Construction of solid-liquid phase diagrams in ternary systems by titration calorimetry

Titration calorimetry was used to construct the solid-liquid equilibrium line in ternary systems containing the solute and an aqueous mixed solvent by measuring the heat of dissolution of the solid solute during successive additions of the liquid solvent. The plot of cumulated heats versus the mole ratio, n_solvent/n_solute, yields two (almost) linear increases of different slopes. These two lines represent successively the enthalpy of dissolution then the enthalpy of dilution of the medium; their intersection gives the solubility and the enthalpy of dissolution of the solute. Phase diagrams have been established over the whole concentration range for o-anisaldehyde, 1,3,5-trimethoxybenzene and vanillin, in water + methanol, +ethanol, or +n-propanol at 303, 313 and 318 K.     

Apparent molar volumes,heat capacities,and molecular excluded volumes of methylated,hydroxy and methoxy derivatives of 1-methylcytosine in aqueous solutions at 25°C

Densities and specific heat capacities of aqueous solutions: 1-methylcytosine; 1-methyl-N⁴-hydroxycytosine; 1,5-dimethylcytosine; I,N⁴-dimethylcytosine; 1,5-dimethyl-N⁴-hydroxycytosine; 1-methyl-N⁴-methoxycytosine; 1,N⁴,N⁴-trimethylcytosine, 1,5-dimethyl-N⁴-methoxycytosine were determined using flow calorimetry and flow densimetry at 25°C. Apparent molar volumes and heat capacities were then determined. Molecular excluded volumes were evaluated. A relationship was found between the values of the increments in partial molar values and the kind of groups substituted. Four types of contributions were distinguished: substitution of hydrogen on C, N, and O (in OH group on N4) atoms by CH₃ group and replacement of hydrogen on N4 atom by OH group. The correlation between the experimental partial molar volumes and calculated molecular excluded volumes was also elaborated.     

Molar heat capacities and volumes of transfer of cytosine,thymine, caffeine and 1,3-diethylthymine to aqueous solutions of glycyl-glycine and L-α-alanyl-L-α-alanine at 25°C

Densities and specific heat capacities of ternary aqueous systems containing dipeptides (glycyl-glycine or L--alanyl-L--alanine) and nucleic acid bases (cytosine or thymine) or their alkyl derivatives (1,3-diethylthymine or caffeine) were determined at 25°C by flow calorimetry and flow densimetry. The partial molar volumes and heat capacities of transfer at infinite dilution of the different nucleic acid bases from water to water+dipeptide solutions were obtained therefrom. Except for the case of the transfer of cytosine to aqueous glycyl-glycine solutions where a small positive dependence of the transfer quantities was observed with the dipeptide concentration, the values of the heat capacities of transfer were in general low, positive or negative, depending on the compensation of hydrophobic-hydrophilic interactions between the dipeptide and the base. The volumes of transfer of most of the bases are very small, within the limit of the experimental error.     

Molar excess heat capacities and volumes for mixtures of alkanoates with cyclohexane at 25°C

Molar excess volumes V ^E at 25°C have been determined by vibrating-tube densimetry, as a function of mole fraction x for different series of an alkanoate (H _2m+1 C _m COOC _n H _2n+1 )+cyclohexane. Three types of alkanoates were investigated, i.e., methanoates (m=0, with n=3 and 4), ethanoates (m=1, with n=2, 3, and 4) and propanoates (m=2, with n=1, 2, and 3). In addition, a Picker flow calorimeter was used to obtain molar excess heat capacities C _p ^E at constant pressure at the same temperature. V ^E is positive for all systems and rather symmetric, with V ^E (x=0.5) amounting to almost identical values in a series of mixtures containing an alkanoate isomer of same formula (say C₄H₈O₂, C₅H₁₀O₂, or C₆H₁₂O₂). The composition dependence of C _p ^E is rather unusual in that two more or less marked minima are observed for most of the mixtures, especially when the alkanoate is a methanoate or an ethanoate. These results are discussed in terms of possible changes in conformation of both the ester and cyclohexane.     

Excess heat capacities of ternary systems containing chlorobenzene or chloronaphthalene

Densities and heat capacities of ternary systems were determined at 25°C. The ternary systems consisted of: a polar molecule (component 1) + a mixture of alkanes (components 2 and 3) of different sizes and shapes. Five such systems were studied: chlorobenzene + cyclohexane + n-heptane; chlrobenzene + cyclohexane + n-hexadecane; chlorobenze + cyclohexane + isooctane; chlorobenzene + isooctane + n-heptane; 1-chloronaphthalene + isooctane + n-heptane. The excess molar volumes and heat capacities were obtained along dilution lines by component 1 (chlorobenzene or 1-chloronaphthalene) of mixtures of components 2 and 3 (at fixed component 2 mole fraction X₂). Unexpectedly the excess heat capacities C _p1(23) ^E of the pseudo-binaries {1+(2+3)} do not always fall between the two (limiting) curves of C _p12 ^E and C _p13 ^E corresponding to the two binaries {1+2} and {1+3}. Instead, especially for {chlorobenzene + cyclohexane + an n-alkane} the C _p1(23) ^E curves are displaced toward less negative values, even beyond the limiting values corresponding to the binaries. This correlates semi-quantitatively with the negative C _p23 ^E of the binary {2+3}.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30-June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Excess molar quantities of (a halogenated n-alkane + an n-alkane) A comparative study of mixtures containing either 1-chlorobutane or 1,4-dichlorobutane

Excess molar volumes V_m^E at 298.15 K were obtained, as a function of mole fraction x, for series I: {x1-C₄H₉Cl + (1 ? x)n-C_lH_{2l + 2}}, and II: {x1,4-C₄H₈Cl₂ + (1 ? x)n-C_lH_{2l + 2}}, for l = 7, 10, and 14. 10, and 14. The instrument used was a vibrating-tube densimeter. For the same mixtures at the same temperature, a Picker flow calorimeter was used to measure excess molar heat capacities C_{p, m}^E at constant pressure. V_m^E is positive for all mixtures in series I: at x = 0.5, V_m^E/(cm³ · mol^?1) is 0.277 for l = 7, 0.388 for l = 10, and 0.411 for l = 14. For series II, V_m^E of {x1,4-C₄H₈Cl₂ + (1 ? x)n-C₇H₁₆} is small and S-shaped, the maximum being situated at x_max = 0.178 with V_m^E(x_max)/(cm³ · mvl^?1) = 0.095, and the minimum is at x_min = 0.772 with V_m^E(x_min)/(cm³ · mol^?1) = ?0.087. The excess volumes of the other mixtures are all positive and fairly large: at x = 0.5, V_m^E/(cm³ · mol^?1) is 0.458 for l = 10, and 0.771 for l = 14. The C_{p, m}^Es of series I are all negative and |C_{p, m}^E| increases with increasing l: at x = 0.5, C_{p, m}^E/(J · K^?1 · mol^?1) is ?0.56 for l = 7, ?1.39 for l = 10, and ?3.12 for l = 14. Two minima are observed for C_{p, m}^E of {x1,4-C₄H₈Cl₂ + (1 ? x)n-C₇H₁₆}. The more prominent minimum is situated at x′_min = 0.184 with C_{p, m}^E(x′_min)/(J · K^?1 · mol^?1) = ?0.62, and the less prominent at x″_min = 0.703 with C_{p, m}^E(x″_min)/(J · K^?1 · mol^?1) = ?0.29. Each of the remaining two mixtures (l = 10 and 14) has a pronounced minimum at low mole fraction (x_min = 0.222 and 0.312, respectively) and a broad shoulder around x = 0.7.     

Thermodynamics of liquid mixtures containing n-alkanes and strongly polar components: VE and C P E of mixtures with either pyridine or piperidine

Excess molar volumes V _E and excess molar heat capacities C _P ^/E at constant pressure have been obtained, as a function of mole fraction x₁, for several binary liquid mixtures belonging either to series I: pyridine+n-alkane (C_lH_2l+2), with l=7, 10, 14, 16, or series II: piperidine+n-alkane, with l=7, 8, 10, 12, 14. The instruments used were a vibrating-tube densimeter and a Picker flow microcalorimeter, respectively. V ^E of pyridine+n-heptane shows a S-shaped composition dependence with a small negative part in the region rich in pyridine (x₁>0.90). All the other systems show positive V ^E only. The excess volumes increase with increasing chain length l of the n-alkane. The excess molar heat capacities of the mixtures belonging to series II are all negative, except for a small positive part for piperidine+n-heptane in the region rich in piperidine (x₁>0.87). The C _P ^/E at the respective minima, C _P ^/E (x_1,min ), become more negative with increasing l, and the x_1,min values range from about 0.26 (l=7) to 0.39 (l=14). Most interestingly, mixtures of series I exhibit curves of C _P ^/E against x₁ with two minima and one maximum, the so-called W-shape curves.Dedicated to Professor A. Néckel on the occasion of his 65^th birthday. Communicated in part at the XVII^èmes Journées de Calorimétrie, d'Analyse Thermique et de Thermodynamique Chimique, Ferrara, Italy, 27–30 October, 1986.     

Isotropic transition behaviour of an amphiphilic di-block copolymer under pressure

The present work deals with the interactions between carbon dioxide, used as pressure medium, either in the gas state (GCO₂) or in the supercritical state (SCCO₂) and amphiphilic di-block copolymers PEO_m-b-PMA(Az)_n. The effect of pressure on the isotropic transition of the PEO_m-b-PMA(Az)_n copolymer was investigated using scanning transitiometry (ST). The experimental results were compared with those measured when using ‘relatively inert’ mercury (Hg) as pressure medium. Morphological observation of a PEO_m-b-PMA(Az)_n thin film submitted to SCCO₂ was performed by atomic force microscopy (AFM) to investigate the nano-structure organization. These results indicate the possibility of modifying the nano-structure in a specific way depending on the CO₂ physical state.     

Simple gases to replace non-environmentally friendly polymer foaming agents. A thermodynamic investigation

Foaming constitutes one of the most important industrial activities in polymer engineering to produce efficient thermal insulating materials. In particular, rigid insulating boards are produced worldwide on a large scale using blowing agents which eventually are released in the environment where they adversely impact the natural friendly stratospheric ozone layer. Concomitantly, the chemicals used as blowing agents contribute to the creation of the unfriendly tropospheric ozone layer generating the disastrous green house effect around our planet. The traditional foaming intermediates currently named freons, like chlorofluorocarbons (CFCs) currently used as blowing agents as well as the hydrochlorofluorocarbons (HCFCs) often considered as alternative blowing agents, must be banned from industrial processes and new (friendly) foaming agents have to be suggested and evaluated in terms of both easy engineering and environmental neutrality. Undoubtedly thermodynamics plays a major role in assessing the effective capability of those chemicals. Some CFCs still accepted and other possible simple gases like carbon dioxide and nitrogen have been considered. The in-depth thermodynamic investigation has been made possible thanks to new experimental developments to determine gas solubility in polymers and associated swelling as well as the thermodynamic properties of (gas + polymer) systems, including the thermophysical properties of polymers under gas sorption. Pertinent data have been generated for such properties over extended T and p ranges.