Clausius-Clapeyron Research Articles

The impact of stratospheric aerosol heating on the frozen hydrometeor transport pathways in the tropical tropopause layer

The exceptionally low temperature in the tropical tropopause layer (TTL) restricts the amount of water vapor entering the stratosphere. However, moisture may also enter the stratosphere in its frozen state, and the amount thereof depends on hydrometeor sedimentation and air vertical velocity. We investigate the sensitivity of frozen hydrometeor transport pathways to substantial perturbations of the TTL temperature structure in global storm-resolving model simulations. A special focus is laid on the question which process—convection, slow upwelling within the background velocity field, in-cloud radiative processes, gravity waves or turbulence—is responsible for most of the transport. The study shows that the main contribution to the frozen hydrometeor flux is cold-point overshooting convection in both the control and perturbed scenario. The average convective event transports an increased amount of frozen hydrometeors at the cold-point tropopause, when the later is warmed. This finding can be explained by scaling of frozen moisture content with Clausius Clapeyron in a saturated environment.

Climate change impacts on rainfall intensity–duration–frequency curves in local scale catchments

The increasing intensity and frequency of rainfall events, a critical aspect of climate change, pose significant challenges in the construction of intensity–duration–frequency (IDF) curves for climate projection. These curves are crucial for infrastructure development, but the non-stationarity of extreme rainfall raises concerns about their adequacy under future climate conditions. This research addresses these challenges by investigating the reasons behind the IPCC climate report’s evidence about the validity that rainfall follows the Clausius-Clapeyron (CC) relationship, which suggests a 7% increase in precipitation per 1 °C increase in temperature. Our study provides guidelines for adjusting IDF curves in the future, considering both current and future climates. We calculate extreme precipitation changes and scaling factors for small urban catchments in Barranquilla, Colombia, a tropical region, using the bootstrapping method. This reveals the occurrence of a sub-CC relationship, suggesting that the generalized 7% figure may not be universally applicable. In contrast, our comparative analysis with Illinois, USA, an inland city in the north temperate zone, shows adherence to the CC relationship. This emphasizes the need for local parameter calculations rather than relying solely on the generalized 7% figure.

On thermodynamics and heat and mass transfer aspects of CH4 adsorption onto coconut shell-based carbonaceous material

The current study investigates the equilibrium methane (CH4) adsorption capacity and the adsorption kinetics of a locally produced coconut shell-derived activated carbon (AC CARB 6X12 60) for pressure and temperatures ranging from 0 to 55 bar and -20 to 70 °C, respectively. The adsorption isotherms and kinetics are determined using an in-house developed adsorption test rig. A maximum methane adsorption uptake of 0.140 kg/kg is obtained at -20 °C and 40 bar pressure. The adsorption equilibrium isotherm data are fitted using Toth, Dubinin-Astakhov (DA), and Modified-DA isotherm models. Afterwards, the kinetics study is done considering pseudo first order, second order, Elovich, and intra-particle diffusion models. In continuation, based on the DA isotherm model, Clausius Clapeyron relation, and Maxwell's relations, the expressions for the crucial thermodynamic parameter of adsorbed phase, i.e., isosteric heat of adsorption, specific heat capacity, enthalpy, and entropy is derived, and same is estimated using DA isotherm parameters. Additionally, the activated carbon's thermophysical properties (i.e., thermal conductivity, thermal diffusivity, and specific heat) are determined using the TPS 2500 S analyzer, which works on the hot-disk principle. Using the most suitable isotherm (DA) and kinetic model (pseudo second order), heat and mass transfer analysis is carried out on novel reactor configuration with an external cooling jacket, double row of cooling pipes with external longitudinal fins for methane storage using a 3D transient model in Comsol Multiphysics. The charge characteristics are studied for gas charging pressure varying from 1 to 50 bar and cooling fluid temperature of -20 to 70 °C. Iso-concentration contours are plotted to identify the pressure-temperature combination resulting in identical storage capacity (i.e., including both gaseous and adsorbed phases). Further simulations are carried out for constant pressure charging and constant flow discharge conditions to expound upon the effects of the dormancy period, gas charging pressure, and cooling/heating fluid temperature. 14% improvement in total discharge amount is obtained with a dormancy period between charging and discharging compared to no dormancy case.

Python-Based Algorithm for Estimating the Parameters of Physical Property Models for Substances Not Available in Database.

An in-house Python-based algorithm was developed using simplified molecular-input line-entry specification (SMILES) strings and a dipole moment for estimating the normal boiling point, critical properties, standard enthalpy, vapor pressure, liquid molar volume, enthalpy of vaporization, heat capacity, viscosity, thermal conductivity, and surface tension of molecules. Normal boiling point, critical properties, and standard enthalpy were estimated by using the Joback group contribution method. Vapor pressure, liquid molar volume, enthalpy of vaporization, heat capacity, and surface tension were estimated by using the Riedel model, Gunn-Yamada model, Clausius-Clapeyron equation, Joback group contribution method, and Brock-Bird model, respectively. Viscosities of liquid and gas were estimated by using the Letsou-Stiel model and the Chapman-Enskog-Brokaw model, respectively. Thermal conductivities of liquid and gas were estimated by using the Sato-Riedel model and Stiel-Thodos model, respectively. Dipole moment was calculated through molecular dynamics simulation using the MMFF94 force field, performed with Avogadro software. A case study was conducted with dihydro-2-methyl-3-furanone (DHMF), 2-furaldehyde diethyl acetal (FDA), 1,1-diethoxy-3-methyl butane (DEMB), glutathione (GSH), vitamin B5 (VITB5), homocysteine (HCYS), and O-acetyl-l-homoserine (AH), which are not present in the existing property database. Cross-validation indicated that the developed Python-based algorithm provided pure component model parameters nearly identical with those obtained with the Aspen Property Constant Estimation System (PCES) method, except for the enthalpy of vaporization. The parameters for estimating the enthalpy of vaporization using the current Python-based algorithm accurately represented the behavior of the actual substances, as determined using the Clausius-Claperyon equation. This Python-based algorithm provides a detailed and clear reference for estimating pure property parameters.

A Novel Generalized Clapeyron Equation-Based Model for Capturing the Soil Freezing Characteristics Curve of Saline Soil: Validation by Small Sample Lab and Field Experiments

The soil freezing characteristic curve (SFCC) describes the relationship between the freezing point and unfrozen water content, which are two critical parameters in depicting the heat, solute, and water transport in frozen soil. In this paper, we propose a novel Generalized Clapeyron Equation (GCE)-based model, the GCE-Salt Model, to better capture the SFCC in frozen soil in the presence of solute. It keeps the matric potential Ψf in the GCE as its original meaning and incorporates the effect of solute potential in the equilibrium freezing temperature. The performance of our GCE-Salt Model was validated by both lab and field experimental data and compared with related models (Combined Model and GCE-Tan Model). The GCE-Salt Model performed exceptionally well in extremely saline soil and it performed well in both non-saline and saline soil. (1) Our GCE-Salt Model could capture the SFCC of non-saline soil equally as well as the Combined Model (NSE = 0.866); (2) our GCE-Salt Model performed similarly well as the Combined Model and a little better than the GCE-Tan Model for the slightly to highly saline soil (NSE ≥ 0.80 for three models); and (3) our GCE-Salt Model (NSE = 0.919) beat the Combined Model (NSE = 0.863) and the GCE-Tan Model (NSE = 0.62) in capturing the SFCC of extremely saline soil, mainly because the inherent expression of our GCE-Salt Model can more accurately capture the freezing point. Our findings highlight the effect of solute potential on the ice–water change and could improve the understanding of the effect of freezing and thawing on the thermal–hydrological processes, structure of saline soil, and landscape evolution in cold regions.

Single-Component Adsorption Equilibria of CO2, CH4, Water, and Acetone on Tapered Porous Carbon Molecular Sieves.

Engineered carbon molecular sieves (CMSs) with tapered pores, high surface area, and high total pore volume were investigated for their CO2, CH4, water, and acetone adsorption properties at 288.15, 298.15, 308.15 K, and pressures of <1 bar. The results were compared with BPL carbon. The samples exhibited higher adsorption capacity for CO2 compared to BPL carbon, with Carboxen 1005 being the highest due to the presence of ultramicropores (pores smaller than 0.8 nm). Similar observations were made for CH4 except at 288.15 K. Although the CMSs exhibited higher hydrophobicity than BPL carbon, the latter had the highest acetone uptake for all investigated temperatures due to its higher oxygen content, which facilitates stronger interactions with polar VOC molecules. Heats of adsorption were calculated using the Clausius-Clapeyron equation after fitting the isotherms with the dual-site Langmuir-Freundlich model, and results largely corroborated the order of adsorption capacities of CO2, CH4, and water on the carbon materials.

Sublimation enthalpies of organic compounds by isothermal thermogravimetry

AbstractAn improved method has been developed to determine the sublimation enthalpies of solid organic compounds using thermogravimetric analysis and applying an isothermal methodology with a TA Instruments® SDTQ600 equipment. This was achieved by measuring the rate of mass loss as a function of the temperature from isothermal experiments in an interval of temperature of 10 to 20 K below the melting temperature of the sample. The resulting rates of mass loss were used by applying the Pieterse and Focke equation, then combined with the integrated Clausius–Clapeyron equation to calculate the heat of sublimation at the experimental temperature and it was corrected to T = 298.15 K. In order to demonstrate the reliability of this methodology, the results for benzoic acid, pyrene and phenanthrene are presented, which are respectively primary, secondary, and tertiary reference compounds in the measurement of enthalpies of sublimation, along with the sublimation enthalpies of picolinic acid, nicotinic acid and isonicotinic acid which are three pyridinecarboxylic acids isomers with the carboxyl group in the ortho, meta and para position, respectively, to the nitrogen of the pyridine.

Sensitivity Analysis of Start Point of Extreme Daily Rainfall Using CRHUDA and Stochastic Models

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).

Numerical implementation and verification of the Zwart-Gerber-Belamri cavitation model with the consideration of thermodynamic effect

In the world of pumps, turbopumps, and industrial applications, the absorption and release of latent heat in high-temperature zones play a pivotal role in the cavitation process. This phenomenon exerts a profound influence on system performance, especially when handling hot and cryogenic fluids, which are particularly susceptible to thermodynamic influences. The pressing need arises for a robust computational approach to address the intricacies of thermodynamic effects on cryogenic cavitation. The study at hand introduces a modification to the Zwart-Gerber-Belamri cavitation model, incorporating thermodynamic considerations to simulate quasi-steady cavitating flow around a NACA0015 hydrofoil. The SST k-ε turbulence model and homogeneous mass transfer cavitation model are employed to account for thermal effects, while the Clausius-Clapeyron equation is utilized to adjust the saturated vapor pressure within the cavitation model. Comparing the results with experimental data from Cervone et al. [1], especially in the thermal domain, reveals congruence in the estimated pressure and temperature drop (ΔT) within the cavity under varying free stream temperature conditions. Notably, thermodynamic effects exert a significant influence on cavitation dynamics during the phase-change process, potentially hindering or delaying cavitation in hot and cryogenic fluids. This enhanced cavitation model offers a marginally improved prediction of cavitation in water.

On the response of daily precipitation extremes to local mean temperature in the Yangtze River basin

This study explores the response of daily extreme precipitation (PEX) to local mean temperatures (T) of the previous 0-day (T0), 1-day (T1), and 1 to 9-days (T1–9) in the Yangtze River basin (YRB) using the non-stationarity test, binning method and copula theory. Results show that the annual scaling rate of PEX with T during 1961–2020 exhibits positive, negative and positive changing trends from southwest to northeast with the maximum magnitudes in the west, and experiences significant abrupt change only at 14.1% grids. The PEX-T scaling relation in the entire study period is predominantly characterized by a peak pattern over the YRB, with precipitation peaking at about 8 °C in the western highlands and at 25 °C in the east-central lowlands. However, the use of T1–9 yields a positive PEX-T pattern at more grids compared to T1 and T0, which highlights the important role of atmospheric moisture residence time in minimizing cooling artefacts in the scaling estimation. Generally, the full scaling rate of PEX with T in the study period is larger in the west-central part but smaller in the eastern YRB, and more sensitive to antecedent temperatures, with the ranges of −8–20%/°C, −8–30%/°C and −10–30%/°C against T0, T1 and T1–9, respectively. As precipitation intensifies, the full scaling decreases in plateau-mountain areas but increases in low-lying regions, gradually approaching the Clausius-Clapeyron (CC) scaling and exhibiting a “super-CC, CC-like and sub-CC scaling” pattern from west to east. Additionally, heavier precipitation events are most likely to occur at higher local temperatures in most areas even with peak structure. These findings provide new insights into the PEX-T relationships, which is conducive to understanding future changes in precipitation extremes and assessing precipitation-related risks under climate change.

Investigating the Relationship between Sea Surface Temperature and the Mechanical Efficiency of Tropical Cyclones

Abstract Previous studies have investigated how sea surface temperature (SST) affects the potential intensity of tropical cyclones (TCs). However, this is an upper bound only on the maximum near-surface azimuthal winds and does not fully account for the effects of atmospheric moisture. Potential intensity might not vary in the same way as the total kinetic energy (WKE) of a TC would with changing SST. The term WKE is related, via the conceptualization of the TC as a heat engine, to TC mechanical efficiency. We investigate how TC mechanical efficiency varies with SST in a series of moist, axisymmetric, radiative–convective numerical experiments with constant SSTs ranging from 295 to 307.5 K. We find a −2.1% K−1 decrease in the mechanical efficiency with SST. While the increase in the net heat energy gained by the TC heat engine acts to increase WKE, the mechanical efficiency still decreases with SST due to the effects of moisture on WKE and on the total heat input to the TC. Moist convection in an unsaturated atmosphere is associated with substantial irreversible entropy production, which detracts from the energy that the TC can use to power its winds. The increasing moisture content in a warmer atmosphere predicted by Clausius–Clapeyron scaling leads this irreversibility to increase in an unsaturated atmosphere, presenting a larger penalty on WKE and decreasing the mechanical efficiency. Our results highlight the importance of giving full consideration to the effects of moisture on the TC heat engine in studies of how climate affects TCs. Significance Statement The purpose of this study is to investigate how the “mechanical efficiency” of tropical cyclones varies with sea surface temperature. This matters because the conceptualization of the tropical cyclone as a heat engine implies that the kinetic energy of its wind field is generated at this efficiency. The mechanical efficiency may be affected by changes in climate. Our results demonstrate that the mechanical efficiency decreases at −2.1% K−1 with sea surface temperature, and in particular highlight the important role of moisture in this result.

Non-local modelling of freezing and thawing of unsaturated soils

A large part of the earth’s surface is covered by seasonally or permanently frozen soils. Considering the negative impact of climate change, future development of such regions can be underpinned by mathematical methods for accurate analysis of heat and moisture transport in freezing and thawing soils. Reported in this paper is a novel non-local formulation of water and heat transport in unsaturated soils. The formulation uses bond-based peridynamics (PD) and consists of a set of integral–difference formulations of energy and mass conservation. Specific features of freezing/thawing soils are incorporated by a combination of van Genuthcen and Clausius–Clapeyron relations. Computational results are compared with four sets of laboratory experiments to demonstrate the efficiency of the developed approach. The model can be used to analyse the effect of water flow on heat transfer in soils during thawing of permafrost soils. Further, it can be applied in modelling climate change effects, and can be used for construction of coupled physically justified models of frost heave.

Constraining the Pattern and Magnitude of Projected Extreme Precipitation Change in a Multimodel Ensemble

Abstract Projections of precipitation extremes over land are crucial for socioeconomic risk assessments, yet model discrepancies limit their application. Here we use a pattern-filtering technique to identify low-frequency changes in individual members of a multimodel ensemble to assess discrepancies across models in the projected pattern and magnitude of change. Specifically, we apply low-frequency component analysis (LFCA) to the intensity and frequency of daily precipitation extremes over land in 21 CMIP-6 models. LFCA brings modest but statistically significant improvements in the agreement between models in the spatial pattern of projected change, particularly in scenarios with weak greenhouse forcing. Moreover, we show that LFCA facilitates a robust identification of the rates at which increasing precipitation extremes scale with global temperature change within individual ensemble members. While these rates approximately match expectations from the Clausius-Clapeyron relation on average across models, individual models exhibit considerable and significant differences. Monte Carlo simulations indicate that these differences contribute to uncertainty in the magnitude of projected change at least as much as differences in the climate sensitivity. Last, we compare these scaling rates with those identified from observational products, demonstrating that virtually all climate models significantly underestimate the rates at which increases in precipitation extremes have scaled with global temperatures historically. Constraining projections with observations therefore amplifies the projected intensification of precipitation extremes as well as reducing the relative error of their distribution.

Prediction of Clausius–Clapeyron Scaling of Daily Precipitation Extremes over China

Abstract Observations and model simulations have confirmed that the higher percentiles of precipitation intensity of all wet days have increased with the local daily dewpoint temperature at the Clausius–Clapeyron (C-C) rate of 7% °C−1 using the binning technique over China. It is uncertain whether the binning scaling rates will remain constant in the future climate. Here, we use daily precipitation and dewpoint temperature (DPT) over China from 20 CMIP6 models to examine and project the change of binning scaling of precipitation extremes. The results of the study suggest that the multimodel ensemble median (MEM) generally captures the spatial distribution of binning scaling rates and binning curves in different climate zones across China. The binning scaling rates have stability in the future but with a large increasing trend (more than 30%) in southeast China in the far future (2061–2100) under the SSP5-8.5 scenario. CMIP6 models project that both the peak of extreme precipitation and the temperature for the plateau mountain zone will increase in the far future under the SSP5-8.5 scenario, implying that the peak structure does not provide an upper limit for future precipitation extremes. Significance Statement The binning scaling rates describe the relationship between precipitation extremes and temperature based on their day-to-day variations. However, it is still unclear whether the binning scaling rates of daily precipitation extremes with daily temperature will change in the future. We use 20 CMIP6 models to project the scaling rates of precipitation extremes with dewpoint temperature over China in the future. The results show that the sensitivity of precipitation extremes to dewpoint temperature will generally be stable, except that southeast China shows an increasing trend of up to 30%. Moreover, the peak of extreme precipitation and the temperature will increase with warming in the plateau mountain zone. Our results have implications for precipitation prediction and risk assessment.

Precipitation Scaling in Extreme Rainfall Events and the Implications for Future Indian Monsoon: Analysis of High‐Resolution Global Climate Model Simulations

AbstractThe increase in water holding capacity of the atmosphere with temperature, given by the Clausius‐Clapeyron (CC) relationship, describes the changes in extreme rainfall intensities at warmer atmospheric states. We study the characteristics of extreme rainfall events (EREs) during the Indian summer monsoon season with respect to thermodynamic changes and precipitation‐scaling over the Indian subcontinent and its homogeneous rainfall zones. We utilize outputs from a present‐day climate simulation and a time‐slice future climate change projection experiments of a high‐resolution global climate model. Large changes are seen for very EREs (vEREs) which suggests their sensitivity to warmer temperatures. In future, the altered radiative forcing will heat up the upper atmosphere, stabilize it and offset the effect of increasing humidity on precipitation intensity. Our analysis also suggests that more convective clouds and the interplay of increased moisture content and circulation will result in future changes in EREs.

Pressure Impact on Lattice Thermal Conductivity and Its Related Parameters in CdSe Bulk, Nanowires, and Thin Film

The hydrostatic pressure effect on lattice thermal conductivity (LTC) in CdSe bulk, nanowires, and thin films was calculated. Values of LTC obtained through Callaway with that of Clapeyron equations are used to correlate those of the experimentally measured curves. Frequency‐dependent relaxation time approximation of phonon‐scattering processes was considered, which scattering due to boundary, imperfections, dislocations, electron, and other phonons via Umklapp and normal processes were used and clarified their effects. The impact of pressure on LTC is clarified according to both sample boundary dislocation concentrations. The influence of pressure is described, along with how the size dependence of the melting temperature, Debye temperature, and phonon group velocity of CdSe nanocrystals is affected. These parameters decrease as pressure increases.

Thermal hazard analysis and fire risk assessment of rocket kerosene in oxygen-enriched environment

Fire hazard of liquid fuel exposed in oxygen-rich environment is significantly greater than that in air, which should be considered in the safety risk assessment of scenarios where oxygen and fuel coexist. To reveal the effect of oxygen concentration on fuel properties and combustion characteristics of liquid fuel, a series of experiments were conducted to measure the liquid-phase component, flash point, lower flammability limit, heat release rate and flame height of rocket kerosene at different oxygen concentrations. The results show that the flash point of rocket kerosene (with an average chemical formula of C11.98H22.64) decreases nonlinearly with the increased oxygen concentrations, while the oxygen concentration has a great enhancement effect on the heat release rate and visible flame height of rocket kerosene pool fire. Prediction models of the flash point and lower flammability limit based on the Clausius-Clapeyron equation, Le Chatelier rule and decreasing temperature assumption, as well as empirical equations of the heat release rate and visible flame height, were derived for different oxygen concentrations in this work, providing a new comprehensive understanding of the effect of oxygen concentration on the rocket kerosene, and could be further applied to fire risk assessment in liquid fuel and oxygen coexisting scenarios.

Non-linear temperature dependences of pseudoelastic stress and stress hysteresis of a nanocrystalline Ni47Ti50Fe3 alloy

This paper reports a study on non-linear temperature dependences of the critical pseudoelastic stress and stress hysteresis for stress-induced martensitic transformation deformation of a nanocrystallined Ni47Ti50Fe3 alloy. Such non-linear temperature dependences were found over a wide low temperature range from -196 °C to 20 °C and they defy the predictions of the Clausius-Clapeyron law for the transformation. The pseudoelastic behaviour exhibited two unusual characteristics, including a progressively decreasing dσ/dT slope and a rapidly widening stress hysteresis with decreasing the temperature. In-situ X-ray diffraction analysis indicated that the starting microstructure of the alloy for pseudoelastic deformation was a mixture of the B2 and a crystallographically suppressed R phase (denoted R*) within -8 °C to -196 °C. The volume fraction, the rhombohedral lattice distortion and the internal atomic shuffle of the suppressed R phase increased upon cooling. These continued evolutions of the crystal structure of the R* phase and the microstructure of the alloy upon cooling are ascribed to be responsible for the abnormal non-linear temperature dependences of the pseudoelastic stresses and the widening of the stress hysteresis.

Experimental thermochemical study of aryl nitriles: A structural energetic approach

The present work comprised a study of the thermochemical properties of three aryl nitriles: Methyl p-cyanobenzoate, p-Acetylbenzonitrile, and p-Methoxybenzonitrile. This study was carried out using calorimetric and thermal analysis techniques. Through differential scanning calorimetry, we obtained the temperatures and enthalpies of fusion, as well as the heat capacities in the crystal phase. Specific combustion energies were determined through static bomb combustion calorimetry, from which, the enthalpies of formation in the condensed phase were derived. Additionally, isothermal thermogravimetry was used to measure the mass loss rate as a function of temperature. Using the Langmuir equation in conjunction with benzoic acid as a calibration material, vapor pressures were determined as a function of temperature. With the obtained vapor pressures and the Clausius-Clapeyron equation, enthalpies of sublimation were calculated. Moreover, entropies and Gibbs sublimation energies were determined at T = 298.15 K. Finally, using these properties, enthalpies of formation in the gaseous phase at T = 298.15 K were calculated for the three mentioned compounds. With these data, an analysis of the energetic effect of different substituents in benzonitrile is presented.

High adsorption selectivity of activated carbon and carbon molecular sieve boosting CO2/N2 and CH4/N2 separation

High adsorption selectivity of activated carbon and carbon molecular sieve boosting CO2/N2 and CH4/N2 separation