Separation of lignosulfonate from its aqueous solution using supported liquid membrane

This paper presents an experimental and theoretical study on facilitated transport of lignosulfonate (LS) through a flat sheet supported liquid membrane using trioctylamine (TOA) as carrier and dichloroethane as diluent. The studies were carried out with various support materials and operating conditions (viz. carrier concentration, strip phase concentration, salt concentration, etc.) and their effects on the transport of LS. The results were analyzed to identify a suitable combination of support and operating condition that would yield best performance of the supported liquid membrane (SLM) in terms of fast and efficient transport of LS. The stability of the SLM was assessed in terms of loss of liquid from the pores of membrane support. The SLM is found to be stable till 10 h. Co-transport mechanism has been adopted in this work by using NaOH as the strip phase. It was observed that extraction of LS is increased with increase in concentration of NaOH up to a limiting value of 0.5 M NaOH. Difference of salt concentration between feed and strip phase considerably affect the separation process. The diffusional resistances of organic membrane (Δorg) and aqueous solution (Δaq) calculated from the permeation model, which is again a combination of three unique mechanisms viz., diffusion through a feed aqueous layer, a fast interfacial chemical reaction, and diffusion of carrier–complex through the organic membrane, are found to be 609.9 and 176.6 s cm⁻¹, respectively. The values of the diffusion coefficient in the membrane (D_org) and in the bulk organic phase (D_complex) are 1.67×10⁻⁹ and 6.68 × 10⁻⁸ m²s⁻¹, respectively. The extraction of LS is about 90%. Nearly 43% of LS can be recovered at optimum condition.     

Flux enhancement of stagnant sandwich compared to supported liquid membrane systems in the removal of Gemfibrozil from waters

Removal of the drug Gemfibrozil (GEM), as a target molecule, from aqueous media by using a carrier mediated transport in supported liquid membrane (SLM) and Stagnant Sandwich LM (SSwLM) systems has been investigated. Optimal chemical conditions to use in the transport tests were determined by means of solubility and liquid–liquid extraction tests. The results showed that the best LM phase to realize stable LM systems was tributylphosphate (TBP) 30% (v/v) in n-decane. Transport tests by using the “traditional” SLM system showed an average flux J_AV(0–CTT) of 0.421 mmol h⁻¹ m⁻² and a system stability of 1410 min. Three different microfiltration membranes, GH-Polypro, FP-Vericel and Supor 200, made of polypropylene, polyvinylidene fluoride and polyethersulphone polymers, respectively, were used to assemble the SSwLM. Contact angle and adsorption measurements evidenced hydrophilic/lypophilic character of the supports. The best results in terms of average flux (0.873 mmol h⁻¹ m⁻²), permeability coefficient (21.88 L h⁻¹ m⁻²) and stability (7170 min ≈120 h) were obtained by using the SSwLM made with the Supor 200 support. The overall results showed that the SSwLM made with this type of support achieves both high flux and high stability compared to the SLM. Thus SSwLMs seems very interesting to employ transport in LM for removing molecular species (e.g. drugs) from aqueous solutions.     

Electrocatalytic response of carbohydrates at copper-alloy electrodes

The voltammetric responses observed for carbohydrates and polyalcohols at 0.60 V in 0.10 M NaOH are significantly larger at preanodized CuMn (95:5) electrodes as compared to preanodized pure Cu electrodes. Apparent values for the number of electrons transferred (n_app) and the corresponding values of heterogeneous rate constants (k_app) are estimated for selected reactants from the slopes and intercepts, respectively, of Koutecký–Levich plots of background-corrected voltammetric currents obtained at CuMn and Cu rotated disk electrodes (RDEs). Values of n_app (and k_app) for sorbitol and glucose are 11.8 (9.2×10⁻³ cm s⁻¹) and 11.7 (8.0×10⁻³ cm s⁻¹), respectively, at a CuMn RDE. These are compared to the values 10.4 (1.8×10⁻³ cm s⁻¹) and 9.6 (2.0×10⁻³ cm s⁻¹) for sorbitol and glucose, respectively, at a Cu RDE. The larger sensitivities observed at the CuMn RDE in comparison to the Cu RDE are concluded to be the beneficial result of larger k_app values at the alloy electrode. Furthermore, the larger k_app values are speculated to result from enhanced preadsorption of the reactant species at Mn(IV) sites in the preanodized CuMn surface. In flow-injection measurements, the peak signals obtained for successive injections of glucose using a CuMn electrode (0.60 V vs. SCE) were quite stable with a standard deviation of 1.5%. However, large day-to-day variations (±15%) observed in the average peak signals are attributed to the temperature sensitivities of the k_app value and the diffusion coefficient for glucose.     

Transport characterisation of a PIM system used for the extraction of Pb(II) using d2ehpa as carrier

The facilitated transport of lead(II) through polymeric inclusion membranes consisting of cellulose triacetate as polymeric support, bis-(2-ethylhexyl)-phosphoric acid (d2ehpa) as carrier, and tris-(2-butoxyethyl)phosphate as plasticiser (tbep), is investigated. The influence of some of the aqueous and membrane components on the permeability of Pb(II) was studied. The maximum flux obtained with these membranes is 3.5×10⁻⁶ mol m⁻² s⁻¹, which is of the same order of magnitude of those reported for supported liquid membranes and is in the upper range of those reported for polymeric inclusion membranes. Aqueous and membranes resistances were determined from a model that describes the transport mechanism across the membranes using the stoichiometric relationship and the extraction equilibrium constant value of 6.2×10⁻⁴ determined independently by solid–liquid extraction. An activation energy of 11 kJ mol⁻¹ was also determined for Pb(II) migration, which suggest that the transport of Pb(II) is controlled by a membrane diffusion mechanism. Membrane characterisation was performed using several techniques including atomic force microscopy, scanning electron microscopy coupled with energy-dispersive spectroscopy, and thermal analysis.     

Rate and Equilibrium Constants of Benzoyl Group Transfer between Pyridine N-Oxides

Kinetic characteristics of 19 transfer reactions of benzoyl group from N-benzoyloxypyridinium salts to pyridine N-oxides and 4-dimethylaminopyridine were studied in acetonitrile by the stopped-flow method. The rate of an identical reaction for 4-methoxypyridine was measured by dynamic NMR spectroscopy. For 5 other identical reactions the rates were estimated from Bronsted correlations. Equilibrium constants were estimated with the use of UV spectrophotometry (6), IR spectroscopy (2), from kinetic data (K _ij = k _ij /k _ji ) (2), and in one case as logK _i−j = logK _i−x − logK _j−x . The second order rate constants (k _ij ) varied in the range 10²–10⁵ l mol⁻¹ s⁻¹, the equilibrium constants (K _ij ) in the range 10²–10⁻²; the activation parameters (ΔH ^≠) were within 15–50 kJ mol⁻¹, (−ΔS ^≠) −20–110 J mol⁻¹ K⁻¹. The reactions under study occur in a single stage following the concerted S_N2 mechanism through an early associative transition state. The benzoyl groups exchange rate and equilibrium are well described by simplified Marcus equation (omitting the quadratic term).__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 788–792.Original Russian Text Copyright © 2005 by Rybachenko, Schroeder, Chotii, Lenska, Red’ko, Kovalenko.     

牛血清白蛋白在修饰氯离子金纳米通道中的迁移研究

采用化学镀的方法在聚碳酸酯模板上沉积金,制成金纳米通道膜,并对它进行Cl-修饰得到带负电荷的通道。再采用电化学方法(i-t法)对牛血清白蛋白(BSA)在修饰通道中的迁移进行研究。在pH7.4PBS中,对通道两端施加1.0V电压,溶液中离子迁移通过纳米通道时产生电流响应。当溶液中加入BSA后,电流响应减小,且响应变化量与浓度在1.50×10-10~1.35×10-9mol/L范围内呈线性关系,其线性回归方程为|Δi|(μA)=0.0069 0.125c(×10-9mol/L),相关系数为0.9980,检出限为9.46×10-11mol/L(S/N=3)。     

The effect of humidity on the degradation of Nafion membrane

Controlling the activity of water in the reactant streams is critical both to the design of fuel–cell systems and to the useable life of membrane separators. In this study, fuel–cell durability tests were conducted under different levels of relative humidity. The emission rates of various degradation products such as HF, SO₄²⁻ and TFA (trifluoroacetic acid) were determined as a function of water activity. The degradation of the membrane was accelerated as the level of water activity is reduced. The membranes become less conductive, more brittle and rigid after fuel–cell testing. ATR-FTIR investigations showed that the decomposition of the ether group in the middle of side chain corresponds well with the detection of a TFA product. Thermogravimetric analysis also showed a decrease in thermal stability after testing at lower humidity. Formation of cracks was observed in membranes degraded under conditions of low humidity. A model of membrane degradation based on the main chain unzipping process indicates that the mechanism changes with water activity. Finally, the representative reaction pathways in each degradation scheme were postulated.     

Phosphate desorption kinetics from goethite as induced by arsenate

The kinetics of the arsenate-induced desorption of phosphate from goethite has been studied with a batch reactor system and ATR-FTIR spectroscopy. The effects of arsenate concentration, adsorbed phosphate, pH and temperature between 10 and 45 °C were investigated. Arsenate is able to promote phosphate desorption because both oxoanions compete for the same surface sites of goethite. The desorption occurs in two steps: a fast step that takes place in less than 5 min and a slow step that lasts several hours. In the slow step, arsenate ions exchange adsorbed phosphate ions in a 1:1 stoichiometry. The reaction is first order with respect to arsenate concentration and is independent of adsorbed phosphate under the experimental conditions of this work. The rate law is then r = k_r[As], where r is the desorption rate, k_r is the rate constant and [As] is the arsenate concentration in solution. The values of k_r at pH 7 are 1.87 × 10⁻⁵ L m⁻² min⁻¹ at 25 °C and 7.95 × 10⁻⁵ L m⁻² min⁻¹ at 45 °C. The apparent activation energy of the desorption process is 51 kJ mol⁻¹. Data suggest that the rate-controlling process is intraparticle diffusion of As species, probably As diffusion in pores. ATR-FTIR spectroscopy suggests that adsorbed phosphate species at pH 7 are mainly bidentate inner-sphere surface complexes. The identity of these complexes does not change during desorption, and there is no evidence for the formation of intermediate species during the reaction.     

Lipid barrier layers on surfaces of synthetic water permeable membranes

Barrier layers (area 0.79 cm²) from oxidized cholesterol or mixtures of oxidized cholesterol with phosphatidyl serine or phosphatidyl ethanol amine were formed on surfaces of different water-permeable synthetic membranes in 0.1 M NaCl as models of biological membranes. Ionic conductivity across the membranes decreased from 10⁻²-10⁻³ to 10⁻⁷-10⁻⁸ Ω⁻¹ cm⁻² when the barrier layers were formed on their surfaces. Average thicknesses of barrier layers 4.5–11 nm were estimated from electric capacitance. The layers were unstable with lifetimes ranging from several minutes to 50 hr according to the support membrane used. The interfacial tension between synthetic membrane surface and either water or lipid solution was calculated from contact angle measurement. The relation between barrier layer stability and hydrophobic and polar interaction of lipids with support surface was studied. The most stable barrier layers (lifetimes 30–50 hr) were formed on cellophane and gelatin membranes with surfaces hydrophobized by reaction with palmytoyl chloride.     

Oxidative cleavage of α, β-unsaturated compounds by pentachlorohydroxoplatinate(IV) in alkaline medium

The kinetics of oxidation of α,β-unsaturated compounds by platinum(IV) in the presence of alkali {[OH⁻]= (1–9) × 10⁻³ mol dm⁻³} have been investigated over the 303–318 K temperature range . The rate of the reaction is dependent on the first power of the concentrations of substrates, oxidant, and alkali. The rate constant increases with an increase in ionic strength and also with increasing dielectric constant of the medium. The oxidation rates follow the order: –CN > –CONH₂ > –COO⁻. The values of the third order rate constant (k₃) for the oxidation of acrylonitrile, acrylamide and acrylate are 1.24, 0.826 and 0.628 mol⁻² dm⁶ s⁻¹ respectively, at 303 K. The oxidations of the substrates by PtCl₅(OH)²⁻ take place by an inner-sphere mechanism. Platinum(IV) is reduced to platinum(II) by the substrates in a one-step two-electron transfer process to give reaction products. The major reaction product, HCHO, is identified from the reaction mixture using i.r. spectrometry, n.m.r. and C, H, N analysis. A tentative reaction mechanism, leading to the formation of products, has been suggested. The activation parameters of the reaction have been evaluated.     

Kinetic Study of Erbium Ion Adsorption on Activated Charcoal from Aqueous Solutions

The kinetics of the adsorption of erbium ions on activated charcoal from aqueous solutions has been studied in the temperature range of 10 to 40∘C. It was observed that the diffusion of erbium ions in to the pores of activated charcoal controls the kinetics of the adsorption process, and the values of intra-particle diffusion rate constant, k_d (g/g ⋅ min^1/2) were evaluated as 0.7 × 10⁻³ to 1.6 × 10⁻³ in the temperature range studied. Various thermodynamic parameters Δ H, Δ G and Δ S were also computed from values of the equilibrium constant K_C. The results showed that the adsorption of erbium ions on activated charcoal is an endothermic process.     

Supported liquid membrane extraction of W(VI) ions using tri-n-octylamine as carrier

Study of the extraction of W(VI) ions using supported liquid membrane has been carried out. The carrier used for this metal ion transport, is tri-n-octylamine (TOA) dissolved in xylene. The liquid was supported in microporous polypropylene film. The parameters studied are effect of carrier concentration in the membrane, acid concentrations in the feed solution, concentration of stripping agent on transport of W(VI) ions and of temperature on the transport properties of these supported liquid membranes. The optimum conditions of transport for these metal ions determined are, TOA concentration, 0.66 mol·dm^–3 (TOA); HF concentration in the feed solution, 0.01 mol·dm^–3 and concentration of NaOH used as stripping agent 2.5 mol·dm^–3. The maximum flux and permeability determined under optimum conditions are 3.06·10^–5 mol·m^–2·s^–1 and 8.44·10^–11 mol· ·m²·s^–1 at 25±2°C and 4.21·10^–5 mol·m^–2·s^–1 and 11.55·10^–11 mol·m²·s^–1 at 65°C, respectively. The diffusion coefficients for the metal ion carrier complex in the membrane have also been determined. Under the optimum conditions the value for the metal ion carrier complex is 0.14·10^–11 mol·m²·s^–1. Mechanism of transport and the complex formed in the presence of HF have also been discussed. The transport process involves two carrier amine molecules and two protons.     

Extraction of Uranium(VI) using D2EHPA/TOPO based supported liquid membrane

This work concerns the extraction of U(VI) using supported liquid membrane (SLM) by di-(2-ethylhexyl) phosphoric acid (D2EHPA) and tri-n-octyl phosphine oxide (TOPO) with polyvinylidene difluoride (PVDF) as a membrane support. The influence of ionic strength (S), stirring rate (V) and extraction time (t) were studied. The effect of membrane thickness on the permeability and extraction yield of uranium was investigated. A comparative study was carried out using a 2³ full factorial design between SLMs with one membrane and two membranes, and to achieve the best conditions of recovery procedure, obtaining the mutual interaction among variables and optimizing these variables. The recovery of U(VI) is almost quantitative, and the supported liquid membrane with two membranes in series is effective.     

Kinetics of the R + HBr RH + Br (CH3CHBr, CHBr2 or CDBr2) equilibrium. Thermochemistry of the CH3CHBr and CHBr2 radicals

The kinetics of the reaction of the CH₃CHBr, CHBr₂ or CDBr₂ radicals, R, with HBr have been investigated in a temperature-controlled tubular reactor coupled to a photoionization mass spectrometer. The CH₃CHBr (or CHBr₂ or CDBr₂) radical was produced homogeneously in the reactor by a pulsed 248 nm exciplex laser photolysis of CH₃CHBr₂ (or CHBr₃ or CDBr₃). The decay of R was monitored as a function of HBr concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature. The reactions were studied separately from 253 to 344 K (CH₃CHBr + HBr) and from 288 to 477 K (CHBr₂ + HBr) and in these temperature ranges the rate constants determined were fitted to an Arrhenius expression (error limits stated are 1σ + Student’s t values, units in cm³ molecule⁻¹ s⁻¹, no error limits for the third reaction): k(CH₃CHBr + HBr) = (1.7 ± 1.2) × 10⁻¹³ exp[+ (5.1 ± 1.9) kJ mol⁻¹/RT], k(CHBr₂ + HBr) = (2.5 ± 1.2) × 10⁻¹³ exp[−(4.04 ± 1.14) kJ mol⁻¹/RT] and k(CDBr₂ + HBr) = 1.6 × 10⁻¹³ exp(−2.1 kJ mol⁻¹/RT). The energy barriers of the reverse reactions were taken from the literature. The enthalpy of formation values of the CH₃CHBr and CHBr₂ radicals and an experimental entropy value at 298 K for the CH₃CHBr radical were obtained using a second-law method. The result for the entropy value for the CH₃CHBr radical is 305 ± 9 J K⁻¹ mol⁻¹. The results for the enthalpy of formation values at 298 K are (in kJ mol⁻¹): 133.4 ± 3.4 (CH₃CHBr) and 199.1 ± 2.7 (CHBr₂), and for α-C–H bond dissociation energies of analogous compounds are (in kJ mol⁻¹): 415.0 ± 2.7 (CH₃CH₂Br) and 412.6 ± 2.7 (CH₂Br₂), respectively.     

Study of the stoichiometry and the kinetics of the Jaffé reaction with a picrate ion-selective electrode

Potentiometric studies with the picrate ion-selective electrode indicate that the species formed as the product of reaction between alkaline picrate and creatinine in the Jaffé reaction is a 1:1 complex. Kinetic studies indicate that the forward reaction is first order with respect to picrate, creatinine, and hydroxide concentration. The second-order rate constant k was found to be in the range 9.1–10.4 M⁻² sec⁻¹ at 27 °C and μ = 1.00, with creatinine or picrate in excess, k increases with increasing μ and temperature. An activation energy of 10.1 kcal/mol was calculated for the Jaffé reaction, with creatinine in excess.     

Palladized aluminum electrode covered by Prussian blue film as an effective transducer for electrocatalytic oxidation and hydrodynamic amperometry of N-acetyl-cysteine and glutathione

The mediated oxidation of N-acetyl cysteine (NAC) and glutathione (GL) at the palladized aluminum electrode modified by Prussian blue film (PB/Pd–Al) is described. The catalytic activity of PB/Pd–Al was explored in terms of Fe^III[Fe^III(CN)₆]/Fe^III[Fe^II(CN)₆]¹⁻ system by taking advantage of the metallic palladium layer inserted between PB film and Al, as an electron-transfer bridge. The best mediated oxidation of NAC and GL on the PB/Pd–Al electrode was achieved in 0.5 M KNO₃ + 0.2 M potassium acetate of pH 2. The mechanism and kinetics of the catalytic oxidation reactions of the both compounds were monitored by cyclic voltammetry and chronoamperometry. The charge transfer-rate limiting step as well as overall oxidation reaction of NAC or GL is found to be a one-electron abstraction. The values of transfer coefficients α, catalytic rate constant k and diffusion coefficient D are 0.5, 3.2 × 10² M⁻¹ s⁻¹ and 2.45 × 10⁻⁵ cm² s⁻¹ for NAC and 0.5, 2.1 × 10² M⁻¹ s⁻¹ and 3.7 × 10⁻⁵ cm² s⁻¹ for GL, respectively. The modifying layers on the Pd–Al substrate have reproducible behavior and a high level of stability in the electrolyte solutions. The modified electrode is exploited for hydrodynamic amperometry of NAC and GL. The amperometric calibration graph is linear in concentration ranges 2 × 10⁻⁶–40 × 10⁻⁶ for NAC and 5 × 10⁻⁷–18 × 10⁻⁶ M for GL and the detection limits are 5.4 × 10⁻⁷ and 4.6 × 10⁻⁷ M, respectively.     

Surface redox polymerized SPEEK–MO2–PANI (M = Si, Zr and Ti) composite polyelectrolyte membranes impervious to methanol

We reported sulfonated poly(ether ether ketone) (SPEEK, 61% degree of sulfonation)–metal oxides (MO₂:SiO₂, TiO₂ and ZrO₂)–polyaniline composite membranes. Metal oxides were incorporated into the swelled SPEEK membrane by sol–gel method and cured by thermal treatment. SPEEK–metal oxide membranes surfaces were modified with polyaniline (PANI) by a redox polymerization process. It was observed that water retention capacity of membrane was increased and methanol permeability was reduced due to synergetic effect of metal oxides and surface modification with polyaniline. These composite membranes showed extremely low methanol permeability (1.9–1.3 × 10⁻⁷ cm² s⁻¹), which was lower than till reported values either for SPEEK–metal oxide or SPEEK/PANI membranes. Relatively high selectivity parameter (SP) values at 343 K of these membranes, especially S–SiO₂–PANI and S–TiO₂–PANI, indicated their great advantages over Nafion117 (N117) membrane for targeting on moderate temperature applications due to the synergetic effect of MO₂ and PANI in SPEEK matrix. S–TiO₂–PANI and N117 showed comparable cell performance in direct methanol fuel cell (DMFC).     

Oxidative degradation of non-ionic surfactant (TritonX-100) by chromium(VI)

Degradation of polyoxyethylene chain of non-ionic surfactant (TritonX-100) by chromium(VI) has been studied spectrophotometrically under different experimental conditions. The reaction rate bears a first-order dependence on the [Cr(VI)] under pseudo-first-order conditions, [TritonX-100]  [Cr(VI)] in presence of 1.16 mol dm⁻³ perchloric acid. The observed rate constant (k_obs) was 3.3 × 10⁻⁴ to 3.5 × 10⁻⁴ s⁻¹ and the half-life (t_1/2) was 33–35 min for chromium(VI). The effects of total [TritonX-100] and [H⁺] on the reaction rate were determined. Reducing nature of non-ionic TritonX-100 surfactant is found to be due to the presence of –OH group in the polyoxyethylene chain. It was observed that monomeric and non-ionic micelles of TritonX-100 were oxidized by chromium(VI). When [TritonX-100] was less than its critical micelle concentration (cmc) the k_obs values increased from 0.76 × 10⁻⁴ to 1.5 × 10⁻⁴ s⁻¹. As the [TritonX-100] was greater than the cmc, the k_obs values increases from 2.1 × 10⁻⁴ to 8.2 × 10⁻⁴ s⁻¹ in presence of constant [HClO₄] (1.16 mol dm⁻³) at 40 °C. A comparison was made of the oxidative degradation rates of TritonX-100 with different metal ion oxidants. The order of the effectiveness of different oxidants was as follows: permanganate > diperiodatoargentate(III) > chromium(VI) > cerium(IV).     

Potentiometric Membrane Sensor for Determination of Saccharin

A potentiometric poly(vinyl chloride) membrane sensor for determination of saccharin is described. It is based on the use of Aliquat 336S-saccharinateion-pair as an electroactive material in plasticized PVC membranes with o-nitrophenyloctylether or dioctylphthalate. The sensor is conditioned for at least two days in 0.1 mol L⁻¹ sodium saccharinate before use. It exhibits fast, stable and Nernstian response for saccharinate ions over the concentration range of 1.0 × 10⁻¹–5.0 × 10⁻⁵ mol L⁻¹ and pH range of 4.5–11. The sensor is used for determination of saccharin in some dosage forms. Results with an average recovery of 101% and a mean standard deviation of 0.2% are obtained which is compared favourably with data obtained using the British pharmacopoeia method. The sensor shows reasonable selectivity towards saccharin in presence of many anions and natural sweeteners.     

Potential-Dependent Rectified Electron Transfer at a Meldola′s Blue Incorporated Decanethiol-Modified Electrode as a Model of Biological Membrane

Meldola′s blue was immobilized into a self-assembled decanethiol monolayer modified on a gold electrode to provide a biological membrane model for electron transport having a molecular gate. Cyclic voltammograms of ferricyanide at this modified electrode showed only its reduction current at potentials where Meldola′s blue was reduced, but not at the redox potential of ferricyanide itself and no reaction was observed for ferrocyanide, indicating the direction of electron flow was controlled through the functionalized monolayer. Similar electrochemical responses were also observed for both octacyanotungustate and octacyanomolybdate. The cathodic peak currents observed in metal cyanide solutions at the modified electrode decreased in the order of Fe(CN)₆³⁻ > W(CN)₈³⁻ > Mo(CN)₈³⁻ at a given pH. From the analysis of the voltammograms using the microelectrode assembly model, the potential-dependent rectified electron flow was explained in terms of a gate function of Meldola′s blue in the monolayer, and the apparent electron transfer rate constant, k⁰_app, and the apparent diffusion coefficient, D_app, of metal cyanide ions in the monolayer were also estimated.