The density of Li2CO3-Na2CO3-K2CO3-Rb2CO3-Cs2CO3-CaCO3-SrCO3-BaCO3 liquids: New measurements, ideal mixing, and systematic trends with composition
The density of Li2CO3-Na2CO3-K2CO3-Rb2CO3-Cs2CO3-CaCO3-SrCO3-BaCO3 liquids: New measurements, ideal mixing, and systematic trends with composition
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Li2CO3-Na2CO3-K2CO3-Rb2CO3-Cs2CO3-CaCO3-SrCO3-BaCO3 液体的密度：新测量、理想混合和成分的系统趋势
DOI：
10.1016/j.gca.2018.12.031
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发表时间：
2019
影响因子：
5
通讯作者：
Lange, Rebecca A.
中科院分区：
文献类型：
--
作者：
Hurt, Sean M.;Lange, Rebecca A.
用铂双点阿基米德法测量了Li2CO3-Na2CO3-K2CO3-Rb2CO3-Cs2CO3-CaCO3-SrCO3-BaCO3system中15种液体的密度，测量范围为758~1455 K，密度为1 bar。熔体组成为≤50 摩尔%CaCO_3，SrCO_3和BaCO_3，≤100%Rb_2CO_3和Cs_2CO_3。结合文献中对Li_2CO_3-Na_2CO_3-K_2CO_3-CaCO_3体系中9种液体的双点密度测量，得到了一个新的多元碳酸盐液体的线性体积方程。回归得到Li2CO3(41.22σ± 0.09)、Na2CO3(53.27 ± 0.11)、K2CO3(71.59 ± 0.13)、Rb2CO3(80.78 ± 0.11)、Cs2CO3(94.00 ± 0.09)、CaCO3(40.18 ± 0.16)、SrCO3(44.33 ± 0.22)和BaCO3(50.99 ± 0.19)在1100 K时的偏摩尔体积(±1 / )。在1100 K时，所有碱土碳酸盐液体组分的热膨胀系数在1-Sigma误差范围内不可区分(22.07 ± 1.66 × 10−5K−1)，但与碱土碳酸盐液体组分的热膨胀系数不同，其热膨胀系数在1-Sigma误差范围内也是不可区分的(16.40 ± 2.85 × 10−5K−1)。线性体积方程在分析误差范围内(±0.3%)对测量结果进行了恢复。所有八种碳酸盐组分的偏摩尔体积都沿着两种不同的趋势线性增加，一个是碱碳酸盐的偏摩尔体积(R2= 0.999)，另一个是碱土碳酸盐的偏摩尔体积(R2= 0.999)，其中金属阳离子-氧配位数是从文献中的分子动力学模拟得到的(碱金属的偏摩尔体积是碱金属的4-6倍，碱土金属的偏摩尔体积是碱土金属的7-8倍)。线性拟合导致碳酸盐离子(CO32−)在1100cm3K的偏摩尔体积(∼38和 31−/摩尔)不同，这反映了碳酸盐离子与碱金属配位4倍与碱土金属配位6倍时的拓扑排列更加开放。结果表明，在已知氧和碳酸盐离子与镁、铁配位的情况下，可以计算出多组分碳酸盐液体中碳酸镁和碳酸铁的偏摩尔体积。例如，在镁和铁与氧和碳酸盐都配位6倍的情况下，1100 K时的估计偏摩尔体积分别为34.4(±0.6)和35.1(±0.6)厘米~3/摩尔，热膨胀系数为16.40(±2.85)10−5K/−1。相反，如果镁和铁与氧和碳酸盐都配位4倍，则在1100 K时估计的偏摩尔体积分别为40.0(±0.6)和40.4(±0.6)厘米~3/摩尔。热膨胀系数为22.07(±1.66)10−5K−1。为了解决这些对摩尔体积的不同估计，需要分子动力学模拟来确定镁和铁在碳酸盐液体中各自的配位环境。
The densities of 15 liquids in the Li2CO3-Na2CO3-K2CO3-Rb2CO3-Cs2CO3-CaCO3-SrCO3-BaCO3system were measured at 1 bar with the Pt double-bob Archimedean method between 758 and 1455 K. Melt compositions contain ≤50 mol% CaCO3, SrCO3and BaCO3, and ≤100% Rb2CO3and Cs2CO3. These results were combined with double-bob density measurements from the literature on nine liquids in the Li2CO3-Na2CO3-K2CO3-CaCO3system to calibrate a new linear volume equation for multicomponent carbonate liquids. The regression led to the following fitted partial molar volumes (±1σ cm3/mol) at 1100 K for Li2CO3(41.22 ± 0.09), Na2CO3(53.27 ± 0.11), K2CO3(71.59 ± 0.13), Rb2CO3(80.78 ± 0.11), Cs2CO3(94.00 ± 0.09), CaCO3(40.18 ± 0.16), SrCO3(44.33 ± 0.22) and BaCO3(50.99 ± 0.19). At 1100 K, the thermal expansion coefficients of all alkali carbonate liquid components are indistinguishable within 1-sigma error (22.07 ± 1.66 × 10−5K−1), but differ from the thermal expansion coefficients of all alkaline-earth carbonate liquid components, which are also indistinguishable within 1-sigma error (16.40 ± 2.85 × 10−5K−1). The linear volume equation recovers the measurements within analytical error (±0.3%). The partial molar volumes of all eight carbonate components increase linearly along two different trends, one for the alkali carbonates (R2= 0.999) and another for the alkaline earth carbonates (R2= 0.999) as a function of cation volumes, where metal cation-oxygen coordination numbers are obtained from molecular dynamic simulations in the literature (ranging from 4- to 6-fold among the alkali metals and 7- to 8-fold among the alkaline-earth metals). The linear fits lead to two different partial molar volumes (∼38 and ∼31 cm3/mole) for the carbonate ion (CO32−) at 1100 K, which reflects a more open topological arrangement of the carbonate ions when in 4-fold coordination with the alkali metals vs. 6-fold coordination with alkaline earth metals. The results permit the partial molar volume of MgCO3and FeCO3in multicomponent carbonate liquids to be calculated if the oxygen and carbonate ion coordination with Mg2+and Fe2+are known. For example, in the case where Mg2+and Fe2+are in 6-fold coordination with both oxygen and carbonate, the estimated partial molar volumes at 1100 K are 34.4 (±0.6), and 35.1 (±0.6) cm3/mol, respectively, with a thermal expansion coefficient of 16.40 (±2.85) 10−5K−1. In contrast, if Mg2+and Fe2+are in 4-fold coordination with both oxygen and carbonate, the estimated partial molar volumes at 1100 K are 40.0 (±0.6), and 40.4 (±0.6) cm3/mol, respectively, with a thermal expansion coefficient of 22.07 (±1.66) 10−5K−1. To resolve these different estimates of molar volume, molecular dynamic simulations are needed to determine the respective coordination environments for Mg2+and Fe2+in carbonate liquids.
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DOI：
10.1107/s0108768103009017
发表时间：
2003-06-01
期刊：
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE
影响因子：
--
作者：
Dusek, M;Chapuis, G;Petricek, V
通讯作者：
Petricek, V
DOI：
10.1021/j100882a515
发表时间：
1966
期刊：
The Journal of Physical Chemistry
影响因子：
--
作者：
S. Ragone;R. K. Datta;D. Roy;O. F. Tuttle
通讯作者：
O. F. Tuttle
熔融碳酸锂的逆蒙特卡罗研究
DOI：
--
发表时间：
1999
期刊：
影响因子：
--
作者：
S. Kohara;K. Suzuya;H. Ohno
通讯作者：
H. Ohno
DOI：
--
发表时间：
1986
期刊：
影响因子：
--
作者：
D. J. Stein;J. Stebbins;I. Carmichael
通讯作者：
I. Carmichael
熔融Li2CO3和Na2CO3的分子动力学模拟
DOI：
--
发表时间：
1990
期刊：
影响因子：
--
作者：
J. Habasaki
通讯作者：
J. Habasaki