Acid–base titration

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Titration NaOH HCl PP.ogv

An acid–base titration is a method of quantitative

analysis for determining the concentration of an acid or
base by exactly neutralizing it with a standard solution of
base or acid having known concentration. A pH indicator
is used to monitor the progress of the acid–base
reaction. If the acid dissociation constant (pKa) of the
acid or base dissociation constant (PKb) of base in the
analyte solution is known, its solution concentration
(molarity) can be determined. Alternately, the pKa can be
determined if the analyte solution has a known solution
concentration by constructing a titration curve.

Alkalimetry and acidimetry

Alkalimetry and acidimetry are a kind of volumetric
analysis in which the fundamental reaction is a
neutralization reaction. Alkalimetry is the specialized
analytic use of acid-base titration to determine the
concentration of a basic (synonymous to alkaline)
substance. Acidimetry, sometimes spelled acidometry, is
the same concept of specialized analytic acid-base
titration, but for an acidic substance.[1]

Indicator choice
 

An acid-base titration using phenolphthalein as the indicator. The conical

flask contained solution that just reached the endpoint.

A suitable pH indicator must be chosen in order to detect

the end point of the titration. The color change or other
effect should occur close to the equivalence point of the
reaction so that the experimenter can accurately
determine when that point is reached. The pH of the
equivalence point can be estimated using the following
rules:

A strong acid will react with a strong base to form a

neutral (pH = 7) solution.
 A strong acid will react with a weak base to form an
acidic (pH < 7) solution.
A weak acid will react with a strong base to form a
basic (pH > 7) solution.

When a weak acid reacts with a weak base, the

equivalence point solution will be basic if the base is
stronger and acidic if the acid is stronger. If both are of
equal strength, then the equivalence pH will be neutral.
However, weak acids are not often titrated against weak
bases because the colour change shown with the
indicator is often quick, and therefore very difficult for the
observer to see the change of colour.

The point at which the indicator changes colour is called

the end point. A suitable indicator should be chosen,
preferably one that will experience a change in colour (an
end point) close to the equivalence point of the reaction.
Mathematical analysis: titration of weak
acid
The pH of a weak acid solution  
being titrated with a strong
base solution can be found at
different points along the way.
These points fall into one of
four categories:[2]

1. initial pH
2. pH before the equivalence point
3. pH at the equivalence point
4. pH after the equivalence point

for more rigorous calculation, using a RICE chart is

required. In fact the equations below are a simplification
of the RICE chart.
 

Animation of titration with base titrant

1. The initial pH is approximated for a weak acid

solution in water using the equation
 

where   is the dissociation constant,   is the

concentration of the acid and   is the initial
concentration of the hydronium ions (divided by
mol/L).
2. The pH before the equivalence point depends on the
amount of weak acid remaining and the amount of
conjugate base formed. The pH can be calculated
 approximately by the Henderson–Hasselbalch
equation:
 

with
  = initial concentration of the acid, divided by
mol/L.
  = concentration of the base added, divided by
mol/L.
  = initial volume of the acid.
  = volume of the base added.
3. At the equivalence point, the weak acid is consumed
and converted to its conjugate base. The pH will be
greater than 7 and can be calculated from an
equation derived from the following relationships:
1.  
2.  
 3.
 
 

with
 

Note that when an acid neutralizes a base, the pH

may or may not be neutral (pH = 7). The pH depends
on the strengths of the acid and base.
4. After the equivalence point, the solution will contain
two bases: the conjugate base of the acid and the
strong base of the titrant. However, the base of the
titrant is stronger than the conjugate base of the
acid. Therefore, the pH in this region is controlled by
 the strong base. As such the pH can be found using
the following:
 

where   is the base volume added until the

equilibrium.

Single formula

More accurately, a single formula[3] that describes the

titration of a weak acid with a strong base from start to
finish is given below:

 
where " φ = fraction of completion of the titration (φ < 1 is
before the equivalence point, φ = 1 is the equivalence
point, and φ > 1 is after the equivalence point)

  = the concentrations of the acid and base

respectively
  = the volumes of the acid and base respectively
  = the fraction of the weak acid that is ionized
  = the dissociation constant for the acid
  = concentrations of the H+ and OH– ions
respectively

This formula is somewhat cumbersome, but does

describe the titration curve as a single equation.

Gallery
  

Graphical methods
The titration process creates solutions with compositions
ranging from pure acid to pure base. Identifying the pH
associated with any stage in the titration process is
relatively simple for monoprotic acids and bases. The
presence of more than one acid or base group
complicates these computations. Graphical methods,[4]
such as the equiligraph,[5] have long been used to account
for the interaction of coupled equilibria. These graphical
solution methods are simple to implement, however they
are infrequently used.

See also
Henderson–Hasselbalch equation

References
1. The Chemical Age – Chemical Dictionary – Chemical
Terms . Hesperides. 2007-03-15. p. 14. ISBN 978-1-
4067-5758-3.
2. Quantitative Chemical Analysis, 7Ed. by Daniel C.
Harris. Freeman and Company 2007.
3. De Levie, Robert (1993). "Explicit expressions of the
general form of the titration curve in terms of
concentration: Writing a single closed-form
expression for the titration curve for a variety of
titrations without using approximations or
 segmentation". Journal of Chemical Education. 70 (3):
209. Bibcode:1993JChEd..70..209D .
doi:10.1021/ed070p209 .
4. "The Equligraph: Revisiting an old tool" . Retrieved
4 October 2015.
5. Freiser, H. (1963). Ionic Equilibria in Analytical
Chemistry. Kreiger. ISBN 0-88275-955-8.

External links

Wikimedia Commons has media related to Acid-base

titration.

Graphical method to solve acid-base problems,

including titrations
Graphic and numerical solver for general acid-base
problems - Software Program for phone and tablets
Simple analytical formulas for the titration of N-protic
acids. Valid for any number of N: 1-monoprotic, 2-diprotic
until N=6 (e.g. EDTA).

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