Molar Entropy Research Articles

Strategic co-doping of ceria for improved oxidation kinetics in solar thermochemical fuel production

La and Yb were incorporated as co-doping elements into Zr-doped ceria to investigate the influence of doping ions by means of ionic radius and valence on the ceria crystal lattice and potentially on thermodynamic and kinetic properties relevant to solar-driven two-step thermochemical CO2 splitting. Both Zr–La and Zr–Yb co-doped ceria clearly exhibited better reduction capability than ceria and partial molar enthalpy and entropy that were in between those of Zr-doped ceria and undoped ceria. In the case of CO2 splitting kinetics, Zr-doped ceria was the slowest in accordance with relevant literature, but La-doped samples were much faster than Yb-doped counterparts suggesting that extrinsic oxygen vacancy formation, even though important, does not primarily determine the CO2 splitting kinetics unlike the hypothesis postulated by previous works. This work elucidates the role of dopant's ionic radius, lattice constant and valence on thermodynamics and CO2 splitting kinetics via experimental demonstration, and provides a new doping strategy not based on the extrinsic oxygen vacancy formation but based on the dopant ionic radius and valence with an insight for the further doped ceria-based redox material discovery.

Physicochemical insights into the micellar delivery of doxycycline and minocycline to the carrier protein in aqueous environment

Physicochemical understanding of the micellar drug delivery is essential for designing efficient drug carrier molecules. An in-depth analysis of the partitioning mechanism of drugs in a quantitative manner and the effects of partitioning on the delivery of drugs through micellar media is a subject of enormous research. This paper focuses on the quantitative measurements of the binding of two antibiotic drugs from tetracycline family, doxycycline and minocycline with the carrier protein human serum albumin (HSA). The partitioning of both the drugs in the micellar system of hexadecyltrimethylammonium bromide (HTAB) and their delivery to HSA through this micellar system was also studied applying spectroscopy and calorimetry. A combination of fluorescence spectroscopy, isothermal titration calorimetry (ITC) and docking studies suggest that both the drugs bind close to Site I of HSA. The ITC results establish that the association of drugs with the protein occurs with an affinity of 103-104 M−1 and the binding is mainly entropy driven. The partitioning mechanisms have been evaluated in terms of the values of the changes in values of standard molar Gibbs free-energy, enthalpy, entropy, and partitioning stoichiometry. The thermodynamic signatures associated with the drug-HSA binding in the presence of HTAB micelles suggest that the partitioning of doxycycline/minocycline in the micelles of HTAB changes their interaction behavior with HSA. These findings provide deep understanding about the micellar drug delivery systems, thereby suggesting their potential applications in strategies for more effective therapeutics.

Thermodynamic properties for some diatomic molecules with the q-deformed hyperbolic barrier potential

In this paper, we obtain analytical vibrational partition function with recent energy spectrum of the deformed hyperbolic barrier potential. We derive different thermodynamic properties for the , , , , and diatomic molecules. In addition, we obtain the total molar entropy for the two last molecules. Our results are in excellent agreement with the experimental data.

Разработка методов получения углеродных адсорбентов на основе Ангренского угля и нефтяных остатков

Currently, activated carbon adsorbents are widely used in the world for industrial wastewater treatment from various organic compounds, sorption of heavy metal ions and life-threatening radioactive substances. Carbon adsorbents with hydrophobic properties are mainly modified based on the brown coal, coke, scape, and bark of plants. The methods of manufacturing coal adsorbents based on Angren coal, petroleum coke and asphaltenes are listed. The physicochemical composition and complete thermodynamic properties of the activated carbon adsorbent were studied. It was found that during the heat treatment of mixtures of carbonaceous raw materials, its mass is lost with increasing temperature. At the same time, the adsorption activity of iodine increases with increasing temperature. Depending on the change in temperature of the obtained carbon adsorbent samples, the calculated surface area with respect to iodine is 280.7 m2/g with a weight loss of 0.2 g. The differential heat of adsorption, isotherm, molar entropy and thermokinetics of the benzene and toluene molecules studied in the article are calculated. The adsorption of 4.5 mmol/g of benzene and 3.5 mmol/g of toluene on the activated carbon adsorbent was determined. It is noted that during the adsorption of benzene and toluene by the obtained adsorbent from activated carbon, the differential heat of reaction gradually decreases. When recalculating the isothermal adsorption of benzene and toluene on activated carbon according to the equation of the volumetric theory of micropore saturation, it was obtained that 84.5 % of benzene and 94.2 % of toluene were adsorbed on the pores of the adsorbent.

Pure vibrational state energies and statistical-mechanical models for the reparameterized scarf oscillator

In this work, the reparameterized Scarf II oscillator was employed to describe the internal vibration of diatomic systems. Analytical equations for bound state pure vibrational energies and canonical partition function were obtained. The equations were used to derive statistical-mechanical models for the prediction of molar entropy, enthalpy, Gibbs free energy and constant pressure (isobaric) heat capacity of gaseous substances. The obtained model equations were used to generate numerical data on bound state energy eigenvalues and, to investigate the thermodynamic properties of the ground states chloroborane (BCl), bromine fluoride (BrF), and bromine chloride (BrCl) molecules. With the aid of the expression for molar entropy of the system, average absolute deviations obtained for the molecules are 0.1878%, 0.1267%, and 0.0586% from experimental data. The isobaric heat capacity model yields average absolute deviation of 2.1608%, 1.8601%, and 1.9805%. The results obtained are in good agreement with available literature data on gaseous molecule. The work could be applicable in the fields of molecular physics, chemical physics, solid-state physics and chemical engineering.

Temperature dependence of hydrogen isotope effect in LaNi5-H(D) system

To study inverse effect of hydrogen isotopes in LaNi5 for hydrogen isotope separation at ambient temperature, temperature dependence of hydrogen isotope effect in LaNi5－H(D) system was investigated in the temperature range -70 °C to 3 °C. Isotherms of hydrogen isotopes were tested in an automated Sieverts apparatus with a thermostat, and pressure differences were studied between H2 and D2. Isotope exchange process was carried out and H2－HD－D2 equilibrium was judged by online chromatography, separation factors were calculated to investigate the thermodynamic isotope effect. In the H2, D2 isotherms, average time interval (0.5h) between each equilibrium point was relatively short due to high precision temperature control. From the plateau pressures at a constant hydrogen (or deuterium) concentration in LaNi5 (2D or 2H atoms/mole of LaNi5) the partial molar enthalpies, ⊿H, and entropies, ⊿S of formation were calculated. ⊿H and ⊿S kept good accordance with the values from references, which indicated good performance of the Sieverts apparatus. The isotope exchange equilibrium was reached within 1h. The results showed that ratio between H2 pressure and D2 pressure, r(H－D) = P(D2)/P(H2), dropped as temperature decreased and the inverse effect was found (r(H－D)<1.0) below -5 °C according to the absorption branch of isotherms, whereas the effect was estimated to appear below 60 °C from the desorption branch. The separation factor of the H2－HD－D2 mixture, decreased as temperature increased and the inverse effect happened below -20 °C. The inverse effect was affected by the isotherm hysteresis and HD existence.

Phase Transitions Equilibria of Five Dichlorinated Substituted Benzenes.

This work reports an experimental study aiming to determine the thermodynamic properties of five chlorinated compounds with environmental impact. The vapor pressures of the crystalline phases of three isomers of dichlorobenzoic acid (2,4-, 2,5-, and 2,6-) and 2,6-dichlorobenzonitrile were measured at several temperatures using the Knudsen effusion technique. Another technique (a static method based on capacitance diaphragm manometers) allowed the measurement of the vapor pressures of both the crystalline and liquid phases of 2,4-dichlorobenzonitrile between 303.0 and 380.0 K. This latter technique also enabled the measurement of sublimation vapor pressures of 2,6-dichlorobenzonitrile over a larger range interval of temperatures, T = 328.7 and 391.8 K. The standard molar enthalpy, entropy, and Gibbs energy of sublimation (for all the compounds studied) and vaporization (for 2,4-dichlorobenzonitrile) were derived, at reference temperatures, from the experimental vapor pressure results. The temperatures and enthalpies of fusion and the isobaric heat capacities of the five crystalline-substituted benzenes were determined using differential scanning calorimetry. The contributions of the three substituents (-COOH, -CN, and -Cl) to the sublimation thermodynamic properties of the compounds studied were discussed.

Adsorption of Organic Compounds on the Surfaces of Silicas with Grafted Acetoacet Ether Groups Saturated with Transition Metal Ions

A set of physicochemical means is used to study the adsorption properties of surfaces of silicas based on Silochrome C-120 with surface-grafted groups of acetoacetic ester saturated with transition metal ions. Gas chromatography is used to study the effect nickel, cobalt, and copper ethylacetoacetates have on the thermodynamic characteristics of adsorption (TCA) of different classes of organic substances on SiO2. Experimental data on the retention of adsorbates with different donor-acceptor properties (n-alkanes and chloroalkanes, alkenes, aromatic and oxygen-containing substances) are used to calculate differential molar heats of adsorption q¯dif,1 the change in the standard differential molar entropy ΔS¯S1,C and deposits Δq¯dif,1(spec) in the energy of dispersion and specific interactions.

Dielectric Behaviour of Metal Complexes Cu (II), Ni (II) and UO2 ((VI) Of the Ligand Oxaloanilic Acid Hydrazone

Abstract: The dielectric behaviour and molecular structure of metal complexes Cu(II),Ni(II) and UO2((VI) of the ligand oxaloanilic acid hydrazine have been investigated using Time Domain Reflectometry (TDR) technique in the frequency range 10 MHz to 10GHz. Cole-Davidson model has been applied for fitting the complex permittivity spectra [ ε* (ω)]. The parameters εs –the static permittivity, τ- the dielectric relaxation time are evaluated at different temperatures from 2880K to 3330K and are discussed in respect of their molecular structural behaviours. The thermodynamic parameters, such as ΔH* - molar enthalpy, ΔS* - the molar entropy are obtained using Eyring.s rate equation. In the light of such data the possible structures of the present complexes are discussed.

Thermodynamic insights into phase behavior a new aqueous two-phase system at different temperatures: Experimental equilibria, data correlation and modeling

In the current research, a novel aqueous ternary-two-phase system (ATPS) containing a deep eutectic solvent (DES formed by mixing choline chloride with polyethylene glycol 400) and the non-ionic surfactant Triton X-100 was designed. The phase behavior of this system including phase diagrams (binodal curves) and tie-line compositions was thermodynamically investigated at the temperature range of 298.15 to 316.15 K under atmospheric pressure. This system presented a DES-rich top phase and a surfactant-rich bottom phase. The plait point of binodal diagrams together with the tie-lines length (TLL) and the slope of tie-lines (STL) were determined at each of the operational temperatures. The influence of temperature on the binodal curves and the tie-lines was analyzed from which it was found that an increase in the temperature expands the two-phase region in the binodal curve as well as increases the length of the tie-lines. Moreover, the binodal curves data and the tie-line compositions were successfully correlated using a series of semi-empirical models with satisfactory results. Finally, the molar Gibbs energy, molar enthalpy and molar entropy of the cloud points of binodal curve were calculated and the results showed that the formation of the two-phase system is spontaneous and endothermic as well as the entropy is its driving force.

Experimental and Computational Characterisation of the Molecular Interactions between 1‐Butyl‐1‐methyl‐pyrrolidin‐1‐ium bis(trifluoromethanesulphonyl)imide and Human Serum Albumin

AbstractRecently, ionic liquids (ILs) have emerged as a therapeutic agent for industrial‐based pharmacology. In this regard, the current study highlights the key aspects of IL, (1‐butyl‐1‐methyl‐pyrrolidine‐1‐ium bis(trifluoromethanesulphonyl)imide), [Pyr C4 NTf3−] such as pharmacodynamics and pharmacokinetics. We performed a detailed experimental and computational analysis of [Pyr C4 NTf3−] with human serum albumin (HSA) using various spectroscopic techniques viz. UV‐vis, steady‐state fluorescence, synchronous fluorescence, time‐resolved fluorescence, steady‐state anisotropy and tensiometry study along with molecular docking. Absorption and emission spectral studies revealed the complex formation between [Pyr C4 NTf3−] and HSA where the binding constant (Kb) was found to be 5.5×103 Lmol−1. Thermodynamic parameters, Gibb's free energy change (ΔG), molar enthalpy change (ΔH), and molar entropy change (ΔS) revealed that the complex formation process is spontaneous, and enthalpy driven where involvement of hydrogen bond and van der Waal forces play a major role. Further, CD spectroscopy and ANS experiment showed the stability of HSA in presence of [Pyr C4 NTf3−]. A site marker study suggested that the binding of [Pyr C4 NTf3−] occurred at site II in HSA which is well supported by a molecular docking study. Also, MD simulation was done which revealed the stability of the complex formed between HSA and [Pyr C4 NTf3−]. The study might help in utilizing [Pyr C4 NTf3−], IL as a therapeutic agent in the pharmaceutical industries.

Basic thermodynamic characteristics of toluene adsorption in Cu2+ZSM-5 Zeolite

This paper presents the results of isotherms and basic (ΔH, ΔF and ΔS) thermodynamic characteristics of toluene adsorption in CuZSM-5 zeolite. For measurements of isotherms and differential heat of adsorption, a system consisting of a universal high-vacuum adsorption unit and an attached differential modified Tian-Calve microcalorimeter DAC-1-1A was used to provide direct quantitative and qualitative characteristics of the nature and forces of adsorption interaction. The correlation between the adsorption-energy characteristics wasfound and the molecular mechanismof toluene adsorption in CuZSM-5 zeolite in the whole filling region was revealed. Toluene adsorbed in CuZSM-5 zeolite is located in the first coordination sphere with Cu2+ cation, forming two-dimensional complexes. It was found that the charge density significantly affects the mechanism, the energy of adsorption and the number of adsorbed molecules. It was determined that the average molar entropy of toluene adsorption in CuZSM5 zeolite indicates that the mobility of toluene molecules in zeolite is below the liquid phase and close to that of the solid phase, indicating that the mobility of toluene molecules on cations is strongly inhibited. This work shows how calorimetric data can be used to complement crystal structure results and detect subtle adsorbent/adsorbate interactions at the molecular level.

Calorimetric study of methanol adsorption in LiZSM-5 and CsZSM-5 zeolites

This paper presents isotherms and basic (ΔH, ΔF, and ΔS) thermodynamic characteristics of methanol adsorption in Li3,37ZSM-5 and Cs3,17ZSM-5 zeolites obtained by the calorimetric method. For measurements of isotherms and differential heat of adsorption, a system consisting of a universal high-vacuum adsorption unit and an attached differential modified Tian-Calvet type microcalorimeter, DAC-1-1A, which directly quantifies and qualifies the nature and forces of adsorption interaction, was used. The adsorption isotherm is described by the equations of the volumetric micropore filling theory (VMOT). The correlation between the adsorption-energy characteristics is found, and the molecular mechanism of methanol adsorption in Li3,37ZSM-5 and Cs3,17ZSM-5 zeolites throughout the filling region is revealed. Methanol adsorbed in Li3,37ZSM-5 and Cs3,17ZSM-5 zeolites is located in the first coordination sphere with cations Li+ and Cs+, forming tetra- and trimeric complexes. It is found that the charge density significantly affects the adsorption mechanism, the adsorption energy, and the number of adsorbed molecules. It was determined that the average molar entropy of ammonia adsorption on LiZSM-5 and CsZSM-5 zeolites indicates that the mobility of methanol molecules in the zeolite is below the liquid phase and close to the mobility of the solid phase, indicating a strong inhibition of mobility of methanol adsorbed on cations. This work shows how calorimetric data can complement crystal structure results and detect subtle adsorbent/adsorbate interactions at the molecular level.

Basic thermodynamic characteristics and isotherm of ammonia adsorption in NaZSM-5 and LiZSM-5 zeolites

This paper presents the results of isotherm and basic (ΔH, ΔF, and ΔS) thermodynamic characteristics of ammonia adsorption in Na zeolites2,87 ZSM-5 and Li3,37 ZSM-5; also the adsorption isotherm is described by the bulk micro-pore filling theory (BFM) equations. The correlation between adsorption-energy characteristics is found, and the molecular mechanism of ammonia adsorption in Na2,87ZSM-5 and Li3,37ZSM-5 zeolites in the whole filling region is revealed. The ammonia adsorbed in NaZSM-5 and LiZSM-5 zeolites is located in the first coordination sphere with Na+ and Li+ cations, forming octa- and hexaammonia complexes. From the adsorption thermokinetics, it was determined that Li+ cations are located in the screened positions of the ZSM-5 zeolite crystal lattice. The adsorption of ammonia molecule results in Li+ cations migration from the zeolite lattice into junctions formed by the intersection of straight and zigzag channels and the formation of ion/molecular complexes of various multiplicity in them. It was determined that the average molar entropy of ammonia adsorption on NaZSM-5 and LiZSM-5 zeolites indicates that the mobility of ammonia molecules in the zeolite is below the liquid phase and close to the mobility of the solid phase, indicating a strong limitation of mobility of ammonia adsorbed on the cations.

Vibrational dynamics of liquid water in an external electric field.

In our present study, we have investigated the effects of an externally applied static electric field on the vibrational dynamics of liquid water (D2O) using ab initio molecular dynamics. The rate of vibrational spectral diffusion is obtained from simulated two-dimensional infrared spectra, three-pulse photon echo intensity, and frequency correlation functions and distributions. We find that the static vibrational frequency distribution undergoes a redshift of 90 cm-1 whereas the overall vibrational dynamics get slower with the relaxation time constant to be around 4.9 ps. Thus we infer that the local hydrogen bond network tends to reorganize in the presence of an external field with an increase in local structural order as evident from the overall slower vibrational dynamics and reduced molar entropy.

Ab Initio Group Additive Values for Thermodynamic Carbenium Ion Property Prediction

Carbenium ions are important intermediates in both zeolite and plasma chemistry. The construction of kinetic models for zeolite and plasma chemistry requires the incorporation of thermodynamic properties of these carbenium ions. In this way, thermodynamic equilibrium is incorporated resulting in more accurate and general kinetic models, which facilitate rational zeolite design and plasma process development. In this work, a consistent set of 46 group additive values (GAVs) and non-nearest neighbor interactions (NNIs) is determined for the standard enthalpy of formation, standard molar entropy, and heat capacity. The GAVs are regressed based on 165 quantum chemistry calculations with the CBS-QB3 composite method for carbenium ions as CBS-QB3 was proven a valid method for carbenium property prediction. The presented group additive approach gives the first GAVs and NNIs for entropy and heat capacity and 33 novel values for enthalpy prediction. The determined non-nearest neighbor interactions account for the effect of longer range hyperconjugation, resonance stabilization, and inductive stabilization, which are shown to be crucial for the carbenium stability. The presented group additivity scheme ensures an accurate prediction of all properties with a mean absolute error of 4.82 kJ/mol, 4.92 J/(mol·K), and 1.95 J/(mol·K) for the standard enthalpy of formation, standard molar entropy, and heat capacity, respectively. The reported GAVs and NNIs ensure the thermodynamic property prediction of paraffinic, olefinic, alkynic, aromatic, and five- and six-ring naphthenic cations.

Interfacial tension of carbon dioxide - water under conditions of CO2 geological storage and enhanced geothermal systems: A molecular dynamics study on the effect of temperature

In recent years, CO2 injection into geological formations under a wide range of temperature conditions, including super-hot geothermal reservoirs, has attracted much attention (i.e., higher than 500 K). Despite the importance, however, no study has been reported on the interfacial tension (IFT) of CO2 - water systems at temperatures higher than 478 K. In this study, we performed molecular dynamics (MD) simulations to estimate the CO2 - water IFT from 278 to 573 K at 8 to 50 MPa. Our results show the IFT at 10 MPa and 573 K is approximately 80% lower than that at a typical reservoir condition for CO2 geological storage. This indicates that the effect of the capillary pressure on the flow of CO2 and water in the geological formation is expected to be significantly reduced in such a super-hot geothermal reservoir.We discuss a possible mechanism for the IFT variation against temperature, including the maxima around 373 K at 8 to 12 MPa, which is reproduced and tackled by MD simulations for the first time. On the basis of the Gibbs-Duhem relation, the temperature dependence is directly related to the interfacial excess molar entropy. Our analyses show (1) the IFT increase is attributed to the substantial variation of the entropy and density of the bulk CO2 phase near the critical point, and (2) this variation is characterized by the distinct behavior of the molecular ordering and the mobility of CO2 at the interface, consistent with the close relationship between the disorder in molecular arrangement and configurational entropy.

The phase structure, thermodynamic properties, and dissolution behavior of Ca5Mg4V6O24

AbstractA Ca5Mg4V6O24 compound was synthesized through solid‐state roasting routes under an air atmosphere, and its crystal structure and thermodynamic properties were determined using various methods. The cell parameters of Ca5Mg4V6O24 indicate that it crystallizes in cubic space group Ia3d with the unit cell parameters a = 12.442 ± 0.001 Å. X‐ray photoelectron spectroscopy also confirmed that the vanadium element in the Ca5Mg4V6O24 sample is present in the +5 state. The melting of Ca5Mg4V6O24 was detected at 1442 K. The molar heat capacity (374 J mol K−1) and entropy (688.2 J mol K−1) of Ca5Mg4V6O24 at 298.15 K were determined using physical properties measurement system, and simultaneous thermal analyzer for the first time. The solubility of Ca5Mg4V6O24 in water at different temperatures was measured and its dissolution behavior in sulfuric acid and kinetics was experimentally established.

Measurements and correlation of activity coefficients at infinite dilution for organic solutes in 1-heptyl-3-methylimidazolium chloride

This work is a continuation of our studies on the determination of activity coefficients at infinite dilution (γi∞) for organic solutes (i) in ionic liquids (ILs) and their use in separation processes. The values of γi∞ for 31 organic solutes including alkanes, cycloalkanes, 1,4-dioxane, aromatic hydrocarbons, cyclohexene, chloromethanes, acetonitrile, acetone, tetrahydrofuran, ethyl acetate and alcohols in the IL 1-heptyl-3-methylimidazolium chloride ([C7MIm]Cl) at six temperatures in range of (313.15–363.15) K were determined by gas-liquid chromatography (GLC). The density of [C7MIm]Cl as a function of temperature at pressure p= 101.33 kPa was measured and the values of gas-liquid partition coefficients (KL) were obtained. The linear relationship between lnγi∞ and 1/T was fitted by the Gibbs-Helmholtz equation. The molar excess thermodynamic functions including the infinite dilution partial molar excess Gibbs free energies (G¯iE,∞), partial molar excess enthalpies (H¯iE,∞) and entropies (TrefS¯iE,∞) at Tref = 298.15 K were calculated. In addition, the solubility parameters (δi) of [C7MIm]Cl were obtained from the regular solution theory combined with Flory “combinatorial” equation. The interaction between the solute and the IL was quantified based on the linear free energy relationship (LFER) model. The infinite dilution selectivity coefficients (Sij∞) of n-hexane (i)/benzene (j) and cyclohexane (i)/benzene (j) were calculated at T = 323.15 K from γi∞ and compared to literature values for [Cl]-based ILs for the same separation problems.

Fabrication process development and basic evaluation of eggshell-based column packing material for reversed-phase preparative separation

Purification of basic drugs in reversed-phase mode is often difficult, mainly due to adsorption of positively charged compounds to the silica gel-based stationary phase. Since this adsorption can be suppressed under alkaline condition, columns with alkali-resistance are required. In addition, compounds with acid-sensitive structures are sometimes degraded during separation on silica gel-based columns which exhibit acidity due to their surface structure. We prepared an alkali-resistant reversed-phase packing material, Eggshell-PMAcO based on eggshells modified with an amphiphilic copolymer, poly(maleic acid-alt-1-octadecene) (PMAcO). The height equivalent to a theoretical plate (HETP) of the Eggshell-PMAcO column was improved by surface treatment with ammonium acetate buffer (900 mM, pH = 3.7), which is an inexpensive reagent, and the retention behavior for hydrophobic compounds was compared to a typical ODS column based on silica gel, resulting in sufficient selectivity of the eggshell-based column for hydrophobic compounds, as indicated by the ratio of retention factors of pentylbenzene and butylbenzene (Eggshell-PMAcO column: 1.55, ODS column: 1.65). Column temperature-dependent retention behavior of naphthalene was investigated in the temperature range from 25 °C to 45 °C, followed by the calculation of thermodynamic parameters. There was little difference in the standard molar enthalpy (Eggshell-PMAcO: −19.6 kJ/mol, ODS: −21.7 kJ/mol). The absolute value of the standard free Gibbs energy for the Eggshell-PMAcO column was much smaller than that of the ODS column (Eggshell-PMAcO: −0.284 kJ/mol, ODS: −13.0 kJ/mol), indicating that the Eggshell-PMAcO column had a weaker retention strength for naphthalene than the ODS column mainly due to the large difference in the standard molar entropy (Eggshell-PMAcO: −64.9 J/mol K, ODS column: −29.2 J/mol K). The retention capacities for imipramine under neutral (water/methanol) and alkaline (0.1% triethylamine water/methanol) conditions were 0.2 mg and 5 mg, respectively, based on injection mass-dependent HETP, retention factor and symmetry factor. Finally, the prepared column was applied to the purification of a building block for nucleic acid drugs. This study demonstrated that reversed-phase columns, which can be fabricated from eggshells and an amphiphilic copolymer in an inexpensive and eco-friendly way, have the ability to purify basic compounds and acid-sensitive compounds.