Marzena Dzida

A high pressure device for measurements of the speed of sound in liquids

A new measuring set for measurements of the speed of sound in liquids under high pressures (up to 300 MPa), designed and constructed in our laboratory, is described. It operates on the principle of the pulse-echo-overlap method. A single transmitting–receiving piezoelectric ceramic transducer operating at 4 MHz and an acoustic reflector were applied. Details concerning the designing and operation of all the elements of the acoustic path, assuring high accuracy of the speed measurements, are given.

Structure and thermal properties of salicylate-based-protic ionic liquids as new heat storage media. COSMO-RS structure characterization and modeling of heat capacities

During this research, we present a study on the thermal properties, such as the melting, cold crystallization, and glass transition temperatures as well as heat capacities from 293.15 K to 323.15 K of nine in-house synthesized protic ionic liquids based on the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate ([H-Im-C1OC(n)][Sal]) with n = 3-11. The 3D structures, surface charge distributions and COSMO volumes of all investigated ions are obtained by combining DFT calculations and the COSMO-RS methodology. The heat capacity data sets as a function of temperature of the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate are then predicted using the methodology originally proposed in the case of ionic liquids by Ge et al. 3-(Alkoxymethyl)-1H-imidazol-3-ium salicylate based ionic liquids present specific heat capacities higher in many cases than other ionic liquids that make them suitable as heat storage media and in heat transfer processes. It was found experimentally that the heat capacity increases linearly with increasing alkyl chain length of the alkoxymethyl group of 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate as was expected and predicted using the Ge et al. method with an overall relative absolute deviation close to 3.2% for temperatures up to 323.15 K.

Isolation of hydrocarbon-degrading and biosurfactant-producing bacteria and assessment their plant growth-promoting traits

Forty-two hydrocarbon-degrading bacterial strains were isolated from the soil heavily contaminated with petroleum hydrocarbons. Forty-one strains were identified based on their whole-cell fatty acid profiles using the MIDI-MIS method. Thirty-three of them belong to species Rhodococcus erythropolis, while the others to the genera Rahnella (4), Serratia (3) and Proteus (1). Isolates were screened for their ability to produce biosurfactants/bioemulsifiers. For all of them the activity of several mechanisms characteristic for plant growth-promoting bacteria was also determined. In order to investigate surface active and emulsifying abilities of isolates following methods: oil-spreading, blood agar, methylene blue agar and determination of emulsification index, were used. Among studied bacteria 12 strains (CD 112, CD 126, CD 131, CD 132, CD 135, CD 147, CD 154, CD 155, CD 158, CD 161, CD 166 and CD 167) have been chosen as promising candidates for the production of biosurfactants and/or bioemulsifiers. Among them 2 strains (R. erythropolis CD 126 and Rahnella aquatilis CD 132) had the highest potential to be used in the bioaugmentation of PH-contaminated soil. Moreover, 15 of tested strains (CD 105, CD 106, CD 108, CD 111, CD 116, CD 120, CD 124, CD 125, CD 130, CD 132, CD 134, CD 154, CD 156, CD 161 and CD 170) showed the activity of four mechanisms (ACC deaminase activity, IAA and siderophore production, phosphate solubilization) considered to be characteristic for plant growth-promoting bacteria. Two of them (R. erythropolis CD 106 and R. erythropolis CD 111) showed the highest activity of above-mentioned mechanisms and thus are considered as promising agents in microbe assisted phytoremediation.

Speed of Sound and Ultrasound Absorption in Ionic Liquids

A complete review of the literature data on the speed of sound and ultrasound absorption in pure ionic liquids (ILs) is presented. Apart of the analysis of data published to date, the significance of the speed of sound in ILs is regarded. An analysis of experimental methods described in the literature to determine the speed of sound in ILs as a function of temperature and pressure is reported, and the relevance of ultrasound absorption in acoustic investigations is discussed. Careful attention was paid to highlight possible artifacts, and side phenomena related to the absorption and relaxation present in such measurements. Then, an overview of existing data is depicted to describe the temperature and pressure dependences on the speed of sound in ILs, as well as the impact of impurities in ILs on this property. A relation between ions structure and speeds of sound is presented by highlighting existing correlation and evaluative methods described in the literature. Importantly, a critical analysis of speeds of sound in ILs vs those in classical molecular solvents is presented to compare these two classes of compounds. The last part presents the importance of acoustic investigations for chemical engineering design and possible industrial applications of ILs.

Ultrasonic Relaxation Study of 1-Alkyl-3-methylimidazolium-Based Room-Temperature Ionic Liquids: Probing the Role of Alkyl Chain Length in the Cation

Ultrasound absorption spectra of four 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides were determined as a function of the alkyl chain length on the cation from 1-propyl to 1-hexyl from 293.15 to 323.15 K at ambient pressure. Herein, the ultrasound absorption measurements were carried out using a standard pulse technique within a frequency range from 10 to 300 MHz. Additionally, the speed of sound, density, and viscosity have been measured. The presence of strong dissipative processes during the ultrasound wave propagation was found experimentally, i.e., relaxation processes in the megahertz range were observed for all compounds over the whole temperature range. The relaxation spectra (both relaxation amplitude and relaxation frequency) were shown to be dependent on the alkyl side chain length of the 1-alkyl-3-methylimidazolium ring. In most cases, a single-Debye model described the absorption spectra very well. However, a comparison of the determined spectra with the spectra of a few other imidazolium-based ionic liquids reported in the literature (in part recalculated in this work) shows that the complexity of the spectra increases rapidly with the elongation of the alkyl chain length on the cation. This complexity indicates that both the volume viscosity and the shear viscosity are involved in relaxation processes even in relatively low frequency ranges. As a consequence, the sound velocity dispersion is present at relatively low megahertz frequencies.

High Pressure Thermodynamic and Acoustic Properties of Decan-1-ol + Heptane Mixtures. A Theoretical and Experimental Study

This paper reports a theoretical study of decan-1-ol+heptane and ethanol+heptane systems and experimental data of decan-1-ol+heptane mixtures as a function of temperature and pressure over the whole composition range. The ability of the modifications introduced into the original ERAS model in determining thermodynamic excess properties of decan-1-ol+heptane and ethanol+heptane mixtures at high pressures is tested. This model was found to be sufficient for describing semiquantitatively excess volumes and excess enthalpies and qualitatively excess heat capacities under high pressure. The densities and speeds of sound in decan-1-ol+heptane mixtures were measured over the whole concentration range within the temperature interval from 293 to 318 K at atmospheric pressure and at pressures up to 101 MPa, respectively. The densities, heat capacities and appropriate excesses of these binaries were calculated for the same temperatures and pressures up to 100 MPa. In the calculations the acoustic method was applied. The effects of pressure and temperature on the excess volume, excess enthalpy, and the excess heat capacity of decan-1-ol+heptane mixtures are analyzed and compared with those of ethanol + heptane and dodecane+heptane mixtures. Properties of the alkan-1-ol+alkane mixtures are explained in terms of the self-association of the alkanols, free volume effect and the nonspecific interactions between the alcohol and heptane basing on the results obtained from the modified ERAS model.

Compressibility and Dielectric Relaxation of Mixtures of Water with Monohydroxy Alcohols.

Isentropic compressibility data and principal dielectric relaxation times, mostly for normal alcohols and for mixtures of monohydroxy alcohols with water, are evaluated and compared to one another. It is found that the microdynamics of the liquids, as reflected by the dielectric relaxation times, can be generally explained in the light of a defect diffusion model. Within the framework of that model, the principal relaxation time is predominantly controlled by the local concentration of hydrogen bonding sites. The alkyl groups of the alcohols are shown to have a 2-fold influence by reducing the concentration of the H-bonding sites and by also contributing to the activation enthalpy of relaxation. The effect of alkyl groups on the compressibility is quite different. The compressibility of methanol exceeds that of water by a substantial amount. Within the series of normal alcohols, in correspondence with the behavior of normal alkanes, the liquids become less compressible with increasing alkyl chain length. Relative molal shifts Bκ and Bd of the compressibility and dielectric relaxation time, respectively, of dilute solutions of alcohols in water are consistent with the behavior of aqueous solutions of other organic solutes. The Bd values increase with hydrophobic character of the solute (ΔBd = 0.045 (mol/kg)(-1) for an additional methyl group per solute molecule or organic ion), whereas Bκ decreases (ΔBκ = -0.012 (mol/kg)(-1)). Reduced orientational mobility combined with decreased compressibility appears to be characteristic of hydration shells around hydrophobic solutes.

Supramolecular structure fluctuations of an imidazolium-based protic ionic liquid

At 20, 25, 30, and 40 °C, the ultrasonic absorption spectra of the protic ionic liquid 3-(butoxymethyl)-1H-imidazol-3-ium salicylate have been measured between 0.6 and 900 MHz. Below 250 MHz, the absorption coefficient decreases with temperature, potentially indicating a major effect of the viscosity and/or a relaxation time. Essentially the broad spectra can be favorably represented by two relaxation terms in addition to an asymptotic high-frequency contribution. One term reflects an asymmetric relaxation time distribution. It is described by a model of noncritical fluctuations in the structure and thermodynamic parameters of the liquid in order to yield the fluctuation correlation length and the mutual diffusion coefficient. Applying the Stokes-Einstein-Kawasaki-Ferrell relation, these quantities can be used to show that the effective shear viscosity controlling the fluctuations is substantially smaller than the steady-state shear viscosity. This result is consistent with dispersion in the shear viscosity as revealed by viscosity measurements at 25, 55, and 81 MHz. The other term can be well described by a Debye-type relaxation function. It has been tentatively assigned to a structural isomerization of the butoxymethyl chain of the imidazole molecule. However, it cannot be completely excluded that this term reflects, at least in parts, a Brønstedt acid-base equilibrium or a specific association process.

Ultrasonic Relaxation Spectra for Pyrrolidinium Bis(trifluoromethylsulfonyl)imides: A Comparison with Imidazolium Bis(trifluoromethylsulfonyl)imides

Ultrasound absorption spectra within the frequency range 10-300 MHz were determined for 1-propyl- and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imides at ambient pressure and at temperatures in the ranges 293.15-313.15 and 293.15-323.15 K, respectively. For both compounds, a single Debye model (relaxation times between 0.451 and 0.778 ns) thoroughly describes the observed ultrasound absorption spectra in the investigated ranges. The spectra resemble those observed for imidazolium-based ionic liquids with the same anion. The ultrasound relaxation is dependent on the alkyl chain length of pyrrolidinium ring. In comparison to adequate imidazolium-based bis(trifluoromethylsulfonyl)imides, the relaxation in pyrrolidinium-based bis(trifluoromethylsulfonyl)imides is stronger; the pyrrolidinium cation causes clearly greater absorption than the imidazolium cation. Also, estimated ultrasound velocity dispersion is stronger in the case of pyrrolidinium imides in comparison to imidazolium imides. In turn, comparison of the ultrasonic data and literature data for the dielectric spectra exemplified for the 1-butyl- side chain in the cation indicates strong coupling in the case of imidazolium ring and weak coupling in the case of pyrrolidinium ring. The effect of absorption on the speed of sound is also discussed.