received 30th March, 1927. The mobilities of the elementary ions possess a special interest as their structure is known more definitely than that of composite ions such as NO,-, and some evidence as to their relative sizes may be obtained from 11 R. Lorenz, Zoc. cif., pp. 87 and 261.394 MOBILITIES OF IONS IN METHYL ALCOHOL H,O. 1 MeOH. ~- Mg . Ca . Sr . Ba . Zn . Cd . - - their effective ionic radii in the crystal lattice which have been shown to be approximately constant in simple polar assemblages. I n water, as is well known, the ions of the alkali metals and of the halogens, which have the largest radii in the crystal lattice, have the highest mobilities, while all the ions of the divalent metals have roughly the same niobilities in spite of a considerable increase in size with atomic number.These facts are usually explained by the assumption that the ions are hydrated, and that the degree of hydration of the small ions is larger on account of the more intense elec- trical field around them, their mobilities being correspondingly reduced. Washburn's determination of the relative number of water molecules asso- ciated with the ions of the alkali metals affords strong evidence in favour of this view. We have been engaged since 192 I in investigating the conductivities of dilute salt solutions in methyl alcohol, and our results, together with the determination of the transport number of the chlorine ion in hydrogen chloride by Nonhebel and Hartley,l now enable us to compare the infinite dilution values of the mobilities of all the univalent elements and most of the divalent metals in methyl alcohol with those in water at 25' C.The values in Table I. for univalent ions in methyl alcohol are taken from Frazer and Hartley's paper, with the exception of T1+, the rest are from unpublished work by McChlery (TI+), Philbrick (Ca++, Sr++, Ba++), and Ross (Mg++, Zn++, Cd++). I H,O. i MeOH. 1- 53.0 I 57.6 59.8 I 60.0 59'8 1 59'0 64.2 I 60.0 54-2 596 53'5 57'4 - - - I - H . Li . Na . K . . Rb . cs . . 3. : H,O. j MeOH. -- 53'8 I n methyl alcohol as in water the mobilities both of the alkali metals and halogens increase with atomic number, the rise being more regular in methyl alcohol (in water for example the mobility of bromine is slightly greater than that of iodine).The mobilities of silver and thallium are high in both cases, and bear roughly the same relation to caesium in each. The mobilities of the divalent metals are even more nearly equal in methyl alcohol than in water. Thus the general relationships of the ionic mobilities are the same in both solvents, as is seen in the figure, in which the mobili- ties of the ions divided by their valencies are plotted against their atomic numbers. This expresses the relative magnitudes of their mobilities under equivalent conditions, as in the same electrical field the force acting on a divalent ion is twice that on a univalent ion. I n spite, however, of the general agreement the relative mobility of the ions in the two solvents is not constant, as is seen in Table 11.for univalent ions. Values for the divalent ions are all approximately unity like lithium. If the change in mobility were due entirely to the change in the viscosity of the solvent, the ratios in Table 11. would all have the value 1'64, the ionsH. HARTLEY AND H. R. RAIKES 395 TABLE 11. Li. Na. K. Rb. Cs. Ag. T1. F. C1. Br. I. Mg Ca Sr Ba Zn Cd moving faster in the less viscous solvent. But some other factor is con- cerned which varies from ion to ion; if it is solvation then the above ratios indicate that the ions are more solvated in methyl alcohol than in water. I t is hard to gain more precise information about solvation in methyl alcohol as experiments similar to Washburn's would be very difficult owing to the volatile and hygroscopic nature of the solvent and to the limited solubility of substances in it.Schmick's however, makes it probable that the electric field around the smaller ions is sufficiently strong to hold firmly the dipole molecules in their immediate vicinity. This accords with 3'44 3-05 3.04 2-83 3.36 3-38 - - Mobilities in Water - ..._. ___-.- Mobditics in Methyl Alcohol 5-19 5-06 4'93 5.02 5-21 4'98 - I 10 20 30 90 50 60 70 80 Atomic Number FIG. I. the general trend of recent experimental work in non-aqueous solvents, which indicates that Stokes' Law is applicable to the motion of ions,l and that the ionic radii calculated by means of it give at any rate the relative magnitudes of the ions in different solvents. Table III. gives a comparison 0'75 1.20 1.40 (0.60) (0.98) 1'02 - TABLE 111.IONIC RADII IN ANGSTROM UNITS. Methyl Crystal Water' Alcohol. Lattice. i i 2'30 3'78 1 0'72 1.79 3'27 1'01 1'22 F 1-67 CI 1'21 Br 1-18 I 1-20 - - - - - i - I - 1 - I396 MOBILITIES OF IONS IN METHYL ALCOHOL of the ionic radii in water and methyl alcohol calculated from their mobili- ties by means of Stokes' Law, together with their effective ionic radii in the crystal lattice as calculated by Wa~astjerna,~ with the exception of the values in brackets which were obtained by subtracting 0.72 from the values given by I3raggG The fact that the ionic radii in water of several of the alkali metals and halogens appear to be smaller than their effective radii in the lattice throws some doubt on the absolute values of the radii obtained by these means.The radii of all ions in methyl alcohol are greater than in water, the increase in apparent size being due presumably either to the larger solvent molecules or the greater number attached to the ion, the increase being greater for the univalent than the divalent ions. The influence of the ionic charge on the degree of solvation is shown by the fact that in both solvents all the divalent ions gave the largest radii, although the radii in the crystal lattice vary from 0.75 Angstroms for magnesium to 1-40 for barium, the greater degree of solvation of the smaller ion just compensating for the increased size of the ions of higher atomic number. The effect of size appears again clearly among the univalent ions, where the order of magnitude is the in- verse of that for the crystal lattice. Silver which is smaller than rubidium and caesium in the lattice has a smaller mobility in both solvents, while thallium which is larger in the lattice is also faster, having roughly the same mobility as rubidium and caesium. I t is worth mentioning in this connec- tion that the mobility of the perchlorate ion in methyl alcohol is 70.8 as compared with 5 1.3 for chlorine. REFERENCES. 1Nonhebel and Hartley, Phil. Mug. (rgzs), (7), 2, 729. Frazer and Hartley, Proc. Roy. SOC. (I~ZS), I ~ A , 351. 3Schmick, 2. Physik. (rgq), q, 56. 4 Ulich, Uber die Bewezlichkeit der elektroly tischen Ioncn, Berlin, 1926. Walden, Ulich, and Busch, 2. physikal. Chem. (1926), 123, 429. 6 Wasastjerna, SOC. Scient. tienn. Comm. Plays. Math. (1gz3), 38, I. GBragg, Phil. Mag. (1926), (7), 2, 258. Physica I Chemistry Laboratory, BaZZiol' CoZZege and Trinity CoZZege, Oxford.

ISSN:0014-7672    

DOI:10.1039/TF9272300393

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13. 396 MOBILITIES OF IONS I N METHYL ALCOHOL NOTES ON THE DEBYE-HUCKEL THEORY. BY H. HARTLEY AND R. P. BELL. Eeceived 9th April, 1927. The Debye-Huckel theory of the conductivity of strong electrolytes postulates that the decrease in ionic mobility with increasin, 0 concentra- tion is due entirely to interionic forces and to cataphoresis of the solvent, the electrolyte being completely dissociated at all concentrations a t which the theory is applicable. In water it is probable that this latter condition is fulfilled for most salts in dilute solution, although certain salts of mercury and cadmium are exceptions; but in non-aqueous solvents the formation of complex ions or of undissociated molecules even in dilute solutions is a much more general phenomenon.ThusH. HARTLEY AND R. P. BELL 397 discrepancies between the Debye-Huckel theory and experimental results may mean Bther that the theory is incorrect, or that the electrolytes in question are not completely dissociated. I t is therefore a matter of great interest to see whether there is a substantial body of evidence in accord with the theory. If this is so, deviations from the theory might be ascribed to abnormal behaviour of the electrolyte and might even be used to detect lack of complete dissociation. Debye and Huckel have made a comprehensive survey of the con- ductivity data for dilute aqueous solutions, and have shown that they are in fair agreement with their theory.Similar comparisons for non- aqueous solvents are more difficult, as the experimental data are far less complete and homogeneous, but as such a comparison affords a more searching test of this general applicability of the theory in view of the large differences in properties between the solvents, we have examined a considerable number of the conductivity data for dilute salt solutions in thirteen different solvents, in order to see how far they are in agree- ment with the theory. Owing to the absence of reliable data for poly- valent ions the comparison is limited to uni-univalent salts. For elec- trolytes of this type Debye and Huclcel’s equation can be written in the form, where K, and K, are universal constants for all solvents varying only with the temperature, D is the dielectric constant of the solvent, 2, and I , being the mobilities of the cation and anion, b is the harmonic mean of the ionic radii and C is the molecular concentration. Obviously the first test of this equation is to see whether there is in all cases a linear relation between the equivalent conductivity and the square root of the concentration, corresponding to the empirical expression found by Kohlrausch to hold for dilute aqueous solutions :- - (2) A, = A, - ~ ~ ’ 1 2 .Hartley and Frazer have shown that this relation does hold for eighteen uni-univalent salts in methyl alcohol up to 0.002 N , and subsequent work has confirmed this for a large number of other salts. Walden, Ulich, and Busch have found the same relation for salts in acetone up to oaooj N! while Ulich has recently used the square root formula in recalcu- lating values of A,, in a number of solvents. We have examined a large number of experimental results in the thirteen non-aqueous solvents mentioned in Table I.by graphic methods, and we find that in general the more accurate and concordant are the data, the more closely do they confirm to the square root relation in dilute solution. In view of the wide range of solvents and the number of salts examined, it is a remark- able fact that the square root law was found to hold so generally. The dilution a t which the linear relationship ceases varies with the solvent, the solute and the temperature. It is interesting to note that in some non-aqueous solvents certain lithium salts do not obey this relation or do so only a t exceptionally high dilutions ; lithium iodide, however, shows no such abnormality, and there is little doubt that the exceptional behaviour of lithium salts is due to the formation of complex 2 7398 NOTES ON THE DEBYE-HUCKEL THEORY ions even in dilute solutions, as in non-aqucous solvents the tendency to form complexes appear t o be less with the iodine ion than with the other halogens or the nitrate ion.Comparatively little work has been done on conductivity in non- aqueous solvents over a wide range of temperature, but the measurements of Duperthuis in pyridine and various alcohols between o0 C. and 80" C. indicate that the range of applicability of the square root relation is diminished a t higher temperatures.However, it must be remembered that the difficulties in the way of accurate conductivity measurements in dilute solution are greatly increased when the temperature exceeds 25" C. Since it seems clear that the square root relation is obeyed a t high dilutions within the limits of experimental error, except where there is reason to suspect the absence of complete dissociation, it is possible to apply a further test t o the theory by considering the slope of the con- ductivity-concentration curve. This depends inter alia on '' b," the harmonic mean of the ionic radii, and by combining equations ( I ) and (2) we have for a uni-univalent electrolyte, b = (xo-- X K, D'io D81n w l ) * (3) I t is therefore possible to calculate values for b if A,, x, K,! K,, D and w1 are known.But Debye and Hucke! assume that a t infinite dilution the motion of the ions obeys Stokes' law, and therefore the radius of the ion Y can be calculated from the equation, where 7 is the viscosity of the solvent. If I, is the mobility of the ion a t infinite dilution, equation (4) becomes 8.15 x I O - ~ 1, = 7x5- ' or considering the sum of the mobilities so that from the known values of A, and 7, values of the harmonic mean of the ionic radii can be calculated and compared with the values of b obtained from the slope of the conductivity curve. The results of such calculations for potassium, sodium, and tetraethyl- ammonium iodides in fourteen solvents are given in Table I. Owing to lack of knowledge of the transport numbers in propyl, isobutyl, and isoamyl alcohol, in acetophenone, sulphur dioxide and ammonia, some uncertainty attaches to the values of b in these solvents.The transport number has been assumed to be 0.5 ; if the ions moved with unequal speeds the effect would be to reduce the value of b (Debye), but in isobutyl alcohol for example, even if one ion had three times the mobility of the other, the value of b for sodium iodide would only be reduced from 13.0 to 10.0. In Table I. the solvents are arranged in the order of their dielectric constants, which are given in column I ; column 2 gives their viscositiesTetraethylammonium Iodide. . . . . - . . . . . . . . . . . Potassium Iodide. 81 35 30 26 26 26 22 22 22 21 21 21 19 '9 I 8 16 16 15'5 13.6 12'3 12.3 Sodium Iodide. Solvent. __ b x id Debye 'I. bx 10s Debye I X I O R ;toke.X . 6 X 101 Debye ' X 108 #tokes. 1.19 2'34 2'55 2.92 - - - - 1-84 2.84 2.78 - - - 3'72 445 1.65 2.48 2'42 - - - 6.57 3.69 3'22 6.30 4.67 4.19 3'46 4'22 5'56 4'34 13.0 17.2 24.6 - 6.78 28-6 7-17 4'47 467 - __ - 2'44 3-07 3-08 2-53 3-30 3'27 2'05 2.86 2-84 2-80 3'34 3.64 2.78 4-60 3-70 2-62 2.82 - 2-2 I - Water . . . Acetonitrile . . Methyl alcohol . Ethyl alcohol . Benzonitrile . . Propyl alcohol . Ammonia . . Acetone . . ? 3 3 , > I 3 , 3, . . I , . . Isobutyl alcohol Me&yI ethyyketonc Isoamyl alcohol . Aretophenone . Sulphur dioxide . Pyridine . . 0.00893 0.00545 0~0109 0-0125 0.00256 000316 0.0035 I - 0-0222 - - - 0-0332 - 0.00402 0.0377 0'0 I80 000452 woo958 - - (a) Duperthuis (20°), Dissertation, Lausanne, ( e ) Gyr (~ 15"), Dissertation, Lausanne, 1907.(f) Kohlrausch (IS'), Sifzungsder. Preuss. Akad., (6) Dutoit and Levier ( 2s0), J. Chim. PAYS., 3, (g) Frankin and Kraus (- 33'5O), Am. ChePz.J., (A) Kraus and Bishop (18"), J. Am. Chem. Sor., (i) Morgan and Lammert (2so), 1. Am. Chem. 1908. 435, '905. 6, 545, Igo8. 109A, 351, 1925. 36, I , 1899. (66) Dutoit and Rappeport ( 2 s 0 ) , J . Cham. PAYS.. 23,277,1800 ; 2 4 , 8 3 , 1 9 ~ . (c) Frazer and Hartley (q0), Proc. Roy. Soc., (d) Gagnaux (2s0), Dissertafion, Lausanne, soc.. 46, 1117, 1924. 44, 2204, 1922. 1907. ( k ) Nicollier (2s0), Dissertation, Lausanne. (1) Ottiker (IS"), Dissertation, Lausanne. (m) Philip and Courtman ( z ~ " ) , J. Ckem. Soc. (0) Walden (25'7, Das Leitwermogen der &sun- ( p ) W'alden, Ulich and Busch (z~"), Z.physik. 97, 1268, 1910. gen, 11, 1924. Chern., 123,429, 1926.400 IONIEATION OF SOME TYPICAL STRONG ELECTROLYTES at 25’ or a t the highest temperature for which conductivity data are given. Under the heading of each salt the first column gives the value of A, a t the temperature shown in the reference to the author a t the foot of the table, the second column the value of x in equation (21, the third column the value of b calculated from the slope of the curve, the fourth column the value of b calculated by Stokes’ law. In some cases values are given for the same salt obtained by different observers in order to show the degree of concordance of independent determinations. The results in the table do not show any well-marked regularity, though it is clear that the values of b calculated from Stokes’ law rarely differ from one another by more than a factor of two, while the values from Debye’s equation show much larger variations, and in general show greater divergencies from the Stokes’ values in solvents of low dielcctric constant, although there are apparent exceptions to this in ammonia, methyl ethyl ketone, and for sodium iodide in pyridine.The contrast between the iodides of sodiuni and potassium in this solvent is curious. Likewise the difference between the behaviour of tetraethylammonium iodide and the two alkali metal iodides in aretonitrile. The table cer- tainly einphasises the need for further experimental work to confirm such differences and to make the data more complete. The rough correspondence between the two sets of values for h in all solvents with a dielectric constant greater than 20 is evidence of the essential correctness of Debye and Huckel’s theory. In view of the two methods of calciilation it is perhaps remarkable that they agree so well. The abnormally large values of b found in the higher alcohols, for instance, shows that conformity to the square root relation is no guarantee that the variation of the conductivity with concentration a41 be in accord- ance with Debye’s equation. The same point emerges from Walden, Ulich and Busch’s work in acetone, where in spite of the validity of the square root relation, the slopes of the curves vary to a much greater extent than could be accounted for by Debye’s theory, and indicate probably lack of complete ionization.

ISSN:0014-7672    

DOI:10.1039/TF9272300396

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9272300400

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9272300404

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9272300408

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No.13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions.Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9272300416

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9272300432

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9272300434

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13. R. H. FOWLER 443 NOTE ON THE INTERIONIC ATTRACTION THEORY OF DEBYE AND HUCKEL. BY D. L. CHAPMAN. Received 30th ,‘March, I 9 2 7. Attempts have from time to time been made to explain the divergence of the properties of strong electrolytes from the laws which approximately hold in the case of slightly ionised substances.The latest theory is that of Debye and Hiicke1.l The theory is simple and the assumed postulates few in number. To quote the words of A. A. Noyes who has given an account of the theory.2 ‘(The fundamental idea underlying the treatment of Debye and Hiickel is that owing to the electrical attraction between the positive and negative ions, there are on an average in the neighbourhood of any ion more ions of unlike sign than of like sign ; and that consequently when a solution is diluted, the separation of the ions involves doing internal work against this electrical attraction and a corresponding increase in the energy content of the solution.” I have found a difficulty in understanding that part of the theory which relates to ions of small dimension.To explain this difficulty it will be sufficient only to consider the case of a uni-univalent electrolyte. Debye and Hiickel determine the mean distribution of the ions surrounding a selected ion by the application of the so-called Boltzmann principle and Poisson’s equation. If I) is the mean potential at a point distant, r, from a central positive ion, then by the Boltzmann principle the number of positive and negative ions respectively present in an element of volume, dv, at the point will be ne- k t d ~ and nektdv, where n is the number of ions in unit volume of the solution, E the magnitude of the charge in electrostatic units of an ion, R Boltzmann’s constant, and t the absolute temperature.The density p of the charge at the point is obviously 2 9 PhySik. Z., 1923, 24, I8 j. ”. Amer. Chem. SOC., 1924, 46, 1080.444 INTERIONIC ATTRACTION THEORY 4 alG- n r ( e - h - ex). Substituting this value of p in Poisson’s equation, w e obtain - J2# ~ Y Z + Y a* a r I 4 y 3 D - e5?) . ’ (1) where D is the dielectric constant of the solvent. the exponential terms of the above equation, we obtain If we neglect all terms of higher order than the first in the expansion of - (4 a2# 2 3# 8rrnc2$ -+--=- a+ Y d~ Dkt The authors state in a footnote : “ We have investigated the influence - 6lG- kt and have thereby been For the I t is however difficult to see how the approximation can be justified in To ( 2 ) there is a simple general solution, namely, - of the higher terms in the expansion of ez - e able to show that this influence on the final result is very small.sake of brevity these calculations are omitted from this communication.” the case of very small ions. where C’ is zero since otherwise the potential would be infinity at an infinite distance, and the constant C has the value 5 because (as the authors state) the potential must reduce to that caused by the central ion when the concentration is infinitesimal and k = 0. Therefore for the particular case under consideration the solution becomes D’ From this result the potenti-a1 due to the atmosphere of ions surrounding the selected ion is found by subtracting from the potential due to the whole system that due to the central ion. We thus obtain - K Y -(e - I) DT which becomes when Y is small - E K D ’ and this is the potential due to the atmosphere of ions at the point occupied by the central ion.Then from the theory of potential the work required to 2 K remove all the ions in the solution to infinity is @-- Under the heading DY’ ‘‘ Ionendurchmesser verschwindend ” the authors gave the above result as the solution of the problem. Nevertheless if the ions are point charges they cannot (under the joint operation of the Boltzmann principle and of electrostatic forces only) be distributed in the manner portrayed. For con- sider two ions of opposite sign. The probability that the negative ion willD. L. CHAPMAN 445 be found at a distance between r and Y + dr from the positive ion is qxr2Ceymdr, and therefore the probability that it will be found in a sphere of radius Y having its centre at the positive ion is 4mC o r 2 e m L d ~ .The probability that it will be found in the shell of radii Y and R is ea 5' 62 R e2 r2eymdr. But 5 7 From which it follows that the ions cannot separate after having once united. Furthermore if the ions are not actually dimensionless but very small, the ratio of the probability that the negative ion would be found in the small sphere of radius Y to the probability that it would be found in the shell of radii Y and R would be given by the quotient obtained by changing the limits of the numerator of (5) from o and Y to c and Y where E is a very small distance, and this quotient would be a large quantity provided that R was of moderate dimensions. Therefore the time during which the ions are united would be very large in comparison with the time during which they are dissociated. Such a distribution could not result in potentials given by equation (4) or to the densities of the two classes of ions calculated from these potentials. The inconsistency of the conclusion expressed by equation ( 5 ) with the result of Debye and Huckel can be accounted for by the fact that they made the assumption that d! 9 k t kt A 2 4 . e - e -__ K t

ISSN:0014-7672    

DOI:10.1039/TF9272300443

出版商:RSC    

年代:1927

数据来源: RSC

摘要:

118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure.This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point.These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility.The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order.The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.118 ELECTRICAL THEORY OF ADBORPTTON The writer considers the double layer as consisting of a swface of rigidly fixed atoms under continuous bombardment of positively and negatively charged ions, any particular point on the rigid surface becoming in turn negative, neutral and positive, these conditions arisdg in any order. The observed contact difference is the average effect of these conditions. Where several kinds of atoms are present in the solution the average number of any one of them at the surface will depend on their concentbration, valency and mobility. The variation of contact Werence from negative to neutral and positive was observed with cotton and aluminium sulphate near the neutral point. These variations occurred during the same experiment, the readings being direct measurements of E.1I.F.s developed by filtration under pressure. This point would be covered by putting n2 = 1 and = 2 or 3 in Mukherjee’s equation No. 13.

ISSN:0014-7672    

DOI:10.1039/TF9272300445

出版商:RSC    

年代:1927

数据来源: RSC