Jul.  15, 2010  16  US 2010/0179368 Al  entirely different buffering capacity as compared to solutions  which comprise monoprotic solvents from Group II. Simi› larly, it will be known to one skilled in the art having the  present specification as their guide that all equilibrium con› stants vary with temperature according to the van’t Hoff equa› tion, and that some solvents will be more likely to promote  ionization of a dissolved acidic molecule if the organic/aque› ous solution comprises:  [0146]  Dimtheylsulfoxide (DMSO) has a lower dielectric  constant than water, is less polar, dissolves non-polar, hydro› phobic substances more readily, and has a measurable  pKa  range of about 1 to 30. Acetonitrile is less basic than DMSO.  Also, acids are generally weaker and bases are generally  stronger in this solvent. Some  pKa  values at 25°  C. for aceto› nitrile and dimethyl sulfoxide (DMSO) are shown in the Table  5, where values for water are included for comparison.  hydrogen.pis a property of the unsubstituted compound, and  a  has a particular value for each substituent. A plot of log  Ka  against  a  is a straight line with intercept log  Ka  $^{O }$and slope p.  This is an example of a linear free energy relationship as log  Ka  is proportional to the standard fee energy change. Ham› mett originally formulated the relationship with data from  benzoic acid with different substituents in the ortho- and  para-positions: some numerical values are in Hammett equa› tion. This and other studies allowed substituents to be ordered  according to their electron-withdrawing or electron-releasing  power. These allow a solution to be tailored for the toxants to  be decontaminated and their location.  [0148]  One aspect of the present invention is the use of  mixed solvents to create decontaminant formulations which  can dissolve threat loads of amphipathic compounds like the  nerve or mustard agents and their respective simulants that  have limited solubility in water. It is a common practice (in  the pharmaceutical industry, for example) to determine  pKa  values in solvent mixture such as water/dioxane or water/  octanol, in which the compound is more soluble. In the  example shown FIG.  4,  the  pKa  value rises steeply with  increasing percentage of 1,4-dioxane, a GROUP III solvent  with two hydrogen bond acceptors, as the dielectric constant  of the mixture is decreasing. A  pKa  value obtained in a mixed  solvent cannot be used directly for aqueous solutions,  because when the solvent is in its standard state, its activity is  defined as one.  [0149]  For example, the standard stateofwater:dioxane 9:1  is precisely that solvent mixture with no added solutes. To  obtain the  pKa  value for use with aqueous solutions it has to  be extrapolated to zero co-solvent concentration from values  obtained from various co-solvent mixtures. These factors are  frequently forgotten by those having ordinary skill in the art,  owing to the omission of the solvent effect from the expres› sion for acid dissociation constants. This is normally used to  define  pKa,  but  pKa  values obtained in a given mixed solvent  can be compared to each other, giving relative acid strengths.  The same is true of  pKa  values obtained in a particular non› aqueous solvent such a DMSO. As of November of 2008, no  universal, solvent-independent scale for acid dissociation  constants had been developed, since there was no known way  to compare the standard states of two different solvents.  Given that there is no basis for any type of comparison  between solvents, the pKa values of the peroxyacids of the  present invention and the buffer systems for chemical activa› tion are novel to the present invention.  [0150]  The total amount of peroxy-oxidant used can vary  according to the embodiments of the invention. The total  decontaminant to toxant ratio can range from about 100 to  about 0.1. The solutions of the invention can be used for  hydrolyzing a substrate in an organic/aqueous solution by  providing both the toxant and the oxidizers with an isotropic  solution in which to react. According to another embodiment  of the invention, toxant hydrolyses can be conducted from  between about -35°  F.  and 140°  F. In another embodiment of  the invention, substrate hydrolysis reactions are conducted  between about-25°  F. and about 125°  F. The total decontami› nant to toxant ratio by volume can range from about 100 to  about 0.1.  [0151]  Biopathogens used for biological warfare, such as  bacterial cells, bacterial spores, viruses, and other biopatho› gens have certain structural features that must be considered.  The organization and structure of phospholipids and proteins  in cell membranes, spore coats and viral capsids can be  [0147]  There are many factors that affect pKa values. For  example, Pauling’s second rule states that the value of the first  pKa  for acids of the formula  XOm(OH)n  is approximately  independent of n and X and is approximately 8 for m=0, 2 for  m=l, -3 for m=2 and <-10 for m=3. This correlates with the  oxidation state of the central atom, X: the higher the oxidation  state the stronger the oxyacid. For example,  pKa  for HClO is  7.2, for HC1O$_{2 }$ is 2.0, for HC1O$_{3 }$ is -1 and HC1O$_{4 }$ is a strong  acid. With organic acids like the percarboxylic acids, induc› tive effects and mesomeric effects affect the  pKa  values. A  simple example is provided by the effect of replacing the  hydrogen atoms in acetic acid by the more electronegative  chlorine atom. The electron-withdrawing effect of the sub› stituent makes ionization easier, so successive  pKa  values  decrease in the series 4.7, 2.8, 1.3, and 0.7 when 0, 1, 2 or 3  chlorine atoms are present. The Hammett equation, provides  a general expression for the effect of substituents:  where  Ka  is the dissociation constant of a substituted com› pound,  Ka  $^{O }$is the dissociation constant when the substituent is  logKa~logKa $^{0}$+pa  [0143]  a protic organic solvent, capable of forming  hydrogen bonds;  [0144]  a solvent with a high donor number, making it a  strong Lewis base; and/or  [0145]  a solvent with a high dielectric constant, making  it a good solvent for ionic species.  TABLES  pKa values of acids in Group I (acetonitrile),  Group III (DMSO) and Group II solvents  Water  Acetonitrile  DMSO  (for comparison)  HAA- + H+  p-Toluenesulfonic  8.5  0.9  strong  acid  2,4-Dinitrophenol  16.66  5.1  3.9  Benzoic acid  21.51  11.1  4.2  Acetic acid  23.51  12.6  4.756  Phenol  29.14  18.0  9.99  BH+B +H•  Pyrrolidine  19.56  10.8  11.4  Triethylamine  18.82  9.0  10.72  Proton sponge  18.62  7.5  12.1  Pyridine  12.53  3.4  5.2  Aniline  10.62  3.6  9.4 