Andreas P. Fröba

Density, refractive index, interfacial tension, and viscosity of ionic liquids [EMIM][EtSO4], [EMIM][NTf2], [EMIM][N(CN)2], and [OMA][NTf2] in dependence on temperature at atmospheric pressure.

The density, refractive index, interfacial tension, and viscosity of ionic liquids (ILs) [EMIM][EtSO 4] (1-ethyl-3-methylimidazolium ethylsulfate), [EMIM][NTf 2] (1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), [EMIM][N(CN) 2] (1-ethyl-3-methylimidazolium dicyanimide), and [OMA][NTf 2] (trioctylmethylammonium bis(trifluoromethylsulfonyl)imide) were studied in dependence on temperature at atmospheric pressure both by conventional techniques and by surface light scattering (SLS). A vibrating tube densimeter was used for the measurement of density at temperatures from (273.15 to 363.15) K and the results have an expanded uncertainty ( k = 2) of +/-0.02%. Using an Abbe refractometer, the refractive index was measured for temperatures between (283.15 and 313.15) K with an expanded uncertainty ( k = 2) of about +/-0.0005. The interfacial tension was obtained from the pendant drop technique at a temperature of 293.15 K with an expanded uncertainty ( k = 2) of +/-1%. For higher and lower temperatures, the interfacial tension was estimated by an adequate prediction scheme based on the datum at 293.15 K and the temperature dependence of density. For the ILs studied within this work, at a first order approximation, the quantity directly accessible by the SLS technique was the ratio of surface tension to dynamic viscosity. By combining the experimental results of the SLS technique with density and interfacial tension from conventional techniques, the dynamic viscosity could be obtained for temperatures between (273.15 and 333.15) K with an estimated expanded uncertainty ( k = 2) of less than +/-3%. The measured density, refractive index, and viscosity are represented by interpolating expressions with differences between the experimental and calculated values that are comparable with but always smaller than the expanded uncertainties ( k = 2). Besides a comparison with the literature, the influence of structural variations on the thermophysical properties of the ILs is discussed in detail. The viscosities mostly agree with values reported in the literature within the combined estimated expanded uncertainties ( k = 2) of the measurements while our density and interfacial tension data differ by more than +/-1% and +/-5%.

Density and Surface Tension of Ionic Liquids

We measured the density and surface tension of 9 bis[(trifluoromethyl)sulfonyl]imide ([Tf(2)N](-))-based and 12 1-methyl-3-octylimidazolium ([C(8)C(1)Im](+))-based ionic liquids (ILs) with the vibrating tube and the pendant drop method, respectively. This comprehensive set of ILs was chosen to probe the influence of the cations and anions on density and surface tension. When the alkyl chain length in the [C(n)C(1)Im][Tf(2)N] series (n = 1, 2, 4, 6, 8, 10, 12) is increased, a decrease in density is observed. The surface tension initially also decreases but reaches a plateau for alkyl chain lengths greater than n = 8. Functionalizing the alkyl chains with ethylene glycol groups results in a higher density as well as a higher surface tension. For the dependence of density and surface tension on the chemical nature of the anion, relations are only found for subgroups of the studied ILs. Density and surface tension values are discussed with respect to intermolecular interactions and surface composition as determined by angle-resolved X-ray photoelectron spectroscopy (ARXPS). The absence of nonvolatile surface-active contaminants was proven by ARXPS.

Saturated Liquid Viscosity and Surface Tension of Alternative Refrigerants

Light scattering by thermally excited capillary waves on liquid surfaces or interfaces can be used for the investigation of viscoelastic properties of fluids. In this work, we carried out the simultaneous determination of the surface tension and the liquid kinematic viscosity of some alternative refrigerants by surface light scattering (SLS) on a gas–liquid interface. The experiments are based on a heterodyne detection scheme and signal analysis by photon correlation spectroscopy (PCS). R23 (trifluoromethane), R32 (difluoromethane), R125 (pentafluoroethane), R143a (1,1,1-trifluoroethane), R134a (1,1,1,2-tetrafluoroethane), R152a (1,1-difluoroethane), and R123 (2,2-dichloro-1,1,1-trifluoroethane) were investigated under saturation conditions over a wide temperature range, from 233 K up to the critical point. It is estimated that the uncertainty of the present surface tension data for the whole temperature range is less than ±0.2 mN·m−1. For temperatures up to about 0.95Tc, the kinematic viscosity of the liquid phase could be obtained with an absolute accuracy of better than 2%. For the highest temperatures studied in this work, measurements for the kinematic viscosity exhibit a maximum uncertainty of about ±4%. Viscosity and surface tension data are represented by a polynomial function of temperature and by a van der Waals-type surface tension equation, respectively. The results are discussed in detail with comparison to literature data.

Accurate Determination of Liquid Viscosity and Surface Tension Using Surface Light Scattering (SLS): Toluene Under Saturation Conditions Between 260 and 380 K

Earlier reported values of the liquid kinematic viscosity and surface tension of the reference fluid toluene between 263 and 383 K under saturation conditions from surface light scattering have been recalculated. For this, an improved data evaluation scheme based on an exact description of the hydrodynamic capillary wave problem for a liquid-vapor interface has been applied. The maximum adjustments amount to 0.9 and 0.6% for the liquid kinematic viscosity and surface tension, respectively. These changes are within the uncertainties as stated in our original work which demonstrates that for the surface light scattering technique a total uncertainty of better than 1.0% for both properties of interest also holds for the revised data of the present work. Thus, in spite of the additional complexity connected with this very precise data evaluation procedure presented here, the surface light scattering technique could still be used with less complexity for a reliable determination of surface tension and liquid kinematic viscosity with an accuracy comparable or even better than that of conventional methods. While almost all of these conventional methods determine viscosity and surface tension in a relative manner with two completely different sets of experimental equipment, for the surface light scattering technique no calibration procedure is needed and both properties can be determined simultaneously without any extra effort.

Thermophysical properties of the ionic liquids [EMIM][B(CN)4] and [HMIM][B(CN)4].

In the present study, the thermophysical properties of the tetracyanoborate-based ionic liquids (ILs) 1-ethyl-3-methylimidazolium tetracyanoborate ([EMIM][B(CN)4]) and 1-hexyl-3-methylimidazolium tetracyanoborate ([HMIM][B(CN)4]) obtained by both experimental methods and molecular dynamics (MD) simulations are presented. Conventional experimental techniques were applied for the determination of refractive index, density, interfacial tension, and self-diffusion coefficients for [HMIM][B(CN)4] at atmospheric pressure in the temperature range from 283.15 to 363.15 K. In addition, surface light scattering (SLS) experiments provided accurate viscosity and interfacial tension data. As no complete molecular parametrization was available for the MD simulations of [HMIM][B(CN)4], our recently developed united-atom force field for [EMIM][B(CN)4] was partially transferred to the homologous IL [HMIM][B(CN)4]. Deviations between our simulated and experimental data for the equilibrium properties are less than ±0.3% in the case of density and less than ±8% in the case of interfacial tension for both ILs. Furthermore, the calculated and measured data for the transport properties viscosity and self-diffusion coefficient are in good agreement, with deviations of less than ±30% over the whole temperature range. In addition to a comparison with the literature, the influence of varying cation chain length on thermophysical properties of [EMIM][B(CN)4] and [HMIM][B(CN)4] is discussed.

On the characteristics of ion implanted metallic surfaces inducing dropwise condensation of steam.

The present work provides new information on the characteristics of ion implanted metallic surfaces responsible for the adjustment of stable dropwise condensation (DWC) of steam. The results are based on condensation experiments and surface analyses via contact angle (CA) and surface free energy (SFE) measurements as well as scanning electron microscopy (SEM). For studying possible influences of the base material and the implanted ion species, commercially pure titanium grade 1, aluminum alloy Al 6951, and stainless steel AISI 321 were treated with N(+), C(+), O(+), or Ar(+) using ion beam implantation technology. The studies suggest that chemically inhomogeneous surfaces are instrumental in inducing DWC. As this inhomogeneity is apparently caused by particulate precipitates bonded to the metal surface, the resulting nanoscale surface roughness may also influence the condensation form. On such surfaces nucleation mechanisms seem to be capable of maintaining DWC even when CA and SFE measurements indicate increased wettability. The precipitates are probably formed due to the supersaturation of ion implanted metal surfaces with doping elements. For high-alloyed materials like AISI 321 or Hastelloy C-276, oxidation stimulated by the condensation process obviously tends to produce similar surfaces suitable for DWC.

Thermal Diffusivity and Sound Velocity of Toluene Over a Wide Temperature Range

The thermal diffusivity and the sound velocity of toluene have been determined in a wide temperature range up to the critical point by dynamic light scattering. Measurements were performed for both the liquid and the vapor phase at saturation conditions. The results obtained corroborate the usefulness of the technique for the determination of thermophysical properties. From the lack of reference data for the thermal diffusivity or other properties from which the thermal diffusivity may be derived in the high-temperature range and from deviations of experimental sound velocity data compared to values derived from the currently established equation of state, the need for further experimental investigations on this important reference fluid was established.

Improvement of Condensation Heat Transfer by Surface Modifications

Condensation processes are of importance for many heat transfer applications where a large amount of energy has to be transferred by a working fluid using the latent heat available during the phase transition. Whether ideal dropwise or filmwise condensation or a mixed condensation form can be realized depends on the properties of the heat transfer surface. The quantities that mainly influence the condensation form are the surface tension of the condensing fluid, the surface roughness or structure, and the surface energy of the condenser surface. During the past two decades at LTT-Erlangen, experimental and theoretical work has been carried out to reduce the surface energy of common heat transfer surfaces in such a way that stable dropwise condensation can be reached and maintained for extended time periods. In this situation, heat transfer is superior to filmwise condensation for at least one order of magnitude. The methods that have been developed and extensively tested for a selective adjustment of dropwise condensation of water at metallic surfaces are surface coating by diamond-like carbon films (DLC) and ion implantation. For both methods, the principles and fundamental experimental investigations are explained, and for ion implantation, a technical utilization is presented in the form of its application to sea water desalination plants based on mechanical vapor compression.

Thermophysical Properties of Binary and Ternary Fluid Mixtures from Dynamic Light Scattering

Several thermophysical properties of R507, a binary refrigerant mixture, and R404A, a ternary mixture, have been determined by dynamic light scattering (DLS), in both the liquid and the vapor states, along the saturation line approaching the vapor–liquid critical point. Data for the thermal diffusivitya and sound speed cS cover a range of temperatures down to 270K, and data for the surface tension σ and kinematic viscosity ν down to 230K. For both mixtures the behavior of all properties determined can be correlated well by the mass-weighted sum of the respective pure component data, when all data are represented as a function of the reduced temperature.

Diffusion Modes of an Equimolar Methane–Ethane Mixture from Dynamic Light Scattering

The hydrodynamic diffusion modes of an equimolar methane–ethane mixture have been investigated by dynamic light scattering. Measurements were performed over a wide temperature range between the plait critical point at 263.55 K and 310 K along the critical isochore. Two relaxation modes have been observed which are commonly associated with pure mass diffusion and pure thermal diffusion, but in near-critical binary fluid mixtures—according to recent theory—may alternatively be interpreted as two effective diffusivities resulting from a coupling between mass and thermal diffusion. Diffusivity values for the slow mode were obtained with typical standard deviations of 1% over the whole temperature range, whereas the low amplitude of the fast mode only allowed values of this component with a large measurement uncertainty. The results are discussed in connection with literature data available for the thermophysical properties of this binary fluid mixture and regarding the various possibilities of theoretical interpretation.