Clouding and hydrodynamic behaviour of Triton X-100 in aqueous media in the presence of linear and cyclic glycols, their oligomers and ethers

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1 Indian Jurnal f Chemistry Vl. 54A, March 2015, pp Cluding and hydrdynamic behaviur f Tritn X-100 in aqueus media in the presence f linear and cyclic glycls, their ligmers and ethers Urja Patel, P Parekh* & P Bahadur a Department f Chemistry, Veer Narmad Suth Gujarat University, Surat , India paresh7884@gmail.cm Received 11 Nvember 2014; revised and accepted 27 February 2015 The effects f varius linear glycl ethers and cyclic ethers n clud pint and hydrdynamic diameter f aqueus micellar slutin f a nninic surfactant Tritn X-100 (TX-100) has been studied spectrphtmetrically. Fr shrt chain glycls (EG, DEG, PG, DPG) and their ligmers, and, mnalkyl ethers, increase in the clud pint with crrespnding decrease in micelle size is bserved, while the ppsite trend is bserved fr their higher hmlgues. The effect f shrt chain glycls n CP/D h is discussed in terms f their slubility in slutin, micelles hydratin and csurfactant/ cslvent f TX-100 micellar system. These effects are strngly dependent n additive cncentratin. Fr lnger chain glycls r mre hydrphbic glycls, the effects can be explained in terms f their partitining in the micellar regin and changes in size and shape f the micelles. A different apprach fr nrmalising the clud pints t their relative values has been made fr a better insight n effect f these glycl ethers. The thermdynamic parameters fr the mixture are als calculated as a functin f glycl ether cncentratins. Keywrds: Surfactants, Nninic surfactants, Thermdynamics parameters, Clud pint, Dynamic light scattering, Glycl ethers Plyethylene cndensates cnstitute an imprtant family f nninic surfactants. Tritn X-100 is ne f the mst extensively studied nninic surfactant fr its aqueus slutin behavir 1,2. Tritn X-100 (p-tert-ctylphenxy plyethylene (9.5) ether) belngs t the alkyl aryl type nninic surfactant. Micrstructures f TX-100 in nn-aqueus media that find applicatins in nanparticle synthesis has als been studied 3,4. It shws excellent detergency and find variety f applicatins in textiles and agrchemicals industries. TX-100 have widespread industrial applicatins as well as in detergent frmulatins. Tritn X-100 is used in extractin f bimlecules like prteins and amin acids 5,6 and hazardus materials 7-9. Glycls and their ligmers are lwer-mlecular weight ethers and alchls having favrable slvent prperties and higher biling pint. Mnalkyl ethers f ethylene glycl (cellslve) and dialkylethers f ethylene glycl (carbitls) and thse f prpyleneglycl/diprpylene glycl are used as slvents and as an ingredient in cleaning frmulatins, csmetics, inks/paints/varnishes, hydraulic fluids, etc Dialkyl ethers/diesters/alkyl esters f glycls are useful slvents/cleaners/diluents/levelling agent 12. Surface active agents in water frm nrmal micelles as a result f hydrphbic interactins. The surfactant self-assembly is greatly influenced by the presence f inrganic salts and rganic additives. The effect f salts n micellizatin and micellar characteristics fr nninic surfactants has been extensively examined Different types f rganic additives/plar slvents like water miscible alchls, amines, amides, ketnes, glycls and their ethers have als been examined fr their effect n the micellar behavir f aqueus nninic surfactant slutins Glycls and their ethers are capable f frming hydrgen bnds. They have mderate chesive energy and a fairly high dielectric cnstant. There are sme reprts n the effect f glycls 19,20, its ligmers and ethers 21,22 n nninic surfactant slutins. Ruiz et al. 19 bserved that the CMC and clud pint (CP) f TX-100 increase in the water-glycl mixture that leads t decrease in size and aggregatin number. This behavir is cntrlled by tw factrs, namely, the structure-breaking ability f EG and the interactin f the cslvent with the ply- (xyethylene) grups f the surfactant. Cantu et al. 23 ascribed a decrease in hydrdynamic radius and aggregatin number f mnddecyl ctaethylene

2 346 INDIAN J CHEM, SEC A, MARCH 2015 glycl micelles in water t the additin f glycerl. Hwever, Penfld et al. 24, frm small-angle neutrn scattering (SANS) f nninic surfactants, bserved an increase in micellar size in water cntaining ethylene glycl, srbitl and glycerl. The interactin between water and additives decreases the hydratin f the plar head grups which results in a reductin f the curvature f the aggregate. Hwever, there is a scarcity f a systematic study n the effect f linear and cyclic glycls and their ethers and n cluding and hydrdynamic behaviur f TX-100 micelles. Herein we had studied the effect f glycl ethers by the nrmalizatin f clud pint fr cmparisn f different glycls and their ethers n clud pint f TX-100. The thermdynamic data f these mixtures are calculated at different glycls cncentratins. Materials and Methds TX-100, ethylene glycl (EG), diethylene glycl (DEG), prpylene glycl (PG), ethylene glycl mnbutyl ether (EGMBE), ethylene glycl is-prpyl ether (EGiPE), ethylene glycl phenyl ether (EGPhE), diethylene glycl mnbutyl ether (DEGMBE), prpylene glycl mnbutyl ether (PGMBE) and diprpylene glycl mnbutyl ether (DPGMBE) and crwn ethers were purchased frm Sigma-Aldrich C. Ltd., diprpylene glycl (DPG) was purchased frm Alfa Aesar C. Ltd., ethylene glycl mnethyl ether (EGMEE) and ethylene glycl mnmethyl ether (EGMME) were purchased frm Lancaster C. Ltd., ethylene glycl mnhexyl ether (EGMHE) was purchased frm Dw Chemical C. Ltd. Deinized water frm a Millipre Milli-Q system was used t prepare slutin fr clud pint and DLS measurements. A Shimadzu (mdel UV-2450) spectrphtmeter including Peltier system (Therm Fishcher) was used t recrd UV-visible spectra t determine clud pint at different temperatures 25. The Peltier system was used t heat the cell hlder f the spectrphtmeter. The ultravilet spectrum f 5% (w/v) TX-100+2% EGPhE at different temperatures is shwn in Fig. 1. It is bvius frm the figure that the absrbance values at C ver the range f nm wavelength are apprximately same. When the temperature was increased by 0.1 C (at 38 C), the absrbance values at ( ) nm and 250 nm interval wavelength significantly increased. This temperature was taken as the CP value f the TX % EGPhE slutin. All clud pints given are the average f tw measurements (the values f CPs were reprducible within ±0.1 C). Dynamic light scattering (DLS) measurements were made at 30 C using a Zetasizer 4800 system (Malvern Instruments, UK) which prvided average diffusin cefficients. The hydrdynamic size was btained by the methd f cumulants. Results and Discussin Clud pint Clud pint gives an idea abut the phase separatin temperature and indicates the wrkable range f given nn-inic surfactants. It is a characteristics f nn-inic surfactant 26. The absrbance spectra f 5% TX-100 in 2% EGPhE is shwn in Fig. 1. A different apprach was used fr simplificatin f clud pints. We have cnverted all the clud pints in their relative frm by dividing the bserved CP by CP f the surfactant withut additives. A clear effect f all the additives is seen which allws us t cmpare the different behaviur f different additives 27. Relative CP = CP Ci /CP C...(1) Here CP C = clud pint with zer cncentratin f additive in the surfactant slutin and CP Ci = clud pint with a particular cncentratin f additive in the surfactant slutin. Additin f glycls has a prminent effect n the CP f TX-100 (Fig. 2) (CP f TX-100 is 65 C) 28. The effect f these glycls are explained by cnsidering Fig. 1 The absrbance spectra f 5% TX-100 in 2% EGPhE at different temperature.

3 PATEL et al.: CLOUDING BEHAVIOUR OF TX-100 IN PRESENCE OF LINEAR AND CYCLIC GLYCOLS 347 Fig. 2 The cluding behaviur f 5% TX-100 as a functin f (a) glycls, (b) crwn ethers, (c) butyl ether f glycls and (d) glycl ethers. their influence n the structure f water. All these glycls have tw terminal hydrxyl grups which frm hydrgen bnd with water mlecule and reduce the dielectric cnstant f water. This makes water a better slvent fr bth parts f the surfactant. The DEG and DPG increases CP mre rapidly than EG and PG because f ne extra ethereal xygen atm which als cntributes t the hydrgen bnding with water. The relative CP values f TX-100 are shwn in Table 1. EG is knwn t be a water structure breaker 29,30 ; it alters the slvent prperty by frming hydrgen bnd with water mlecules. The presence f EG and shrt chain alkxy ethers (EGMME, EGMEE, EGiPE) reduce the dielectric cnstant f water and behaves as a better slvent fr TX-100, which is reflected in the increase in its CP. The EG has tw terminal hydrxyl grups; ne r bth can be etherified giving alkyl ethers. EGMME, EGMEE, EGiPE, EGMHE and EGPhE have different alkxy grups at ne terminal. As the chain length f alkxy grup increases, the hydrphbicity als increases. The EGMME, EGMEE, EGiPE with smaller alkxy grup shwed much mre prnunced effect n the CP than EG (shwn in Fig. 2(d)). This may be because EG behaves as a gd slvent fr the hydrphilic part f TX-100. Hwever, as the alkxy chain length increases, the ther ethers may behave as a gd slvent fr bth parts f TX-100, leading t increase in the CP. The hydrphbic alkxy grup cntaining glycl ethers (EGMHE and EGPhE) may act as shrt chain amphiphiles. These ethers may frm mixed micelles as they are able t penetrate deeper in the micelles and increase the aggregatin number with verall decrease in CP f TX-100. The effect f butyl ether f EG, DEG, PG and DPG n CP f TX-100 are presented in Fig. 2(c). DEGMBE is mre efficient in increasing/decreasing CP f TX-100 than the ther mnbutyl ethers. The

4 348 INDIAN J CHEM, SEC A, MARCH 2015 Table 1 Relative clud pint values f 5% TX-100 as a functin f linear and cyclic glycls ethers Cnc. f Relative clud pint additives EG DEG PG DPG 12 crwn 4 15 crwn 5 18 crwn 6 Dicyclhexan- (v/v) (%) 18-crwn EGMME EGMEE EGiPE EGMHE EGMPhE EGMBE DEGMBE PGMBE DPGMBE EGMBE has a nminal effect n CP f TX-100 and remains almst unaltered in the cncentratin range studied. The increase in CP in the presence f DEGMBE is due t the presence f additinal EO grup as cmpared t EGMBE. PGMBE and DPGMBE may get slubilized in the micellar crna regin and increase the hydrphbic envirnment t favur the micellizatin f TX-100. The effect f crwn ether r cyclic ethers n CP f TX-100 is als shwn in Fig. 2(b). It may be bserved that all the crwn ethers increase the CP except dicyclhexan-18-crwn-6. The crwn ethers are cyclic ligmers f ethylene xides and have the same effect as linear glycls. 12-crwn-4, 15-crwn-6 and 18-crwn-6 increase the CP whereas n intrducing tw cyclhexane ring t 18-crwn-6, a decrease in CP is bserved. Dynamic light scattering Dynamic light scattering (DLS) measurements were made t knw the hydrdynamic size f TX-100 micelles in the absence and in the presence f ethylene glycl and its ethers (Fig. 3). The dash line in the Fig. 3(a r b) shws the D h f 5% TX-100 withut additives. As we can see EG and its shrter chain ethers (EGMEE and EGiPE) d nt have a prminent effect n D h f TX-100 micelles. The slutes which are hydrphilic in nature prmte Fig. 3 (a) Effect f chain length f aliphatic EG and ethers (1%) n hydrdynamic diameter f 5% TX-100 slutins; (b) Effect f chain length f aliphatic butyl ethers f glycls (5%) n hydrdynamic diameter f 5% TX-100 slutins. demicellizatin and being a gd slvent, increase the CMC and decrease the aggregatin number f TX-100 micelles. EG, EGMEE and EGiPE increase the D h f TX-100 micelles t a smaller extent while EGMBE r EGMHE, EGPhE are less sluble in water and increase the D h f micelles. The hydrphbic chain and EO chain f TX-100 are hydrated in aqueus medium by the structuraly hydrated shell 31. Additin f higher chain glycl ether replaces water mlecules surrunding the hydrphbic chain and

5 PATEL et al.: CLOUDING BEHAVIOUR OF TX-100 IN PRESENCE OF LINEAR AND CYCLIC GLYCOLS 349 interactin between alkyl chain f ether and hydrphbic chain segments f TX-100 takes place 32. Due t a relatively less plar nature f higher chain ethers, there wuld be a decrease in water cntent in the micellar cre and increase the hydrphbicity. The lcatin f slubilized EG-ethers may be in the cre and/r palisade layer f micelles. The effect f butyl ether f EG, DEG, PG and DPG n D h f TX-100 micelles is shwn in Fig. 3(b). The D h remains almst cnstant in the presence f EGMBE while a slight decrease is seen with DEGMBE, which is due t the presence f an additinal ethereal linkage and hence it may act as a gd slvent fr surfactant. In the case f PGMBE and DPGMBE, increase in D h f TX-100 micelles is bserved. PG and DPG being mre hydrphbic remain in the palisade layer, leading t increase in the micelle size. The added crwn ethers have n remarkable effect n D h f TX-100 micelles ver the entire cncentratin range studied (figure nt shwn). Fr dicyclhexan-18-crwn-6, there is an increase in the D h after an initially slight decrease. Due t the lw cncentratin, the crwn ethers remain at the micellar water interface, making micelles slightly cmpact. Thermdynamic parameters The thermdynamic parameters f nn-inic surfactants were calculated by using the CP value at the phase separatin 33, 34. The standard free energy change ( ), enthalpy ( ) and the entrpy ( S cp G cp H cp ) f change in cluding phenmenn were calculated as given in Eqs 2-4. Table 2 - Thermdynamic parameters f TX-100 and different glycl ethers and crwn ethers Additive Cnc. (v/v) ( %) G (kj ml -1 ) H (kj ml -1 ) T S (kj ml -1 ) EG DEG PEG DPG EGMME EGMEE EGiPE EGMBE EGMHE EGPhE PGMBE DPGMBE DEGMBE Crwn Crwn Crwn Cyclhexan-18-crwn Gcp = RT ln X s (2) d G 2 cp Hcp = T dt T (3) T Scp = Hcp Gcp (4) where X s is the mle fractin f additives in the surfactant slutin, R is the gas cnstant and T is the temperature in K (Kelvin). We calculated the enthalpy value frm the slpe f a plt f G / T versus T at a particular temperature. The entrpy f the micellizatin was estimated frm the values f the calculated enthalpy and Gibbs free energy. The additin f shrt chain glycl ethers and crwn ethers t TX-100 slutin increases the CP by breaking the micelles. Sme lng chain ethers decrease the CP f TX-100 and favur micellizatin. The thermdynamic parameters f TX-100 at cluding temperatures have psitive values in the presence f shrt chain glycl ethers. The thermdynamic parameters are shwn in Table 2. The standard Gibbs free energy ( G ) increases with increase in hydrphilic nature f ethers r increasing number f ethereal xygen. Hwever, it decreases with increase in cncentratin fr shrt chain ethers and crwn ethers. The psitive values f G indicate that the prcess prceeds nnspntaneusly. The H and T S values are psitive and decrease with increase in the hydrphilicity. Hwever, these parameters increase with increase in cncentratin since shrt chain glycl cp

6 350 INDIAN J CHEM, SEC A, MARCH 2015 ethers increase the slubility f TX-100 and decrease the aggregatin. Hence, the values f H and T S are psitive 35,36. The psitive values f H is attributed t break dwn f water structure and frmatin f hydrgen bnds with slvent. The H and T S values are negative fr the lnger r medium chain glycl ethers and cyclhexan 18-crwn-6, because these glycl ethers insert in the micellar crna regin and induce micellizatin. The negative values f H is attributed t increase in hydrphbic interactin f alkyl chain. Due t micellizatin, the system becme mre stable and the value f T S becme negative. Cnclusins The TX-100 underges cluding phenmenn in the presence f varius linear and cyclic glycl ethers. The effect f additives are explained in terms f their interactin with water structure. The effect f additives als depends n their site f slubilizatin. The shrt chain glycl ethers alter the slvent prperties and increase slubility f surfactant while the medium chain r lng chain glycl ethers inserts int micelles and increase the hydrdynamic diameter and decrease the CP. Additives which increase the micelle size r aggregatin number decrease the randmness f the system and hence, cp S value becmes negative. On the ther hand, additives which cause breakdwn f micelles and are water structurebreakers shw psitive H cp and S cp values. Frm the abve study, we can cnclude that the slubility f nninic surfactant TX-100 can be altered by adding different additives. Acknwledgement PP thanks Cuncil f Scientific and Industrial Research, New Delhi, India, fr Senir Research Assciateship. UP thanks UGC, New Delhi, India, fr Fellwship under BSR scheme. References 1 Paradies H H, J Phys Chem, 84 (1980) Brwn W, Rymden R, Van Stam J, Almgren M & Svensk G, J Phys Chem, 93 (1989) Gu G, Sun Y, Wang Z & Gu H, Ceram Int, 31 (2005) Chaudhuri R G & Paria S, J Cllid Interf Sci, 343 (2010) Singh S K & Kishre N, J Phys Chem B, 110 (2006) Liu Y-M, Schneider M, Sticha C M, Tyka T & Sweedler J V, J Chrmatgr A, 800 (1998) Liu W, Zha W-j, Chen J-b & Yang M-m, Anal Chim Acta, 605 (2007) Purkait M K, Das Gupta S & De S, J Hazard Mater, 137 (2006) Bezerra M d A, Arruda M A Z & Ferreira S L C, Appl Spectrsc Rev, 40 (2005) de Ketttenis P, Txicl Lett, 156 (2005) Queste S, Bauduin P, Turaud D, Kunz W & Aubry J-M, Green Chem, 8 (2006) Queste S, Michina Y, Dewilde A, Neueder R, Kunz W & Aubry J-M, Green Chem, 9 (2007) Parekh P, Yerramilli U R & Bahadur P, Indian J Chem, 52A (2013) Kumbhakar M, Mukherjee T & Pal H, Chem Phys Lett, 413 (2005) Charltn I D & Dherty A P, J Phys Chem B, 104 (2000) Raghuraman H, Pradhan S K & Chattpadhyay A, J Phys Chem B, 108 (2004) Das J & Ismail K, J Cllid Interf Sci, 337 (2009) Mlina-BlÍVar J A, Aguiar J, Peula-GarcÍA J M & Ruiz C C, Ml Phys, 100 (2002) Ruiz C C, Mlina-Blívar J A, Aguiar J, MacIsaac G, Mrze S & Palepu R, Langmuir, 17 (2001) MacIsaac G, Al-Wardian A, Glenn K & Palepu R M, Can J Chem, 82 (2004) Mahajan R, Vhra K, Kaur N & Aswal V, J Surfact Deterg, 11 (2008) Ge L, Zhang X & Gu R, Plymer, 48 (2007) Cantù L, Crti M, Degirgi V, Hffmann H & Ulbricht W, J Cllid Interf Sci, 116 (1987) Penfld J, Staples E, Tucker I & Cummins P, J Cllid Interf Sci, 185 (1997) Batıgöç Ç, Akbaş H & Bz M, J Chem Thermdyn, 43 (2011) Diaz-Fernandez Y, Rdriguez-Calv S & Perez-Gramatges A, Phys Chem Chem Phys, 4 (2002) Patel T, Bahadur P & Mata J, J Cllid Interf Sci, 345 (2010) Akbaş H, Bz M & Batıgöç Ç, Spectrchim Acta A, 75 (2010) Silva R C d & Lh W, J Cllid Interf Sci, 202 (1998) Varade D & Bahadur P, J Surfact Deterg, 7 (2004) Su Y-l, Wei X-f & Liu H-z, Langmuir, 19 (2003) Caragherghepl A, Caldararu H, Dragutan I, Jela H & Brwn W, Langmuir, 13 (1997) Alam M S, Kabir ud D & Mandal A B, Cllid Surface B, 76 (2010) Alam M S, Kabir ud D & Mandal A B, J Disper Sci Technl, 31 (2010) Panchal K, Desai A & Nagar T, J Disper Sci Technl, 27 (2006) Alam M S, Mandal A & Mandal A B, J Chem Eng Data, 56 (2011) 1540.

Effect of Temperature on the Micelle Formation of Anionic Surfactants in the Presence of Different Concentrations of Urea

Effect of Temperature on the Micelle Formation of Anionic Surfactants in the Presence of Different Concentrations of Urea Internatinal Jurnal f Theretical & Applied Sciences 6(1): 43-49(2014) ISSN N. (Print): 0975-1718 ISSN N. (Online): 2249-3247 Effect f Temperature n the Micelle Frmatin f Aninic Surfactants in the Presence