A method and apparatus are disclosed for a large scale, electrochemical production of anhydrous nitric acid and N.sub.2 O.sub.5. The method includes oxidizing a solution of N.sub.2 O.sub.4 /aqueous-HNO.sub.3 at the anode, while reducing aqueous HNO.sub.3 at the cathode, in a flow electrolyzer constructed of special materials. N.sub.2 O.sub.4 is produced at the cathode and may be separated and recycled as a feedstock for use in the anolyte. The process is controlled by regulating the electrolysis current until the desired products are obtained. The chemical compositions of the anolyte and catholyte are monitored by measurement of the solution density and the concentrations of N.sub.2 O.sub.4.
The United States Government has rights in this invention pursuant to Contract No. W-7405-ENG-48 between the U.S. Department of Energy and the University of California, for the operation of Lawrence Livermore National Laboratory.