Two-Phase Isochoric Heat Capacity Measurements for Nitrogen Tetroxide in the Critical Region and Yang–Yang Relation

The two-phase isochoric heat capacity of nitrogen tetroxide was measured in the temperature range from 261.74 K to the critical temperature (431.072 K) at densities between 201.21 and 1426.5 kg·m^–3 using a high-temperature and high-pressure adiabatic calorimeter. The measurements were performed in the two-phase region for 26 isochores (15 liquid and 11 vapor densities) including the coexistence curve and critical region. Uncertainties of the measurements are estimated to be 2%. The original temperatures and C _V data were converted to the ITS-90. The liquid and vapor two-phase isochoric heat capacities, temperatures, and densities at saturation were extracted from experimental data for each measured isochore. From measured (T _S, _S, C _V2, C _V2) data, the values of second temperature derivatives of vapor-pressure d ² P _S/dT ² and chemical potential d ² /dT ² were derived using the Yang–Yang relation. The results were compared with values calculated from other vapor-pressure equations. The values of saturated densities and critical parameters derived in calorimetric experiments were compared with literature data. The unusual temperature behavior of d ² P _S/dT ² and d ² /dT ² was found at low temperatures around 351 K and near the critical point.     

The structural treatment of a number of effective centers of polymeric chains in the process of the thermooxidative degradation

It is shown that the effective number of the polymeric macromolecule reactive centers depends on the macromolecular coil structure. The quantitative characteristic of the latter one can be received within the framework of the fractal analysis. The increase in macromolecular coil fractal dimension, meaning the rise of a degree of its compactness, results in lowering the effective number of the reactive (accessible to the molecules of oxidant) sites of a polymeric macromolecule. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1764–1767, 2003     

Sustained hydrogen photoproduction by phosphorus-deprived Chlamydomonas reinhardtii cultures

This study demonstrates that, besides sulfur deprivation, sustained H₂ photoproduction in Chlamydomonas reinhardtii cultures can be generated by incubating algae under phosphorus-deprived (−P) conditions. However, phosphorus deficiency in algal cells could not be obtained by resuspension of algae in −P medium, evidently due to a significant reserve of phosphorus in cells. In this study, phosphorus deficiency was accomplished by inoculating the washed algae into the −P medium at low initial cell densities (below 2 mg Chl l⁻¹). After the initial growth period, where cells utilize intracellular phosphorus, algae established anaerobic environment followed by the period of H₂ photoproduction. The maximum H₂ output (∼70 ml l⁻¹) was obtained in cultures with the initial Chl content ∼1 mg l⁻¹. Cultures with Chl above 2 mg l⁻¹ did not produce H₂ gas. The physiological response of algal cultures to phosphorus deprivation demonstrated significant similarities with the response of algae to sulfur depletion.     

Sustainable Hydrogen Photoproduction by Phosphorus-Deprived Marine Green Microalgae Chlorella sp.

Previously it has been shown that green microalga Chlamydomonas reinhardtii is capable of prolonged H₂ photoproduction when deprived of sulfur. In addition to sulfur deprivation (-S), sustained H₂ photoproduction in C. reinhardtii cultures can be achieved under phosphorus-deprived (-P) conditions. Similar to sulfur deprivation, phosphorus deprivation limits O₂ evolving activity in algal cells and causes other metabolic changes that are favorable for H₂ photoproduction. Although significant advances in H₂ photoproduction have recently been realized in fresh water microalgae, relatively few studies have focused on H₂ production in marine green microalgae. In the present study phosphorus deprivation was applied for hydrogen production in marine green microalgae Chlorella sp., where sulfur deprivation is impossible due to a high concentration of sulfates in the sea water. Since resources of fresh water on earth are limited, the possibility of hydrogen production in seawater is more attractive. In order to achieve H₂ photoproduction in P-deprived marine green microalgae Chlorella sp., the dilution approach was applied. Cultures diluted to about 0.5–1.8 mg Chl·L⁻¹ in the beginning of P-deprivation were able to establish anaerobiosis, after the initial growth period, where cells utilize intracellular phosphorus, with subsequent transition to H₂ photoproduction stage. It appears that marine microalgae during P-deprivation passed the same stages of adaptation as fresh water microalgae. The presence of inorganic carbon was essential for starch accumulation and subsequent hydrogen production by microalgae. The H₂ accumulation was up to 40 mL H₂ gas per 1iter of the culture, which is comparable to that obtained in P-deprived C. reinhardtii culture.     

Isochoric Heat-Capacity Measurements for Pure Methanol in the Near-Critical and Supercritical Regions

Isochoric heat-capacity measurements for pure methanol are presented as a function of temperature at fixed densities between 136 and 750 kg·m⁻³. The measurements cover a range of temperatures from 300 to 556 K. The coverage includes the one- and two-phase regions, the coexistence curve, the near-critical, and the supercritical regions. A high-temperature, high-pressure, adiabatic, and nearly constant-volume calorimeter was used for the measurements. Uncertainties of the heat-capacity measurements are estimated to be 2–3% depending on the experimental density and temperature. Temperatures at saturation, T _S(ρ), for each measured density (isochore) were measured using a quasi-static thermogram technique. The uncertainty of the phase-transition temperature measurements is 0.02 K. The critical temperature and the critical density for pure methanol were extracted from the saturated data (T _S,ρ_S) near the critical point. For one near-critical isochore (398.92 kg·m⁻³), the measurements were performed in both cooling and heating regimes to estimate the effect of thermal decomposition (chemical reaction) on the heat capacity and phase-transition properties of methanol. The measured values of C _V and saturated densities (T _S,ρ_S) for methanol were compared with values calculated from various multiparametric equations of state (EOS) (IUPAC, Bender-type, polynomial-type, and nonanalytical-type), scaling-type (crossover) EOS, and various correlations. The measured C _V data have been analyzed and interpreted in terms of extended scaling equations for the selected thermodynamic paths (critical isochore and coexistence curve) to accurately calculate the values of the asymptotical critical amplitudes ( and B ₀).     

PVT measurements of water-ammonia refrigerant mixture in the critical and supercritical regions

The PVTx properties of H₂O + NH₃ mixture (0.2607 mole fraction of ammonia) have been measured in the near- and supercritical regions. Measurements were made along 40 liquid and vapor isochores in the range from 120.03 to 727.75 kg m⁻³ and at temperatures from 301 to 634 K and at pressures up to 28 MPa. Temperatures and densities at the liquid–gas phase transition curve, dew- and bubble-pressure points, and the critical parameters for the 0.7393 H₂O + 0.2607 NH₃ mixture were obtained using the quasi-static thermograms and isochoric (P–T) break-point techniques. The expanded uncertainty of the density, pressure, temperature measurements at the 95% confidence level with a coverage factor of k = 2 is estimated to be 0.06%, 0.02–0.09%, and 15 mK, respectively.     

Thermodynamic Properties at Saturation Derived from Experimental Two-Phase Isochoric Heat Capacity of 1-Hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide

New measurements are reported for the isochoric heat capacity of the ionic liquid substance 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C6mim][NTf2]). These measurements extend the ranges of our earlier study (Polikhronidi et al. in Phys Chem Liq 52:657, 2014) by 5 % of the compressed liquid density and by 75 K. An adiabatic calorimeter was used to measure one-phase \((C_{\mathrm{V1}})\) liquid and two-phase \((C_{\mathrm{V2}})\) liquid + vapor isochoric heat capacities, densities \((\rho _s)\), and phase-transition temperatures \((T_s)\) of the ionic liquid (IL) substance. The combined expanded uncertainty of the density \(\rho \) and isochoric heat capacity \(C_\mathrm{V}\) measurements at the 95 % confidence level with a coverage factor of \(k = 2\) is estimated to be 0.15 % and 3 %, respectively. Measurements are concentrated in the immediate vicinity of the liquid + vapor phase-transition curve, in order to closely observe phase transitions. The present measurements and those of our earlier study are analyzed together and are presented in terms of thermodynamic properties \((T_s\), \(\rho _s\), \(C_{\mathrm{V1}}\) and \(C_{\mathrm{V2}})\) evaluated at saturation and in terms of key-derived thermodynamic properties \(C_\mathrm{P}\), \(C_\mathrm{S}\), \(W_\mathrm{S}^{{\prime }}\), \(K_{\mathrm{TS}}^{{\prime }}\), \(\left( {\partial P/\partial T} \right) _{\mathrm{V}}^{\prime }\), and \(\left( {\partial V/\partial T} \right) _\mathbf{P}^{\prime })\) on the liquid + vapor phase-transition curve. A thermodynamic relation by Yang and Yang is used to confirm the internal consistency of measured two-phase heat capacities \(C_{\mathrm{V2}} \), which are observed to fall perfectly on a line as a function of specific volume at a constant temperature. The observed linear behavior is exploited to evaluate contributions to the quantity \(C_{\mathrm{V2}} = f(V, T)\) from chemical potential \(C_{{\mathrm{V}\upmu }} =-T\frac{\mathrm{d}^{{2}}\mu }{\mathrm{d}T^{2}}\) and from vapor pressure \(C_{\mathrm{VP}} =VT\frac{\mathrm{d}^{2}P_{\mathrm{S}} }{\mathrm{d}T^{2}}\). The physical nature and specific details of the temperature and specific volume dependence of the two-phase isochoric heat capacity and some features of the other derived thermodynamic properties of IL at liquid saturation curve are considered in detail.     

Experimental Study of the Thermodynamic Properties of Diethyl Ether (DEE) at Saturation

The isochoric heat capacities \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\), saturation densities (\({\rho _{\rm S}^{\prime}}\) and \(({\rho_{\rm S}^{\prime\prime})}\)), vapor pressures (P _S), thermal-pressure coefficients \({\gamma_V=\left({\partial P/\partial T}\right)_V}\), and first temperature derivatives of the vapor pressure γ _S = (dP _S/dT) of diethyl ether (DEE) on the liquid–gas coexistence curve near the critical point have been measured with a high-temperature and high-pressure nearly constant-volume adiabatic piezo-calorimeter. The measurements of \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) were made in the liquid and vapor one- and two-phase regions along the coexistence curve. The calorimeter was additionally supplied with a calibrated extensometer to accurately and simultaneously measure the PVT, C _V VT, and thermal-pressure coefficient, γ _V , along the saturation curve. The measurements were carried out in the temperature range from 416 K to 466.845 K (the critical temperature) for 17 liquid and vapor densities from 212.6 kg · m^?3 to 534.6 kg · m^?3. The quasi-static thermo- (reading of PRT, T ? τ plot) and baro-gram (readings of the tensotransducer, P ? τ plot) techniques were used to accurately measure the phase-transition parameters (P _S ,ρ _S ,T _S) and γ _V . The total experimental uncertainty of density (ρ _S), pressure (P _S), temperature (T _S), isochoric heat capacities \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\), and thermal-pressure coefficient, γ _V , were estimated to be 0.02 % to 0.05 %, 0.05 %, 15 mK, 2 % to 3 %, and 0.12 % to 1.5 %, respectively. The measured values of saturated caloric \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) and saturated thermal (P _S, ρ _S, T _S) properties were used to calculate other derived thermodynamic properties C _P , C _S, W, K _T , P _int, ΔH _vap, and \({\left({\partial V/\partial T}\right)_P^{\prime}}\) of DEE near the critical point. The second temperature derivatives of the vapor pressure, (d² P _S/dT ²), and chemical potential, (d² μ/dT ²), were also calculated directly from the measured one- and two-phase liquid and vapor isochoric heat capacities \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) near the critical point. The derived values of (d² P _S/dT ²) from calorimetric measurements were compared with values calculated from vapor–pressure equations. The measured and derived thermodynamic properties of DEE near the critical point were interpreted in terms of the “complete scaling” theory of critical phenomena. In particular, the effect of a Yang–Yang anomaly of strength R _μ on the coexistence-curve diameter behavior near the critical point was studied. Extended scaling-type equations for the measured properties P _S (T), ρ _S (T), and \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) as a function of temperature were developed.     

Experimental Study of the Critical Behavior of the Isochoric Heat Capacity of Aqueous Ammonia Mixture

The isochoric heat capacity of a NH₃ + H₂O (0.2607 mole fraction of ammonia) mixture has been measured in the near- and supercritical regions. Measurements were made in the single- and two-phase regions including the coexistence curve using a high-temperature, high-pressure, nearly constant-volume adiabatic calorimeter. Measurements were made along 38 liquid and vapor isochores in the range from 120.03 kg · m⁻³ to 671.23 kg · m⁻³ and at temperatures from 478 K to 634 K and at pressures up to 28 MPa. Temperatures at the liquid–gas phase transition curve, T _S(ρ), for each measured density (isochore) and the critical parameters (T _C and ρ _C) for the 0.2607 NH₃ + 0.7393  H₂O mixture were obtained using the quasi-static thermograms technique. The expanded uncertainty of the heat-capacity measurements at the 95 % confidence level with a coverage factor of k = 2 is estimated to be 2 % to 3 % in the near-critical and supercritical regions, 1.0 % to 1.5 % in the liquid phase, and 3 % to 4 % in the vapor phase. Uncertainties of the density, temperature, and concentration measurements are estimated to be 0.06 %, 15mK, and 5×10⁻⁵ mole fraction, respectively. An unusual behavior of the isochoric heat capacity of the mixture was found near the maxcondetherm point (in the retrograde region). The value of the Krichevskii parameter was calculated using the critical properties data for the mixture and vapor-pressure data for the pure solvent (H₂O). The derived value of the Krichevskii parameter was used to analyze the critical behavior of the strong (C _P , K _T ) and weakly (C _V ) singular properties in terms of the principle of isomorphism of critical phenomena in binary mixtures. The values of the characteristic parameters (K ₁, K ₂), temperatures (τ ₁, τ ₂), and the characteristic density differences (Δρ ₁, Δρ ₂) were calculated for the NH₃ + H₂O mixture by using the critical-curve data.