Search Results
Abstract
Selectivity of hydrous titanium dioxide as an ion exchanger for alkali metal and tetraalkylammonium ions, has been studied using radioactive indicators:22Na and137Cs. The equilibrium distribution of trace amounts of sodium and cesium ions between the exchanger and aqueous solutions containing macroamounts of other univalent cations was studied over the temperature range of 15 to 80°C. The selectivity sequence in slightly acidic and neutral solutions is as follows: (CH3)4N+<Li+<Na+<K+<Rb+<Cs+, whilst in alkaline solutions it is partly reversed. From the values of selectivity coefficients and the calculated values of thermodynamic functions one can infer that whilst hydrated ions are exchanged from acidic and neutral solutions, from alkaline solutions partly dehydrated ions enter the exchanger phase. The existence of ion-sieve effects for the univalent cations studied was observed, and the presence of at least two kinds of hydroxyl functional groups of different acidities is postulated. Ion exchange reactions of alkali metal cations on hydrous titanium dioxide, as well as the selectivity sequences observed have been interpreted on the basis of EISENMAN theory.
Abstract
The specific heat of N(CH3)4CdBr3 from 50 to 300 K has been measured by adiabatic calorimetry, using both static and dynamic methods. The obtained results have permitted a careful study of the ferro-paraelectric phase transition the crystal shows at 160 K. The available spectroscopic data have been used to generate a reliable baseline which accounts for the normal lattice contribution to the specific heat. These results allow for an accurate estimation of the phase transition thermodynamic functions: ΔH=2620 J·mol−1 and ΔS=18.04 J·(mol°C)−1. These high values are in agreement with the predictions of the 6 well potential Frenkel model.
Abstract
Several DTA experiments followed by calorimetric works are reviewed here to emphasise the importance of complementary role of both techniques. The thermal analysis is advantageous in the sense that it gives quickly the overall view of thermal behaviour of a material under various conditions. Calorimetric work provides accurate heat capacity data which enable to derive thermodynamic functions including the enthalpy and entropy. The latter quantity is especially important in judging whether the material obeys the third law of thermodynamics. However, calorimetric work leads occasionally to an erroneous conclusion if the work is not preceded by thermal analysis performed under various conditions. Sometimes, quality of information obtained by DTA exceeds that obtained by laborious calorimetry.
Abstract
Due to improvements of high temperature calorimetry, the quantity of liquid alloys showing large negative departures from ideality increased strongly during the last decades. Such a behaviour is now explained by the occurence of chemical short-range order (CSRO), the stoichiometry of which is often elucidated from direct structural determinations as well as from modelization of the thermodynamic functions. In some extreme cases, the destruction of CSRO by increasing temperature lead to a genuine second order transition. The short rewiev of experimental results concerning the variation of physical properties of some liquid alloysvs. temperature and concentration agrees well with CSRO. Some examples of structural determination of CSRO in metallic melts are given. Finally, links between CSRO and phase diagrams and between CSRO and glass-forming ability are also examined.
A numerical method for the calculation of the composition of two phases in equilibrium is proposed for the case when the composition of one of the phases is known as function of the temperature. The thermodynamic properties of the phases are not needed to be known in the proposed procedure. The feature of this approach is the possibility to use fictitious thermodynamic functions in the intermediate stages of computation. The method has been applied for calculation of solidus in phase diagrams of potassium-rubidium, potassium-cesium and cesium-rubidium systems from experimental liquidus data.
Thermodynamic investigation of room temperature ionic liquid
Heat capacity and thermodynamic functions of BMIBF4
Abstract
The molar heat capacities of the room temperature ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMIBF4) were measured by an adiabatic calorimeter in temperature range from 80 to 390 K. The dependence of the molar heat capacity on temperature is given as a function of the reduced temperature X by polynomial equations, C P,m (J K–1 mol–1)= 195.55+47.230 X–3.1533 X 2+4.0733 X 3+3.9126 X 4 [X=(T–125.5)/45.5] for the solid phase (80~171 K), and C P,m (J K–1 mol–1)= 378.62+43.929 X+16.456 X 2–4.6684 X 3–5.5876 X 4 [X=(T–285.5)/104.5] for the liquid phase (181~390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BMIBF4 relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass translation of BMIBF4 was observed at 176.24 K. Using oxygen-bomb combustion calorimeter, the molar enthalpy of combustion of BMIBF4 was determined to be Δc H m o= – 5335±17 kJ mol–1. The standard molar enthalpy of formation of BMIBF4 was evaluated to be Δf H m o= –1221.8±4.0 kJ mol–1 at T=298.150±0.001 K.
Abstract
Molar heat capacities (C p,m) of aspirin were precisely measured with a small sample precision automated adiabatic calorimeter over the temperature range from 78 to 383 K. No phase transition was observed in this temperature region. The polynomial function of C p,m vs. T was established in the light of the low-temperature heat capacity measurements and least square fitting method. The corresponding function is as follows: for 78 K≤T≤383 K, C p,m/J mol-1 K-1=19.086X 4+15.951X 3-5.2548X 2+90.192X+176.65, [X=(T-230.50/152.5)]. The thermodynamic functions on the base of the reference temperature of 298.15 K, {ΔH T -ΔH 298.15} and {S T-S 298.15}, were derived. Combustion energy of aspirin (Δc U m) was determined by static bomb combustion calorimeter. Enthalpy of combustion (Δc H o m) and enthalpy of formation (Δf H o m) were derived through Δc U m as - (3945.262.63) kJ mol-1 and - (736.411.30) kJ mol-1, respectively.
Abstract
The heat capacities of chrysanthemic acid in the temperature range from 80 to 400 K were measured with a precise automatic adiabatic calorimeter. The chrysanthemic acid sample was prepared with the purity of 0.9855 mole fraction. A solid-liquid fusion phase transition was observed in the experimental temperature range. The melting point, T m, enthalpy and entropy of fusion, Δfus H m, Δfus S m, were determined to be 390.7410.002 K, 14.510.13 kJ mol-1, 37.130.34 J mol-1 K-1, respectively. The thermodynamic functions of chrysanthemic acid, H (T)-H(298.15), S (T)-S(298.15) and G (T)-G (298.15) were reported with a temperature interval of 5 K. The TG analysis under the heating rate of 10 K min-1 confirmed that the thermal decomposition of the sample starts at ca. 410 K and terminates at ca. 471 K. The maximum decomposition rate was obtained at 466 K. The purity of the sample was determined by a fractional melting method.
Abstract
The 'hydrophobic effect' of the dissolution process of non-polar substances in water has been analysed under the light of a statistical thermodynamic molecular model. The model, based on the distinction between non-reacting and reacting systems explains the changes of the thermodynamic functions with temperature in aqueous systems. In the dissolution of non-polar substances in water, it follows from the model that the enthalpy change can be expressed as a linear function of the temperature (ΔH app =ΔH ø +n w C p,w T ). Experimental solubility and calorimetric data of a large number of non-polar substances nicely agree with the expected function. The specific contribution of n w solvent molecules depends on the size of solute and is related to destructuring (n w >0) of water molecules around the solute. Then the study of 'hydrophobic effect' has been extended to the protein denaturation and micelle formation. Denaturation enthalpy either obtained by van't Hoff equation or by calorimetric determinations again depends linearly upon denaturation temperature, with denaturation enthalpy, ΔH den , increasing with T . A portion of reaction enthalpy is absorbed by a number n w of water molecules (n w >0) relaxed in space around the denatured moieties. In micellization, an opposite process takes place with negative number of restructured water molecules (n w <0) because the hydrophobic moieties of the molecules joined by hydrophobic affinity occupy a smaller cavity.
Abstract
The heat capacities of fenpropathrin in the temperature range from 80 to 400 K were measured with a precise automatic adiabatic calorimeter. The fenpropathrin sample was prepared with the purity of 0.9916 mole fraction. A solid—liquid fusion phase transition was observed in the experimental temperature range. The melting point, T
m, enthalpy and entropy of fusion, 
fus
H
m,
fus
S
m, were determined to be 322.48±0.01 K, 18.57±0.29 kJ mol–1 and 57.59±1.01 J mol–1 K–1, respectively. The thermodynamic functions of fenpropathrin, H
(T)—H
(298.15), S
(T)—S
(298.15) and G
(T)—G
(298.15), were reported with a temperature interval of 5 K. The TG analysis under the heating rate of 10 K min–1 confirmed that the thermal decomposition of the sample starts at ca. 450 K and terminates at ca. 575 K. The maximum decomposition rate was obtained at 558 K. The purity of the sample was determined by a fractional melting method.
