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Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: Influence of temperature

机译:非晶态氢氧化铁对钇和稀土元素的吸附:温度的影响

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The sorption of yttrium and the rare earth elements (YREEs) by amorphous ferric hydroxide was investigated between 10 and 40 degrees C over a range of pH (4.7-7.1) in the absence of solution complexation. Distribution coefficients, defined as K-i(Fe) = [MSi](T)/([M](T)[Fe3+](S)), where [MSi](T) is the concentration of sorbed YREEs, [M](T) is the total dissolved YREE concentration, and [Fe3+](S) is the concentration of precipitated iron, increased with increasing temperature over the entire investigated pH range. The observed increase in K-i(Fe) was largest for the heavy REEs, indicating that relative log K-i(Fe) values (i.e., YREE patterns) vary somewhat with temperature. The pH dependence of YREE sorption was described by a surface complexation model of the form K-i(Fe) = ((S)beta(1)[H+](-1) + (S)beta(2)[H+](-2))/(K-S(1)[H+] + 1), where (S)beta(n) are stability constants for sorption of free YREE ions (M3+) and K-S(1) is a surface protonation constant for amorphous ferric hydroxide. The influence of temperature on the YREE surface stability constants ((S)beta(1) and (S)beta(2)) was characterized by calculating molar enthalpies for M3+ sorption (Delta H-1(0) and Delta H-2(0)) using the van 't Hoff equation. The Delta H-1(0) values appropriate to (S)beta(1) range from 11.8 to 13.4 kcal/mol, whereas the Delta H-2(0) values appropriate to (S)beta(2) range between 7.7 and 12.3 kcal/mol. These values are on the same order of magnitude as enthalpies of the first hydrolysis step for a variety of cations.
机译:在不存在溶液络合的情况下,在pH范围(4.7-7.1)的10至40摄氏度之间,研究了非晶态氢氧化铁对钇和稀土元素(YREEs)的吸附。分布系数,定义为Ki(Fe)= [MSi](T)/([M](T)[Fe3 +](S)),其中[MSi](T)是吸附的YREEs的浓度,[M]( T)是总溶解YREE浓度,[Fe3 +](S)是在整个研究的pH范围内随温度升高而增加的沉淀铁浓度。对于重稀土元素,观察到的K-i(Fe)增加最大,表明相对log K-i(Fe)值(即YREE模式)随温度变化。 YREE吸附的pH依赖性通过表面络合模型Ki(Fe)=((S)beta(1)[H +](-1)+(S)beta(2)[H +](-2 ))/(KS(1)[H +] + 1),其中(S)beta(n)是自由YREE离子(M3 +)吸附的稳定常数,而KS(1)是无定形氢氧化铁的表面质子化常数。温度对YREE表面稳定性常数((S)beta(1)和(S)beta(2))的影响通过计算M3 +吸附的摩尔焓(Delta H-1(0)和Delta H-2( 0))使用van't Hoff方程。适用于(S)beta(1)的Delta H-1(0)值范围为11.8至13.4 kcal / mol,而适用于(S)beta(2)的Delta H-2(0)值范围为7.7至1。 12.3大卡/摩尔对于各种阳离子,这些值与第一水解步骤的焓处于相同的数量级。

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