Aqueous solution of poly (hexamethylene guanidine hydrochloride) and poly (diethylenamine guanidine hydrochloride) as studied with acid-base indicators

Keywords: polycation, indicator dye, apparent ionization constant, poly (hexamethylene guanidine hydrochloride), poly (diethylenamine guanidine hydrochloride), sulfonefluorescein, methyl orange, sulfonephthaleins


In this paper, the properties of cationic polyelectrolytes as tools for governing the protolytic equilibrium of acid-base indicators in water were examined. For this purpose, water-soluble and pH-dependent poly (hexamethylene guanidine hydrochloride), PHMG, and poly (diethylenamine guanidine hydrochloride), PDEG, were studied. As molecular probes, a set of anionic indicator dyes were used; the key parameter is the so-called apparent ionization constant, Kaapp. The electrokinetic potential of the above polycationic species in the acidic pH region is substantially positive. As a rule, the polyelectrolytes display marked influence on the absorption spectra and state of the acid-base equilibrium of the anionic dyes at pH < 7, especially in the case of PHMG. Both effects resemble those known for the same dyes in aqueous solutions of cationic surfactants but are less expressed. Normally, the acid-base equilibria were studied at polyelectrolyte : dye ratio of 150 : 1, at ionic strength 0.05 M, and 25 oC. The decrease in the pKaapp (≡ –logKaapp) value on going from water to the PHMG solution is most expressed for bromocresol green (HBB2– + H+): pKa,2app – pKa,2w = –1.93. For bromophenol blue, bromocresol purple, and sulfonefluorescein, the shift of the equilibrium is less expressed. Some kinds of specific interactions with the polyelectrolytes were revealed for methyl orange and bromophenol blue. Also, the dependence of pKaapp on logarithm of ionic strength allows estimating the degree of counterion binding by the polycation: β = 0.40.1.


Download data is not yet available.


Wojciechowski K., Klodzinska E. Zeta potential study of biodegradable antimicrobial polymers. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2015, 483 (Supplement C), 204-208.

Kabanov V.A. From synthetic polyelectrolytes to polymer-subunit vaccines. Pure and Applied Chemistry. 2004, 76 (9), 1659-1677.

Jia Q., Song C., Li H., Zhang Z., Liu H., Yu Y., Wang T. Synthesis of strongly cationic hydrophobic polyquaternium flocculants to enhance removal of water-soluble dyes in wastewater. Research on Chemical Intermediates. 2017, 43 (5), 3395-3413.

Li Q., Yue Q.-Y., Sun H.-J., Su Y., Gao B.-Y. A comparative study on the properties, mechanisms and process designs for the adsorption of non-ionic or anionic dyes onto cationic-polymer/bentonite. Journal of Environmental Management. 2010, 91 (7), 1601-1611.

Szyguła A., Guibal E., Palacín M.A., Ruiz M., Sastre A.M. Removal of an anionic dye (Acid Blue 92) by coagulation–flocculation using chitosan. Journal of Environmental Management. 2009, 90 (10), 2979-2986.

Masadome T. Determination of cationic polyelectrolytes using a photometric titration with crystal violet as a color indicator. Talanta. 2003, 59 (4), 659-666.

Chmilenko T.S., Ivanitsa L.A., Chmilenko F.A. Substituent and environment influence on analytical properties of associates of xanthene dyes with polyhexamethyleneguanidine chloride. Bulletin of Dnipropetrovsk National University. 2014, 21 (20), 10.

Chmilenko T.S., Chmilenko F.A. Analytical chemistry of polyelectrolytes (in Russian). Dnipropetrovsk University Press: 2012.

Kharchenko A.Y., Moskaeva O.G., Klochaniuk O.R., Marfunin M.O., Mchedlov-Petrossyan N.O. Effect of poly (sodium 4-styrenesulfonate) on the ionization constants of acid-base indicator dyes in aqueous solutions. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2017, 527, 132-144.

Mchedlov-Petrossyan, N.O., Kamneva N.N., Kharchenko A.Y., Shekhovtsov S.V., Marinin A.I., Kryshtal A.P. The influence of the micellar pseudophase of the double-chained cationic surfactant di-n-tetradecyldimethylammonium bromide on the absorption spectra and protolytic equilibrium of indicator dyes. Colloids and Surfaces A: Physicochemical and Engineering Aspects. 2015, 476, 57-67.

Kamneva N.N., Kharchenko A.Y., Bykova O.S., Sundenko A.V., Mchedlov-Petrossyan N.O. The influence of 1-butanol and electrolytic background on the properties of CTAB micelles as examined using a set of indicator dyes. Journal of Molecular Liquids. 2014, 199, 376-384.

Baumgartner E., Fernandez-Prini R., Turyn D. Change of apparent acidity constant of indicators in polyelectrolyte solutions. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 1974, 70, 1518-1526.

Medjahed K., Tennouga L., Mansri A., Chetouani A., Hammouti B., Desbrières J. Interaction between poly(4-vinylpyridine-graft-bromodecane) and textile blue basic dye by spectrophotometric study. Research on Chemical Intermediates. 2013, 39 (7), 3199-3208.

Egawa Y., Hayashida R., Anzai J.-i. Multilayered Assemblies Composed of Brilliant Yellow and Poly(allylamine) for an Optical pH Sensor. Analytical Sciences. 2006, 22 (8), 1117-1119.

Shen J.-J., Ren L.-L., Zhuang Y.-Y. Interaction between anionic dyes and cationic flocculant P(AM-DMC) in synthetic solutions. Journal of Hazardous Materials. 2006, 136 (3), 809-815.

Yanova K.V., Kutyanina V.S., Solovyev V.M. A study of methods of synthesis of poly (hexamethylene guanidine hydrochloride). Voprosy Khimii I Khimicheskoi Tekhnologii. 2000, No.1, 281–284.

Yanova K.V., Kutyanina V.S., Solovyev V.M. A study of methods of synthesis of poly (diethylenamine guanidine hydrochloride). Voprosy Khimii I Khimicheskoi Tekhnologii. 2000, No.4, 72–74.

Mchedlov-Petrossyan N.O. Protolytic equilibrium in lyophilic nanosized dispersions: Differentiating influence of the pseudophase and salt effects. Pure and Applied Chemistry. 2008, 80 (7), 1459-1510.

Mchedlov-Petrossyan N.O., Vodolazkaya N.A., Kamneva N.N. Acid-base equilibrium in aqueous micellar solutions of surfactants. In Micelles: Structural Biochemistry, Formation and Functions & Usage, Bradburn, D.; Bittinger, J., Eds. Nova Science Publishers: N. Y., 2013; pp. 1-71.

Vleugels L.F.W., Domańska I., Voets I.K., Tuinier R. On the driving forces for complexation of methyl orange with polycations. Journal of Colloid and Interface Science. 2017, 491, 141 150.

Quadrifoglio F., Crescenzi V. The interaction of methyl orange and other azo-dyes with polyelectrolytes and with colloidal electrolytes in dilute aqueous solution. Journal of Colloid and Interface Science. 1971, 35 (3), 447-459.

Drummond C.J., Grieser F., Healy T.W. Acid-base equilibria in aqueous micellar solutions. Part 4.-Azo indicators. Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases. 1989, 85 (3), 561-578.

Boily J.-F., Seward T.M. On the Dissociation of Methyl Orange: Spectrophotometric Investigation in Aqueous Solutions from 10 to 90 ∘C and Theoretical Evidence for Intramolecular Dihydrogen Bonding. Journal of Solution Chemistry. 2005, 34 (12), 1387 1406.

Nikiforova E.M., Bryleva E.Yu., Mchedlov-Petrosyan N.O. The distribution of the anion and zwitterion forms of methyl orange between the disperse microemulsion pseudophase and continuous water phase. Russian J. Phys. Chem. A. 2008, 82(9), 1434-1437.

Plaisance M., Ter-Minassian-Ssaraga L. Spread Insoluble Cationic Polysoap Monolayers II. Specific Effect of Counterion Binding on Surface Density Pressure and Potential at Collapse Point. Journal of Colloid and Interface Science. 1977, 59(1), 113-122.

Itaya T., Ochiai H. Counterion Binding to Poly (allylammonium) Cation. Journal of Polymer Science: Part B: Polymer Physics. 1992, 30, 587-590.

Kharchenko A.Yu., Kamneva N.N., Mchedlov-Petrossyan N.O. The properties and composi-tion of the SDS – 1-butanol mixed micelles as determined via acid-base indicators. Colloids Surf. A. 2016, 507, 243-254.

0 article
How to Cite
Kharchenko, A., Romakh, M., Yanova, K., Tereshchuk, M., & Mchedlov-Petrossyan, N. (2019). Aqueous solution of poly (hexamethylene guanidine hydrochloride) and poly (diethylenamine guanidine hydrochloride) as studied with acid-base indicators. V. N. Karazin Kharkiv National University Bulletin. Chemical Series, (33), 65-76.

Most read articles by the same author(s)

1 2 > >>