Determination of Acid Dissociation Const
Determination of Acid Dissociation Const
Determination of Acid Dissociation Const
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
Abstract: UV-visible electronic absorption spectra of methyl red (MR) aqueous solutions are characterized
by the overlap of a principal peak at λmax ((520±15) nm) with a shoulder peak at λmax ((435±20) nm), which
are assigned to acidic species (HMR) and basic species 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 cMR-/cHMR, the average acid dissociation constant (pKa) 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 pKa were also investigated via this method. The multi-peaks
Gaussian fitting method was shown to determine pKa 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
Received: December 22, 2011; Revised: March 1, 2012; Published on Web: March 2, 2012.
∗
Corresponding author. Email: [email protected]; Tel: +86-20-39366908.
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).
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
Ⓒ Editorial office of Acta Physico-Chimica Sinica
No.5 ZHANG Jian-Hua et al.: Determination of pKa of Methyl Red by Multi-Peaks Gaussian Fitting Method 1031
fitting procedure on certain spectra and gave the line-shape Table 1 Results of the multi-peaks Gaussian fitting method on
parameters of the UV-visible spectra in the result window. the spectra of methyl red solution at different
pH values and 298.15 K
pH A1 A2 λmax1/nm λmax2/nm w1/nm w2/nm Height1 Height2 R2
3 Results and discussion
4.63 28.80 76.43 456.5 532.0 122.0 66.3 0.30 0.85 0.997
3.1 Principle of multi-peaks Gaussian fitting method 4.93 46.01 43.12 448.9 535.1 120.5 63.1 0.38 0.59 0.998
Ionization equilibrium of methyl red in aqueous solution is 5.39 52.40 21.81 445.5 541.8 124.7 46.2 0.46 0.27 0.996
given as the following equation 5.68 55.83 11.81 436.5 546.9 114.0 46.2 0.49 0.15 0.997
HMR⇌MR-+H+ (1) Height1 and Height2 are the heights of absorbance peaks for MR- and HMR.
red yellow
The pH value range of color change of methyl red in aqueous gives the λmax1, λmax2, w1, w2, A1, A2 and these data are listed in
solution is well known as 4.4-6.2. When pH values are 4.63, Table 1.
4.93, 5.39, 5.68, the UV-visible absorption spectra and their 3.2 Relationship between pKa and the relative
multi- peaks Gaussian fitting results are shown in Fig.1. It is integrated absorbance
shown that integrated absorbance A1 of base MR- peaks increas- Acid dissociation constant of methyl red is given as follow-
es and integrated absorbance A2 of acid HMR peaks decreases ing equation
[H+][MR -]
[HMR]
with the increase of pH value. The increase and decrease of the Ka = (3)
integrated absorbance of the MR- and HMR are objectively
[MR -]
thus pKa = pH - lg
[HMR]
due to the change of the relative concentrations of MR- and (4)
HMR.
A1 ε1[MR -]
A 2 ε 2[HMR]
Existence simultaneously of HMR and MR- in methyl red
where = (5)
solution results in spectra with two peaks at a certain pH value.
[MR -] ε 2 A1
[HMR] ε1 A 2
Multi-peaks Gaussian fitting on the spectra with two peaks sat-
= (6)
isfies following equation
exp(-2((x - λ max1)/w1)2) + where, ε1 and ε2 are the molar absorption coefficients of MR-
A1
y = y0 +
w1 π 2 and HMR, respectively. Then, the methyl red absorption spec-
exp( - 2((x - λ max2)/w 2)2)
A2 tra (Fig.2) were measured in base (pH=9) and acid (pH=2) con-
(2)
w2 π 2 ditions respectively.
where, y0 is baseline, λmax1 and λmax2 are the maximum absorption When the value of pH is 9, there is only MR- in methyl red
wavelengths, w1 and w2 are half peak widths, A1 and A2 are the solution and the [MR-]=C, then
integrated absorbances of the two peaks for MR- and HMR. A1=ε1[MR-]=ε1C (7)
Multi-peaks Gaussian fitting method based on the spectra When the value of pH is 2, there is only HMR in methyl red so-
Fig.1 UV-visible absorption spectra of methyl red at different pH values and their multi-peaks Gaussian fitting results
experiment, fitting, MR-, HMR
No.5 ZHANG Jian-Hua et al.: Determination of pKa of Methyl Red by Multi-Peaks Gaussian Fitting Method 1033
Fig.3 Relationship between lgKa and 1/T 0.018 28.12 10.01 449.5 537.9 120.0 58.1
Fig.5 Relationships between pKa of methyl red and the SDS Fig.6 Dependence of the maximum absorption wavelengths of
concentration at different temperatures MR- and HMR on the concentration of SDS at 298.15 K
No.5 ZHANG Jian-Hua et al.: Determination of pKa of Methyl Red by Multi-Peaks Gaussian Fitting Method 1035
Table 4 Spectrum line-shape parameters and effect of aggregation behavior of CTAB on pKa of methyl red with different concentra
CCTAB/(mol·L-1) No. A1/A2 lg(A1/A2) pH pKa Average of pKa
0.0001 1 0.45 -0.35 4.62 4.71 4.67
2 0.94 -0.03 4.88 4.65
3 2.81 0.45 5.38 4.67
4 5.30 0.74 5.67 4.67
0.001 1 8.83 0.94 4.61 3.41 3.32
2 25.10 1.40 4.89 3.23
3 absorption peak of MR- 5.37 - -
4 absorption peak of MR- 5.66 - -
4 Conclusions
In this study, a multi-peaks Gaussian fitting method based
on the UV-visible absorption spectra is firstly used to deter-
mine the pKa value of organic dyes such as methyl red. The reli-
ability of the method is adequately proved by an excellent
agreement of the measurement results with literature. There are
several advantages, such as the easy operational procedure, ex-
plicit physical meaning, and the accurate measurement results
for the method.
The relative concentration of the MR- and HMR in solution
has been determined by the relative integrated absorbance cal-
culated from multi-peaks Gaussian fitting method based on the
UV-visible spectra. This method avoids successfully the sys-
tematic error of 3%-5% of pKa measurement from the stan-
dard curves which is established from the absorbance of MR-
maximum absorption wavelength at 425 nm and HMR maxi-
Fig.7 Dependence of the half-widths of MR- and HMR on the mum absorption wavelength at 520 nm versus concentration of
concentration of SDS at 298.15 K MR- and HMR at the methyl red color range, respectively.
1036 Acta Phys. -Chim. Sin. 2012 Vol.28
Moreover, the effect of SDS and CTAB on ionization equilibri- 化学学报, 2000, 16, 351.]
um of methyl red also has been studied and some reliable re- (22) Kolthoff, I. M.; Chantooni, M. K. J. Phys. Chem. 1966, 70, 856.
sults with the method have been obtained. The spectral line- (23) Nag, S.; Datta, D. Indian J. Chem. 2007, 46A, 1263.
shape parameters such as A1, A2, λmax1, λmax2, w1 and w2 of MR- (24) Wan, H.; Holmen, A. G.; Wang, Y.; Lindberg, W.; Englund, M.;
and HMR that obtained from multi-peaks Gaussian fitting Nagard, M. B.; Thompson, R. A. Rapid Commun. Mass Sp.
method on the UV-visible spectra of SDS-methyl red and 2003, 17, 2639.
CTAB-methyl red solutions have been firstly discovered to be (25) Szakacs, Z.; Hagele, G. Talanta 2004, 62, 819.
sensitive to aggregation behavior of surfactants SDS and (26) Rabenstein, D. L.; Hari, S. P.; Kaerner, A. Anal. Chem. 1997, 69,
CTAB. The CMC values can be determined by the dependence 4310.
of the three sets of parameters on the surfactant concentration (27) Rabenstein, D. L.; Sayer, T. L. Anal. Chem. 1976, 48, 1141.
which should support each other.
(28) Wang, J.; Rabenstein, D. L. Anal. Chem. 2007, 79, 6799.
(29) Oumada, F. Z.; Rafols, C.; Roses, M.; Bosch, E. J. Pharm. Sci.
References
2002, 91, 991.
(1) Kara, D.; Alkan, M. Spectrochim. Acta A 2000, 56, 2753.
(30) Lebrón-Paler, A.; Pemberton, J. E. Anal. Chem. 2006, 78, 7649.
(2) Niyazi, A.; Yazdanipour, A.; Ramezani, M. Chin. Chem. Lett.
(31) Lachenwitzer, A.; Li, N.; Lipkowski, J. J. Electroanal. Chem.
2007, 18, 989.
2002, 532, 85.
(3) Babić, S.; Horvat, A. J. M.; Pavlović, D. M.; Kaštelan-Macan,
(32) Edwards, H. G. M. Spectrochim. Acta A 1989, 45, 715.
M. Trends Anal. Chem. 2007, 26, 1043.
(33) Cagigal, E.; Gonzalez, L.; Alonso, R. M.; Jimenez, R. M.
(4) Allen, R. I.; Box, K. J.; Comer, J. E. A.; Peake, C.; Tam, K.Y.
J. Pharmaceut. Biomed. Anal. 2001, 26, 477.
J. Pharmaceut. Biomed. Anal. 1998, 17, 699.
(34) Ferrari, V.; Cutler, D. J. J. Pharmaceut. Sci. 1987, 76, 554.
(5) Beltran, J. L.; Sanli, N.; Fonrodona, G.; Barron, D.; Ozkanb, G.;
(35) Cessna, A. J.; Grover, R. J. Agric. Food Chem. 1978, 26, 289.
Barbosa, J. Anal. Chim. Acta 2003, 484, 253.
(36) Foulon, C.; Duhal, N.; Lacroix-Callens, B.; Vaccher, C.; Bonte,
(6) Erdemgil, F. Z.; Sanli, S.; Sanli, N.; Ozkan, G.; Barbosa, J.;
J. P.; Goossens, J. F. Eur. J. Pharm. Sci. 2007, 31, 165.
Guiteras, J.; Beltran, J. L. Talanta 2007, 72, 489.
(37) Barbosa, J.; Barron, D.; Jimenez-Lozano, E.; Sanz-Nebot, V.
(7) Tang, R. C.; Tang, H.; Yang, C. Ind. Eng. Chem. Res. 2010, 49,
Anal. Chim. Acta 2001, 437, 309.
8894.
(38) Jang, Y. H.; Hwang, S. G.; Chang, S. B.; Ku, J.; Chung, D. S.
(8) Simon, E. W.; Beevers, H. New Phytol. 1952, 51, 163.
J. Phys. Chem. A 2009, 113, 13036.
(9) Adam, R. S., Jr. Res. Rev. 1973, 47, 1.
(39) Tobey, S. W. J. Chem. Educ. 1958, 35, 514.
(10) Weber, J. B. Adv. Chem. Ser. 1972, 111, 55.
(40) Tam, K. Y.; Takacs-Novak, T. Anal. Chim. Acta 2001, 434, 157.
(11) Halling-Sørensen, B.; Nielsen, S. N.; Lanzky, P. F.; Ingerslev, F.;
(41) Tam, K. Y.; Hadley, M.; Patterson, W. Talanta 1999, 49, 539.
Lutzhoft, H. C. H.; Jørgensen, S. E. Chemosphere 1998, 36,
(42) Khalafi, L.; Rohani, M.; Afkhami, A. J. Chem. Eng. Data 2008,
357.
53, 2389.
(12) Burns, D. C.; Ellis, D. A.; Li, H. X.; McMurdo, C. J.; Webster,
(43) Zarei, K.; Atabati, M.; Abdinasab, E. E. J. Anal. Chem. 2009, 4,
E. Environ. Sci. Technol. 2008, 42, 9283.
314.
(13) Lin, J. H.; Lu, A. Y. Pharmacol. Rev. 1997, 49, 403.
(44) Jimenez-Lozano, E.; Marques, I.; Barron, D.; Beltran, J. L.;
(14) Frey, P. A.; Kokesh, F. O.; Westheimer, F. H. J. Am. Chem. Soc.
Barbosa, J. Anal. Chim. Acta 2002, 464, 37.
1971, 93, 7266.
(45) Li, X. G.; Zhang, J. H.; Liu, Z. Q.; Chen, S.; Su, Y. Z.; Xu, C.
(15) Poole, S. K.; Patel, S.; Dehring, K.; Workman, H.; Poole, C. F.
W. Global J. Phys. Chem. 2011, 2, 34.
J. Chromatogr. A 2004, 1037, 445.
(46) Zhang, J. H.; Kong, K. Q.; He, Z. L.; Liu, Z. L. Spectroscopy
(16) Hardcastle, J. E.; Jano, I. J. Chromatogr. B 1998, 717, 39.
and Spectral Analysis 2007, 27, 1412. [张建华, 孔凯清, 何争
(17) Ye, L.; Zhu, Q. Q.; Wu, S. K. Acta Phys. -Chim. Sin. 1987, 3,
玲, 刘自立. 光谱学与光谱分析, 2007, 27, 1412.]
272. [叶 玲, 朱琴琴, 吴世康. 物理化学学报, 1987, 3, 272.]
(47) Feng, W. S.; Fang, Y.; Xu, J. X.; Fang, C. H.; Jia, Q. J.; Wang,
(18) Qiang, Z.; Adams, C. Water Res. 2004, 38, 2874.
H. H.; Jiang, X. M. Acta Phys. -Chim. Sin. 2008, 24, 497. [冯
(19) Zhang, W. M.; Yang, Z. D.; Liu, J.; Sun, Z. X. Acta Phys. -Chim.
望生, 房 艳, 徐继香, 房春晖, 贾全杰, 王焕华, 姜晓明. 物理
Sin. 2010, 26, 2109. [张卫民, 杨振东, 刘 嘉, 孙中溪. 物理
化学学报, 2008, 24, 497.]
化学学报, 2010, 26, 2109.]
(48) Patterson, G. S. J. Chem. Educ. 1999, 76, 395.
(20) Li, L. F.; Hou, W. G.; Jiao, Y. N.; Liu, C. X. Acta Phys. -Chim.
(49) Ehlerova, J.; Trevani, L.; Sedlbauer, J. J. Sol. Chem. 2008, 37,
Sin., 2004, 20, 459. [李丽芳, 侯万国, 焦燕妮, 刘春霞. 物理
857.
化学学报, 2004, 20, 459.]
(50) Mukerjee, P.; Mysels, K. National Standards Reference, Data
(21) Zhang, X. D.; Liu, Y.; Sun, J. Y.; Liu, Q. T. Acta Phys. -Chim.
Series; National Bureau of Standards. US. Government Printing
Sin. 2000, 16, 351. [张向东, 刘 岩, 孙锦玉, 刘祁涛. 物理
Office: Washington, D.C., U. S., 1971; Vo1. 36, pp 8-71.