电感耦合等离子发射光谱法快速测定对苯二甲酰氯中氯化亚砜残留量  

Determination of Thionyl Chloride Residue in Terephthaloyl Chloride by Inductively Coupled Plasma-Optical Emission Spectrometry

作　　者：曾坤 马源源 郭庆中[1] 段太成[2] ZENG Kun;MA Yuan-Yuan;GUO Qing-Zhong;DUAN Tai-Cheng(Materials Science and Engineering,Wuhan Institute of Technology,Wuhan 430074,China;Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,China)

机构地区：[1]武汉工程大学材料科学与工程学院,武汉430074 [2]中国科学院长春应用化学研究所电分析化学国家重点实验室,长春130022

出　　处：《分析化学》2019年第3期410-414,共5页Chinese Journal of Analytical Chemistry

基　　金：国家自然科学基金项目(No.21275138)资助~~

摘　　要：基于电感耦合等离子发射光谱法(ICP-OES)建立了对苯二甲酰氯(TPC)中氯化亚砜(SOCl_2)残留量的快速测定方法。样品以有机溶剂溶解后,经水溶液液-液萃取,使SOCl_2原位水解,并氧化为稳定态硫酸根,进一步通过ICP-OES测定S含量,实现SOCl_2残留量的准确分析。优化了样品溶解的溶剂类型及用量,发现以四氯化碳为溶剂,且溶剂/溶质比为10(mL∶g)时可获得最佳的样品溶解效果;优化了振荡萃取的水相酸度、时间以及氧化剂类型和用量,发现水相萃取酸度为10%(V/V)HNO_3、振荡萃取时间在2 min左右,氧化剂加入量为2%(V/V) H_2O_2时,可实现SOCl_2的充分水解及水解产物的完全吸收与氧化固定,并有效避免了TPC基体的大量水解对两相分离的影响。全流程加标回收率为92.7%～104.6%;方法检出限(LOD,3s)为0.22 mg/kg(以S计),测定精密度(RSD,n=6)为2.1%。采用本方法对TPC实际生产及提纯工艺中不同阶段样品进行了分析,所得结果与理论预测值符合。A method for determination of thionyl chloride(SOCl2)residue in terephthaloyl chloride by inductively coupled plasma-optical emission spectrometry(ICP-OES)was developed.The samples were firstly dissolved with organic solvents and then subjected to liquid-liquid extraction,by which the hydrolization of thionyl chloride could lead to the formation of inorganic sulfate,which was then accurately determined by ICP-OES and the content of thionyl chloride residue thus could be calculated.The type of the organic solvent and its volume to sample mass ratio were optimized,and it was found that the sample could be readily dissolved in carbon tetrachloride as the solvent and the ratio of solvent volume to sample mass being 10(mL:g).Also,the conditions for the extraction procedure were studied,and it was found that when the aqueous phase solution contained 10%(V/V)nitric acid and 2%(V/V)hydrogen peroxide and the shaking time was kept in about 2min,the full hydrolization of thionyl chloride and the complete oxidation of H2SO3 could be accomplished,as well as a quick separation of the two organic/water phase was realized.The results showed that the limit of detection(LOD,3s)of the method was 0.22mg/kg(calculated as S),the relative standard deviation(RSD)was 2.1% for six real sample analysis,and the recoveries of spiked test were 92.7%-104.6%.The established method was finally applied to the analysis of the real samples collected from the purification process of the terephthaloyl chloride production plant and the results were highly in accordance with theoretically predicted value.

关 键 词：氯化亚砜 对苯二甲酰氯 电感耦合等离子发射光谱法 液-液萃取 

分 类 号：O657.31[理学—分析化学] TQ246[理学—化学]