L'extraction des lanthanides et des actinides par les oxydes d'alkylphosphine : L'extraction de L'acide nitrique par les oxydes de tri-n-hexylphosphine,de tri-cyclohexylphosphine et de tri-n-octylphosphine

The distribution of nitric acid between an aqueous phase and a solution of THPO, TcHPO and TOPO in benzene was measured at 25°. The apparent stability constants K₁' were found to be 17.2±1.0 (M)^-2 for THPO.HNO₃, 7.0±0.8 (M)^-2 for TcHPO.HNO₃ and 15.2 ± I.I (M)^-2 for TOPO.HNO3. The stoichionetry of the last complex was confirmed in n-octane solution at constant ionic strength in the aqueous phase.     

L'extraction des lanthanides et des actinides par les oxydes d'alkylphosphine: Tome 1. l'extraction de l'acide nitrique par l'oxyde de tri-n-butylphosphine

The distribution of TBPO, water and nitric acid has been measured between an aqueous phase and various inert diluents at 25°. This study allowed the determination of the apparent stability constants for two molecular complexes, TBPO . HNO₃ (K₁=17.5±1.3 (M/l)^-2 (benzene); 20.1±0.8 (M/l)^-2 (toluene); II±2(M/l)^-2 (n-hexane) and TBPO . 2HNO₃.H₂O (K₂=(2.9±0.3) 10^-3(M/l)^-2 (benzene)).     

Spectrophotometric investigation of monobromo and dibromo complexes of copper(II) in methanolic medium

Complex formation between copper(II) and bromide in anhydrous methanol was investigated spectrophotometrically. At a constant copper(II) concentration of 3.0 x 10^?4M, Cu²⁺ and CuBr⁺ are at equilibrium for [Br^?] < 1.0 x 10^?3M while CuBr⁺ and CuBr₂ exist at equilibrium in the range of [Br^?] 2.0 x 10^?3 ?40 x 10^?3M. An isosbestic point at 235 nm indicated the equilibrium of Cu²⁺ and CuBr⁺ while a second isosbestic point at 290 nm showed the equilibrium of CuBr⁺ and CuBr₂. Stability constants for the formation of CuBr⁺ and CuBr₂ (K₁, and K₂, respectively) were determined as a function of ionic strength in the range 0.01–0.10. Log K₁ and log K₂ values at zero ionic strength were obtained by extrapolation of the plot of log K vs ionic strength, the values being 3.97 ± 0.01 and 2.31 ± 0.01.     

Étude quantitative d'équilibres chimiques en solution dans les sels fondus par spectrophotométrie d'absorption: Application au neptunium

The following reactions: NpO₂⁺+4 HCl ? Np⁴⁺ + 2 H₂O + $\text{1}\text{2}$ Cl₂ + 3Cl^- NpO₂⁺+$\text{1}\text{2}$ Cl₂ ? NpO₂²⁺ +Cl^- 2HCl+O^2- ? H₂O +Cl^- have been examined quantitatively. The reactions were studied in fused LiCl-KCl sparged with gas mixtures of definite compositions. The concentrations of the diffrent neptunium species were measured by absorption spectrophotometry. The values of respective equilibrium constants are: K = (9.3±0.4)· 10^-6 atm(^{-$\text{1}\text{2}$}); K₁ = (2.3±0.1)·10^-2 atm(^{-$\text{1}\text{2}$}); k = 10^3.8 1 mol^-1 atm^-1 The standard potential of the system NpO₂²⁺ / NpO₂⁺ was determinedto be E⁰ = 0.220 V (vs.standard chlorine electrode).     

Cinetique complexe de l'halogenation de cetones en milieu acide—I : Iodation des enols

The kinetics of the iodination of acetone, diethylketone and di-isopropylketone in aqueous media ([H₂SO₄] = 0·1 to 1·0 N; [I₂]_a^o = 10^?7 to 10^?5M) have been studied by couloamperometry under irreversible conditions. At these concentrations the rates of formation of the enol and of its iodination are similar. The general equation, which assumes the steady state approximation for the enol, is applicable, and is used to separate the rate constants of enolisation (k₁) and the apparent enol iodination rate constant (k_II^I₂ = K_Ek₂^I₂). For acetone, the value given by Schwarzenbach for the enol equilibrium constant (K_E = 2·5 x 10^?6) leads to an elementary rate constant for the addition of iodine to the enol (k₂^I₂ = 6·5 x 10⁶ M^?1s^?1). This value is not, however, consistent with k_I2 = 1·5 x 10⁸ M^?1s^?1, the rate constant for the iodination of the corresponding ether 2-ethoxypropene.     

Studies of solid-state ion-selective electrodes prepared from semiconducting organic radical-ion salts

The primary redox reactions for solid-state ion-selective electrodes prepared from electronically semiconducting salts of 7,7,8,8-tetracyanoquinodimethane (tcnq) can be identified by considering the redox properties of their constituent ions or molecules. Three different processes involving the couples, Mⁿ⁺/M⁰, 2tcnq^o/(tcnq^-)₂ and (tcnq^-)₂/2tcnq^2- are possible depending on salt composition. Ionic product values determined by potentiometric and atomic absorption methods are in excellent agreement for several such salts; K_s(K₂tcnq₂)=5.8±1.2·10^-11(pot.), 1.7±1·10^-11 (a.a.s.); K_s(Cdtcnq₂) = 3.0±0.5·10^-9 (pot.), 2.9±0.3·10^-9(a.a.s.); K_s(Pbtcnq₂) = 1.3±0.3·10^-10 (pot.), 0.96±0.2·10^-10(a.a.s.); and indicate that the lower activity limit for electrode response is controlled by the solubility of the sensor material itself. Comparisons of predicted and observed standard electrode potentials provide quantitative support for an ion-exchange mechanism of interference. The behaviour of electrodes prepared from Cu₂tcnq₂ (copper(I)) and Cutcnq₂ (copper(II)) is explained on the basis of an interference mechanism and considerations of solid-state equilibria.     

Cinetique complexe de l'halogenation de cetones en milieu acide—II : Controle par la diffusion des vitesses d'halogenation des enols-consequences

The kinetics of the bromination and chlorination of acetone, diethylketone and di-isopropylketone (bromination only) have been studied at [X₂]_a^o ≈ 10^?7 to 10^?5 M; the apparent rate constants k_II^X₂ = K_Ek₂^X₂ (where K_E is the keto-enol equilibrium constant) for iodination, bromination and chlorination are approximately equal. This result is attributed to diffusion-controlled kinetics. The order of magnitude of such a limiting rate constant, 10⁹ M^?1s^?1 calculated from Smoluchowski's equation, leads to new values for K_E in solution (1·5 x 10^?8 for acetone) much smaller than those in the literature. The rate constants derived for enol ketonisation are then in good agreement with those from proton addition to the corresponding enol ethers.     

Macrocycle-mediated cation transport from binary Hg2+Mn+ mixtures in A 1 M HNO3CHCI31 M HNO3 liquid membrane system

The macrocycle-mediated flux of Hg²⁺ individually and of Hg²⁺ and Mⁿ⁺ (Mⁿ⁺ = K⁺, Tl⁺, Ag⁺, Sr²⁺, Cd²⁺, or Pb²⁺) in cation mixtures has been measured at 25°C in a I M HNO₃CHCl₃1 M HNO₃ liquid membrane system. Of the ten macrocycles used, 18-crown-6(18C6), dicyclohexano-18-crown-6(DC18C6), and 21-crown-7(21C7)were most effective in transporting Hg²⁺ individually. Relative cation fluxes in the metal ion mixtures correlated well with relative log K values for cation--macrocycle interaction and with relative partition coefficients for the distribution of the resulting complex between the aqueous and organic phases     

Kinetics and mechanism of the aquation of pentaaqua (trichloroacetato-O)-chromium(2+) ion

The kinetics of the aquation of (H₂O)₅Cr(O₂CCCl₃)²⁺ have been examined at 35–55°C and 1.00M ionic strength with [H⁺] = 0.01?1.00M. The reaction follows the rate equation -d ln [Cr_total]/dt = (a[H⁺]^?1 + b + c[H⁺])/(1 + d[H⁺]), where [Cr_total] is the stoichiometric concentration of the complex. At 45°C a = (1.41 ± 0.03) × 10^?7M/s, b = (1.66 ± 0.02) × 10^?5 s^?1, c = (7.0 ± 0.8) × 10^?5M^?1·S^?1 and d = 2.3 ± 0.3M^?1. Two mechanisms consistent with this rate law are discussed, with evidence being presented in favor of an ester hydrolysis mechanism involving steady-state intermediates. Equilibrium and activation parameters were determined.     

A laser flash photolysis kinetic study of reactions of the Cl2− radical anion with oxygenated hydrocarbons in aqueous solution

A laser photolysis–long path laser absorption (LP‐LPLA) experiment has been used to determine the rate constants for H‐atom abstraction reactions of the dichloride radical anion (Cl₂⁻) in aqueous solution. From direct measurements of the decay of Cl₂⁻ in the presence of different reactants at pH = 4 and I = 0.1 M the following rate constants at T = 298 K were derived: methanol, (5.1 ± 0.3)·10⁴ M⁻¹ s⁻¹; ethanol, (1.2 ± 0.2)·10⁵ M⁻¹ s⁻¹; 1‐propanol, (1.01 ± 0.07)·10⁵ M⁻¹ s⁻¹; 2‐propanol, (1.9 ± 0.3)·10⁵ M⁻¹ s⁻¹; tert.‐butanol, (2.6 ± 0.5)·10⁴ M⁻¹ s⁻¹; formaldehyde, (3.6 ± 0.5)·10⁴ M⁻¹ s⁻¹; diethylether, (4.0 ± 0.2)·10⁵ M⁻¹ s⁻¹; methyl‐tert.‐butylether, (7 ± 1)·10⁴ M⁻¹ s⁻¹; tetrahydrofuran, (4.8 ± 0.6)·10⁵ M⁻¹ s⁻¹; acetone, (1.41 ± 0.09)·10³ M⁻¹ s⁻¹. For the reactions of Cl₂⁻ with formic acid and acetic acid rate constants of (8.0 ± 1.4)·10⁴ M⁻¹ s⁻¹ (pH = 0, I = 1.1 M and T = 298 K) and (1.5 ± 0.8) · 10³ M⁻¹ s⁻¹ (pH = 0.42, I = 0.48 M and T = 298 K), respectively, were derived. A correlation between the rate constants at T = 298 K for all oxygenated hydrocarbons and the bond dissociation energy (BDE) of the weakest C‐H‐bond of log k_2nd = (32.9 ± 8.9) − (0.073 ± 0.022)·BDE/kJ mol⁻¹ is derived. From temperature‐dependent measurements the following Arrhenius expressions were derived: k (Cl₂⁻ + HCOOH) = (2.00 ± 0.05)·10¹⁰·exp(−(4500 ± 200) K/T) M⁻¹ s⁻¹, E_a = (37 ± 2) kJ mol⁻¹ k (Cl₂⁻ + CH₃COOH) = (2.7 ± 0.5)·10¹⁰·exp(−(4900 ± 1300) K/T) M⁻¹ s⁻¹, E_a = (41 ± 11) kJ mol⁻¹ k (Cl₂⁻ + CH₃OH) = (5.1 ± 0.9)·10¹²·exp(−(5500 ± 1500) K/T) M⁻¹ s⁻¹, E_a = (46 ± 13) kJ mol⁻¹ k (Cl₂⁻ + CH₂(OH)₂) = (7.9 ± 0.7)·10¹⁰·exp(−(4400 ± 700) K/T) M⁻¹ s⁻¹, E_a = (36 ± 5) kJ mol⁻¹ Finally, in measurements at different ionic strengths (I) a decrease of the rate constant with increasing I has been observed in the reactions of Cl₂⁻ with methanol and hydrated formaldehyde. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 169–181, 1999     

Actinide(III) carbonate complexation

The following equations have been developed to estimate trivalent actinide and lanthanide carbonate stability constants: log B₁⁰ = −6.128+35.206R−21.557R²; log B₂⁰ = 14.797+7.945R−10.304R², where B₁⁰ = aMCO₃⁺/(aM³⁺aCO₃²⁻, B₂⁰ = aM(CO₃)₂⁻(aM³⁺(aCO₃²⁻), aX is the activity of ion X, M indicates a metal ion and R is the effective ionic radius of the metal ion in six-fold coordination. These equations describe carbonate stability constants for cerium, europium and ytterbium at zero ionic strength. Constants at zero ionic strength were estimated from experimental determinations made in 0.68 molal NaClO₄ by accounting for medium effects.     

Kinetics and mechanism of the reduction of monochloramine by hydroxylamine and hydroxylammonium ion

The kinetics and mechanism by which monochloramine is reduced by hydroxylamine in aqueous solution over the pH range of 5–8 are reported. The reaction proceeds via two different mechanisms depending upon whether the hydroxylamine is protonated or unprotonated. When the hydroxylamine is protonated, the reaction stoichiometry is 1:1. The reaction stoichiometry becomes 3:1 (hydroxylamine:monochloramine) when the hydroxylamine is unprotonated. The principle products under both conditions are Cl^–, NH⁺₄, and N₂O. The rate law is given by ?[d[NH₂Cl]/dt] = k₊[NH₃OH⁺][NH₂Cl] + k₀[NH₂OH][NH₂Cl]. At an ionic strength of 1.2 M, at 25°C, and under pseudo‐first‐order conditions, k₊= (1.03 ± 0.06) ×10³ L · mol^?1 · s^?1 and k₀=91 ± 15 L · mol^?1 · s^?1. Isotopic studies demonstrate that both nitrogen atoms in the N₂O come from the NH₂OH/NH₃OH⁺. Activation parameters for the reaction determined at pH 5.1 and 8.0 at an ionic strength of 1.2 M were found to be ΔH? = 36 ± 3 kJ · mol^–1 and Δ S? = ?66 ± 9 J · K^?1 · mol^?1, and Δ H? = 12 ± 2 kJ · mol^?1 and Δ S? = ?168 ± 6 J · K^?1 · mol^?1, respectively, and confirm that the transition states are significantly different for the two reaction pathways. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 124–135, 2006     

Acid–Base Properties, Solubility, Activity Coefficients and Na+ Ion Pair Formation of Complexons in NaCl(aq) at Different Ionic Strengths

The protonation constants and solubilities of three complexons [ethylenediamine-N,N′-disuccinic acid (EDDS), ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA) and 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA)] are reported in aqueous solutions of NaCl with different ionic strength values (0 ≤ I ≤ 4.8 mol·L^?1) and, in the case of CDTA, in (CH₃)₄NCl (0.1 ≤ I ≤ 2.7 mol·L^?1). The dependence on ionic strength of the protonation constants of these three complexons and four other complexons that were previously reported (NTA, EDTA, DTPA and TTHA), is analyzed in NaCl solution; the ionic strength influences quite strongly the protonation constants (as an example for CDTA, log₁₀ K ₁ = 10.54 and 9.25 at I = 0.1 and 1 mol·L^?1, respectively), while the effect of (CH₃)₄NCl concentration is lower. Based on the total solubility S ^T and the protonation constant data at different salt concentrations, the solubility of the neutral species S ⁰ and the solubility products K _S0 are obtained. The Setschenow coefficients k _m and the solubility values S ₀ ⁰ in pure water are also reported (S ₀ ⁰  = 0.55, 0.21 and 0.75 mmol·kg^?1 for EDDS, EGTA and CDTA, respectively). The dependence of the protonation constants on ionic strength is also interpreted in terms of ion pair formation, and the formation constants of Na⁺ species are reported.     

IR and <Superscript>31</Superscript>P NMR spectroscopic study of complexation of carbamoyl methyl phosphinates with U<Superscript>VI</Superscript> and Th<Superscript>IV</Superscript> in nitric acid solutions

The composition of complexes formed upon the extraction of U^VI and Th^IV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by ³¹P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO₃ as the [UO₂(L)₂(NO₃)₂] complex, while thorium(IV) is extracted from 5 M HNO₃ as the [Th(L)₃(NO₃)₃]⁺·NO ₃ ⁻ complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO₃ and L· (HNO₃)₂, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.     

Die Kristallstrukturen von [Cu2Cl2(AA · H+)2](NO3)2 und [AA · H+]Pikr− (AA · H+ = Allylammonium; Pikr− = Pikrat)

The Crystal Structures of [Cu₂Cl₂(AA · H⁺)₂](NO₃)₂ and [AA · H⁺]Picr^? (AA · H⁺ = Allylammonium; Picr^? = Picrat) By an alternating current electro synthesis the crystal-line π-complex [Cu₂Cl₂(AA · H⁺)₂](NO₃)₂ has been obtained from CuCl₂ · 2H₂O, allylamine (AA), and HNO₃ in ethanolic solution. X-ray structure analysis revealed that the compound crystallized in the monoclinic system, space group P2₁/a, a = 7.229(3), b = 7.824(3), c = 26.098(6) Å, γ = 94.46(5)°, Z = 4, R = 0.025 for 2 023 reflections. The crystal structure is built up of Cu_nCl_n chains which are connected by π-bonding bidentate AA · H⁺ …? ON(O)O …? H⁺ · AA units. For comparision with the above complex the structure of [AA · H⁺]Picr^? (Picr^? = picrate anion) is also reported.     

Spektrophotometrische Untersuchung der Eisen(III)-Komplexe mit o-Methylbenzamidoxim

The complex formation of Fe³⁺ with o-methyl benzamide oxime was studied spectrophotometrically in methanol solution. The stepwise process gives complexes 1∶1, 1∶2 and 1∶3. The formation constants are lgK ₁ = lg β₁ = 1,88 ± 0,12, lgK ₂ = 3,53 ± 0,2, lgK ₃ = 4,96 ± 0,2, lg β₂ = 1,65 ± 0,32 and lg β₃ = 1,43 ± 0,4, whereK ₃ = β₁ · β₂ · β₃. All measurements were carried out at 25°C and an ionic strength μ=1.     

Calorimetric studies on the thermal decomposition of tri n-butyl phosphate-nitric acid systems

Thermal decomposition of neat TBP, acid-solvates (TBP·1.1HNO₃, TBP·2.4HNO₃) (prepared by equilibrating neat TBP with 8 and 15.6?M nitric acid) with and without the presence of additives such as uranyl nitrate, sodium nitrate and sodium nitrite, mixtures of neat TBP and nitric acid of different acidities, 1.1?M TBP solutions in diluents such as n-dodecane (n-DD), n-octane and isooctane has been studied using an adiabatic calorimeter. Enthalpy change and the activation energy for the decomposition reaction derived from the calorimetric data wherever possible are reported in this article. Neat TBP was found to be stable up to 255?°C, whereas the acid-solvates TBP·1.1HNO₃ and TBP·2.4HNO₃ decomposed at 120 and 111?°C, respectively, with a decomposition enthalpy of ?495.8?±?10.9 and ?1115.5?±?8.2?kJ?mol^?1 of TBP. Activation energy and pre exponential factor derived from the calorimetric data for the decomposition of these acid-solvates were found be 108.8?±?3.7, 103.5?±?1.4?kJ?mol^?1 of TBP and 6.1?×?10¹⁰ and 5.6?×?10⁹?S^?1, respectively. The thermochemical parameters such as, the onset temperature, enthalpy of decomposition, activation energy and the pre-exponential factor were found to strongly depend on acid-solvate stoichiometry. Heat capacity (C _p ), of neat TBP and the acid-solvates (TBP·1.1HNO₃ and TBP·2.4HNO₃) were measured at constant pressure using heat flux type differential scanning calorimeter (DSC) in the temperature range 32?C67?°C. The values obtained at 32?°C for neat TBP, acid-solvates TBP·1.1HNO₃ and TBP·2.4HNO₃ are 1.8, 1.76 and 1.63?J?g^?1?K^?1, respectively. C _p of neat TBP, 1.82?J?g^?1?K^?1, was also measured at 27?°C using ??hot disk?? method and was found to agree well with the values obtained by DSC method.     

Copolymerization of vinyl chloride with sulphur dioxide—I molecular association between vinyl chloride and sulphur dioxide

The formation of VC-SO₂ and VC-(SO₂)₂ complexes in liquid mixtures of vinyl chloride (VC) and sulphur dioxide has been shown by (a) the freezing point composition diagram and (b) chemical shifts in the PMR spectrum of VC over the complete composition range. It is postulated that SO₂ can associate with the CC bond and the Cl atom. These complexes may be involved in the copolymerization and influence the composition and stereochemistry of the product. PMR spectra of VC-SO₂-ethane(E) mixtures with [SO₂] ? [E] ? [VC] gave K_v = 2·0 ± 0·5, 1·5 ± 0·1 and 1·1 ± 0·3 at 232·6, 272·6 and 301·3 K with ΔH_f⁰H_f = ?6·6 ± 1·4 kJ mol^?1 for the VC -(SO₂)₂ complex. The chemical shift of the trans β-proton was twice that of the other two protons. indicating that SO₂ adopts an asymmetric orientation to the double bond.     

838 — An electrochemical study of energy-dependent potassium accumulation in E. coli: Part XI. The Trk system in anaerobically and aerobically grown cells

The interaction of H⁺-ATPase complex ECF₁·F₀ and the Trk system of K₊ accumulation was studied in E.coli grown quasi-anaerobically in peptone media with glucose (anaerobia) and aerobically in salt medium with succinate (aerobia). In anaerobia the Trk system takes part in H⁺-K⁺ exchange, displaying k_m = 3.7 mM, ν_max =1.6 mM g⁻¹ min⁻¹ and in aerobia in the Trk system has K_m = 3.4 mM, ν_max = 0.45 mM g⁻¹ min⁻¹. The K⁺ accumulation is blocked by DCC in anaerobia and by cyanide together with DCC in aerobia, whereas protonophores and arsenate block the K⁺ uptake in bacteria grown under either condition. Valinomycin decreases the K⁺ accumulation in anaerobia and increases (or has no effect) that in aerobia. ECF₁·F₀ is sensitive and the Trk system is insensitive to variation of the external osmotic pressure in both cases. The ratio H⁺ : K⁺ is stable and equal to 2:1 in anaerobia and is changed from 0.5 to 5.0 in aerobia in response to variation of pH, K⁺ activity and temperature, Q₁₀ is about 2.8 both for ECF₁·F₀ and for the Trk system in anaerobia, but 2.4 and near 1.0 respectively in aerobia. The distribution of K⁺ in anaerobia is 2500 (potassium equilibrium potential of − 210 mV) which is much more than the measured U_m of −145 mV. The distribution of K₊ in aerobia is 720, which is in good conformity with the measured membrane potential of −175 mV. The structural association of ECF₁·F₀ and the Trk system, forming a H⁺-K⁺ pump, has been assumed previously to take place in anaerobically grown E.coli; these systems operate separately in aerobic cells. According to Bakker and Helmer et al. the Trk system transports K⁺ along the electrical field, its function being regulated by ATP.     

Yttrium and Rare Earth Element Complexation by Chloride Ions at 25°C

Formation constants for yttrium and rare earth element (YREE) chloride complexation have been measured at 25°C by examining the influence of medium (NaClO₄ and NaCl) on YREE complexation by fluoride ions and methyliminodiacetate (MIDA). YREE chloride complexation constants _Clβ₁(M) obtained in this work using dissimilar procedures are in good agreement and indicate that, at constant temperature and ionic strength, _Clβ₁(M) does not vary significantly across the fifteen-member series of elements. The ionic strength μ dependence of YREE chloride formation constants between 0 and 6 molar ionic strength can be written, for all YREE, as ${\text{log}}_{{\text{CI}}} \beta _1 \left( M \right) = \log _{{\text{CI}}} \beta _1^0 \left( M \right) - 3.066\mu ^{0.5} /\left( {1 + 1.727\mu ^{0.5} } \right)$ where _Clβ₁(M) = [MCl²⁺][M³⁺]^?1[Cl^?1]^?1 and log_Clβ₁ ^o(M) represents the MCl²⁺ formation constant for all YREE at zero ionic strength: log_Clβ₁ ^o = 0.65 ± 0.05.