Search Results (53)

Carbon dioxide (CO₂) injection into geologic formations has gained global traction, including in South Africa, to mitigate anthropogenic emissions through carbon capture, utilisation, and storage technology. These technological and technical developments require a comprehensive and reliable study of CO₂ sorption equilibria under in situ unmineable coal reservoir conditions. This paper presents novel findings on the study of the equilibrium adsorption of CO₂ on two South African coals measured at four temperatures between 30 and 60 °C and pressures up to 9.0 MPa using the volumetric technique. Additionally, the sorption mechanism and thermodynamic nature of the process were studied by fitting the experimental data into Langmuir–Freundlich (Sips), Tóth, and Dubinin–Astakhov (DA) isotherm models, and the Clausius–Clapeyron equation. The findings indicate that the sorption process is highly exothermic, as presented by a negative temperature effect, with the maximum working capacity estimated to range between 3.46 and 4.16 mmol/g, which is also rank- and maceral composition-dependent, with high-rank vitrinite-rich coal yielding more sorption capacity than low-rank inertinite-rich coal. The experimental data fit well in Sips and Tóth models, confirming their applicability in describing the CO₂ sorption behaviour of the coals under the considered conditions. The isosteric heat of adsorption varied from 7.518 to 37.408 kJ/mol for adsorbate loading ranging from 0.4 to 3.6 mmol/g. Overall, the coals studied demonstrate well-developed sorption properties that characteristically make them viable candidates for CO₂ sequestration applications for environmental sustainability. Full article

Urbanization increases the number of impervious surfaces in watersheds, reducing infiltration and evapotranspiration, which increases runoff volumes and the risks of flooding and the pollution of water resources. Nature-based solutions (NBS) mitigate these effects by managing water volume and quality, restoring the hydrological cycle, and creating sustainable livelihoods that can promote socioeconomic equity by providing green space. In light of the aforementioned information, this study analyzes the hydrological response of NBS in La Guapil, a densely populated and socioeconomically vulnerable area of Costa Rica with approximately 80% impervious surfaces, focusing on their effectiveness in stormwater management and improving hydrological conditions. Field data from the study area’s storm drainage system, as well as hydrological analyses, were collected and processed to evaluate RCP8.5 climate change scenarios using the Clausius–Clapeyron (CC) relationship. Three scenarios were proposed: (1) the “status quo”, reflecting current conditions, (2) green roofs and green improvements, and (3) detention ponds and green improvements, evaluated using the SWMM, with the latter scenario also using the Iber model. Simulations showed that Scenario 2 achieved the greatest reduction in peak flow (53.74%) and runoff volume (57.60%) compared to Scenario 3 (peak: 28.37%; volume: 56.42%). Both scenarios demonstrate resilience to climate change projections. The results of this study provide a foundation for further research into NBS in Costa Rica and other comparable regions. Full article

Modeling peatland hydraulic processes in cold regions requires defining near-surface hydraulic parameters. The current study aims to determine the soil freezing and water characteristic curve parameters for organic soils from peatland-dominated permafrost mires. The three research objectives are as follows: (i) Setting up an in situ soil freezing characteristic curve experiment by installing sensors for measuring volumetric water content and temperature in Storflaket mire, Abisko region, Sweden; (ii) Conducting laboratory evaporation experiments and inverse numerical modeling to determine soil water characteristic curve parameters and comparing three soil water characteristic curve models to the laboratory data; (iii) Deriving a relationship between soil freezing and water characteristic curves and optimizing this equation with sensor data from (i). A long-lasting in situ volumetric water content station has been successfully set up in sub-Arctic Sweden. The soil water characteristic curve experiments showed that bimodality also exists for the investigated peat soils. The optimization results of the bimodal relationship showed excellent agreement with the soil freezing cycle measurements. To the best of our knowledge, this is one of the first studies to establish and test bimodality for frozen peat soils. The estimated hydraulic parameters could be used to better simulate permafrost dynamics in peat soils. Full article

Climate change is a crucial issue of the 21st century, leading to more frequent and severe extreme precipitation events globally. These events result in significant social and economic disruptions, including flooding, loss of life, and damage to infrastructure. Projections suggest that extreme rainfall will intensify in the latter half of the century, underscoring the need for accurate and timely forecasting. Despite advancements in meteorological and climate models that offer high accuracy for various weather parameters, these models still struggle to detect extreme values, particularly for precipitation. This research examines the sensitivity of extreme precipitation events to temperature, based on the Clausius-Clapeyron relationship, focusing on Thessaloniki, Greece. It also evaluates the effectiveness of reanalysis data in identifying extreme precipitation and explores how rainfall-temperature relationships can enhance prediction accuracy. The findings are vital for improving the estimation of extreme rainfall events and informing the design of flood-resilient infrastructure. Full article

Metal–organic frameworks (MOFs) are promising materials for processes such as carbon dioxide (CO₂) capture or its storage. In this work, the adsorption of CO₂ and nitrogen (N₂) in Co₃(ndc)₃(dabco) MOF (ndc: 2,6-naphthalenedicarboxylate; dabco: 1,4-diazabicyclo[2.2.2]octane) is reported for the first time over the temperature range of 273–323 K and up to 35 bar. The adsorption isotherms are successfully described using the Langmuir isotherm model. The heats of adsorption for CO₂ and N₂, determined through the Clausius–Clapeyron equation, are 20–27 kJ/mol and 10–11 kJ/mol, respectively. The impact of using pressure and/or temperature swings on the CO₂ working capacity is evaluated. If a flue gas with 15% CO₂ is fed at 6 bar and 303 K and regenerated at 1 bar and 373 K, 1.58 moles of CO₂ can be captured per kg of MOF. The analysis of the multicomponent adsorption of typical flue gas streams (15% CO₂ balanced with N₂), using the ideal adsorbed solution theory (IAST), shows that at 1 bar and 303 K, the CO₂/N₂ selectivity is 11.5. In summary, this work reports essential data for the design of adsorption-based processes for CO₂ capture using a Co₃(ndc)₃(dabco) MOF, such as pressure swing adsorption (PSA). Full article

This study utilizes waste Albizia lebbeck wood from a sawmill to prepare activated carbon adsorbents and explores their potential application in adsorption cooling systems with a novel hydrofluoroolefin (HFO) refrigerant characterized by a low global warming potential. Activated carbon was synthesized through a simple and green steam activation method, and the optimal carbon shows a specific surface area of 946.8 m²/g and a pore volume of 0.843 cm³/g. The adsorption isotherms of HFO-1234ze(E) (Trans-1,3,3,3-tetrafluoropropene) on the activated carbon were examined at 30, 40, and 50 °C up to 400 kPa using a customized constant-volume variable-pressure system, and significant adsorption of 1.041 kg kg⁻¹ was achieved at 30 °C and 400 kPa. The experimental data were fitted using both the Dubinin–Astakhov and Tóth models, and both models provided excellent fit results. The D–A adsorption model simulated the net adsorption capacity at possible operating temperatures. The isosteric of adsorption was determined using the Clausius–Clapeyron and modified Dubinin–Astakhov equations. In addition, the specific cooling effect and coefficient of performance were also studied. Full article

Capturing carbon dioxide (CO₂) is still a major obstacle in the fight against climate change and the reduction of greenhouse gas emissions. To address this problem, we employed a simple Friedel–Crafts alkylation to investigate the effectiveness of porous organic polymers (POPs) based on triphenylamine (TPA) and trihydroxy aryl terms derived from chloranil (CH), designated as TPA-CH POP. We then treated the TPA-CH POP with (3-mercaptopropyl)trimethoxysilane (3-MPTS), forming a TPA-CH POP-SH nanocomposite to enhance CO₂ capture. Utilizing FTIR, solid-state NMR, SEM, TEM, along with XPS techniques, the molecular makeup, morphological characteristics, as well as physical features of TPA-CH POP and the TPA-CH POP-SH nanocomposite were thoroughly explored. Upon scorching to 800 °C, the TPA-CH POP-SH nanocomposite demonstrated more thermal durability over TPA-CH POP, achieving a char yield of up to 71.5 wt.%. The TPA-CH POP-SH nanocomposite displayed a 2.5-times better CO₂ capture, as well as a comparable adsorption capacity of 48.07 cm³ g⁻¹ at 273 K. Additionally, we found that the TPA-CH POP-SH nanocomposite exhibited an improved CO₂/nitrogen (N₂) selectivity versus the original TPA-CH POP. Typical enthalpy changes for CO₂ capture were somewhat increased by the 3-MPTS coating, indicating greater binding energies between CO₂ molecules and the adsorbent surface. Our outcomes demonstrate that a TPA-CH POP composite coated with MPTS is a viable candidate for effective CO₂ capture uses. Our findings encourage the investigation of different functional groups and optimization strategies. Full article

This paper reports the vapor pressure and enthalpy of vaporization for a promising phase change material (PCM) guanidinium methanesulfonate ([Gdm][OMs]), which is a typical guanidinium organomonosulfonate that displays a lamellar crystalline architecture. [Gdm][OMs] was purified by recrystallization. The elemental analysis and infrared spectrum of [Gdm][OMs] confirmed the purity and composition. Differential scanning calorimetry (DSC) also confirmed its high purity and showed a sharp and symmetrical endothermic melting peak with a melting point (T_m) of 207.6 °C and a specific latent heat of fusion of 183.0 J g⁻¹. Thermogravimetric analysis (TGA) reveals its thermal stability over a wide temperature range, and yet three thermal events at higher temperatures of 351 °C, 447 °C, and 649 °C were associated with vaporization or decomposition. The vapor pressure was measured using the isothermogravimetric method from 220 °C to 300 °C. The Antoine equation was used to describe the temperature dependence of its vapor pressure, and the substance-dependent Antoine constants were obtained by non-linear regression. The enthalpy of vaporization (Δ_vapH) was derived from the linear regression of the slopes associated with the linear temperature dependence of the rate of weight loss per unit area of vaporization. Hence, the temperature dependence of vapor pressures ln P_vap (Pa) = 10.99 − 344.58/(T (K) − 493.64) over the temperature range from 493.15 K to 573.15 K and the enthalpy of vaporization Δ_vapH = 157.10 ± 20.10 kJ mol⁻¹ at the arithmetic mean temperature of 240 °C were obtained from isothermogravimetric measurements using the Antoine equation and the Clausius–Clapeyron equation, respectively. The flammability test indicates that [Gdm][OMs] is non-flammable. Hence, [Gdm][OMs] enjoys very low volatility, high enthalpy of vaporization, and non-flammability in addition to its known advantages. This work thus offers data support, methodologies, and insights for the application of [Gdm][OMs] and other organic salts as PCMs in thermal energy storage and beyond. Full article

Forecasting extreme precipitation is one of the basic actions of warning systems in Latin America and the Caribbean (LAC). With thousands of economic losses and severe damage caused by floods in urban areas, hydrometeorological monitoring is a priority in most countries in the LAC region. The monitoring of convective precipitation, cold fronts, and hurricane tracks are the most demanded technological developments for early warning systems in the region. However, predicting and forecasting the onset time of extreme precipitation is a subject of life-saving scientific research. Developed in 2019, the CRHUDA (Crossing HUmidity, Dew point, and Atmospheric pressure) model provides insight into the onset of precipitation from the Clausius–Clapeyron relationship. With access to a historical database of more than 600 storms, the CRHUDA model provides a prediction with a precision of six to eight hours in advance of storm onset. However, the calibration is complex given the addition of ARMA(p,q)-type models for real-time forecasting. This paper presents the calibration of the joint CRHUDA+ARMA(p,q) model. It is concluded that CRHUDA is significantly more suitable and relevant for the forecast of precipitation and a possible future development for an early warning system (EWS). Full article

One of the impacts of climate change is an increase in the frequency and intensity of extreme rainfall events. This has very significant social and economic consequences for the affected areas (flooding, loss of life, destruction of infrastructure, etc.). Future trends indicate a further increase in extreme rainfall in the second half of the century, making the need for the timely and accurate forecasting of these phenomena more urgent than ever. However, despite the technological development of weather and climate models in recent years, there are still limitations in detecting the extremes, especially regarding the precipitation parameter. Extreme precipitation events show a link with temperature. The Clausius–Clapeyron (CC) equation, which relates temperature to saturation vapor pressure (e_s), is used to study the sensitivity of precipitation to temperature increase because it can estimate the increase in the available atmospheric water vapor with respect to temperature. Focusing on the Thessaloniki region in Greece, the aim of this paper is to investigate the applicability of the Clausius–Clapeyron relation to the scaling relationship between extreme precipitation intensity and surface air temperature. An additional attempt is also made to test the possibility of improving the underestimation that the reanalysis models exhibit in recording the extremes and in particular the ERA5 Land dataset. Full article

In general, for an organic compound a plot of the log vapor pressure versus inverse temperature is linear over a wide temperature range. This however can lead to a point of confusion in an undergraduate thermodynamics course. This linear behavior is typically explained using the Clausius/Clapeyron equation. That is, starting with the Clapeyron equation one first assumes (1) that the change in compressibility upon vaporization is approximately 1, or equivalently that the vapor phase may be treated as an ideal gas where the molar volume of the vapor is much greater than that of the liquid, which may be assumed negligible. And second (2), that the enthalpy of vaporization is constant. While the resulting linear behavior is captured, the underlying assumptions are not applicable over the wide range of temperatures of interest. Here we discuss the shortcomings of the conventional explanation of the Clausius/Clapeyron equation. We further demonstrate that a simple solution is to instead assume that the enthalpy of vaporization relative to the change in compressibility upon vaporization is constant. We provide a series of examples and MATLAB code that can be used in an undergraduate thermodynamics course. Full article

In the context of global warming, the Clausius–Clapeyron (CC) relationship has been widely used as an indicator of the evolution of the precipitation regime, including daily and sub-daily extremes. This study aims to verify the existence of links between precipitation extremes and 2 m air temperature for the Ottawa River Basin (ORB, Canada) over the period 1981–2010, applying an exponential relationship between the 99th percentile of precipitation and temperature characteristics. Three simulations of the Canadian Regional Climate Model version 5 (CRCM5), at three different resolutions (0.44°, 0.22°, and 0.11°), one simulation using the recent CRCM version 6 (CRCM6) at “convection-permitting” resolution (2.5 km), and two reanalysis products (ERA5 and ERA5-Land) were used to investigate the CC scaling hypothesis that precipitation increases at the same rate as the atmospheric moisture-holding capacity (i.e., 6.8%/°C). In general, daily precipitation follows a lower rate of change than the CC scaling with median values between 2 and 4%/°C for the ORB and with a level of statistical significance of 5%, while hourly precipitation increases faster with temperature, between 4 and 7%/°C. In the latter case, rates of change greater than the CC scaling were even up to 10.2%/°C for the simulation at 0.11°. A hook shape is observed in summer for CRCM5 simulations, near the 20–25 °C temperature threshold, where the 99th percentile of precipitation decreases with temperature, especially at higher resolution with the CRCM6 data. Beyond the threshold of 20 °C, it appears that the atmospheric moisture-holding capacity is not the only determining factor for generating precipitation extremes. Other factors need to be considered, such as the moisture availability at the time of the precipitation event, and the presence of dynamical mechanisms that increase, for example, upward vertical motion. As mentioned in previous studies, the applicability of the CC scaling should not be generalised in the study of precipitation extremes. The time and spatial scales and season are also dependent factors that must be taken into account. In fact, the evolution of precipitation extremes and temperature relationships should be identified and evaluated with very high spatial resolution simulations, knowing that local temperature and regional physiographic features play a major role in the occurrence and intensity of precipitation extremes. As precipitation extremes have important effects on the occurrence of floods with potential deleterious damages, further research needs to explore the sensitivity of projections to resolution with various air temperature and humidity thresholds, especially at the sub-daily scale, as these precipitation types seem to increase faster with temperature than with daily-scale values. This will help to develop decision-making and adaptation strategies based on improved physical knowledge or approaches and not on a single assumption based on CC scaling. Full article

The applicability of clinoptilolite zeolites in controlling the emission of greenhouse gases (GHGs) such as CO₂, the most significant GHG, is investigated herein. In this research, Mexican natural zeolites (ATN) originating from an Atzinco deposit in the state of Puebla were used. Samples of modified clinoptilolite (ATH4, ATH3, ATH2 and ATH1) were obtained from the starting material by acid treatment of various intensities. Inverse gas chromatography was used to evaluate CO₂ adsorption in clinoptilolite, natural and chemically modified. Adsorption of CO₂ was investigated in the temperature range of 433–573 K, using a TCD detector, and He as a carrier gas. The experimental CO₂ adsorption data were processed by Freundlich and Langmuir equations. The degree of interaction between CO₂ and the dealuminated clinoptilolite samples was examined through the evaluation of the isosteric enthalpy of adsorption. This calculation was made by using the Clausius–Clapeyron equation, which established the following sequence: ATH1 > ATH2 > ATH4 > ATN > ATH3. The nanoporosity of these clinoptolite zeolites from new deposit in sedimentary rocks was studied through HRADS adsorption of N₂. Simultaneously, these zeolites were, respectively, characterized by XRD, EDS, and SEM. Micropores are described by the Dubinin–Asthakov distribution. Various adsorption mechanisms that occur in these nanoporous materials at different relative pressures can be visualized. The quantitative determination of starting mineral is described as: Ca-Clinoptilolite (88.76%) >> Montmorillonite (11.11%) >> quartz (0.13%). The Si/Al molar ratio after acid treatment is: ATH4 > ATH2 > ATN > ATH3 > ATH1. The Langmuir specific surface area (A_SL) varies as follows: ATN > ATH2 > ATH4 > ATH3 > ATH1. At the same time, the V_Σ values are as follows: ATN > ATH4 > ATH3 > ATH1 > ATH2. Full article

A hydrological–thermal coupling discrete element model depicting the unidirectional freezing process of unsaturated silty clay was developed in order to investigate the migration law of unfrozen water in unsaturated silty clay under unidirectional freezing circumstances. The model uses the contact heat transfer equation to calculate the heat transfer process while taking into account the latent heat of phase transition. To obtain the silty clay’s freezing characteristic curve, the model combines the unfrozen water content curve with the Clausius–Clapeyron equation. The water migration from the unfrozen zone to the frozen zone was calculated using Harlan’s model and the frozen fringe hypothesis. The discrete element application MatDEM 3.0 was used to incorporate the mathematical model for computation, and the output was compared to the result of indoor unidirectional freezing tests. The soil closest to the stable freezing front had the largest water content, according to the findings of numerical modeling and laboratory testing, and unfrozen water in the soil would move from the unfrozen zone to the frozen zone under the action of water potential difference. The results of laboratory tests and numerical simulations can accurately describe the temperature variation and water migration of soil during freezing, demonstrating the accuracy of the established discrete element model and proving the viability of the discrete element method in the study of frozen soil. Full article

N₂ and O₂ adsorption isotherms in chemically modified clinoptilolite-Ca zeolites were experimentally estimated by inverse adsorption chromatography. Natural zeolites (CLINA) were chemically treated with HCl at different concentrations (H1-H4). The adsorption of N₂ and O₂ on these zeolites was studied in the temperature zone of 398–498 K using gas chromatography. This technique used a thermal-conductivity detector and He as carrier gas, at a rate of 30 mL min⁻¹. The Langmuir and Henry equations were used to describe the experimental results of these gases’ adsorption. To evaluate the selectivity of the components of atmospheric air, the chemical activation of the zeolite clinoptilolite-Ca has been carried out. The results are attractive because of the ability to separate the gases these nanomaterials present under dynamic conditions. The structural modifications of the crystalline phases of the studied zeolites were carried out through X-ray diffraction, where the average crystal size was evaluated with the Scherrer equation, finding values of 25.86 nm for CLINA and 15.12 nm for H3 zeolites. The variation of their chemical composition was carried out by energy-dispersive EDS, while the adsorption of N₂ carried out their texture properties at 77 K. The selectivity coefficients (α) were evaluated for these gases in pure form and in a mixture (atmospheric air), finding the highest values in zeolites H4 and H3. The interaction energies between these gases with the porous structures of the studied zeolites were evaluated from the evolution of the isosteric enthalpies of adsorption through the Clausius–Clapeyron equation. Full article