Browsing by Subject "Salts"

Now showing 1 - 7 of 7

Open Access
Coarse-grained electrostatic model including ion-pairing equilibrium that explains DC and AC X-ray photoelectron spectroscopy measurements on ionic liquids
(American Chemical Society, 2019) Uzundal, Can Berk; Aydoğan-Göktürk, Pınar; Süzer, Şefik; Ülgüt, Burak
The dynamics of the electrochemical double layer in ionic liquids can be experimentally probed by a number of experimental techniques. Earlier, we reported on the results of an X-ray photoelectron spectroscopic investigation under applied square-wave bias of two distinct frequencies. Our studies had revealed counterintuitive properties involving the physical and temporal progression of the effect of the electrochemical double layer that could not be modeled with conventional equivalent-circuit approaches. Herein, we present a new coarse-grained modeling methodology that accounts for particle diffusion, migration, and ion-association equilibrium. Our model is computationally efficient enough to be used to predict and match the results at extended time scales and distances of the experiment. Modeling efforts predict that a crucial component of the behavior is controlled by the ion-pairing equilibrium, an often overlooked aspect of ionic liquids.
Open Access
The effect of anions of transition metal salts on the structure of modified mesostructured silica films and monoliths
(Elsevier, 2007) Demirörs, A. F.; Arslan, M.; Dag, Ö.
The structure of the preformed LC mesophase of water:transition metal salt ([M(H2O)6]X2):acid (HX):oligo(ethylene oxide) (or Pluronics):tetramethylorthosilicate (TMOS) mixture during hydrolysis and partial polymerization of the silica source is maintained upon further polymerization and condensation of the silica species in the solid state. The liquid mixture in early stage of the silica polymerization could be casted or dip coated to a surface of a glass or silicon wafer to produce mesostructured silica monoliths and films, respectively. The silica species and ions (metal ions and anions) influence the structure of the LC mesophases (as a result, the structure of silica) and the hydrophilic and hydrophobic balance in the reaction media. The silica structure can be changed from hexagonal to cubic by increasing, for example, the nitrate salt concentration in the nitrate salt systems. A similar transformation takes place in the presence of very low perchlorate salt concentration. The salt concentration in the mesostructured silica can be increased up to 1.1/1.0 salt/SiO2 w/w ratio, in mesostructured silica materials by maintaining its lamella structure in P123 and cubic in the CnEOm systems. However, the materials obtained from the P123 systems undergo transformation from lamella to 2D hexagonal upon calcinations. The method developed in this work can be used to modify the internal surface of the pores with various transition metal ions and metal oxides that may find application in catalysis. © 2006 Elsevier Inc. All rights reserved.
Open Access
Electronic structure, insulator-metal transition and superconductivity in K-ET2X salts
(1998) Ivanov V.A.; Ugolkova, E.A.; Zhuravlev, M.Ye.; Hakioǧlu, T.
The electronic structure and superconductivity of layered organic materials based on the bis(ethylenedithio)tetrathiafulvalene molecule (BEDT-TTF, hereafter ET) with essential intra-ET correlations of electrons are analysed. Taking into account the Fermi surface topology, the superconducting electronic density of states (DOS) is calculated for a realistic model of K-ET2X salts. A d-symmetry of the superconducting order parameter is obtained and a relation is found between its nodes on the Fermi surface and the superconducting phase characteristics. The results are in agreement with the measured non-activated temperature dependences of the superconducting specific heat and NMR relaxation rate of central 13C atoms in ET. © 1998 John Wiley & Sons, Ltd.
Open Access
Liquid crystalline mesophases of pluronics (L64, P65, and P123) and transition metal nitrate salts ([M(H2O)6](NO 3)2)
(American Chemical Society, 2005) Demirörs, A. F.; Eser, B. E.; Dag, Ö.
The triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) copolymers, Pluronics (L64, P65, and P123), form liquid crystalline (LC) mesophases with transition metal nitrate salts (TMS), [M(H2O) n] (NO3)2, in the presence and absence of free water in the media. In this assembly process, M-OH2 plays an important role as observed in a TMS:CnEOm (C nEOm is oligo(ethylene oxide) nonionic surfactants) system. The structure of the LC mesophases and interactions of the metal ion-nitrate ion and metal ion-Pluronic were investigated using microscopy (POM), diffraction (XRD), and spectroscopy (FTIR and micro-Raman) techniques. The TMS:L64 system requires a shear force for mesophase ordering to be observed using X-ray diffraction. However, TMS:P65 and TMS:P123 form well structured LC mesophases. Depending on the salt/Pluronic mole ratio, hexagonal LC mesophases are observed in the TMS:P65 systems and cubic and tetragonal LC mesophases in the TMS:P123 systems. The LC mesophase in the water/salt/Pluronic system is sensitive to the concentration of free (H2O) and coordinated water (M-OH2) molecules and demonstrates structural changes. As the free water is evaporated from the H2O:TMS:Pluronic LC mesophase (ternary mixture), the nitrate ion remains free in the media. However, complete evaporation of the free water molecules enforces the coordination of the nitrate ion to the metal ion in all TMS:Pluronic systems. © 2005 American Chemical Society.
Open Access
Local electric fields in aqueous electrolytes
(American Chemical Society, 2021-07-27) Drexler, C. I.; Cracchiolo, O. M.; Myers, R. L.; Okur, Halil İbrahim; Serrano, A. L.; Corcelli, S. A.; Cremer, P. S.
Vibrational Stark shifts were explored in aqueous solutions of organic molecules with carbonyl- and nitrile-containing constituents. In many cases, the vibrational resonances from these moieties shifted toward lower frequency as salt was introduced into solution. This is in contrast to the blue-shift that would be expected based upon Onsager’s reaction field theory. Salts containing well-hydrated cations like Mg2+ or Li+ led to the most pronounced Stark shift for the carbonyl group, while poorly hydrated cations like Cs+ had the greatest impact on nitriles. Moreover, salts containing I– gave rise to larger Stark shifts than those containing Cl–. Molecular dynamics simulations indicated that cations and anions both accumulate around the probe in an ion- and probe-dependent manner. An electric field was generated by the ion pair, which pointed from the cation to the anion through the vibrational chromophore. This resulted from solvent-shared binding of the ions to the probes, consistent with their positions in the Hofmeister series. The “anti-Onsager” Stark shifts occur in both vibrational spectroscopy and fluorescence measurements.
Open Access
Lyotropic liquid crystal to soft mesocrystal transformation in hydrated salt-surfactant mixtures
(Wiley, 2013) Albayrak, C.; Barım, G.; Dag, Ö.
Hydrated CaCl2, LiI, and MgCl2 salts induce self-assembly in nonionic surfactants (such as C12H 25(OCH2CH2)10OH) to form lyotropic liquid-crystalline (LLC) mesophases that undergo a phase transition to a new type of soft mesocrystal (SMC) under ambient conditions. The SMC samples can be obtained by aging the LLC samples, which were prepared as thin films by spin-coating, dip-coating, or drop-casting of a clear homogenized solution of water, salt, and surfactant over a substrate surface. The LLC mesophase exists up to a salt/surfactant mole ratio of 8, 10, and 4 (corresponding to 59, 68, and 40wt % salt/surfactant) in the CaCl2, LiI, and MgCl2 mesophases, respectively. The SMC phase can transform back to a LLC mesophase at a higher relative humidity. The phase transformations have been monitored using powder X-ray diffraction (PXRD), polarized optical microscopy (POM), and FTIR techniques. The LLC mesophases only diffract at small angles, but the SMCs diffract at both small and wide angles. The broad surfactant features in the FTIR spectra of the LLC mesophases become sharp and well resolved upon SMC formation. The unit cell of the mesophases expands upon SMC transformation, in which the expansion is largest in the MgCl2 and smallest in the CaCl2 systems. The POM images of the SMCs display birefringent textures with well-defined edges, similar to crystals. However, the surface of the crystals is highly patterned, like buckling patterns, which indicates that these crystals are quite soft. This unusual phase behavior could be beneficial in designing new soft materials in the fields of phase-changing materials and mesostructured materials, and it demonstrates the richness of the phase behavior in the salt-surfactant mesophases.
Open Access
Phase separation in liquid crystalline mesophases of [Co(H 2O)6]X2: P65 Systems (X = NO3-, Cl-, or ClO4-)
(2007) Albayrak, C.; Gülten, G.; Dag, Ö.
Transition-metal aqua complex salts [M(H2O)6]X 2 (where M is Mn(II), Co(II), Ni(II), Zn(II), or Cd(II) and X is NO3-, Cl-, or ClO4-) can be dissolved in triblock poly(ethylene oxide) - poly(propylene oxide) - poly(ethylene oxide) copolymers (Pluronics, such as P65) to form homogeneous liquid crystalline (LC) mesophases. However, the [Co-(H2O) 6]X2:P65 LC mesophases slowly undergo phase separation into a disordered ion-free phase and an ordered ion-rich LC mesophase. The phase separation also takes place in the two-salt systems [Co(H2O) 6](NO3):[Co(H2O)6]-(ClO 4)2:P65 in which the ion-free disordered domains separate out from the initially ordered homogeneous mesophase. The phase separation results in a physical mixture of a hexagonal nitrate-rich and cubic perchlorate-rich LC and disordered ion-free domains in the mixed salt systems. The driving force in the phase separation in the [Co(H2O) 6]-X2:P65 system is Co(II)-catalyzed aerobic oxidation of P65 into ester and/or other oxidation products. The separation of ions in the [Co(H2O)6](NO3)2:[Co(H 2O)6](ClO4)2:P65 system is related to the mesostructures of the two-salt systems that are different, hexagonal in the [Co(H2O)6](NO3)2:P65 system and cubic in the [Co(H2O)6](ClO4)2:P65 system. There is no visible phase separation in the other transition-metal salt:P65 systems. The phase separation in the [Co-(H2O) 6]X2:P65 systems can also be eliminated by keeping the mesophase under a N2 atmosphere. © 2007 American Chemical Society.