GENCATVOL28_Section5_TitrationSystems_Layout 1 7/19/11 2:55 PM Page 5.

Titration
Introduction

Titration is a quantitative measurement of an analyte in solution by it’s complete reaction

General procedure used without a reagent. Titration is used in analytical chemistry to determine the amount or
in manual titration concentration of a substance. In a titration, one reagent (the titrant) is slowly added to a
solution containing the species being measured (the analyte). As it is added, a chemical
Before starting, make sure that all reaction occurs between the titrant and analyte. The point where all analyte is consumed,
glassware, especially the burette, is and an equal quantity of titrant and analyte are present, it is called the equivalence-point.
clean and dry. This is determined by one type of indicator that it is also present in the solution, or by a
measurable physical change in the solution, like pH, electrode potential, conductivity, or light
Accurately measure a volume of the
absorption (color). In practice, an abrupt change of this physical property signals the end of
reactant into to a beaker or Erlenmeyer
titration, called the endpoint.
flask.
The purpose of titration (also called volumetric analysis) is to determine the analyte quantity
Add a suitable indicator to the flask.
or concentration, the titrant concentration being known beforehand. Titrations are based on
Pour the titrant into the burette, read chemical reactions, and these reactions must fulfill four requirements:
the start-point of the liquid on the
burette. • The reaction must be fast, so that after the titrant’s addition, the reaction occurs
within approximately one second
Turn the tap of the burette to allow the
titrant to slowly fall into the reactant. • The reaction must go to completion
Swirl the flask with the other hand or • The reaction must have well-known stoichiometry (reaction ratios)
with a magnetic stirrer.
• A convenient method of endpoint detection must be available
The indicator should change colour as
the titrant is added, but then quickly
In any titration, there must be a quick, quantitave reaction taking place as the titrant is added.
return to its original color.
Manual titration is done with a burette and a long graduated tube that holds the titrant. The
As the end-point is approached, the
amount of titrant used in the titration is determined by reading the difference between the
indicator takes longer to turn back to its
volume of titrant in the burette before the titration and when the endpoint is reacted. The
starting color. Add the titrant more
most important factor for making accurate titrations is to read the burette volumes
slowly at this point (one drop at a time).
repeatedly. Generally, chemists use the bottom of the meniscus (rounded liquid level) to
When the indicator remains at its end read the reagent volume in the burette. Additional required instrumentation would be: a
colour, the reaction has reached the burette, a beaker, a pipette - to measure the sample volume, an indicator solution and the
end point. (standardized) titrant.

Measure the amount of titrant liquid

used, as shown on the scale of the
burette.

Repeat as many trials as needed, and

then average the volumes.

Once the number of moles of reactant

that have been neutralised has been
determined then calculate the
concentration in moles per litre or
other unit.

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Titration
Introduction

Automatic Titration
Automatic titration is done with automatic titrators. These titrators deliver the titrant, stop

TITRATION
at the endpoint and calculate the concentration of the analyte automatically. They are the
best for repeatitive titrations. A certain type of electrochemical measurement usually
detects the endpoint.

Some complex analysis performed by automatic titrators are...

• Acid-base, specific ion redox determination by pH/mV measurement

with potentiometric detection.
• Determination of water with Karl Fischer reagent using
coulumetric detection.
• Determination of chlorine in aqueous solution with
phenylarsene oxide using amperometric detection.

The required equipment would be the automatic titrator, the (standardized) titrant, a titrant
reservoir, a pipette (to measure the sample volume), a beaker, and possibly a magnetic
stir-bar for stirring.

The automatic titrator must have an accurate liquid dispensing system. In high accuracy
In 1855, the German chemist, Friedrich
systems, this is typically a stepper motor driven piston burette, a valve system to switch
Mohrn, defined titration as the "weighing
between titrant inlet and outlet, and a titration tip to dispense the titrant into the sample
without scale" method, because this
solution. These three main subsystems must be as accurate as possible, with very low gear
process allows determination of the
backlash in the burette drive mechanism, low piston seal flexing, accurate burette glass
concentration of a sample without using
cylinder diamter, low dead volume in the valve, evaporation/permeation and chemically
complex instrumentation.
resistant tubing and an anti-diffusion titrant dispensing tip.
A manual titration requires high accuracy
and precision, both in the preparation of
the material, and the use of precisely
Standards and Standardization dosed reagents. The operation must be
repeated at least 3 times to obtain a
One of the substances involved in a titration must be used as a standard for which the
reliable measured value. This procedure
amount of substance is present is accurately known. The standard can be present either
makes the manual analytical technique
in the form of a pure substance or as a standard solution, a solution whose composition
very long and fastidious; however, the
is accurately known. The titrant solution can be standardized in two ways; using a
infinite applications that titration
primary standard, or more commonly, titrating it against a previously standardized solution.
presents, can't be neglected for both
organic and inorganic parameters. In
some applications, for example, in the
Type of Titrations food industry, the determination of the
content of sulphur dioxide in must and
Acid-base titrations This is the most common type of titration - an acid-base reaction
wine and the level of acidity in cheese are
(simply exchange of protons). On the following table and graph you can see the variation of
still determined manually using the
pH during the titration of a solution of 0.1 M HCl with one solution of NaOH 0.1 M
Soxhlet method.

Volume of NaOH, mL pH The growing need for faster results has

0.00 1.00 lead HANNA to develop the HI 901 and
10.00 1.18 HI 902C titrators, two instruments that
20.00 1.37 permit the automation of the titration
30.00 1.60 procedures, while providing quick and
40.00 1.95
reliable data.
49.00 3.00
49.90 4.00
49.99 5.00
50.00 7.00
50.01 9.00
50.10 10.00
51.00 11.00
60.00 11.96

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Titration
Introduction

Potentiometric titrations are those where the potential from an in-situ from iodide, by passing electricity across two platinum
electrode system is used as the analytical signal for the change electrodes immersed in the reagents solution. A separate dual-
occuring during the titration. Examples include pH electrodes used platinum indicator electrode monitors the end-point, just as in the
for acid-base titrations, ORP electrodes (platinum) used in a redox volumetric KFT. The quantity of passed electricity is measured and it
titration, ion selective electrodes used in a specific ion titration, and is used to calculate the quantity of water that was present in sample.
silver electrodes used to follow the silver ion concentration in
The fundamental calculation for all titrations is based on:
argentometric titrations.
C1V1 = C2V2 or N1V1 = N2V2 or C1V1E1 = C2V2E2
Precipitation titrations
Where C is the concentration in moles/liter, V is volume in liters or
Complexometric titrations In a complexometric titration metal
mL, N is the concentration in normality in equivalents. Liter, and E is
ions are titrated using a titrant that binds strongly to the metal ions.
the equivalents/mole factor for the analyte and titrant.
Amperometric titrations
Csample = Ctitrant Vtitrant / Vsample
Spectrophotometric titrations
This equation is the most basic form used for calculating the result
Back-titrations In this type of titration, a large excess of a reagent of a titration. As will be shown in following illustrations, there are
is added to the sample solution, helping a slow reaction to go to modifications to this basic equation necessary for obtaining results
completion; the unreacted excess reagent is then titrated. in other certain situations.

Multiple endpoints titrations Methods for determining the equivalence point of a potentiometric
titration curve (including acid-base titrations):
Instrumental End-point Determination

Karl Fischer titrations (KFT) (HI 903) KFT use the Karl Fischer
reaction between water, iodine and sulfur dioxide. There are 2 types
of Karl fischer titrations: coulometric and volumetric. In the
volumetric KFT, methanol solvent is pretitrated to the dryness end-
point, sample is added, and the water in the sample solution that is
titrated. The titrant contains iodine and SO2. The CH3OH solvent and
SO2 react to form (CH3SO3)- that reacts in the Karl Fischer reaction
with water:

CH3OH + SO2 + RN → [RNH]CH3SO3 The first derivative (a); the equivalence point corresponds to the top
of the peak.
H2O + I2 + [RNH]CH3SO3 + 2RN → [RNH]CH3SO4 + 2 [RNH]I

Were RN = base

In the coulometric KFT, the sample is added to a special reagent

solution that contains CH3OH solvent, SO2 and iodide. During the
titration, iodine (the active titrant) is generated electrochemically

The second derivative (b); the equivalence point is where the curve
crosses the V-axis.

The Gran plot (c); this method consists of the mathematical

transformation of the titration curve into straight lines via
rearranged Nernst equations (titration of a strong acid with a strong
base; Vi is the initial volume of acid and V the volume of base added)

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