Synthesis,extraction, and anti‐bacterial studies of some new bis‐1,2,4‐triazole derivatives part I

A series of new bis triazole Schiff base derivatives (4) were prepared in good yields by treatment of 4‐amino‐3,5‐diphenyl‐4H‐1,2,4‐triazole (3) with bisaldehydes (1). Schiff bases (4) were reduced with NaBH₄ to afford the corresponding bisaminotriazoles (5). All the new compounds were characterized by IR, ¹H NMR and ¹³C NMR spectral data. Their overall extraction (log K_ex) constants for 1 : 1 (M : L) complexes and CHCl₃/H₂O systems were determined at 25 ± 0.1°C to investigate the relationship between structure and selectivity toward various metal cations. The extraction equilibrium constants were estimated using CHCl₃/H₂O membrane transfer with inductively coupled plasma‐atomic emission spectroscopy spectroscopy. The stability sequence of the triazole derivatives in CHCl₃ for the metal cations was exhibited a characteristic preference order of extractability to metal ions [Fe(III) > Cu(II) > Pb(II) > Co(II) > Ni(II) > Mn(II) > Zn(II) > Mg(II) > Ca(II)]. The compounds were tested for anti‐microbial activity applying agar diffusion technique for 11 bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Interactions of Some Hofmeister Cations with Sodium Dodecyl Sulfate in Aqueous Solution

In this work, we have investigated the influence of some alkali metal ions on the Krafft temperature (T_K) and critical micelle concentration (CMC) of a classical ionic surfactant, sodium dodecyl sulfate (SDS), over a wide range of temperature. The alkali metal cations such as Li⁺, Na⁺, Cs⁺, and K⁺ are found to affect the solubility and hence the T_K of the surfactant. It was observed that kosmotropic Li⁺ lowers the T_K of the surfactant. Due to the common ion effect, the solubility of SDS decreases in the presence of Na⁺, resulting in an increase in the T_K. On the other hand, chaotropic K⁺ and Cs⁺, capable of forming contact ion pairs with the chaotropic dodecyl sulfate ion, lower the solubility and hence elevate the T_K. In terms of decreasing the T_K, the ions follow the trend: Li⁺ > Na⁺ > Cs⁺ > K⁺ except for 0.0025 M CsCl. The added cations screen the charge of the micelle surface and facilitate closer packing of the surfactant with a consequent decrease in the CMC. In terms of the effectiveness in lowering the CMC, the ions follow the order: Cs⁺ > K⁺ > Na⁺ > Li⁺. In the presence of added electrolytes, the γ_CMC values are found to be lower than the corresponding values in pure water. The thermodynamic parameters (Gibbs free energy, enthalpy, and entropy changes) of micellization were calculated to gain insights into the mechanism of the process.     

Determination of the charge of complex species that are reduced at the dme and of the coefficient of transfer, α, in the Cu(II)aq. M citrate (M: Li+, Na+ and K+) system

The minimum presented by the polarograms of the reduction of Cu(II) in Li⁺, Na⁺ and K⁺ citrate is analysed in order to determine the charge of the reacting species and the coefficient of transfer, α, of the process. The results obtained allow the participation of the complex anions (Cu₂Cit₂)^2? and (CuCit₂)^4? in dilute and concentrated citrate solutions to be established, respectively, as well as a cation—reacting anion interaction, increasing in the order K⁺ > Na⁺ > Li⁺. The value of the coefficient of transference α = 0.40 is in agreement with that found by other techniques.     

Extraction and pertraction of phenol through bulk liquid membranes

The extraction and pertraction of phenol through a bulk liquid membrane (BLM) with Cyanex^® 923, Amberlite^® LA‐2 and trioctylamine (TOA) as carriers were studied. Cyanex^® 923 was selected as the best carrier for pertraction. The distribution coefficient of phenol for solvents with carrier and pure n‐alkanes, the individual mass‐transfer coefficient at the extraction interface and the initial flux of phenol through the extraction interface (J_Fo) decreased in the order: Cyanex^® 923 > Amberlite^® LA‐2 > TOA ? pure n‐alkanes. The opposite order was observed for the value of the mass‐transfer coefficient in BLM and the maximum flux of phenol through the stripping interface (J_Rmax). At constant driving forces the maximum fluxes through the extraction and stripping interfaces were similar when amine carriers were used. However, J_Rmax was lower than J_Fo for Cyanex^® 923. Although the kinetics of stripping was the rate‐determining step, the flux of phenol was significantly higher than in pertraction with amine carriers. The adsorption of the carrier at aqueous phase/membrane interfaces was probably responsible for the rapid and slow transfer of phenol through the extraction and stripping interface, respectively. Copyright © 2004 Society of Chemical Industry     

Temperature Effects on the Molecular Dynamics of Modified Nafion® Membranes Incorporating Ionic Liquids' Cations: A 1H NMRD Study

Nafion® is the polymer electrolyte membrane most used in fuel cells (PEMFC), however Nafion® presents some limitations due to the water loss with increasing temperature. In this work is presented the study of the molecular dynamics in modified Nafion®/ionic liquids (IL) cations membranes with increasing temperature, by proton NMR relaxometry (¹H NMRD). Three Nafion® membranes modified with Phenyltrimethylammonium (TMPA⁺), 1‐n‐butyl‐3‐methylimidazolium (BMIM⁺) and n‐dodecyltrimethylammonium (DTA⁺) IL cations were considered. This study allowed the evaluation of the effect of the IL cations incorporation in Nafion® membranes and to assess the degree of confinement of the IL cations in the membranes matrix in relation with the water content. Thermogravimetry analysis was also performed to study the water loss with increasing temperature of the Nafion®/IL cations membranes. It was possible to establish a correlation between the water content and the IL cations self‐diffusion coefficients. The sequential order of the hydration level obtained for the studied systems was Nafion®/DTA⁺>Nafion®/BMIM⁺ ≳ Nafion®/H⁺>Nafion®/TMPA⁺, while the water loss follows the sequence Nafion®/H⁺>Nafion®/BMIM⁺∼Nafion®/DTA⁺>Nafion®/TMPA⁺. The Nafion®/BMIM⁺ presented the largest temperature variation of both the self‐diffusion coefficient and the hydration conditions. In terms of PEMFCs efficiency, the Nafion®/DTA⁺ modified membrane seems to offer the largest and stable hydration conditions with temperature.     

Electrochemical properties of modified copper-thallium hexacyanoferrate electrode in the presence of different univalent cations

The preparation of copper(II) hexacyanoferrate (CuHCF) films on the surface of gold electrodes as well as their characterization in solutions of various alkali metal and NH₄⁺ cations and in the presence of thallium(I) are described. The electrochemical quartz crystal microbalance and cyclic voltammetric techniques were used. In 0.50 M lithium nitrate, even at submillimolar concentration of Tl(I), the formal potential of CuHCF was shifted to more positive values. At higher Tl(I) concentrations, the formal potential of the CuHCF redox reaction changed linearly with the logarithm of Tl(I) concentration (in the 0.50 M solution of lithium or another alkali metal nitrate). From such dependencies, selectivity coefficients K_Tl/M were calculated, and they show that the CuHCF film on the gold electrode interacts preferentially with Tl(I). High affinity of Tl(I) to copper hexacyanoferrate, that was observed in the presence of alkali metal cations, was explained by relatively strong donor-acceptor interactions of Tl(I) ions with nitrogen in CN groups of the CuHCF film.It was also shown for simple M₄[Fe(CN)₆] metal ferrocyanate salts (where M = Li⁺, Na⁺, K⁺, Rb⁺, Cs⁺ and Tl⁺) that there is a preferential interaction of Tl⁺ with CN group consistent with formation of a Tl-NC-Fe bridge.     

Electroless immobilization and electrochemical characteristics of nickel hexacyanoruthenate film at an aluminum substrate

The surface of an aluminum (Al) electrode was modified with a thin film of nickel hexacyanoruthenate (NiHCR) as a novel electrode material. The modification procedure of Al surface, includes two consecutive procedures: (i) the electroless deposition of metallic nickel on the Al electrode surface from NiCl₂ solution, and (ii) the chemical transformation of deposited nickel to nickel hexacyanoruthenate films in solution of 20 mM K₃[Ru(CN)₆] + 0.5 M KNO₃. Cyclic voltammogram of the modified Al electrode showed a well-defined redox reaction due to [Ni^IIRu^III/II(CN)₆]^1−/2− system. The effects of different supporting electrolytes and solution pH were studied on the electrochemical characteristics of the modified electrode. The diffusion coefficients of K⁺ and Na⁺ cations in the film (D), the transfer coefficient (α), and the charge transfer rate constant at the modifying film/electrode interface (k_s), were calculated in the presence of both K⁺ and Na⁺ cations. The stability of the modified electrode was investigated under various experimental conditions.     

Adsorption of Pb(II) from aqueous solution to MX-80 bentonite: Effect of pH, ionic strength, foreign ions and temperature

The adsorption of Pb(II) from aqueous solution to MX-80 bentonite was studied using batch technique under ambient conditions. Removal percent (%) and distribution coefficient (K_d) were determined as a function of shaking time, pH, ionic strength and temperature. The results showed that the adsorption behavior of Pb(II) on bentonite was strongly dependent on pH and ionic strength. The presence of complementary cations depressed the adsorption of Pb(II) on bentonite in the order of Li⁺ ≈ Na⁺ > K⁺ at pH 2–5. The adsorption isotherms were simulated by the Langmuir, Freundlich, and Dubinin–Radushkevich (D–R) models very well. The thermodynamic parameters (ΔH⁰, ΔS⁰, and ΔG⁰) for the adsorption of Pb(II) were determined at three different temperatures of 291 K, 308 K and 328 K. The adsorption reaction was exothermic and the process of adsorption was favored at low temperature. The results suggest that bentonite is suitable as a sorbent material for the recovery and adsorption of Pb(II) from aqueous solution.     

Cation Field Strength Effects on Boron Coordination in Binary Borate Glasses

The field strength of modifier cations in boron‐containing oxide glasses has important but complex effects on boron coordination, and has long been known to have major effects on glass and liquid properties. With well‐constrained compositional and fictive temperature information in three binary borate glass series, we report how different modifier cations (Na⁺, Ba²⁺, Ca²⁺) affect boron coordination (¹¹B MAS NMR), as well as glass transition temperatures and configurational heat capacities (DSC). Using estimated reaction enthalpies for converting a ^[4]B to a ^[3]B with an NBO from previous studies, we compare boron coordinations in glasses with different modifier cations on an isothermal basis. Temperature and modifier cation effects can thus be isolated. At low modifier contents [R = (Na₂,Ca,Ba)O/B₂O₃<0.45], N₄ is systematically higher in the order Na>Ba>Ca, suggesting the enhanced stabilization of NBO for the divalent cations, especially for the smaller Ca²⁺. At higher R values, N₄ for Na borates drops below values for Ca and Ba borates. The trend in N₄ with modifier field strength reverses at high R values (~ R > 0.7), with Ca > Ba > Na. The transition may be related to the enhanced stabilization of ^[4]B‐O‐^[4]B groups by higher field strength cations in NBO‐rich glasses in which boron is the primary network component.     

Thermodynamics of lithium,potassium and thallium electrode in propyléne carbonate

Standard potentials (E°) of Li, K and Tl electrodes in propylene carbonate (PC) have been determined, at 25°, on the basis of the “solvent-independent” half-reaction: Ferricinium⁺ +e ?Ferrocene. In addition, estimates of ΔG°, ΔH°, and ΔS° for the formation of Li⁺, K⁺, and Tl⁺ in PC have been obtained from temperature-dependence studies. The observed values of E° are in the order Tl > Li > K as compared to the order Tl > K > Li in water. The decrease in entropy, which would serve as a measure of the order-promoting ability of an ion, follows the sequence Li > K > Tl. From a consideration of the crystallographic radii of the cations involved this trend would suggest that such ordering is primarily a result of electrostatic solvation in the immediate vicinity of the ions. The somewhat large decrease in entropy observed in the case of Li⁺ reflects very extensive solvation of this particular cation. The free energies of transfer for the three cations from water (D = 78·54) to PC (D = 64·4) are calculated to be +1·81 (Li⁺), ?2·42 (K⁺), and ?2·88 (Tl⁺) kcal/mole. Although an approximately linear relationship exists between these free energies of transfer and the reciprocals of crystallographic radii of the ions, both the magnitudes and the signs of these free energies are not readily understood in terms of the Born equation. The relatively large free energy decrease associated with the transfer of Tl⁺ might be attributed to a fairly strong solvation encountered by this cation due to its empty 5f orbital, aided by the possibility that the solvating carbonyl oxygen of PC is more accessible to the cations in general.     

A novel one-dimensional nickel(II) complex with a hydrogen-bond-link

A novel compound [Ni(L)(H₂O)₂]_0.5[Ni(L)(WO₄)₂]_0.5·4H₂O (1) (L=3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0^1.18,0^7.12]docosane) has been structurally and magnetically characterized. The nickel(II) ions are shown to be in distorted octahedral environments with secondary amines of macrocycles in which two trans water molecules and two trans tungstate ions are assembled around each metal center. Two nickel(II) complexes are connected into a one-dimensional chain via hydrogen bonds. The magnetic susceptibility measurement for 1 indicates weak antiferromagnetic interaction (J=−1.01(2) cm⁻¹; H=−JΣS_i·S_i+1) between the S=1 nickel(II) paramagnetic centers.     

The Kinetic Stability of Cationic Benzyl Titanium Complexes that Contain a Linked Amido-Cyclopentadienyl Ligand: The Influence of the Amido-Substituent on the Ethylene Polymerization Activity of “Constrained Geometry Catalysts”

Cationic benzyl titanium complexes [Ti(η⁵: η¹-C₅Me₄SiMe₂NR')-(CH₂Ph)]⁺ were cleanly formed by the reaction of the dibenzyl titanium complexes [Ti(η⁵: η¹-C₅Me₄SiMe₂NR')(CH₂Ph)₂] with B(C₆F₅)₃ and [Ph₃C][B(C₆F₅)₄] in bromobenzene. NMR spectroscopic studies suggest that the benzyl titanium cations contain a fluxional η²-coordinated benzyl ligand. Kinetic analysis showed that the benzyl titanium cations decompose according to first-order kinetics and that the amido substituents R' (R' = Me, ⁱPr, ^tBu) in the linked amido-cyclopentadienyl ligand influence the lability of these benzyl titanium cations. The order of the kinetic stability of the benzyl titanium cations was found for both anions to follow the order R' = Me > ⁱPr > ^tBu. The benzyl titanium cations generated with [Ph₃C][B(C₆F₅)₄] were found to undergo faster decomposition than those generated with B(C₆F₅)₃. The ethylene polymerization activity order for both systems was found to be the reverse: R' = ^tBu > ⁱPr > Me. The decomposition of the benzyl titanium cations was suggested to occur via C—H activation with concomitant toluene elimination.     

CO<Subscript>2</Subscript> retention ability on alkali cation exchanged titanium silicate,ETS-10

ETS-10 was ion exchanged by various alkali cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) and the BET surface area and pore volume was exactly consistent with cationic size; that is, in the order of Li⁺ > Na⁺ > K⁺ > Rb⁺ > Cs⁺. It was observed that a single point adsorption capacity was inversely proportional to cationic size. The largest CO₂ capacity was observed for Li⁺-ETS-10 and it is attributed to greater cation–quadrupole interactions with CO₂ than larger cation. The results also suggests that as the CO₂ loading is increased, the accessibility of adsorbing CO₂ to framework basic O⁻ sites should have become difficult with the increase in cationic size due to the blocking effect by extra-framework CO₂-M⁺. The slight decrease in the slope of adsorption capacity with temperature, especially beyond 373 K for Li⁺-ETS-10 and K⁺-ETS-10 suggests that the adsorption of CO₂ on small alkali cation exchanged-ETS-10 at high temperature is somewhat associated with basic oxygen anion sites in framework due to the existence of large pore. The CO₂-TPD results show that the amount of desorbed CO₂ at higher temperature was proportionally increased due to the increased basicity of oxygen anions in framework. It also shows that the desorption temperature associated with alkali cations in extra-framework (corresponding to low temperature desorption peak) has been lowered with the increase in cationic size, indicating weak cation–quadrupole interactions with CO₂ for larger cations.     

Selective Removal of Carbon Dioxide from Wet CO2/H2 Mixtures via Facilitated Transport Membranes containing Amine Blends as Carriers

The selective separation of carbon dioxide (CO₂) from a wet gaseous mixture of CO₂/H₂ through facilitated transport membranes containing immobilized aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), ethylenediamine (EDA) and monoprotonated ethylenediamine (EDAH⁺) and their blends was experimentally investigated. The effect of CO₂ partial pressure, amine concentration, feed side pressure and amine species on the CO₂ and H₂ permeances were studied. The CO₂ permeability through amine solution membranes decreased with increasing CO₂ feed partial pressure but the H₂ permeance was almost independent of the H₂ partial pressure. A comparison of experimental results showed that single or blended amines with low viscosity and a moderate equilibrium constant, i.e., large forward and reverse reaction rate of CO₂‐amine, are suitable for effective separation of CO₂. The permeability of CO₂ generally increased with an increase in amine concentration, although this increase may be compromised by the salting out effect and decrease in diffusivities of species. The results obtained indicated that CO₂ permeance across a variety of amines are in the order of DEA (2 M) > MD (2 M) > MD (1 M) > MEA (2 M) > MEA (4 M) > MD (4 M) > DEA (1 M) > DEA (4 M) > MEA (1 M) for various concentrations of MEA + DEA blend and are in the order of EDAH⁺ (2 M) > DEA (2 M) > MH (2 M) > DH (2 M) > ED (2 M) > EDA (2 M) > MEA (2 M) for various blends of amine.     

Electrochemical behavior of a novel palladium pentacyanonitrosylferrate modified aluminum electrode

Novel inorganic film modified electrodes have been prepared by chemical deposition of a thin palladium pentacyanonitrosylferrate (PdPCNF) film on the surface of aluminum substrate. The modification process including the electroless deposition of metallic palladium on the aluminum electrode surface from PdCl₂+25% ammonia solution and chemical derivatization of deposited palladium to the PdPCNF film in 0.1 M Na₂[Fe(CN)₅NO]+0.5 M KNO₃+HNO₃ solution (pH 1.5-2.5), are described. The aluminum-based modified electrodes exhibit, one pair of well-defined voltammetric peaks which correspond to the Fe(III)/Fe(II) transition in complex structure. The effect of pH, ammonium, alkali metal and alkaline earth metal cations of supporting electrolyte on the electrochemical characteristics of the modified electrode was studied in detail. Diffusion coefficients of hydrated ammonium and alkali metal cations in the film (D), transfer coefficient (α) and transfer rate constant for electron (k_s), were determined. The high stability of this modified electrode makes it attractive in practical application.     

Membrane transport of organics. I. Sorption and permeation of carboxylic acids in perfluorosulfonic and perfluorocarboxylic polymer membranes

Experimental studies have been made on the sorption and permeation of propionic (PA), acetic (AA), and formic (FA) acid in perfluorosulfonic Nafion, and perfluorocarboxylic Flemion membranes. The sorption isotherms show the increase of distribution coefficients K_d = C_m/C_e with the pK of acids, i.e., K_d,PA > K_d,AA > K_d,FA. The transmembrane fluxes (J) and permeabilities (P) change their values in the same order for C_e < 0.1M and in the order J_PA > J_FA > J_AA for higher concentrations. The differentiation of fluxes in single-component dialyses does not result in the effective separation of AA and PA during their competitive permeation through the Nafion-120 membrane. Under the same conditions, the Flemion membrane exhibits the preference toward propionic acid and transports PA and AA with the selectivity coefficient a_AA^PA equal to 1.5. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 355–362, 1997     

ION EXCHANGE PROPERTIES OF THE SODIUM PHLOGOPITE AND BIOTITE

ABSTRACT

The ion exchange behavior of three sodium micas (phlogopite, Ward's Sci.; phlogopite, Suzorite Inc., biotite, Ward's Sci.) towards Li⁺, K⁺, Rb⁺, Cs⁺, Mg²⁺. Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺ Hg²⁺, Co²⁺, Cu²⁺ Cd²⁺ and Zn²⁺ ions has been studied. The ion exchange isotherms of alkali, alkaline earth and some other divalent cations were determined and concentration equilibrium constants as a function of metal loading and temperature were analyzed. Sodium micas exhibit high affinity for heavy alkali metals with the selectivity order Rb⁺ > Cs⁺ > K⁺. By studying the cesium uptake in the presence of NaNO₃, CaCl₂, NaOH, NaOH+KOH, HNO₃ electrolytes (in the range of 0.01–6 M) it was found that sodium micas could remove cesium efficiently in neutral and alkaline media, which make them promising for certain types of nuclear waste treatment.     

Lithium-metal potential in Li<Superscript>+</Superscript> containing ionic liquids

Impedance spectroscopy studies of the interface between lithium and ionic liquid (IL) showed the formation of a film (solid electrolyte interface, SEI), protecting metal from its further dissolution. Consequently, the potential of metallic lithium immersed in an electrolyte containing Li⁺ cations may be described as a Li|SEI|Li⁺ system, rather than simply Li/Li⁺. The potential of lithium-metal in a series of ionic liquids (and in a number of molecular liquids) containing Li⁺ cation (0.1 M) was measured versus the Ag|(Ag⁺ 0.01 M, cryptand 222 0.1 M, in acetonitrile) reference. The lithium-metal potential (E(Li|SEI|Li⁺)) was ca. −2.633 ± 0.017 V in ILs based on the [N(CF₃SO₂)₂ ^– ] anion, while −2.848 ± 0.043 V in ILs containing [BF₄ ^– ] anion (the difference is ca. 200 mV). In the case of ILs based on the triflate anion ([CF₃SO₃ ^– ]), the cation of ionic liquid also influences the E(Li|SEI|Li⁺) value: it was ca. −1.987 ± 0.075 V for imidazolium based cations and much lower (−2.855 V) for the pyrrolidinium based cation. In ionic liquid based on the imidazolium cation and hexafluorophosphate anion ([PF₆ ^– ]), the Li/SEI/Li⁺ potential was −2.245 V. The Li|SEI|Li⁺ potential measured in cyclic carbonates was −2.780 ± 0.069 V while in dimethylsulfoxide showed the lowest value of ca. −3.285 V. The measured potentials were also expressed versus the formal potential of the ferrocene/ferrocinium redox couple, obtained from cyclic voltammetry.     

Neutral Dissociation of Pyridine Evoked by Irradiation of Ionized Atomic and Molecular Hydrogen Beams

The interactions of ions with molecules and the determination of their dissociation patterns are challenging endeavors of fundamental importance for theoretical and experimental science. In particular, the investigations on bond-breaking and new bond-forming processes triggered by the ionic impact may shed light on the stellar wind interaction with interstellar media, ionic beam irradiations of the living cells, ion-track nanotechnology, radiation hardness analysis of materials, and focused ion beam etching, deposition, and lithography. Due to its vital role in the natural environment, the pyridine molecule has become the subject of both basic and applied research in recent years. Therefore, dissociation of the gas phase pyridine (C₅H₅N) into neutral excited atomic and molecular fragments following protons (H⁺) and dihydrogen cations (H₂⁺) impact has been investigated experimentally in the 5–1000 eV energy range. The collision-induced emission spectroscopy has been exploited to detect luminescence in the wavelength range from 190 to 520 nm at the different kinetic energies of both cations. High-resolution optical fragmentation spectra reveal emission bands due to the CH(A²Δ→X²Π_r; B²Σ⁺→X²Π_r; C²Σ⁺→X²Π_r) and CN(B²Σ⁺→X²Σ⁺) transitions as well as atomic H and C lines. Their spectral line shapes and qualitative band intensities are examined in detail. The analysis shows that the H₂⁺ irradiation enhances pyridine ring fragmentation and creates various fragments more pronounced than H⁺ cations. The plausible collisional processes and fragmentation pathways leading to the identified products are discussed and compared with the latest results obtained in cation-induced fragmentation of pyridine.     

UNIFAC model for ionic liquid‐CO2 systems

The new group binary interaction parameters of UNIFAC model (a_nm and a_mn) between CO₂ and 22 ionic liquid (IL) groups were obtained by means of correlating the solubility data of CO₂ in pure ILs at different temperatures (>273.2 K). We measured the CO₂ solubility at low temperatures down to 243.2 K in pure ILs, i.e., [OMIM]⁺[BF₄]^? and [OMIM]⁺[Tf₂N]^?, and their equimolar amount of mixture, in order to fill the blank of solubility data at low temperatures and also to justify the applicability of UNIFAC model over a wider temperature range. It was verified that UNIFAC model can be used for predicting the CO₂ solubility in pure ILs and in the binary mixture of ILs both at high (>273.2 K) and low temperatures (<273.2 K) effectively, as well as identifying the new structure–property relation. This is the first work to extend the UNIFAC model to IL‐CO₂ systems. © 2013 American Institute of Chemical Engineers AIChE J 60: 716–729, 2014