International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

Acid Dissociation Constant of N-Alkyl-Bis(Styryl) Pyridinium Bromide Dyes in Surfactant Solutions

S. N. Panda1, P. K. Behera2 and S. B. Seth3
Photochemistry Research Group School of Chemistry, Sambalpur University Jyoti Vihar, Sambalpur, India
1, 2, 3

Abstract: The absorption and emission spectral behavior of synthesized N-alkylbis(styryl) pyridinium bromide dye (1) has been investigated in at pH in aqueous and micellar media. From the results it is found that in ground state the dye is in neutral form whereas in excited state it is in anionic form. Localization of dye in micelle and nature of surfactant plays important role on the dissociation constant. Keywords: Absorption Spectra, Emission Spectra, Dissociation Constant, N-alkylbis(styryl) pyridinium bromide dye.

INTRODUCTION
Dyes exhibiting acid-base behavior act as indicators in in-vitro and in-vivo studies of biological assemblies. The quantification of proton dissociation and association for the molecules has been used in various chemical, analytical, biochemical and pharmaceutical processes. Artificial-organized assemblies such as micelles, reversed micelles, micro emulsions, vesicles etc. have been used extensively to mimic biological systems [1-3]. Extensive work in such microheterogeneous media has led to conclude that the physical and chemical processes differ significantly from the analogous processes in homogenous media. The compartmentalization process of the dyes in the micro heterogeneous media has also been found to have potential applications in the study of acid-base behavior [4-7] and self association [8] of the dyes. Dutta et al. [9] have proposed a model for the indicator-surfactant system in which either the acid or the base form of the indicator predominantly binds to the micelles. In this model, the shift in pKa of an indicator in micellar solutions is calculated from the knowledge of the association constant of the indicator with the micelles at any desired concentration of the surfactant. Moulik et al. [10] have investigated the acid-base equilibrium for a dye neutral red, in AOT micelles and have proposed that the localization site of the dye in the micellar system is the interface. Similarly, Paul and Ismail [11] have proposed the solubilization site of neutral red to be the interfacial region of SDS micro-emulsion and have studied the acid-base equilibria of neutral red in benzene-in oil micro-emulsion. The pKa of the compound was found to be 6.88 and 7.05 in microemulsions with n-propanol and n-butanol as the co-surfactant respectively. Acid dissociation constants of some N-alkyl p/o-hydroxy styryl pyridinium halides have been investigated by Mishra and coworkers [12] using spectrophotometric method. The authors reported that the alkyl chain does not have any substantial effect on the pKa values in aqueous and cationic surfactant (cetyl trimethylammonium bromide: CTAB) system. However, with longer 1
Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

alkyl chain the pKa values increase in anionic surfactant (sodium laural sulphate: NaLS). These results have been attributed to the variation in solubilization sites of the surfactants. Paraffin substituted cyanine dyes consisting of rigid molecular frame work with flexible non-absorbing aliphatic chain such as n-alkyl styryl pyridinium dyes have been of potential use to study the structure and polymer solution. Keeping this in view N-alkyl-bis(styryl) pyridinium bromide (1) has been synthesized and their absorption and emission spectral behavior have been investigated in at pH in aqueous and micellar media.

(1)

MATERIALS AND METHODS

The dibromoalkane (Sisco-chem) and p-hydroxy benzaldehyde (Polaska OdezynaikChem) were used without purification. -Picoline (Qualigen) was distilled just before used. Methanol was of spectroscopic grade and was used after distillation. Cetyl trimethylammonium bromide: CTAB (Merck India) was crystallize twice from methanol, sodium laural sulphate: NaLS (Merck India) was crystallize twice from absolute ethanol and Tritonix-100 (Spectrochem) was used without further purification. Millipore water was used throughout the experiment. Nalkyl-bis(styryl) pyridinium bromide (1) have been synthesized by the procedure as reported earlier [13]. In the analytical solution the volume of methanol was maintained at 2% v/v and the concentration of the dye was maintained at 210-5 M by mixing with water and various concentrations of surfactant solutions. The concentration of the surfactants were varied between 0.001-0.013 M for NaLS, 0.0001-0.0013 M for CTAB and 0.1-1.1 vol% for TX -100 in the experimental solution. The pH was maintained at 7-13 with buffers prepared from citric acid, boric acid, phosphoric acid, sodium hydroxide and hydrochloric acid in different compositions. An Elico LI-120 digital pH meter was used for pH measurements. Absorption and emission spectra were recorded in Shimadiu-2450 UV-Visible spectrophotometer and Hitachi F-7000 spectrofluorophotometer maintaining temperature at 3000.5 K by using INSREF Ultracryostat. The pK values of ground state and excited state have been determined by using Henderson equation [14] and Forster cycle method [15] from the absorbance and fluorescence values of the substrate at varied pH.

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Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

RESULT AND DISCUSSION

The dye (I) under investigation has bis-styryl pyridinium chromophoric group containing delocalized positive charges and hydroxyl groups in both the ends. The dye is as such insoluble in water suggesting overall hydrobhobic characteristics and thus was made soluble in 2% methanol aqueous medium. The absorption and emission spectrum of the dye (I) in various concentrations of NaLS (anionic) CTAB(cationic) and TX-100 (neutral) have been analysed. 1.1. Absorption Spectra

Absorption spectra of the dye (I) in NaLS, CTAB and TX-100 micelles are shown in fig 1. The absorption maxima and optical density of the dye (I) in various concentrations of NaLS, CTAB and TX-100 are reported in tables 1.

Fig. 1: Absorption spectra of dye (I) in NaLS, CTAB, TX-100 micelle at 27 OC. Table 1: Absorption maxima (max) and optical density (OD) of dye (I) in NaLS, CTAB and TX-100 surfactants at 27 0C. [NaLS] in M 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.010 0.011 0.012 0.013 abs in nm 409 410 412 413 413 414 415 415 415 416 416 416 416 OD 0.377 0.379 0.384 0.385 0.385 0.386 0.389 0.395 0.398 0.401 0.406 0.409 0.411 [CTAB] in M 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006 0.0007 0.0008 0.0009 0.0010 0.0011 0.0012 0.0013 abs in nm 396 396 396 396 396 396 397 397 397 397 397 397 397 3
Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India

OD 0.394 0.395 0.400 0.405 0.406 0.407 0.411 0.432 0.435 0.450 0.462 0.465 0.394

[TX-100] in v/v % 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1

abs in nm 409 410 412 413 413 414 415 415 415 416 416

OD 0.377 0.379 0.384 0.385 0.385 0.386 0.389 0.395 0.398 0.401 0.406

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

It can be seen from the table, in case of CTAB and TX-100 surfactant dye (I) absorbs in the range of 396-398 nm. Increase of surfactant concentration (for both CTAB and TX-100) has got no effect in the abs except enhancement of optical density. But in case of NaLS surfactant it absorbs in the region of 409 nm. As the surfactant concentration of NaLS increases abs also increases and it remains constant at 416 nm. No other peak is also observed at higher wavelength. This infers that in case of CTAB and TX-100 the environment is aqueous like (abs of dye (I) in 2% methanol solution is 396). But the localization site of the dye (I) in NaLS differs from CTAB and TX-100. This is due to the nature of surfactant and dye interactions. Dye (I) is cationic in nature where as NaLS, CTAB and TX-100 are respectively anionic, cationic and neutral in nature. In case of NaLS surfactant there will be columbic attraction between the dye and surfactant. With increase in surfactant concentration, attraction force also increases and dye enters into the micelle. Once it binds with micelle, increase of surfactant concentration has no effect on abs value. In case of CTAB due to columbic repulsion, dye (I) remains in aqueous phase of the micelle. 1.2. Emission Spectra

The emission maxima and intensity of the dye (I) in aqueous medium and various concentrations of NaLS CTAB, TX-100 are given in the table 2. Table 2: Emission maxima (em) and fluorescence intensity (FI) of dye (I) in NaLS, CTAB and TX-100 surfactants at 27 0C. [NaLS] in M 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008 0.009 0.010 0.011 0.012 0.013 em in nm 531 532 532 533 533 534 534 533 536 536 535 535 536 FI 221.88 231.72 256.7 250.7 258.17 255.3 252.6 257.14 260.89 263.22 264.89 262.45 271.18 [CTAB] in M 0.0001 0.0002 0.0003 0.0004 0.0005 0.0006 0.0007 0.0008 0.0009 0.0010 0.0011 0.0012 0.0013 em in nm 531 531 531 531 531 531 531 531 531 531 531 531 531 FI 81.52 81.57 81.31 83.81 84.45 81.12 84.22 85.91 92.51 95.37 89.66 95.93 81.52 [TX-100] in v/v % 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 em in nm 531 531 532 531 531 531 532 534 534 533 534 FI 78.78 87.74 89.66 92.11 115.39 115.39 103.52 109.66 111.29 115.39 131.77

It can be seen from the table that dye (I) emits at 531 nm in aqueous medium whereas in various concentration of surfactant solutions the dye emits in the range of 531-536 nm. It implies that in excited state the environment of the dye in all the three surfactants used are almost similar in nature. This explained that in the excited state, dye (I) remains in the anion form (Scheme-1) 4
Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

only in the entire medium (aqueous medium and various concentrations of NaLS CTAB and TX100 surfactants). Scheme-1

*
N+ 2Br
-

N+ OH

2Br

O-

N+ OH

N+ O-

Neutral Form

Anionic Form

As only one emission peak due to anionic form of the dye is observed. The anionic form of the dye remains in the aqueous layer of the micelle so em value does not change appreciably. From the table 2, it can be seen that as the surfactant concentration increases, the intensity value increases. However, the trend of intensity in various surfactant is found to be INaLS > ITX-100 = ICTAB. Fluorescence intensity is directly proportional to the rate of fluorescence (kf) and inversely proportional to the rate of internal conversion (kIC). In the rigid system rate of fluorescence increases whereas rate of internal conversion decreases. In surfactant solution as the surfactant concentration increases the rigidity of the medium increases and in consequence emission intensity of the dye increases. The order of emission intensity in the various surfactant solutions can be explained via dye-surfactant interaction due to columbic force. 1.3. Dissociation constant (pK) of the Dye in ground state

Absorption spectra of the dye (I) investigated in various pH in aqueous medium. Another peak at 485 nm is appeared at higher pH. The peak height increases as the pH value increases. The peak at higher wavelength is due to anion form of the dye (Scheme-2). Scheme-2

The effect of pH on the absorption spectra of Dye (I) in NaLS (110 -2 M ), CTAB (110 -3 M ) and TX-100 (0.6% v/v) micelles have been studied. Anion peak of dye (I) appeared at 10.34 pH in aqueous medium, CTAB and TX-100 micelles whereas for NaLS micelle it appears 5
Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

at 11.3 pH. The dissociation constant (pK) of the dye in all the mediums are calculated by using Henderson equation (eq. 1).

pK pH x log

ODb OD x OD x ODa

(1)

where, ODx=Absorbance at any pH, ODa=Absorbance of strongly acid solution and ODb=Absorbance in strongly alkaline solution of the dye (I). The pK values calculated using eq. 1 are given in table 3. Table 3: Ground state pK and excited state pK* of dye (I) in aqueous medium as well as in NaLS (110 -2 M ), CTAB (110 -3 M ) and TX-100 (0.6% v/v) micelles at 27 0C. Sl. No 1 2 3 4 Medium Water NaLS CTAB TX-100 pK 10.36 11.60 10.20 10.43 pK* 0.70 3.2 0.60 0.98

From the table 3 it can be seen that the pK values are in the trend NaLS > TX-100 > CTAB water. The effect of the pH can be explained as follows; (a) The cationic dye is localized close to the anionic surface of the NaLS micelle due to electrostatic attraction. The OH- at alkaline pH is repelled by the anionic surface and a high pH is necessary to interact with the dye to enable it to dissociate. (b) In case of CTAB micelle, the pK value is found to be less than the aqueous medium and neutral micelle. The OH- at alkaline pH is attracted by the cationic surface and a low pH is necessary to interact with the dye to enable it to dissociate. (c) But in case of TX-100 micelle, the pK value is in between CTAB and NaLS micelles. Here the OH- has no significant effect, as the surface is neutral. Thus the charge at the interface is found to have major role on the dissociation of the dye. 1.4. Dissociation Constant (pK*) of the Dye in Excited State

Emission spectra of the dye (I) in various pH in aqueous medium as well as NaLS, CTAB and TX-100 micelle is recorded. In the excited state only anionic form of the dye (I) is observed in neutral pH as well as in alkaline pH. The fluorescence intensity increases as the pH increases and at pH > 10.3 it starts decreasing sharply and becomes negligible in higher pH. This may be due to the formation of mero-cyanine in the excited state at higher pH (Scheme-3).

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Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

Scheme-3

The dissociation constant of the dye (I) in the excited state is calculated using Forstercycle method [15].

pK pK *

hc 2.303RT

(2)

where is the difference in electronic transition frequencies in cm-1 of the two species. The excited dissociation constants of the dye in all the media are calculated and are reported in table 3. The trends of excited state dissociation constant (pK*) and ground state dissociation constant (pK) values in different media have the similar trend except the pK* values are less. In excited state the dye dissociates in acidic pH. This is due to decrease of electron density around oxygen atom in the excited state. So the release of H+ ion is faster in the excited state. Similar results have been obtained for 1- and 2- naphthol [16, 17]. 1- and 2-naphthol (1-and 2- ROH) are extremely weak acids in their ground electronic states (pK =9.39 and 9.63) and in the excited state their pK*a being 0.4 and 2.78 respectively.

REFERENCES
[1]. W. Konche and R. Schomacker, Reactions in Compartmentalized Liquids; Springer Verlag, Berlin (1988). [2]. E.W. Jones and D.M. Bloor, Structure Dynamics and Equlibrium Properties of Colloidal Systems, Kluwer, Doedrech (1990), pp 324. [3]. Kitahara, Adv. Colloid Interface Sci., 12 (1980) 109. [4]. R.C. Vieira and O.A.E. Seoud, J. Colloid Interface Sci., 141 (1991) 295. [5]. Oldfield, B.N. Robinson and R.B. Freeman, J. Chem. Soc. Faraday Trans., 86 (1990) 833. [6]. O.A. Amire, J. Colloid Interface Sci., 126 (1988) 508. [7]. A.M. Chinelatto, L.T. Okano and O.A.E. Seoud, Colliod Polym. Sci., 269 (1991) 264. [8]. O. Ortona, V. Vitagliano and B.H. Robinson, J. Colloid Interface Sci., 125 (1988) 271. [9]. R.K. Dutta, R Chowdhury and S.N. Bhat, J. Chem. Soc. Faraday Trans., 91 (1995) 681. [10]. S.P. Moulik, B.K. Paul and D.C Mukherjee, J Colloid Interface Sci., 161 (1993) 72. [11]. B.C. Paul and K. Ismail, Indian J Chem, 38A (1999) 496. 7
Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India

International Journal of Creative Mathematical Sciences & Technology (IJCMST) 1(1): 1-8, 2012

ISSN (P): 2319 7811, ISSN (O): 2319 782X

[12]. B K Mishra, P.K. Behera and R Rath, Indian J Chem, 40A (2001) 155. [13]. J K Mishra, P.K. Behera, S K Parida and B.K Mishra, Indian J Chem, 31B (1992) 118. [14]. A. Albert and E P Serjent, The determination of ionization constants, Chapmann and Hall, London, (1984) pp70. [15]. K K Rohatgi-Mukharjee, Fundamental of Photochemistry, New Age India, (1996) pp 106. [16]. A.M. Harris and B.K. Selinger, J. Phys. Chem., 84 (1980) 891. [17]. D.W. Ellis, J. Chem. Educ., 43 (1966) 259.

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Corresponding Author: S. N. Panda, Photochemistry Research Group, Sambalpur University, Jyoti Vihar, Burla, Odisha, India