Enthalpy and Entropy of Formation of Alkali and Alkaline-Earth Macrobicyclic Cryptate Complexes [1]

The enthalpies and entropies of complexation of alkali and alkaline-earth metal cations by several macrobicyclic ligands have been obtained from calorimetric measurements and from the previously determined stability constants [2]. Both enthalpy and entropy changes play an important role in the stability and selectivity of the complexes. Particularly noteworthy are the large enthalpies and the negative entropies of complexation obtained for the alkali cation complexes (Na⁺, K⁺, Rb⁺ and Cs⁺ cryptates). The Sr²⁺ and Ba²⁺ as well as [Li⁺ ? 2.1.1]

1 For use of the symbols see [2].

and [Na⁺ ? 2.2.1] cryptates are of the enthalpy dominant type with also a favourable entropy change. The Ca²⁺ and [Li⁺ ? 2.2.1] cryptates are entirely entropy stabilized with about zero heat of reaction. The high stability of the macrobicyclic complexes as compared to the macromonocylcic ones, the cryptate effect, is of enthalpic origin. The enthalpies of complexation display selectivity peaks, as do the stabilities, whereas the entropy changes do not. The high M²⁺/M⁺ selectivities found in terms of free energy, may be reversed when enthalpy is considered in view of the very different role played by the entropy term for M²⁺ and M⁺ cations. The enthalpies and entropies of ligation show that whereas the cryptate anions are similar in terms of entropy irrespective of which cation is included, the ligands, despite being more rigid than the hydration shell, are nevertheless able to adjust to some extent to the cation. This conclusion agrees with published X-rays data. The origin of the enthalpies and entropies of complexation is discussed in terms of structural features of the ligands and of solvation effects.     

Regularities in the Influence of Water-Organic Solvents on the Thermodynamics of Complex Formation: II.1 Changes in Enthalpy and Entropy of Formation of Ammonia and Carboxylate Complexes

The role of enthalpy, entropy contributions to the shift of complex formation equilibria inwater-organic solvents was studied. The formation of both ammonia and carboxylate complexes of d-metalions was found to be presumably enthalpy-controlled. The role of entropy changes increases in binary solvents with a high level of supramolecular organization, and also in the case of formation of complexes of the highest orders, when the coordination of ligands is accompanied either by a complete displacement of solvent molecules from the inner coordination sphere or by a change in the complex structure. Thus found regularities can be applied for the prediction of heat effects of complex formation in water-organic solvents. In the fist communication [1] of this series we have considered the effects of the nature and composition of water-organic solvents on the stability of ammonia and carboxylate complexes of d-metal ions. This work is based on the data of our recent thermochemical works [2-22] and is dedicated to the study of the role of enthalpy and entropy contributions to the shift of the complex formation equilibria in water-organic solvents.     

Formation Enthalpy and Entropy of Exciplexes with Variable Extent of Charge Transfer in Solvents of Different Polarity

Temperature dependence was studied for relative quantum yields of emission from some exciplexes of pyrene, 1,12-benzoperylene, and 9-cyanoanthracene with methoxybenzenes or methylnaphthalenes in solvents of different polarity (ranging from toluene to acetonitrile). The enthalpy H _Ex ^*, the entropy S _Ex ^*, and the Gibbs free energy G _Ex ^*of formation of the exciplexes were determined. Depending of the Gibbs free energy of excited-state electron transfer (G _et ^*) and solvent polarity, the values of H _Ex ^*, S _Ex ^*, and G _Ex ^*vary over the ranges from –5 to –40 kJ mol^–1, from +3 to –90 J mol^–1K^–1, and from +3 to –21 kJ mol^–1, respectively. The possibility is discussed that the effect of solvent polarity G _et ^*on the exciplex formation enthalpies can be rationalized in terms of the model of correlated polarization of an exciplex and the medium.     

Activation Enthalpy and Entropy for the Formation of 9-Cyanophenanthrene Exciplexes

Exciplexes of 9-cyanophenanthrene with a series of weak electron donors with the Gibbs energy of electron transfer G _et * varying in the range –(0.02–0.09) eV were studied. The exciplexes exhibited fairly intense emission both in nonpolar and aprotic polar solvents. The kinetics of the exciplex formation was found to be controlled mainly by diffusion and reactant orientation. This is clearly manifested in the low-temperature region in which the activation enthalpy of exciplex formation is very close to the activation enthalpy of diffusion, and the activation entropy of exciplex formation does not exceed 18 J mol^–1 K^–1 in absolute value.     

用微机估算单体及其聚合反应的焓与熵

采用ABW (Anderson Beyer Watson)基团贡献法 ,通过建立数据库、计算机编程 ,分别在UC DOS 6.0环境、MicrosoftFoxPro 2 .6编辑平台和Windows 95环境、BorlandDelphi 3.0编辑平台上运行。对常见烯类单体及其聚合反应的焓与熵进行估算 ,其结果与文献值很接近、操作简单、显示直观。     

Entropy Changes in Aqueous Solutions of Non-polar Substances and in Bio-complex Formation

The entropy changes, ΔS _app, (i) for dissolution in water of non-polar substances and (ii) for protein-ligand complexation show linear dependences on the logarithm of the absolute temperature. For every compound, the slope m _(S)=ΔC _p for the line ΔS _app=f(ln T) depends on the size of the molecule and is exactly equal to the slope m _(H)=ΔC _p found in the diagram ΔH _app=f(T). This means that the slopes are rigorously proportional (with a ratio m _(S)/n _w=C _p,w) where n _w is the number of involved water molecules as determined from the enthalpy change ΔH _app=f(T). It is also worth noting that the value of n _w is positive (as well as m _(S) and m _(H)) in the dissolution of non-polar substances, whereas it is negative (as well as m _(S) and m _(H)) in bio-complex formation and in micelle formation. The number n _w (n _w>0) involved in the dissolution of non-polar substances depends on the size of the cavity (excluded volume) formed in the structure of water. These water molecules that have been excluded from the structure of the solvent absorb thermal energy that compensates for the negative enthalpy change, whereas the formation of the cavity implies there should be a large negative entropy contribution. The low solubility of non-polar substances in water depends on the highly negative entropy effect due both to cavity formation and to loss of configurational entropy by the gas trapped in a cage of water molecules. In processes involving association, as in micelle formation and in protein complexation, the cavities surrounding the separate units coalesce and the resultant cavity is smaller than the sum of the previous ones. The n _w water molecules (n _w<0) needed to fill the excess cavity return to the structure of the bulk solvent and release thermal energy, which compensates for the endothermic enthalpy. The affinity in the association processes is bound, for the most part, to the entropy produced by occupation of part of the cavity by condensation of water molecules. The association processes are therefore entropy driven.     

Determination of the Solubility, Dissolution Enthalpy and Entropy of Donepezil Hydrochloride Polymorphic Form III in Different Solvents

The solubilities of donepezil hydrochloride polymorphic form III in methanol, ethanol, 1-propanol and dimethyl formamide were measured at temperatures ranging from 278.15 to 333.15 K at atmosphere pressure using a gravimetrical method. The modified Apelblat model fitted the experimental data well with the root-mean-square deviations less than 6.287 × 10^?4. The dissolution enthalpy and entropy of solute were predicted from the solubility data in different solvents using the van’t Hoff equation. The relationships among solubility, temperature, the intermolecular force and hydrogen bonding between solute and solvent, and the viscosity of solvents were investigated. The viscosity and surface tension of solvents affect the dissolution enthalpy and entropy of donepezil hydrochloride polymorphic form III.     

Activation Enthalpy and Entropy for the Decay of 9-Cyanophenanthrene Exciplexes

Activation parameters were studied for the decay of 9-cyanophenanthrene exciplexes with some weak electron donors (the Gibbs energy of electron transfer G ^* _et ranging from –0.02 to –0.09 eV), which displayed fairly high emission in both nonpolar and polar aprotic solvents. It was shown that the activation enthalpy of decay for the exciplexes is low, while the activation entropy reaches –(100–150) J mol^–1 K^–1, which is consistent with the two possible decay mechanisms: by dissociation into free radical ions or by intersystem crossing into the triplet state.     

Group Additive Values for the Gas‐Phase Standard Enthalpy of Formation,Entropy and Heat Capacity of Oxygenates

A complete and consistent set of 60 Benson group additive values (GAVs) for oxygenate molecules and 97 GAVs for oxygenate radicals is provided, which allow to describe their standard enthalpies of formation, entropies and heat capacities. Approximately half of the GAVs for oxygenate molecules and the majority of the GAVs for oxygenate radicals have not been reported before. The values are derived from an extensive and accurate database of thermochemical data obtained by ab initio calculations at the CBS‐QB3 level of theory for 202 molecules and 248 radicals. These compounds include saturated and unsaturated, α‐ and β‐branched, mono‐ and bifunctional oxygenates. Internal rotations were accounted for by using one‐dimensional hindered rotor corrections. The accuracy of the database was further improved by adding bond additive corrections to the CBS‐QB3 standard enthalpies of formation. Furthermore, 14 corrections for non‐nearest‐neighbor interactions (NNI) were introduced for molecules and 12 for radicals. The validity of the constructed group additive model was established by comparing the predicted values with both ab initio calculated values and experimental data for oxygenates and oxygenate radicals. The group additive method predicts standard enthalpies of formation, entropies, and heat capacities with chemical accuracy, respectively, within 4 kJ mol^?1 and 4 J mol^?1 K^?1 for both ab initio calculated and experimental values. As an alternative, the hydrogen bond increment (HBI) method developed by Lay et al. (T. H. Lay, J. W. Bozzelli, A. M. Dean, E. R. Ritter, J. Phys. Chem.­ 1995 , 99, 14514) was used to introduce 77 new HBI structures and to calculate their thermodynamic parameters (Δ_fH°, S°, C_p°). The GAVs reported in this work can be reliably used for the prediction of thermochemical data for large oxygenate compounds, combining rapid prediction with wide‐ranging application.     

溶解量热法测三氧化钼标准生成焓

用溶解量热法,以KIO_4和KOH组成的弱碱性溶液为量热溶剂,设计3个不同的热化学循环,用RD-1型热导式自动量热计测定了MoO_3的标准生成焓,并推荐其值为ΔH_(t(moO_3))~0(298.15K)=-765.0±6.8kJ·mol~(-1)。     

碳酸盐标准生成焓的计算

碳酸盐标准生成焓的计算戴长文，王振民，徐琰，戴晓弘（郑州大学化学系，郑州，４５００５２）（郑州高新技术开发区，郑州，４５０００１）关键词热力学性质，标准生成焓，碳酸盐预测无机化合物生成热的计算方法已见报道［１，２］，但引入经验参数过多，且计算偏差亦较...     

Standard Enthalpy of Formation of Monoclinic Ammonium Paratungstate

Monoclinicammoniumparatlingstate,(NH.),,H,W,,O.,4H,O(s),isanessentialintermediatecompoundintheextractionoftungstenfromitsoresl.Theknowledgeofthepropertiesofammoniumparatungstateisdesirableforcontrollingitscrystallizationanditsthermaldecomposition.However,thestudyonthethermodynamicpropertieshasnotbeenreported.Inthepresentwork,theenthalpyofreactionforthethermaldecompositionofammoniumparatungstatewasmeasured,anditsstandardenthalpyofformationat298.15Kisobtained.Thesampleofmonoclinicanunoniumpa…     

Enthalpy of Solution of Terfenadine in Different Solvents

Enthalpies of solution of various terfenadine samples in methanol and in ethanol were measured. Samples were prepared by crystallization in different solvents. The calorimetric results give important information on crystal structure of the terfenadine forms and on the solute/solvent interactions of this compound with the solvents.This revised version was published online in November 2005 with corrections to the Cover Date.     

Formation and Stability of Cadmium(II)/Phytate Complexes by Different Electrochemical Techniques. Critical Analysis of Results

In the present work the stability constants of various cadmium(II)/phytate (Phy) species were determined at T=298.15 K in NaNO₃(aq) at I=0.1 mol⋅L⁻¹ by DP-ASV (Differential Pulse Anodic Stripping Voltammetry) and by potentiometric titrations using an ISE-Cd²⁺. Cyclic voltammograms were also recorded to check the electrochemical behavior of cadmium in the presence of phytate. The results were analyzed together with previous data determined by ISE-H⁺ measurements. Data obtained were used to provide an exhaustive speciation scheme for the phytate/cadmium(II) system at different conditions, as well as a comprehensive representation of the binding ability of phytate toward cadmium(II). Different pL₅₀ values {a previously proposed empirical parameter, expressed as −log ₁₀ C _Phy, where C _Phy is the total phytate concentration necessary to bind 50% cadmium(II)} were also calculated by modeling its dependence on pH.     

Synthesis and Spectroscopic Characterization of Two Different Types of Heterobimetallic Glycolate Complexes of Niobium(V)

An entirely new class of heterobimetallic homoleptic glycolate complexes of the type Nb(OGO)₃{Ta(OGO)₂} [where G=CMe₂CH₂CH₂CMe₂ (G¹) (3); CMe₂CH₂ CHMe(G²) (4); CHMeCHMe (G³) (5); CH₂CMe₂CH₂ (G⁴) (6); CMe₂CMe₂(G⁵) (7); CH₂CHMeCH₂ (G⁶) (8); CH₂CEt₂CH₂ (G⁷) (9); CH₂CMe(Prⁿ)CH₂ (G⁸) (10)] have been prepared by the reactions of Nb(OGO)₂(OGOH) [G=G¹ (1a); G² (1b); G³ (1c); G⁴ (1d); G⁵ (1e); G⁶ (1f); G⁷ (1g); G⁸ (1h)] with Ta(OGO)₂ (OPrⁱ) (G=G¹ (2a); G² (2b); G³ (2c); G⁴ (2d); G⁵ (2e) G⁶ (2f); G⁷ (2g); G⁸ (2h). In addition to the novel derivatives (2)–(10), our earlier investigations on heterobimetallic glycolate-alkoxide derivatives have been extended to derivatives of the type Nb(OGO) [where M=A1 n=3, G=G³ (11);G⁴ (12); G⁶ (13) G⁷ (14); G^s (15); G⁹=CH₂CH₂CH₂ (16) and M=Ti (n=4, G=G⁴) (17), Zr(n=4,G=G⁴) (18)], which are conveniently prepared by the reactions of metalloligands Nb(OGO)₂(OGOH) [G=G³ (1c); G⁴ (1d); G⁶ (1f); G⁷ (1g); G⁸ (1h); G⁹ (1i)] with different metal alkoxides. All of these new complexes have been characterized by elemental analyses, molecular weight determinations, and spectroscopic (I.r. and ¹H, ²⁷Al-n.m.r.) studies. Structural features of the new derivatives have been elucidated on the basis of molecular weight and spectroscopic data.     

The Enthalpy of Solution in Water of Complexes of Zinc with Methionine

The enthalpies of solution in water of L--methionine and its zinc complexes Zn(Met)Cl₂, Zn(Met)₂Cl₂·2H₂O, Zn(Met)(NO₃)₂·1/2H₂O, Zn(Met)₃(NO₃)₂·H₂O and Zn(Met)SO₄·H₂O have been measured at 298.15 K. The standard enthalpy of formation of met(aq) has been calculated. The experimental results have been discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

The Enthalpy of Solution in Water of Histidine Complexes of Re Nitrates

The enthalpies of solution in water of RE(His)(NO₃)₃H₂O (RE=La—Nd, Sm—Lu, Y) were measured calorimetrically at 298.15 K, and the standard enthalpies of formation of RE(His)_aq³⁺ (RE=La—Nd, Sm—Lu, Y) were calculated. The plot of the enthalpies of solution vs. the atomic numbers of the elements in the lanthanide series exhibits the tetrad effect.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effect of Molecular Mass on the Melting Temperature,Enthalpy and Entropy of Hydroxy-Terminated PEO

This paper studies the effect of molecular mass on the melting temperature, enthalpy and entropy of hydroxy-terminated poly(ethylene oxide) (PEO). It aims to correlate the thermal behaviour of PEO polymers and their variation of molecular mass (MW). Samples ranging from 1500 to 200,000 isothermally treated at 373 K during 10 min, were investigated using DSC and Hot Stage Microscopy (HSM). On the basis of DSC and HSM results, melting temperatures were determined, and melting enthalpies and entropies were calculated. Considering the melting temperatures, it was found that the maximum or critical value of MW was found around 4000, and then these remain almost constant. This behaviour was interpreted assuming that lower MW fractions (MW<4000) crystallize in the form of extended chains and higher MW fractions (MW>4000), as folded chains. The melting enthalpies showed a scattering effect at least up to MW 35,000. It was difficult to obtain any relationship between melting enthalpies in J g^–1 and MW. These variations seem to be of statistical nature. Corrected enthalpy data on a molar basis (kJ mol^–1) exhibited a linear relationship with MW. Considering the solid—liquid equilibrium, the melting entropies (in kJ mol^–1) were calculated. These values were more negative as compared with molar enthalpy increases. It was explained because the changes in melting temperatures are much smaller than those observed in the enthalpy values. Linear relationship between enthalpies andentropies as a function of MW was deduced.This revised version was published online in November 2005 with corrections to the Cover Date.