Application of Activated Carbon Adsorbents Prepared from Prickly Pear Fruit Seeds and a Conductive Polymer Matrix to Remove Congo Red from Aqueous Solutions

The present work was aimed to evaluate the adsorption properties of activated carbons based on prickly pear seeds (PPS) and conductive polymer matrix based on polyaniline (PANI) for the removal of anionic Congo red (CR) dye from aqueous solutions. The adsorbent was prepared by polymerization of aniline in the presence of activated PPS by phosphoric acid and sodium hydroxide. The samples were characterized using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and the Brunauer–Emmett–Teller (BET) methods. The adsorption kinetics were studied using UV-visible (UV/Vis) spectroscopy. The characterization data suggest that the adsorption of the Congo red dye is enhanced because PANI chain molecules, which are especially accountable for removal through π—π interaction and H-bonding with the CR, are adsorbed/tethered onto the acid-activated PPS (PPSH), and thus surmount the mass transfer limitation by being best exposed to the CR-adsorbed molecule. The adsorption kinetics follows the pseudo-second order process. The correlation coefficients (R2) for Langmuir, Freundlich and Tempkin showed that the adsorption values obey Freundlich and Tempkin isotherm models. Moreover, the isotherm was most accurately described by the Freundlich model, and the maximum removal percentage was calculated to be 91.14% under optimized conditions of pH 6.6, 1 g/L of adsorbent dosage, and an initial CR dye concentration of 20 mg·L−1. Importantly, the hybrid adsorbent exhibited the highest adsorption capacity (80.15%) after five cycles of the adsorption–desorption process. Thermodynamic parameters, such as entropy changes, enthalpy changes and Gibbs free energy, were also evaluated. These results indicated that the PANI matrix can generally be better utilized for the removal of Congo red dye when appropriately dispersed on the surface of suitable support materials. These results provide a new direction to promote the separable adsorbents with increasing performance for adsorption of dye impurities from wastewater.

Tetracycline Adsorption from Aqueous Media by Magnetically Separable Fe3O4@Methylcellulose/APTMS (Isotherm, Kinetic and Thermodynamic Studies)

This study aimed to synthesize Fe3O4@Methylcellulose/3-Aminopropyltrimethoxysilane (Fe3O4@MC/APTMS) as a new magnetic nano-biocomposite by a facile, fast, and new microwave-assisted method and to be utilized as an adsorbent for tetracycline (TC) removal from aqueous solutions. Fe3O4@MC/APTMS was characterized by Fourier transform-infrared (FTIR), Field emission scanning electron microscopy (FESEM), Energy dispersive spectroscopy (EDS), Mapping, X-ray diffraction (XRD), Thermal gravimetric analysis (TGA), Brunauer–Emmett–Teller (BET) and vibrating sample magnetometer (VSM). The point of zero charge (pHzpc) value of the nano-biocomposite was estimated to be 6.8 by the solid addition method. Optimum conditions were obtained in TC concentration: 10 mg L−1, adsorbent dosage: 80 mg L−1, contact time: 90 min, and solution pH: 6 with the maximum TC removal of 90% and 65.41% in synthetic and actual samples, respectively. The kinetic and isotherm equations pointed to a pseudo-second order kinetic and Langmuir isotherm optimum fitting models. Based on the values of entropy changes (ΔS) (50.04 J/mol k), the enthalpy changes (ΔH) (9.26 kJ/mol), and the negative Gibbs free energy changes (ΔG), the adsorption process was endothermic, random, and spontaneous. The synthesized adsorbent exhibited outstanding properties, including proper removal efficiency of TC, excellent reusability, and simple separation from aqueous media by a magnet. Consequently, it is highly desirable that Fe3O4@MC/APTMS magnetic nano-biocomposite could be used as a promising adsorbent for TC adsorption from aqueous solutions.

Thermodynamic Solution Properties of a Biodegradable Chelant (L-glutamic-N,N-diacetic Acid, L-GLDA) and Its Sequestering Ability toward Cd2+

The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect was also interpreted in terms of the formation of weak complexes between the ligand and the cations of supporting electrolytes, resulting in a greater tendency of GLDA to chemically interact with Na+ rather than K+ and, in turn, (CH3)4N+. Formation constants of GLDA with Cd2+ were determined in NaCl(aq) at different ionic strength values. Five complex species were found, namely CdL2−, CdHL−, CdH2L0(aq), Cd2L0(aq), and Cd(OH)L3−, whose formation constant values at infinite dilution were log β = 12.68, 17.61, 20.76, 17.52, and 1.77, respectively. All the species results were relevant in the pH range of natural waters, although the Cd2L0(aq) was observed only for CCd ≥ CGLDA and concentrations of >0.1 mmol dm−3. The sequestering ability of GLDA toward Cd2+, evaluated by means of pL0.5, was maximum at pH~10, whereas the presence of a chloride containing a supporting electrolyte exerted a negative effect. Among new generation biodegradable ligands, GLDA was the most efficient in Cd2+ sequestration.

The Thermodynamics of Copper (II) and Nickel (II)- Diamine Complex Formation in Aqueous Solution

<p>This work describes the accurate measurement of the thermodynamic functions Delta G degree and Delta H degree for the step-wise coordination equilibria between each of the ions H+, Ni2+, Cu2+, and, a series of C1-substituted 1,2-diaminoethanes in aqueous solution. The study Involved. (a) The construction of a sensitive constant temperature environment calorimeter for measuring the enthalpy changes in the complex-formation reactions, (b) The rigorous calibration of an electrode system, incorporating a glass electrode, for the direct potentiometric measurement of equilibrium hydrogen ion concentrations in the solutions containing complex ions. The thermodynamic functions Delta G degree and Delta H degree led to accurate Delta S degree values for the step-wise complex-formation reactions. The thesis considers the contribution of the entropy of ligation to the stability of complex ions. The molar entropies of the complex ions have been calculated and their values considered with respect to the coordination number and the possible structure, degree of hydration and steric properties of the ions.</p>

The Thermodynamics of Copper (II) and Nickel (II)- Diamine Complex Formation in Aqueous Solution

<p>This work describes the accurate measurement of the thermodynamic functions Delta G degree and Delta H degree for the step-wise coordination equilibria between each of the ions H+, Ni2+, Cu2+, and, a series of C1-substituted 1,2-diaminoethanes in aqueous solution. The study Involved. (a) The construction of a sensitive constant temperature environment calorimeter for measuring the enthalpy changes in the complex-formation reactions, (b) The rigorous calibration of an electrode system, incorporating a glass electrode, for the direct potentiometric measurement of equilibrium hydrogen ion concentrations in the solutions containing complex ions. The thermodynamic functions Delta G degree and Delta H degree led to accurate Delta S degree values for the step-wise complex-formation reactions. The thesis considers the contribution of the entropy of ligation to the stability of complex ions. The molar entropies of the complex ions have been calculated and their values considered with respect to the coordination number and the possible structure, degree of hydration and steric properties of the ions.</p>

Investigation of the phase transformation characteristics of Fe-Co elastrocalaric refrigeration alloy

Mechanical alloying (AM) and powder metallurgy(PM) have been widely used in many fields especially in the development of new alloy materials due to the advantages of simple process, high material utilization rate and accurate material ratio. In this investigation, experimental procedures were proposed to explore the phase transformation characteristics, elastrocalaric refrigeration effect of Fe-Co alloys synthesized by AM and PM. The samples of Fe-Co elastrocalaric refrigeration alloy with different phase transformation temperatures and different enthalpy changes have been successfully prepared by changing the initial ratio of Co element. The results show that the phase transformation characteristics have changed with the increase of Co content and showed different changing trends.

The first-order phase transition of melting for molecular crystals by Frost–Kalkwarf vapor- and sublimation-pressure equations

Thermodynamic quantities in the coexistence of the liquid and the solid phases for Frost–Kalkwarf vapor- and sublimation-pressure equations are investigated at an isobaric process. Gibbs free energy changes in the gaseous and the liquid phases, ΔG GL, has been derived from the Frost–Kalkwarf vapor-pressure equation. Similarly, Gibbs free energy changes in the gaseous and the solid phases, ΔG GS, may be estimated by the Frost–Kalkwarf sublimation-pressure equations which are determined by data of sublimation pressures and temperatures for 24 substances. In coexistence between the liquid and the solid phases, Gibbs free energy changes in the liquid and the solid phases, ΔG LS, may be expressed as the difference of ΔG GL and ΔG GS. The melting temperatures and enthalpy changes of melting are evaluated by numerical calculations for 24 substances. The behaviors of H2O for the neighborhood at the melting and the boiling points are investigated. The Gibbs free energy indicates two polygonal lines. Entropy, volume and enthalpy jump from the solid to the liquid phase at the melting point and from the liquid to the gaseous phase at the boiling point. The heat capacity does not diverge to infinity but shows a finite discrepancy at the melting and the boiling points. This suggests that first-order phase transitions at the melting and the boiling points may occur.

First and Second Dissociation Enthalpies in Bi-Component Crystals Consisting of Maleic Acid and L-Phenylalanine

The energetics of the stepwise dissociation of a A:B2 bi-component crystal, according to A:B2(cr) → A:B(cr) + B(cr) and A:B(cr) → A(cr) + B(cr), was investigated using MA:Phe2 and MA:Phe (MA = maleic acid; Phe = L-phenylalanine) as model systems. The enthalpy changes associated with these sequential processes and with the overall dissociation reaction A:B2(cr) → A(cr) + 2B(cr) were determined by solution calorimetry. It was found that they are all positive, indicating that there is a lattice enthalpy gain when MA:Phe2 is formed, either from the individual precursors or by adding Phe to MA:Phe. Single-crystal X-ray diffraction (SCXRD) analysis showed that MA:Phe2 is best described as a protic salt containing a maleate anion (MA−) and two non-equivalent L-phenylalanine units, both linked to MA− by NH···O hydrogen bonds (H-bond): one of these units is protonated (HPhe+) and the other zwitterionic (Phe±). Only MA− and HPhe+ molecules are present in the MA:Phe lattice. In this case, however, NH···O and OH···O H-bonds are formed between each MA− unit and two HPhe+ molecules. Despite these structural differences, the enthalpy cost for the removal of the zwitterionic Phe± unit from the MA:Phe2 lattice to yield MA:Phe is only 0.9 ± 0.4 kJ mol−1 higher than that for the dissociation of MA:Phe, which requires a proton transfer from HPhe+ to MA− and the rearrangement of L-phenylalanine to the zwitterionic, Phe±, form. Finally, a comparison of the dissociation energetics and structures of MA:Phe and of the previously reported glycine maleate (MA:Gly) analogue indicated that parameters, such as the packing coefficient, density, hydrogen bonds formed, or fusion temperature, are not necessarily good descriptors of dissociation enthalpy or lattice enthalpy trends when bi-component crystals with different molecular composition are being compared, even if the stoichiometry is the same.

Preparation and DFT Study for New Three-Ring Supramolecular H-Bonded Induced Liquid Crystal Complexes

Supramolecular three-ring Schiff base novel liquid crystal complexes have been prepared and investigated. Schiff bases of para-substituted aniline derivatives and para-pyridine carbaldehyde have been prepared and then mixed in equimolar quantities with para-alkoxy benzoic acids. On one side, the alkoxy chain length varies from 8 to 16 carbon atoms. On the other side, terminal small compact groups substituting aniline with various polarities are used. Hydrogen-bonding interaction was elucidated by FTIR spectroscopy. The mesomorphic thermal and optical characteristics of the samples were obtained by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). All samples exhibit enantiotropic mesophases. Experimental results obtained for the induced mesophases were correlated with density functional theory (DFT) theoretical calculations. The results revealed that both the polar compact groups’ polarity and the alkoxy chain lengths contribute strongly to mesomorphic characteristics and thermal stabilities of the mesophases. Surprisingly, the observed values of enthalpy changes associated with the crystalline mesomorphic transitions lie in the range of 2.2–12.5 kJ/mol. However, the enthalpy changes corresponding to the mesomorphic–isotropic transitions vary from 0.9 to 13.9 kJ/mol, depending on the polarity of para-attached groups to the aniline moiety.

Pyridine-Based Three-Ring Bent-Shape Supramolecular Hydrogen Bond-Induced Liquid Crystalline Complexes: Preparation and Density Functional Theory Investigation

A series of new supramolecular three-ring bent-shape Schiff base liquid crystal (LC) complexes were prepared and studied. On one side, two alkoxy chain lengths of the carboxylic acids were used, namely eight and sixteen carbons. Moreover, on the other side, terminal small compact groups, which substituted aniline, with different polarities were utilized. Furthermore, the hydrogen-bonding interactions in the formed complexes were elucidated by Fourier-transform infrared (FT–IR) spectroscopy. The mesomorphic thermal and optical characteristics of the samples were determined by differential thermal analysis (DSC) and polarized optical microscopy (POM). The complexes exhibited enantiotropic and dimorphic mesophase behaviors. The results indicate that the polarity of the compact groups and the lengths of the alkoxy chains greatly impacted the mesomorphic characteristics and thermal stabilities of the mesophases. The observed values of the enthalpy changes (ΔH) associated with the crystalline smectic-A (TCr-SmA) transitions were extremely small compared with the conventional values that characterize supramolecular hydrogen-bonded liquid crystalline complexes. ΔH, which corresponded to the nematic isotropic transitions (TN-I), varied from 0.13 to 9.54 kJ/mol depending mainly on the polarity of the groups that were para-attached to the aniline moiety. Finally, the theoretical results obtained by density functional theory (DFT) calculations were discussed. The DFT geometrical structures showed non-coplanar structures. The mesomorphic range was correlated with the calculated dipole moment, polarizability and the aspect ratios of the investigated compounds.