2,918,400 United States P?t?nt ‘O “ice Patented Dec. 22, 1959 1 2 and NaIO3.3Na2SO4 (Am. J. $0., '19,‘ 203413, 1930), or, I may employ mixtures of these ‘two salts, this‘bei-ng 2,918,400 particularly advantageous because of thetrelative ease of , preparation of such mixtures as compared with the prep SANITIZ‘IN‘G COMPOSITIONS aration of the individual complexes. Alternatively, 'I Alfred C. Loonam, New York, N.Y., assignor to‘ Chilean may employ double salts of sodium iodate and sodium Nitrate Sales Corporation, New York, N.Y., a corpo iodide, such as 2NaIO3.3NaI.xH2O ((J. Am. Chem. Soc. ration of New York ‘ 56, 295-299, 1934), where x is less than 10, i.e., preferably No Drawing. Application ‘April 16, ‘1956 'the double salt of lowest possible water content'since it ‘Serial No. 578,189 10 will have the smallest vapor pressure of this substance. Of the double salts. speci?ed, I ?nd that the sodium iodate-sodium sulfate double salts are superior in that they are anhydrous. In this connection, it should be explained that the iodide-iodate-acidifying agent‘ composi~ This invention relates to new'compositions of matter. 15 tions of the present invention are sensitive to moisture More particularly, the invention contemplates the‘pro and :even relatively small proportions of water tend to vision of new and improved sanitizing compositionsof promote undesirable production of free iodine upon stor the type ‘containing available iodine‘ as the sanitizing age. For this reason, I prefer to employ a sodium iodate agent in an inactive or relatively stable form but capable sodium sulfate double salt, or mixtures of these salts of being released upon contact or admixture of the com 20 within the santiizing compositions of the invention. Fur positions with water in the preparation of sanitizing solu thermore, the mixed double ‘salts, NaIO3.4Na2SO4 and tions. NaIO3.3Na2SO4, contain only 6.25% and 7.7% avail-. Compositions containing iodine or‘capable'of producing able oxygen, respectively, as‘compared with 24.2% for iodine upon admixture with a suitable solvent are highly the pure iodate, NalO3. ' . useful in the preparation of liquid germicidal composi 25 vAs the acidifying agent, I may employ any acidic com tions for use as antiseptics and for applications in sani pound capable of reacting in accordance with the equation tizing‘food-handling utensils and similar‘equipment. lFor set forth hereinbefore, and preferably, an acid which will solid formations of the general class described, it is known not react with iodine in solution rapidly enough to im that the system comprising a mixture of‘ an alkali‘io‘clide, pair its bactericidal action. I may also employ com an alkali iodate, and a solid acid in the relative propor 30 pounds such as acid anhydrides, provided they rehydrate tions capableof releasing free iodine‘in accordance with to the acids rapidly in solution, and substances such as the reaction ‘ aluminum sulfate and aluminum acetate, which, although normal salts, hydrolyze in solutions to yield acids which SNal +NalO3 + 312 6Na2SO4+ are elfective in promoting the iodidedodate reaction, or, shows promise, provided a bisulfate, an acid phosphate 35 I may employ acid phosphates, sodium bisulfate or glu or even sulfamic acid be employed as-the acid component, tamic acid. In actual practice, however, I prefer to em since such a system is preferably‘safe to ship and store ploy critric acid as the acidifying acid because of its avail under normal conditions. ‘For reasons of economy and ability and low cost. Of course, the invention resides in efficiency of operation, however, it is highly desirable to the discovery of means which render it safe to employ employ as ‘the acid ‘component of such a system, an 40 iodate in formulations containing organic constituents, organic acid such as citric acid in conjunction with other and, as such, is actually independent of ‘the speci?c kind organic substances such as ethylenediaminetetracetic ‘acid, of acid employed as the acidifying agent. for its chelating action, wetting agents, detergents, coro The iodide and iodate constituents of the compositions sion inhibitors, tableting agents or binders, and similar of the invention may be employed in stoichiometric quan additives of an organic nature. Such ‘mixtures, contain 45 tities .or any different proportion depending upon the use ing ‘both iodate with large quantities of reactive oxygen, to which the formulations are to be put. For example, and organic matter, are inherently dangerous vto prepare, provided the iodine concentration of the resulting solu handle and store since they aretcombustible and possibly tion is to ‘be less than that corresponding to saturation even explosive. under ‘normal conditions of use (162 p.p.m. at ° C. and The unique compositions of the present invention are 50 340 p.p.m. at 25° C.), the iodide and iodate should be intended to insure reasonable and safe ‘stability within‘a employed in the stoichiometric ratio or with an excess system of the foregoing type while retaining the desirable of the iodate. In fact, this is very much to be desired iodate content of the system. Speci?cally, the invention in solutions to be used for sanitizing purposes‘, as any contemplates stabilizing of the iodate ‘constituent to reduce excess iodide tends .to form triiodide ion, 13-, which has its activity and concentration such that it offers little or 55 been shown to have much less bactericidal action. than no tendency to react violently with organictsubstances or free diatomic iodine, 12. An excess of iodate, however, other combustible materials which one may desire‘ito ‘in would tend to prevent loss of free iodine by reduction to corporate in formulations of the general class described iodide during use of the solution. On the other hand, to confer special propertieson the mixtureor their result if, for example, the composition was; desired to provide 60 ing solutions, such, for example, as compatible organic a two percent iodine solution to replace the conventional substances of the types of acids, wetting agents, detergents, liquid tincture or the N.F.-type solutions, then an excess tableting agents or binders, corrosion inhibitors, chelat ing agents, etc. I accomplish this in accordance with the of iodide would be needed to keep the iodine in solution. present ‘invention by employing the iodate constituent as Further, if the resulting solution was to be used imme one component of a double salt or complex, the other 65 diately and thereafter discarded, a ratio of residual iodide component of which is poor in available oxygen .as com ion to free iodine of approximately 1 would be satisfac pared with the iodate, or entirely oxygen~free.. Thus, 'I tory, Whereas if the solution was to be stored for some am able ‘to reduce the effective thermodynamic activity period under varying conditions of temperature, the ratio of the iodate with reduction in the relative concentration should be increased to about 1.5. ofavailable oxygen. 70 The following examples are illustrative of typical sani As double salts, ‘I may employ salts of sodium ‘iodate tizing compositions embodying theprineiples of my in and sodium sulfate, such, for example, as NaIO3.4Na2SO4 vention: 2,918,400 3 Example I The sulfate-iodate complex was added to the foregoing formulations to react with the iodide ion in the Nal3 The following mixture, which can be prepared either complex and convert the same, as well as its own iodine, in powder form or as tablets and packed in a moisture to the free element. With respect to formulation “B,” proof container, when added to 2.5 gallons of water, it also functioned to provide a reserve of iodate to re yielded a solution containing approximately 50 parts per oxidize any free iodine which might be reduced to iodide. million free iodine at a pH of approximately 3.0. The The iodate-sulfate complex used in these formulations vresulting solution is particularly well adapted to the sani contained 12.6 percent iodine, compared to a theoretical tization of dishes and other food-handling utensils. content of 16.6 percent for NaIO3.4Na2SO4. Grams 10 Sodium iodide (anhydrous) _________________ __ 0.466 Example V NaIO3.xNa2SO4 (12.66% I) (or 0.477 gram Formulations containing the following range of ingre NalO3.4Na2SO4) ________________________ __ 0.623v dients yielded solutions containing 96.6 parts per million Citric acid (anhydrous) ____________________ __ 5.402 of available iodine when added to one liter of water. The Example II 15 resulting solutions had pH values of approximately 2.7, a highly desirable value for high germicidal activity. The The mixture prepared in Example I was modi?ed by iodate-sulfate complex contained 12.66 percent-iodine, the addition of 1.419 grams of sodium laurylsulfate to equivalent to 19.75 percent NaIO3 or a molar ratio of promote smooth runoff of the resulting sanitizing solution sulfate to iodate of 5.66. upon draining. The resulting mixture was found to be 20 Grams totally stable. NalO3.xNa2SO4 0. l 3 l Example III KI 0370-0174 The following mixture, also prepared in either powder Na2SO4—NaHSO¢ (50-50 mixture) __________ __ 0.2 or tablet form, when added to 2 ?uid ounces of water 25 yielded a solution ideally suited for antiseptic uses, con Total 0.701 taining 2% free iodine and 2.4% NaI, i.e., equivalent Having thus described the subject matter of my in concentrations as contained within Iodine Solution N.F.: vention, what it is desired to secure by Letters Patent is: Grams 1. A composition capable of producing iodine