Volumetric Properties for the Aqueous Solution of Yttrium Trichloride at Temperatures from 283.15 to 363.15 K and Ambient Pressure

Jiang, Zhenzhen; Ma, Chi; Liu, Gaoling; Sun, Kangrui; Li, Mingli; Guo, Yafei; Meng, Lingzong; Deng, Tianlong

doi:https://doi.org/10.1155/2021/4541213

Journal of Chemistry

On this page

Abstract Introduction Experimental Results and Discussion Conclusions Data Availability Conflicts of Interest Acknowledgments Supplementary Materials References Copyright Related Articles

Research Article | Open Access

Volume 2021 | Article ID 4541213 | https://doi.org/10.1155/2021/4541213

Volumetric Properties for the Aqueous Solution of Yttrium Trichloride at Temperatures from 283.15 to 363.15 K and Ambient Pressure

Zhenzhen Jiang,^1,2Chi Ma,¹Gaoling Liu,²Kangrui Sun,¹Mingli Li,²Yafei Guo,¹Lingzong Meng,³and Tianlong Deng¹

Academic Editor: Elena Gomez

Received13 May 2021

Revised25 Sept 2021

Accepted13 Oct 2021

Published09 Nov 2021

Abstract

To effectively develop the rare earth elements resources from the geothermal waters, it is essential to understand the volumetric properties of the aqueous solution system to establish the relative thermodynamic model. In this study, densities of YCl₃ (aq) at the molalities of 0.08837–1.60639 mol·kg⁻¹ from 283.15 K to 363.15 K at 5 K intervals and ambient pressure were measured experimentally by an Anton Paar digital vibrating-tube densimeter. Based on experimental data, the volumetric properties including apparent molar volume (V_ϕ) and the coefficient of thermal expansion of the solution (α) of the binary systems (YCl₃ + H₂O) were derived. The 3D diagram (m_i, T, V_ϕ) of apparent molar volumes against temperature and molality was plotted. On the basis of the Pitzer ion-interaction model of electrolyte, the Pitzer single-salt parameters (, , and ) for YCl₃ and temperature-dependence equation F(i, p, T) = a₁ + a₂ln(T/298.15) + a₃(T-298.15) + a₄/(620-T) + a₅(T-227) as well as their coefficients a_i (i = 1–5) in the binary system were obtained for the first time. The values of Pitzer single-salt parameters of YCl₃ agree well with the calculated values corresponding to the temperature-dependence equations, indicating that single-salt parameters and temperature-dependent formula obtained in this work are reliable.

1. Introduction

Rare earth elements (REEs) are vital ingredients of modern technologies, especially in energy, environmental protection, digital technology, the nuclear industry, and medical applications. REEs are also an integral part of electronic devices serving as magnets, catalysts, and superconductors, owing to their chemical, catalytic, electrical, magnetic, and optical properties [1–7]. What is more, in nuclear medicine, many radioisotopes such as yttrium have been used in diagnostic or therapeutic procedures to treat a wide range of diseases, including cancer [8]. The continuously increasing demand for yttrium has led to the high economic importance of yttrium. Tibet is one of the famous geothermally active regions, and the geothermal water resources with high concentrations of rare earth elements are distributed widely [9]. It is well known that thermodynamic properties such as solubilities of phase equilibria and apparent molar volumes at wide temperatures are essential to explore novel methods for more effective and efficient extraction of yttrium and provide information about the ion interactions. Therefore, revealing the ion-interaction to construct a thermodynamics model at multitemperatures for the binary system (YCl₃ + H₂O) is of great importance.

As to the volumetric behaviors of YCl₃ aqueous solutions, data reported in the literature [10, 11] were mainly focused on 298.15 K, even using the traditional pycnometric measurement method [11]. With the progress of technology, the density measurement for the aqueous solution at multiple temperatures with a vibrating-tube densimeter is more convenient and accurate than that of the pycnometric measurement [12–14]. However, up to now, there are no data reported on the apparent molar volumes at temperatures from 283.15 K to 363.15 K and 101.325 kPa. Hence, studying the volumetric properties of the binary system (YCl₃ + H₂O) at multitemperatures is essential for utilizing rare earth elements from geothermal water resources.

In this study, densities of YCl₃ aqueous solutions in the range of 0.08837–1.60639 mol·kg⁻¹ from 283.15 to 363.15 K and 101.325 kPa were measured by an Anton Paar digital vibrating-tube densimeter. The derived properties of apparent molar volumes (V_ϕ), partial molar volumes (), and the coefficients of thermal expansion of the solution (α) for YCl₃ aqueous solutions were obtained, and their variation tendency against temperature and molality have been discussed in detail. The Pitzer single-salt parameters of YCl₃ at multitemperatures and temperature-dependence equations were also obtained for the first time.

2. Experimental

2.1. Materials

Extra pure reagent YCl₃·6H₂O (CAS: 10025-94-2) in 0.99999 in the mass fraction was obtained from Aladdin Industrial Co., Ltd., without any further purification. The fresh CO₂-free doubly deionized water (DDW) was produced by ULUP-II-10T (Chongqing Jiuyang Co., Ltd., China), with a conductivity less than 1 × 10⁻⁴·S·m⁻¹, and pH = 6.60 at 298.15 K was used in the whole study.

2.2. Apparatus and Procedure

Stock solutions of YCl₃ were prepared in the glove box filled with nitrogen gas (UNIlab Plus, MBraun, Germany), in which precise YCl₃·6H₂O and DDW were weighted using the analytical balance (Mettler Toledo, Swiss) with an uncertainty 0.2 mg, followed by vigorous shaking of the solution and then filtering through a prewashed 0.2 μm Nylon “low extractable” membrane filtering unit. The stock solution concentration of YCl₃ expressed in molality was determined by titrimetric analysis using mercuric nitrate with uncertainty within 0.003 in the mass fraction [15]. The concentration of Y³⁺ can be obtained via ion balance and evaluated through measurement by an inductively coupled plasma optical emission spectrometer (ICP-OES, Prodigy, Leeman Corporation, America) with an uncertainty of ±0.005 in mass fraction. Moreover, all the aqueous solutions employed in experimental measurements were prepared by mass dilution of the stock solution in the nitrogen glove box and stored in glass bottles at 4°C in the refrigerator.

All the density measurements for each solution were completed within two days after the stock solution was prepared. Densities of these solutions were measured using an Anton Paar digital vibrating-tube densimeter (DMA4500, Anton Paar Co., Ltd., Austria) with an uncertainty of ±1.4 mg·cm⁻³, and the densimeter has a heating attachment (Anton Paar) that keep the temperature fluctuations within ±0.01 K. Before the measurement, the densimeter was calibrated during each series of measures with dry air and freshly DDW at 293.15 K under atmospheric pressure. The results were 0.00120 g·cm⁻³ for dry air and 0.99820 g·cm⁻³ for DDW, which agree well with the values in the literature [16]. The reliability of the density data was ascertained by making measurements of DDW using the calibrated apparatus at a 10 K interval from 279.15 to 369.15 K and atmospheric pressure, and the density values of pure water are given in Table 1, which agree well with the data in the literature [17]. The maximum relative deviation is less than 0.003%. Finally, all measurements for the densities of YCl₃ (aq) were conducted at temperature intervals of 5 K from 283.15 to 363.15 K and atmospheric pressure.

3. Results and Discussion

3.1. Densities

Densities of YCl₃ aqueous solution against molality and temperature were determined in triplicate, and the results are given in Table 2.

Based on the experimental data in Table 2, a 3D diagram of the density for the YCl₃ aqueous solution against temperature and molality is shown in Figure 1. It was clearly seen that the densities of YCl₃ aqueous solutions decreased with the increasing temperature at constant molality. Nevertheless, at the same temperature, the density values of YCl₃ aqueous solutions are increased indistinctively with the increase of YCl₃ molality. The clear changing trend for density data may be caused by the rise in solvent-solvent and solute-solvent interactions. As the temperature increases, the volume of the aqueous solutions increases, and the density decreases. The density values at constant molality have been fitted against (T − 273.15) by the least-squares method.where ρ is the density (g·cm⁻³) of the solution; θ = (T − 273.15) K, T is the absolute temperature, and A_i is the empirical constant. The relevant parameters and the correlation coefficients r related to the density-temperature fit obtained by applying equation (1) are given in Table S1 (Supplementary Materials). The values of the correlation coefficients (r) are close to 1.

According to the definition [18], the coefficient of thermal expansion of the solution is expressed with the following equations.

Based on the calculation using equation (4), the thermal expansion α (K⁻¹) values of YCl₃ aqueous solutions with various molalities at different temperatures were calculated and are given in Table 3. According to the calculated data, the relation diagram of the thermal expansion coefficient (α) and the molality at temperature intervals of 5 K from 283.15 to 363.15 K is shown in Figure 2. It can be seen that the thermal expansion coefficient of YCl₃ aqueous solution is increased with the increase of temperature at the constant molality. With the rising of molality, the thermal expansion coefficient increased obviously at T = (283.15–303.15) K, almost unchanged at T = 308.15 K, and then decreased slightly at T = (313.15–363.15) K.

3.2. Apparent Molar Volumes

The apparent molar volumes can be derived from the measured densities of pure water and YCl₃ aqueous solutions. Their values are calculated with the following equation [19]:where and ρ are the densities (g·cm⁻³) of the pure water and YCl₃ aqueous solutions, respectively; m_i is the molality (mol·kg⁻¹) for YCl₃ aqueous solution, and M_a is the molar mass (g·mol⁻¹) of YCl₃. The calculated apparent molar volumes are given in Table 4, and the 3D surfaces (m_i, T, V_ϕ) are shown in Figure 3. It can be seen that the apparent molar volumes of YCl₃ aqueous solutions increased with the increase of molality at the constant temperature. With the increasing temperature, the apparent molar volumes increase when the temperature is varied within 283.15–308.15 K, and the variation tendency is opposite when the temperature is higher than 308.15 K. It can be concluded that the ionic association of yttrium and chlorine ions is strong at low temperatures [20].

3.3. Partial Molar Volumes of Solute

The relationship between the apparent molar volume, V_ϕ (m_i, T), and the partial molar volume can be expressed.where V_ϕ refers to the apparent molar volume (cm³·mol⁻¹), m_i is the molality (mol·kg⁻¹) for YCl₃, and can be obtained from equations (7) and (8).where B_i is the empirical constant for fitting apparent molar volume and molality at invariable temperature by the least squares, and the values of the parameters with the correlation coefficients r are presented in Table S2.

Substitution of the above equation into equation (6) yields

The calculated values for partial molar volumes of solute are given in Table 5 and shown in Figure 4. It shows that the partial molar volumes of YCl₃ are increased with the increase of molality at the constant temperature.

3.4. Pitzer Parameters of YCl3

Pitzer’s electrolyte solution theory was developed based on ion-interaction and statistical mechanics, and it can accurately express the thermodynamic properties of the aqueous electrolyte solution [21]. The apparent molar volumes of YCl₃ were calculated using the following Pitzer equation [22].

In the case of , the ionic strength dependence of a solution can be imposed as follows.where M and X are Y³⁺ and Cl⁻, m_i is the molality (mol·kg⁻¹) of the aqueous YCl₃ solutions, given in Table 4, is the volume of 1 kg pure water, is the volume of m_r, in which m_r = 1.00 mol·kg⁻¹, n_r = 1.00 mol, which is the number of moles of solute in this quantity of solution, z_M and z_X are the number of ionic charges of the positive and negative ion in electronic units, for YCl₃ (z_M = 3 and z_X = 1), and are the numbers of M and X ions formed by stoichiometric dissociation of one molecule of MX, and , for YCl₃ (, , and ), is the Debye–Hückel limiting law slope for the apparent molar volume [23, 24], α_B1 = 2.0 kg^1/2·mol^1/2, b = 1.2 kg^1/2·mol^-1/2, I is the total ionic strength given by I = , R = 8.314472 cm³·MPa K⁻¹·mol⁻¹ is the gas constant, T is a temperature in K. Pitzer’s parameters account for short-range interactions between M and X, and the third virial coefficient means for triple ion interactions.

The Pitzer ion-interaction parameters are expressed as functions F (i, p, T).with F (i, p, T) represented as [23]where T is a temperature in Kelvin, p is a pressure in kPa, and a_i are the polynomial coefficients for equation (16). All parameters were calculated by the IAPWS-95 for the thermodynamic properties of water and the international formulation for the dielectric properties of water [25].

The available experimental data were fitted by the least-squares method to evaluate single-salt parameters by Pitzer ion-interaction theory. Based on the apparent molar volumes for (YCl₃ + H₂O) from 283.15 to 363.15 K in Table 4, the single-salt parameters for YCl₃ at each temperature were fitted based on equations (10)–(12) and are given in Table 6. The multiple correlation coefficients (r) were almost equal to 1, and the mean standard deviations (σ) were within ±0.0359. The temperature correlation coefficients (a_i) were fitted based on equations (13)–(16) and are given in Table 7. The deviation of single-salt parameters (, , and ) for YCl₃ between all parameterization data obtained by the Pitzer model and temperature-dependence data obtained by equation (16) is within ±0.022, which indicated that the temperature-dependence equation (16) and the temperature correlation coefficients fitted in this work are reliable.

4. Conclusions

The volumetric properties of the (YCl₃ + H₂O) aqueous solution system from 283.15 K to 363.15 K at 101 kPa are investigated for the first time. Apparent molar volumes (V_ϕ), partial molar volumes (), and the coefficient of thermal expansions of the solution (α) of YCl₃ aqueous solution were derived. In addition, the Pitzer single-salt parameters (, , and ) of YCl₃ were parameterized from the Pitzer ion-interaction model, the temperature-dependence equation was established, and its correlation coefficients (a_i) were obtained for the first time.

Data Availability

The data used to support the findings of this study are available in the article and the supplementary materials.

Conflicts of Interest

The authors declare that they have no conflicts of interest.

Acknowledgments

The authors gratefully acknowledge partial financial supports from the National Natural Science Foundation of China (22073068 and 21773170), the Natural Science Foundation of Tibet Autonomous Region (XZ202001ZR0080G), the Major Scientific and Technological Project of the Tibet Autonomous Region (XZ201801-GB-01), and the Yangtze Scholars and Innovative Research Team of the Chinese University (IRT_17R81).

Supplementary Materials

The relevant parameters and the correlation coefficients r related to the density-temperature fit obtained by applying equation (1) are listed in Table S1. The values of the parameters in equation (7) with the correlation coefficient (r) are presented in Table S2. (Supplementary Materials)

References

T. Li, S. Kaercher, and P. W. Roesky, “Synthesis, structure and reactivity of rare-earth metal complexes containing anionic phosphorus ligands,” Chemical Society Reviews, vol. 43, no. 1, pp. 42–57, 2014.
View at: Publisher Site | Google Scholar
C. Liu, Y. Hou, and M. Gao, “Are rare-earth nanoparticles suitable for in vivo applications,” Advanced Materials, vol. 26, no. 40, pp. 6922–6932, 2014.
View at: Publisher Site | Google Scholar
T. Prasada Rao and R. Kala, “On-line and off-line preconcentration of trace and ultratrace amounts of lanthanides,” Talanta, vol. 63, no. 4, pp. 949–959, 2004.
View at: Publisher Site | Google Scholar
Z. M. Migaszewski and A. Gałuszka, “The characteristics, occurrence, and geochemical behavior of rare earth elements in the environment: a review,” Critical Reviews in Environmental Science and Technology, vol. 45, no. 5, pp. 429–471, 2015.
View at: Publisher Site | Google Scholar
F. Sadri, A. M. Nazari, and A. Ghahreman, “A review on the cracking, baking and leaching processes of rare earth element concentrates,” Journal of Rare Earths, vol. 35, no. 8, pp. 739–752, 2017.
View at: Publisher Site | Google Scholar
Y. Zhang, W. Wei, G. K. Das, and T. T. Yang Tan, “Engineering lanthanide based materials for nanomedicine,” Journal of Photochemistry and Photobiology C: Photochemistry Reviews, vol. 20, pp. 71–96, 2014.
View at: Publisher Site | Google Scholar
P. Zhang, L. Zhang, and J. Tang, “Lanthanide single-molecule magnets: progress and perspective,” Dalton Transactions, vol. 44, no. 9, pp. 3923–3929, 2015.
View at: Publisher Site | Google Scholar
P. S. Conti, “Radioimmunotherapy with yttrium 90 ibritumomab tiuxetan (Zevalin): the role of the nuclear medicine physician,” Seminars in Nuclear Medicine, vol. 34, no. 1, pp. 2-3, 2004.
View at: Publisher Site | Google Scholar
J.-L. Feng, Z.-H. Zhao, F. Chen, and H.-P. Hu, “Rare earth elements in sinters from the geothermal waters (hot springs) on the Tibetan Plateau, China,” Journal of Volcanology and Geothermal Research, vol. 287, pp. 1–11, 2014.
View at: Publisher Site | Google Scholar
A. W. Hakin, M. J. Lukacs, J. L. Liu, and K. Erickson, “The volumetric and thermodynamics of YCl₃(aq), YbCl₃(aq), DyCl₃(aq), SmCl₃(aq), and GdCl₃(aq) at T = (288.15, 298.15, 313.15, and 328.15) K and p = 0.1 MPa,” The Journal of Chemical Thermodynamics, vol. 35, no. 11, pp. 1861–1895, 2003.
View at: Publisher Site | Google Scholar
F. H. Spedding, V. W. Saeger, K. A. Gray et al., “Densities and apparent molal volumes of some aqueous rare earth solutions at 25°C. I. Rare earth chlorides,” Journal of Chemical & Engineering Data, vol. 20, no. 1, pp. 72–81, 1975.
View at: Publisher Site | Google Scholar
C. Xiao and P. R. Tremaine, “Apparent molar heat capacities and volumes of LaCl₃(aq), La(ClO₄)₃(aq), and Gd(ClO₄)₃(aq) between the temperatures 283 K and 338 K,” The Journal of Chemical Thermodynamics, vol. 28, no. 1, pp. 43–66, 1996.
View at: Publisher Site | Google Scholar
J. J. Spitzer, I. V. Olofsson, P. P. Singh, and L. G. C. Hepler, “Apparent molar heat capacities and volumes of aqueous electrolytes at 298.15 K: Ca(NO₃)₂, Co(NO₃)₂, Cu(NO₃)₂, Mg(NO₃)₂, Mn(NO₃)₂, Ni(NO₃)₂, and Zn(NO₃)₂,” Journal of Chemical Thermodynamics, vol. 11, pp. 233–238, 1979.
View at: Publisher Site | Google Scholar
C. Xiao and P. R. Tremaine, “The thermodynamics of aqueous trivalent rare earth elements. Apparent molar heat capacities and volumes of Nd(ClO₄)₃(aq), Eu(ClO₄)₃(aq), Er(ClO₄)₃(aq), and Yb(ClO₄)₃(aq) from the temperatures 283 K to 328 K,” Journal of Chemical Thermodynamics, vol. 29, pp. 827–852, 1997.
View at: Publisher Site | Google Scholar
Qinghai Institute of Salt Lakes of CAS, Analytical Methods of Brines and Salts, Chinese Science Press, Beijing, China, 2nd edition, 1988.
P. G. Hill, “A unified fundamental equation for the thermodynamic properties of H₂O,” Journal of Physical and Chemical Reference Data, vol. 19, pp. 1233–1274, 1990.
View at: Publisher Site | Google Scholar
J. A. Dean, Lange’s Handbook of Chemistry, Science Press, Beijing, China, 1991.
W. G. Xu, Y. Qin, F. Gao, J. G. Liu, C. W. Yan, and J. Z. Yang, “Determination of volume properties of aqueous vanadyl sulfate at 283.15 to 323.15 K,” Industrial & Engineering Chemistry Research, vol. 53, pp. 7217–7223, 2014.
View at: Publisher Site | Google Scholar
Y. F. Guo, K. Y. Zhao, L. Li et al., “Volumetric properties of the aqueous solution of lithium tetraborate from 283.15 to 363.15 K at 101.325 kPa,” Journal of Chemical Thermodynamics, vol. 120, pp. 151–156, 2018.
View at: Publisher Site | Google Scholar
K. Y. Zhao, L. Li, Y. F. Guo et al., “Apparent molar volumes of aqueous solutions of lithium pentaborate from 283.15 to 363.15 K and 101.325 kPa: an experimental and theoretical study,” Journal of Chemical and Engineering Data, vol. 64, pp. 944–951, 2019.
View at: Publisher Site | Google Scholar
B. S. Krumgalz, R. Pogorelsky, A. Sokolov, and K. S. Pitzer, “Volumetric ion interaction parameters for single–solute aqueous electrolyte solutions at various temperatures,” Journal of Physical and Chemical Reference Data, vol. 29, pp. 1123–1140, 2000.
View at: Publisher Site | Google Scholar
F. J. Millero, “Estimation of the partial molar volumes of ions in mixed electrolyte solutions using the Pitzer equations,” Journal of Solution Chemistry, vol. 43, pp. 1448–1465, 2014.
View at: Publisher Site | Google Scholar
D. Zezin, T. Driesner, and C. Sanchez-Valle, “Volumetric properties of Na₂SO₄ – H₂O and Na₂SO₄ – NaCl − H₂O solutions to 523.15 K, 70 MPa,” Journal of Chemical and Engineering Data, vol. 60, pp. 1181–1192, 2015.
View at: Publisher Site | Google Scholar
D. P Fernandez, A. R. H. Goodwin, E. W. Lemmon, J. M. H. Levelt Sengers, and R. C. Williams, “A formulation for the static permittivity of water and steam at temperatures from 238 to 873 K at pressures up to 12 MPa, including derivatives and Debye-Hückel coefficients,” Journal of Physical and Chemical Reference Data, vol. 26, pp. 1125–1166, 1997.
View at: Publisher Site | Google Scholar
W. Wagner and A. Pruß, “The IAPWS formulation 1995 for the thermodynamic properties of ordinary water substance for general and scientific use,” Journal of Physical and Chemical Reference Data, vol. 31, pp. 387–535, 2002.
View at: Publisher Site | Google Scholar

Copyright

Copyright © 2021 Zhenzhen Jiang et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

PDF Download Citation

Download other formats

Order printed copies

Views

236

Downloads

536

Citations