New electrodes, new design - C&EN Global Enterprise (ACS

Nov 6, 2010 - In one move, Orion Research, Inc., is doubling its line of specific ion electrodes. Moreover, three of the five new electrodes that the ...
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Upjohn cancels ads

Robert C. Gunness Half of the gains

Petroleum, Sinclair Oil & Gas, and Skelly Oil. The many other companies active on the Alaskan oil scene include Atlantic Richfield, Shell Oil, Union Oil Co. of California, Mobil Oil, Texaco, and Standard Oil Co. (Calif.). In eying Alaska's role in the West Coast market, Mr. Gunness points out that the West Coast is currently deficient in crude oil; it will remain so for the foreseeable future. But rising population and industry, particularly in California, will greatly increase oil consumption in the area. Mr. Gunness adds that his company's own forecasts put 1975 West Coast petroleum demand 39% ahead of what it is now. This growth includes a 4 4 % increase in gasoline demand. Japan, as well as the West Coast, may particularly benefit from Alaskan oil and natural gas. For instance, Phillips Petroleum and Marathon Oil are arranging to export liquefied methane from Alaska to Japan. And Union Oil, through its Collier Carbon and Chemical subsidiary, has started to build a 1000 ton-per-day urea plant on Alaska's Kenai Peninsula (C&EN, March 14, page 2 3 ) . The plant will be jointly owned by Japan Gas-Chemical. Raw materials will come from Union's large gas reserves on the peninsula. Collier is also building a 1500 ton-per-day ammonia plant on its own at the same site. In addition, Skelly Oil and a Japanese group are considering building an 1100 ton-ayear methanol plant in Alaska or Canada (C&EN, Nov. 7, page 3 9 ) . Key areas of oil industry interest in and around Alaska include North Slope, above the Arctic Circle; Bristol Bay to the west; the Gulf of Alaska to the south; and the Cook Inlet basin, the center of greatest activity today.

The Upjohn Co. has canceled all of its advertising for prescription drug products in all medical journals, pending clarification of the Food and Drug Administration's advertising regulations. And FDA and the Pharmaceutical Manufacturers' Association are fighting over promotional rules. R. T. Parfet, Jr., president and general manager of the Kalamazoo, Mich., drug firm, says that recent FDA action involving one advertisement of the company's antibiotic Lincocin was unjustified. FDA questioned neither the safety nor the efficacy of the antibiotic, he says. What the Government questions is the lack of emphasis on certain precautions. Lincocin remains on the market. "The company has never intended either to mislead or misinform," Mr. Parfet says. "Our medical staff, our legal staff, and our advertising agency believed our advertisement conformed to regulations. We had no prior notice of specific objections from the FDA even though variations of the advertisement had been running for many months. Under such circumstances we are in constant threat of court action until we are more certain of the interpretation of the regulations." The action referred to was a seizure of the antibiotic Lincocin on Oct. 27 in Cincinnati, Ohio, by the U.S. District Court. The court action, at the request of FDA, is based on an advertisement for the drug in the Oct. 3 issue of the Journal of the American Medical Association. In other developments on the FDAdrug industry battlefront, the warm debate between FDA and PMA grew warmer. First, C. Joseph Stetler, president of PMA, cited an instance in which FDA accused "one third of the members of the PMA" of advertising violations, b u t he said FDA's list of violators fell "considerably short" of one third of PMA membership. Not to be outdone, FDA sent out a news release naming 39 drug makers for 89 alleged violations. Replied Mr. Stetler, "the list published by the FDA includes 39 companies whose ads have been questioned over the past two and a half years, eight of which are not even members of the PMA. In its past statements the FDA has referred to these cases as being 'in violation of the regulations/ In its release today, the FDA correctly identifies many of the instances as 'alleged violations.' " "Finally," continued Mr. Stetler, "FDA twice during the past summer rejected our efforts to obtain details of these problems in order that we might undertake appropriate educational or self-policing measures to help improve prescription drug advertising. These

rejections were on the stated ground that disclosure to us might prejudice the legal rights of the companies involved." In the latest move, FDA and PMA have agreed to meet for further clarification of promotional rules, but no date has been set.

New electrodes, new design In one move, Orion Research, Inc., is doubling its line of specific ion electrodes. Moreover, three of the five new electrodes that the Cambridge, Mass., company is introducing this week at the Eastern Analytical Symposium in New York represent a new construction concept. The three electrodes, which the company calls solid-state types, measure bromide, chloride, and iodide ions. In addition, two new ion exchange membrane types will be available for the measurement of chloride and perchlorate. Since Orion started to make electrodes in April, it has already put five on the market. These measure calcium ion, divalent cation, and fluoride, cupric, and sulfide ions. Of these, the calcium, divalent cation, and cupric electrodes are of the liquid ion exchange membrane type. The fluoride and sulfide electrodes employ yet another nonconventional electrode concept, single crystals. The fluoride electrode, for example, uses a single crystal doped with rare earth. The company calls its three new

Electrode packers Solid state, five new ions NOV. 14, 1966 C&EN 23

electrodes "solid state" to differentiate them from silver chloride wire types. The solid-state electrodes are made with cast solid pellets of silver halides, which act as the membranes. An advantage of the construction, Or­ ion explains, is that they are immune from reduction-oxidation potentials and poisoning. Price of the three solid-state elec­ trodes is $120 each. The two ion ex­ change membrane types are $145 each. Concentration ranges and inter­ ferences shape up like this: • Bromide measures from below 10- 6 M up to about 1M. Iodide is an interfering ion. • Chloride (solid state) measures from 10 - δ Μ up to about 1M. Bro­ mide and iodide are interfering ions. • Iodide measures from below 10 - 6 M up to about 1M. It has essen­ tially no interferences except in solu­ tions that develop silver halide. '· Chloride (ion exchange type) measures from 10 - 4 M up to 1M. A few anions interfere and chloride should be the predominant ion present. Bicarbonate, sulfate, and phosphate do not interfere, however. • Per chlorate measures from l O ^ M u p to 1M. Although it is not com­ pletely specific, it is essentially free of interference. At present, all of Orion's electrodes (and those of other makers) are spe­ cific to various inorganic ions. This represents the bulk of analytical de­ terminations currently being made, Orion says. But the company sees no reason why the principles of electro­ chemical sensing cannot be extended to many organic species as well.

New cell uses lithium, organic A new high energy-density battery that operates effectively from —40° to 160° F . has been developed by Electrochimica Corp., Menlo Park, Calif. Patent applications have been filed on the lithium organic-electrolyte system by Dr. Morris Eisenberg, president and director of research of Electrochimica, which makes and sells silverzinc and silver-cadmium batteries. A rechargeable version of the new bat­ tery is under development and might be used to power automobiles. Two new principles are involved in the battery. One is a porous lithium anode plate. (The cathode is made of cupric chloride. ) A special process for making the anode ensures that it has the correct degree of porosity to allow high current density, for example, 100 amp. per sq. ft. of plate surface. T h e other novel feature is an organic electrolyte that replaces the waterbased systems of conventional wet cells. The electrolyte has a high de24 C&EN NOV. 14, 1966

Swelling estimates cross-link

Inventor Eisenberg Rechargeable version on the way

gree of conductivity and good reversi­ bility toward the electrode reactions, Dr. Eisenberg claims. He won't spec­ ify its chemical nature, however. Dr. Eisenberg says the new battery has a theoretical energy density of 503 watt-hours per pound. A comparable silver-zinc cell has a theoretical energy density of 200 watt-hours per pound, a lead-acid cell about 60 watt-hours. The practical energy density in bat­ teries is a function both of rate of dis­ charge and of cell size. Because the Electrochimica battery uses light­ weight components, its net energy den­ sity is 68 to 72 watt-hours per pound for a 6 amp.-hr. cell when discharged during 10 hours. The corresponding value for the silver-zinc cell is 40 to 43 watt-hours per pound, Dr. Eisenberg says, and 8 to 10 watt-hours per pound for the lead-acid cell. Electrochimica has obtained Faradaic efficiencies—the percentage of utilization of active materials in the battery—of more than 80% at all tem­ peratures between —40° and 160° F. In comparison, silver-zinc and leadacid batteries don't operate outside a range of 0° to 130° F. Because lithium is cheaper and more abundant than silver, the new battery should eventually cost less than a sil­ ver-zinc one, Dr. Eisenberg believes. He sees many uses for his battery: portable communications equipment, portable TV's, cordless appliances. Also at hand is the rechargeable ver­ sion of the battery that Dr. Eisenberg believes could be used in an electric automobile power system. The bat­ tery's high energy density, he believes, should allow a car to operate up to 65 miles per hour and cover 160 miles be­ tween recharging. More important, the battery would operate at ambient temperature.

Cross-link density in polymeric films can be estimated by a method devel­ oped at Rohm and Haas. The tech­ nique uses a specially designed mi­ crometer to measure the swelling of a cured film, which is bonded to glass, after the addition of suitable solvent. The thickness of the swollen film is di­ vided by the original dry film thickness to give a linear swelling ratio, Dr. Sheldon N. Lewis told the Federation of Societies for Paint Technology, in Washington, D.C. Rohm and Haas finds the linear swelling ratio a useful index of one-di­ mensional swelling of a glass-bonded film. A large ratio, reflecting a large swell effect, corresponds to a low de­ gree of cross-linking, since cross-linked networks give more structural integrity to the polymer. Although mathematical relationships are difficult to establish between linear swell ratios and absolute cross-link density, the method measures relative degrees of cross-linking within a poly­ mer type with good precision, Dr. Lewis points out. Moreover, this method has the advantage of testing thin bonded films directly without the need for thicker films freed from their substrates, as present techniques re­ quire. While the method is applicable to most cured films, he says, the instru­ ment and procedure were designed to provide rapid measurements for crosslinking studies on acrylics. Rohm and Haas was evaluating the efficacy of various difunctional, copolymerized acrylics to bring about cross-linking in polyethyl acrylate. Emphasis was placed on determining minimum catalyst and heat requirements needed to ensure complete cross-linking in the thermosetting films. In the study, thin films of the emul­ sions were cured on glass slides at 300° F. The slides were inserted in a mov­ able stage beneath the micrometer. Lowered onto the slide, a round, steel sleeve confined the solvent to the test area. The solvent—p-xylene—was added in sufficient amounts to keep the sample film submerged. The film-solvent system usually reached equilibrium within 10 minutes. During this swelling time, the deli­ cately counterbalanced plunger of the micrometer was periodically lowered, coming to rest on and measuring the upper surface of the expanding film. A series of such measurements gave data for plotting swelling rate curves. These continuous functions have been useful, Dr. Lewis mentions, in deter­ mining initial swell rates, which are re­ lated to a polymer's diffusion co­ efficient, and in following the system to equilibrium.