Dimethylsulfoxide Binary Mixtures Research Articles

Compressibility Studies of Solvation Behaviour of Lithium and Sodium Ions in Nitromethane + Dimethylsulfoxide Binary Mixtures at 298.15 K

The isentropic compressibilities (Ks) and apparent molal isentropic compressibilities (Ks,φ) of lithium perchlorate (LiClO4), sodium perchlorate (NaClO4), sodium tetraphenylborate (NaBPh4), tetrabutylammonium tetraphenylborate (Bu4NBPh4) and tetrabutylammonium perchlorate (Bu4NClO4), have been calculated from measured ultrasonic velocity (u) and density (ρ) of these salts in the concentration range 0.001 to 0.60 mol Kg-1 in the mixed binary solutions of nitromethane (NM) and dimethyl sulfoxide (DMSO) containing 0, 20, 40, 60, 80 and 100 mol% of DMSO in NM at 298.15 K. Limiting values of apparent molal isentropic compressibilities (K°s,φ) for various salts were evaluated and split into the contributions (K°s,φ)± of the individual ions. Exceptionally large and negative (K°s,φ)± values were obtained whose variation with solvent composition shows strong solvation of both Li+ and Na+ in NM + DMSO mixtures at all compositions of the mixed binary solutions. Solvation of Li+ and Na+ increases as mol% of DMSO in NM increases. Solvation exhibited by Li+, however, is much stronger than Na+ in all compositions of the mixtures. Solvation exhibited by ClO4 – in NM + DMSO mixtures is weak which perchlorate ion shows by having some interactions with DMSO in the DMSO-rich compositions of the mixtures. The large and positive values for Bu4N+ and Ph4B– are indicative of some special type of interactions, mainly solvophobic with the solvent molecules.

Investigation of temperature dependent dielectric relaxation studies of 1,4-Butanediol/DMSO binary mixtures at the microwave frequency

In the present manuscript, we are reporting the complex dielectric permittivity of 1,4-Butanediol/Dimethylsulfoxide binary mixtures for entire concentrations in the temperature range of 298.15 K–323.15 K. The complex dielectric permittivity is measured in the frequency range of 20 MHz–20 GHz. The dielectric relaxation time (τ) of the binary mixtures are analyzed by using the Havriliak-Negami equation. Redlich-Kister polynomial equation is used to fit the excess molar volume (VmE), excess permittivity (εE), excess refractive index (nDE), excess inverse relaxation time (1/τ)E. The molecular association and structural packing in the liquid mixture are analyzed by using thermal expansion coefficient (αP) parameter. The ordering nature of the molecular dipoles is discussed by evaluating the Kirkwood correlation factor(geff) and stability of the system by thermodynamic quantities. The experimental dipole moments of the pure and equimolar binary system are determined by using Higasi's method and compared with the theoretical dipole moment values obtained from DFT/B3LYP methods. Confirmation of hydrogen bond between 1,4-butanediol and DMSO is supported with the FT-IR and UV-Vis spectroscopy methods. The experimental dielectric and spectroscopic studies confirm the existence of hydrogen bond between the liquid mixtures.

Comments on “Reply to comments on study of density, dynamic viscosity, excess property and intermolecular interplay studies for 1,4-butanediol + dimethyl sulfoxide binary mixture”

A polemic is given regarding the volumetric properties reported in the authors' reply to an earlier commentary. The recalculated partial molar volumes of the individual mixture components, given in the authors' reply, are found to be thermodynamically inconsistent with the experimental excess molar volumes.

Preferential Solvation of 4-Carboxyl-2,6-Dinitrophenylazohydroxynaphthalenes in Aqueous Dimethylformamide and Dimethylsulfoxide Binary Mixtures by UV-VIS Spectroscopy

The objective of this study was to evaluate the influence of partly aqueous solvent mixtures on the solubility and azohydrazone equilibrium processes for a group of phenylazohydroxynaphthalenes, AZ-01, AZ-02, AZ-03, and AZ-04, whose applications as potential color additives and chemosensors have been demonstrated in previous studies. The UV-visible spectrum was acquired between 190–900 nm at concentrations of the dyes that precluded molecular aggregation for each dye in aqueous dimethylformamide and dimethylsulfoxide binary mixtures of varying compositions. The plots of E12 against mole fractions of the co-solvent showed deviation from ideality in the behaviors of the four dyes in the aqueous solvent mixtures. The solvation data were largely influenced by the structural chemistry of the dyes. In particular, AZ-01, which contains a free parahydroxyl group that can donate hydrogen to hydrogen bond acceptor solvents showed substantial bathochromic shifts in the aqueous DMF and DMSO mixtures as well as a local accumulation of the organic solvent in its solvation sphere. Conversely, the positional isomer AZ-02 with its ortho hydroxyl group being involved in intramolecular hydrazone rearrangement exhibited dielectric enrichment in both aqueous solvent mixtures. In addition, synergism through formation of the water–DMSO and water–DMF complexes was observed with all the dyes in the solvent mixtures with AZ-01 being solvated by the more polar component of the complex while AZ-02 and AZ-04 were solvated by the less polar solvent mixture component. Thus, the preferential solvation of the phenylazohydroxynaphthalene series from AZ-01 to AZ-04 in the partly aqueous DMSO and DMF solvent mixtures has been successfully studied using UV-visible spectroscopy.

Reply to “Comments on study of density, dynamic viscosity, excess property and intermolecular interplay studies for 1,4-butanediol + dimethyl sulfoxide binary mixture”

Reply to “Comments on study of density, dynamic viscosity, excess property and intermolecular interplay studies for 1,4-butanediol + dimethyl sulfoxide binary mixture”

Comment on “Density, dynamic viscosity, excess property and intermolecular interplay studies for 1,4-butanediol + dimethyl sulfoxide binary mixture”

A polemic is given regarding the calculated volumetric properties reported by Yue and coworkers for binary mixtures containing 1,4-butanediol and dimethyl sulfoxide. The calculated excess molar volumes reported by the authors for 293.15 K are not thermodynamically consistent with the calculated partial molar volumes of the mixture components. The calculated excess molar volumes at 293.15 K are negative, while the partial molar volumes suggest that the excess molar volumes should be positive. Thermodynamic inconsistencies were found at other temperatures as well.

Density, dynamic viscosity, excess property and intermolecular interplay studies for 1,4-butanediol + dimethyl sulfoxide binary mixture

The density (ρ) and kinematic viscosity (v) in the scope of T = (298.15 to 323.15) K were systemically studied for 1,4-butanediol (BDO) (1) + dimethyl sulfoxide (DMSO) binary mixture with various compositions at atmospheric pressure. From the ρ and v values, the dynamic viscosity (η) were also obtained. According to the above experimental values, viscosity deviation (∆η), excess molar volume (VmE), partial molar volumes (V1¯ and V2¯), apparent molar volume (Vφ,1 and Vφ,2) and isostatic pressing thermal expansion (αp) were determined. The ρ, VmE and ∆η values were fitted by using Jouyban-Acree model, Eyring equation, and Redlich-Kister equation, respectively. Additionally, the intermolecular interplay was analyzed using FTIR, NMR, and UV–vis spectra, which suggested the formation of hydrogen bonds between the hydroxyl H atoms in BDO and the O atoms in DMSO.

Viscosity Coefficients of KCl, NaCl, NaI, KNO3, LiNO3, NaBPh4 and Bu4NI in Water - Dimethyl Sulfoxide Binary Mixtures With a Low Organic Solvent Content

Viscosity Coefficients of KCl, NaCl, NaI, KNO3, LiNO3, NaBPh4 and Bu4NI in Water - Dimethyl Sulfoxide Binary Mixtures With a Low Organic Solvent Content

Kinetics of Fading of Some Triphenylmethane Dyes: Effects of Electric Charge, Substituent, and Aqueous Binary Mixtures of Dimethyl Sulfoxide and 2‐Propanol

ABSTRACTThe rate constants of alkaline fading of a number of triphenylmethane (TPM) dyes including methyl green (ME2+), brilliant green (BG+), fuchsin acid (FA2−), and bromophenol blue (BPB2−) were obtained in aqueous binary mixtures of 2‐propanol (protic solvent) and dimethyl sulfoxide (DMSO) (aprotic solvent) at different temperatures. It was observed that the reaction rate constants of BG+ and ME2+ increased and those of FA2− and BPB2− decreased with an increase in weight percentages of aqueous 2‐propanol and DMSO binary mixtures. 2‐Propanol and DMSO interact with the used TPM molecules through hydrogen bonding and ion–dipole interaction, respectively, in addition to their hydrophobic interaction with TPM dyes. The fundamental rate constants of a fading reaction in these solutions were obtained by the SESMORTAC model. Also, the effect of electric charge and substituent groups of a number of TPM dyes on their alkaline fading rate was studied.

Competitive 7Li NMR study of complexation of different metal ions with tetraethyleneglycol-bis(8-quinolyl) ether in acetonitrile–dimethylsulfoxide and nitromethane–dimethylsulfoxide binary mixtures

7Li NMR spectroscopy was used to determine the stoichiometry and stability of the Li + ion complex with tetraethyleneglycol-bis(8-quinolyl) ether ( L) in acetonitrile–dimethylsulfoxide (97.2:2.8, w/w) and nitromethane–dimethylsulfoxide (97.2:2.8, w/w) binary mixtures. A competitive 7Li NMR spectroscopy was also employed to probe the complexation of Na +, Ag +, Ca 2+, Mg 2+, Zn 2+, Cd 2+, Pb 2+ and UO 2 2+ ions with L in the same solvent systems. The 7Li chemical shift data indicated that all studied cations form 1:1 complexes with the ligand and all the resulting 1:1 complexes in nitromethane–dimethylsulfoxide are more stable than those in acetonitrile–dimethylsulfoxide solution. In both solvent systems, the stability of the resulting complexes was found to vary in the order Ag + > Pb 2+ > Na + > Cd 2+ > Zn 2+ > Li + > Ca 2+ > UO 2 2+ > Mg 2 +.

Thermodynamic Investigation of Dimethyl Sulfoxide Binary Mixtures at 293.15 and 313.15 K

Densities (ρ), speeds of sound (u), and isentropic compressibilities (kS) of binary mixtures of dimethyl sulfoxide (DMSO) with water, methanol, ethanol, 1-propanol, 2-propanol, acetone and cyclohexanone have been measured over the entire composition range at 293.15 and 313.15 K. The excess molar volumes (VE), the deviations in speed of sound (uE) and the deviations in isentropic compressibility (kSE) have been determined. The VE, uE and kSE values were fitted by the Redlich-Kister polynomial equation and the Ak coefficients as well as the standard deviations (d) between the calculated and experimental values have been derived. The results obtained are discussed from the viewpoint of the existence of interactions between the components of the binary mixtures.

Effects of medium on decarboxylation kinetics: 3-carboxybenzisoxazoles and their potential use as environmental probes in biochemistry.

The decarboxylation rate of the tetramethylguanidinium salt of 3-carboxy-6-nitrobenzisoxazole in 24 pure solvents and 36 dimethyl sulfoxide binary mixtures with diglyme, acetonitrile, benzene, dichloromethane, chloroform, and methanol was analyzed in the light of the SPP, SA, and SB pure solvent scales. The results allow one to rationalize the high sensitivity of this kinetics to the reaction medium and to assess the potential use of this compound as a probe in biochemical environments. The natural environment for comparison of this kinetics was found to be the gas phase rather than the aqueous medium. In the latter, the process is much faster owing to such high polarity, which, however, is strongly diminished by the high acidity of the medium. Based on our calculations, the rate constant for the decarboxylation kinetics in the gas phase must be in the region of 2 x 10(-10) s(-1) (i.e., 3 orders of magnitude smaller than in water).