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
|
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 (SOCl_2) 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 2 min,the full hydrolization of thionyl chloride and the complete oxidation of H_2SO_3 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,3 s) of the method was 0. 22 mg/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.
A method for determination of thionyl chloride (SOCl_2) 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 2 min,the full hydrolization of thionyl chloride and the complete oxidation of H_2SO_3 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,3 s) of the method was 0. 22 mg/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.
引文
1 JIN Dong.Fine Chemical Industrial Raw Materials&Intermediates,2012,(8):17-20金栋.精细化工原料及中间体,2012,(8):17-20
2 WANG Rong-Hai,LI Yun-Long,LI Wen-Juan,GUO Qiang.China Chlor-Alkali,2011,(5):22-25王荣海,李云龙,李文娟,郭强.中国氯碱,2011,(5):22-25
3 ZHOU Ting,ZHAO Hai-Jun,ZHU Xin-Bao.Chemistry and Adhesion,2015,37(2):141-145周婷,赵海军,朱新宝.化学与黏合,2015,37(2):141-145
4 SHENG Qing-Quan,XIAO Jian-Mou,LUAN Wei-Li,LIU Tai-Ze.Jiangxi Chemical Industry,2007,4(14):15-18盛庆全,肖鉴谋,栾伟丽,刘太泽.江西化工,2007,4(14):15-18
5 YANG Chen-Lin.Fine and Specialty Chemicals,2012,20(2):4-7杨臣林.精细与专用化学品,2012,20(2):4-7
6 ZHUANG Liu-Xing,LI Fan-Xiu,BAI Lu.Henan Chemical Industry,2011,28(3):56-57庄六星,李反修,白璐.河南化工,2011,28(3):56-57
7 ZHU Dan-Qi,LIU Zeng-Jie,LYU Guo-Feng.Guangzhou Chemical Industry,2016,44(3):121-122朱丹琪,刘增杰,吕国锋.广州化工,2016,44(3):121-122
8 ZOU Min,HU Jin-Feng.Jiangxi Chemical Industry,2003,(3):94-95邹敏,胡金凤.江西化工,2003,(3):94-95
9 SU Hong-Wei.Hebei Chemical Industry,2005,(1):64苏红维.河北化工,2005,(1):64
10 JI Kai-Zhong,DONG Hong-Wen.Shangdong Pharmaceutical Industry,2000,19(6):19-20季开忠,董洪文.山东医药工业,2000,19(6):19-20
11 HU Jin-Feng,ZOU Min.Jiangxi Chemical Industry,2003,4(39):143-145胡金凤,邹敏.江西化工,2003,4(39):143-145
12 LUO Yi,LI Jian-Guo,LIU Dai-Li,LI Zhi-Hua,HU Jian.Chinese Journal of Industrial Hygiene and Occupational Diseases,2003,21(3):240罗毅,李建国,刘黛莉,李志华,扈健.中华劳动卫生职业病杂志,2003,21(3):240
13 Zhang J J,Tan F,Robert H.Anal.Chim.Acta,2015,891:255-260
14 ZHANG Ying,WANG Hong-Min,WANG Xiao-Jing,WANG Sai,CUI Jing-Jing,LI Chuan-Shun,LIU Ji-Hua.Chinese J.Anal.Chem.,2018,46(4):570-577张颖,汪虹敏,王小静,王赛,崔菁菁,李传顺,刘季花.分析化学,2018,46(4):570-577
15 GAO Guang-Jie-Zi,LI Yan-Ping,FENG Sheng-Ya,XIE Yan-Jun,KUANG Chun-Jiang,CAO Cheng.Chinese J.Anal.Chem.,2014,42(3):457-458高光洁子,李艳萍,冯圣雅,谢琰军,况春江,曹枨.分析化学,2014,42(3):457-458
16 Nomvano M,Philiswa N N,Catherine N.Talanta,2018,182:567-573
17 Diogo L R N,Rodrigo M P,Vanize C C,Carla A H,Marcia F.M.Food Chem.,2018,246:422-427
18 Berti W R,Wolstenholme B W,Kozlowski J J,Sobocinski R L,Freerksen R W.Environ.Sci.Technol.,2006,40(20):6330-6335
2 WANG Rong-Hai,LI Yun-Long,LI Wen-Juan,GUO Qiang.China Chlor-Alkali,2011,(5):22-25王荣海,李云龙,李文娟,郭强.中国氯碱,2011,(5):22-25
3 ZHOU Ting,ZHAO Hai-Jun,ZHU Xin-Bao.Chemistry and Adhesion,2015,37(2):141-145周婷,赵海军,朱新宝.化学与黏合,2015,37(2):141-145
4 SHENG Qing-Quan,XIAO Jian-Mou,LUAN Wei-Li,LIU Tai-Ze.Jiangxi Chemical Industry,2007,4(14):15-18盛庆全,肖鉴谋,栾伟丽,刘太泽.江西化工,2007,4(14):15-18
5 YANG Chen-Lin.Fine and Specialty Chemicals,2012,20(2):4-7杨臣林.精细与专用化学品,2012,20(2):4-7
6 ZHUANG Liu-Xing,LI Fan-Xiu,BAI Lu.Henan Chemical Industry,2011,28(3):56-57庄六星,李反修,白璐.河南化工,2011,28(3):56-57
7 ZHU Dan-Qi,LIU Zeng-Jie,LYU Guo-Feng.Guangzhou Chemical Industry,2016,44(3):121-122朱丹琪,刘增杰,吕国锋.广州化工,2016,44(3):121-122
8 ZOU Min,HU Jin-Feng.Jiangxi Chemical Industry,2003,(3):94-95邹敏,胡金凤.江西化工,2003,(3):94-95
9 SU Hong-Wei.Hebei Chemical Industry,2005,(1):64苏红维.河北化工,2005,(1):64
10 JI Kai-Zhong,DONG Hong-Wen.Shangdong Pharmaceutical Industry,2000,19(6):19-20季开忠,董洪文.山东医药工业,2000,19(6):19-20
11 HU Jin-Feng,ZOU Min.Jiangxi Chemical Industry,2003,4(39):143-145胡金凤,邹敏.江西化工,2003,4(39):143-145
12 LUO Yi,LI Jian-Guo,LIU Dai-Li,LI Zhi-Hua,HU Jian.Chinese Journal of Industrial Hygiene and Occupational Diseases,2003,21(3):240罗毅,李建国,刘黛莉,李志华,扈健.中华劳动卫生职业病杂志,2003,21(3):240
13 Zhang J J,Tan F,Robert H.Anal.Chim.Acta,2015,891:255-260
14 ZHANG Ying,WANG Hong-Min,WANG Xiao-Jing,WANG Sai,CUI Jing-Jing,LI Chuan-Shun,LIU Ji-Hua.Chinese J.Anal.Chem.,2018,46(4):570-577张颖,汪虹敏,王小静,王赛,崔菁菁,李传顺,刘季花.分析化学,2018,46(4):570-577
15 GAO Guang-Jie-Zi,LI Yan-Ping,FENG Sheng-Ya,XIE Yan-Jun,KUANG Chun-Jiang,CAO Cheng.Chinese J.Anal.Chem.,2014,42(3):457-458高光洁子,李艳萍,冯圣雅,谢琰军,况春江,曹枨.分析化学,2014,42(3):457-458
16 Nomvano M,Philiswa N N,Catherine N.Talanta,2018,182:567-573
17 Diogo L R N,Rodrigo M P,Vanize C C,Carla A H,Marcia F.M.Food Chem.,2018,246:422-427
18 Berti W R,Wolstenholme B W,Kozlowski J J,Sobocinski R L,Freerksen R W.Environ.Sci.Technol.,2006,40(20):6330-6335