Thermodynamics of climate change between cloud cover, atmospheric temperature and humidity

On a global and annual average, we find a parameterization in which the cloud cover increase is proportional to the mid tropospheric temperature increase, with a negative proportionality factor. If the relative humidity is conserved throughout the troposphere, a 1 °C heating (cooling) of the mid troposphere, decreases (increases) the cloud cover by 1.5 percentage points (pp). But if the relative humidity is not conserved, then the cloud cover decreases (increases) by 7.6 pp. If the shortwave reflection effect of the cloud cover is dominant on a global scale, this parameterization leads to a predominant positive feedback: if the temperature increases like in the current climate change, the cloud cover decreases and more solar radiation reaches the surface increasing the temperature even more. The contribution of the present work consists in finding that the negative sign of the proportionality factor is due to the Clausius–Clapeyron equation; that is, to the magnitude of the derivative of the saturation vapor pressure at the typical standard surface temperature of 288 K. The negative sign of the factor is independent on the conservation or non-conservation of relative humidity in the troposphere under climate change.

Description of the liquid-vapor phase equilibrium line of pure substances within the bounds of scale theory based on the Clapeyron equation

On the basis of the Clapeyron equation and the scale theory, expressions are developed for the “apparent” heat of vaporization r * = r * (T), vapor ρ- = ρ- (T) and liquid ρ+ = ρ+ (T) branches of the saturation line of individual substances for the range of state parameters from the triple point (pt,Tt,ρt ) to the critical (pc,Tc,ρc ). The peculiarity of the proposed approach to the description of the saturation line is that all exponents of the components of the equations ρ- = ρ- (T) and ρ+ = ρ+ (T) are universal up to the universality of the critical indices α, β and Δ. In this case, the order parameter ds = (ρ+ − ρ-)/(2ρc) and the average diameter df = (ρ+ + ρ-)/(2ρc) − 1 of the saturation line satisfy the saturation line model [2β,1−α], which follows from the modern theory of critical phenomena. The method is tested on the example of describing the phase equilibrium line of refrigerant R1233zd(E) in the range from Tt = 195.15 K to Tc = 439.57 K. It is found that in the temperature range [Tt,Tc ], the developed system of the mutually consistent equations ps = ps (T), r * = r * (T), ρ- = ρ- (T) and ρ+ = ρ+ (T) allows describing the data on the saturated vapor pressure ps and densities ρ- and ρ+ on the saturation line within the experimental uncertainty of these data.

Assessment of the contribution of the air-vapor mixture volume exceeding over the volumes injected to oil and petroleum product losses from evaporation

В настоящее время при экспериментальном определении потерь нефтепродуктов от «больших дыханий» резервуаров используют формулу Черникина - Валявского. При этом «однако» не учитывается, что объем вытесняемой в атмосферу паровоздушной смеси, как правило, превышает объем закачиваемой нефти (нефтепродукта). Соответствующий параметр - коэффициент превышения, - по экспериментальным данным, может принимать значения более 8. До недавнего времени не до конца были ясны даже причины этого явления, соответственно, эмпирические зависимости для расчета коэффициента превышения не учитывали всех влияющих факторов. Авторами статьи на основе уравнения Менделеева - Клапейрона в дифференциальной форме получено аналитическое выражение для вычисления среднего коэффициента превышения. Установлено, что данная величина зависит от молярной массы и температуры паровоздушной смеси в начале и конце закачки, а также от соотношения объемов газового пространства резервуара и закачиваемого продукта. Для анализа полученной зависимости был спланирован и проведен вычислительный эксперимент, предусматривающий изменение определяющих параметров в широком диапазоне. Расчеты выполнялись для нефти и бензина. По результатам 25 вычислительных «опытов» определено, что при операциях с бензином средний коэффициент превышения (за одну операцию заполнения резервуара) в исследованном диапазоне температур принимает значения от 1,029 до 1,678, а при операциях с нефтью - от 1,016 до 1,338, то есть, как правило, превышает погрешность инструментальных замеров потерь нефти (нефтепродуктов) от испарения. Математическое ожидание рассматриваемой величины при операциях с бензином составляет 1,26, с нефтью - 1,16. Таким образом, учет среднего коэффициента превышения при обработке результатов инструментальных измерений потерь углеводородов от испарений вследствие «больших дыханий» резервуаров является обязательным. Currently, the Chernikin - Valyavsky formula is used in the experimental determination of petroleum product losses from “large breaths” of reservoirs. However, it does not take into account that the volume of air-vapor mixture displaced into the atmosphere usually exceeds the volume of pumped oil/petroleum product. The corresponding parameter, the excess ratio, according to the experimental data can have values of more than 8. Until recently, even the causes of this phenomenon were not completely clear, and thus, the empirical dependencies for calculating the excess ratio did not take into account all the influencing factors. Based on the Mendeleev-Clapeyron equation in differential form, the analytic expression to calculate the average excess ratio was obtained. It was found that this value depends on the molar mass and temperature of the air-vapor mixture at the beginning and the end of the injection, as well as on the ratio of the tank gas space volume and the injected product volume. To analyze the resulting dependency, a computational experiment involving changes in the defining parameters over a wide range was planned and conducted. The calculations were performed for oil and gasoline. According to the results of 25 computational experiments, it was determined that during operations with gasoline the average excess ratio (per one tank filling operation) in the investigated temperature range has values from 1.029 to 1.678, and during operations with oil - from 1.016 to 1.338; that generally exceeds the instrument error of oil/petroleum product losses from vaporization measurement. The mathematical expectation of the value in question during operations with gasoline is 1.26, it is 1.16 with oil. It is therefore mandatory to take into account the average excess ratio when processing the results of instrumental measurements of hydrocarbon losses from evaporation due to “large breaths” of reservoirs.

Modelling Methane Hydrate Saturation in Pores: Capillary Inhibition Effects

Experimental and field observations evidence the effects of capillarity in narrow pores on inhibiting the thermodynamic stability of gas hydrates and controlling their saturation. Thus, precise estimates of the gas hydrate global inventory require models that accurately describe gas hydrate stability in sediments. Here, an equilibrium model for hydrate formation in sediments that accounts for capillary inhibition effects is developed and validated against experimental data. Analogous to water freezing in pores, the model assumes that hydrate formation is controlled by the sediment pore size distribution and the balance of capillary forces at the hydrate–liquid interface. To build the formulation, we first derive the Clausius–Clapeyron equation for the thermodynamic equilibrium of methane and water chemical potentials. Then, this equation is combined with the van Genuchten’s capillary pressure to relate the thermodynamic properties of the system to the sediment pore size distribution and hydrate saturation. The model examines the influence of the sediment pore size distribution on hydrate saturation through the simulation of hydrate formation in sand, silt, and clays, under equilibrium conditions and without mass transfer limitations. The results show that at pressure–temperature conditions typically found in the seabed, capillary effects in very fine-grained clays can limit the maximum hydrate saturation below 20% of the host sediment porosity.

Pressure-induced liquid-liquid transition in a family of ionic materials

Liquid−liquid transition (LLT) between two disordered phases of single-component material remains one of the most intriguing physical phenomena. Here, we report a first-order LLT in a series of ionic liquids containing trihexyl(tetradecyl)phosphonium cation [P666,14]+ and anions of different sizes and shapes, providing an insight into the structure-property relationships governing LTT. In addition to calorimetric proof of LLT, we report that ion dynamics exhibit anomalous behavior during the LLT, i.e., the conductivity relaxation times (τσ) are dramatically elongated, and their distribution becomes broader. This peculiar behavior is induced by both isobaric cooling and isothermal compression with the τσ(TLL,PLL) being constant for a given system. The latter observation proves that LLT, in analogy to liquid-glass transition, has an isochronal character. Finally, the magnitude of discontinuity in a specific volume at LLT was examined using the Clausius-Clapeyron equation.

Isosteric Enthalpy Behavior of CO2 Adsorption on Micro-Mesoporous Materials: Carbon Microfibers (CMFs), SBA-15, and Amine-Functionalized SBA-15

The isosteric enthalpy of adsorption (∆adsh ) of CO2 in three different micro and mesoporous materials was evaluated in this work. These materials were a microporous material with functional groups of nitrogen and oxygen (CMFs, carbon microfibers), a mesoporous material with silanol groups (SBA-15, Santa Barbara Amorphous), and a mesoporous material with amine groups (SBA-15_APTES, SBA-15 amine-functionalized with (3-Aminopropyl)-triethoxysilane). The temperature interval explored was between 263 K and 303 K, with a separation of 5 K between each one, so a total of nine CO2 isotherms were obtained. Using the nine isotherms and the Clausius–Clapeyron equation, the reference value for ∆adsh was found. The reference value was compared with those ∆adsh obtained, considering some arrangement of three or five CO2 isotherms. Finally, it was found that at 298 K and 1 bar, the total amount of CO2 adsorbed is 2.32, 0.53, and 1.37 mmol g−1 for CMF, SBA-15, and SBA-15_APTES, respectively. However, at a coverage of 0.38 mmol g−1, ∆adsh is worth 38, 30, and 29 KJ mol−1 for SBA-15_APTES, CMFs, and SBA-15, respectively. So, physisorption predominates in the case of CMF and SBA-15 materials, and the ∆adsh values significantly coincide regardless of whether the isotherms arrangement used was three or five. Meanwhile, in SBA-15_APTES, chemisorption predominates as a consequence of the arrangements used to obtain . This happens in such a way that the use of low temperatures (263–283 K) tends to produce higher ∆adsh values, while the use of high temperatures (283–303 K) decreases the ∆adsh values.

Equilibrium Conditions of Methane Hydrates in Seawater From Krishna-Godavari Basin, India

Immense gas hydrate reservoirs have been reported in the Krishna-Godavari Basin, India. They mostly constitute methane gas and could serve as an alternative energy source. For efficient exploitation of methane from hydrates, it is crucial to know the region's stability conditions. The present study reports the stability and equilibrium conditions of methane hydrates, synthesized with seawater obtained from the Krishna-Godavari Basin. At Station MD161/02/GH, the water samples are collected at depths ranging from 500 to 1,500 m. The influence of salinity on methane hydrate formation and dissociation in the presence of seawater is established. The hydrate dissociation patterns in seawater and saline water (4 wt% NaCl) are similar and follow the phase equilibrium around 6 wt% NaCl. The identical dissociation behavior of the two systems ascertains seawater to have ~4 wt% salinity. The salinity concentration varies little with depth because the hydrate dissociation temperatures are the same for all the samples collected at the three depths. Using the Clausius-Clapeyron equation, dissociation enthalpies are calculated. The dissociation enthalpy in saline systems is about 6% higher. The hydrate growth kinetics is marginally faster in the saline system.

RESEARCH INTO PECULIARITIES OF PHASE TRANSITIONS DURING THE DISSOCIATION OF GAS HYDRATES

Purpose. Analytical study of the dissociation process of gas hydrates taking into account the peculiarities of phase transitions occurring during their dissociation and described by the Clausius-Clapeyron equation. Methods. The research uses an integrated approach, which includes the analysis and generalization of literature sources devoted to studying the peculiarities and thermobaric properties of gas hydrates; processes of hydrate formation and accumulation; methods for the development of gas hydrate deposits and technologies for extracting the methane gas from them; analytical calculations of phase transitions of gas hydrates. Findings. The conditions for the formation of gas hydrate deposits have been analyzed and the peculiarities of stable existence of gas hydrates have been revealed. The existing experience in the development of gas hydrate technologies by leading scientists, world research laboratories, advanced design institutes and organizations is summarized. The mechanism of hydration formation in rocks is studied and some classifications of gas hydrate deposits occurring in sedimentary rock stratum are presented. It has been determined that gas hydrates in natural conditions usually occur not only in the form of pure hydrate reservoirs, but most often contain a certain share of rock intercalations, which makes the deposit structure heterogeneous. The mechanisms of hydrate formation and dissociation of gas hydrates have been revealed. It has been determined that the Clausius-Clapeyron equation in a modified form can be used to describe phase transitions both during the formation and dissociation of gas hydrates, taking into account the deposit heterogeneity. Originality. The Clausius-Clapeyron equation for the analysis of phase transformations in solid phases during hydrate formation and dissociation of gas hydrates is defined more exactly, taking into account the consumption of additional heat due to the influence of the properties of rock intercalations. Practical implications. The research results are useful for designing the rational thermobaric parameters (pressure and temperature) in the dissociation of natural or technogenic gas hydrates, as well as for optimal control of the kinetics of the process.

Application of a Clapeyron-Type Equation to the Volume Phase Transition of Polymer Gels

The applicability of the Clapeyron equation to the volume phase transition of cylindrical poly(N-isopropylacrylamide)-based gels under external force is reviewed. Firstly, the equilibrium conditions for the gels under tension are shown, and then we demonstrate that the Clapeyron equation can be applied to the volume phase transition of polymer gels to give the transition entropy or the transition enthalpy. The transition enthalpy at the volume phase transition obtained from the Clapeyron equation is compared with that from the calorimetry. A coefficient of performance, or work efficiency, for a gel actuator driven by the volume phase transition is also defined. How the work efficiency depends on applied force is shown based on a simple mechanical model. It is also shown that the force dependence of transition temperature is closely related to the efficiency curve. Experimental results are compared with the theoretical prediction.