PH EFFECTS ON PHENOLPHTHALEIN

Juan David Marin Chiguachi Universidad de Caldas, Manizales, Colombia

Chemistry and Biology degree‘s

Fig. 1. Structure of Phenolphthalein

INTRODUCTION

Titrations are the basic chemistry laboratory technique for the quantitative analysis of substances
with unknown concentrations using standard solutions of known concentration [1]. The substance
with unknown concentration and the standard solution are termed analyte and titrant respectively
[2].
pH indicators are usually weak acids or weak bases which change colour according to the pH of the
solution to which it is added [3].
The most exploited chromic types are thermochromism and photochromism, [4,5] but halochromism
(pH sensitivity) is also increasingly studied and put into practice. Phenolphthalein adopts four
different states in aqueous solution: Under strongly acidic conditions, it exists in protonated form
(HIn+), providing an orange coloration. Between strongly acidic and slightly basic conditions, the
lactone form (HIn) is colorless. The doubly deprotonated (In2–) phenolate form (the anion form of
phenol) gives the familiar pink color. In strongly basic solutions, phenolphthalein is converted to its

In(OH)3(OH)3 form, and its pink color undergoes a rather slow fading reaction and becomes
completely colorless above 13.0 pH [2]
The experimentally measured dissociation of phenolphthalein is described using four dissociation
structures Figure 2, where the ionization of two phenolic hydroxyl groups converts the neutral
molecular form into the red quinoid form. Further dissociation from the quinoid structure to the
alcoholic form eliminates the color. The dissociation mechanisms can also be described using three
structures without the need for a transition structure

Fig. 2. Dissociation scheme of phenolphthalein

II COMPUTATIONAL WORK

The computational work begins by drawing the phenolphthalein molecule and carrying out the
reaction as if it were in conditions of acidity and basicity, knowing the possible structures in different
pH ranges. The calculation of opt + freq was performed using the Ground state-DFT-B3LYP
method and as a basis set 3-21G, taking into account the loads of the different species\\In the
work of the influence of pH on phenolphthalein, it is see the changes in ΔG as the pH increases and
also analyze the stability of the molecules according to their calculated energy

III RESULTS
The table contains the pH range and delta G data corresponding to the calculations. Scheme Figure
3 representing the corresponding reactions and pH ranges
Fig. 3. Phenolphthalein dissociation scheme in different pH ranges with the ΔG of the reaction.

Looking at the ΔG results, it can be known that the first two dissociation schemes are
spontaneous. Also below are the energies of each structure in the order of dissociation 314.88
Kj/mol, -357.14 Kj/mol, -5.2e-10 Kj/mol, -412.71 Kj/mol. Thus giving figure 4 as the most stable
structure of phenolphthalein dissociation.

Fig. 4. Structure of the most stable phenolphthalein in the aqueous system

 BIBLIOGRAPHY

[1] P. Bamfield, Chromic Phenomena, Technological applications of colour chem- istry, Royal
Society of Chemistry, 2001.

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Speybroeck, Investigating the halochromic properties of azo dyes in an aqueous environment by
using a combined experimental and theoretical ap- proach., Chem. Eur. J. 18 (2012) 8120–9.

[3] T. Kuwabara, H. Nakajima, M. Nanasawa, A. Ueno, Color change indicators for molecules using
methyl red modified cyclodextrins, Anal. Chem. 71 (1999) 2844–2849.

[4] L. Van der Schueren, T. Mollet, O. Ceylan, K. De Clerck, The development of polyamide 6.6
nanofibres with a pH-sensitive function by electrospinning, Eur. Polym. J. 46 (2010) 2229–2239.

[5] L. Van der Schueren, K. De Clerck, Textile materials with a pH-sensitive func- tion, Int. J.
Cloth. Sci. Tech. 23 (2011) 269–274274.