TECHNOLOGY FOCUS - BIOLOGY - Preferred Composition: The biomass comprises cellulosic biomass. The fermentation medium further comprises glycol or alcohol. The fermentation medium further comprises one or more 8-22C fatty acids, where the electrolysis converts the fatty acids or their salts to hydrocarbons and hydrogen. The inoculum further comprises supplemental inoculum chosen from Clostridium kluyveri, C.butyricum, C.tyrobutyricum, and Butyrivibrio fibrisolvens, where the mixed culture of microorganisms derived from rumen, sewage sludge, landfills, soil or aquatic environments, gut of insects, and their mixtures. Preferred Method: The fermenting is conducted without the addition of significant amount of methane production inhibitors. The fermenting is conducted for 1-4 days or 2-36 days. The biomass is not subjected to chemical or enzymatic pretreatment prior to the fermenting which pretreatment would be effective to substantially increase the availability of fermentable substrates in the biomass to the microorganisms. The mixed culture of microorganisms derived from the rumen contents are produced by adaptation to anaerobic growth in a biomass containing fermentation medium. The method further involves contacting the medium containing the volatile fatty acids with second inoculum chosen from C.kluyveri, C.butyricum, C.tyrobutyricum, and B.fibrisolvens, where the mixed culture of microorganisms derived from rumen, sewage sludge, landfills, soil or aquatic environments, gut of insects, and their mixtures, and incubating under anaerobic conditions for sufficient time to further increase the production of, or change the molar proportions of, volatile fatty acids in the medium. The method further involves removing one or more of cells of the microorganisms, lignin-containing residues, or carbonates or other non-carboxylate anions from the medium prior to the electrolysis. The cells, lignin-containing residues, or carbonates or other non-carboxylate anions are removed by filtration, flocculation, settling, centrifugation, precipitation or their combinations. The volatile fatty acids in the medium are subjected to the electrolysis without extraction. The electrolysis is conducted in an aqueous medium. The electrolysis is conducted in the absence of significant amount of non-aqueous solvents for the volatile fatty acids. The electrolysis is conducted using carbon or graphite anode electrodes and cathode electrodes. The conditions of the electrolysis comprise an anode current density above 1 mA/cm2. The conditions of the electrolysis comprise potential of 2 or 3 volts DC or higher. The volatile fatty acids or their salts are further separated into individual volatile fatty acids or their salts prior to electrolysis. The method further involves extracting or separating the volatile fatty acids or their salts from the medium prior to the electrolysis and then concentrating the volatile fatty acids or their salts prior to the electrolysis. The electrolysis further produces carbon dioxide. The method further involves collecting the hydrocarbons, hydrogen, and carbon dioxide from the electrolysis in gaseous phase, compressing the gaseous hydrocarbons, hydrogen, and carbon dioxide in high pressure tanks, and separating the gaseous hydrocarbons, hydrogen, and carbon dioxide by gas liquefaction. The method further involves adding one or more 8-22C fatty acids or their salts to the medium prior to the electrolysis. The anode is separated from the cathode by a semipermeable membrane effective to substantially prevent the passage of non-carboxylate anions larger than carboxylate anions of the volatile fatty acids, lignins, cells, and proteins. The method further involves removing the volatile fatty acids from the fermentation medium during the fermenting. The volatile fatty acids are removed by capacitive deionization or flow through capacitor. The volatile fatty acids are removed by capacitive deionization by positioning an anode and cathode electrode within the fermentation medium and applying first voltage which is effective to adsorb and concentrate carboxylate anions of the volatile fatty acids at the anode but which first voltage is below the water oxidation voltage. Preferred Components: The biomass is chosen from plants, plant portion, plant materials, agricultural crops, forages, grasses, aquatic plants, bagasse, corn stover, corn cobs, dried distillers grains, hay, flax straw, oat hulls, wood, sawdust, paper products, paper processing wastes, cardboard, yard or landscape waste, animal wastes, animal processing wastes, animal carcasses, and spent sausage casings.    TECHNOLOGY FOCUS - ORGANIC CHEMISTRY - Preferred Composition: The volatile fatty acids comprise 2-6C linear or branched chain fatty acids or their salts. The volatile fatty acids comprise acetic acid, propionic acid, butyric acid, isobutyric acid, 2-methyl butyric acid, valeric acid, isovaleric acid, caproic acid or their salts. The hydrocarbons comprise alkanes, alkenes, dienes, trienes or their mixture. The hydrocarbons comprise methane, ethane, propane, butane, pentane, hexane, heptane, octane, ethylene, propylene, butene, pentene, or isomers, or their mixtures. EXAMPLE - No suitable example given.