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
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.
The heat capacities (Cp,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 (Tm), the molar enthalpy (ΔfusHm0), and the molar entropy (ΔfusSm0) 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 (HT-H298.15 and ST-S298.15) were calculated. The molar energy of combustion and the standard molar enthalpy of combustion were determined, ΔUc(C6H8N2,cr)= −3500.15±1.51 kJ mol−1 and ΔcHm0 (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, ΔrHm0 (C6H8N2,cr)= −1.74±0.57 kJ mol−1.
The low-temperature heat capacity Cp,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 Cp-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 [HT-H298.15] and [ST-S298.15], 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: ΔcHm0(C4H10O4, cr)= −2102.90±1.56 kJ mol−1 and ΔfHm0(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.
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.
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 F1/3 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.
The molar heat capacities Cp,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 Cp-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, Cp,m/(J K−1 mol−1)=117.72+58.8022x+3.0964x2+6.87363x3−13.922x4+9.8889x5+16.195x6; x=[(T/K)−195]/115. In the temperature range of 325 to 395 K, Cp,m/(J K−1 mol−1)=290.74+22.767x−0.6247x2−0.8716x3−4.0159x4−0.2878x5+1.7244x6; x=[(T/K)−360]/35. The thermodynamic functions HT−H298.15 and ST−S298.15, 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
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, TD=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 (Cp,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)] (ΔsolHm,l0) and the Zn(Val)SO4·H2O(s) (ΔsolHm,20) in 100.00 mL of 2 mol dm−3 HCl(aq) at T=298.15 K were determined to be, ΔsolHm,l0=(94.588±0.025) kJ mol−1 and ΔsolHm,20=–(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: ΔfHm0 (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).
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, Cp,m[La(Me2dtc)3(C12H8N2)] = 542.097 + 229.576 X − 27.169 X2 + 14.596 X3 − 7.135 X4 (J K−1 mol−1), Cp,m[Pr(Me2dtc)3(C12H8N2)] = 500.252 + 314.114 X − 17.596 X2 − 0.131 X3 + 16.627 X4 (J K−1 mol−1), Cp,m[Nd(Me2dtc)3(C12H8N2)] = 543.586 + 213.876 X − 68.040 X2 + 1.173 X3 + 2.563 X4 (J K−1 mol−1) and Cp,m[Sm(Me2dtc)3(C12H8N2)] = 528.650 + 216.408 X − 16.492 X2 + 12.076 X3 + 4.912 X4 (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.
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, CP,m (J K−1 mol−1) = 204.75 + 81.421X − 23.828 X2 + 12.044X3 + 2.5442X4 [X = (T − 132.5)/52.5] for the solid phase (80–185 K), CP,m (J K−1 mol−1) = 368.99 + 2.4199X + 1.0027X2 + 0.43395X3 [X = (T − 230)/35] for the glass state (195 − 265 K), and CP,m (J K−1 mol−1) = 415.01 + 21.992X − 0.24656X2 + 0.57770X3 [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 ΔHg = 2.853 kJ mol−1 and ΔSg = 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 ΔHm = 20.67 kJ mol−1 and ΔSm = 73.34 J K−1 mol−1.
In the present work temperature dependence of heat capacity of rubidium niobium tungsten oxide has been measured first in
the range from 7 to 395 K and then between 390 and 650 K, respectively, by precision adiabatic vacuum and dynamic calorimetry.
The experimental data were used to calculate standard thermodynamic functions, namely the heat capacity
, for the range from T→0 to 650 K. The high-temperature X-ray diffraction and the differential scanning calorimetry were used for the determination
of temperature and decomposition products of RbNbWO6.