Thermodynamic Investigation of Polyhydroxylated Derivatives of Light Fullerenes

Isobaric heat capacities of C[Formula: see text](OH)[Formula: see text] and C[Formula: see text](OH)[Formula: see text] fullerenols were measured using adiabatic calorimetry in the temperature range of 0–320[Formula: see text]K along with standard thermodynamic functions: [Formula: see text], [[Formula: see text]] and [[Formula: see text]]. Furthermore, the molar entropy of formation and the molar third law entropy of C[Formula: see text](OH)[Formula: see text] and C[Formula: see text](OH)[Formula: see text] in crystalline state at 298.15[Formula: see text]K were calculated.

Second Law and Non-Equilibrium Entropy of Schottky Systems—Doubts and Verification–

Meixner’s historical remark in 1969 “... it can be shown that the concept of entropy in the absence of equilibrium is in fact not only questionable but that it cannot even be defined....” is investigated from today’s insight. Several statements—such as the three laws of phenomenological thermodynamics, the embedding theorem and the adiabatical uniqueness—are used to get rid of non-equilibrium entropy as a primitive concept. In this framework, Clausius inequality of open systems can be derived by use of the defining inequalities which establish the non-equilibrium quantities contact temperature and non-equilibrium molar entropy which allow to describe the interaction between the Schottky system and its controlling equilibrium environment.

Second Law and Non-Equilibrium Entropy of Schottky Systems --Doubts and Verification--

Meixner's historical remark in 1969 "... it can be shown that the concept of entropy in the absence of equilibrium is in fact not only questionable but that it cannot even be defined...." is investigated from today's insight. Several statements --such as the three laws of phenomenological thermodynamics, the embedding theorem and the adiabatical uniqueness-- are used to get rid of non-equilibrium entropy as a primitive concept. In this framework, Clausius inequality of open systems can be derived by use of the defining inequalities which establish the non-equilibrium quantities contact temperature and non-equilibrium molar entropy which allow to describe the interaction between the Schottky system and its controlling equilibrium environment.

EFFECT OF PRESSURE ON EXCESS THERMODYNAMIC CHARACTERISTICS OF WATER + FORMAMIDE MIXTURE

Using the experimental data on the densities at atmospheric pressure and compressibility coefficients, k=(Vo-V)/Vo, of water + FA mixture the changes in the following thermodynamic parameters were calculated under the pressure increase up to 100 MPa within the temperature range from 288.15 to 323.15 K: excess molar Gibbs energy, ΔPo→PGmE, excess molar entropy ,ΔPo→PSmE, and excess molar entropy ΔPo→PHmE. It was established that ΔPo→PGmEvalues were negative over the whole concentration range and minima appeared on ΔPo→PGmE= f(x2) functions at x2≈0.33. The pressure growth up to 100 MPa resulted in ΔPo→PGmE absolute values increase within entire concentration and temperature intervals. The changes in entropy component, -(ΔPo→PTSmE), of ΔPo→PGmEvalues were almost canceled by the enthalpy component changes. Minimal values of ΔPo→PSmE corresponded to x2≈ 0.33, exactly at that composition 2Н2О-FA associate formed. The isobaric temperature lowering caused the structure ordering also at x2≈ 0.33. The pressure growth promoted the increasing in exothermicity of the mixing enthalpies, HmE, of water and formamide. The changes in HmE value under the mixture compression are indicative of the larger exothermal contribution from new H-bonds formation as compared with the endothermic contribution from the decreasing in the total amount of hydrogen bonds. The temperature lowering decreases ΔPo→PHmEvalues as well; maximal isotherms dispersion is observed at concentrations corresponding to maximal content of 2:1 or 1:1 associates of water and FA.