Reactions of Phenolphthalein at Various pH Values
Georg Wittke
Justus Liebig Universitat, Fachbereich 14 Chemie, 6300 Giessen, Federal Republic of Germany
Phenolphthalein has been used as an acid-base indicator
for a long time. I t shows a well-known color change from col-
orless in acid range to purple a t pH 8-9. The cause of the ob-
served color change is a modification of the structure: the
lactoide form P h l of phenolphthalein is stable in acid range,
a t pH 8-9 the y-lactone ring is broken and the molecule Ph2
with the characteristic chromophore of the triphenylmethane
dyes results. As i t is known from the triphenylmethane dyes
1
%o.c
Ph 1 Ph2
you can explain the coloring of the form Ph2 hy forming a
conjugated T-electron system using the free p-orbital of the
central sp2-hybridized carbon atom. We can elucidate the
delocalization of the T-electrons by describing the structure
by the following mesomere formulas:
we n anee-red can he observed in the reaction of P h l with 60%
In the following I will give only one mesomere formula for the
individual compounds in order to make the reaction equations
clearer.
Spectral Data of Light Absorption
i. (cm-'1 A (nm)
Phl 36 390 275
Ph2 18 000 555
PhR
Reaction of Phenolphthalein with Sulfuric Acid
Ninety-eight percent sulfuric acid reacts with 1%ethanolic
solution of phenolphthalein to give an orange-red coloring
instead of the expected colorless he reaction of
concentrated sulfuric acid leads after a protonation of the
y-lactone ring to a ring opening and formation of molecule
Ph3, the corresponding triphenylmethyl cation. (In addition,
Ph 1 Ph3
a ring sulfonation probably takes place, as we see later.)
The color reaction described is not restricted to 98% sulfuric
acid; moreover, by addition of P h l to sulfuric acids in the
range 9 8 7 4 5 % the equilibrium is displaced to the side of Ph3.
Experiments with other mineral acids like nitric acid, hy-
drochloric acid, or phosphoric acid do not lead to similar re-
sults. But a corresponding color change from colorless to or-
peychloric acid. We can conclude that a very high concentra-
tion of H+-ions is needed to get a ring opening. The pH values
of the acids used are lower than -1.
Reaction of Phenolphthalein with Sodium Hydroxide
In order to describe the possible reactions of phenol-
phthalein completely I would like to mention the addition of
concentrated aqueous sodium hydroxide to a purple solution
of Ph2. We observe a decolorization to a colorless solution,
when pH value increases to greater than 11. In strong basic
medium the addition of a hydroxyl group occurs to form the
colorless carbinol Ph4.
Ph2 Pt. 1
The light absorption in the UVNIS region of the individual
forms of phenolphthalein was registered and the data listed
in the table. The values of maximal light absorption are in-
dicated in wave numbers ;(cm-I) and wave lengths X
(nm).
The well-known reaction scheme A of phenolphthalein in
acid or hasic medium has to he completed by the reactions
above described (Band C).
- -
' Hammett, L. P., and Deyrup, A. J., J. Amer. Chem. Soc., 54, 1721
(1932).
Volume 60 Number 3 March 1983 239
 compound P h 5 is poured into water producing a cloudy so-
lution. After filtration of the precipitate a solution of P h 6 is
obtained.

Ph 1 Ph2
~010~rless purple

Several experimental results have led t o this conclusion.

1) Phenol reacts w t h concentrated sulfuric acid at room temperature
to farm an ortho-sulfonatedphenol.
2) The reaction of p-hydroxybenzoic acid with concentrated sulfuric
acid results in a manosulfonated product ortho to the hydroxvl
. .
group.
3) In contrast to P h l the resulting product Ph6 is soluble in water.
4) P h l and Ph6 can he distinguished hy thin-layer chromatography
.
where thev show different R~values.
~~ ~~

5) ~easuremintsof conductivity show that monosubstitution by two

Phl Ph5
Sulfonation of Phenolphthalein
B y t h e addition of concentrated sulfuric acid t o P h l n o t
only does t h e described change in structure occur b u t also
there is very probably a sulfonation of t h e rings ortho t o t h e
hydroxyl g r o ~ p s T. ~o get a nearly complete sulfonation t h e
reaction mixture of solid phenolphthalein a n d concentrated
sulfuric acid was allowed t o stand overnight. T h e resulting
SOaH-groups has taken place.3
-
6) The comparison of the spectral data of P h l and Ph6 indicates a
slight hathochrome shift (36,390 35,550 em-'), which is caused
by the small amount of sulfo groups to light absorption.
Conclusion
T h e well-known experimental fact t h a t phenolphthalein
exhibits a purple color in basic medium and reacts in acid
medium t o a colorless solution is strictly correct only over a
limited range of pH. Even under extreme conditions like
strong basic or strong sulfuric and perchloric acid the relations
a r e turned upside down. It could be shown t h a t phenol-
phthalein reacts a t very high proton concentration under ring
opening t o form a n orange-red compound. T h e reaction of the
purple form of phenolphthalein t o t h e colorless carbinol a t
high hydroxyl concentration has also been cited.
Acknowledgment
I would like t o thank Mr. BoykinReynolds for his assistance
in formulating t h e English text.
2Hopkinson, A. C., and Wyatt, P. A. H., J. CHEM.Scc., (B) 60, 530
(1970).
Hopkinson, A. C., J. Chern. Soc., (B) 61, 1752 (1971).

Travel to the Seventh International Conference on Chemical Education

The Committee on the Teaching of Chemistry of the International Union of Pure and Applied Chemistry organizes
a lknnial International Conference on Chemical Education for the purpose of augmenting the exchange of ideas and in-
formation among secondary and tertiaryteachers of chemistry throughout the world. The seventh conference of this series
is scheduled for 22-28 August 1983 at the Universitb des Sciences e l Techniques dur Languedoe in Montpellier, France.
The American delegation is expected to consist of approximately thirty chemical educators. Both secondary and college
teachers will he represented in the group. The American Chemical Society has submitted a travel proposal to the National
Science Foundation to provide round trip airfare between the US. and Montpellier for thirty participants. While there
is no assurance that NSF will provide travel funds, it is necessary to proceed with participant selection-with travel awards
contingent on Cavorable action hy NSF.
Anyone wishine to be considered for a travel award may obtain additional information ahout the conference. the selection

240 Journal of Chemical Education