ANALmcA

CHIMICA
AClA
ELSEVIER Analytica Chimica Acta 318 (1996) 373-376

Solid based titrimetry

Norooz Maleki *, Zahra Ramezani, Helena Kaabi
Department of Chemisrry Shiraz University, Shiraz 71454, Iran

Received 27 March 1995; accepted 6 September 1995

Abstract

A solid based titrimetric method is introduced in which a solid titrant is poured to a solution by a vibrating spatula fixed
to the pan of a balance. The spatula, the balance, and the responses of the detector are measured and controlled by a personal
computer. The precision and reliability of the method are evaluated by a series of potentiometric and photometric titrations.
In potentiometric titrations 20 to 40 equilibrium pH data points near the equivalence point are collected within an acceptable
time. Titrations within the concentration range 10d4 to 0.1 mol kg-’ are accomplished. Both potentiometric and
photometric titrations exhibit a precision of about a few tenths of a per cent.

Keywords: Gravimetry; Titrimetry; Solid based titrimetry

1. Introduction reviewed the field of automated titrimetric analysis.

Titrimetry is the determination of a substance
through the measurement of the amount of a reagent
necessary to just complete a definite chemical reac-
tion in a solution containing that substance [l]. Titri-
metric methods are neither as rapid nor as sensitive
as instrumental methods such as atomic absorption
or emission spectroscopy, but have the distinct ad-
vantage of higher precision. This makes titrations
important in those analytical applications where high
precision is of most importance. Precision of a titra-
tion is I 0.1%. In contrast to instrumental methods,
titrations are non-comparative and do not require
calibration, if the stoichiometries implied by the
chemical reactions reflect what is actually occurring
in the analytical process. Titrimetric methods can
also easily be automated. Pungor et al. [2] have
?? Corresponding author.
Volumetric and weight or gravimetric titrimetry
have been used for many years. In volumetric titra-
tions the amount of the titrant is obtained by measur-
ing the volume of a standard solution and in the
gravimetric approaches its weight is measured in-
stead. Both methods use a solution of a standard. In
this respect they both are solution based. Titrations
with highest accuracy have been performed by weight
titrimetry [3]. Measurement of the mass of the titrants
besides being intrinsically more accurate than vol-
ume measurement is not subject to errors related to
the temperature expansion coefficient of the solvent.
Errors due to evaporation of the solvent of the
standard solution, instability of the titrant solution
and dilution during the titration still occur in weight
titrations. The advantages of measuring t&ants by
weight rather than volume, particularly concerning
accuracy and precision, have long been recognized
[4]. Gravimetric titration systems were improved by
Kratochvil et al. [5,6], but because of the inconve-

0003-2670/96/%15.00 0 1996 Elsevier Science B.V. All rights reserved

SSDZ 0003-2670(95)00453-X
374 N. Maleki et al./Analytica
nience of the instrumentation and the lack of distinct
advantages, these systems have since been little used.
Most titrations require the addition of several mg
of a titrant (e.g., 0.5 ml of a 0.1 M solution that is
equivalent to 5 mg of a standard with MW = 100).
This amount can directly be measured with an ana-
lytical balance. By the introduction of modern ana-
lytical balances that can precisely, accurately, and
rapidly measure amounts of 0.01 mg the advantages
of using volumetric methods in many applications
have disappeared.
In this study we describe a new titrimetric method
in which the titrant is added as a solid. Measuring
the weight of a titrant, in a controlled environment,
during a titration eliminates all errors except the
error due to the measurement of mass. Since a solid
titrant is used, the dilution effect is eliminated, it
becomes possible to use reagents with limited solu-
bility, more economical use of titrants is possible for
non-routine titrations, and the use of unstable solu-
tions is also made possible. In non-aqueous media,
solid based titrimetry has the extra advantage of
decreasing the amount of solvent required.
2. Experimental
Various parts of the system and their interconnec-
tions are shown in Fig. 1. Details are as follows.
Phototransisto
To Interface
LED
Balance Pan
Fig. 1. Schematic
Chimica Acta 318 (1996) 373-376
2.1. The control and data processing system
This system consists of a 386 IBM-compatible
personal computer with two communication ports,
one is connected to the balance and the other to a
computer interface described elsewhere [7].
2.2. The delivery system
It is composed of a Mettler AT261 Deltarange
balance (Mettler, Greifensee, Switzerland), having a
weight capacity of 200 g and a resolution of 0.1 mg
over the entire range and a movable fine range with
a resolution of 0.01 mg. A Mettler LV3 vibrating
spatula is fixed to the pan of the balance. The spatula
is modified so that it can be controlled with a
phototransistor. The phototransistor is triggered by a
light emitting diode (LED). The intensity of the light
from the LED is controlled by the output of &bit
digital-to-analog converter (DAC) which changes the
rate of vibration of the spatula. The input of the
DAC is connected to the output of the interface. The
output of the interface is controlled by the computer.
All the eight bits of the interface are not necessarily
used for this purpose. One or more of the bits can be
used to control a solenoid valve for purging or other
purposes. The balance pan compartment, the titration
vessel and the spatula containing titrant were en-
closed in a draft shield made of aluminum.
diagram of the titration system.
 N. Maleki et al./Analytica Chimica Acta 318 (1996) 373-376 375

2.3. The detection system Table 1

Potentiometric and photometric titration data

A Metrohm 691 pH Meter (Metrohm, Herisau, Analyte Titrant and No. Mean results R.S.D. (%) b
and cont. of titrations (mol g - 1)
Switzerland) or a PU 8625 UV-visible spectro-
(mol g - ’)
photometer (Pye Unicam, Cambridge, UK), con-
nected to the computer through the analog input of l.oooX 1o-4 KHP, 4 9.84X10-’ 0.05
the interface, serves as the detection system. Ab- NaOH (aq)
1.000x lo-’ KHP, 6 9.61 X lo- 6 0.42
sorbance is monitored by circulating solution from
NaOH (aq)
the titration vessel with a PLG-Peristaltic pump (De- 3.80X lo-’ KHP, 10 3.64X 10-7 2.99
saga, Heidelberg, Germany) through a l-cm, 80-1.1.1 NaOH (aq)
flow cell (Pye Unicam) inserted into the cell com- 9.96~ 1O-3 EDTA, 5 9.85~10-~ = 0.14
partment of the spectrophotometer. cu2+

a mol kg-‘.
2.4. The titrator control software b Titrations were consecutive and no data was omitted in between.

The program to control the hardware and process

the data was written in Quick-Basic. All facilities
such as acquiring the data, plotting the titration
curve, and end-point calculations were included in
the program. The titration curve or data can be
displayed during the titration. Two routines were
written to support linear and sigmoidal titration
curves.
2.5. Reagents and materials
All solutions were prepared with triply distilled
water. Carbonate-free sodium hydroxide was pre-
pared by dilution of 0.1 mol kg-’ NaOH (AnalarR,
BDH, Poole, UK). Potassium hydrogenphthalate
&HP) (Merck, Darmstadt, Germany) was recrystal-
lized from water and was dried for 1 h at 120°C
before titration. Copper nitrate trihydrate, ammonia,
and ethylenediaminetetraacetic acid disodium salt
rized in Table 1. As expected, the relative standard
deviation increased as the concentration decreases.
The precision obtained is as good as that presented
in [5]. A typical potentiometric titration curve is
shown in Fig. 2. It is to be noted that for the titration
of 3.8 X lop7 mol g-’ NaOH, 1 1 of the solution is
used and about 74 mg of KHP is poured into the
solution to reach the end point.
The most crucial part of an automatic titration
system is the delivery. In volumetric titrations an
automatic burette performs this task, in which the
titrant is added through a narrow tube immersed in
the sample. Besides the problems associated with
volumetric titrations cited by Kratochvil and Maitra
[4], one of the less-noticed drawbacks is the diffusion
13

(EDTA) (Fluka, Buchs, Switzerland) were used as 12

received.
11

2.6. Procedure 10

53
For potentiometric titrations a sodium hydroxide
solution was titrated with sodium hydrogenphthalate. 8

In photometric titrations a solution of copper was 7

titrated with EDTA [8].
6

S I
3. Results and discussion 0 100 200 300 400

IilgOfKHP

Results for potentiometric acid-base titrations of Fig. 2. Titration curve of 5 X lo-’ mol g-’ NaOH with solid
three different concentrations of NaOH are summa- potassium hydrogenphthalate.
376 N. Maleki et al. /Analytica
of the sample through the tip of the tube to the
titrant, when the tip is immersed in the titrant. This
effect is particularly pronounced when the equilibra-
tion time is long. This and other problems associated
with volumetric titrations is not observed in solid-
based titrations.
In solid-based titration a vibrating spatula per-
forms the delivery. The delivered amount is deter-
mined by the pulse duration and the rate is controlled
by the intensity of the light of the LED set by the
software. By careful control of the two variables,
increments as small as 0.05 mg can be delivered and
a large number of data can be obtained in the course
of the titration, particularly near the end point.
The mesh size of the solid titrant also affects the
delivery rate and hence the precision of the potentio-
metric titration. Crystalline solids are more conve-
nient than powders that tend to stick to each other.
Finely crystalline solids are obtained by rapid recrys-
tallization and drying the titrant in an oven. Some-
times it is necessary to sift the solids in order to
obtain a more uniform solid that can be delivered
more smoothly.
In photometric titrations equal amounts of the
titrant are added and the absorbance is recorded.
Titration curves obtained in this way are more linear
than solution-based titrations, since virtually no dilu-
tion occurs. The photometric end point is determined
by the intersection of the least squares lines of the
two linear parts of the titration curves. The result of
a photometric titration is also presented in Table 1.
The titrations took 20 to 30 min mostly because of
the delay introduced to allow time for mixing and
equilibration. The precision obtained is consistent
with that presented in [5].
Chimica Acta 318 (1996) 373-376
In the case of sigmoidal titration curves, the rou-
tine that controls the titration is somewhat more
complicated. At first, titrant delivery can be contin-
ued until a predetermined weight is attained. After
this point the slope calculation determines the rate
and duration of delivery. This is performed between
each two successive points during the titration. In
this way the program controls the delivery rate. At
points far from end point, where the slope does not
change considerably, the delivery rate is fast, and
near or at the end point, where the slope changes
abruptly, the delivery rate becomes slow, so more
data points can be collected near the end point. Each
potentiometric titration took 15 to 25 min with about
20 to 40 collected data points near the end point.
Most of the titration time is used for dissolution and
mixing. More efficient means of dissolution, such as
ultrasonic agitation, will help to shorten the titration
time without loss of precision.
References
[l] C.M. Beck, Anal. Chem., 66 (1994) 224A.
[2] E. Pungor, Z. Feher, G. Nagy and K. Toth, CRC Crit. Rev.
Anal. Chem., 14 (1983) 175.
[3] B. Kratochvil and P.F. Quirk, Anal. Chem., 42 (1970) 492.
[4] B. Kratochvil and C. Maitra, Am. Lab. (Fairfield, Corm.), 1.5
(1983) 22.
[5] B. Kratochvil and J.E. Nolan, Anal. Chem., 56 (1984) 586.
161 R. Guevremont and B. Kratochvil, Anal. Chem., 50 (1978)
1945.
171 N. Maleki and B. Haghighi, J. Chem. Educ., 72 (4) (1995)
A78.
[8] D.T. Sawyer, W.R. Heineman and J.M. Beebe, Chemistry
Experiments for Instrumental Methods, Wiley, New York,
1984, p. 187.