Measuring the rate constant of the reaction between chlorine atoms and CHF<Subscript>2</Subscript>Br by Cl atom resonance fluorescence

The rate constant of the reaction between Cl atoms and CHF₂Br has been measured by chlorine atom resonance fluorescence in a flow reactor at temperatures of 295–368 K and a pressure of ~1.5 Torr. Lining the inner surface of the reactor with F-32L fluoroplastic makes the rate of the heterogeneous loss of chlorine atoms very low (k_het ≤ 5 s^–1). The rate constant of the reaction is given by the formula k = (4.23 ± 0.13) × 10^–12e^{(–15.56 ± 1.58)/RT} cm³ molecule^–1 s^–1 (with the activation energy in kJ/mol units). The possible role of this reaction in the extinguishing of fires producing high concentrations of chlorine atoms is discussed.     

Effect of solvent nature on the photoreduction kinetics of substituted benzoquinones

Effect of the solvent nature on the kinetics of photoreduction of substituted benzoquinones in the presence of hydrogen donors has been studied. It has been found that the effective photoreduction rate constant (k_H) for quinones decreases with an increase in solvent polarity. For the 3,6-di-tert-butylbenzoquinone–1,2-N,N-dimethylaniline pair, the dependence of ln k_H on the difference of the reciprocals of optical and static solvent permitivities (1/ε _∞–1/ε₀) is stepwise with a break point corresponding to CH₂Cl₂. A similar relationship lnk_H = f(1/ε _∞–1/ε₀) is observed for the p-chloranil–mesitylene pair. In the study of the photoreduction kinetics for a series of seven o-benzoquinones in the presence of p-derivatives of N,N-dimethylaniline in CH₂Cl₂, it has been found that the dependence of k_H on the free energy of electron transfer (ΔG_e) has a maximum for the 3,6-di-tert-butylquinone-1,2–N,N-dimethylaniline pair at ΔG_e = 0.11 eV.     

Electronic absorption spectra of solutions of molecular chlorine in molten alkali metal chlorides

Electronic reflection absorption spectroscopy has been used for measuring the electronic spectra of chlorine solutions in molten alkali metal chlorides 2CsCl-NaCl, KCl-NaCl, and CsCl in the range 240–400 nm. Absorption bands of chloride melts are interpreted as electronic transitions in the molecular group Cl₂ and in the triatomic linear group Cl ₃ ^? of symmetry D _∞h and C _∞V .     

Influence of Synthesis Conditions on the Morphology and Spectral-Luminescent Properties of Films of Organic-Inorganic Perovskite CH<Subscript>3</Subscript>NH<Subscript>3</Subscript>PbI<Subscript>2.98</Subscript>Cl<Subscript>0.02</Subscript>

The influence of the synthesis conditions (rotation speed used for spin-coating deposition of the film, film drying temperature, and the ratio of the PbI₂ and CH₃NH₃I reactants in solutions) on the microstructure, phase composition, and spectral-luminescent properties of films of organic-inorganic perovskite CH₃NH₃PbI_3–xCl _x (x = 0, 0.02) was elucidated.     

Crystal structure and spectroscopic characterization of a coordination polymer of Copper(II) chloride with ethylenediamine and the 2-hydroxybenzoate ion

A new mixed-ligand one-dimensional copper(II) coordination polymer [Cu(en)(sal)Cl] _n where en = ethylenediamine(C₂H₈N₂) and Hsal = 2-hydroxybenzoic acid (salicylic acid; C₇H₆O₃) is synthesized and characterized by FTIR spectroscopy and single crystal X-ray diffraction. The structure contains Cu²⁺ ions in two different distorted octahedral coordination environments: an axially extended CuN₄Cl₂ moiety arising from a pair of bidentate en ligands and a CuO₄Cl₂ moiety arising from a pair of asymmetrically coordinated sal^– anions. The chloride ions bridge the copper ions into a zigzag chain propagating in [001]. The structure is consolidated by N–H???O and N–H???Cl hydrogen bonds which generate a layered network. Crystal data: C₉H₁₃ClCuN₂O₃, M _r = 296.20, monoclinic, P2₁/c, a = 13.9179(10) Å, b = 10.4900(8) Å, c = 8.5181(6) Å, β = 105.518(4)°, V = 1198.30(15) ų, Z = 4, R(F) = 0.026, w R(F ²) = 0.068.     

Abstraction of chlorine atoms from chloromethanes by the cyclohexyl radical

The kinetics of chlorine atom abstraction from the chloromethanes (CM)CCl₄, CHCl₃, and CH₂Cl₂ by radiolytically generated cyclohexyl radicals has been studied in the liquid phase by a competitive method. The halogen abstraction data have been put on an absolute basis by comparing the rates of the metathetical reactions with the known rate of addition of cyclohexyl radicals to C₂Cl₄. The following Arrhenius parameters were obtained:

Catalytic effects of cationic nanoparticle (CTABr/NaX/H<Subscript>2</Subscript>O,X = Cl,Br) for the piperidinolysis of phenyl salicylate ions

The expression of pseudo-second-order rate constants (k _X) for cationic nanoparticle (CN) [CTABr/NaX/H₂O, X = Br, Cl, CTABr = cetyltrimethylammonium bromide] catalyzed piperidinolysis-ionized phenyl salicylate (PSa^–), at constant [CTABr]_T, 0.1 M piperidine (Pip), and 35°C, were calculated from the relationship: k _obs = (k ₀ + k _X[NaX])/(1 + K ^X/S[NaX]), in which k ₀, k _X, and K ^X/S are constant kinetic parameters and k _obs represents the pseudo-first-order rate constant for Pip reaction with phenyl salicylate ion in the presence of CN. The source of the large catalytic effect of CN catalyst was shown to be due to the transfer of PSa^– from pseudo-phase of the CNs to the bulk aqueous phase through X^–/PSa^– ion exchange at the surface of the CNs.     

Potentiometric study of the kinetics and equilibria of formation of chloroglycinate palladium(II) complexes from bis-glycinato palladium(II) complexes

The equilibria and kinetics of the reaction of Pd(gly)₂ complexes with hydrogen ions and chloride ions has been studied by a potentiometric method. The underlying idea of the method is the measurement of solution pH as a function of reaction time t using a glass electrode. The solutions used had the following initial compositions: xM Pd(gly)₂, xM Hgly, and 1 M NaCl with x = 1 × 10^?4, 5 × 10^?4, and 1 × 10^?3; initial pH₀ was from ～3.5 to ～4.4. The experimentally determined pH versus t dependences and the rate equation for a pseudo-second-order reaction were used to determine the equilibrium constant of formation of Pd(gly)(Hgly)Cl complexes from Pd(gly)₂ complexes and the observed rate constant for this reaction, k _obs. The dependence of k _obs on the pH of the acid solutions studied was assigned to a change in the sequence of the reactions of addition of a hydrogen ion and a chloride ion to the complex Pd(gly)₂.     

Synthesis and structure of Pt(II) acetamidate complexes containing <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethyl-substituted ethylenediamine and trimethylenediamine

Reactions of acetamide with platinum(II) diamines [Pt(N,N-DimeEn)Cl₂], [Pt(Tm)Cl₂], and [Pt(N,N-DimeTm)Cl₂] (N,N-DimeEn = (CH₃)₂N(CH₂)₂NH₂, Tm = NH₂(CH₂)₃NH₂, N,N-DimeTm = (CH₃)₂N(CH₂)₃NH₂) with preliminary precipitation of chlorine ions by silver salts gave binuclear Pt(II) acetamidates [Pt₂(CH₃)₂N(CH₂)₂NH₂)₂(μ-NHCOCH₃)₂](NO₃)₂ · H₂O (I), [Pt₂(NH₂(CH₂)₃NH₂)₂)(μ-NHCOCH₃)₂](NO₃)₂ · H₂O (II), and [Pt₂(CH₃)₂N(CH₂)₃NH₂)₂(μ-NHCOCH₃)₂](HSO₄)₂ (III), whose crystal structures were determined. Crystals of I are monoclinic: a = 14.459(2) Å, b = 17.197(3) Å, c = 9.822(2) Å, β = 105.923(10)°, V = 3348.6(8) ų, space group P2(1)/c, Z = 4, R _hkl = 0.0419 for 6663 reflections. Complex I is a binuclear acetamidate with bridging (NHCOCH₃)^? ligands, one of which is bound to two Pt atoms through the N and O atoms, and the other ligand is bound only through the N atom. The Pt-Pt distance is 2.987(1) Å. Crystals of II are monoclinic: a = 10.213(7) Å, b = 13.373(9) Å, c = 16.533(11) Å, β = 97.971(9)°, V = 2236(3) ų, space group P2(1)/n, Z = 4, R _hkl = 0.557 for 6462 reflections. The Pt-Pt distance is 3.057(1) Å. Crystals of III are monoclinic: a = 10.557(12) Å, b = 18.531(2) Å, c = 14.4744(17) Å, β = 108.705(2)°, V = 2682(5) ų, space group P2(1)/n, Z = 4, R _hkl = 0.569 for 8506 reflections. The Pt-Pt distance is 3.202(1) Å. Complexes II and III are binuclear acetamidates, in which two chelating Pt(Tm) or Pt(N,N-DimeTm) moieties are coordinated through the N and O atoms of (NHCOCH₃)^? cis-bridges.     

Crystal structure of [Ir(NH<Subscript>3</Subscript>)<Subscript>5</Subscript>Cl]<Subscript>2</Subscript>[OsCl<Subscript>6</Subscript>]Cl<Subscript>2</Subscript>. Crystal-chemical analysis of the iridium-osmium system

The [Ir(NH₃)₅Cl]₂[OsCl₆]Cl₂ binary complex salt has been prepared, and its structure was investigated by single crystal X-ray diffraction. Crystal data: a = 11.1901(13) Å, b = 7.9138(13) Å, c = 13.4384(18) Å; β = 99.640(3)°, V = 1190.0(2), space group C2/m, Z = 2, FW = 1099.47, d _x = 3.068 g/cm³. Thermolysis products of [Ir(NH₃)₅Cl]₂[OsCl₆]Cl₂, [Ir(NH₃)₅Cl][OsBr₆], (NH₄)₂[OsCl₆]_x[IrCl₆]_1?x , and K₂[OsCl₆]_x[IrCl₆]_1?x were studied by X-ray phase analysis; the unit cell parameters were refined, and the dependence of volume per atom (V/Z) on the composition of the Ir Os_1?x solid solution has been plotted.     

Thermodynamic and kinetic stability of cerium(IV) complexes with a series of aminopolyacetic acids

The compositions, stability constants, and rate constants of intramolecular redox decomposition of cerium(IV) complexes with anions of aminoacetic (H₂NCH₂COOH), iminodiacetic [HN(CH₂COOH)₂], nitrilotriacetic [N(CH₂COOH)₃], ethylenediaminetetraacetic [(CH₂COOH)₂N(CH₂)₂N(CH₂COOH)₂], and hexamethylenediaminetetraacetic [(CH₂COOH)₂N(CH₂)₆N(CH2COOH)₂] acids were determined by potentiometric, spectrophotometric, and kinetic methods at pH in the range 1.3?2.0 in perchlorate and nitrate media at an ionic strength I = 0.1 and a temperature of 298.15 K. Direct linear correlation between the logarithms of the stability constants of the complexes, log β₁₀₁, and logarithms of the cumulative protonation constants, log В _m+k (k = 1–2), of aminopolyacetic acid anions L ^m–, and inverse linear correlation between log β₁₀₁ and logarithms of the rate constants of intramolecular redox decomposition of the complexonates [CeL]^4–m (m = 1–4), log k _n=1, were found.     

Structure of aminonitrones and electronic effect of substituents on their acid-base properties

A series of para-substituted aromatic aminonitrones p-RC₆H₄C(NH₂)=N⁺(Me)O^– (R = NMe₂, H, Br, Cl, CF₃) have been prepared. Acidity constants of the conjugate acids RC₆H₄C(NH₂)N⁺(Me)OH at 25°C in a EtOH–H₂O mixture (5: 95) have been determined by potentiometric titration. A linear correlation between log (k_R/k_H) and σ_para values has been revealed, and a ρ²⁹⁸(σ_para) parameter has been determined as of 0.635.     

Abstraction of chlorine atoms from chloroalkanes. III. The kinetics of liquid phase reactions of trichlorosilyl radicals with chloromethanes

The kinetics of chlorine atom abstraction from the chloromethanes (ClM), CCl₄, CHCl₃, CH₂Cl₂, and CH₃Cl by radiolytically generated trichlorosilyl radicals was studied in the liquid phase by a competitive method. Arrhenius parameters of chlorine atom abstraction from chloromethanes relative to that of bromine atom abstraction from cyclohexyl bromide (RBr) were as follows: The error limits are two standard deviations (2σ) from least mean square Arrhenius plots. From the linear correlation between E_cl values derived from the reactions of SiCl₃ and cyclohexyl radicals with the ClM series it is estimated that E_cl (R + CH₃Cl) ? 16 kcal/mole. In addition the relative Arrhenius parameters for the hydrogen atom abstraction from SiHCl₃ and chlorine atom abstraction from CCl₄ by cyclohexyl radicals were obtained log A_H/A_cl = 0.12 ± 0.15 and E_H ? E_cl = 0.24 ± 0.26. The E_H ? E_cl value was combined with existing data on E(R + CCl₄) to yield the E_H(R + SiHCl₃) value.     

Alkali (alkaline-earth) metal,aluminum, and titanium complex orthophosphates: Synthesis and characterization

Phase formation in the A_{1 + x} Al _x Ti_{2 ? x} P₃O₁₂ (A = Li, Na, K, Rb, or Cs; 0 ≤ x ≤ 2.0) and B_{0.5(l + x)}Al _x Ti_{2 ? x} P₃O₁₂ (B = Mg, Ca, Sr, or Ba; 0 ≤ x ≤ 2.0) systems was studied using X-ray powder diffraction, electron probe microanalysis, and IR spectroscopy. The following double and triple orthophosphates were found to exist: A_{1 + x} Al _x Ti_{2 ? x} (PO₄)₃ with A = Li (0 ≤ x ≤ 0.3), Na (0 ≤ x ≤ 1.0), K (x = 0, 1.0, or 2.0), Rb (x = 0, 1.0, or 2.0), or Cs (0 ≤ x ≤ 1.0) and B_{0.5(l + x)}Al _x Ti_{2 ? x} (PO₄)₃ with B = Mg and Ba (x = 0), Ca and Sr (0 ≤ x ≤ 0.2). These orthophosphates crystallize in the structure types of kosnarite, langbeinite, cesium titanium arsenate, potassium aluminum phosphate, or rubidium aluminum phosphate. Their crystal parameters were calculated. For CsTi₂(PO₄)₃ (x = 0), Rietveld refinement was carried out: space group Ia \(\bar 3\) d, Z = 32, a = 19.909(5) Å, V = 7892(1) ų. This compound has a framework structure. The framework is built of TiO₆ octahedra and PO₄ tetrahedra; eight- and 12-coordinated Cs⁺ cations populate interstices.     

Ab Initio Theoretical Studies on the Kinetics of Hydrogen Abstraction Type Reactions of Hydroxyl Radicals with CH<Subscript>3</Subscript>CCl<Subscript>2</Subscript>F and CH<Subscript>3</Subscript>CClF<Subscript>2</Subscript>

The hydrogen abstraction reactions from CH₃Cl₂F (R-141b) and CH₃CClF₂ (R-142b) by OH radicals are studied theoretically by semi-classical transition state theory. The stationary points for the reactions are located by using KMLYP density functional method along with 6-311++G(2d,2p) basis set and MP2 method along with 6-311+G(d,p) basis set. Single-point energy calculations are performed by the CBS-Q and G4 combination methods on the geometries optimized at the KMLYP/6-311++G(2d,2p) level of theory. Vibrational anharmonicity coefficients, x _ij , which are needed for semi-classical transition state theory calculations, are computed at the KMLYP/6-311++G(2d,2p) and MP2/6-311+G(d,p) levels of theory. The computed barrier heights are slightly sensitive to the quantum-chemical method. Thermal rate coefficients are computed over the temperature range from 200 to 2000 K and they are shown to be in accordance with available experimental data. On the basis of the computed rate coefficients, the tropospheric lifetime of the CH₃CCl₂F and CH₃CClF₂ are estimated to be about 6.5 and 12.0 years, respectively.     

New Phosphate-Sulfates with NZP Structure

NaZr_2–xB_x(PO₄)_3–2x(SO₄)_2x (0 ≤ x ≤ 1.25, B = Mg, Co, Ni, Cu, Zn), and NaZr_2–xR_x(PO₄)_3–x(SO₄)_x (0 ≤ x ≤ 1.25, R = Al, Fe) phosphate-sulfates series have been prepared by a sol–gel process. These compounds belong to the NaZr₂(PO₄)₃ (NZP) structure family and crystallize in hexagonal crystal system, space group R\(\bar 3\)c. Limited solid solution series were found to exist; their formation temperatures and thermal stability limits were determined. Particle sizes as determined by microstructure observation were 50–200 nm, and for Cu- and Zn-containing samples, 200–500 nm. The thermal expansion of phosphate-sulfate NaZr_1.25Cu_0.75(PO₄)_1.5(SO₄)_1.5 was studied in the range 25–700°C. Thermal expansion coefficients and thermal expansion anisotropy were found to be α_a =–5.40 × 10^–6 °C^–1, α_с = 18.88 × 10^–6 °C^–1, α_avg = 2.69 × 10^–6 °C^–1, and Δα = 24.28 × 10^–6 °C^–1.     

A study of phase formation in the subsolidus region of the system Na<Subscript>2</Subscript>MoO<Subscript>4</Subscript>-MnMoO<Subscript>4</Subscript>-Cr<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>

Phase relationships in the subsolidus region of the system Na₂MoO₄-MnMoO₄-Cr₂(MoO₄)₃ were studied by means of X-ray diffraction and differential-thermal analyses. The possibility of obtaining a variablecomposition phase Na_1?x Mn_1?x Cr_1+x (MoO₄)₃ (0 ≤ x ≤ 0.5) and ternary molybdate NaMn₃Cr(MoO₄)₅ was examined. The temperature dependence of the conductivity of the phase Na_1?x Mn_1?x Cr_1+x (MoO₄)₃ was analyzed.     

Hirshfeld Surface Analysis,Crystal Structure and Spectroscopic Studies of a New Cu(II) Halocuprate Salt with Protonated N-Amino-Ethyl-Piperazine

(C₆H₁₈N₃)₄[CuCl₅]₂[CuCl₄]₃·1.42H₂O is prepared and characterized by various physicochemical techniques. The single crystal X-ray diffraction structural analysis reveals that the title compound belongs to the orthorhombic system with the space group Cmca. Its unit cell dimensions are: a = 24.286(2) Å, b = 14.3082(14) Å, c = 16.6160(16) Å, Z = 4, V = 5773.8(10) ų. Its crystal structure is determined and refined down to R = 0.024 and wR(F²) = 0.059. The structure contains three crystallographically independent Cu²⁺ ions coordinated to chlorine anions in various fashions. Cu1 is five-coordinated in a distorted square pyramidal fashion, while Cu2 and Cu3 are four-coordinated in square planar and distorted tetrahedral fashions, respectively. The entities are interconnected by means of the hydrogen bonding [O(W)–H…Cl, N–H…Cl, C–H…Cl and C–H…O(W)], forming a three-dimensional network. Intermolecular interactions are investigated by Hirshfeld surfaces and the contacts of the eight different chloride atoms are notably compared. The vibrational absorption bands are identified by infrared spectroscopy. The optical study is performed by UV-vis absorption.     

Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XLI. Solvent Effect on the Rate of 3-Methyl-3-chloro-1-butene Solvolysis. Correlation Analysis of Solvation Effects and Role of Solvent Nucleophilicity

The kinetics of 3-methyl-3-chloro-1-butene solvolysis at 25°C in MeOH, EtOH, BuOH, i-BuOH, PentOH, 2-PrOH, 2-BuOH, HexOH, OctOH, t-BuOH, t-PentOH, cyclohexanol, and allyl alcohol was studied by the verdazyl method; v = k[C₅H₉Cl], SN1 + E1 mechanism. The reaction rate shows a satisfactory correlation with the parameter of the solvent ionizing power E _T and is independent of the solvent nucleophilicity.     

Synthesis and equilibria in solutions of hafnium fluoro complexes with phosphoryl-containing bases Ph<Subscript>3</Subscript>PO,Bu<Subscript>3</Subscript>PO,and (Me<Subscript>2</Subscript>N)<Subscript>3</Subscript>PO

The composition and equilibria in solutions of the products of reaction of HfF₄(dmso)₂ with monodentate phosphoryl-containing bases L = Ph₃PO, Bu₃PO, and (Me₂N)₃PO in CH₂Cl₂ are studied by ¹⁹F NMR. Octahedral molecular complexes cis-[HfF₄L₂] and minor amounts of trans-[HfF₄L₂] and fac-[HfF₃L₃]⁺ cations were the main products for all ligands. The oxytrifluoride complex (μ-O)[HfF₃(Bu₃PO)₂]₂ and the [HfF₅(Bu₃PO)]^– anion were identified in the case of Bu₃PO. The conclusion about the formation of the hafnium oxytrifluoro complex was verified via hydrolysis of the product of reaction between HfF₄ and Ph₃PO upon exposure to air. As a result, (μ-O)[HfF₃(Ph₃PO)₂]₂ were detected; fine-structure ¹⁹F NMR resonance lines were obtained and the spin–spin coupling constant J_FF was measured for the first time. Hydrolysis via adding a Bu₄NOH solution in i-PrOH to the HfF₄L₂ solutions in CH₂Cl₂ did not yield the expected zirconium oxyfluoro complexes with the smaller number of fluorine atoms. Due to deeper hydrolysis, equilibrium in fluoride complexes shifted towards species with higher fluorine contents, [ZrF₅L]^– and [ZrF₆]^2–, resulting in the formation of Hf(O)_x(OH)_у(i-PrOH)_z complexes that were not observed in the ¹⁹F NMR spectra and the substitution of the released fluoride ions for molecular ligands in HfF₄L₂ complexes.