Electrolytic synthesis of organic compounds from gaseous reactant

Discloses electro-organic synthesis of fluorocarbons, and organic sulfur compounds.

DESCRIPTION OF THE INVENTION 
Electrolytic synthesis of organic compounds in an electrolytic cell has 
generally proven to be industrially unsatisfactory. This is because of the 
necessity of providing a current carrier, i.e., an ionizable molecule, to 
carry charge between the anode and the cathode. The organic reactants and 
products themselves generally will not perform this function because of 
their lack of ionic character. 
One attempt at eliminating the requirement for a dissolved, ionized, or 
liquid current carrying supporting electrolyte is disclosed in U.S. Pat. 
No. 3,427,234 to Guthke et al. and Japanese Patent 56/23290 to Yoshizawa 
et al., both of which describe the use of a solid polymer electrolyte 
electrolytic cell to carry out the electrolytic synthesis of organic 
compounds. In a solid polymer electrolytic cell the anode is in contact 
with one surface of the solid polymer electrolyte, and the cathode is in 
contact with the other surface of the solid polymer electrolyte. The solid 
polymer electrolyte itself is a polymeric material having pendant ionic 
groups which enhance the ionic conductivity of the underlying polymer 
matrix. Thus, negatively charged particles may flow from the cathode 
through the solid polymer electrolyte to the anode, without ever 
contacting the organic media or positively charged particles may travel 
from the anode through the solid polymer electrolyte to the cathode, 
likewise without ever contacting the organic media. In the solid polymer 
electrolyte as described in Guthke et al. and Yoshizawa et al., the 
cathodic reaction takes place at an electrode-liquid organic reactant 
interface, a surface of the cathode being in contact with the solid 
polymer electrolyte. The anodic reaction takes place at an 
electrode-liquid organic reactant interface, a surface of the anode being 
in contact with the solid polymer electrolyte. Charged particles traverse 
the solid polymer electrolyte as described hereinabove. 
However, the provision of a solid polymer electrolyte in contact with both 
the anode and the cathode, does not, alone, provide an industrially useful 
electrolytic cell for electroorganic synthesis. For example, the typical 
prior art permionic membrane materials, such as DuPont NAFION.RTM. 
described, for example, in U.S. Pat. Nos. 3,041,317 to Gibbs, 3,718,617 to 
Grot, and 3,849,243 to Grot, the Asahi Glass Company, Ltd. permionic 
membrane described, e.g., in U.S. Pat. Nos. 4,065,366 to Oda et al., 
4,116,888 to Ukihashi et al., and 4,126,588 to Ukihashi et al., and the 
Asahi Chemical Company permionic membrane materials, described in U.S. 
Pat. No. 4,151,053 to Seko et al., require water of hydration. The 
combination of water of hydration and immobilized ionic sites, bonded to 
the polymer, provide ionic conductivity through the permionic membrane. In 
the absence of water of hydration, the electrical resistivity of the 
permionic membrane and more particularly, the resistance to ionic 
transport of the permionic membrane, is objectionably higher. As organic 
media are typically non-aqueous, the aforementioned permionic membranes 
when employed in such organic media are unable to attain or maintain an 
equilibrium content of water of hydration. Similarly, where the reaction 
medium is an anhydrous gas phase medium, the reactants and products also 
being anhydrous gases, the aforementioned permionic membrane materials are 
incapable of maintaining an equilibrium water of hydration content. 
Therefore, means must be provided within the permionic membrane to provide 
continuing ionic mobility in the presence of anhydrous reactants and 
products, including gaseous organic reactants and products. As herein 
described, ionic mobility may be provided by providing ionic means within 
the solid polymer electrolyte structure itself. Exemplary ionic means 
within the solid electrolyte structure include, e.g., entrapped but mobile 
ionic means as a strong electrolyte, the presence of an aqueous 
electrolyte in a solid polymer electrolyte structure having hydrophobic 
boundaries whereby to maintain the aqueous electrolyte therein, or the 
presence of polar, ionic organic moieties within the permionic membrane or 
solid electrolyte with means either for preventing their escaping 
therefrom or for retaining them therein. 
Moreover, when such means are provided within the solid electrolyte, e.g., 
the solid polymer electrolyte, electroorganic or other non-aqueous 
reactions may be carried out in either a divided cell, i.e., a cell where 
the solid electrolyte, solid polymer electrolyte, or permionic membrane 
divides the cell into anolyte and catholyte compartments, or in 
electrolytic cells where the reaction medium, i.e., the reactants, 
products, and any other materials are present in one unitary medium, 
containing both the anode and the cathode. Thus, it is further herein 
contemplated to utilize a solid electrolyte, which may be a solid polymer 
electrolyte, in an electrolytic cell where the anode and cathode are in 
contact with essentially the same reaction medium, the external surfaces 
of the anode and cathode being in contact with the reaction medium, and 
other surfaces, e.g., the internal surfaces of the anode and cathode, 
being in contact with a solid electrolyte as a solid polymer electrolyte, 
or permionic membrane, or inorganic solid electrolyte as described in the 
commonly assigned copending application of N. R. DeLue and S. R. Pickens 
for Electro Organic Method And Apparatus For Carrying Out Same, Ser. No. 
478,928. In this way, the reactions principally occur at a site on the 
cathode or anode which is not embedded in the solid electrolyte. That is 
the reactions principally occur at the external surfaces of the respective 
electrodes, i.e., at the interfaces of the respective electrodes with the 
reaction medium, while ionic transport is through the solid electrolyte. 
The contemplated structure may be used with either liquid or gaseous 
reactants and products. 
The solid electrolyte itself may be an inorganic material as a crystalline 
inorganic material, a solid polymer electrolyte, or a solid polymer 
electrolyte or inorganic material comprised of multiple zones having a 
highly ionizable current carrier therein. 
The electrodes may be removably in contact with the external surfaces of 
the solid electrolyte, bonded to external surfaces of the solid 
electrolyte, or bonded to and embedded in the solid electrolyte, the 
catalyst may independently be covalently bonded to reactive ligands which 
ligands are in contact with, bonded to, or reactive with the solid polymer 
electrolyte. 
As herein contemplated the supporting electrolyte and polar solvents 
normally required in the prior art may be substantially reduced or even 
eliminated. This results in a product of higher purity, greater ease of 
separation, and fewer side reactions, and constant potential. Moreover, 
the invention herein contemplated permits greater choice in the selection 
of the organic solvent, without regard to the presence or absence of a 
supporting electrolyte.

DETAILED DESCRIPTION OF THE INVENTION 
The invention herein contemplated resides in a method of electrolytically 
synthesizing organic compounds, and in solid electrolytes useful in the 
synthesis of organic compounds. More particularly, the invention relates 
to solid electrolyte electrolytic methods for the essentially anhydrous 
electrolytic synthesis of compounds, especially organic compounds. 
According to one exemplification of the invention herein contemplated gas 
phase organic reactions may be carried out. Gas phase organic electrolytic 
reactions present special problems because of the absence of water of 
hydration, polarizable liquids, or ionic liquids. Thus, as herein 
contemplated, gas phase organic reactions may be carried out by reacting 
an organic reactant at an electrode of an anode-cathode electrode pair to 
form an organic product. The method herein contemplated comprises 
contacting one member of the electrode pair, i.e., the anode-cathode pair 
with the organic gaseous reactant while externally imposing an electrical 
potential across the electrode pair, the reactant and the organic product 
being gaseous, and both electrodes of the electrode pair being in contact 
with solid electrolyte means therebetween, e.g., as shown in FIGS. 1 
through 3, inclusive. 
More particularly, in distinction to fuel cell reactions, the contemplated 
reactions provide useful chemical products other than water or oxides of 
carbon. Moreover, the reactions contemplated herein require energy to be 
supplied to the system whereby to form the product, as by externally 
imposing an electrical potential across the anode and cathode. 
An electrolytic cell structure for carrying out the method of this 
invention is shown in FIGS. 1, 2 and 3. As there shown, an electrolytic 
cell (1) has a structure of an anode (3), a solid electrolyte (5) in 
contact with the anode, a second solid electrolyte (9) in contact with the 
cathode (11), and a seal (7) between the two solid electrolyte portions 
(5) and (9). The structure of the anode side solid electrolyte portions 
(5), the cathode side of the solid electrolyte portion (9), and seal (7), 
contain a highly ionizable material whereby to provide ion transport 
between the anode and cathode. Also shown in FIGS. 1 and 2 is an anode 
contact (23), cathode contact (25), and a unitary reaction medium (31) of 
reagent and reactant which may be in contact with both the anode and 
cathode, or, the anode and cathode may be separated from each other by the 
solid electrolyte structure of solid electrolyte (5), seal (7), and solid 
electrolyte (9), with separate anolyte liquors and catholyte liquors. The 
ionizable current carrier (41) is between the two portions (5) and (9) of 
the solid electrolyte, the anode (3), and the cathode (11). 
While the anode-solid electrolyte-cathode is shown in the figures as an 
assembly of planar elements, it may also be an assembly that is of an open 
construction, i.e., to allow the organic medium to flow through the 
anode-solid electrolyte-cathode structure. 
In a further exemplification of the method of this invention, which may 
utilize the above-described structure, a gaseous phase reaction may be 
carried out at either the anode or the cathode or both, by contacting the 
appropriate electrode or electrodes with the gas phase reactant or 
reactants in forming gas phase product or products. By a gas phase 
reactant or product is meant a reactant or product that is gaseous at the 
temperature and pressures within the electrolytic cell. 
According to a preferred exemplification of the method of this invention 
there is provided a method of producing a liquid or gaseous organic 
fluorocarbon compound at an anode of an anode-cathode pair by contacting 
the anode with an alkyl halide and hydrogen fluoride and externally 
imposing an electrical potential across the anode-cathode pair. It is 
contemplated herein that the anode and cathode are both in contact with 
the above-described solid electrolyte means and the hydrogen fluoride is a 
gas, e.g., an anhydrous gas. 
According to a further exemplification of the method of this invention, 
organic sulfur compounds, e.g., chosen from the group consisting of 
sulfides, sulfoxides, and sulfonyls, may be electrolytically prepared in 
an electrolytic cell having an anode, a cathode, and the afore-described 
solid electrolyte means therebetween and in contact therewith. As herein 
contemplated, the organic sulfur compounds are formed by contacting either 
the cathode or the anode with a gaseous sulfur compound, e.g., H.sub.2 S, 
SO.sub.2, SO.sub.3, SOCl.sub.2, SO.sub.2 Cl, or the like, and a gaseous or 
liquid organic compound. Exemplary organic compounds include olefins, 
e.g., C.sub.2 and C.sub.8 olefins, primary alcohols, e.g., C.sub.1 to 
C.sub.6 primary alcohols, secondary alcohols, e.g., C.sub.3 to C.sub.6 
secondary alcohols, and tertiary alcohols, e.g., C.sub.4 to C.sub.8 
tertiary alcohols. Additionally, organic halides, for example, primary and 
secondary alkyl and aryl chlorides, bromides and iodides may be reacted 
according to the method herein contemplated to form the organic sulfur 
compounds. Especially preferred organic reactants are C.sub.2 to C.sub.6 
olefins, C.sub.1 to C.sub.4 primary alcohols, C.sub.3 to C.sub.6 secondary 
alcohols, C.sub.4 to C.sub.8 tertiary alcohols, and alkyl or aryl bromides 
and iodides having from 1 to 8 carbon atoms. 
As described in U.S. Pat. No. 4,445,985, the gas phase reactions may be 
carried out at a lower voltage and higher efficiency by providing packing 
means in contact with one of the anode and cathode, and feeding the 
gaseous organic reactant to the electrolytic cell at a velocity high 
enough to induce turbulence therein while externally imposing an 
electrical potential across the anode and cathode. 
The solid electrolyte contains means for transporting ions therethrough. 
This is especially significant in processes involving non-aqueous media, 
such as organic media, where by nonaqueous is meant that the behavior of 
the media of reactant and/or product is substantially that of 
non-ionizable organic material, incapable of carrying charge at 
industrially feasible voltages. That is, the reactant and product medium 
functions as an insulator or dielectric rather than as a conductor. By 
non-aqueous media is meant substantially or essentially anhydrous media. 
The non-aqueous medium is not necessarily electrolyzed. It may simply 
serve as a solvent or diluent for the product or reactant. In the method 
herein contemplated, utilizing the structure above-described, the reagent 
is electrolyzed at an electrode means, where the anode is in contact with 
one surface of the solid electrolyte means and the cathode is in contact 
with the opposite surface of the solid electrolyte means. As herein 
contemplated, the non-aqueous medium containing an organic reactant is 
provided in contact with one or both of the anode and cathode and an 
electrical potential is externally imposed across the anode and cathode so 
as to evolve product at an anode or a cathode or both and transport ionic 
species across the solid electrolyte means. 
The structure of anode (3) solid electrolyte means (5), (7), (9), cathode 
(11) may divide the electroytic cell into separate anolyte and catholyte 
compartments. When the cell is so divided, the anode is in contact with 
anode compartment reactant and product, and the cathode is in contact with 
cathode compartment reactant and product, the anode compartment medium and 
cathode compartment medium being capable of supporting different 
chemistries and conditions. Alternatively, the anode (3), solid 
electrolyte means (5), (7), (9), and cathode (11) may be in contact with 
the same non-aqueous medium, e.g., the structure may be porous or immersed 
in a single medium. As, for example, shown in FIGS. 1 and 2, the solid 
electrolyte means (5), (7), (9), provides electrical conductivity between 
the anode (3) and cathode (11), and the liquid (31) contains the reaction 
medium. 
The solid electrolyte means (5), (7), (9), may include a hollow or 
laminated permionic membrane structure having an ionizable aqueous or 
non-aqueous liquid (41) therebetween. Thus, the solid electrolyte means 
may comprise two sheets (5), and (7) of ion-exchange resin material having 
a zone, volume, or layer (41) of ionic aqueous material therebetween. 
Additionally, one or both of the sheets (5), (9) of the ion-exchange resin 
material may have a hydrophobic layer, not shown, thereon, whereby to 
retain the ionic aqueous material within the structure of the permionic 
membrane sheets and ionizable current carrier compartment (41). 
Alternatively, the solid electrolyte means (5), (7), (9), may be a single 
sheet of permionic membrane material, containing a highly ionizable 
aqueous material therein, and having hydrophobic layers on the external 
surfaces thereof whereby to retain the ionic aqueous material within the 
solid electrolyte means. 
Alternatively, the current carrier medium (41), may contain an oxidation 
and reduction resistant polarizable compound capable of solvating ions. 
Exemplary materials include glycols, glycol ethers, ammonium salts, crown 
ethers, alcohols, nitro compounds, carboxylic acids, esters, sulfoxides, 
and the like. 
The permionic membrane interposed between the anode and the cathode may be 
formed of a polymeric fluorocarbon copolymer having immobile, cation 
selective ion exchange groups on a halocarbon backbone. The membrane may 
be from about 2 to about 25 mils thick, although thicker or thinner 
permionic membranes may be utilized. The permionic membrane may be a 
laminate of two or more membrane sheets. It may, additionally, have an 
internal reinforcing structure. 
The functional group of the permionic membrane, A, may be a cation 
selective group. It may be a sulfonic group, a phosphoric group, a 
phosphoric group, a carboxylic group, or a reaction product thereof, e.g., 
an ester thereof. Thus, as herein contemplated, A in the structural 
formulas shown below is chosen from the group consisting of: 
--COOH, 
--COOR.sub.1, 
--COOM, 
--COF, 
--COCl, 
--CN, 
--CONR.sub.2 R.sub.3 
--SO.sub.3 H, 
--SO.sub.3 M, 
--SO.sub.2 F, 
--SO.sub.2 Cl, and 
--SO.sub.2 NH.sub.2, 
where R.sub.1 is a C.sub.1 to C.sub.10 alkyl group, R.sub.2 and R.sub.3 are 
hydrogen or C.sub.1 to C.sub.10 alkyl groups, and M is an alkali metal or 
a quaternary ammonium group. According to a preferred exemplification, A 
is: 
--COCl, 
--COOH, 
--COOR.sub.1, 
--SO.sub.2 F, 
--SO.sub.2 Cl, or 
--SO.sub.2 NH.sub.2, 
where R.sub.1 is a C.sub.1 to C.sub.5 alkyl. 
As herein contemplated, when a perfluorinated, cation selective permionic 
membrane is used, it is preferably a copolymer which may have: 
(I) flurovinyl ether acid moieties derived from 
EQU CF.sub.2 .dbd.CF--O--[(CF.sub.2).sub.b (CX'X").sub.c (CFX').sub.d (CF.sub.2 
--O--CX'X").sub.e (CX'X"--O--CF.sub.2).sub.f ]--A, 
where b, c, d, e, and f are integers from 0 to 6, exemplified by 
##STR1## 
(II) fluorovinyl moieities derived from 
EQU CF.sub.2 .dbd.CF--(O).sub.a --(CFX').sub.d --A, 
where a and d are integers from 0 to 6, exemplified by 
EQU CF.sub.2 .dbd.CF(CF.sub.2).sub.2-4 COOCH.sub.3, 
EQU CF.sub.2 .dbd.CF(CF.sub.2).sub.2-4 COOC.sub.2 H.sub.5, 
EQU CF.sub.2 .dbd.CF(CF.sub.2).sub.2-4 COOH, 
EQU CF.sub.2 .dbd.CFO(CF).sub.2-4 COOCH.sub.3, 
EQU CF.sub.2 .dbd.CFO(CF.sub.2).sub.2-4 COOC.sub.2 H.sub.5, and 
EQU CF.sub.2 .dbd.CFO(CF.sub.2).sub.2-4 COOH, inter alia; 
(III) fluorinated olefin moieties derived from 
EQU CF.sub.2 .dbd.CXX' 
as exemplified by tetrafluoroethylene, dichlorodifluoroethylene, 
chlorotrifluoroethylene, hexafluoropropylene, trifluoroethylene, 
vinylidene fluoride, and the like; and 
(IV) vinyl ethers derived from 
EQU CF.sub.2 .dbd.CFOR.sub.4 
where R is a perfluoroalkyl group having from 1 to 6 carbon atoms. 
The cation selective membrane need not be perfluorinated. Cation selective 
membranes may be made from resins prepared, for example, by the 
copolymerization of styrene, divinylbenzene and an unsaturated acid, 
ester, or anhydride, such as acrylic acid, methacrylic acid, methyl 
methacrylate, methyl acrylate, maleic anhydride, or the like. Other resins 
useful in forming cation selective membranes may be prepared, for example, 
from polymers or copolymers of unsaturated acids or their precursors, such 
as unsaturated acids or nitriles, or by the introduction of acid 
functional groups into cross-linked, non-perfluorinated polymers such as 
polyolefins, polyethers, polyamides, polyesters, polycabonates, 
polyurethanes, polyethers, or poly(phenol formaldehydes) by means of 
reaction with a sulfonating, carboxylating, or phosphorylating reagent. 
Alternatively, the ion exchange group A may be an anion selective group, 
such as a quaternary ammonium group, a secondary amine group, or a 
tertiary amine group. Exemplary anion selective permionic membranes 
include ammonium derivatives of styrene and styrene-divinyl benzene 
polymers, amine derivatives of styrene and styrene-divinyl benzene, 
condensation polymers of alkyl oxides, e.g, ethylene oxide or 
epichlorohydrin with amines or ammonia, ammoniated condensation products 
of phenol and formaldehyde, the ammono products of acrylic and methacrylic 
esters, iminodiacetate derivatives of styrene and styrene-divinylbenzene. 
A useful permionic membrane herein contemplated has an ion exchange 
capacity of from about 0.5 to about 2.0 milliequivalents per gram of dry 
polymer, preferably from about 0.9 to about 1.8 milliequivalents per gram 
of dry polymer, and in a particularly preferred exemplification, from 
about 1.0 to about 1.6 milliequivalents per gram of dry polymer. A useful 
perfluorinated permionic membrane herein contemplated may have, in the 
ester form, a volumetric flow rate of 100 cubic millimeters per second at 
a temperature of 150 to 300 degrees Centigrade, and preferably at a 
temperature between 160 to 250 degrees Centigrade. The glass transition 
temperatures of such permionic membrane polymers are desirably below 
70.degree. C., and preferably below about 50.degree. C. 
The permionic membrane herein contemplated may be prepared by the methods 
described in U.S. Pat. No. 4,126,588, the disclosure of which is 
incorporated herein by reference. 
Most commonly the ion exchange resins will be in a thermoplastic form, 
i.e., a carboxylic acid ester, e.g., a carboxylic acid ester of methyl, 
ethyl, propyl, isopropyl, or butyl alcohol, or a sulfonyl halide, e.g., 
sulfonyl chloride or sulfonyl fluoride, during fabrication, and can 
thereafter be hydrolyzed. 
When the solid electrolyte is a solid polymer electrolyte composed of a 
hydrated polymeric gel, as described above, it is essential to provide or 
retain water of hydration therein as described in the commonly assigned 
copending application of M. Korach, referred to hereinabove. This may be 
accomplished by adding moisture, i.e., water vapor, to the gaseous 
reactant. In this way the polymeric ion exchange resin membrane is 
maintained hydrated. 
According to an alternative exemplification, the permionic membrane useful 
in carrying out this invention may have a porous, gas and liquid 
permeable, non-electrode layer bonded to either the anodic surface, or the 
cathodic surface, or both the anodic and cathodic surfaces thereof, as 
described in British Laid Open Patent Application No. 2,064,586 of Oda et 
al. As described by Oda et al., the porous, non-catalytic, gas and 
electrolyte permeable, non-electrode layer does not have a catalytic 
action for the electrode reaction, and does not act as an electrode. 
The porous, non-electrode layer is formed of either a hydrophobic or a 
non-hydrophobic material, either organic or inorganic. As disclosed by Oda 
et al., the non-electrode material may be electrically non-conductive. 
That is, it may have an electrical resistivity above 0.1 ohm-centimeter, 
or even above 1 ohm-centimeter. Alternatively, the porous, non-electrode 
layer may be formed of an electrically conductive material having a higher 
overvoltage than the electrode material placed outside the porous, 
non-electrode layer, i.e., the porous, non-electrode layer may be formed 
of an electrically conductive material that is less electrocatalytic than 
the electrode material placed outside the porous, non-electrode layer. 
The material in the porous, non-electrode layer is preferably a metal, 
metal oxide, metal hydroxide, metal nitride, metal carbide, or metal 
boride of a Group IVA metal, e.g., Si, Ge, Sn, or Pb, a Group IVB metal, 
e.g., Ti, Zr, or Hf, a Group V-B metal, e.g., V, Nb, or Ta, a Group VIB 
metal, e.g., Cr, Mo, or W, or a Group VIII "Iron Triad" metal, Fe, Co, or 
Ni. Especially preferred non-electrode materials are Fe, Ti, Ni, Zr, Ta, 
V, and Sn, and the oxides, hydroxides, borides, carbides, and nitrides 
thereof, as well as mixtures thereof. Such material may have hydrophobic 
coatings thereon. For example, such materials may have hydrophobic 
coatings on at least a portion thereof whereby to exhibit hydrophobic and 
non-hydrophobic zones. 
Alternatively, the film, coating, or layer may be formed of a 
perfluorocarbon polymer as such or rendered suitably hydrophilic, i.e., by 
the addition of a mineral, as potassium titanate. 
The non-electrode material is present in the porous film, coating, or layer 
as a particulate. The particles have a size range of from about 0.01 
micron to about 300 microns, and preferably of from about 0.1 to 100 
microns. The loading of particles is from about 0.01 to about 30 
milligrams per square centimeter, and preferably from about 0.1 to about 
15 milligrams per square centimeter. 
The porous film, coating or layer has a porosity of from about 10 percent 
to 99 percent, preferably from about 25 to 95 percent, and in a 
particularly preferred exemplification from about 40 to 90 percent. 
The porous film, coating or layer is from about 0.01 to about 200 microns 
thick, preferably from about 0.1 to about 100 microns thick, and in a 
particularly preferred embodiment, from about 1 to 50 microns thick. 
When the particles are not directly bonded to and embedded in the permionic 
membrane a binder is used to provide adhesion. The binder may be a 
fluorocarbon polymer, preferably a perfluorocarbon polymer, as 
polytetrafluoroethylene, polyhexafluoropropylene, or a perfluoroalkoxy, or 
a copolymer thereof with an olefinically unsaturated perfluorinated acid, 
e.g., having sulfonic or carboxylic functionality. 
In an electrolytic cell environment where perfluorinated polymers are not 
required, the binder may be a hydrocarbon polymer such as a polymer or 
copolymer of ethylene, propylene, butylene, butadiene, styrene, 
divinylbenzene, acrylonitrile, or the like. Other polymeric materials such 
as polyethers, polyesters, polyamides, polyurethanes, polycarbonates, and 
the like may be employed. Such polymeric binding agents may also have 
acidic or basic functionality. 
The electrodes (3), (11), bear upon the porous, non-electrode surface. 
Alternatively, as described in the commonly assigned, copending application 
of J. D. Mansell for Electro Organic Method And Apparatus For Carrying Out 
Same, Ser. No. 478,929, the solid electrolyte may be provided by a 
polymeric matrix having crown ethers grafted thereto and metal ions 
chelated to the crown ethers. Thus, the permionic membrane may be a 
polymeric matrix having a low degree of cross-linking and a glass 
transition temperature at least about 20 degrees Centigrade below the 
intended temperature of the electrolyte and/or the reaction medium. 
Exemplary are polyolefins, polyethers, polyesters, polyamides, 
polyurethanes, polyphenol formaldehydes, and other polymers stable to cell 
conditions. The crown ether bonded thereto is chosen from the group 
consisting of cyclic polymers of ethylene oxide having from 4 to 6 
(CH.sub.2 CH.sub.2 O) units, e.g., 12-crown-4, 15-crown-5, 18-crown-6, and 
dicyclohexano and dibenzo derivatives thereof. 
Exemplary chelated metals are alkali metals such as sodium potassium, and 
lithium. 
Especially desirable results are obtained where the crown ether is about 1 
to about 50 weight percent of the permionic membrane, basis weight of 
polymeric matrix and crown ether. Thus, as herein contemplated, 
electrolysis may be carried out in an electrolytic cell having an anode, 
cathode, and a permionic membrane therebetween, by externally imposing an 
electrical potential across the electrolytic cell whereby to cause an 
ionic current to flow from the anode through the permionic membrane to the 
cathode, the permionic membrane being an anion selective permionic 
membrane comprising the above-described polymeric matrix having crown 
ethers grafted thereto. 
In a still further exemplification of this invention, there is provided an 
electrolytic cell having an anode, a cathode, and a solid electrolyte 
therebetween where the anode contacts one surface of the solid electrolyte 
and the cathode contacts the opposite surface of the solid electrolyte, 
the solid electrolyte contains a major portion of a fast ionic conductor 
inorganic crystalline material. Where a fast ionic conductor inorganic 
crystalline material is used, there is no necessity of introducing 
ionizable species into the solid electrolyte. Exemplary fast ionic 
conductor materials are crystalline materials such as beta alumina, uranyl 
hydrogen phosphate tetrahydrate, and polyoxymetallates such as 
polytungstic acid and polymolybdic acid. Fast proton transport crystalline 
materials are frequently hexagonal, close-packed structure where the 
interplanar spacing is such as to allow the movement of protons, i.e., 
bare protons without water of hydration, through the crystal. 
Alternatively, body centered cubic materials may be utilized. 
Various electrode structures may be utilized herein. For example, the 
electrode may be adhered to the solid electrolyte, as a film, coating, or 
layer thereon, either with or without hydrophilic or hydrophobic 
additives. Alternatively, the electrodes may be on separate catalyst 
carriers which removably bear on the solid electrolyte. Suitable 
electrocatalyst materials depend upon the particular reaction to be 
catalyzed, and may typically include transition metals, oxides of 
transition metals, semi-conductors, and oxygen deficient crystalline 
materials. Alternatively, such materials as transition metals having "d" 
subshell or orbital activity may be utilized, e.g., iron, cobalt, nickel, 
and the platinum group metals. 
According to a still further exemplification of this invention, the 
electrode, i.e., the electrocatalyst in contact with the ion selective 
solid electrolyte may be chemically bonded thereto, e.g., by polydentate 
ligands. Thus, the solid electrolyte may have ion selective groups, e.g., 
cation or anion selective groups as well as having, e.g., carboxyl 
linkages to transition metal ions. 
Various reactions may be carried out according to the method of this 
invention. For example, organic compounds may be reduced at the cathode or 
oxidized at the anode.