Temperature Dependence Of Adsorption Isotherms Research Articles

Insight into the Mechanisms of Low Coverage Adsorption of N-Alcohols on Single Walled Carbon Nanohorn.

We report for the first time the chromatographic study of n-alcohols (from methanol to butanol) adsorption on single walled carbon nanohorn (SWCNH). Using measured temperature dependence of adsorption isotherms (373–433 K) the isosteric adsorption enthalpy is calculated and compared with the data reported for a graphite surface. It is concluded that a graphite surface is more homogeneous, and the enthalpy of adsorption on SWCNHs at zero coverage correlates well with molecular diameter and polarizability, suggesting leading role of dispersive interactions, i.e., no heteroatoms presence in the walls of SWCNH structures. Next using modern DFT approach we calculate the energy of n-alcohols interactions with a graphene sheet and with a single nanocone finally proposing a more realistic—double nanocone model. Obtained results suggest alcohols entrapping between SWCNH with OH groups located toward nanocones ends, leading to the conclusions about very promising future applications of SWCNHs in catalytic reactions with participation of n-alcohols.

Hydrogen adsorption simulations in isomorphous borohydride and imidazolate frameworks: Evaluations using interpolation

We simulate hydrogen adsorption on two topologically identical crystalline solids using the grand canonical Monte Carlo (GCMC) method. One solid is the γ - magnesium borohydride, γ-Mg(BH4)2, the first borohydride crystal with a permanent porosity. The other solid is ZIF-72, Zn(dcIm)2, a zinc imidazolate framework synthesized with dichloroimidazole (dcIm) ligands. Both solids maintain narrow sized pore networks, capable of storing molecular hydrogen. We introduce an interpolation scheme for the temperature dependence of adsorption isotherms. The interpolation employs a special control function based on the adsorption enthalpy. We compare the hydrogen capacities of the two samples at variable temperatures and pressures and attribute the discrepancies to the implicit surface texture and size of the confinements. Notably, the porous Mg(BH4)2 can physically adsorb 3.44 wt% H2 at cryogenic temperatures that is cumulative to the already high content of 14.9 wt% of atomic hydrogen bound on the boron atoms. This content makes the γ-Mg(BH4)2 one of the most hydrogen rich solids reported to date.

Effect of amine double-functionalization on CO2 adsorption behaviors of silica gel-supported adsorbents

Amine double-functionalized adsorbents were fabricated using silica gel as supports and their capabilities for CO2 capture were examined. Aminopropyltrimethoxysilane (1N-APS), and N1-(3-trimethoxysilylpropyl)diethylenetriamine (3N-APS) were used as grafted amine compounds, and tetraethylenepentamine and polyethyleneimine were used as impregnated species. The influence of double-functionalization method on the CO2 adsorption performance and textural properties of adsorbents was investigated. The adsorption capacity, the amine efficiency, and the thermal stability of double-functionalized sorbents depend strongly upon molecular variables associated with two different functional states (i.e., chemically grafted and physically impregnated amines). The temperature dependence of adsorption isotherms reveals that the CO2 adsorption behavior in the double-functionalized adsorbents follow the diffusion limitation model proposed by Xu et al. (Energy Fuels 16:1463–1469, 2002) where the CO2 adsorption is helped by the diffusion of impregnated amines. It is also found that the adsorption isotherm in the double-functionalized sorbent system with a proper choice for grafted and impregnated amines is nearly independent of temperature, which may offer a novel means to fabricate practically useful sorbents that can be used in a wide range of temperature without loss of CO2 adsorption capacity.

Alkali metal cation doped Al-SBA-15 for carbon dioxide adsorption

Mesoporous aluminosilicate adsorbents for carbon dioxide were prepared by the grafting of aluminium into SBA-15 silica using an aqueous solution of aluminium chlorohydrate. As the ion exchange sites are primarily associated with the presence of tetrahedrally coordinated aluminium, extra-framework aluminium on the SBA-15 surface was inserted into the silica matrix by a treatment with an aqueous solution of NH(4)OH. Synthesized mesoporous aluminosilicate preserving all the characteristic features of a mesoporous molecular sieve was finally modified by the alkali metal cation exchange. To examine carbon dioxide adsorption on prepared materials, adsorption isotherms in the temperature range from 0 °C to 60 °C were measured. Based on the known temperature dependence of adsorption isotherms, isosteric adsorption heats giving information on the surface energetics of CO(2) adsorption were calculated and discussed. The comparison of carbon dioxide isotherms obtained on aluminosilicate SBA-15, aluminosilicate SBA-15 containing cations Na(+) and K(+) and activated alumina F-200 reveals that the doping with sodium or potassium cations dramatically enhances adsorption in the region of equilibrium pressures lower than 10 kPa. Therefore, synthesized aluminosilicate adsorbents doped with Na(+) or K(+) cations are suitable for carbon dioxide separation from dilute gas mixtures.

Calculation of immersion enthalpy data from adsorption isotherms

The thermodynamic equations for the calculation of binary and ternary immersion data in excess formalism are presented. Immersion enthalpies and entropies of the n-hexane/ n-octane, n-octane/ n-tetradecane and n-hexane/ n-tetradecane binary mixtures as well as the n-hexane/ n-octane/ n-tetradecane ternary mixture on activated carbon are calculated from the temperature dependence of adsorption isotherms. In order to evaluate the quality of the calculations, the calculated immersion enthalpies of the binary mixtures on activated carbon are compared with those that were measured calorimetrically. It is shown that phenomenological thermodynamics can be used successfully to predict calorimetric data on the basis of adsorption excess isotherms.

The formation and emission of dioxins in large scale thermal processes

The paper assesses extensive data of PCDD/F measurements on flue gas emissions from thermal processes, including, e.g. municipal solid waste incinerators (MSWIs), combustors of wood and industrial waste, coal fired powerplants and boilers, ferro and non-ferro processes. Numerous investigators have conducted laboratory experiments to assess the formation mechanisms of PCDD/F. The results, obtained from fixed-bed experiments, have been critically evaluated and indicate that de novo synthesis is the dominant mechanism in actual thermal processes where conditions that favour the precursor formation are not experienced. The analysis of PCDD/F profiles from the large scale thermal processes in general, and MSWIs in particular, supports the dominant role of the de novo synthesis, irrespective of the type of thermal process considered. The PCDF/PCDD ratio exceeds 1 and the degree of chlorination points towards the dominant presence of HpCDD and OCDD within the dioxin group, and of PeCDF, HxCDF and HpCDF within the furan group. Since real-time measurement of PCDD/F is impossible, the correlation of PCDD/F emissions with operating parameters and/or emission levels of other more easily measured pollutants could be a tool in predicting the PCDD/F formation levels. Data of Flemish MSWIs were used to statistically assess such correlations. From an evaluation of the data at a given operating temperature, misleading conclusions can be drawn. Only the effect of temperature is evident. After converting all data at a reference temperature of, e.g. 230°C, PCDD/F concentrations achieve nearly constant values, irrespective of the values of other parameters, thus stressing that the major controlling parameter for the PCDD/F emission is the temperature of the ESP. The PCDD/F concentrations increase with temperature in the range up to 280°C. The ESP temperature should be kept preferably between 180°C and 200°C, where de novo synthesis is reduced and where PCDD/Fs are increasingly adsorbed on the fly ash, in line with the standard temperature dependence of adsorption isotherms.

Adsorption Isotherms of Hydrogen Isotopes on Molecular Sieves 5A at Low Temperature

Cryogenic Molecular Sieve Bed (CMSB) is considered to be applied to the bred tritium recovery system or the helium glow discharge exhaust gas cleanup system of nuclear fusion reactor. Molecular Sieves 5A (MS5A) is one of the most possible candidate adsorbents for CMSB. To design the CMSB, adsorption isotherm of hydrogen isotopes for MS5A must be investigated in liquid nitrogen temperature region (around 77 K) and above, and isotherm equation which can express the experimental data obtained in wide pressure range with good accuracy needs to obtaining. The present authors carried out the experiments using the volumetric method to obtain the adsorption isotherm of H2 and D2 for MS5A. Adsorption isotherms were obtained in the pressure range between about lPa and 0.2MPa at 77K (liquid nitrogen), 87K (liquid argon), 113K (isopentane), 143 K (n-pentane), 155 K (ethanol) and 195 K (dry ice/ethanol). Two Sites Langmuir Model was applied to understand adsorption isotherms, and was able to express the experimental observation with fairly good accuracy. The apparent heats of adsorption for two kinds of activated adsorption sites were obtained from temperature dependence of adsorption isotherms. Furthermore, parameters of adsorption isotherms for residual 4 hydrogen isotopes (HD, HT, DT and T2) were estimated using reduced mass.

Adsorption Isotherms of Hydrogen Isotopes on Molecular Sieves 5A at Low Temperature.

Cryogenic Molecular Sieve Bed (CMSB) is considered to be applied to the bred tritium recovery system or the helium glow discharge exhaust gas cleanup system of nuclear fusion reactor. Molecular Sieves 5A (MS5A) is one of the most possible candidate adsorbents for CMSB. To design the CMSB, adsorption isotherm of hydrogen isotopes for MS5A must be investigated in liquid nitrogen temperature region (around 77 K) and above, and isotherm equation which can express the experimental data obtained in wide pressure range with good accuracy needs to obtaining. The present authors carried out the experiments using the volumetric method to obtain the adsorption isotherm of H2 and D2 for MS5A. Adsorption isotherms were obtained in the pressure range between about lPa and 0.2MPa at 77K (liquid nitrogen), 87K (liquid argon), 113K (isopentane), 143 K (n-pentane), 155 K (ethanol) and 195 K (dry ice/ethanol). Two Sites Langmuir Model was applied to understand adsorption isotherms, and was able to express the experimental observation with fairly good accuracy. The apparent heats of adsorption for two kinds of activated adsorption sites were obtained from temperature dependence of adsorption isotherms. Furthermore, parameters of adsorption isotherms for residual 4 hydrogen isotopes (HD, HT, DT and T2) were estimated using reduced mass.

Adsorption of Liquids and Swelling of Wood IV. Temperature Dependence on the Adsorption

Summary For the purpose of understanding the swelling phenomenon of wood in liquids, the contributions of enthalpic and entropic terms to the standard free energy change of adsorption have been determined by measuring the temperature dependence of adsorption isotherms. The values of standard enthalpy change of adsorption are smaller for alcohols having both proton-accepting and -donating properties than for acetone having only a proton-accepting property. The results are discussed in terms of the proton-accepting power and the cohesive energy of the respective adsorbate liquids. Methanol showed a larger isosteric heat of adsorption to dried wood than to pre-swollen wood, and the amounts of methanol and acetone adsorbed on dried wood exceeded those on swollen wood within the low activity range. These results indicate the presence of more exothermic sites in dried wood than in pre-swollen wood, and of pre-existing spaces and/or parts loosely hydrogen-bonded between wood constituents in the cell walls of dried wood.

Heterogeneous Three-Site Lattice Model for Adsorption of Aromatics in ZSM-5 Zeolites: Temperature Dependence of Adsorption Isotherms

The three-site lattice model of collective localized adsorption of aromatics in ZSM-5 zeolites, presented in our previous publications, is extended by taking into account the effects of energetic heterogeneity of the sites of the same type. The appropriate theoretical equations are derived and used for simultaneous description of the experimental adsorption isotherms and heats of adsorption of benzene and p-xylene in silicalite at 303 K. It is shown that taking into account this additional level of heterogeneity leads to a much better description of both the adsorption isotherms and the related heats of adsorption in these systems. The extended model also allows one to predict correctly the adsorption isotherms of benzene and p-xylene in silicalite at different temperatures using the parameters found at one temperature.

Application of the partially mobile adsorption model in studies of the temperature dependence of adsorption isotherms

Article Application of the partially mobile adsorption model in studies of the temperature dependence of adsorption isotherms was published on January 1, 1984 in the journal Zeitschrift für Physikalische Chemie (volume 265O, issue 1).

Partially mobile and partially localized monolayer films of gases on solid surfaces V: Application of the model to adsorption of simple gases on graphite and boron nitride

Experimental adsorption isotherms of krypton, xenon, methane and oxygen on graphite and of methane on boron nitride were compared with those predicted by the model of partially localized and partially mobile monolayer adsorption. A previously proposed procedure for investigating the temperature dependence of adsorption isotherms was applied and a satisfactory agreement between experimental and calculated adsorption isotherms was obtained.

Partially mobile and partially localized monolayer films IV: Prediction of the temperature dependence of adsorption isotherms

A previously developed model of partially mobile and partially localized monolayer adsorption is used to construct a method of investigating the temperature dependence of adsorption isotherms. This method is based on the properties of inflexion points of adsorption isotherms. The procedure is used in the interpretation of the physical adsorption of oxygen on graphite.

Temperature Dependence of Adsorption Isotherms of Primary Alcohols at the Liquid-air Interface

IN this communication, we report data on the temperature dependence of surface pressure as a function of concentration for butan-1-ol, hexan-1-ol, and octan-1-ol in aqueous solution. The results are presented in Figs. 1–3.