Validity of Molecular Dynamics by Quantum Mechanics

One of the goals of the Saltstone variability study is to identify (and quantify the impact of) the operational and compositional variables that control or influence the important processing and performance properties of Saltstone grout mixtures. The heat capacity of the Saltstone waste form is one of the important properties of Saltstone mixes that was last measured at SRNL in 1997. It is therefore important to develop a core competency for rapid and accurate analysis of the specific heat capacity of the Saltstone mixes in order to quantify the impact of compositional and operational variations on this property as part of the variability study. The heat capacity, coupled with the heat of hydration data obtained from isothermal calorimetry for a given Saltstone mix, can be used to predict the maximum temperature increase in the cells within the vaults of the Saltstone Disposal Facility (SDF). The temperature increase controls the processing rate and the pour schedule. The maximum temperature is also important to the performance properties of the Saltstone. For example, in mass pours of concrete or grout of which Saltstone is an example, the maximum temperature increase and the maximum temperature difference (between the surface and the hottest location) are controlled to ensure durability of the product and prevent or limit the cracking caused by the thermal gradients produced during curing. This report details the development and implementation of a method for the measurement of the heat capacities of Saltstone mixes as well as the heat capacities of the cementitious materials of the premix and the simulated salt solutions used to batch the mixes. The developed method utilizes the TAM Air isothermal calorimeter and takes advantage of the sophisticated heat flow measurement capabilities of the instrument. Standards and reference materials were identified and used to validate the procedure and ensure accuracy of testing. Heat capacities of Saltstone mixes were {approx} 55% higher than the previous measurement of specific heat capacity on a reference Saltstone mix in 1997. Values of mixes prepared using Deliquification, Dissolution and Adjustment (DDA), Modular Caustic Side Solvent Extraction Unit (MCU) and Salt Waste Processing Facility (SWPF) simulants and premix at 0.60 w/cm ratio were {approx} 1.95 J/g/{sup o}C and were equivalent within experimental error. The simple law of mixtures was used to predict the heat capacities of the Saltstone and the results were in excellent agreement with experimental data. This simple law of mixtures can therefore be used to predict the heat capacities of Saltstone mixes in those cases where measurements have not been made. The time dependence of the heat capacity is important as an input to the modeling of temperature increase in Saltstone vaults. The heat capacity of a mix of MCU and premix at 0.60 w/cm ratio was measured immediately after initial mixing and then periodically up to times greater than 100 days. Within experimental error, the heat capacity did not change with time. Therefore, the modeling is not complicated by requiring a time dependent function for specific heat capacity. The water to cementitious material (w/cm) ratio plays a key role in determining the value of the heat capacity. Both experimental and predictive values for SWPF mixes as function of the w/cm ratio were obtained and presented in this report. Predictions of the maximum temperatures of the Saltstone mixes were made using the heat of hydration data from previous isothermal measurements and the newly measured heat capacities for DDA, MCU and SWPF mixes. The maximum temperature increase ranged from 37 to 48 C for these mixes. The presence of aluminate at 0.33 M produced a temperature increase of 68 C which is close to the adiabatic temperature rise of 74 C observed by Steimke and Fowler in 1997 for a mix containing 0.35 M aluminate. Aluminum dissolution of the sludge will increase the aluminate in the DSS which in turn will result in a larger temperature increase in the Saltstone vaults during the curing period. The initial temperature of the Saltstone mixes in the Saltstone Production Facility (SPF) can be predicted using the specific heat capacities of Decontaminated Salt Solutions (DSS), the specific heat capacities of cementitious materials, and the initial temperatures of the DSS and the premix. This initial mix temperature is dominated by the DSS temperature due to its high heat capacity relative to the cementitious materials. Therefore, controlling the initial temperature of the DSS to lower temperatures will lead to lower maximum temperatures in the vault for a given batch of Saltstone.

Theoretical foundations of molecular magnetism: By Roman Boca, in the Series, Current Methods in Inorganic Chemistry, vol. 1, Elsevier, Amsterdam, 1999, 874 pp. ISBN 0-444-50229-7 (hard bound); US$ 356.00

The physical interaction of gases with crystalline solids: III. Heat capacity and the localized-to-mobile transition

Contribution of hydration and non-covalent interactions to the heat capacity effect on protein unfolding

Heat capacities and thermodynamic properties of urea phosphate and its aqueous solutions at various temperatures

An extensive thermodynamic study of N-methylformamide (CAS RN: 123-39-7) and N,N-dimethylformamide (CAS RN: 68-12-2), is presented in this work. The liquid heat capacities of N-methylformamide were measured by Tian-Calvet calorimetry in the temperature interval (250-300) K. The vapor pressures for N-methylformamide and N,N-dimethylformamide were measured using static method in the temperature range 238 K to 308 K. The ideal-gas thermodynamic properties were calculated using a combination of the density functional theory (DFT) and statistical thermodynamics. A consistent thermodynamic description was developed using the method of simultaneous correlation, where the experimental and selected literature data for vapor pressures, vaporization enthalpies, and liquid phase heat capacities and the calculated ideal-gas heat capacities were treated together to ensure overall thermodynamic consistency of the results. The resulting vapor pressure equation is valid from the triple point to the normal boiling point temperature.

Temperature dependences of thermal conductivities and heat capacities for As2S3 and As2Se3-glasses were measured by continuous heating method in the temperature range from the room temperature to the transition temperature range. The following conclusions were obtained.(1) By continuous heating method, thermal conductivities and heat capacities were measured easily and in a short time.(2) Thermal conductivities of these glasses increased slowly with rising temperature and, above the transition range, the conductivities slightly decreased with increase of temperature.(3) Heat capacities of these glasses increased with rising temperature, and in the transition range the temperature dependence showed a sudden change and had a maximum.(4) Temperature dependences of specific heats were determined from the observed heat capacities and specific gravities.(5) The contribution of radiation heat transfer to the total heat transfer was estimated. It is reasonable to consider the heat to be transfered only by conduction, since the contribution of radiation was negligible small in the present work.

Thermal properties of compacted pharmaceutical excipients

Owing to their lower adverse environmental impacts, natural refrigerants have recently attracted a huge deal of attention. In this regard, the present study is aimed to evaluate the thermodynamic properties of different gaseous natural refrigerants at the molecular level using molecular dynamics (MD) simulations. In this context, the density (as a representative of structural features), enthalpy, and specific heat capacity (as representatives of energy properties) of several natural gaseous refrigerants including helium, nitrogen, methane, and ethane were assessed. Lennard-Jones potential was used for simulation of helium and nitrogen while AIREBO potential and OPLS-AA force-fields were employed for simulation of methane and ethane as polyatomic hydrocarbon refrigerants. Simulations are carried out at various temperatures above the boiling point and pressures of 1, 2, and 5 bar. MD results were in good agreement with the experimental data. Among the applied potentials, AIREBO potential offered results closer to the experimental data as compared with OPLS-AA force-field. The methane-ethane mixture was also addressed at different pressures and compared with the Peng-Robinson equation of state. The results of this study indicated that molecular dynamics can be employed as a reliable tool for predicting the thermodynamic properties of natural refrigerants. The results can be used in the refrigeration cycles.

Ni-Co bimetallic nanoparticles with core-shell, alloyed, and Janus structures explored by MD simulation

Structure of methanol-methanol associates in dilute methanol-water mixtures from molecular dynamics simulation

With the limited production and use of R245fa, environmentally friendly refrigerant has attracted the attention of researchers. Due to the similar thermal characteristics, R1233zd(E) is considered to be an ideal substitute for R245fa in heat pump systems. In this study, the performance and economic analysis of heat pump systems with R245fa and R1233zd(E) as refrigerants are carried out. The results show that the total cost of R1233zd(E) system is more than 10% higher than that of R245fa system under the same heating load. With the increase of condensation temperature, the heating capacity of both systems decreases, and with the increase of evaporation temperature, the heating capacity increases. The variation trend of coefficient of performance (COP) of the two systems is similar to that of heating capacity. Under the same operating conditions, the COP of R1233zd(E) system is 19.2% higher than that of R245fa system, and the volumetric heat capacity of R1233zd(E) is 9.0%–13.9% lower than that of R245fa. The economic analysis results show that the investment cost of R1233zd(E) system is low under the same heat load.

Thermal vibration of a circular single-layered graphene sheet with simply supported or clamped boundary

We measured thermal diffusivity and heat capacity of polymers by laser flash method, and the effects of measurement condition and sample size on the accuracy of the measurement are discussed. Thermal diffusivities of PTFE films with thickness 200–500 μm were the same as those data that have been reported. But, the data for film thickness less than 200 μm have to be corrected by an equation to cancel thermal resistance between sample film and graphite layers for receiving light and detecting temperature. Thermal diffusivity was almost unaffected by the size of area vertical to the direction of laser pulse, because heat flow for the direction could be negligible. Specific heat capacity of polymer film was exactly measured at room temperature, provided that low absorbed energy (< 0.3 J) and enough sample mass (> 25 mg) were satisfied as measuring conditions. Thermal diffusivity curve of PS or PC versus temperature had a terrace around Tg, whereas that of PE decreased monotonously with increasing in temperature until Tm. Further, we estimated relative specific heat capacity (RCp) by calculating ratios of heat capacities at various temperatures to the one at 299 K. RCp for PS obtained by laser flash method was larger than that obtained by DSC method, whereas the RCps for PE obtained by the both methods agreed with one another until Tm (305 K). RCp for PS decreased linearly, with increase in temperature after it increased linearly until Tg (389 K), showing similarity to temperature dependency of thermal conductivity. RCp for PE also decreased until Tm, similar to thermal conductivity. ©1995 John Wiley & Sons, Inc.

If the Hamiltonian contains nonquadratic terms, the energy contribution per particle and degree of freedom deviates from 12kT (classical approximation). A very simple case which can be easily treated is that of a particle in a sinusoidal potential field. Energy, free energy, and molar heat are calculated as an example of the resulting deviations from equipartition.