Transference Numbers in Molten Salta

Sundheim, Benson R.

doi:10.1021/j150544a012

Cited by 44 publications

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“…In the case of aqueous solutions, the ever-plentiful solvent could absorb this L equivalent of MX and register the transfer as a concentration change Hence, the transfer leads to a mass increase near the anode, as was first suggested by Schwartz (1912) and proved mathematically by Sundheim (1956).…”

Section: 47a Some Ideas About Transport Numbers In Fused Saltsmentioning

confidence: 81%

Ionic Liquids

Bockris¹,

Reddy²

1970

Modern Electrochemistry

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Section: 47a Some Ideas About Transport Numbers In Fused Saltsmentioning

confidence: 81%

Ionic Liquids

Bockris¹,

Reddy²

1970

Modern Electrochemistry

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“…On the other hand, the two simulated values for Δ + and A~ in molten Agl are almost negative and especially those for Δ" are quite large, as seen in Fig. Once an iodine ion moves toward the cathode, the neighboring iodine ions on the side of the cathode could be collectively moved in the direction 8 10 of the cathode by a large repulsion, as if the collective ions moved like a caterpillar, which mechanism has already been proposed by Yokota /14/ in order to explain the transport properties of superionic conductors. The question is why A~s are so large in their negative signs.…”

Section: σ~ D~'mentioning

confidence: 94%

Transport Properties in Molten Salts

Tamaki¹,

Kondo²,

Arai³

1999

High Temperature Materials and Processes

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The partial conductivities in molten salts have been analyzed using a phenomenological theory and it was found that their ratio was expressed in terms of the inverse mass ratio of the constituents. This is confirmed by computer simulation for molten NaCl and Agl, when using proper pairwise potentials and the nonequilibrium molecular dynamics method.The diffusion constants for positive and negative ions in molten NaCl and Agl are also simulated. By using both results for the partial conductivities and the diffusion constants, it is found that the deviation from the Nernst-Einstein relation Δ is not unique but Δ + * Δ-Α new method has also been presented for experimentally deriving the diffusion constants D + and D~ in molten salts. Actual application has been carried out for molten Agl and the results are comparable to those obtained by computer simulation It is suggested that the AC measurement is useful for obtaining both Δ + and Δ".

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“…If, on the other hand, interactions of importance occurred only between ions of opposite charge, the interaction forces would cancel, and the controlling factor should be the momentum balance which depends on the masses of the ions. Sundheim (6) has shown that the mass dependence under these special conditions would be: mt+-, where the m's are the equivalent re+q-m_ weights of the ions. This transport number is of little significance because, in the general case, one would expect the two ions to impart momentum to the membrane, due to unequal interactions with the membrane.…”

Section: Table I Transport Numbers and Equivalent Conductances Of Thmentioning

confidence: 99%

Transport Numbers of the Pure Fused Salts, LiNO[sub 3],NaNO[sub 3],KNO[sub 3],and AgNO[sub 3]

Duke

Owens

1958

J. Electrochem. Soc.

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Fig. 2. Section perpendicular to the surface of a silver electrode from which silver was dissolved anodically. Magnification 500X. by x -r a y fluorescence; a n d chemical analysis showed that the slime was s u b s t a n t i a l l y all silver.F i g u r e 1 shows a p h o t o m i c r o g r a p h of some of the slime particles. U n d e r the microscope they a p p e a r e d s h i n y a n d looked metallic. F i g u r e 2 shows a section p e r p e n d i c u l a r to the edge of a s p e c i m e n from which some silver had been dissolved. The surface is v e r y rough, and contains several p r o m o n t o r i e s which look as t h o u g h t h e y were a b o u t to be cut off b y the dissolution process.It is concluded t h a t the anode slime on silver consists of metallic silver; p r e s u m a b l y the anode slime on other m e t a l s also consists of particles of the electrode metal. It seems likely t h a t the m e c h a n i s m of slime f o r m a t i o n is as follows. O r d i n a r y solutions c o n t a i n m a n y impurities, some of which adsorb on m e t a l surfaces and cause "passivation." It is typical of silver p a r t i c u l a r l y t h a t electrodeposition from simple salt solutions results in the g r o w t h of only a few crystals, most of the surface of the electrode r e m a i n i n g inactive. It seems p r o b a b l e t h a t in dissolution a s i m i l a r p a s s i v a t i o n occurs, a n d t h a t dissolution occurs o n l y at isolated points. A p p a r e n t l y some sections of the m e t a l surface r e m a i n passive a n d are cut off by dissolution from the sides, f o r ming the silver particles w h i c h c o n s t i t u t e the anode slime.The e x p e r i m e n t a l w o r k described in this note was p e r f o r m e d by W. R. Young, to w h o m the a u t h o r is v e r y grateful. ManuscriptThe alkali nitrates through potassium and silver nitrate were chosen for transport experiments as a series of salts similar in conductivity and charge type; the sizes and masses of the cations, however, are widely variant. Thus the series appears to be one in which the effects on mobility of size and mass of ions may be tested. ExperimentalThe t r a n s p o r t e x p e r i m e n t s were done in a cell which has b e e n described p r e v i o u s l y (1). In all cases the electrodes w e r e of solid Ag s u r r o u n d e d b y m o l t e n AgNO3. W h e n s t u d y i n g salts other t h a n AgNO~, cells were used which c o n t a i n e d a c a p i l l a r y constriction b e t w e e n the alkali n i t r a t e which filled the u p p e r portion of the cell and the AgNO~ at the b o t t o m in contact w i t h the silver. The m i x i n g t h a t did occur took place in the c a p i l l a r y and is not i mp o r t a n t because it has b e e n s h o w n t h a t t h e r e is v e r y little v o l u m e change w h e n these salts are m i x e d with AgNO,. C u r r e n t s of about 50 m a for 1000 to 5000 sec w e r e used w h e n v o l u m e changes in the c a p i l l a r y w e r e observed and several r e a d i n g s w e r ...

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Transference Numbers in Molten Salta

Cited by 44 publications

References 0 publications

Ionic Liquids

Ionic Liquids

Transport Properties in Molten Salts

Transport Numbers of the Pure Fused Salts, LiNO[sub 3],NaNO[sub 3],KNO[sub 3],and AgNO[sub 3]

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