拉曼光谱法研究硝酸钙溶液的离子缔合

王琼瑶; 张文华; 赵继颖; 杨林

doi:doi:10.13883/j.issn1004-5929.201803009

光散射学报, 2018, 30 (3): 251, 网络出版: 2018-10-06

拉曼光谱法研究硝酸钙溶液的离子缔合

A Study on Ion Association of Calcium Nitrate Solution by Raman Spectroscopy

论文大纲

王琼瑶 ^*张文华赵继颖杨林

作者单位

青海师范大学化学与化工学院,西宁 810000

硝酸钙拉曼光谱缔合物种高斯多峰曲线拟合 alcium nitrate Raman spectroscopy associating species the multi-peak gaussian fitting

摘要

采用显微拉曼光谱技术研究水盐摩尔比(WSR)为4.0~160.0的硝酸钙溶液中的缔合物种分布情况及物种间的转换关系。研究表明当WSR从160.0降低到4.0时溶液中硝酸根离子的对称伸缩振动频率(v1-NO-3)从1048.3 cm-1蓝移至1052.9 cm-1,半峰高宽(FWHM)从7.6 cm-1增大到15.3 cm-1。采用组分分析方法对v1-NO-3峰分析得出,WSR≥16.3时为第一浓度区域,主要物种为溶剂共享离子对(shared ion pair,SIP),次要物种为接触离子对(contact ion pair,CIP)和自由水合离子(free hydrated ion,Free ion),且WSR=16.3时,SIP和CIP的量相等;当8.4≤WSR＜16.3时为第二浓度区域,主要物种为CIP,复杂离子簇(complex ion cluster,Complex)的量快速增加;当WSR＜8.4时为第三浓度区域,主要物种为Complex,CIP和SIP的量快速下降;WSR<4时,由曲线拟合得出溶液中CIP和SIP均逐渐转换为Complex,Complex的量趋近于1。硝酸钙溶液过饱和度越高,结晶越困难,溶液的结构构型与四水硝酸钙熔融盐结构相似,即推测出过饱和硝酸钙溶液(1≤WSR≤4,没有新相生成)的结构构型是单齿六配位［(H2O)m(HO3)nCa(NO3)Ca(NO3)p(H2O)q］(m+n=p+q=5)。

Abstract

Association species distribution and the transformation relationship among species in the calcium nitrate solution with water and salt molar ratio(WSR) of 4.0 ~ 160.0 were studied by mcroscopic Raman spectroscopy.The results showed that the symmetric stretching vibration frequency(v1-NO-3) of nitrate ions in solution was shifted from 1048.3 cm-1 to 1052.9 cm-1,and FWHM(the full width at half-maximum) was changed from 7.6 cm-1 to 15.3 cm-1 with the WSR decreased from 160.0 to 4.0 The v1-NO- peak was studied by the component analysis method.It was found that WSR≥16.3 was the first concentration region,the main species was shared ion pair(SIP),the second species was contact ion pair(CIP) and free hydrated ion(free ion),there were the same amount of SIP and CIP when WSR=16.3;it was the second concentration region when 8.4≤WSR<16.3,The main species was CIP,the amount of complex structure(Complex) was increased;it was the third concentration region when WSR<8.4,The main species was Complex,the amounts of CIP and SIP was decreased rapidly;When WSR <4,CIP and SIP were transformed rapidly into Complex,the amount of Complex approached 1.The higher the supersaturation of calcium nitrate solution is,the more difficult the crystallization be.The structure of this solution was similar to molten salt of calcium nitrate tetrahydrate,the structural configuration of the calcium nitrate solution(1≤WSR≤4,new phase is not generated)might be monodentate hexacoordination［(H2O)m(HO3)nCa(NO3)Ca(NO3)p(H2O)q］(m+n=p+q=5).

参考文献

[1] 杨家振,孙柏,宋彭生.离子缔合作用［J］.化学通报,1995,5: 62-64.(YANG Jiazhen,SUN Bai,SONG Pengsheng.Ionic association［J］.Chemistry,1995,5: 62-64)

[2] 刘绍璞,刘忠芳,李明.离子缔合物二级散射光谱的分析应用,硒(恻)一碘化物一罗丹明B体系［J］.化学学报,1995,53: 1178-1184.(LIU Shaopu,LIU Zhongfang,LI Ming.Analytieal applieation of double scattering spetra of ion-association complex.I.selenium(VI)-I- -rhodamine B system［J］.Acta Chimic Sinica,1995,53: 1178-1184)

[3] 轩小朋,汤俊明,王键吉,等.高浓度NaBF4/DMF溶液中的离子溶剂化和离子缔合［J］.光谱学与光谱分析,2005,5(4): 548-522.(XUAN Xiaopeng,TANG Junpeng,WANG Jianji,et al.Ion solvation and Ion association in high-concentration of NaBF4/DMF solutions.spectroscopy and spectral analysis,2005,5(4): 548-522)

[4] 丁皓,朱宇,王俊,等.高温及超临界条件下MgCl2与CaCl2水溶液中离子水化与缔合的量子化学计算［J］.化学学报,2004,62(14): 1287-1292.(DING Hao,WANG Jun,ZHU Yu,et al.Quantum chemical calculations on the hydration and association of MgCl2 and CaCl2 solutions at high and supercritical temperatures［J］.Acta Chimic Sinica,2004,62(14): 1287-1292)

[5] EIGEN M,TAMM K Z.Schallabsorption in elektrolytlsungen als folge chemischer relaxation［Z］.Elektrochem,1962,66: 93-121

[6] ZHANG Hao,ZHUANG Yunhong.Ab initio investigation on the ion-associated species and process in Mg(NO3)2 solution［J］.J Comput Chem,2010,31: 2772-2782

[7] 张浩,于健康,孙家锺.从头算量子化学计算方法对硝酸锂溶液中离子缔合物种和缔过程的研究［J］.分子科学学报,2010,26: 75-79.(ZHANG Hao,YU Jiankang,SUN Jiazhong.Ab initio investigation on the ion-associated species and process in LiNO3 solution［J］.Journal of Molecular Science.2010,26: 75-79)

[8] 王陈琛,林珂,胡乃银,等.利用超额拉曼光谱研究硝酸镁水溶液中的离子对［J］.物理化学学报,2012,28(8): 1823-1829.(WANG Chenchen,LIN Ke,HU Niaiyin,et al.Ion Pairs in aqueous magnesium nitrate solution by excess Raman spectroscopy［J］.Acta Phys-Chim Sin,2012,28(8): 1823-1829)

[9] YU Junying,ZHANG Yu,TAN Seehua,et al.Observation on the ion association equilibria in NaNO3 droplets using micro-Raman spectroscopy［J］.J Phys Chem B,2012,116: 12581-12589.

[10] 阎波,周桓,李文轩.拉曼光谱法研究Na+,Mg2+//SO2-4,Cl-,H2O四元体系中离子缔合结构特征及其变化规律［J］.物理化学学报,2016,32(2): 405-414.(YAN Bo,ZHOU Heng,LI Wenxuan.Studies on the characteristics and behaviors of the ion association structures of system by Raman spectroscopy［J］.Acta Phys-Chim Sin,2016,32(2): 405-414)

[11] GUO Xin;SHOU Jingjing,ZHANG Yunhong,et al.Micro-Raman analysis of association equilibria in supersaturated NaClO4 droplets［J］.Analyst,2010,135(3): 495-502

[12] 曹语晴,李军,罗建洪,等.硝酸钙结晶介稳区的研究［J］.磷肥与复肥,2012,27(5): 19-21.(CHAO Yuqing,LI Jun,LUO Jianhong,et al.Study on the crystallization metastable zone of calcium nitrate［J］.Phosphate＆Compound Fertilizer,2012,27(5): 19-21)

[13] 王晓勉,黄志宇,翟智拓,等.流化床中硝酸钙晶体生长的实验研究［J］.磷肥与复肥,2010,25(4): 20-22.(WANG Xiaomian,HUANG Zhiyu,ZHAI Zhituo,et al.Experimental study on calcium nitrate crystal growth in a fluidized bed［J］.Phosphate＆Compound Fertilizer,2010,25(4): 20-22)

[14] 程干华.硝酸磷肥工艺中硝酸钙结晶的分离过程［J］.磷肥与复肥,2001,16(4): 34-36.(CHENG Ganhua.Separation of calcium nitrate crystals in nitrophosphate process［J］.Phosphate＆Compound Fertilizer,2001,16(4): 34-36)

[15] LI Xiaohong,WANG Feng,LU Peidong,et al.Confocal Raman observation of the efflorescence/deliquescence processes of individual NaNO3 particles on quartz［J］.J Phys Chem B,2006,110(49): 24993-24998.

[16] 房艳,房春晖,林联君等.四水硝酸钙熔盐的结构研究［J］.盐湖研究,2007,1(15),39-43.(FANG Yan,FANG Chunhui,LIN Lianjin,et al.A Study on the structure of calcium nitrate tetrahydrate molten salt［J］.Journal of Saltlakes Reseach,2007,1(15): 39-43)

王琼瑶, 张文华, 赵继颖, 杨林. 拉曼光谱法研究硝酸钙溶液的离子缔合[J]. 光散射学报, 2018, 30(3): 251. WANG Qiongyao, ZHANG Wenhua, ZHAO Jiying, YANG Lin. A Study on Ion Association of Calcium Nitrate Solution by Raman Spectroscopy[J]. The Journal of Light Scattering, 2018, 30(3): 251.

拉曼光谱法研究硝酸钙溶液的离子缔合

关于本站 Cookie 的使用提示

全站搜索

拉曼光谱法研究硝酸钙溶液的离子缔合

相关论文

相关资讯

关于本站 Cookie 的使用提示

全站搜索