Influence of temperature on the structure of liquid water

Molecular dynamics simulations have been carried out for liquid water at 7 different temperatures to understand the nature of hydrogen bonding at molecular level through the investigation of the effects of temperature on the geometry of water molecules. The changes in bond length and bond angle of water molecules from gaseous state to liquid state have been observed, and the change in the bond angle of water molecules in liquid against temperature has been revealed, which has not been seen in literature so far. The analysis of the radial distribution functions and the coordinate numbers shows that, on an average, each water molecule in liquid acts as both receptor and donor, and forms at least two hydrogen bonds with its neigbors. The analysis of the results also indicates that the water molecules form clusters in liquid.     

Simple modification of the temperature dependence of the Sanchez–Lacombe equation of state

In this work, the interaction energy term of the Sanchez–Lacombe equation of state (SL EOS) was modified to take into account the temperature dependence of hydrogen bonding and ionic interactions. A simple function was used in the form of the Langmuir equation that reduces to the original SL EOS at high temperature. Comparisons are shown between the ?*-modified SL EOS and the original SL EOS. The ?*-modified SL EOS could represent volumetric data for the group of non-polar fluids, polar fluids and ionic liquids to within an absolute average deviation (AAD) of 0.85%, 0.51%, and 0.054%, respectively whereas, the original Sanchez–Lacombe EOS gave AAD values of 0.99%, 1.2%, and 0.21%, respectively. The ?*-modified SL EOS provides remarkably better PVT representation and can be readily applied to mixtures.     

Resolving the controversy on the glass transition temperature of water?

We consider experimental data on the dynamics of water (1) in glass-forming aqueous mixtures with glass transition temperature T(g) approaching the putative T(g) = 136 K of water from above and below, (2) in confined spaces of nanometer in size, and (3) in the bulk at temperatures above the homogeneous nucleation temperature. Altogether, the considered relaxation times from the data range nearly over 15 decades from 10(-12) to 10(3) s. Assisted by the various features in the isothermal spectra and theoretical interpretation, these considerations enable us to conclude that relaxation of un-crystallized water is highly non-cooperative. The exponent β(K) of its Kohlrausch stretched exponential correlation function is not far from having the value of one, and hence the deviation from exponential time decay is slight. Albeit the temperature dependence of its α-relaxation time being non-Arrhenius, the corresponding T(g)-scaled temperature dependence has small steepness index m, likely less than 44 at T(g), and hence water is not "'fragile" as a glassformer. The separation in time scale of the α- and the β-relaxations is small at T(g), becomes smaller at higher temperatures, and they merge together shortly above T(g). From all these properties and by inference, water is highly non-cooperative as a glass-former, it has short cooperative length-scale, and possibly smaller configurational entropy and change of heat capacity at T(g) compared with other organic glass-formers. This conclusion is perhaps unsurprising because water is the smallest molecule. Our deductions from the data rule out that the T(g) of water is higher than 160 K, and suggest that it is close to the traditional value of 136 K.     

Mechanism of the molecular mobility of water in the temperature range 298–359 K

The Raman spectra of liquid water in the region of O-H stretching vibrations were obtained in the temperature range 298–359 K. The Raman spectra were decomposed into the components using the XPSPEAK-4.1 program, and their temperature dependence was evaluated. The number of bifurcate hydrogen bonds and the percentage of rotational conformers containing bifurcate bonds were shown to increase with temperature. The defect mechanism of the molecular mobility of water on the hydrogen bond network in the temperature range 298–359 K was proposed.     

Effect of temperature and pH on the aggregation and the surface hydrophobicity of bovine κ-casein

κ-Casein (κ-CN) aggregation by heating has been studied at pH 7.2 and 5.2 using UV-visible spectrophotometry, sodium dodecyl sulfate polyacrylamide gel electrophoresis, spectrofluorometric study of the 1–8 aniline naphtalene sulfonate (ANS)–κ-CN binding and circular dichroism (CD) spectroscopy. The aggregation process to form aggregates like micelles or submicelles and the structural characteristics of these aggregates were pH dependent. Far-UV CD showed that the aggregates obtained by heating presented changes in the κ-CN secondary structure. Near-UV CD spectra showed a certain degree of tertiary organization in the Tyr environment for the protein heated or unheated, only at pH 5.2. ANS binding at both pH was quite different and depends on the self-association process. Heating produced exposition of hydrophobic binding sites only at pH 7.2, including those in the neighborhood of the κ-CN Trp residue.     

Stabilization of the γ form of the rare earth sesquisulfides at lower temperature by doping with Calcium

The preparation of several samples forming a solid solution that can be formulated as Ca_(3/2)yR_2−y_{0.25−(1/2)y}S₃ (R = Ce, Sm, Gd) (0 ≤ y ≤ 0.30) is reported, together with their structural characterization, mainly through transmission electron microscopy. The introduction of Ca²⁺ into the rare earth metal sesquisulfide matrix stabilizes the γ form phase at 900 °C. This effect can be related to the non-stoichiometric nature of this phase, R_3−x_xS₄, because the introduction of Ca²⁺ requires the elimination of cation vacancies from the structure: 2R³⁺ + → 3Ca²⁺ (R = rare earth metal;  = cation vacancies). However, a NaCl-type solid solution is formed for R = Eu, formulated as Eu_1−yCa_yS. Well-ordered crystals are found in every sample, as it is revealed by transmission electron microscopy images and diffraction patterns. The color properties of the samples have been evaluated with reflectance spectra in the visible range and with L*–a*–b* coordinates.     

Are the integrated absorption coefficients temperature dependent? FT-NIR study of the first overtone of the OH stretching mode of octanoic acid

The integrated molar absorption coefficients of the first overtone of an OH stretching mode of free octanoic acid were determined through a series of FT-NIR measurements in a CCl₄ solution at different temperatures. A few methods of calculation of the molar absorption coefficient were applied; the results were compared and discussed. It was shown that not all of the methods can be applied for the calculation if the plot of Beer's law does not pass through the origin. The results clearly show that the integrated molar absorption coefficient is strongly temperature dependent; its value increases approximately 0.6 dm³ mol⁻¹ cm⁻¹ per one degree and the use of a constant value of the coefficient through a temperature range may lead to significant errors.     

Phase diagram of the eutectic benzoic acid-naphthalene system in the temperature range of 300–400 K

Liquid-solid phase equilibria are studied in the eutectic benzoic acid-naphthalene system by means of thermic analysis (DTA, CTA), on the basis of which the liquidus line and eutectic point (x _e ≈ 50 mol %, T _e ± 340 K) are determined and the phase diagram is constructed. Average precrystallization supercooling temperatures ΔT _L ^? of the liquid phase relative to liquidus temperature T _L are determined, allowing us to locate the region of solution metastability on the phase diagram. Excessive functions of the components in the liquid phase are found via thermodynamic modeling using the Margules equation and experimental data. The boundaries of the region of liquid solution metastability are estimated from the thermodynamic conditions of solution stability.     

Investigation of the electrical resistance of single-walled carbon nanotube films in the temperature range 4.2–290 K

Electrical resistance of films made of the source material and purified HiPCO and Arc single-walled carbon nanotubes (SWCNTs) with a thickness of 20−40 μm is 2.4 to 45 Ω (electrical conductivity of 0.42 × 10³ to 5.03 × 10³ S/m) at room temperature. The films have been formed by vacuum microfiltration of SWCNT suspensions in toluene and characterized by Raman and X-ray photoelectron spectroscopy and scanning electron microscopy. The conductivity of the films at room temperature depends on the type and degree of purity of the material of nanotubes. The resistance of the films decreases with the increasing temperature over the range of 4.2–290 K, and the rate of the step-down decreases with increasing purity of the material of the nanotubes. The conductivity of the films is semiconducting in character, and the electron transport is consistent with three-dimensional hopping conductivity.     

Kinetics of the reaction of CF3 with O2 over the temperature range 233–373 K

The rate constant of the reaction CF₃ + O₂ + M → CF₃O₂ + M has been measured as a function of temperature in the fall-off region between 1 and 10 Torr, by laser photolysis and time-resolved mass spectrometry. The values of the fall-off parameters measured at room temperature are in good agreement with previous values and the temperature dependence of k₁₍₀₎ is reasonably well accounted for by the theoretical analysis proposed by Troe and co-workers. With M = N₂k₁₍₀₎ = (1.9 ± 0.2) × 10⁻²⁹ (T/298)^{(−4.7 ± 0.4)} cm⁶ molecule⁻² s⁻¹. Reliable values of k_1(∞) cannot be derived from these low pressure measurements. The rate expression proposed, k_1(∞) = (9 ± 2) X 10⁻¹² (T/298)^(0±1) cm³ molecule⁻¹ s⁻¹, is consistent with a “broadening parameter” of the form F_c = exp(−T/395) and previous values reported at room temperature.     

The influence of the temperature on the liquid–liquid equlibria of the mixture limonene + ethanol + H2O

In this work, experimental liquid–liquid equilibria (LLE) of the limonene + ethanol + water system are presented. The LLE of this system has been measured at 293.15, 303.15, 313.15 and 323.15 K. The equilibrium data presented are correlated using NRTL and UNIQUAC equations. Finally, the reliability of these models is tested by comparison with experimental results.     

The influence of the temperature on the liquid–liquid equilibrium of the ternary system 1-pentanol–ethanol–water

Liquid–liquid equilibrium data for the ternary system 1-pentanol–ethanol–water have been determined experimentally at 25, 50, 85 and 95°C. These results have been correlated simultaneously by the uniquac method obtaining two sets of interaction parameters: one of them independent of the temperature and the other with a linear dependence. Both sets of parameters fit the experimental results well.     

Resonance of relaxation time in the temperature modulated Schlögl model

We show the possibility to accelerate-in a resonant way-a nonlinear chemical reaction by imposing a small temperature modulation. This classical resonance, which happens for particular modulation frequencies, is illustrated on the athermic cubic Schlogl model, which allows us to get analytical expressions for both the reaction relaxation time and the frequency-resonant delay.     

Modification of the Peng–Robinson equation of state for helium in low temperature regions

Helium shows the nearest behaviour to ideal gas in the room conditions. In contrast, thermodynamic behaviour of helium in the critical region, in which its liquefaction is possible, is extremely complicated. The equation of state (EOS), which is in common use for helium, is the modified Benedict–Webb–Rubin (MBWR) EOS developed by McCarty and Arp which is a 13th-order equation with 32 substance-dependent parameters. MBWR is a complicated EOS and its use is time consuming. In this work, the modified Peng–Robinson EOS introduced by Feyzi et al. is customised with 10 adjustable parameters for helium in the temperature range of 2.20–15.20 K and pressures up to 16 bar. The proposed EOS is able to predict the properties of helium in the vapour–liquid equilibrium (VLE) conditions and in the single gas-phase region. In addition, a temperature-dependent correlation for constant pressure heat capacity of helium from very low up to normal temperatures is proposed. The liquefaction process of helium, which is being done by cooling it to very low temperatures by passing through a Joule–Thomson valve, is predicted by the proposed EOS. Very accurate results are observed.     

Room temperature phosphorescence of α-bromonaphthalene induced by β-cyclodextrin in the presence of cyclohexane

β-Cyclodextrin (β-CD) can induce a-bromonaphthalene (BrN) to emit strong room temperature phosphorescence (RTP) in the presence of micro amounts of cyclohexane (c-hexane). Experiments of luminescence spectra, phosphorescence lifetime and fluorescence polarization prove the formation of c-hexane/β-CD/BrN ternary inclusion complex. The apparent formation constant of the ternary inclusion complex was determined and the effect mechanism of c-hexane on the RTP of BrN induced by β-CD is discussed.     

Influence of organic modifier and temperature on the enantiomeric separation of γ-lactams by HPLC

Summary A high-performance liquid chromatographic method is reported for the resolution of the enantiomers of a series of fused -lactams (2,7-diaza-3-oxo[3.3.0]octan-6-ones) with probable anti-HIV and anticancer activity. Resolution was achieved on a Chiralcel^® OD column, cellulose tris-(3,5-dimethylphenyl carbamate) adsorbed on macroporous silica gel; mixtures ofn-hexane and isopropyl alcohol in different proportions were used as the mobile phase. The analysis was studied at different temperatures.     

On the continuity of the diffusion behaviour at amorphous polymer–polymer interfaces on both sides of the bulk glass transition temperature

The diffusion behaviour at amorphous polystyrene (PS)–PS interfaces has been investigated over an interval of temperatures (T) from below to above the bulk glass transition temperature (T _g ^bulk) using the Arrhenius and Vogel-Fulcher approaches. No discontinuity in the variation of the logarithm of the diffusion coefficient versus 1/T has been observed when going through the PS T _g ^bulk over a broad interval of T, from T _g ^bulk???50 °C to T _g ^bulk?+?50 °C. The molecular mechanism of interdiffusion has been discussed.     

Estimation of the normal boiling points of water and 1,2-dimethoxyethane through the viscosity–temperature dependence in the corresponding binary mixtures

Excess quantities calculated from literature values of experimental density and viscosity in 1,2-dimethoxyethane + water binary systems (from 303.15 to 323.15 K) can lead us to test different correlation equations as well as their corresponding derivative properties. Inspection of the Arrhenius activation energy (Ea) and the enthalpy of activation of viscous flow (ΔH*) shows very close values; here, we can define partial molar activation energies Ea₁ and Ea₂ for 1,2-dimethoxyethane and water, respectively, along with their individual contribution separately. Correlation between the two Arrhenius parameters of viscosity in all compositions shows existence of main distinct interaction behaviours delimited by particular mole fractions in 1,2-dimethoxyethane. Moreover, we add that correlation between Arrhenius parameters reveals interesting Arrhenius temperature which is closely related to the vapourisation temperature in the liquid vapour equilibrium, and the limiting corresponding partial molar properties can permit us to estimate the boiling points of the pure components.     

Topological transformation of the phase diagram of a potassium perchlorate-water-tetrahydrofuran ternary system in the temperature range of 40 to 140°C

Phase equilibria and critical phenomena in a potassium perchlorate-water-tetrahydrofuran ternary system are studied by visual polythermal means in the range of 40 to 140°C; the solubility diagram of the liquid subsystem is characterized by the presence of isolated binodal curve. The temperature of formation for the critical node of the monotectic state (107.3°C) and the dependences of the composition that corresponds to the critical points of solubility in the delayering field vs. temperature in the ranges of 70.3 to 107.3°C and 137.1 to 140.2°C are determined. The topological transformation of the investigated ternary system’s phase diagram upon a change in temperature is studied using isothermal sections of the system’s temperature concentration prism, plotted at nine temperatures. It is found that potassium perchlorate has only a salting-in effect on mixtures of water and tetrahydrofuran at temperatures below 107.3°C; at higher temperatures, it has both a salting-in and a salting-out effect, depending on its concentration and the composition of mixed solvent. It is shown that potassium perchlorate’s effect of salting tetrahydrofuran out of aqueous solutions grows slightly with an increase in temperature.