1.

TITRIMETRIC METHODS OF ANALYSIS

Titrimetric analysis consists in determining the number of moles of reagent
(titrant), required to react quantitatively with the substance being determined. The
titrant can be added (a) volumetrically, with a glass or automatic burette or with a
low flow-rate pump, or (b) coulometrically, with an electrochemical generation
from a proper electrolyte.
Titrimetric methods of analysis have the virtue of being like gravimetric
methods, absolute in that the concentration of the substance in question is
determined from the basic principles of chemistry, and no calibration curves are
required.
Various methods are available for end-point determination:
spectrophotometry, potentiometry, amperometry, conductometry, etc. The
potentiometric end-point determination is the most widely used.

1.1. Modes of titration

Titrations are performed manually point by point, or automatically, where
the titrant is introduced continuously (monotonically or dynamically). In modern
analytical chemistry automation is of increasing importance. Automation of a
point-by-point titration is seldom trivial. Kinetic factors concerning the chemical
reaction and the response of the indicating system are of paramount importance.
Cell configuration, stirring, positioning of end-point detector and of input of titrant
are to be considered for ensuring high accuracy.
Equilibrium throughout the titration curve can be attained only when the
titrant is added at an infinitely low rate. Two factors determine the rate at which a
potentiometric curve approaches the state of equilibrium: the kinetics of the
chemical reaction and the kinetics of the electrode process. Both factors are slowest
in the vicinity of the equivalent point (why?), the region with utmost importance,
from which the end point is determined (Fig.1-1a). (In conductometric titrations, on
the contrary, the region around the end point is of no analytical importance; the end
point is determined by extrapolation from the left and right branches of the titration
curve away of the end point). At faster titration rates compared to the kinetics of the
system, a delayed end point is obtained (Fig.1-1b).
Fig.1-1 Continuous potentiometric titrations
 The degree of the delay of the end point depends on the concentration of
analyte, the composition of the solution, the concentration of titrant and the rate of
the titrant adding. The larger the concentration of the analyte, the smaller the delay.
The larger the amount of titrant added per unit of time, the larger the delay.
Several strategies are used to virtually eliminate the delay:
(a) Modifying the rate of titrant adding, either by reducing it throughout the entire
titration curve - the monotonic mode, or by reducing it only along the vicinity of
the equivalence point - the dynamic mode(Fig.1-1b; the delay of the dynamic
curve is exaggerated for the purpose of the illustration). With the dynamic mode,
the rate of the titration is inversely proportional to the rate of potential
change, (Fig.1-1c), where  is the progress of the titration.
(b) Performing a repetitive-monotonic titration1 (Fig.1-1d). In this mode a series
of titrations is performed in a consecutive manner. The measurements are made
under non-equilibrium conditions. The titrant is introdused, or electrochemically
generated, at a fast and constant rate. Each titration is discontinued at some time
after the end point (the actual time is of no importance). A new portion of sample
is added to the cell and the titration is resumed at the previous rate. The new
aliquot can be added also without suspending the flow of the titrant. The end points
of the titrations are usually delayed. Each end point in a series of titrations is
delayed only once, by a period of time depending on the specific type of titration.
Previous delays are not accumulated. The delay of the previous titration is always
nullified a short time after a new portion of an analyte is added, since the response
of the system is slow only around the equivalence point, but not far away from it.
The basic requirement for a successful series of consecutive titrations is the
reproducibility in the delay of the response around the end point of the individual
titrations. When the delay remains constant, the difference between two successive
equivalence points is the same as the difference between two successive end
points. In such case the measurable difference between the nth and (n-1)th end
point leads to the concentration of the nth sample.
The repetitive-monotonic mode plays a double role: (i) canceling delay due
to slow (but reproducible) electrode response, (ii) fulfilling the role of a
pretitration, in which traces of chemically active impurities in the background are
neutralized.
All modes of automatic titrations have to be tested for accuracy if no
previous knowledge is available (what test would you suggest for the repetitive-
monotonic titration?).

1.2. Pretitration
 In trace analysis, it is common practice to neutralize chemically active
species present in the background prior to the titration of the analyte. The principle
of pretitration is as follows: a small excess of titrant is introduced into the
background solution, and the signal of the indicating system is measured. Then the
analyte is added and titrated till the intensity of the signal of the indicating system
equals to that of the pretitration step. This simple form of pretitration has been used
in the determination of As(III) with electrogenerated I2. A small excess of iodine
is electrogenerated till a light blue coloration with the starch indicator is formed.
The sample is then introduced and titrated till the same intensity of color is
reached. The pretitration serves here two purposes: one is to oxidize possible
impurities in the buffer, and the other is to take care of the fact that in very dilute
solutions (with respect to the analyte) the change of color of the indicator is not
abrupt, but gradual. A suitable transition, recognizable by the human eye, is chosen
as end point.

1.3. Manual volumetric titrations

The classical method of titration comprises in manual introdusing of titrant
using glass burettes or piston burettes.
It is recommended to run a fast preliminary titration in order to estimate the
location of the end point and the magnitude of the potential jump. The first few
additions of titrant may be rather large, and when the potential begins to change
rapidly, the size of the additions should be decreased. In the neighborhood of the
equivalence point the additions should be reduced to (V e.p./500) ml and time should
be allowed for stable reading to be achieved. In following titrations the titrant may
be added in large amounts almost up to the equivalence point. If an automatic
burette is used, equal additions around the end point are recommended.

1.4. Automatic volumetric titrations

In modern analytical practice automation of titrations is essential for the
following reasons: (i) convenience and speed, (ii) performing analysis without
supervision, (iii) enable application of elaborate techniques for analyzing the data
(with computerized systems).
Several devices for automatic transfer of titrant can be used:
 Piston burettes are highly reliable, do not require calibration, but are
expensive.
 Peristaltic pumps are of relatively low cost and highly versatile. However,
they require frequent calibration due to the continual changes in the physical
properties of the flexible tubes employed (ID of the tubes is about 0.5 mm). It is
recommended that the calibration be performed at the same time as the titration.
 Note: Flexible tubing is the only sensitive element in the
peristaltic pump. Potential leaching of plastisizers or bland
materials is to be taken into account when working with
polypropylene-based tubing (PharMed or Norprene). Viton
tubing withstands harsh solvents and aggressive chemicals, but
has a relatively short lifetime.
 Suction-stroke piston pumps (metering pumps) are as versatile as the
peristaltic pumps, but more precise and require less calibration.
The peristaltic and the suction-stroke pumps have several common
advantages: simplicity of operation, simple control of flow rate, suitability for
automation, convenience in exchange of titrant, low wastage of reagents. However,
there are limitations in the use of corrosive reagents.
All these devices enable work in a wide range of flow rates of titrant
transfer. For titrations in small volumes low flow rates are used (0.1 - 1 ml/min).
An experimental setup for potentiometric titration using a peristaltic pump
is shown on Fig.1-2.

Fig.1-2 Experimental setup for a potentiometric titration using a peristaltic pump

as titrator.

1.5. Location of end point

There are several methods of end-point determination. We shall mention
only few of them.
 For potentiometric indicating system with a reference electrode (Fig.1-3)
the end point is determined from the first derivative of the titration curve. For the
indicating system with two identical electrodes, the end point is determined
directly from the titration curve.
It is advised to attempt to estimate the end point with a precision of 0.2% or
better.

Fig.1-3 Titration and derivative curves for determination of Ca2+ with EDTA.
Sample: 1 ml drinking water; titrant: 5 mM EDTA; pH 10.5; total volume ~5 ml;
indicating electrode: mercury-coated silver electrode, reference electrode:
Ag/AgCl/1 M KCl.
(Data from Exp.1 in section "Potentiometric titrations").

Repetitive-monotonic mode of titration

In continuous follow-up of the progress of a titration, the main problem is
the slow response of the electrodes, mainly in the vicinity of the end point. In
commercial instrumentation the rate of titration is decreased when approaching the
end point. A different (simpler) approach is proposed here.
The titration is carried out at constant rate (constant generating current).
Due to the slow response of the electrode, the end point lags behind the
equivalence point. Performing a series of titrations by adding the sample to
the previously titrated solution solves the problem (Fig.1-4). The
distance between the successive end points corresponds to the true value of the
end-point time. (This is correct only for cases in which the response of the
electrodes does not change from titration to titration).
Fig.1-4 Repetitive-monotonic coulometric titration of chlorides.
Initial composition: 0.500 ml 5.10 mM NaCl, 0.25 ml 1.2 M HClO4, 4 ml
methanol.
Generating electrodes: a mercury-coated silver wire and a small-area tungsten
electrode (0.1 cm2); ig = 2 mA.
Potentiometric indicating system: twin mercury-coated silver wires, iind = 2 A.
End-point times are printed; first end point is delayed. Arrows correspond to new
additions of analyte.

Treatment of potentiometric titration curves for the case of incomplete reactions

at the equivalence point. Gran's approach
The end point in a potentiometric titration is taken as the inflection point of
the titration curve. At low concentration of analyte or insufficiently large
equilibrium constant, the degree of incompleteness of the reaction is highest
around the equivalence point (why?).
Gran's approach is based on transformation of the potentiometric plot (in
which the signal is a logarithmic function of the concentration) to a plot where the
transformed function is linear in concentration. Extrapolation of the linear part
enables a more accurate determination of the end point. Different types of
transformation are available in the literature.
Example of Gran's treatment is presented in Fig.1-5. Vt/Vin is a correction
for the dilution. (Vt is the volume of the titrated solution in the cell at a given time
t, Vin is the initial volume in the cell prior to the start of the titration).
Fig.1-5 Determination of bicarbonates in drinking water.
Sample: 5 ml tap water from Tel-Aviv University. Titrant: 10.00 mM HCl.

We shall apply the Gran treatment to the potentiometric titration of a weak base
(bicarbonate) with strong acids.
(
1)
The titration is conducted by measuring the pH with a glass electrode.
The titration curve, expressed as pH or E vs volume of titrant, yields an S-
shape plot. The end point is determined from data around an ill-defined inflection
point (the later results from an incomplete reaction between the weak base and the
strong acid; cf., Fig.1-5, left). If however, the titration curve is displayed as
[H+] vs volume of titrant, it consists of a pair of straight lines, with the end point at
the intersection of the two branches (Fig.1-5, right).
The form of the [H+]/volume plot is explained as follows. Previous to the
end point, [H+] is virtually zero and the left branch of the titration curve is a
straight line with zero slope. In the vicinity of the end point the plot is curved, due
to the incompleteness of the reaction. Beyond the end point the carbonic acid is
totally undissociated and the concentration of H+ is proportional to the number of
moles of H+added, yielding a rising straight line. The advantage of the right-side
plot in Fig.1-5 is obvious.
The transformation from one type of titration display to another is achieved
using eq.2:
 (
2)
where k’ is a constant, s is equal to (2.3RT/F) and fH+ is the activity coefficient.
From eq. (2): , where
For applying the treatment, k and s should be accurately known. These
quantities can be determined from a blank titration, performed under conditions
similar to those of the sample titration (temperature, ionic strength, flow rate of
titrant, etc.) and as near as possible to the time of the main titration.

1.6. Operation with low flow-rate pumps

Calibration: determination of the flow rate. The exact amount of titrant
used in a titration is calculated upon the value of flow rate of the pump and the
time of titration. The calibration consists of determination of the flow rate of the
pump and represents the amount of liquid transferred through the flexible pump
tube during a measured period of time. It is recommended to perform the
calibration as near as possible to the time of the analysis. To achieve a statistically
acceptable result, the measurement must be repeated several times. The values of
the mean and the standard deviation (STD) of such group of measurements are the
important factors, which mainly determine the precision of the method. In the case
of a peristaltic pump the flow rate should be measured frequently due to changes in
physical properties of the flexible tubing.
The arrangement used for calibration is shown in the figure below. Two 10-
ml plastic test tubes are located at both sides of the pump: one of them is filled
with deionized water, the other (the recipient vessel) is empty. A flexible pump
tube connects between the two test tubes. Note, that one end of the flexible tube is
dipped into the water, while the other end is placed into an additional small Teflon
tube and touches its inside wall. The purpose of the small Teflon tube is to prevent
loss of liquid while removing the pump tube at the end of the measurement.
To perform the calibration, place the recipient vessel (the empty 10-ml test tube
with the small Teflon tube inside) in a beaker and weigh both of them. Gently
touch the end of the pump tube with soft tissue to remove excess of liquid. Insert
carefully the end of the pump tube into the Teflon tube. Turn the pump on and
transfer deionized water for a predetermined time (~1 min). Stop the pump and
remove the pump tube from the recipient test tube. Weigh again. Calculate the flow
rate in g/min and ml/min. Repeat the calibration three more times.
Operating parameters for peristaltic pump. The required flow rate of
titrant is achieved by choosing the proper tubing size and rotation rate of the
peristaltic pump. For optimal operation the pressure applied on the flexible tube is
chosen in the plateau region of the experimental plot in Fig.1-6. The shape of the
plot depends on size and type of tubing material.

Fig.1-6 Effect of pressure applied by the micrometer screw on the flexible tube of
a peristaltic pump.

Adding the titrant. Remove any drops on the outside of the pump tube with
absorbent tissue and insert the tube into the titrant. To fill the pump tube with the
titrant turn the pump on and let the titrant flow through the tube for about 30 s.
At the end of the working session the pump tube should be rinsed with
distilled water. Rinse the free end of the tube with water. Dip it into distilled water
and operate the pump for several minutes. For the peristaltic pumps after rinsing
the tube release the tension on the tube. This prolongs its life.

1.7. Cell
The geometry of the titrating cell is of lesser importance in point-by-point
titrations. However, for automatic mode of titrations several requirements should
be fulfilled. The stirring should be efficient, but smooth. Vortexes and air bubbles
should be avoided in order to keep the relevant parts of the sensor in constant touch
with the solutions. The volume of the solution in the cell and the intensity of the
stirring should be such as to ensure efficient transport throughout the solution. The
cell shown in Fig.1-7 is found to be convenient for automatic titrations (in this
specific cell the volume of the solution should not extend beyond the lower part of
the cell).
Components inserted into the cell should not touch the cell walls or each
other. Such situation would cause formation of pockets of stagnant solution,
perturbing the distribution of reactants. In volumetric titrations the tip of the
burette (Teflon tube with inner diameter not larger than 0.8 mm or antidiffusional
microvalves) should be dipped into the analyte solution, but not in the immediate
vicinity of the indicator electrodes. It is important to position it in the bottom part
of the cell to ensure fast mixing of the titrant. The tip, if not antidiffusional, should
be inserted just before the start of the titration.