酸性条件下H+Ca2+在红壤表面反应的能量特征
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*国家自然科学基金项目(批准号:40071046,49831005);国家重点基础研究发展规划项目(批准号:19990118013)资助


ENERGEY CHARACTERISTICS OF REACTION KINETICS OF H+-Ca2+ ON RED SOIL SURFACE UNDER ACIDIC CONDITIONS
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    摘要:

    用自行设计的动力学装置研究了酸性条件下H+-Ca2+在红壤表面的反应动力学能量特征.结果表明,酸性条件下Ca2+吸附分为快反应和慢反应.用一级动力学方程拟合的Ca2+最大吸附量随酸度增加显著下降,随温度升高提前达到平衡.用双常数方程描述Ca2+在吸附点位能量分布的不均匀性,用扩散速率常数计算的活化能(Eb)随酸度的增加而增加,Ca2+扩散需克服的能障加大;ΔH值为正,温度升高可促进Ca2+的扩散;ΔS值均为负,说明吸附反应使体系有序度增加.原液pH为4.5和5.6时,流出液的pH急剧下降,H+表观释放量用一级动力学和双常数方程拟合为最佳模型,其次是Elovich方程、扩散方程和零级方程;pH5.6处理时H+、Al3+扩散进入溶液克服的能障比pH4.5处理的小,后者质子扩散需热能较大而不易进行;H+扩散活化焓变为正,其扩散是吸热过程.pH3.5时流入液比流出液的pH高,是由于土壤的缓冲作用、土壤表面质子化和硫酸根专性吸附释放羟基;当溶液中H+超过一定数量后,向颗粒表面扩散的H+量比向外释放的多,反应初期的H+消耗是快反应过程.H+消耗的活化能及热焓比其释放的低,更有利于H+的吸附,因H+对矿物的溶蚀成为速率控制步骤,H+对矿物的溶解可用扩散方程和Elovich方程描述.

    Abstract:

    Energy characteristics of the reaction kinet ics of H+ -Ca2+ on red soil surface under acidic conditions were investigated by using a home-made dynamic device.The results showed that Ca2+ adsorption could be divided into rapid and slow reactions.The maximal Ca2+ adsorption fitted by the first order equation remarkably decreased with increase in acidity and reached equilibrium in advance with increase in temperature.A two-constant equation could be used to describe unevenness of the energy distribution of Ca2+ adsorption on the sites of the soil surface.Activation energy(Eb) of Ca2+ diffusion was calculated by using b value of the rate constant of Parabolic Diffusion Low and increased with increase in acidity,which reflected that the energy barrier to be overcome by Ca2+ diffusion would rise up and the rate of diffusion in Ca2+ adsorption decrease accordingly.Enthalpy of activation(H) was positive in value and rising temperature could contribute to Ca2+ diffusion.Entropy of activation(S*) was nagative in all cases,suggesting that system could improve its degree of order.pH of effluent drast ically dropped when the influent solution was pH 4.5 and pH 5.6.H+ release could be best described by the first order equation and the power-function equation,which were followed by Elovich equation,Parabolic Diffusion Low and zero order equation.Energy barrier to be overcome by H+ (Al3+) diffusion in pH 5.6 treatment was lower than that in pH 4.5 treatment.△H values of H+ diffusion were positive indicating an endothermic reaction and the increase in temperature speeded up H+ diffusion.There was the consumption process of H+ ion by using influent of pH 3.5,which was attributed to soil buffer mechanism and specific adsorption of SO42-.The energy of activation of H+ consumption was lower than that of H+ release,showing that more H+ was diffused to the surface of soil particles than H+ released to bulk solution when the amount of H+ in the bulk solution exceeded a certain quantity.H+ consumption was rapid at the initial stage of the reaction.△H of H+ consumption,in comparison with that of H+ release,could contribute to H+ adsorption.Since H+ dissolution of minerals became a controlling process,it could be best described by Elovich equation and Parabolic Diffusion Low.

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王代长,蒋新,贺纪正,卞永荣,王芳.酸性条件下H+Ca2+在红壤表面反应的能量特征[J].土壤学报,2004,41(4):536-543. DOI:10.11766/trxb200306310407 Wang Daizhang, Jiang Xin, He Jizheng, Bian Yongrong, Wang Fang. ENERGEY CHARACTERISTICS OF REACTION KINETICS OF H+-Ca2+ ON RED SOIL SURFACE UNDER ACIDIC CONDITIONS[J]. Acta Pedologica Sinica,2004,41(4):536-543.

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  • 收稿日期:2003-06-30
  • 最后修改日期:2003-12-06
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  • 在线发布日期: 2013-02-25
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