紫外-可见吸收光谱结合高斯多峰拟合技术测定甲基红酸离解常数

doi:10.3866/PKU.WHXB201203025

物理化学学报 >> 2012, Vol. 28 >> Issue (05): 1030-1036.doi: 10.3866/PKU.WHXB201203025

紫外-可见吸收光谱结合高斯多峰拟合技术测定甲基红酸离解常数

张建华, 刘琼, 陈玉苗, 刘兆清, 徐常威

广州大学化学化工学院, 广州 510006

收稿日期:2011-12-22 修回日期:2012-03-01 发布日期:2012-04-26
通讯作者: 徐常威 E-mail:cwxuneuzsu@126.com
基金资助:
国家自然科学基金(20903028), 留学回国人员科研启动基金及羊城学者青年科研骨干培养对象项目(10A041G)资助

Determination of Acid Dissociation Constant of Methyl Red by Multi-Peaks Gaussian Fitting Method Based on UV-Visible Absorption Spectrum

ZHANG Jian-Hua, LIU Qiong, CHEN Yu-Miao, LIU Zhao-Qing, XU Chang-Wei

School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, P. R. China

Received:2011-12-22 Revised:2012-03-01 Published:2012-04-26
Contact: XU Chang-Wei E-mail:cwxuneuzsu@126.com
Supported by:
The project was supported by the National Natural Science Foundation of China (20903028), Scientific Research Foundation for Returned Scholars from Ministry of Education of China, and Scientific Research Foundation for Yangcheng Scholar, China (10A041G).

摘要/Abstract

摘要： 在一定pH 值范围内, 甲基红(MR)水溶液紫外-可见吸收光谱特征是酸式甲基红(HMR)最大吸收峰((530±15) nm)与碱式甲基红(MR^-)最大吸收峰((435±20) nm)叠合在一起. 本文用高斯多峰拟合技术实现了HMR和MR^-叠合峰的分峰拟合计算. 拟合计算输出两个吸收峰的积分面积即峰强度A₁和A₂, A₁和A₂之比与MR^-和HMR浓度之比. 进而计算甲基红水溶液酸离解平衡常数pK_a. 用本方法测量298.15 K 时的pK_a值为4.76. 拟合优度高, 拟合度R²、拟合优度χ²分别达到0.998 和10^-5以下. 深入探讨了表面活性剂十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTAB)聚集行为对甲基红pK_a的影响. 与传统分光光度测量方法相比, 紫外-可见吸收光谱结合高斯多峰拟合技术结果更可靠, 测量步骤和数据处理过程更简单, 更具有普适性.

关键词: 甲基红, 紫外-可见吸收光谱, 叠合峰, 酸离解常数, 高斯多峰拟合

Abstract: UV-visible electronic absorption spectra of methyl red aqueous solutions are characterized by the overlap of a principal peak at λ_max ((520±15) nm) with a shoulder peak at λ_max ((435±20) nm), which are assigned to acidic species (HMR) and basic species (MR^-) of methyl red, respectively. In this study, the spectra and the integrated absorbance of the MR^- and HMR peaks (denoted A₁ and A₂, respectively) were interpreted using a new multi-peaks Gaussian fitting method. From the absorbance ratio A₁/A₂ and the concentration ratio c_MR-/c_HMR, the average acid dissociation constant (pK_a) was determined as 4.76 at 298.15 K. The goodness is high and the values of R² (degree of fitting) and χ² (chi-square test for goodness of fit) were 0.998 and below 10^-5, respectively. The effects of aggregation behavior of sodium dodecyl sulfate (SDS) and cetylammonium bromide (CTAB) on pK_a were also investigated via this method. The multi-peaks Gaussian fitting method was shown to determine pK_a more reliably and simply than traditional spectrophotometric techniques.

Key words: Methyl red, UV-visible absorption spectrum, Overlap peak, Acid dissociation constant, Multi-peaks Gaussian fitting

张建华, 刘琼, 陈玉苗, 刘兆清, 徐常威. 紫外-可见吸收光谱结合高斯多峰拟合技术测定甲基红酸离解常数[J]. 物理化学学报, 2012, 28(05), 1030-1036. doi: 10.3866/PKU.WHXB201203025

ZHANG Jian-Hua, LIU Qiong, CHEN Yu-Miao, LIU Zhao-Qing, XU Chang-Wei. Determination of Acid Dissociation Constant of Methyl Red by Multi-Peaks Gaussian Fitting Method Based on UV-Visible Absorption Spectrum[J]. Acta Phys. -Chim. Sin. 2012, 28(05), 1030-1036. doi: 10.3866/PKU.WHXB201203025

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201203025

https://www.whxb.pku.edu.cn/CN/Y2012/V28/I05/1030

参考文献

(1) Kara, D.; Alkan, M. Spectrochim. Acta A 2000, 56, 2753.

(2) Niyazi, A.; Yazdanipour, A.; Ramezani, M. Chin. Chem. Lett. 2007, 18, 989.

(3) Babic, S.; Horvat, A. J. M.; Pavlovic, D. M.; Kastelan-Macan, M. Trends Anal. Chem. 2007, 26, 1043.

(4) Allen, R. I.; Box, K. J.; Comer, J. E. A.; Peake, C.; Tam, K.Y. J. Pharmaceut. Biomed. Anal. 1998, 17, 699.

(5) Beltran, J. L.; Sanli, N.; Fonrodona, G.; Barron, D.; Ozkanb, G.; Barbosa, J. Anal. Chim. Acta. 2003, 484, 253.

(6) Erdemgil, F. Z.; Sanli, S.; Sanli, N.; Ozkan, G.; Barbosa, J.; Guiteras, J.; Beltran, J. L.Talanta. 2007, 72, 489.

(7) Tang, R. C.; Tang, H.; Yang, C. Ind. Eng. Chem. Res. 2010, 49, 8894.

(8) Simon, E. W.; Beevers, H. New Phytol. 1952, 51, 163.

(9) Adam, R. S., Jr. Res. Rev. 1973, 47, 1.
(10) Weber, J. B. Adv. Chem. Ser. 1972, 111, 55.

(11) Halling-Sørensen, B.; Nielsen, S. N.; Lanzky, P. F.; Ingerslev, F.; Lutzhoft, H. C. H.; Jørgensen, S. E. Chemosphere. 1998, 36, 357.

(12) Burns, D. C.; Ellis, D. A.; Li, H. X.; McMurdo, C. J.; Webster, E. Environ. Sci. Technol. 2008, 42, 9283.

(13) Lin, J. H.; Lu, A. Y. Pharmacol. Rev. 1997, 49, 403.
(14) Frey, P. A.; Kokesh, F. O.; Westheimer, F. H. J. Am. Chem. Soc. 1971, 93, 7266.

(15) Poole, S. K.; Patel, S.; Dehring, K.; Workman, H.; Poole, C. F. J. Chromatogr. A 2004, 1037, 445.

(16) Hardcastle, J. E.; Jano, I. J. Chromatogr. B 1998, 717, 39.

(17) Ye, L.; Zhu, Q. Q.; Wu, S. K. Acta Phys. -Chim. Sin. 1987, 3, 272. [叶玲, 朱琴琴, 吴世康. 物理化学学报, 1987, 3, 272.]
(18) Qiang, Z.; Adams, C. Water Res. 2004, 38, 2874.

(19) Zhang, W. M.; Yang, Z. D.; Liu, J.; Sun, Z. X. Acta Phys. -Chim. Sin. 2010, 26, 2109. [张卫民, 杨振东, 刘嘉, 孙中溪. 物理化学学报, 2010, 26, 2109.]
(20) Li, L. F.; Hou W. G.; Jiao Y. N.; Liu C. X. Acta Phys. -Chim. Sin., 2004, 20, 459. [李丽芳, 侯万国, 焦燕妮, 刘春霞. 物理化学学报, 2004, 20, 459.]
(21) Zhang, X. D.; Liu, Y.; Sun, J. Y.; Liu, Q. T. Acta Phys. -Chim. Sin., 2000, 16, 351. [张向东, 刘岩, 孙锦玉, 刘祁涛. 物理化学学报,. 2000, 16, 351]
(22) Kolthoff, I. M.; Chantooni, M. K. J. Phys. Chem. 1966, 70, 856.

(23) Nag, S.; Datta, D. Indian. J. Chem. 2007, 46A, 1263.
(24) Wan, H.; Holmen, A. G.; Wang, Y.; Lindberg, W.; Englund, M.; Nagard, M. B.; Thompson, R. A. Rapid Commun. Mass Sp. 2003, 17, 2639.

(25) Szakacs, Z.; Hagele, G. Talanta 2004, 62, 819.

(26) Rabenstein, D. L.; Hari, S. P.; Kaerner, A. Anal. Chem. 1997, 69, 4310.

(27) Rabenstein, D. L.; Sayer, T. L. Anal. Chem. 1976, 48, 1141.

(28) Wang, J.; Rabenstein, D. L. Anal. Chem. 2007, 79, 6799.

(29) Oumada, F. Z.; Rafols, C.; Roses, M.; Bosch, E. J. Pharm. Sci. 2002, 91, 991.

(30) Lebrón-Paler, A.; Pemberton, J. E. Anal. Chem. 2006, 78, 7649.

(31) Lachenwitzer, A.; Li, N.; Lipkowski, J. J. Electroanal. Chem. 2002, 532, 85.

(32) Edwards, H. G. M. Spectrochim. Acta A 1989, 45, 715.

(33) Cagigal, E.; Gonzalez, L.; Alonso, R. M.; Jimenez, R. M. J. Pharmaceut. Biomed. Anal. 2001, 26, 477.

(34) Ferrari, V.; Cutler, D. J. J. Pharmaceut. Sci. 1987, 76, 554.

(35) Cessna, A. J.; Grover, R. J. Agric. Food Chem. 1978, 26, 289.

(36) Foulon, C.; Duhal, N.; Lacroix-Callens, B.; Vaccher, C.; Bonte, J. P.; Goossens, J. F. Eur. J. Pharm. Sci. 2007, 31, 165.

(37) Barbosa, J.; Barron, D.; Jimenez-Lozano, E.; Sanz-Nebot, V. Anal. Chim. Acta. 2001, 437, 309.

(38) Jang, Y. H.; Hwang, S. G.; Chang, S. B.; Ku, J.; Chung, D. S. J. Phys. Chem. A .2009, 113, 13036.

(39) Tobey, S. W. J. Chem. Educ. 1958, 35, 514.

(40) Tam, K. Y.; Takacs-Novak, T. Anal. Chim. Acta 2001, 434, 157.

(41) Tam, K. Y.; Hadley, M.; Patterson, W. Talanta 1999, 49, 539.

(42) Khalafi, L.; Rohani, M.; Afkhami, A. J. Chem. Eng. Data 2008, 53, 2389.

(43) Zarei, K.; Atabati, M.; Abdinasab, E. E. J. Anal. Chem. 2009, 4, 314.
(44) Jimenez-Lozano, E.; Marques, I.; Barron, D.; Beltran, J. L.; Barbosa, J. Anal. Chim. Acta. 2002, 464, 37.

(45) Li, X. G.; Zhang, J. H. ; Liu, Z. Q.; Chen, S.; Su, Y. Z.; Xu, C. W. Global J. Phys. Chem. 2011, 2, 34.
(46) Zhang, J. H.; Kong, K. Q.; He, Z. L.; Liu, Z. L. Spectroscopy and Spectral Analysis 2007, 27, 1412. [张建华, 孔凯清, 何争玲, 刘自立. 光谱学与光谱分析, 2007, 27, 1412]
(47) Feng, W. S.; Fang, Y.; Xu, J. X.; Fang, C. H.; Jia, Q. J., Wang, H. H; Jiang, X. M. Acta Phys. -Chim. Sin., 2008, 24, 497. [冯望生, 房艳, 徐继香, 房春晖, 贾全杰, 王焕华, 姜晓明. 物理化学学报, 2008, 24, 497.]
(48) Patterson, G. S. J. Chem. Educ. 1999, 76, 395.

(49) Ehlerova, J.; Trevani, L.; Sedlbauer, J. J. Sol. Chem. 2008, 37, 857.

(50) Mukerjee, P.; Mysels, K. National Standards Reference, Data Series; National Bureau of Standards. US. Government Printing Office: Washington, D.C., U. S., 1971; Vo1. 36, pp 8–71.

[1]	郑东,袁相爱,马晶. 邻位甲基红水溶液的光谱性质随pH值的变化：含时密度泛函理论计算与实验研究[J]. 物理化学学报, 2016, 32(1): 290 -300 .
[2]	武红英, 仲敬荣, 李英秋, 王少飞. 盐酸中Pu(III), Pu(IV), Pu(VI)的制备及紫外-可见吸收光谱[J]. 物理化学学报, 2015, 31(Suppl): 49 -53 .
[3]	何文英, 姚小军, 华英杰, 黄国雷, 吴秀丽, 李小宝, 韩长日, 宋小平. 考拉维酸对人血清白蛋白结构的影响[J]. 物理化学学报, 2014, 30(11): 2142 -2148 .
[4]	李颖若, 张洪涛, 齐传民, 郭雪峰. 新型螺吡喃衍生物: 离子传感和分子水平的信息处理[J]. 物理化学学报, 2012, 28(10): 2471 -2479 .
[5]	王艳艳, 姜艳霞, 沙德礼, 罗德礼, 孙世刚. 电化学和紫外-可见吸收光谱法研究pH和金纳米粒子对细胞色素c的影响[J]. 物理化学学报, 2012, 28(05): 1127 -1133 .
[6]	张晓红, 郭洪瑞, 矫志, 闫伟伟, 阮文娟, 朱志昂. 不对称卟啉体系中的弱相互作用[J]. 物理化学学报, 2011, 27(04): 774 -780 .
[7]	施晶莹;冷文华;程小芳;张鉴清;曹楚南. TiO₂光电化学电池催化氧化甲基红[J]. 物理化学学报, 2005, 21(09): 971 -976 .
[8]	陈婷婷;黄晓华;杜江燕;冯玉英;刘长鹏;邢巍;陆天虹. La^3＋或Eu^3＋与微过氧化物酶-8相互作用强弱的研究[J]. 物理化学学报, 2004, 20(08): 887 -891 .
[9]	吴卫东;张占文;罗江山;唐永建;郑永铭;陆晓明;赵鹏骥. Cu_xC₆₀薄膜紫外-可见吸收光谱研究[J]. 物理化学学报, 2001, 17(01): 83 -86 .
[10]	王融;杨钧;董玺娟;王卉;汤大新;江雷;李铁津;张宝文. 热释电Langmuir-Blodgett膜结构的光谱研究[J]. 物理化学学报, 1993, 9(05): 597 -603 .

紫外-可见吸收光谱结合高斯多峰拟合技术测定甲基红酸离解常数

Determination of Acid Dissociation Constant of Methyl Red by Multi-Peaks Gaussian Fitting Method Based on UV-Visible Absorption Spectrum

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 10

Metrics

推荐阅读 0