pH indicator

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pH indicators: a graphic view
A pH indicator is a halochromic chemical
compound added in small amounts to a
solution so the pH (acidity or basicity) of
the solution can be determined visually.
Hence, a pH indicator is a chemical
detector for hydronium ions (H3O+) or
hydrogen ions (H+) in the Arrhenius model.
Normally, the indicator causes the color of
the solution to change depending on the
pH. Indicators can also show change in
other physical properties; for example,
olfactory indicators show change in their
odor. The pH value of a neutral solution is
7.0 at 25°C (standard laboratory
conditions). Solutions with a pH value
below 7.0 are considered acidic and
solutions with pH value above 7.0 are
basic (alkaline). As most naturally
occurring organic compounds are weak
protolytes, carboxylic acids and amines,
pH indicators find many applications in
biology and analytical chemistry.
Moreover, pH indicators form one of the
three main types of indicator compounds
used in chemical analysis. For the
quantitative analysis of metal cations, the
use of complexometric indicators is
preferred,[1][2] whereas the third compound
class, the redox indicators, are used in
titrations involving a redox reaction as the
basis of the analysis.

Theory
In and of themselves, pH indicators are
frequently weak acids or weak bases. The
general reaction scheme of a pH indicator
can be formulated as:

+ −
HInd + H2O ⇌ H3O + Ind

Here, HInd stands for the acid form and

Ind− for the conjugate base of the
indicator. The ratio of these determines
the color of the solution and connects the
color to the pH value. pH indicators that
are weak protolytes, the Henderson–
Hasselbalch equation for them can be
written as:

−
 [Ind ] 
pH = pKa + log10  [HInd] 

The equation, derived from the acidity

constant, states that when pH equals the
pKa value of the indicator, both species are
present in a 1:1 ratio. If pH is above the
pKa value, the concentration of the
conjugate base is greater than the
concentration of the acid, and the color
associated with the conjugate base
dominates. If pH is below the pKa value,
the converse is true.

Usually, the color change is not

instantaneous at the pKa value, but a pH
range exists where a mixture of colors is
present. This pH range varies between
indicators, but as a rule of thumb, it falls
between the pKa value plus or minus one.
This assumes that solutions retain their
color as long as at least 10% of the other
species persists. For example, if the
concentration of the conjugate base is 10
times greater than the concentration of the
acid, their ratio is 10:1, and consequently
the pH is pKa + 1. Conversely, if a 10-fold
excess of the acid occurs with respect to
the base, the ratio is 1:10 and the pH is
pKa − 1.

For optimal accuracy, the color difference

between the two species should be as
clear as possible, and the narrower the pH
range of the color change the better. In
some indicators, such as phenolphthalein,
one of the species is colorless, whereas in
other indicators, such as methyl red, both
species confer a color. While pH indicators
work efficiently at their designated pH
range, they are usually destroyed at the
extreme ends of the pH scale due to
undesired side reactions.

Application

pH measurement with indicator paper

pH indicators are frequently employed in
titrations in analytical chemistry and
biology to determine the extent of a
chemical reaction. Because of the
subjective choice (determination) of color,
pH indicators are susceptible to imprecise
readings. For applications requiring
precise measurement of pH, a pH meter is
frequently used. Sometimes, a blend of
different indicators is used to achieve
several smooth color changes over a wide
range of pH values. These commercial
indicators (e.g., universal indicator and
Hydrion papers) are used when only rough
knowledge of pH is necessary.

Tabulated below are several common

laboratory pH indicators. Indicators usually
exhibit intermediate colors at pH values
inside the listed transition range. For
example, phenol red exhibits an orange
color between pH 6.8 and pH 8.4. The
transition range may shift slightly
depending on the concentration of the
indicator in the solution and on the
temperature at which it is used. The figure
on the right shows indicators with their
operation range and color changes.
 Low pH Transition Transition
Indicator High pH color
color low end high end

Gentian violet (Methyl violet 10B) yellow 0.0 2.0 blue-violet

Malachite green (first transition) yellow 0.0 2.0 green

Malachite green (second transition) green 11.6 14.0 colorless

Thymol blue (first transition) red 1.2 2.8 yellow

Thymol blue (second transition) yellow 8.0 9.6 blue

Methyl yellow red 2.9 4.0 yellow

Bromophenol blue yellow 3.0 4.6 blue

Congo red blue-violet 3.0 5.0 red

Methyl orange red 3.1 4.4 yellow

Screened methyl orange (first transition) red 0.0 3.2 purple-grey

Screened methyl orange (second

purple-grey 3.2 4.2 green
transition)

Bromocresol green yellow 3.8 5.4 blue

Methyl red red 4.4 6.2 yellow

Methyl purple purple 4.8 5.4 green

Azolitmin (litmus) red 4.5 8.3 blue

Bromocresol purple yellow 5.2 6.8 purple

Bromothymol blue (first transition) magenta <0 6.0 yellow

Bromothymol blue (second transition) yellow 6.0 7.6 blue

Phenol red yellow 6.4 8.0 red

Neutral red red 6.8 8.0 yellow

Naphtholphthalein pale red 7.3 8.7 greenish-blue

reddish-
Cresol red yellow 7.2 8.8
purple
Cresolphthalein colorless 8.2 9.8 purple

Phenolphthalein (first transition) orange-red <0 8.3 colorless

Phenolphthalein (second transition) colorless 8.3 10.0 purple-pink

Phenolphthalein (third transition) fuchsia 12.0 13.0 colorless

Thymolphthalein (first transition) red <0 9.3 colorless

Thymolphthalein (second transition) colorless 9.3 10.5 blue

Alizarine Yellow R yellow 10.2 12.0 red

Indigo carmine blue 11.4 13.0 yellow

Universal Indicator
pH range Description Colour

<3 Strong acid Red

3–6 Weak acid Orange or yellow

7 Neutral Green

8–11 Weak base Blue

> 11 Strong base Violet or Indigo

Precise pH measurement
 

Absorption spectra of bromocresol green at different

stages of protonation

An indicator may be used to obtain quite

precise measurements of pH by
measuring absorbance quantitatively at
two or more wavelengths. The principle
can be illustrated by taking the indicator to
be a simple acid, HA, which dissociates
into H+ and A−.
 HA ⇌ H+ + A−

The value of the acid dissociation

constant, pKa, must be known. The molar
absorbances, εHA and εA− of the two
species HA and A− at wavelengths λx and
λy must also have been determined by
previous experiment. Assuming Beer's law
to be obeyed, the measured absorbances
Ax and Ay at the two wavelengths are
simply the sum of the absorbances due to
each species.

 
These are two equations in the two
concentrations [HA] and [A−]. Once solved,
the pH is obtained as

If measurements are made at more than

two wavelengths, the concentrations [HA]
and [A−] can be calculated by linear least
squares. In fact, a whole spectrum may be
used for this purpose. The process is
illustrated for the indicator bromocresol
green. The observed spectrum (green) is
the sum of the spectra of HA (gold) and of
A− (blue), weighted for the concentration
of the two species.

When a single indicator is used, this

method is limited to measurements in the
pH range pKa ± 1, but this range can be
extended by using mixtures of two or more
indicators. Because indicators have
intense absorption spectra, the indicator
concentration is relatively low, and the
indicator itself is assumed to have a
negligible effect on pH.

Equivalence point
In acid-base titrations, an unfitting pH
indicator may induce a color change in the
indicator-containing solution before or
after the actual equivalence point. As a
result, different equivalence points for a
solution can be concluded based on the
pH indicator used. This is because the
slightest color change of the indicator-
containing solution suggests the
equivalence point has been reached.
Therefore, the most suitable pH indicator
has an effective pH range, where the
change in color is apparent, that
encompasses the pH of the equivalence
point of the solution being titrated.[3]

Naturally occurring pH
indicators
Many plants or plant parts contain
chemicals from the naturally colored
anthocyanin family of compounds. They
are red in acidic solutions and blue in
basic. Anthocyanins can be extracted with
water or other solvents from a multitude of
colored plants or plant parts, including
from leaves (red cabbage); flowers
(geranium, poppy, or rose petals); berries
(blueberries, blackcurrant); and stems
(rhubarb). Extracting anthocyanins from
household plants, especially red cabbage,
to form a crude pH indicator is a popular
introductory chemistry demonstration.

Litmus, used by alchemists in the Middle

Ages and still readily available, is a
naturally occurring pH indicator made
from a mixture of lichen species,
particularly Roccella tinctoria. The word
litmus is literally from 'colored moss' in Old
Norse (see Litr). The color changes
between red in acid solutions and blue in
alkalis. The term 'litmus test' has become
a widely used metaphor for any test that
purports to distinguish authoritatively
between alternatives.

Hydrangea macrophylla flowers can

change color depending on soil acidity. In
acid soils, chemical reactions occur in the
soil that make aluminium available to
these plants, turning the flowers blue. In
alkaline soils, these reactions cannot
occur and therefore aluminium is not
taken up by the plant. As a result, the
flowers remain pink.
 Indicator Low pH color High pH color

Hydrangea flowers blue pink to purple

Anthocyanins red blue

Litmus red blue

  

Hydrangea in acid soil

Hydrangea in alkaline soil

  

A gradient of red cabbage extract pH

indicator from acidic solution on the left to
basic on the right
  

Purple cauliflower soaked in baking soda

(left) and vinegar (right). Anthocyanin acts
as an pH indicator.

See also
Chromophore
Fecal pH test
Nitrazine
pH meter
 Universal indicator

References
1. Schwarzenbach, Gerold (1957).
Complexometric Titrations. Translated
by Irving, Harry (1st English ed.).
London: Methuen & Co. pp. 29–46.
2. West, T. S. (1969). Complexometry
with EDTA and related reagents (3rd
ed.). Poole, UK: BDH Chemicals Ltd.
pp. 14–82.
3. Zumdahl, Steven S. (2009). Chemical
Principles (6th ed.). New York:
 Houghton Mifflin Company. pp. 319–
324.
Long indicator list
"Complete indicator list" (PDF) (in
French). (57.3 KiB)

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