Journal of Laboratory Chemical Education 2013, 1(2): 34-38

DOI: 10.5923/j.jlce.20130102.04

A Novel, Inexpensive and Less Hazardous Acid-Base

Indicator
D. Jeiyendira Pradeep* , Kapil Dave

Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) M ohali, Sector-81, Knowledge city, SAS
Nagar, Punjab, PO M anauli, 140306, India

Abstract A new acid -base indicator wh ich is less hazardous and inexpensive is proposed. It is capable of d istinguishing
between the acids and bases. Titrations were carried out to ensure that the proposed indicator yields quantitative results. The
results of titrations were quite satisfactory. The indicator was giving a distinct sustained colour even in the case of weak base
and weak acid titrations. Colour of standard indicators like phenolphthalein reappears in titrations even after reaching the end
point, but this does not happen in the case of our indicator. Pyrogallol is the chemical wh ich is being used to prepare the
indicator solution. Historically, it was heavily used for various purposes like dying and photographic developments. The
cost-benefit analysis shows that this indicator is inexpensive when compared with the available standard indicators. Certain
indicators have the carcinogenic and flammability issues associated with them, while a study of the MSDS of pyrogallo l
reveals its less hazardous nature.
Keywords Acids, Bases, Indicator, pH

titration, the unknown concentration of an acid or base is

1. Introduction determined by exact neutralization with a base or acid of
known. The co mmonly used indicators in acid -base titrations
Titrations are the basic chemistry laboratory technique for are shown in Figure 1. ; With the corresponding pH range
the quantitative analysis of substances with unknown and colour change.
concentrations using standard solutions of known pH indicators are usually weak acids or weak bases which
concentration. The substance with unknown concentration change colour according to the pH of the solution to which it
and the standard solution are termed analyte and titrant is added. Some of the standard pH indicators are
respectively. phenolphthalein, methyl orange, methylene b lue etc. There
Whether it is the task of determining the hardness of water are no indicators which have a sharp colour change at one
due to calciu m and magnesium ions or that of determining particular pH. The colour change happens over a range of pH,
the free fatty acid content to be removed fro m waste which is different for d ifferent indicators.
vegetable oil to get biodiesel, one can possibly determine the The most commonly used acid-base indicator “lit mus” has
unknown concentration of any chemical substance through a wide pH range for colour change. Therefore it is useful for
titrations. detecting acids and bases over a wide range of pH, whereas
In titrations, the titrant in the calibrated burette is slowly phenolphthalein and methyl orange are employed only if the
added to a known volume of analyte with a suitable indicator solutions are highly basic or acidic respectively. Th is is
in an Erlen meyer flask. When there is any change in colour because phenolphthalein has a pH range of 8.3 -10.0 and
of the analyte solution due to indicator, the titration is methyl orange has a pH range of 3.1-4.4 for the colour
complete and the final volu me of t itrant is noted down using change.
which further calculat ions are made to find the unknown Following reaction scheme describes the working of a pH
concentration of analyte. Indicators are used as the markers indicator:-
of the end point of any titrations. HInd + H2 O H3 O+ + Ind -
The common types of titrations include acid-base Here HInd stands for the acid form and Ind - for the
titrations, complexo metric and redo x t itrations. In acid-base conjugate base of the indicator. It is the ratio o f these two
species that determines the colour of the solution. For pH
* Corresponding author:
indicators that are weak protolytes, the Henderson-Hasselba
ms10001@iisermohali.ac.in (D. Jeiyendira Pradeep)
Published online at http://journal.sapub.org/jlce lch equation is written as:
Copyright © 2013 Scientific & Academic Publishing. All Rights Reserved pH = p Ka +( log 10 {[Ind -]÷[Hind] })
 Journal of Laboratory Chemical Education 2013, 1(2): 34-38 35

Indicator Colour change pH range

Gentian Violet 0.1-1.8

Thymol Blue 1.2-2.8

Bromophenol blue 3.0-4.6

M ethyl orange 3.1-4.4

Bromocresol green 3.8-5.4

M ethyl red 4.2-6.3

Bromocresol purple 5.2-6.8

Bromothymol blue 6.2-7.6

Phenol red 6.8-8.4

Ph enolphthalein 8.3-10.0

Figure 1. pH indicator chart

When pH equals the pKa value of the indicator, both and powerful reducing agent. It was first prepared by Scheele
species HInd and Ind - are present in 1:1 ratio. If the pH is by heating gallic acid. It was also used in quantitative
above the pKa value, the concentration of the conjugate base analysis of atmospheric oxygen. Its use stopped then due to
is greater than the concentration of the acid, and the color its suspected its toxicit ies[2]. In the early 80’s its use was
associated with the conjugate base dominates. If the pH is revived. Current studies reveal that pyrogallol is safe for use
below the pKa value, the reverse happens. This is the theory in cosmetics[3].
behind colour transition of indicators in acid -base titrations. Pyrogallo l is often used to investigate the role of O2 ·- in
Most of the co mmercially available standard indicators are biological systems. It has been demonstrated that pyrogallol
expensive. In addition to that, they are flammab le and toxic is an active co mponent of flavonoid for displaying high O2 ·-
too. The hazard risks of the standard indicators are quite scavenging activity because it is much mo re efficient in
evident fro m the Material Safety Data Sheet[1]. scavenging O2 ·- than catechol[4].
Certain indicators do not show any colour change in weak In a recent study, where litchi fru its were treated with
base versus weak acid tit rations. In some cases the colour of pyrogallol at 1 mM and then stored at 25°C or 4°C.
the standard indicator like phenolphthalein reappears again Co mpared with control, pyrogallol significantly reduced
and creates confusion in the visual detection of the end point. pericarp browning and delayed the rotting of fruit on day 4 at
We have tried to make an acid -base indicator that works 25°C, and on day 30 at 4°C[5].
well in all acid-base titrations. A study of the structure and
mechanis m of existing standard indicators like
phenolphthalein, methyl orange and methyl red indicated
that the colour of the indicator is due to extended conjugation
and the presence of OH groups in the compounds. Therefore
we chose pyrogallol, (1, 2, 3 benzenetrio l Figure 2.), a
simp le aro mat ic co mpound with three OH groups and tested
its potential to act as an acid-base indicator.
Historically, pyrogallol was used in Hair Dye and as
photographic developing agent. Pyrogallol is a white powder Figure 2. Chemical Structure of Pyrogallol
36 D. Jeiyendira Pradeep et al.: A Novel, Inexpensive and Less Hazardous Acid-Base Indicator

2. Experiment 3. Results and Discussion

2.1. Materials and Methods In Table 1 the Colour change of the Indicator in all the
above titrations are recorded. In Table 2 the mean volume of
The chemicals and apparatus used during the study are
base consumed is reported.
listed below:-
Chemicals Required: Pyrogallo l, hydrochloric acid, Table 1. Colour Change of Indicator in Titrations
glacial acet ic acid, sodium hydroxide, sodium bicarbonate, Acid Base Colour Change
and demineralised-water. HCl NaOH Colourless to Golden yellow
Apparatus: reagent bottle, weighing balance, spatulas, HCl NaHCO3 Colourless to Golden yellow
test tubes, test tube stand, droppers, 50mL burettes, pipettes, CH3 COOH NaOH Colourless to Golden yellow
pipette filler, funnel, clamp stand, tissue paper, magnetic CH3 COOH NaHCO3 Colourless to Golden yellow
stirrer, magnetic bead, watch glass, volumetric flasks of
25mL & 50mL, conical flask, pH paper (1.0-12.0), Table 2. Mean Volume of Base consumed in various titrations
measuring cylinders. Mean Volume
NaOH/ HCl 10.1mL ± 0.2 mL
2.2. Preparati on of Indicator Solution NaHCO3 /HCl 5.4mL ± 0.2 mL
About 33-35 mg of pyrogallol (pure) was weighed on a NaOH/ CH3 COOH 5.7mL ± 0.2 mL
weighing balance and added to 125mL of water in a reagent NaHCO3 / CH3 COOH 5.4mL ± 0.3 mL
bottle. The solution was shaken and swirled well, until the Sample Size = 3 and[HCl] = 0.5M,[NaOH] = 0.5M,[NaHCO3 ] = 0.5M
and[CH3 COOH] = 0.5M
entire co mpound dissolved completely. The indicator is a
colourless solution (Figure 3.). Pyrogallo l is to be kept in Fro m Table 2 it is evident that the observed mean values
dark bottle and away fro m any source of heat and light. of volu me are appro ximately in good match with the
expected theoretical values. Around 30 students used our
2.3. Procedure
indicator for titrat ions and they were satisfied with the
At room temperature the fo llowing titrations were carried performance of the indicator.
out: Addition of our indicator to an acid leads to no colour
a) Strong Acid versus Strong Base: 10mL 0.5 M HCl was (Figure 4, Figure 5.), and to base gives a golden yellow
titrated with 0.5 M NaOH. colour (Figure 5.).
b) Weak Acid versus Strong Base: 5mL 0.5 M CH3 COOH pH range of our indicator is 7.4 - 10.0.
was titrated with 0.5 M NaOH. Out of the available standard indicators, only
c) St rong Acid versus Weak Base: 5mL 0.5 M HCl was phenolphthalein gives distinct colour variation fro m
titrated with 0.5 M NaHCO3 . colourless in acids to pink in bases. Our indicator has a
d) Weak Acid versus Weak Base: 5mL 0.5 M CH3 COOH colour transition fro m co lourless to golden yello w (Figure
was titrated with 0.5 M NaHCO3 . 4.), which is easy to identify.
While preparing solutions of the weak base a little heating Indicators like phenolphthalein do not show up at all in
was given for co mplete d issolution of the base. When base weak base weak acid titrations[6]. Even if they do, the colour
was titrated with the weak acid, the acid was constantly change is short lived.
stirred on a magnetic stirrer. Similarly it was carried out for Making a basic golden yello w coloured solution acidic,
the other weak bases and weak acids for better results. transforms it into a colourless solution, with very tiny litt le
For titrations involving a weak base our indicator was pale yellowish colour, as in case of methyl orange.
added in excess (3mL) and for other t itrations five drops The cost of 100 gram pyrogallo l is around ₹ 4500
were added. (Currency: Indian Rupees-₹) fro m Sig ma Aldrich as on
March 2013. We use only 30 mg pyrogallol in 125mL to
prepare the indicator solution. In contrast indicators like
phenolphthalein cost around ₹ 3000 for 100 g, and around 2
g of compound is dissolved in 150mL water-ethanol mixtu re
to make the indicator solution. Clearly, the proposed
indicator is less expensive.
Pyrogallo l in lesser concentrations is less toxic and less
hazardous. Pyrogallol in large concentrations is toxic to
aquatic organisms. It’s harmfu l for hu mans only if
swallowed[7]. Pyrogallo l does not have any carcinogenic
effects. Our indicator is made in perhaps the greenest solvent
“water”.
Pyrogallo l can be disposed properly by dissolving or
Figure 3. Indicator Solution mixing it with a co mbustible solvent and burnt in a chemical
 Journal of Laboratory Chemical Education 2013, 1(2): 34-38 37

incinerator equipped with an afterburner and scrubber[7]. Henderson-Hasselbalch equation to identify the underlying
Studies have shown that human erythrocytes can mechanis m of colour transition of the ind icator[9].
metabolize pyrogallol, wh ich in turn can also be used in The Henderson-Hasselbalch equation for these different
metabolism of certain drugs[8]. reactions is written as:-
pH = pka1 + log 10 ([B]/[A]) (1)
pH = pka2 + log 10 ([C]/[B]) (2)
The concentration of A is 0.002 M & the pka values are
pKa1 = 9.01, p ka2 = 11.64[10], where p Ka1 refers to abstraction
of the 2-hydro xy p roton of 1, 2, 3 ben zene trio l and pka2
refers to the abstraction of either 1 or 3 hydro xy proton of 1,
2, 3 ben zene trio l.
So at pH = 9,
Substituting pka1 and[A] in Eq1 , g ives
9 = 9.01 + log 10 [B] – log[0.002]
[B] = 0.002 M
Now substituting[B] in Eq2 . Gives,
9 = 11.64 + log 10 ([C] /[B])
[C] = 0 M
Similarly solving the Henderson-Hasselbalch equation at
pH = 10, gives[B] = 0.0195 M &[C] = 0.0004 M, and at pH =
11, g ives[B] = 0.1955 M &[C] = 0.0448 M, wh ich again
implies the concentration of[B] to be mo re at pH > 8.
Figure 4. Acid and Base Solutions (Without Indicator)
Fro m the above calculations, we found that the
concentration of[B] is more in the pH range of the indicator,
imply ing that the format ion of “B” might be the reason for
the change in colour.
Pyrogallo l also undergoes aerial o xidation in presence of
base to give give 3 hydroxy, 1, 2 ben zoquinone by electron
delocalization within the aro matic ring fro m the phenoxide
ion[11].
Some other aro matic alcohols like resorcinol can be
investigated for their v iability to perform as suitable
acid-base indicators.

4. Conclusions
Pyrogallo l is a chemical which is in quick access of many
laboratories. Also the preparation of this indicator solution is
Figure 5. Colourless as well as golden yellow coloured acidic and basic
solution, respectively after adding the indicator an easy task. Since this indicator has a sustained colour in
titrations, students can locate the end point properly.
The aquatic plant Myriophyllum spicatum produces Pyrogallo l is less hazardous when compared with
pyrogallol. The indicator when co mmercialized, pyrogallol carcinogenic and flammable standard indicators.
can be synthesized out from the large scale cultivation of this We can use Pyrogallol, the inexpensive and safe chemical
aquatic plant. as an indicator in acid-base titrations carried out in
The possible products after different hydrogen preliminary chemistry laboratories.
abstractions in pyrogallol are as follows:

ACKNOWLEDGEMENTS
We thank Professor N. Sathyamurthy (Director IISER
Mohali), Dr. Samrat Ghosh (IISER Mohali) and the
Depart ment of Chemical Sciences, IISER Mohali for
A B C encouraging us and providing us the facilities to carry out our
experiments .
Using the above reaction sequence and the knowledge that
pyrogallol is a weak acid; we propose to use the
38 D. Jeiyendira Pradeep et al.: A Novel, Inexpensive and Less Hazardous Acid-Base Indicator

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