Search Results
Abstract
The extraction of thorium(IV) from nitric acid solutions by di-n-butyl sulfoxide (DBSO) in xylene has been investigated as a function of acid, extractant and the metal concentration. The effect of contact time and diverse ions on the extraction has been examined. Phosphate, fluoride, oxalate and perchlorate reduce the extraction to some extent. The extraction of other metal ions, especially impurities associated with thorium in ores, has been measured under optimised conditions selected for thorium extraction. Na(I), K(I), Ca(II), Sr(II), Mn(II), Fe(II), Ni(II), Zn(II), Pb(II), Al(III), Ti(IV) and Hf(IV) are not extracted. Among the stripping solutions employed for back-extraction, deionized water is found to be the best and more than 99% thorium can be back-extracted in three stages. The extracted species is supposed to be Th(NO3)4·2DBSO. The extraction is found to be almost independent of the thorium concentration in the range between 4.3·10–4–4.3·10–2M and inversely dependent upon the temperature. The values of thermodynamic functions 
H,
G and
S for extraction equilibrium have been evaluated to be –19.6±2.9 kJ·mole–1, –18.1±2.0 kJ·mole–1 and –5.0±2.9 J·mole–1·K–1, respectively.
Abstract
The heat capacities (C p,m) of 2-amino-5-methylpyridine (AMP) were measured by a precision automated adiabatic calorimeter over the temperature range from 80 to 398 K. A solid-liquid phase transition was found in the range from 336 to 351 K with the peak heat capacity at 350.426 K. The melting temperature (T m), the molar enthalpy (Δfus H m 0), and the molar entropy (Δfus S m 0) of fusion were determined to be 350.431±0.018 K, 18.108 kJ mol−1 and 51.676 J K−1 mol−1, respectively. The mole fraction purity of the sample used was determined to be 0.99734 through the Van’t Hoff equation. The thermodynamic functions (H T-H 298.15 and S T-S 298.15) were calculated. The molar energy of combustion and the standard molar enthalpy of combustion were determined, ΔU c(C6H8N2,cr)= −3500.15±1.51 kJ mol−1 and Δc H m 0 (C6H8N2,cr)= −3502.64±1.51 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. The standard molar enthalpy of formation of the crystalline compound was derived, Δr H m 0 (C6H8N2,cr)= −1.74±0.57 kJ mol−1.
Thermodynamic investigation of several natural polyols
Part III. Heat capacities and thermodynamic properties of erythritol
Abstract
The low-temperature heat capacity C p,m of erythritol (C4H10O4, CAS 149-32-6) was precisely measured in the temperature range from 80 to 410 K by means of a small sample automated adiabatic calorimeter. A solid-liquid phase transition was found at T=390.254 K from the experimental C p-T curve. The molar enthalpy and entropy of this transition were determined to be 37.92±0.19 kJ mol−1 and 97.17±0.49 J K−1 mol−1, respectively. The thermodynamic functions [H T-H 298.15] and [S T-S 298.15], were derived from the heat capacity data in the temperature range of 80 to 410 K with an interval of 5 K. The standard molar enthalpy of combustion and the standard molar enthalpy of formation of the compound have been determined: Δc H m 0(C4H10O4, cr)= −2102.90±1.56 kJ mol−1 and Δf H m 0(C4H10O4, cr)= − 900.29±0.84 kJ mol−1, by means of a precision oxygen-bomb combustion calorimeter at T=298.15 K. DSC and TG measurements were performed to study the thermostability of the compound. The results were in agreement with those obtained from heat capacity measurements.
Abstract
The binary manganese and calcium dihydrogen phosphate monohydrate Mn0.5Ca0.5(H2PO4)2 · H2O was synthesized by a rapid and simple co-precipitation method using phosphoric acid, manganese metal, and calcium carbonate at ambient temperature. Thermal transformation shows complex processes and the final decomposed product was the binary manganese calcium cyclotetraphosphate MnCaP4O12. The activation energies of some decomposed steps were calculated by Kissinger method. Activated complex theory has been applied to each step of the reactions and the thermodynamic functions are calculated. These values for transformation stages showed that they are non-spontaneous processes without the introduction of heat. The differences of physical and chemical properties of the synthesized compound and its decomposed product are compared with M(H2PO4)2 · H2O and M2P4O12 (M = Mn and Ca), which indicate the effects of the presence of Ca ions in substitution of Mn ions and confirm the formation of solid solution.
Abstract
The thermal decomposition of magnesium hydrogen phosphate trihydrate MgHPO4 · 3H2O was investigated in air atmosphere using TG-DTG-DTA. MgHPO4 · 3H2O decomposes in a single step and its final decomposition product (Mg2P2O7) was obtained. The activation energies of the decomposition step of MgHPO4 · 3H2O were calculated through the isoconversional methods of the Ozawa, Kissinger–Akahira–Sunose (KAS) and Iterative equation, and the possible conversion function has been estimated through the Coats and Redfern integral equation. The activation energies calculated for the decomposition reaction by different techniques and methods were found to be consistent. The better kinetic model of the decomposition reaction for MgHPO4 · 3H2O is the F 1/3 model as a simple n-order reaction of “chemical process or mechanism no-invoking equation”. The thermodynamic functions (ΔH*, ΔG* and ΔS*) of the decomposition reaction are calculated by the activated complex theory and indicate that the process is non-spontaneous without connecting with the introduction of heat.
Abstract
The molar heat capacities C p,m of 2,2-dimethyl-1,3-propanediol were measured in the temperature range from 78 to 410 K by means of a small sample automated adiabatic calorimeter. A solid-solid and a solid-liquid phase transitions were found at T-314.304 and 402.402 K, respectively, from the experimental C p-T curve. The molar enthalpies and entropies of these transitions were determined to be 14.78 kJ mol−1, 47.01 J K−1 mol− for the solid-solid transition and 7.518 kJ mol−1, 18.68 J K−1 mol−1 for the solid-liquid transition, respectively. The dependence of heat capacity on the temperature was fitted to the following polynomial equations with least square method. In the temperature range of 80 to 310 K, C p,m/(J K−1 mol−1)=117.72+58.8022x+3.0964x 2+6.87363x 3−13.922x 4+9.8889x 5+16.195x 6; x=[(T/K)−195]/115. In the temperature range of 325 to 395 K, C p,m/(J K−1 mol−1)=290.74+22.767x−0.6247x 2−0.8716x 3−4.0159x 4−0.2878x 5+1.7244x 6; x=[(T/K)−360]/35. The thermodynamic functions H T−H 298.15 and S T−S 298.15, were derived from the heat capacity data in the temperature range of 80 to 410 K with an interval of 5 K. The thermostability of the compound was further tested by DSC and TG measurements. The results were in agreement with those obtained by adiabatic calorimetry.
Low-temperature heat capacities and standard molar enthalpy of formation of the complex
Zn(Val)SO4·H2O(s) (Val=L-α-valine)
Abstract
Low-temperature heat capacities of a solid complex Zn(Val)SO4·H2O(s) were measured by a precision automated adiabatic calorimeter over the temperature range between 78 and 373 K. The initial dehydration temperature of the coordination compound was determined to be, T D=327.05 K, by analysis of the heat-capacity curve. The experimental values of molar heat capacities were fitted to a polynomial equation of heat capacities (C p,m) with the reduced temperatures (x), [x=f (T)], by least square method. The polynomial fitted values of the molar heat capacities and fundamental thermodynamic functions of the complex relative to the standard reference temperature 298.15 K were given with the interval of 5 K.
Enthalpies of dissolution of the [ZnSO4·7H2O(s)+Val(s)] (Δsol H m,l 0) and the Zn(Val)SO4·H2O(s) (Δsol H m,2 0) in 100.00 mL of 2 mol dm−3 HCl(aq) at T=298.15 K were determined to be, Δsol H m,l 0=(94.588±0.025) kJ mol−1 and Δsol H m,2 0=–(46.118±0.055) kJ mol−1, by means of a homemade isoperibol solution–reaction calorimeter. The standard molar enthalpy of formation of the compound was determined as: Δf H m 0 (Zn(Val)SO4·H2O(s), 298.15 K)=–(1850.97±1.92) kJ mol−1, from the enthalpies of dissolution and other auxiliary thermodynamic data through a Hess thermochemical cycle. Furthermore, the reliability of the Hess thermochemical cycle was verified by comparing UV/Vis spectra and the refractive indexes of solution A (from dissolution of the [ZnSO4·7H2O(s)+Val(s)] mixture in 2 mol dm−3 hydrochloric acid) and solution A’ (from dissolution of the complex Zn(Val)SO4·H2O(s) in 2 mol dm−3 hydrochloric acid).
Abstract
The heat capacities of Ln(Me2dtc)3(C12H8N2) (Ln = La, Pr, Nd, Sm, Me2dtc = dimethyldithiocarbamate) have been measured by the adiabatic method within the temperature range 78–404 K. The temperature dependencies of the heat capacities, C p,m [La(Me2dtc)3(C12H8N2)] = 542.097 + 229.576 X − 27.169 X 2 + 14.596 X 3 − 7.135 X 4 (J K−1 mol−1), C p,m [Pr(Me2dtc)3(C12H8N2)] = 500.252 + 314.114 X − 17.596 X 2 − 0.131 X 3 + 16.627 X 4 (J K−1 mol−1), C p,m [Nd(Me2dtc)3(C12H8N2)] = 543.586 + 213.876 X − 68.040 X 2 + 1.173 X 3 + 2.563 X 4 (J K−1 mol−1) and C p,m [Sm(Me2dtc)3(C12H8N2)] = 528.650 + 216.408 X − 16.492 X 2 + 12.076 X 3 + 4.912 X 4 (J K−1 mol−1), were derived by the least-squares method from the experimental data. The heat capacities of Ce(Me2dtc)3(C12H8N2) and Pm(Me2dtc)3(C12H8N2) at 298.15 K were evaluated to be 617.99 and 610.09 J K−1 mol−1, respectively. Furthermore, the thermodynamic functions (entropy, enthalpy and Gibbs free energy) have been calculated using the obtained experimental heat capacity data.
Thermodynamic investigation of room temperature ionic liquid
The heat capacity and thermodynamic functions of BMIPF6
Abstract
The molar heat capacities of the room temperature ionic liquid 1-butyl-3-methylimidazolium hexafluoroborate (BMIPF6) 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) = 204.75 + 81.421X − 23.828 X 2 + 12.044X 3 + 2.5442X 4 [X = (T − 132.5)/52.5] for the solid phase (80–185 K), C P,m (J K−1 mol−1) = 368.99 + 2.4199X + 1.0027X 2 + 0.43395X 3 [X = (T − 230)/35] for the glass state (195 − 265 K), and C P,m (J K−1 mol−1) = 415.01 + 21.992X − 0.24656X 2 + 0.57770X 3 [X = (T − 337.5)/52.5] for the liquid phase (285–390 K), respectively. According to the polynomial equations and thermodynamic relationship, the values of thermodynamic function of the BMIPF6 relative to 298.15 K were calculated in temperature range from 80 to 390 K with an interval of 5 K. The glass transition of BMIPF6 was measured to be 190.41 K, the enthalpy and entropy of the glass transition were determined to be ΔH g = 2.853 kJ mol−1 and ΔS g = 14.98 J K−1 mol−1, respectively. The results showed that the milting point of the BMIPF6 is 281.83 K, the enthalpy and entropy of phase transition were calculated to be ΔH m = 20.67 kJ mol−1 and ΔS m = 73.34 J K−1 mol−1.
