Properties of electrolyte solutions relevant to high concentration chloride leaching. III. Solubility of pertinent solids and iron(III)/iron(II) redox potential measured in concentrated magnesium chloride solutions

Results of solubility measurements of nickel chloride, manganese chloride, iron(II) chloride, hematite and akaganeite in aqueous solutions of MgCl₂ (0.5–3.5 mol L^− 1) at temperatures of 60 and 90 °C are reported. Solubilities of metal(II) chlorides decrease almost linearly with MgCl₂ concentration due to the common ion effect. Nickel chloride and iron(II) chloride solubilities are very similar, while manganese chloride is about 30% more soluble.Hematite is more stable (i.e. less soluble) than akaganeite under all conditions investigated in this study, while ferrihydrite is considerably less stable. In other words, there is no change in the relative stabilities of these phases effected by the presence of high magnesium chloride concentrations. The solubility of all of these phases decreases with temperature and, for each temperature, the solubility constants increase linearly with the MgCl₂ concentration. The present results allow the prediction of the iron concentration as a function of the H⁺ and MgCl₂ molality at equilibrium with hematite or akaganeite.The Fe(III)/Fe(II) redox behaviour has been characterized in concentrated aqueous solutions of MgCl₂ (1.5–3.5 mol L^− 1) at a temperature of 25 °C. Standard redox potentials are ca. 100 mV lower than at infinite dilution and change linearly by only 13 mV in the range 2–4 mol L^− 1 MgCl₂.     

Properties of electrolyte solutions relevant to high concentration chloride leaching I. Mixed aqueous solutions of hydrochloric acid and magnesium chloride

A computer code based on a Pitzer model has been developed for the comprehensive prediction of the thermodynamic properties of MgCl₂–HCl aqueous solutions over a wide range of conditions from 25 to 120 °C and from 0–350 g L^− 1 chloride. This code was applied to the calculation of (i) water activities and mean ionic activity coefficients for mixed aqueous solutions of hydrochloric acid and magnesium chloride over a wide range of concentrations and to 100 °C, (ii) solubilities of MgCl₂·6H₂O in MgCl₂–HCl solutions to 80 °C, (iii) partial pressures of HCl(g) and H₂O(g) over MgCl₂–HCl aqueous solutions at various temperatures and (iv) partial pressures of HCl(g) at the normal boiling point of these mixed electrolyte solutions. The model predictions are in excellent agreement with available experimental data and confirm evidence from the literature that MgCl₂(aq) and HCl(aq) mix almost ideally at constant water activity.     

Stability of 3CaO · Al2O3 · 6H2O in KOH + K2CO3 + H2O system for chromate production

In the novel clean chromate production process, the alkali liquor recycled to decompose the chromite ore mainly consists of KOH and K₂CO₃ which accumulates aluminium impurity and affects the quality of the product greatly. Aluminium impurity can be removed by adding CaO to precipitate as 3CaO · Al₂O₃ · 6H₂O (C₃AH₆). A study of the effects of various parameters, such as KOH concentration, K₂CO₃ concentration and temperature on the behaviour of C₃AH₆ show that C₃AH₆ is decomposed to 3CaO · Al₂O₃ · CaCO₃ · 11H₂O and CaCO₃ below 150 g L^− 1 KOH, and decomposed to Ca(OH)₂ above 150 g L^− 1 KOH. With K₂CO₃ concentration increasing, C₃AH₆ decomposes significantly, which results in more CaCO₃ or 3CaO · Al₂O₃ · CaCO₃ · 11H₂O produced. Temperature has a large positive effect on the decomposition of C₃AH₆ at 45 g L^− 1 KOH but has no significant effect at 150 g L^− 1 KOH. The optimal condition for removing aluminium impurity in the KOH + K₂CO₃ + H₂O system is 150 g L^− 1 KOH, 50 g L^− 1 K₂CO₃ and 80 °C.     

Adsorption of rhenium(VII) on 4-amino-1,2,4-triazole resin

The adsorption properties of 4-amino-1,2,4-triazole resin (4-ATR) for Re(VII) were investigated by static and dynamic adsorption–desorption measurements with ultraviolet–visible spectroscopy. The influence of conditions such as temperature, initial solution pH and contact time on the adsorption curve was studied. It was found that the 4-amino-1,2,4-triazole resin was suitable for adsorption of Re(VII). The saturated adsorption capacity was 354 mg·g^− 1resin at pH 2.6 in HAc–NaAc medium at 298 K. The adsorption rate constant was k₂₉₈ = 8.2 × 10^− 5 s^− 1. The adsorption behavior of 4-ATR for Re(VII) obeyed the Freundlich empirical equation; whilst changes in adsorption with temperature gave an enthalpy change ΔH  = − 11.8 kJ·mol^− 1. The molar ratio of the functional group of 4-ATR to Re(VII) was about 2:1. Re(VII) adsorbed on 4-ATR was eluted by 1.0 ~ 5.0 mol·L^− 1 HCl with 100% quantitative elution in 4.0 mol·L^− 1 HCl solution. The resin can be regenerated and reused without apparent decrease in adsorption capacity.     

Extraction of Fe(III) from hydrochloric acid solutions using Amberlite XAD-7 resin impregnated with trioctylphosphine oxide (Cyanex 921)

Ferric ions were efficiently removed from HCl solutions using Amberlite XAD-7 resin impregnated with trioctylphosphine oxide (Cyanex 921). Iron was removed under the form HFeCl₄ through direct binding on the resin or by extraction with Cyanex 921 involving a solvation mechanism. High concentrations of HCl and intermediary extractant loadings were required for maximum sorption efficiency and rationale use of the extractant. At intermediary extractant loading (in the range 300–450 mg Cyanex 921 g^− 1) the maximum sorption capacity increased with extractant loading. Maximum sorption capacity slightly increased with temperature, the reaction is endothermic and the enthalpy change was found close to − 30.8 kJ mol^− 1. Sorption isotherms were fitted with the Langmuir equation and maximum sorption capacity reached values as high as 20–22 mg Fe g^− 1 in 3 M HCl solutions. Despite the good fit of experimental data with the pseudo second-order rate equation, sorption kinetics was controlled by the resistance to intraparticle diffusion. The intraparticle diffusion coefficient (D_e) varying in the range 1.2 × 10^− 11–4.7 × 10^− 10 m² min^− 1 was found to increase with metal concentration and with temperature, while varying the extractant loading it reached a maximum at a loading close to 453 mg Cyanex 921 g^− 1. The desorption of Fe(III) can be achieved using 0.1 M solutions of nitric acid, sulfuric acid, sodium sulfate and even water, maintaining high efficiencies for sorption and desorption for at least 5 cycles.     

Adsorption behavior of Cd(II) from aqueous solutions onto gel-type weak acid resin

The adsorption and desorption behaviors of Cd(II) on gel-type weak acid resin (GTWAR) have been investigated. The influence of operational conditions such as contact time, initial concentration of Cd(II), initial pH of solution and temperature on the adsorption of Cd(II) has also been examined. The results show that the optimal adsorption condition of GTWAR for Cd(II) is achieved at pH = 5.95 in HAc–NaAc medium. The maximum uptake capacity of Cd(II) is 282 mg/g GTWAR at 298 K. The adsorption of Cd(II) follows the Langmuir isotherm and Freundlich isotherm, and the correlation coefficients have been evaluated. Even kinetics on the adsorption of Cd(II) has been studied. The apparent activation energy E_a and adsorption rate constant k₂₉₈ values are 2.95 kJ/mol and 3.02 × 10^− 5 s^− 1, respectively. The calculation data of thermodynamic parameters which ΔS value of 110 J/(mol K) and ΔH value of 13.1 kJ/mol indicate the endothermic nature of the adsorption process. Whilst, a decrease of Gibb's free energy (ΔG) with increasing temperature indicates the spontaneous nature of the adsorption process. Finally, Cd(II) can be eluted by using 0.5 mol/L HCl solution and the gel-type weak acid resin can be regenerated and reused. The sample was described by IR spectroscopy and scanning electron micrographs (SEM).     

Speciation of the Fe(II)–Fe(III)–H2SO4–H2O system at 25 and 50 °C

This work presents theoretical and experimental results on the speciation of the Fe(II)–Fe(III)–H₂SO₄–H₂O system in concentrated solutions (up to 2.2 m H₂SO₄ and 1.3 m Fe). The aim was to study the chemical equilibria of iron at 25 and 50 °C in synthetic aqueous sulphuric acid solutions that contain dissolved ferric and ferrous ion species. Raman spectroscopy, volumetric titration and conductivity measurements have been carried out in order to study the presence of specific ions and to characterize the ionic equilibrium. A thermochemical equilibrium model incorporating an extended Debye–Hückel relationship was used to calculate the activities of ionic species in solution. Model calculations were compared with experimental results. Model simulations indicate that anions, cations and neutral complexes coexisted in the studied system, where the dominant species were HSO₄⁻, H⁺, Fe²⁺ and FeH(SO₄)₂⁰. This indicated that these solutions showed a high buffer capacity due to the existence of bisulphate ions (HSO₄⁻), which presented the highest concentration. A decrease in the concentration of H⁺ and Fe³⁺ took place with increasing temperature due to the formation of complex species. Standard equilibrium constants for the formation of FeH(SO₄)₂⁰ were obtained in this work: log K_f⁰ = 8.1 ± 0.3 at 25 °C and 10.0 ± 0.3 at 50 °C.     

Desilication of sodium aluminate solution by Friedel's salt (FS: 3CaO·A12O3·CaCl2·10H2O)

Controlling silica level in Bayer liquor is critical in order to prevent scaling or alumina quality issues. The conventional method of removing silicates from aluminate solutions requires the introduction of calcium oxide or calcium hydroxide. In this work, Friedel's salt (FS: 3CaO·A1₂O₃·CaCl₂·10H₂O) is proved for the first time to remove up to 95% silica from sodium aluminate solution. FS is a mineral anion exchanger belonging to the layered double hydroxides (LDHs) which was prepared by adding calcium chloride to sodium aluminate over the temperature range of 50–90 °C. It was characterized by XRD, SEM, Particle Size Analyzer and TG-DSC. FS prepared at 50 °C has a relatively high desilication capacity, better than calcium oxide.Experimental parameters affecting the desilication process, such as temperature, sodium aluminate liquor composition, initial silica concentration (4–10 g/L) and FS dosage were investigated in detail and a comparison of desilication between FS and CaO was carried out. The desilication products (DSP) were mainly calcium aluminium silicates, identified by XRD to be Chabazite and Wadalite and the final chloride concentration in the sodium aluminate solution after anion exchange with FS was  0.015 g/L. The rate of desilication by FS was first order with a rate constant 2.582 × 10⁶ min^− 1. The apparent activation energy was estimated to be 57.7 kJ mol^− 1 over the temperature range of 80–110 °C.     

Solubility prediction of malachite in aqueous ammoniacal ammonium chloride solutions at 25 °C

The solubility of malachite in the presence of ammonia, ammonium chloride and their mixed solution is calculated by a geochemical modeling code and is measured in a series of dissolution experiments using synthetic malachite at 25 °C. The simulated results show a good agreement with the experimental data gained at 25 °C. The predicted and experimental results indicate that the precipitate CuO limits the copper solubility in aqueous ammonia and Cu(OH)_1.5Cl_0.5 in aqueous ammonium chloride. For a mixed solution containing ammonia and ammonium chloride, highest copper solubility can be achieved by adjusting the [NH₃]/[NH₄Cl] ratio to about 2:1. The thermodynamic model presented rationalises the interactions between the different components and predicts the influence of changes in the concentration of ammonia and ammonium chloride on the copper solubility of malachite.     

Palladium(II) complexes adsorption from the chloride solutions with macrocomponent addition using strongly basic anion exchange resins, type 1

The use of the strongly basic anion exchange resins, type 1 such as Lewatit MP-500 and Lewatit MP-500A for palladium(II) complexes adsorption has been investigated. The adsorption process was carried out from the chloride solutions with macrocomponent (sodium chloride) addition (x M HCl–1.0 M NaCl; x M HCl–2.0 M NaCl) where the concentration of hydrochloric acid was constant and equal to x = 0; 0.1; 0.5; 1.0; and 2.0 M, respectively. The breakthrough curves of Pd(II) were determined and the sorption parameters (weight and bed distribution coefficients, working anion exchange capacity) were calculated. The pseudo-second kinetic order was applied in kinetic studies as well as to calculate the kinetic parameters. The values of the working anion exchange capacities (0.029 g/cm³; 0.028 g/cm³) for Lewatit MP-500 and Lewatit MP-500A (0.028 g/cm³; 0.027 g/cm³) in the 1.0 M NaCl and 0.1 M HCl–1.0 M NaCl solutions, respectively are really close and in other solutions under discussion Lewatit MP-500 possess slightly higher values of capacities, and therefore is insignificantly more efficient in the adsorption process of palladium(II) ions than Lewatit MP-500A. The equilibrium adsorption capacities changed in the range 8.84–9.99 and 8.40–9.38 mg/g for Lewatit MP-500 as well as 8.12–9.57 and 7.26–8.85 mg/g for Lewatit MP-500A in the chloride x M HCl-1.0 M NaCl and x M HCl-2.0 M NaCl solutions, respectively. The adsorption process proceeds according to the pseudo-second kinetic order.     

Removal of molybdenum from MnSO4 solution with freshly precipitated “nascent” Mn3O4

The scavenging of molybdenum from MnSO₄ solution with freshly precipitated “nascent” Mn₃O₄ is reported. Firstly, nascent Mn₃O₄ was prepared from MnSO₄ solution by adding NaOH and aerating. The aeration time had a significant influence on the preparation of nascent Mn₃O₄, but other factors such as pH and ageing time had little effect. SEM, XRD, particle size and surface area analysis were used to characterize nascent Mn₃O₄. A study was then carried out on the effects of time, concentration of Mn, initial pH, temperature and dosage of nascent Mn₃O₄ on the adsorption of Mo from MnSO₄ solution. The results showed that the concentration of Mo in 70–200 g L^− 1 MnSO₄ at pH 1–3 could be reduced from about 1 mg L^− 1 to less than 0.015 mg L^− 1 in 30 min at 80 °C by the addition of about 0.3 g L^− 1 nascent Mn₃O₄ in suspension. Accordingly, the removal capacity of nascent Mn₃O₄ can reach 4.42 mg Mo/g Mn₃O₄. This Mo removal exceeds the requirement for special electrolytic MnO₂ used in the production of alkaline zinc–manganese batteries.     

Arsenic removal from copper ores and concentrates through alkaline leaching in NaHS media

Removal of arsenic impurity in ores and concentrates containing copper (Cu) through alkaline leaching in NaHS media was investigated in this work. Samples containing Cu from 10 to 40 wt.% and arsenic from 0.8 to 14 wt.% with enargite (Cu₃AsS₄) as main arsenic bearing mineral were used as starting materials and all leaching tests were conducted at 80 °C under normal atmospheric pressure. Solution and/or slurry potential and pH were maintained consistently below − 500 mV (SHE) and above 12.5 respectively with the addition of NaHS and NaOH, creating a reducing environment for arsenic dissolution and conversion of Cu₃AsS₄ to Cu₂S. Pulp density ranged from 100 to 1000 g/L, NaHS and NaOH reagents were added at 50–200 g/L each and leaching time varied from 10 min to 10 h.Characterization of solid samples (original and leach residue) by XRD and XRF analyses and chemical analysis of both solid and solution samples by ICP analysis showed that Cu₃AsS₄ in the starting material was completely decomposed or transformed to Cu₂S and arsenic released into solution as As (III)/As³⁺ ions (Na₃AsS₃). Over 90% of arsenic in the starting materials was removed within 1–3 h for materials with arsenic content from 1 to 4 wt.% and within 3–6 h for materials with arsenic content over 4–10 wt.%. Dissolution and analysis of leach residues obtained after leaching by ICP indicated that arsenic in the starting materials has been reduced in all cases to below 0.5 wt.%. In all test conditions dissolution of Cu and Fe into solution was not detected, indicating selective leaching of arsenic. NaHS application for removal of arsenic in Cu-ores and/or concentrates was demonstrated in this work and further research is in progress to develop a process to include treatment of arsenic leached into solution.     

Effect of phosphate on lead removal during a copper recycling process from wastes using ammoniacal chloride solution

Techniques for the removal of lead have been studied in order to develop a hydrometallurgical copper recycling process consisting of copper leaching from wastes using an ammoniacal chloride solution and subsequent copper electrowinning. The solubility of Pb(II) in the ammoniacal chloride solution increased with ammonia concentration; this was attributable to the formation of a lead ammine complex. The lead dissolution was depressed from the order of 10^− 3 M to the order or 10^− 5 M by the addition of phosphate into the leaching solution because of the precipitation of chloropyromorphite (Pb₅(PO₄)₃Cl), while no significant effect was observed by the addition of carbonate. Linear sweep voltammetry and potentiostatic electrolysis in the solution containing Pb(II) revealed that lead was deposited during the copper electrowinning, even in the potential region more positive than the equilibrium redox potential for the Pb/Pb(II) couple on the lead electrode, because of the alloy formation with copper. In a galvanostatic electrolysis, however, the lead content at the electrodeposited copper cathode was found to be lower than 5 ppm at the current density range of 125–400 A/m², when the Pb(II) concentration in the electrolyte was 5 × 10^− 5 M. Since this Pb(II) concentration was achieved by the phosphate addition, these results indicated the effectiveness of phosphate for lead removal in the copper recycling process using the ammoniacal chloride solution.     

Possible Involvement of NADPH Oxidase in Lanthanide Cation-Induced Superoxide Anion Generation in BY-2 Tobacco Cell Suspension Culture

A rapid and concentration-dependent generation of superoxide anion (·O-2), measured with a superoxide-specific Cypridina luciferin-derived chemiluminescent reagent, was observed when two lanthanide salts (LaCl3 and GdCl3) were added to tobacco (Nicotiana tabacum) cell suspension culture.Addition of superoxide dismutase (480 U·ml-1) and Tiron (5 μmol·L-1) to cell culture suspension decreases the level of lanthanide cation-induced ·O-2 generation, suggesting that ·O-2 generation is extra-cellular.Pretreatment of the cell culture suspension with diphenyleneiodonium (10 and 50 μmol·L-1), quinacrine (1 and 5 mmol·L-1) and imidazol (10 mmol·L-1), inhibitors of NADPH oxidase, notably inhibits the generation of superoxide induced by lanthanide cation, implying the possible involvement of activation of NADPH oxidase.In addition, addition of SHAM (1 and 5 mmol·L-1), azide (0.2 and 1 mmol·L-1), inhibitor of peroxidase, has no influence on ·O-2 generation.     

Investigation on pumping oxygen characteristics of （Bi2O3）0.73（Y2O3）0.27 solid electrolyte

（Bi2O3）0.73（Y2O3）0.27 fine powders prepared by wet chemical precipitation method were cold isostatically pressed to form solid electrolyte tubes, and sintered at 900 ℃ for 10 h in the air. Their pumping oxygen characteristics in non-dehydrated Ar gas were investigated, where a ZrO2 （Y2O3 stabilized） oxygen sensor was used to measure the oxygen partial pressure Po2. The results showed that the Po2 value reached magnitudes of 1×10^-2-1×10^-10 Pa at the applied pumping oxygen voltage of 0.5 V, 1×10^-37-1×10^-27 Pa at 1.0 V and 1×10^-53-1×10^47 Pa at 2.0 V within the temperature range from 550 to 650 ℃. Moreover, no cracks were found in the tested solid electrolyte tubes. Thus, the Bi2O3-Y2O3 system might be used in solid electrolyte oxygen pump for purifying gases.     

Phase control of magnetron sputtering deposited Gd2O3 thin films as high-κ gate dielectrics

Gd2O3 thin films as high-κ gate dielectrics were deposited directly on Si（001） substrates by magnetron sputtering at a pressure of 1.3 Pa and different temperatures. X-ray diffraction results revealed that all the films grown from 450 to 570 ℃ were crystalline, and the Gd2O3 thin films consisted of a mixture of cubic and monoclinic phases. The growth temperature was a critical parameter for the phase constituents and their relative amount. Low temperature was favorable for the formation of cubic phase while higher temperature gave rise to more monoclinic phase. All the Gd2O3 thin films grown from different temperatures exhibited acceptable electrical properties, such as low leakage current density （JL） of 10-5 A/cm^2 at zero bias with capacitance equivalent SiO2 thickness in the range of 6-13 nm. Through the comparison between films grown at 450 and 570 ℃, the existence of monoclinic phase caused an increase in JL by nearly one order of magnitude and a reduction of effective dielectric constant from 17 to 9.     

Nitric Oxide Alleviates Oxidative Stress Caused by Lanthanum in Rice Leaves

The effect of NO on lanthanum-induced antioxidant activities in rice was evaluated. The results showed that the uptake and translocation of La from root to shoot were obviously inhibited by 10μmol·L^-1 sodium nitropmsside （SNP）, a donor of NO, in the seedlings grown in Mura B nutrient solution with 100μmol·L^-1 La. Although the content of ascorbate acid （AsA） were scarcely affected by La or NO in our experiment, La decreased significantly the activity of SOD and content of GSH, while promoted H202 content in leaves. Furthermore, NO blocked these La effects. Taken together, the results suggested that NO relieved La toxicity in rice. A possible role for NO effects on antioxidant activity was discussed.     

Adsorption behavior of rare earth elements using polyethyleneglycol (phosphomolybdate and tungstate) heteropolyacid sorbents in nitric solution

A new type of crystalline sorbent was prepared by the reaction of polyethyleneglycol (PEG) with phosphomolybdic (PMo) and phosphotungstic (PW) heteropolyacids. The morphology of the obtained sorbents was studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). It has been shown that a complexing reaction occurs between PEG and the heteropolyacids. By using these sorbents, the adsorption behaviors of rare earth elements in nitric solution were studied. The effects of temperature, contact time, nitric acid and initial metal ion concentration on the adsorption were investigated. In 0.1–5.0 mol L^− 1HNO₃, the adsorption percentage decreases with the increase of acid concentration. H,PEG400,PW and H,PEG400,PMo exhibited a different selectivity for rare earth metals, with H,PEG400,PW adsorbing in the order of La³⁺ > Y³⁺ > Pr³⁺ > Gd³⁺ > Sm³⁺, and H,PEG400,PMo in the order of Y³⁺ > La³⁺ > Pr³⁺ > Gd³⁺ > Sm³⁺. The experimental maximum adsorption capacities of the sorbents are in the range of 90–225 mg g^− 1 for Y³⁺, La³⁺, Pr³⁺, Sm³⁺ and Gd³⁺. In all cases, the maximum adsorption capacities of H,PEG400,PW are near to those of H,PEG400,PMo. The equilibrium data were evaluated according to the Freundlich and Langmuir isotherms and the Langmuir equation gave a better fit and modeled the adsorption well.     

Corrosion Protection of Electro-Galvanized Steel by Green Conversion Coatings

A A cerium-based chemical conversion process was studied. First, zinc coating obtained from a free-cyanide alkaline bath, with derivative of imidazol with new brightener, was investigated, zinc-plated steel specimens were treated with a solution of 50 mmol· L^-1 Ce（NO3 ）3 The corrosion behavior of bare and treated mild galvanized steel was evaluated during exposure to 0.5 mol · L^-1 NaCl for different immersion time, using Tafel polarization curves and electrochemical impedance spectroscopy （EIS） measurements. The surface morphology of the coating was studied using scanning electron microscopy （SEM）. The composition and chemical percent of the coating were examined by X-ray dispersion energy （EDAX）. The results of these measurements showed that the newly developed cerium-based conversion coating process was a promising candidate for replacing the conventional chromate treatments used at present for galvanized steel.     

Thermochemical Study on Ternary Solid Complex of La(Gly)2 (Ala)3 Cl3 ·2H2O (s)

The complex of lanthanum chloride with Glycine and Alanine, La(Gly)₂(Ala)₃Cl₃ · 2H₂O, was synthesized and characterized by IR, elementary analysis, thermogravimetric analysis, and chemical analysis. The dissolution enthalpies of LaCl₃ · 7H₂O(s), 2Gly(s) + 3Ala(s) and La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) were determined in 2 mol · L⁻¹ HCl by a solution-reaction isoperibol calorimeter. By designing a thermochemical cycle in terms of Hess' Law and through calculation, the reaction enthalpy of lanthanum chloride seven-hydrate with Glycine and Alanine was obtained: Δ_rH^θ_m(298.15 K) = (29.652 ± 0.504) kJ · mol⁻¹, and the standard enthalpy of formation of La(Gly)₂(Ala)₃Cl₃ · 2H₂O(s) Δ_fH^θ_m[La(Gly)₂ (Ala)₃Cl₃ · 2H₂O, s, 298.15 K] = −4467.6 ± 8.3 kJ · mol⁻¹.