Orientational and positional disorder of ions and its freezing in the CsNO2-TlNO2 system2

The heat capacities of Cs_0.695Tl_0.305NO₂ (Specimen I) and Cs_0.385Tl_0.615NO₂ (Specimen II) have been measured between 14 and 350 K. Specimen I underwent a phase transition at (197.7 ± 0.1) K, with ΔS = (19.2 ± 1.5) JK^?mol^?, and specimen II at (214.5 ± 0.2) K, with ΔS = (5.4 ± 1.0) JK^?1mol^?1, respectively. Above the phase transition, an exothermic temperature drift due to phase separation was observed. Annealing of the sample at 203 K for 300 hr brought about complete phase separation. The solid solution system annealed at 203 K gave two heat capacity peaks at (203.3 ± 0.1) K, with ΔS = (13.8 ± 0.8) JK^?1 mol^?1, and (242.4 ± 0.2) K, with ΔS = (10.6 ± 1.3) JK^?1 for Specimen I, and at (203.0 ± 0.1) K with ΔS = (6.7 ± 0.5) JK^?1 mol^?1, and (257.5 ± 0.2) K with ΔS = (17.9 ± 1.7) JK^?1 mol^?1 for Specimen II. The phase diagram of the CsNO₂-TlNO₂ binary system was constructed on the basis of DTA, heat capacity and dielectric measurements. In the metastable phase, the existence of a residual entropy due to the freezing of a random distribution of Cs⁺₁ and Tl⁺ cations in addition to the orientational disorder of the NO₂^?1 ion was confirmed by a comparison of entropies of the stable and the metastable phases.     

Heat capacities of copper(II) formate tetrahydrate and tetradeuterate: A comparative study of phase transitions in layer hydrate crystals

The heat capacities of copper(II) formate tetrahydrate and tetradeuterate have been measured from 12 to 300 K with an adiabatic calorimeter. They have sigmoidal temperature dependence except near the antiferroelectric-paraelectric transition temperatures, 235.78 ± 0.05 K and 245.64 ± 0.05 K, respectively. The corresponding enthalpy changes are 836.0 ± 1.0 J mol^?1 and 936.9 ± 0.5 J mor^?1. The entropy changes are 3.546 ± 0.005 JK^?1mol^?1 and 3.814 ± 0.002 JK^?1 mol^?1. The heat capacities are larger in the high temperature phase than in the low temperature phase, the difference amounting to 5.74 JK^?1 mol^?1 and 7.15 JK^?1 mol^?1 for the hydrate and the deuterate, respectively. The heat capacity anomaly is compared with those in tin(II) chloride dihydrate and potassium hexacyanoferrate trihydrate and discussed in relation to the structure of the hydrogen bond networks in these substances. The discussion is extended to include possible properties of the hydrogen bond frameworks in ices I_h and II.     

Heat capacity and phase transition of a five-coordinated antiferromagnet,IODOBIS (N,N-diethyldithiocarbamato) iron (III), in the temperature range from 0.4 TO 300 K

The heat capacity of iodobis (N,N-diethyldithiocarbamato) iron (III) has been measured between 0.4 and 300 K. A phase transition from an antiferromagnetic to a paramagnetic state was found at T_N = (1.937 ± 0.010) K, and a Schottky-type anomaly arising from a zero-field single ion splitting was observed around 12 K. The total magnetic entropy and enthalpy, including the phase transition and the Schottky-type anomaly, are 11.36JK^?1mol^?1 and 134.5 J mol^?1, respectively. The entropy is approximately equal to Rln 4 ( = 11.53 JK^?1mol^?1), confirming that the spin manifold is really a quartet. The entropy and enthalpy due to the phase transition are estimated to be (5.57±0.01)JK^?1mol^?1 and (13.2±0.05)Jmol^?1, respectively. The entropy and enthalpy above t_n are quite large, as in the case of the related compound chlorobis (N,N-diethyldithiocarbamato) iron (III). This fact suggests that the present complex may be considered to have a two-dimensional type of magnetic structure from a thermodynamic point of view. A correlation diagram between the transition entropy and energy is proposed, this being a diagnostic for the determination of the magnetic dimensionality.     

Phonon coupled cooperative low-spin 1A1high-spin 5T2 transition in [Fe(phen)2(NCS)2] and [Fe(phen)2(NCSe)2] crystals

Heat capacities of [Fe(phen)₂(NCS)₂] and [Fe(phen)₂(NCSe)₂] were measured between 13⁵ and 375 K. A heat capacity anomaly due to the spin-transition from low-spin ¹A₁ to high-spin π₂ electronic ground state was found at 176·29 K for the SCN-compound and at 231·26 K for the SeCN-compound, respectively. Enthalpy and entropy of transition were determined to be ΔH = 8·60 ± 0·14 kJ mol^?1 and ΔS = 48·78 ± 0·71 J K^?1 mol^?1 for the SCN-compound and ΔH = 11·60 ± 0·44 kJ mol^?1 and ΔS = 51·22 ± 2·33 J K^?1 mol^?1 for the SeCN-compound. To account for much larger value of ΔS compared with the magnetic contribution, we suggest that there is significant coupling between electronic state and phonon system. We also present a phenomenological theory based on heterophase fluctuation. Gross aspects of magnetic, spectroscopic, and thermal behaviors were satisfactorily accounted for by this model. To examine closely the transition process, infrared spectra were recorded as a function of temperature in the range 4000 ? 30 cm^?1. The spectra revealed clearly the coexistence of the ¹A₁, and the ⁵T₂ ground states around T_c.     

On the phase transition in α-NH4HgCl3, a two-dimensional version of ammonium chloride

Heat capacity of α-NH₄HgCl₃ crystal has been measured with an adiabatic calorimeter from 11 to 300 K. A sharply peaked anomaly due to an order-disorder change of the ammonium ions was found at 54.97 ± 0.04 K. The entropy and enthalpy changes were estimated to be ΔS = 5.2 ± 1.0JK^?1 mol^?1 and ΔH = 342 ± 65 J mol^?1. In accordance withthe structural two-dimensionality of α-NH₄HgCl₃ crystal, Onsager's solution of the two-dimensional Ising model was used in calculation of the transition temperature. On the assumption that the octopole-octopole interaction is responsible for the ordering of the ammonium ions in the present crystal and in ammonium chloride, the calculation gives 74.44 K for the transition temperature. Several possibilities were discussed for explaining the remaining discrepancy between the observed and calculated transition temperatures.     

High-resolution heat capacity of SnCl2·2H2O single crystal

The heat capacity of SnCl₂·2H₂O single crystal was measured in the close vicinity of the phase transition temperature, T_c = 217.994 ± 0.01 K. Its anomalous part ΔC could be expressed as ΔC = A_± ⊥ (T ? T_c)/T_c⊥^-α_±, where α₊ = 0.492 ± 0.02, α_- = 0.492 ± 0.02, A₊ = 1.148 JK^?mol^?, and A_- = 1.155 JK^?mol^?. A quasi-isothermal absorption of the enthalpy amounting to 34 J mol^? was observed at T_c.     

Heat capacity and thermodynamic properties of α-Fe2O3 in the region 300–1050 K. antiferromagnetic transition

The heat capacity of synthetic α-Fe₂O₃ has been measured in the range 300–1050K by adiabatic shield calorimetry with intermittent energy inputs and temperature equilibration in between. A λ-type transition, related to the change from antiferro- to paramagnetism in the compound, is delineated and a maximum heat capacity of about 195 JK^?1 mole^?1 is observed over a 3 K interval around 955 K. Values of thermodynamic functions have been derived and C_P (1000K), [H⁰(1000K)-H⁰(0)], and [S⁰(1000K)-S⁰(0)] are 149.0JK^?1 mole^?1, 115.72 kJ mole^?1, and 252.27 JK^?1 mole^?1, respectively, after inclusion of earlier low-temperature results [X⁰ (298.15K)-X⁰(0)]. The non-magnetic heat capacity is estimated and the thermodynamic properties of the magnetic transition evaluated. The results are compared with spin-wave calculations in the random phase approximation below the Néel temperature and the Oguchi pair model above. An upper estimate of the total magnetic entropy gives 32.4JK^?1 mole^?1, which compares favorably with that calculated for randomization of five unpaired electron spins on each iron, ΔS = 2R ln 6 = 29.79 JK^?1 mole^?1 for α-Fe₂O₃. The critical exponent α in the equation $\text{C}{}_{\mathrm{m}}\text{= (}\text{A}\text{α}\text{) [(|T}{}_{\mathrm{<mtext>n</mtext>}}\text{?T|/T}{}_{\mathrm{<mtext>n</mtext>}}\text{)?1]}{}^{\mathrm{?\alpha }}\text{+ B}$ is ?(0.50±0.10) below the maximum and 0.15±0.10 above, for T_n = 955.0K. The high temperature tail is discussed in terms of short range order.     

The heat capacity of the layer compounds (CH3CH2CH2NH3)2MnCl4 and (CH3CH2CH2NH3)2CdCl4 from 10 K TO 300 K

The heat capacity of the layer compounds tetrachlorobis (n-propylammonium) manganese II and tetrachlorobis (n-propylammonium) cadmium II, (CH₃CH₂CH₂NH₃)₂MnCl₄ and (CH₃CH₂CH₂NH₃)₂CdCl₄ respectively, has been measured over the temperature range 10 K ?T ? 300 K.Two known structural phase transitions were observed for the Mn compound in this temperature region: at T = 112.8 ± 0.1 K (ΔH_t= 586 ± 2 J mol^?1; ΔS_t = 5.47 ± 0.02 J K^?1mol^?1) and at T =164.3 ± (ΔH_t = 496 ± 7 J mol^?1; ΔS_t =3.29 ± 0.05 J K^?1mol^?1). The lower transition is known to be from a monoclinic structure to a tetragonal structure, while the upper is from the tetragonal phase to an orthorhombic one. From comparison with the results for the corresponding methyl Mn compound it is deduced that the lower transition primarily involves changes in H-bonding while the upper transition involves motion in the propyl chain.A new structural phase transition was observed in the Cd compound at T= 105.5 ± 0.1 K (ΔH_t= 1472.3 ± 0.1 J mol^?1; ΔS_t = 13.956 ± 0.001 J K^?1mol^?1), in addition to two transitions that have been observed previously by other techniques. The higher of these transitions(T = 178.7 ± 0.3 K; ΔH_t = 982 ± 4 J mol^?1 ΔS_t = 6.16 ± 0.02 J K^? mol^?1) is known to be between two orthorhombic structures, while the structural changes at the lower transition (T= 156.8 ± 0.2 K; ΔH_t = 598 ± 5 J mol^?1, ΔS_t = 3.85 ± 0.03 J K^?1 mol^?1) and at the new transition are not known. It is proposed that these two transitions correspond respectively to the tetragonal to orthorhombic and monoclinic to tetragonal transitions in the propyl Mn compounds.In addition to the structural phase transitions (CH₃CH₂CH₂NH₃)₂MnCl₄ magnetically orders at t? 130 K. The magnetic contribution to the heat capacity is deduced from the heat capacity of the corresponding diamagnetic Cd compound and is of the form expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

Heat capacity of a five-coordinated iron(III) complex with spin S = 32, bromobis(N,N-diethyldithiocarbamato)iron(III), between 0.4 and 300 K

Heat capacity measurements have been made for six kinds of specimens prepared by different methods. Among them, Sample A exhibited a A-type ferromagnetic pahse transition at 1.347 K and a Schottky-type anomaly due to the zero-field splitting around 9K. The total entropy and enthalpy were (11.05 ± 0.04) J K^?1mol^?1 and (97.0 ± 0.4) J mol^?1, respectively. Sample B exhibited a Sehottky-type anomaly around 0.4 K due to the ferro-magnetic dimeric coupling with $\text{J}{}_{\mathrm{D}}\text{k}\text{= + 0.30}\text{K}$ as well as the Schottky-type anomaly at 9K. The total magnetic entropy and enthalpy were (11.45 ± 0.03) JK^?1 mol^?1 and (93.8 ± 0.8) J mol^?1, respectively. The remaining samples are simple mixtures of the λ-type modification and the dimeric modification. Irrespective of the magnetic behavior at low temperatures, all the samples showed a non-magnetic first-order phase transition around 270 K. The heat capacity and entropy of this phase transition have been accounted for in terms of the Frenkel theory of heterophase fluctuation. Construction of an adiabatic-type calorimeter workable between 1.5 and 393 K has been also presented.     

Absolute coverage and isostemc heat of adsorption of deuterium on Pt(111) studied by nuclear microanalysis

The absolute coverage (θ) of deuterium adsorbed on Pt(111) in the ranges 180< T<440 K and 5 × 10^?6 < P < 5 × 10^?2 Pa D₂ has been determined by nuclear microanalysis using the D(³He, p)⁴He reaction. From these data, the isosteric heat of adsorption (E_a) has been determined to be 67 ± 7 kJ mol^?1 at θ ? 0.3. This heat of adsorption yields values of the pre-exponential for desorption (10^?5 to 10^?2 cm² atom^?1 s^?1) that lie much closer to the normal range for a second order process than those determined from previous isosteric heat measurements. The E_a versus θ relationship indicates that the adsorbed D atoms are mobile and that there is a repulsive interaction of 6–8 kJ mol^?1 at nearest neighbour distances. At 300 K the coverage decreases to ? 0.05 monolayer (? 8 × 10¹³ D atoms cm^?2) as P→ 0, apparently invalidating a recent model of site exchange in the adsorbed layer.     

High pressure 17O NMR study of solvent exchange on square planar complexes: Water exchange on [Pd(dien)H2O]2+

Abstract

The water exchange reaction of [Pd(dien)H₂O]²⁺ (dien = diethylenetriamine) was studied as function of temperature (268-308 K) and pressure 0.1-197 MPa) using ₁₇O NMR techniques. The rate and activation parameters are: k_cx = 5100 s^?1 at 298 K; ΔH^# =38 kJ mol^?1; ΔS^# = -47 JK^?1 mol^?1; ΔV^# = -2.8 cm³ mol^?1 at 296 K. The results are discussed in reference to solvent exchange data for other Pt(II) and Pd(II) complexes, and are interpreted in terms of an associatively activated substitution process.     

Phase transition in ammonium hexafluorovanadate (III)

Heat capacity of ammonium hexafluorovanadate (NH₄)₃ [VF₆] has been measured with a miniaturized adiabatic calorimeter from 20 to 300 K. A phase transition was found at 280.44 ± 0.05 K with the associated entropy change Δ_trs S = 24.9 ± 0.5 JK^?1 mol^?1. The entropy transition is accounted for by the orientational order-disorder changes of hexafluorovanadate ion and ammonium ion occupying respective octahedral sites, as in the cases of (NH₄)₃AlF₆ and (NH₄)₃FeF₆ crystals. Changes in infrared spectra relative to v₃ vibrational mode of [VF₆]^3? ion can be explained by an orientational disorder of the anions in the high-temperature phase (HTP). The dependence of cubic root of the unit-cell volume of a family of ammonium cryolites on their transition temperatures is discussed in relation to the nature of interactions which induce the phase transition.     

Molecular beam reactive scattering of Br2 from Pd(111) using an electrochemical effusive source

A computer-controlled modulated molecular beam source is used to investigate the kinetics of the surface reactions which occur when bromine is reactively scattered by Pd(111). The reaction products are atomic bromine and molecular bromine: the latter species arises from an adatom recombination process and gives rise to a product vector modulated at twice the frequency of the incident beam (2ω.) By making suitable measurements of the temperature dependence of the product vector phase shifts at ω and 2ω, the four kinetic parameters which characterise the first-order and second-order rate processes are obtained. These are: A₁ = 2.5×10⁹ s^?1, E₁ = 177 kJ mol^?1, A₂ = 3.6×10^?10 m² s^?1, E₂ = 131 kJ mol^?1. The significance of these values is discussed in terms of the properties of the transition state to desorption.     

Kinetics of the gas‐phase homogeneous unimolecular elimination of selected ethyl esters of 2‐oxo‐carboxylic acids

The gas‐phase elimination kinetics of selected ethyl esters of 2‐oxo‐carboxylic acid have been studied over the temperature range of 270–415 °C and pressures of 37–114 Torr. The reactions are homogeneous, unimolecular, and follow a first‐order rate law in a seasoned static reaction vessel, with an added free radical suppressor toluene. The observed overall and partial rate coefficients are expressed by the following Arrhenius equations:

• Ethyl oxalyl chloride
• log k_overall (s^?1) = (13.22 ± 0.45) ? (179.4 ± 4.9) kJ mol^?1 (2.303 RT)^?1
• Ethyl piperidineglyoxylate
• log k_(CO2) (s^?1) = (12.00 ± 0.30) ? (191.2 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (12.60 ± 0.09) ? (210.7 ± 1.2) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (12.22 ± 0.26) ? (193.4 ± 3.4) kJ mol^?1 (2.303 RT)^?1
• Ethyl benzoyl formate
• log k_(CO2) (s^?1) = (12.89 ± 0.72) ? (203.8 ± 9.0) kJ mol^?1 (2.303 RT)^?1
• log k_(CO) (s^?1) = (13.39 ± 0.31) ? (213.3 ± 3.9) kJ mol^?1 (2.303 RT)^?1
• log k_t(overall) (s^?1) = (13.24 ± 0.60) ? (205.8 ± 7.6) kJ mol^?1 (2.303 RT)^?1

The kinetic and thermodynamic parameters of these reactions, together with those reported in the literature, lead to consider three different mechanistic pathways of elimination. Copyright © 2010 John Wiley & Sons, Ltd.     

High pressure cyanide exchange study on a square-planar tetracyanometalate complex of Pt(II)

Abstract

Previous studies of cyanide exchange on square planar tetracyanoplatinate complex [Pt(CN)₄]^2- have been undertaken only at a high pH. For a more complete fundamental understanding of this system we extended the investigations of these exchanges over a large pH range. NMR kinetics methods (magnetisation transfer, isotopic exchange) proved to be very useful for obtaining quantitative rate data of the cyanide exchange on this complex. In fact it is quite significant that the reactivity of this metal center spans a ca. 9-order of magnitude range as a function of pH.

Variable temperature and variable pressure studies were undertaken in aqueous solutions and the following activation parameters obtained: ΔH? = (25.1 ± 0.4) kJmol^?1 and activation entropy ΔS? = -(142±2)JK^?1mol^?1 and activation volume ΔV? = -(27±2)cm³mol^?1.     

Kinetics of the oxidation of 2-Propanol with molecular oxygen under conditions of selective inhibition

The specifics of the mechanism of chain propagation in the radical-chain oxidation of 2-propanol at 323 K were studied by the method of selective inhibition with the use of nitrobenzene and ionol. The rate constants for the interaction of the 1-hydroxy-1-methylethylperoxy (k _2.1 = (0.097 ± 0.004) L mol^?1 s^?1) and hydroperoxy (k _2.2 = 0.13 ± 0.05 L mol^?1 s^?1) radicals with alcohol and their relative contributions to the chain propagation reactions were determined.     

The heat capacity of the layer compound tetrachlorobis (methylammonium) manganese—II (CH3NH3)2MnCl4, from 10 to 300k

The heat capacity of the layer compound, tetrachlorobis (methylammonium) manganese II, (CH₃NH₃)₂MnCl₄, has been measured over the range 10K <T<300K. In this region, two structural phase transitions have been observed previously by other techniques: one transition is from a monoclinic low temperature (MLT) phase to a tetragonal low temperature (TLT) phase, and the other is from TLT to an orthorhombic room temperature (ORT) phase. The present experiments have shown that the lower transition (MLT→TLT) occurs at T = 94.37±0.05K with ΔH_t = 727±5 J mol^?1 and ΔS_t = 7.76±0.05 J K^?1 mol^?1, and the upper transition (TLT→ORT) takes place at T = 257.02±0.07K with ΔH_t = 116±1J mol^?1 and ΔS_t = 0.451±0.004 J K^?1mol^?1. These results are discussed in the light of recent measurements on (CH₃NH₃)₂CdCl₄, and also with regard to a recent theoretical model of the structural phase transitions in compounds of this type.In addition to the structural phase transitions, (CH₃NH₃)₂MnCl₄ also undergoes magnetic ordering at T < 150K. The magnetic component to the heat capacity, as deduced from a corresponding states comparison of the heat capacity of the present compound with that of the Cd compound, is shown to be consistent with the behaviour expected for a quasi 2-dimensional Heisenberg antiferromagnet.     

NQR, NMR and Crystal Structure Studies of [C(NH2)3]2HgX4 (X = Br, I)

The crystal structure of [C(NH₂)₃]₂HgBr₄ has been determined at room temperature: monoclinic, space group C2/c, with a = 10.035(2), b = 11.164(2), c = 13.358(3) Å, β = 111.67(3)°, and Z = 4. The crystal consists of planar [C(NH₂)₃]⁺ and distorted tetrahedral [HgBr₄]^2? ions. The Hg atom is located on a two-fold axis such that two sets of inequivalent Br atoms exist in an [HgBr₄]^2? ion. In accordance with the crystal structure, two ⁸¹Br NQR lines widely separated in frequency were observed between 77 and ca. 380 K. [C(NH₂)₃]₂HgI₄ yielded four ¹²⁷I NQR lines ascribable to m = ±1/2 ? ±3/2 transitions, indicating that its crystal structure is different from the bromide complex. The ¹H NMR T ₁ measurements showed a single minimum for the bromide but two minima for the iodide. The analyses based on the C₃ reorientations of the planar [C(NH₂)₃]⁺ ions gave the activation energies of 29.8 kJ mol^?1 for the bromide, and 30.2 and 40.0 kJ mol^?1 for the iodide.     

Crystal structure and thermodynamic properties of phase change material bis(1-dodecylammonium) tetrachlorochromate (C12H25NH3)2CdCl4(s)

A novel complex bis(1-dodecylammonium) tetrachlorochromate (C₁₂H₂₅NH₃)₂CdCl₄(s) (abbreviated as C₁₂Cd(s)) was synthesized by liquid phase reaction. Crystal structure and composition of the complex were determined by X-ray crystallography, chemical analysis, and elemental analysis. It is triclinic, the space group is P?1 and Z = 2. Lattice potential energy (LPE) of the complex was calculated to be kJ·mol^?1 from crystallographic data. Low-temperature heat capacities were measured by a precise automatic adiabatic calorimeter over the temperature range from 78 to 370 K. The temperature, molar enthalpy, and entropy of the phase transition of the complex were determined to be 331.88 ± 0.02 K, 55.79 ± 0.46 kJ·mol^?1, and 168.10 ± 1.38 J·K^?1·mol^?1, respectively. Two polynomial equations of the heat capacities as a function of temperature were fitted by least-square method. Smoothed heat capacities and thermodynamic functions of the complex were calculated.