The structure of adsorbed water in cellulose acetate membranes

 The structure of water adsorbed in cellulose acetate membranes is determined by the fundamental and overtone IR spectra. Water is weakly H-bonded to ester and ether groups of the membrane, at low water contents. With increasing water content, more and more liquid-like water is observed. In addition, a small amount of a third type of water is present. The amounts of these three species are estimated from the spectra. At high water contents, the amount of liquid-like water increases strongly. The H-bond cooperativity of such water may be the cause for this increase and for the common anomalous water adsorption isotherms. The H-bond energy of the first hydration shell is relatively small, contrary to the anomalous large adsorption heats ΔH _ad. This could be described by larger van der Waals interactions between this type of water and the membrane groups as a result of a higher coordination number compared with Z=4.4 of liquid-like water. This model is in agreement with the decrease of ΔH _ad with increasing water sorption reaching the evaporization enthalpy of pure water at high water contents. Received: 24 May 1997 Accepted: 1 July 1997     

Influence of Cycle Temperatures on the Thermochemical Heat Storage Densities in the Systems Water/Microporous and Water/Mesoporous Adsorbents

The adsorption equilibrium of water on microporous adsorbents (zeolites of NaA-, NaY- and NaX-type as well as their ion exchanged forms) and on mesoporous adsorbents (different silica gels and composite material i.e. silica gel + salt hydrate) has been studied experimentally and theoretically. Using the Dubinin theory of pore filling the characteristic curves of the adsorption systems and other relevant dependences such as isotherms, isobars, isosteres and the curve of the differential heat of adsorption were calculated. For all systems investigated the adsorption were calculated. A_ads and the desorption potential A_des of the closed heat storage system were estimated. These values define the working range of the adsorption/desorption cycle and allow to calculate the specific heat storage density Δ h_sp. On the basis of Δ h_sp the different adsorbents were compared in order to select the optimal porous storage material for a given application. The presented experimental and theoretical investigations show that the adsorption systems water-zeolite and water-composites are promising working pairs for thermochemical heat storage processes for hot tap water supply and space heating of single family dwellings. The advantage of the water-composite system is the low desorption temperature (solar energy) the main shortcoming the low temperature lift. The advantage of the water zeolite system is the high temperature lift, the shortcoming are the relative high desorption temperatures.     

Thermodynamic investigation of effect of salt concentrations on denatured α-Amylase adsorbed onto a moderately hydrophobic surface

The displacement adsorption enthalpies (ΔH) of denatured α-Amylase (by 1.8 mol L⁻¹ GuHCl) adsorbed onto a moderately hydrophobic surface (PEG-600, the end-group of polyethylene glycol) from solutions (x mol L⁻¹ (NH₄)₂SO₄, 0.05 mol L⁻¹ KH₂PO₄, pH 7.0) at 298 K are determined by microcalorimeter. Further, entropies (ΔS), Gibbs free energies (ΔG) and the fractions of ΔH, ΔS, and ΔG for net adsorption of protein and net desorption of water are calculated in combination with adsorption isotherms of α-Amylase based on the stoichiometric displacement theory for adsorption (SDT-A) and its thermodynamics. It is found that the displacement adsorptions of denatured α-Amylase onto PEG-600 surface are exothermic and enthalpy driven processes, and the processes of protein adsorption are accompanied with the hydration by which hydrogen bond form between the adsorbed protein molecules favor formation of β-sheet and β-turn structures. The Fourier transformation infrared spectroscopy (FTIR) analysis shows that the contents of ordered secondary structures of adsorbed α-Amylase increase with surface coverages and salt concentrations increment.     

Entropy of adsorption of carbon monoxide on energetically heterogeneous surfaces

Standard entropies of adsorption (Δs ⁰) of CO on different materials (Cu catalysts, Au catalysts, ZnO and to TiO₂) are obtained from static adsorption microcalorimetry, adsorption isobars and temperature-programmed desorption, based on the thermodynamics of adsorption on energetically heterogeneous surfaces. Vibrational entropies of the surfaces s _vib^α are normally between the rotational and the standard translational entropy of CO in gas phase, and decrease with increasing adsorption energy, which agrees with the explanation of statistical thermodynamics. Δs ⁰ reflects both the mobility of adsorbates and the specific adsorbate-adsorbent interaction. Limits for reasonable values of the entropy of adsorption are proposed.     

Thermodynamics of Copper Adsorption-Desorption by Ca-Kaolinite

The temperature effect on Cu adsorption and desorption on kaolinite has been investigated at four temperatures (8°C, 25°C, 30°C and 40°C). The clay sample was saturated with Ca. Copper was sorbed from solutions containing eleven Cu concentrations between 0.0010 and 0.0211 M, equilibrated for 2 days. Cu adsorption decreased, but desorption increased with increasing temperature, indicating that adsorption is an exothermic process while desorption is endothermic. These conclusions are confirmed by the values of H ⁰ estimated for adsorption and desorption.The initial copper concentration is a significant factor influencing mainly the adsorption process, which is spontaneous (G ⁰ < 0) only for low initial Cu concentrations. The desorption process is spontaneous for all Cu concentrations. S ⁰ values have also been calculated. Experimental adsorption data were successfully fitted to the Freundlich isotherm and to the Gouy-Chapman model in order to express the process quantitatively.     

Adsorption kinetic,thermodynamic and desorption studies of phosphate onto hydrous niobium oxide prepared by reverse microemulsion method

A type of Nb₂O₅⋅3H₂O was synthesized and its phosphate removal potential was investigated in this study. The kinetic study, adsorption isotherm, pH effect, thermodynamic study and desorption were examined in batch experiments. The kinetic process was described by a pseudo-second-order rate model very well. The phosphate adsorption tended to increase with a decrease of pH. The adsorption data fitted well to the Langmuir model with which the maximum P adsorption capacity was estimated to be 18.36 mg-P g⁻¹. The peak appearing at 1050 cm⁻¹ in IR spectra after adsorption was attributed to the bending vibration of adsorbed phosphate. The positive values of both ΔH° and ΔS° suggest an endothermic reaction and increase in randomness at the solid-liquid interface during the adsorption. ΔG° values obtained were negative indicating a spontaneous adsorption process. A phosphate desorbability of approximately 68% was observed with water at pH 12, which indicated a relatively strong bonding between the adsorbed phosphate and the sorptive sites on the surface of the adsorbent. The immobilization of phosphate probably occurs by the mechanisms of ion exchange and physicochemical attraction. Due to its high adsorption capacity, this type of hydrous niobium oxide has the potential for application to control phosphorus pollution.     

Adsorption and desorption of small molecules for the characterization of solid acids

The relative acid strength and acid amount of solid acids has been determined from the adsorption and desorption of small molecules, such as argon. The order of activation energy for desorption of Ar from a solid acid, determined using temperature-programmed desorption (TPD), is sulfated zirconia > Cs_2.5H_0.5PW₁₂O₄₀ > proton-type zeolites > silica–alumina. The adsorption isotherms were analyzed using Langmuir and Henry equations. The Henry-type adsorption isotherms were also analyzed using the theory of Cremer and Flügge. The heat of Ar adsorption was 22 kJ mol⁻¹ for sulfated zirconia and ca. 17 kJ mol⁻¹ for mordenite, ZSM-5, and beta-zeolite. Molybdenum oxides reduced at 623 and 773 K exhibited a large heat of adsorption (19.3 and 19.7 kJ mol⁻¹, respectively), and these materials are classified as superacids. W-Nb mixed-oxides and tungstated tin oxide (calcined at 1373 K), which are newly developed solid acids, had a heat of adsorption of 18.1 and 16.9 kJ mol⁻¹, respectively. The type of acid site could be distinguished by comparing the heat of adsorption of Ar and N₂. Our data indicate that Ar is useful for the characterization of solid acids.     

The structuredness of solvents

The parameterization of the structuredness of a solvent as the difference between its molar heat of vaporization, Δ_vap H ^° and the sum of its internal donor-acceptor interactions (in terms of DN and AN) and its vdW interactions (in terms of Δ_vap H ^° of n-alkanes of the same molar volume) is criticized. As an alternative, the excess of the reduced Trouton constant, Δ_vapS^°/R over 12 and of Kirkwood's dipole correlation parameter g over 1.7 are suggested as criteria for the decision of whether a solvent is structured, both having to be met. Conversely, if either Δ_vapS^°/R is less than 11.6 or g is less than 1.3, then the solvent is to be considered unstructured. Exceptions are discussed.     

Interpretation of water isotherm hysteresis for an activated charcoal using stochastic pore networks

Water vapor adsorption equilibria on activated carbons typically exhibit hysteresis. The size and shape of the hysteresis loop which separates the adsorption and desorption branches is a strong function of the pore size and interconnectivity of the pores. Neither conventional pore filling models nor statistical thermodynamics approaches provide a means for predicting the extent of hysteresis from only adsorption measurements. This work uses the Kelvin Equation in conjunction with the structural concept of a stochastic pore network to describe measured water isotherms on BPL carbon. Using a pore segment distribution function determined from the adsorption branch, it is shown that totally random assemblies underestimate the extent of hysteresis. It is possible, however, to closely fit the measured BPL-water hysteresis loop using a patchy heterogeneity in which a proportion of the larger pores are preferentially located on the exterior, mid-range pores are concentrated in a sub-surface layer and some large pores form shielded voids behind much smaller pores.Nomenclature p vapor phase partial pressure of sorbate - p _sat saturation vapor pressure of sorbate - R gas constant - r pore radius - T absolute temperature - t adsorbed layer thickness - V _L molar volume of adsorbed phase - surface tension - contact angle     

Studies of the heat of vaporization of water associated with cellulose fibers characterized by thermal analysis

The heat of vaporization (H _vap) of water associated with cellulose fibers versus moisture ratio was determined using modulated differential scanning calorimetry. A steep increase in the H _vap for decreasing moisture ratio was observed at low moisture ratios (0.0–0.3 g/g), indicating a higher energy required to evaporate water interacting with the cellulose. The water molecules with elevated H _vap correspond to non-freezing bound water. This may be attributed to (a) energy to break mono and/or multilayer sorption and (b) energy to overcome capillary forces. For polypropylene and glass fibers, H _vap was constant versus moisture ratio, in agreement with no non-freezing bound water existing in these systems. It is suggested that non-freezing bound water could be used as an indicator of H _vap, and vice versa, at low moisture ratios.     

Removal and recovery of vanadium(V) by adsorption onto ZnCl2 activated carbon: Kinetics and isotherms

Adsorption of vanadium(V) from aqueous solution onto ZnCl₂ activated carbon developed from coconut coir pith was investigated to assess the possible use of this adsorbent. The influence of various parameters such as agitation time, vanadium concentration, adsorbent dose, pH and temperature has been studied. First, second order, Elovich and Bangham’s models were used to study the adsorption kinetics. The adsorption system follows second order and Bangham’s kinetic models. Langmuir, Freundlich, Dubinin-Radushkevich and Temkin isotherms have been employed to analyze the adsorption equilibrium data. Equilibrium adsorption data followed all the four isotherms—Langmuir, Freundlich, D-R and Temkin. The Langmuir adsorption capacity (Q ₀) was found to be 24.9 mg g^{− 1} of the adsorbent. The per cent adsorption was maximum in the pH range 4.0–9.0. The pH effect and desorption studies showed that ion exchange mechanism might be involved in the adsorption process. Thermodynamic parameters such as ΔG ⁰, ΔH ⁰ and ΔS ⁰ for the adsorption were evaluated. Effect of competitive anions in the aqueous solution such as PO₄ ^{3 −}, SO₄ ²⁻, ClO₄ ⁻, MoO₄ ²⁻, SeO₃ ²⁻, NO₃ ⁻ and Cl⁻ was examined. SEM and FTIR were used to study the surface of vanadium(V) loaded ZnCl₂ activated carbon. Removal of vanadium(V) from synthetic ground water was also tested. Results show that ZnCl₂ activated coir pith carbon is effective for the removal of vanadium(V) from water.     

Effect of the solvent on the thermodynamic parameters of conformational transformations: Pseudo effects of the medium

The vaporization enthalpies (ΔH _vap) of 97 primary, secondary, and tertiary alkylphosphines and alkyl(aryl)phosphines with different spatial structures were calculated using the Trouton and Wadso equations and the first-order topological solvation index¹χ^s. The contributions of the H₂P and HP groups and the phosphorus atom to the vaporization enthalpies of primary, secondary, and tertiary phosphines, respectively, were calculated. The results obtained can be used in calculations of ΔH _vap for related phosphorus compounds. For Part 16, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 32–37, January, 2000.     

Thermochemistry of heteroatomic compounds

The vaporization enthalpies (ΔH _vap) of 97 primary, secondary, and tertiary alkylphosphines and alkyl(aryl)phosphines with different spatial structures were calculated using the Trouton and Wadso equations and the first-order topological solvation index¹χ^s. The contributions of the H₂P and HP groups and the phosphorus atom to the vaporization enthalpies of primary, secondary, and tertiary phosphines, respectively, were calculated. The results obtained can be used in calculations of ΔH _vap for related phosphorus compounds. For Part 16, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 32–37, January, 2000.     

Contribution of thermal analysis to the description of transport phenomena of pesticides

The vaporization enthalpies of two acetanilide pesticides, alachlor (2’,6’-diethyl-N-(methoxymethyl)-2-chloroacetanilide) and metolachlor (2-chloro-N-(2-ethyl-6-methylphenyl)-N-[(1S)-2-methoxy-1-methylethyl] acetamide), were determined by processing non-isothermal thermogravimetry data according to the Clausius-Clapeyron equation. The reliability of the procedure proposed was tested carrying out some experiments at different heating rates using acetanilide as a reference compound. A good agreement is found among the vaporization enthalpies derived from all the multi-heating rate experiments as well as with the one predicted from the vapor pressure data taken from literature. The vaporization temperatures (T _vap=470±2 K and T _vap=479±2 K) and enthalpies (Δ_vap H°(436 K)=85±1 kJ mol^–1 and Δ_vap H°(436 K)=70±1 kJ mol^–1) for alachlor and metolachlor, were selected, respectively.     

Time dependent desorption: A memory function approach

A formalism for the adsorption kinetics of systems where the desorption rate is a function of the residence time of the adsorbed particle is presented. The adsorbed density at time t is expressed simply as a convolution of a memory kernel, Q(t), and the available surface function, (t). For completely irreversible adsorption, Q(t) = 1, while for a system which approaches an equilibrium state, Q tends to zero at sufficiently large times. When the desorption rate, k _d , is constant, Q(t) = exp(–k _d t). Two models for the memory kernel are considered. In the first, the molecule is assumed to interact with the surface via two ligands which bind and debind at rates and µ respectively. In the second model, the adsorption is assumed to be partially reversible: molecules transform to a permanently bound state at a rate and desorb at a rate µ. In both models, the adsorption kinetics and memory kernels are found analytically. Strategies for determining the memory function from experimental data are discussed.     

Enthalpies of Dehydrations of Oxalate,Sulfate and Chloride Hydrates by Transpiration Method and DSC

Transpiration method was used to measure the equilibrium water vapor pressures of the dehydration of the respective hydrates, such as oxalates, sulfates,chlorides and acetate, and the enthalpies of dehydrations (ΔH _Tr ⁰) of these hydrates were obtained. The heats of dehydrations (ΔH _DSC ⁰) were also determined by TG-DSC method. From the comparison with ΔH _Tr ⁰ of ΔH _DSC ⁰, the relation of ΔH _DSC ⁰/ΔH _Tr ⁰=R (=dehydration molar number determined by TG-DSC peak/stoichiometric dehydration molar number) was yielded. From these results, the following relations were found: ΔH _DSC ⁰(corrected)=ΔH _DSC ⁰/R=ΔH _Tr ⁰ This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermodynamic parameters of TI+, Ra2+, Bi3+and Ac3+ adsorption onto polyhydroxyethylmethacrylate-hydroxyapatite composite

In this research, a new composite, poly (hydroxyethylmethacrylate-hydroxyapatite) [P(HEMA-Hap)], was synthesized and its adsorptive features for natural radionuclides (TI⁺, Ra²⁺, Bi³⁺and Ac³⁺ in a leaching solution) were investigated at differing initial pH, concentration and temperature ranges. The natural radionuclides were counted by gamma spectrometer using a type NAI (Tl) detector. The adsorption data obtained were well represented by Langmuir and Freundlich type isotherms. The magnitude of determined monolayer adsorption capacities (X _L) for the adsorbed radionuclides were TI⁺ = Ac³⁺ > Ra²⁺ = Bi³⁺. These results demonstrated that P(HEMA-Hap) had high affinity to the natural radionuclide. The thermodynamic parameters indicated that the adsorption mechanisms were spontaneous (ΔG < 0) in terms of adsorption free enthalpy, and changes in the enthalpy and entropy values showed that the overall adsorption process was endothermic (ΔH > 0), thus increasing entropy (ΔS > 0).     

Adsorption of reactive brilliant red K-2BP on activated carbon developed from sewage sludge

Activated carbon was prepared from the sewage sludge of municipal wastewater treatment plant by chemical activation (activation reagent is ZnCl₂) and was used for the adsorption of dye (reactive brilliant red K-2BP). The impact of adsorbent amount, adsorption time and pH value on adsorption effect, the adsorption kinetics, and the adsorption thermodynamics were discussed according to batch adsorption tests. The results indicated that the activated carbon developed from sewage sludge (ACSS), which was mesoporous, possessed opened porous structures. The iodine number of the ACSS was 326 mg·g⁻¹. The rate of achievement was 51.31%. The BET surface area was 298 m²·g⁻¹ and the contents of heavy metals in the leachate didn’t exceed the contents limit. The adsorption kinetics of reactive brilliant red K-2BP on the ACSS was accorded with the two-step kinetics rate equation and pseudo-second-order kinetics equation. Compared to the Freundlich isotherm equation, the Langmuir isotherm equation showed better applicability for the adsorption. The adsorption which was favorable was an endothermic (enthalpy ΔH > 0) and spontaneous (free energy ΔG < 0) process and was accompanied by an increase in entropy (ΔS > 0). __________ Translated from Journal of Shandong University (Natural Science), 2007, 42(3): 64–70 [译自: 山东大学学报(理学版)]     

A comparative study of trace enrichment of chlorophenols in water by extraction with C6 and C8 alkanes and by C18 reversed-phase adsorption

The efficiency, reproducibility and sensitivity ofn-hexane and iso-octane extraction and of C₁₈ reversed-phase adsorption for accumulation of 4-chloro-, 2,4-dichloro-, 2,4,5- and 2,4,6-trichloro-, 2,3,4,6-tetrachloro- and pentachlorophenol from aqueous solutions were compared. In extraction procedures the acetyl and pentafluorobenzoyl derivatives of chlorophenols were extracted from water. In adsorption procedure chlorophenols adsorbed on a Sep-Pak C₁₈ cartridge were eluted with acetone and after that derivatized analogously.All three procedures were found to be applicable for an efficient trace enrichment of chlorophenols in water, the proper choice being dependent on the required sensitivity of the analysis. Lower detection limits of single compounds at 10 ng·1^–1 levels were achieved by adsorption procedure owing to the more uniform and for most chlorophenols higher adsorption than extraction recoveries as well as owing to the possibility of treating larger volumes of water samples. The extraction procedure could be successfully applied to the concentrations of chlorophenols in water 1g·1^–1.Owing to its higher efficiency and better sensitivity the C₁₈ reversed-phase adsorption procedure was chosen as the more suitable one for the determination of chlorophenol levels in surface, ground and drinking waters. The conversion of chlorophenols accumulated from a water sample parallel to both acetyl and pentafluorobenzoyl derivatives and the analysis of both types of derivatives on two basically different gas Chromatographic columns were recommended for a more reliable identification and quantitation of the compounds analyzed.     

Determination of the adsorption volume and surface of carbon adsorbents with developed mesoporosity

The isotherms of excess adsorption of CH₄ (atP=0.001–160 MPa), SF₆ (atP=0.001–2.4 MPa), and C₆H₆ (atP=0.0001–0.1 MPa) on carbon adsorbents—microporous carbons CMS and FAS with developed mesoporosity and graphitized soot—were measured in the 298–408 K temperature region. Calculation of the isotherms of absolute adsorption of the total content of these substances requires knowledge of the adsorption volume, which was determined by different methods: by the Dubinin—Radushkevich equation; by the experimental isotherm of excess adsorption and the equation of absolute adsorption; by the method using the intersection of nonlinear isosteres of excess adsorption and isosteres of absolute adsorption; by the comparative plot of values of the excess C₆H₆ adsorption Γ_FAS—Γ_soor; by the method using the difference of molecular radii of adsorptives and the surface of the specific adsorbent; and by the calculation of the adsorption layer thickness using the FHH equation for mesoporous systems. The results of determination of the adsorption volume for microporous systems of these carbons agree well with each other and with the passport data for the adsorbents. Analysis of the results revealed the peculiarity of the sulfur hexafluoride adsorption related to the formation of associates on the surface of the carbon adsorbents. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 688–696, April, 2000.