Mortimer J. Kamlet

Chemistry of Detonations. I. A Simple Method for Calculating Detonation Properties of C–H–N–O Explosives

Detonation pressures of C–H–N–O explosives at initial densities above 1.0 g/cc may be calculated by means of the simple empirical equation Pu2009=u2009Kρ02φ, Ku2009=u200915.58, φu2009=u2009NM1u2009/u20092Q1u2009/u20092, detonation velocities by the equation Du2009=u2009Aφ1u2009/u20092(1u2009+u2009Bρ0), Au2009=u20091.01, Bu2009=u20091.30. N is the number of moles of gaseous detonation products per gram of explosive, M is the average weight of these gases, Q is the chemical energy of the detonation reaction (u2009−u2009ΔH0per gram), and ρ0 is the initial density. Values of N, M, and Q may be estimated from the H2O–CO2 arbitrary decomposition assumption, so that the calculations require no other imput information than the explosives elemental composition, heat of formation, and loading density. Detonation pressures derived in this manner correspond quite closely to values predicted by a computer code known as RUBY, which employs the most recent parameters and covolume factors with the Kistiakowsky‐Wilson equation of state.

Chemistry of Detonations. II. Buffered Equilibria

At low loading densities, values of N, M, and Q calculated from the H2O–CO2 “arbitrary” show poor individual agreement with estimates of these quantities from the RUBY computer code. Nevertheless, when substituted into the equation Pu2009=u200915.58 NM1u2009/u20092Q1u2009/u20092ρ02 they lead to detonation pressures which correspond closely to RUBY predictions. That incorrect input information should yield results which are very nearly “correct” is rationalized on the basis that the equilibria whose shifting engenders the changes in N, M, and Q are “buffered” in the sense that “errors” in N are offset by compensating “errors” in M and Q. As a consequence of the fact that most of the important equilibria in the detonation of C–H–N–O explosives are buffered, calculated (and actual) mechanical properties of detonations appear to be extremely insensitive to exact product compositions. A number of other interesting consequences of these buffered equilibria are discussed.

Chemistry of Detonations. III. Evaluation of the Simplified Calculational Method for Chapman‐Jouguet Detonation Pressures on the Basis of Available Experimental Information

It is shown that the simplified calculational scheme discussed in Parts I and II of this series accomodates the total body of inexact and often self‐contradictory experimental information almost as well as might reasonably be expected of any computational method. Some possibly systematic discrepancies in the reported experimental C‐J pressures are discussed on the basis of methods used to carry out and interpret the measurements in the various laboratories.

Some observations regarding different retention properties of HPLC stationary phases

SummaryThe retention of 32 monocyclic aromatic compounds and 14 polynuclear aromatic hydrocarbons (PAHs) has been studied on four different bonded phases in each of two mobile phases. An additional data set of 21 monocyclic aromatics judiciously chosen for their well-established solvatochromic parameters, 12 PAHs and 12 polychlorinated biphenyls (containing up to 10 chlorines), were studied on a single column. The results indicate that despite the accuracy of the solvatochromic linear solvation energy method for predicting and correlating the octanol/water partition coefficients and water solubilities of these environmentally important materials, the methodology is limited to only certain types of bonded phases. As a corollary to this observation, we caution others that the common practice of estimating log Kow (Kow=octanol-water partition coefficient) based on measurement of the reversed-phase capacity factors should be limited to specific types of columns.

Chemistry of Detonations. IV. Evaluation of a Simple Predictional Method for Detonation Velocities of C–H–N–O Explosives

Measured detonation velocities of a variety of C–H–N–O explosives agree with values predicted from the equation Du2009=u20091.01φ1u2009/u20092(1u2009+u20091.30ρ0), where φu2009=u2009NM1u2009/u20092Q1u2009/u20092, with an average absolute error of ∼1%. The H2O–CO2 arbitrary assumption of detonation product compositions is used in the calculation of N, the number of moles of detonation gases per gram of explosive; M, the average molecular weight of these gases; and Q, the chemical energy of the detonation reaction.

Linear solvation energy relationships Solvent effects on some fluorescence probes

Abstract Solvent effects on the fluorescence probes, 7-amino-4-methylcoumarin, 7-(N,N-dimethylamino)-4-methylcoumarin, and potassium 2-( p -toluidino)-6-naphthalenesulfonate are unravelled and rationalized in terms of multiple dependences on the solvatochromic parameters π * , α, and β.

Solubility properties in polymers and biological media. II. A new method for the characterisation of the adsorption of gases and vapours on solids.

Henrys constants at zero solute pressure have been determined by the gas chromatographic peak shape method for twenty-two solutes on four adsorbents (Rohm and Haas Ambersorb XE-348F carbonaceous adsorbent at 323 and 373 K, Sutcliffe Speakman 207A and 207C at 323 K, and Calgon Filtrasorb activated carbon at 323 K). The limiting values of log KH have been analysed in terms of solute dipolarity (pi 2*), solute hydrogen-bond acidity (alpha 2), and basicity (beta 2), and a new solute parameter (log L16), the solute Ostwald absorption coefficient on eta-hexadecane. The multiple linear regression equation, SP = SP0 + l.log L16 + s(pi 2* + d delta 2) + a alpha 2 + b beta 2 where in this instance SP = -log KH, can be used to identify the nature of the solute-adsorbent interactions, and to predict further values of log KH. For the solutes and solids we have studied, only the l.log L16 term is statistically significant, and hence--log KH is proportional to l.log L16. It is concluded that interactions between the gaseous solutes (that include alcohols and amines) and the four adsorbents involve just general dispersion forces.

Linear solvation energy relationships. A comparison of molar volume and intrinsic molecular volume as measures of the cavity term in reversed phase liquid chromatography

SummaryReversed-phase liquid chromatographic capacity factors are well correlated by an equation of the form:n

Solubility properties in polymers and biological media: 10. The solubility of gaseous solutes in polymers, in terms of solute-polymer interactions

logk = (logk)_0 + mV/100 + spi ^* + bbeta + aalpha