A simplex search for conditions giving maximal and/or minimal concentrations of species in distribution plots

A new method is proposed for finding the conditions which maximize or minimize the concentration of a particular species in a multicomponent system. A Simplex procedure is combined with an iterative method for solving mass-balance equations from the total concentrations of the constituents of the system, its pH and the pertinent equilibrium constants. The following examples of application are given: (a) the optimum conditions for maximizing the concentration of mixed-ligand species in systems with more than one ligand; (b) the conditions for maximal or minimal formation of monomeric and dimeric species in the Cu(II)-triethanolamine system; (c) a search for local maximum/minimum in species distribution plots.     

O-羧甲基壳聚糖纳米微粒制备及对Ni~(2+)吸附研究

将壳聚糖与氯乙酸反应,通过控制反应条件制备了取代度为0.71的O-羧甲基壳聚糖,将改性后的O-羧甲基壳聚糖与多聚磷酸钠反应,制备了粒径分布在370-710nm的O-羧甲基壳聚糖纳米微粒,透射电镜观察表明该微粒呈球状,平均粒径为450nm.在此基础上研究了O-羧甲基壳聚糖纳米微粒对工业电镀镍废水Ni~(2+)吸附性能,考察了溶液pH、Ni~(2+)起始浓度、平衡吸附时间、粒径等因素的影响,结果表明:O-羧甲基壳聚糖微粒最佳吸附条件是Ni~(2+)溶液pH为8.0、Ni~(2+)溶液起始浓度为33.28mg/ml、平衡吸附时间为0.5h、粒径较小的O-羧甲基壳聚糖纳米微粒对Ni~(2+)的吸附量要大于粒径较大的吸附量.     

Uranyl and strontium salt solvation in room-temperature ionic liquids. A molecular dynamics investigation

Using molecular dynamics simulations, we compare the solvation of uranyl and strontium nitrates and uranyl chlorides in two room-temperature ionic liquids (ILs): [BMI][PF(6)] based on 1-butyl-3-methylimidazolium(+),PF(6)(-) and [EMI][TCA] based on 1-ethyl-3-methylimidazolium(+),AlCl(4)(-). Both dissociated M(2+),2NO(3)(-) and associated M(NO(3))(2) states of the salts are considered for the two cations, as well as the UO(2)Cl(2) and UO(2)Cl(4)(2)(-) uranyl complexes. In a [BMI][PF(6)] solution, the "naked" UO(2)(2+) and Sr(2+) ions are surrounded by 5.8 and 10.1 F atoms, respectively. The first-shell PF(6)(-) anions rotate markedly during the dynamics and are coordinated, on the average, monodentate to UO(2)(2+) and bidentate to Sr(2+). In an [EMI][TCA] solution, UO(2)(2+) and Sr(2+) coordinate 5.0 and 7.4 Cl atoms of AlCl(4)(-), respectively, which display more restricted motions. Four Cl atoms sit on a least motion pathway of transfer to uranyl, to form the UO(2)Cl(4)(2)(-) complex. The free NO(3)(-) anions and the UO(2)Cl(4)(2)(-) complex are surrounded by imidazolium(+) cations ( approximately 4 and 6-9, respectively). The first shell of the M(NO(3))(2) and UO(2)Cl(2) neutral complexes is mostly completed by the anionic components of the IL, with different contributions depending on the solvent, the M(2+) cation, and its counterions. Insights into energy components of solvation are given for the different systems.     

Application of a chemical equilibrium model to thermodynamic functions of transfer of alcohols from water to aqueous surfactants

In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models.     

Calcium-containing diatomic dications in the gas phase

Sputtering (ion surface bombardment) of various calcium-containing powder samples with an energetic (17 keV), high-current (16)O(-) beam has produced the diatomic dications of CaSi(2+), CaP(2+), CaF(2+), CaH(2+), CaCl(2+), CaBr(2+) and CaI(2+). These molecular gas-phase species have been identified in positive ion mass spectra at half-integer m/z values; their ion flight times through a magnetic-sector mass spectrometer were roughly 10(-5) s. Most of them appear to be novel molecular ions; the stability of the latter four (CaH(2+), CaCl(2+), CaBr(2+) and CaI(2+)) had been demonstrated in previous theoretical studies, whereas only CaF(2+) and CaBr(2+) had been observed before. Here we combine the results of our experimental search with a detailed theoretical study of the remaining three systems CaSi(2+), CaP(2+) and CaF(2+). All electronic states correlating with the first dissociation channel are characterized using high level ab initio electronic structure calculations. In their ground states, we find CaSi(2+) to be a long-lived metastable molecule, whereas CaF(2+) and CaP(2+) are thermodynamically stable, with respective equilibrium internuclear distances of 6.253, 4.740, and 5.731 a(0). CaSi(2+) has a well depth of 7116 (0.88) cm(-1) (eV) and a dissociation asymptote 7956 (0.99) cm(-1) (eV) below the ground state minimum. The dissociation energy of CaF(2+) is estimated to be 3404 (0.42) cm(-1) (eV), whereas for CaP(2+) we found 2547 (0.32) cm(-1) (eV), and a barrier height of 8118 (1.01) cm(-1) (eV). Their adiabatic double ionisation energies are 22.87, 16.91, and 17.32 eV, respectively, for the F, Si, and P containing dications.     

Thermoresponsiveness of hybrid micelles from poly(ethylene glycol)-block-poly(4-vinylpyridium) cations and SO4(2-) anions in aqueous solutions

The SO4(2-)-induced micellization of poly(ethylene glycol)-block-poly(4-vinylpyridium) (PEG110-b-P(4-VPH+)35) and the thermoresponsiveness of these hybrid micelles are studied by dynamic and static light scattering. When the concentration of H2SO4 is high enough, PEG110-b-P(4-VPH+)35 forms stable hybrid micelles with an ionic core of P(4-VPH+)35/SO4(2-) and a PEG corona at 25 degrees C. The formation of the hybrid micelles is reversible. A thermodynamic equilibrium exists between the hybrid micelles and PEG110-b-P(4-VPH+)35 unimers. The shifts of the equilibrium are mainly attributed to the variation of the electrostatic energy and entropic energy of the system. Therefore, the temperature can determine the states of the equilibrium, which means that the dissociation or the formation of the hybrid micelles can be triggered by just varying the temperature.     

Thermochromism of metal ion complexes of semiquinone radical anions. Control of equilibria between diamagnetic and paramagnetic species by Lewis acids

Metal ion complexes of semiquinone radical anions exhibit different types of thermochromism depending on metal ions and quinones. Metal ion complexes of 1,10-phenanthroline-5,6-dione radical anion (PTQ(.-)) produced by the electron-transfer reduction of PTQ by 1,1'-dimethylferrocene (Me(2)Fc) in the presence of metal ions (Mg(2+) and Sc(3+)) exhibit the color change depending on temperature, accompanied by the concomitant change in the ESR signal intensity. In the case of Mg(2+), electron transfer from Me(2)Fc to PTQ is in equilibrium, when the concentration of the PTQ(.-)-Mg(2+) complex (lambda(max) = 486 nm) increases with increasing temperature because of the positive enthalpy for the electron-transfer equilibrium. In contrast to the case of Mg(2+), electron transfer from Me(2)Fc to PTQ is complete in the presence of Sc(3+), which is a much stronger Lewis acid than Mg(2+), to produce the PTQ(.-)-Sc(3+) complex (lambda(max) = 631 nm). This complex is in disproportionation equilibrium and the concentration of the PTQ(.-)-Sc(3+) complex increases with decreasing temperature because of the negative enthalpy for the proportionation direction, resulting in the remarkable color change in the visible region. On the other hand, the p-benzosemiquinone radical anion (Q(.-)) forms a 2:2 pi-dimer radical anion complex [Q(.-)-(Sc(3+))(2)-Q] with Q and Sc(3+) ions at 298 K (yellow color), which is converted to a 2:3 pi-dimer radical anion complex [Q(.-)-(Sc(3+))(3)-Q] with a strong absorption band at lambda(max) = 604 nm (blue color) when the temperature is lowered to 203 K. The change in the number of binding Sc(3+) ions depending on temperature also results in the remarkable color change, associated with the change in the ESR spectra.     

Multi-competitive interaction of As(III) and As(V) oxyanions with Ca(2+), Mg(2+), PO(3-)(4), and CO(2-)(3) ions on goethite

Complex systems, simulating natural conditions like in groundwater, have rarely been studied, since measuring and in particular, modeling of such systems is very challenging. In this paper, the adsorption of the oxyanions of As(III) and As(V) on goethite has been studied in presence of various inorganic macro-elements (Mg(2+), Ca(2+), PO(3-)(4), CO(2-)(3)). We have used 'single-,' 'dual-,' and 'triple-ion' systems. The presence of Ca(2+) and Mg(2+) has no significant effect on As(III) oxyanion (arsenite) adsorption in the pH range relevant for natural groundwater (pH 5-9). In contrast, both Ca(2+) and Mg(2+) promote the adsorption of PO(3-)(4). A similar (electrostatic) effect is expected for the Ca(2+) and Mg(2+) interaction with As(V) oxyanions (arsenate). Phosphate is a major competitor for arsenate as well as arsenite. Although carbonate may act as competitor for both types of As oxyanions, the presence of significant concentrations of phosphate makes the interaction of (bi)carbonate insignificant. The data have been modeled with the charge distribution (CD) model in combination with the extended Stern model option. In the modeling, independently calculated CD values were used for the oxyanions. The CD values for these complexes have been obtained from a bond valence interpretation of MO/DFT (molecular orbital/density functional theory) optimized geometries. The affinity constants (logK) have been found by calibrating the model on data from 'single-ion' systems. The parameters are used to predict the ion adsorption behavior in the multi-component systems. The thus calibrated model is able to predict successfully the ion concentrations in the mixed 2- and 3-component systems as a function of pH and loading. From a practical perspective, data as well as calculations show the dominance of phosphate in regulating the As concentrations. Arsenite (As(OH)(3)) is often less strongly bound than arsenate (AsO(3-)(4)) but arsenite responses less strongly to changes in the phosphate concentration compared to arsenate, i.e., deltalogc(As(III))/deltalogc(PO(4)) approximately 0.4 and deltalogc(As(V))/deltalogc(PO(4)) approximately 0.9 at pH 7. Therefore, the response of As in a sediment on a change in redox conditions will be variable and will depend on the phosphate concentration level.     

Kinetics of aluminium fluoride complexation in single- and mixed-ligand systems

The complexation reaction between Al(3+) and fluoride was studied over concentration ranges 2-50muM fluoride, 0.5-500muM aluminium, pH 2.5-5.0 at ionic strength 0.1 and temperatures of 298 and 283 K. The initial rate of formation of AlF(2+) was strongly dependent on pH, reaching a minimum at pH 3, and was considerably slower at the lower temperature. Addition of salicylate increased the reaction rate, probably because of the corresponding increase in the initial concentration of AlOH(2+). These effects of pH, temperature and competing ligands will therefore be critical in determining the composition of acid natural water systems and in particular the speciation of soluble aluminium.     

ZrO_2表面上Zr~(3+)中心上的O_2吸附平衡

以ESR为主要研究手段,研究了一种最可几粒径为9.8 nm的ZrO_2样品在室温不 同气体（He,H_2,O_2,空气,温空气）中及经不同温度处理后ZrO_2中Zr~(3+)中 心信号的变化。根据ZrO_2样品中Zr~(3+)浓度在室温下对于介质气体中O_2分压改 变的响应极快及Zr~(3+)浓度在室温下对于介质气体变化可逆性等特点提出, ZrO_2中Zr~(3+)中心绝大多数存在于样品的表面上,Zr~(3+)是ZrO_2晶体表面上那 些O~(2-)配位不饱和的Zr原子点位。ZrO_2表面上ESR活性Zr~(3+)中心的数目与其 上氧吸附平衡有关。由ESR法对ZrO_2样品中Zr~(3+)中心的定量和对ZrO_2晶体的粒 度分析,推测ZrO_2表面上Zr~(3+)中心是那些位于ZrO_2微晶的晶角处O~(2-)配位 不饱和的Zr原子。     

Europium complexation by an aquatic fulvic acid - effects of competing ions

Effects of competing ions, Fe (2+)Fe (3+) and Al(3+), on Eu(3+) complexation with an aquatic fulvic acid (FA), have been investigated using an ion exchange technique. The influence of different concentrations (10(-6), 10(-4) M) of the competing ions on the distribution coefficient for Eu was measured, and the overall complex formation function, beta(ov), was resolved for the Eu systems with Fe and Al. All systems showed pH-dependent beta(ov)-functions. The presence of 10(-4) M concentration of competing ion reduced the resolved complex formation function (logbeta(ov)) for Eu complexation with fulvic acid by 0.6 and 0.4 log units at pH 5 for Fe and Al, respectively. this indicates that Fe has a more perturbing effect on Eu-FA complexation than Al. In similar competition studies Sr and Eu were found not to perturb each others complexation with fulvic acid, suggesting therefore that the two metals probably bind to different sites on the fulvic acid molecule.     

Donnan equilibrium of ionic drugs in pH-dependent fixed charge membranes: theoretical modeling

We have studied theoretically the partition equilibrium of a cationic drug between an electrolyte solution and a membrane with pH-dependent fixed charges using an extended Donnan formalism. The aqueous solution within the fixed charge membrane is assumed to be in equilibrium with an external aqueous solution containing six ionic species: the cationic drug (DH(+)), the salt cations (Na(+) and Ca(2+)), the salt anion (Cl(-)), and the hydrogen and hydroxide ions. In addition to these mobile species, the membrane solution may also contain four fixed species attached to the membrane chains: strongly acid sulfonic groups (SO(3)(-)), weakly acid carboxylic groups in dissociated (COO(-)) and neutral (COOH) forms, and positively charged groups (COO...Ca(+)) resulting from Ca(2+) binding to dissociated weakly acid groups. The ionization state of the weak electrolyte groups attached to the membrane chains is analyzed as a function of the local pH, salt concentration, and drug concentration in the membrane solution, and particular attention is paid to the effects of the Ca(2+) binding to the negatively charged membrane fixed groups. The lipophilicity of the drug is simulated by the chemical partition coefficient between the membrane and external solutions giving the tendency of the drug to enter the membrane solution due to hydrophobic interactions. Comparison of the theoretical results with available experimental data allows us to explain qualitatively the effects that the pH, salt concentration, drug concentration, membrane fixed charge concentration, and Ca(2+) binding exert on the ionic drug equilibrium. The role of the interfacial (Donnan) electric potential difference between the membrane and the external solutions on this ionic drug equilibrium is emphasized throughout the paper.     

Redox method for the determination of stability constants of some trivalent metal complexes

Stability constants determination of very stable metal complexes using the redox method, based on the equilibrium of Fe (3+)Fe (2+) followed by a couple of platinum/reference electrodes, was undertaken and tested to complexes of some trivalent metal ions with well known polyaminopolycarboxymethylated linear ligands (edta, nta, cdta, dtpa and ttha) and also to some new macrocyclic ligands. SUPERQUAD program was used for the calculations, after adaptation of the experimental data. The method proved to be very useful for Fe(3+) and In(3+) complexes, if no polynuclear complexes are formed or/and if the kinetics of the complexation reaction is not very slow. However, for the Ga(3+) complexes the applicability of this method is very limited and the competition with OH(-) using the displacement reaction which occurs at pH higher than 6 with formation of Ga(OH)(4)(-) seems to give more accurate results. A complete data of stability constants for the case of the complexes of ttha with In(3+) is given.     

Ion pairing in fast-exchange host-guest systems: concentration dependence of apparent association constants for complexes of neutral hosts and divalent guest salts with monovalent counterions

An equilibrium treatment of complexation of neutral hosts with dicationic guests having univalent counterions includes two possible modes: (1) dissociation of the ion pair prior to interaction of the free dication with the host to produce a complex that is not ion paired and (2) direct complexation of the ion pair to produce an ion paired complex. This treatment is easily modified for complexation of neutral guests by dianionic hosts, or divalent hosts by neutral guests. The treatment was tested by a study of fast-exchange host-guest systems based on paraquats or viologens (G(2+)2X(-)) and crown ethers (H). The bis(hexafluorophosphate) salts of viologens are predominantly ion paired in acetone; the value of the dissociation constant of paraquat bis(hexafluorophosphate) was determined to be 4.64 (+/- 1.86) x 10(-4) M(2). The complex based on dibenzo-24-crown-8 and paraquat bis(hexafluorophosphate) is not ion paired in solution, resulting in concentration dependence of the apparent association constant K(a,exp), (= [complex]/[H][G(2+)2X(-)]) which is well fit by the treatment, according to mode (1), yielding K(ap) = 106 (+/-42) M(-1). However, the four complexes of two different bis(m-phenylene)-32-crown-10 derivatives and bis(p-phenylene)-34-crown-10 with paraquat derivatives are all ion paired in solution and therefore K(a,exp) is not concentration dependent for these systems, mode (2). X-ray crystal structures support these solution-based assessments in that there is clearly ion pairing of the cationic guest with its PF(6)(-) counterions in the solid states of the latter four examples in which access of the counterions to the guests is granted by the relatively large cavities of the hosts and dispositions of the guest species within them.     

Kinetic evidence for intramolecular proton transfer between nickel and coordinated thiolate

The complexes [Ni(YR)(triphos)]BPh(4) (Y = S, R = Ph or Et or Y = Se, R = Ph; triphos = (Ph(2)PCH(2)CH(2))(2)PPh) have been prepared and characterized, and the X-ray crystal structure of [Ni(SPh)(triphos)]BPh(4) has been solved. In MeCN, [Ni(YR)(triphos)](+) are protonated by [lutH](+) (lut = 2,6-dimethylpyridine) to give [Ni(YHR)(triphos)](2+). Studies on the kinetics of these equilibrium reactions reveal an unexpected difference in the reactivities of [Ni(SPh)(triphos)](+) and [Ni(SEt)(triphos)](+). In both cases, the reactions exhibit a first-order dependence on the concentration of complex. When R = Ph, the dependence on the concentrations of [lutH(+)] and lut is given by k(obs) = k(1)(Ph)[lutH(+)] + k(-1)(Ph)[lut], which is typical of an equilibrium reaction where k(1)(Ph) and k(-1)(Ph) correspond to the forward and back reactions, respectively. Analogous behavior is observed for [Ni(SePh)(triphos)](+). However, for [Ni(SEt)(triphos)](+), the kinetics are more complicated, and k(obs) = (k(1)k(2)[lutH(+)] + (k(-2) + k(2)))/(k(1)[lutH(+)] + k(-1)[lut]), which is indicative of a mechanism involving two coupled equilibria in which the initial protonation of the thiolate is followed by a unimolecular equilibrium reaction that is assumed to involve the formation of an eta(2)-EtS-H ligand. The difference in reactivity between the complexes with alkyl and aryl thiolate ligands is a consequence of the (Ni(triphos))(2+) site "leveling" the basicities of these ligands. The pK(a)'s of the PhSH and EtSH constituents coordinated to the (Ni(triphos))(2+) are 16.0 and 14.6, respectively, whereas the difference in pK(a)'s of free PhSH and EtSH differ by ca. 4 units. The pK(a) of [Ni(SeHPh)(triphos)](+) is 14.4. The more strongly sigma-donating EtS ligand makes the (Ni(triphos))(2+) core sufficiently electron-rich that the basicities of the sulfur and nickel in [Ni(SEt)(triphos)](+) are very similar; therefore, the proton serves as a bridge between the two sites. The relevance of these observations to the proposed mechanisms of nickel-based hydrogenases is discussed.     

Single-point titration of metal ions and ligands by measuring change in pH

A single-point titration method is described for the determination of metal ions and ligands. The method is based on deprotonation of a ligand on complexation with a metal. The resultant change in pH is used to calculate the concentration of the analyte. The limits and advantages of the method are discussed. Four selected systems, Pb(2+)-HPO(2-)(4), Cu(2+)-HCO(-)(3), Cd(2+)-EDTA and Ni(2+)-ethylenediamine are used to demonstrate the validity of the equations. The method is applied to determination of total carbonate in serum.     

Ion Exchange and Protonation Equilibria of an Amphoteric Ion-exchange Resin in the Presence of Simple Salt

The influence of simple salts on the ion exchange and protonation equilibria of an amphoteric ion-exchange resin, which has strong base and weak acid moieties in a single functional group fixed onto the styrene-DVB matrix, has been investigated. Concentrations of ionic species in the amphoteric ion-exchange resin in equilibrium with various sodium salt solutions were estimated by (23)Na NMR spectroscopy. For the NaClO(4) system, the ratio of sodium ion concentration in the resin phase to that in the equilibrium solution was greater than 1 and increased with a decrease in the salt concentration. In contrast to an ordinary cation-exchange resin, the ion exchange behavior of Mg(2+) and Ca(2+) on the amphoteric ion-exchange resin showed a marked dependence on the kinds of salts: the distribution coefficients for the NaCl system were independent of the salt concentration, while the log D vs. log[Na(+)] plots for the NaClO(4) system showed linear relationships with slopes being neither -2 nor 0. Apparent protonation constants of the carboxylate in the functional group of the resin in equilibrium with NaClO(4) solutions were greater than those with NaCl solutions. The ion exchange and protonation properties of the amphoteric ion-exchange resin were elucidated on the basis of the information about the salt concentrations in the resin phase estimated by the NMR method.     

Voltammetry of Plastocyanin at a Graphite Electrode: Effects of Structure, Charge, and Electrolyte

Comparative voltammetric studies on Anabaena variabilis plastocyanin (positively charged at neutral pH) and spinach and poplar plastocyanins (negatively charged at neutral pH) have been undertaken at an edge-plane graphite electrode as a function of ionic strength, pH, and Mg(2+) concentration at 3 degrees C. The aim was to provide a more detailed understanding of the influence of the electrode-protein (solution) interfacial characteristics, as well as the variation of the formal potential with both the nature of the plastocyanin species and the pH. As might be expected, some of the interfacial properties associated with the positive charge on A. variabilis plastocyanin are the opposite of those observed with the negatively charged plastocyanins. For example, the linear diffusion component of the mass transport process for A. variabilis plastocyanin under the conditions of cyclic voltammetry is decreased and the radial diffusion component is increased by the addition of Mg(2+), whereas the reverse occurs with poplar and spinach plastocyanins. The voltammetrically determined reversible potentials for A. variabilis plastocyanin are considerably less positive than those for spinach and poplar plastocyanins, in agreement with values calculated from chemically based redox studies. Ionic strength effects, as determined by addition of NaClO(4) over the concentration range 0.005-0.20 M, are negligible for all three proteins. The addition of Mg(2+) causes a significant shift in the reversible potential toward more positive values for spinach and poplar plastocyanin but only a small positive shift for A. variabilis plastocyanin. The difference is attributed to a specific binding effect. The addition of Mg(2+) also dramatically alters the pH dependence of the reversible potential, indicating that the equilibrium between the protonated and unprotonated forms of reduced plastocyanin is modified by binding of Mg(2+) to the protein. It is concluded that the effects of biologically relevant redox-inactive cations such as Mg(2+) or Ca(2+) have to be considered carefully in studies of the redox chemistry of metalloproteins.     

Self-Consistency of the Theory of Elementary Stage Rates of Reversible Processes and the Equilibrium Distribution of Reaction Mixture Components

An analysis is presented of one of the key concepts of physical chemistry of condensed phases: the theory self-consistency in describing the rates of elementary stages of reversible processes and the equilibrium distribution of components in a reaction mixture. It posits that by equating the rates of forward and backward reactions, we must obtain the same equation for the equilibrium distribution of reaction mixture components, which follows directly from deducing the equation in equilibrium theory. Ideal reaction systems always have this property, since the theory is of a one-particle character. Problems arise in considering interparticle interactions responsible for the nonideal behavior of real systems. The Eyring and Temkin approaches to describing nonideal reaction systems are compared. Conditions for the self-consistency of the theory for mono- and bimolecular processes in different types of interparticle potentials, the degree of deviation from the equilibrium state, allowing for the internal motions of molecules in condensed phases, and the electronic polarization of the reagent environment are considered within the lattice gas model. The inapplicability of the concept of an activated complex coefficient for reaching self-consistency is demonstrated. It is also shown that one-particle approximations for considering intermolecular interactions do not provide a theory of self-consistency for condensed phases. We must at a minimum consider short-range order correlations.     

Comparison of n-tetradecane/electrolyte emulsions properties stabilized by DPPC and DPPC vesicles in the electrolyte solution

The properties of n-tetradecane/electrolyte emulsions with DPPC or DPPC vesicles in the electrolyte solution were investigated. The DPPC molecules form different aggregates, which possess different surface affinity, size and structure, and therefore we assumed some differences in the adsorption at the oil droplet/water interface. The n-tetradecane emulsions in 1:1, 1:2 and 1:3 electrolytes were prepared by mechanical stirring in the presence of DPPC at natural pH. Electrokinetic properties of the systems were investigated taking into account the effective diameter and multimodal size distribution of the droplets as well as the zeta potentials using the dynamic light scattering technique. The zeta potential of the droplets was negative in all systems with NaCl. In the emulsions with CaCl(2) at a higher concentration of electrolyte and emulsions with LaCl(3) with all investigated concentrations, positive values were observed. Similar measurements were performed for DPPC vesicles in the electrolyte solution. The pH and ionic strength changes induce those in the electrical charge of DPPC layer or vesicle surface. This is due to the fact that the DPPC molecule contains -PO(-) and -N(CH(3))(3) groups, which are in equilibrium with H(+) and OH(-), as well as other ions present in the solution, i.e. Na(+), Ca(2+), La(3+) or Cl(-). In the n-tetradecane/electrolyte emulsion stabilized by DPPC or DPPC vesicles the zeta potential may be also related to acid-base interactions. The effect of the ions from the solution on the DPPC layer adsorbed on n-tetradecane droplets or DPPC vesicles is discussed.