Calculated Exchange Parameters Research Articles

Aqueous Geochemistry and the Exchangeable Cation Composition of Glauconite in the Aquia Aquifer, Maryland

ABSTRACTThe cation composition of water in the Aquia aquifer of southern Maryland changes systematically in the direction of ground‐water flow. In the upgradient parts of the aquifer, calcium is the dominant cation in solution. Between 10 and 20 miles downgradient, calcium and magnesium are dominant. Between 20 and 35 miles downgradient, magnesium and potassium are dominant, and, beyond 40 miles downgradient, sodium is the most abundant cation in solution. The exchangeable cation composition of glauconite in the Aquia aquifer changes systematically in the direction of flow in a manner similar to the changes in water chemistry. These observations are interpreted as evidence that cation exchange reactions are processes that simultaneously alter water composition and glauconite composition along the flowpath.Exchange parameters K’and n for glauconite in the Aquia aquifer were determined for the reactions: image image image The exchange parameters for each reaction were tested by an indirect method. Molar ratios of exchangeable cations or glauconite were calculated from water chemistry data using the derived k’and n values. In each case, the trend of calculated molar ratios compared favorably with measured molar ratios. The calculated exchange parameters demonstrate that the exchange process is not linear for the Ca2+ ‐Na+ and Mg2+ ‐Na+ ion pairs.The sum of exchangeable cations on glauconite samples is significantly lower in the outcrop area than downgradient. Corresponding to this, the concentration of dissolved silica and dissolved oxygen in Aquia water is high near the outcrop area and decreases downgradient. This pattern suggests that incongruent dissolution of glauconite is an additional process that modifies glauconite composition near the outcrop area but is less important downgradient.

Relation between Exchange Interaction and Crystal Structure of Verdazyl Radicals. As Studied by Means of McConnell’s Spin Density Hamiltonian

Abstract The exchange interactions in four kinds of verdazyl crystals, 2,4,6-triphenylverdazyl (TPV), 2,4,6-triphenyl-3-methylverdazyl (MeTPV), 2,4,6-tri-p-tolylverdazyl (TTV), and 2,6-di-p-tolyl-4-phenylverdazyl (DTPV), have been studied by means of McConnell’s spin density Hamiltonian. The calculated exchange parameters, J, have been compared with the experimental values derived from the magnetic susceptibilities. The observed order of J’s J⁄k=−5.4 (TPV), −9.1 (MeTPV), −11.1 (DTPV), and 0–−0.3 K (TTV), can be qualitatively explained by the following equation: J∝\undersetijΣ (−1⁄rij)ρilρjl+1, where ρil and ρjl+1 are π-spin densities on atoms i and j of the l-th and (l+1)-th molecules in the crystallographic column and rij is the interatomic distance between atoms i and j. The magnetic susceptibility data of MeTPV and TTV between 1.6 and 300 K are presented and interpreted with the Heisenberg linear chain model. The susceptibility of DTPV is re-interpreted in the same framework as above.