Analytica Chimica Acta 555 (2006) 391394

Gravimetric analysis of high purity tellurium for purity evaluation

Toshihiro Suzuki, Akiharu Hioki
National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST),
AIST Tsukuba Central 3-10, 1-1-1 Umezono, Tsukuba-shi, Ibaraki 305-8563, Japan
Received 4 July 2005; received in revised form 12 September 2005; accepted 12 September 2005
Available online 10 October 2005

Abstract
Gravimetric analysis was utilized for purity evaluation of high purity tellurium, which was a raw material of a tellurium standard solution. Using
a method in which tellurium was precipitated as elemental tellurium with hydrazinium after dissolution of the high purity tellurium, an avoidable
positive error (ca. 0.02%) was observed. It seems that a cause of the positive error is oxidation of the tellurium or occlusion of the solvent during
the precipitation. On the other hand, when the precipitated elemental tellurium was further converted into tellurium oxide by heating at 600 C, the
positive error disappeared. Finally, the purity of the starting tellurium was evaluated from the recovery of tellurium oxide with sufficient accuracy
for a raw material of a tellurium standard solution (0.017% expanded uncertainty (k = 2)).
2005 Elsevier B.V. All rights reserved.
Keywords: Tellurium; Tellurium oxide; Gravimetric analysis; Hydrazinium; Uncertainty; Primary method of measurement

1. Introduction

2. Experimental

In the development of a standard material, use of a primary

method of measurement [1,2] based on calculations relying on
physical and/or chemical principles is preferred. Coulometry,
titrimetry or gravimetric analysis has a potential as a primary
method of measurement. There are several studies exploiting
these techniques for tellurium determination, e.g., gravimetric analysis where there is precipitation as elemental tellurium
[35], tellurium dioxide [3], or any other compound [68],
titrimetry as back-titiration after oxidation of tellurium(IV)
[9,10] or iodometry [11], coulometry with electrically generated cerium(IV) [12]. There are, however, few studies that have
the precision to fill the requirements for development of a standard material and that take into account an uncertainty of a
result. In the present work, we studied a new approach of precise
gravimetric analysis of tellurium by both recovering elemental
tellurium and subsequent converting into tellurium oxide. Considering estimation of an uncertainty, we evaluated the purity of
high purity tellurium as a raw material of a standard tellurium
solution.

2.1. Reagents and apparatus

Corresponding author. Fax: +81 29 861 6890.

E-mail address: aki-hioki@aist.go.jp (A. Hioki).

0003-2670/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2005.09.028

Reagent-grade chemicals were used unless specified otherwise. Water was purified by subboiling distillation of Milli-Q
water. High purity metal tellurium (99.9999%: Osaka Asahi
Metal, Japan) was used for a sample. Any trace elements in the
metal were not detected by the manufacturer by spectrochemical analysis. Trace metals in the metal tellurium were determined by the authors with an inductively coupled plasma-atomic
emission spectrometer (ICP-AES) SPS3000 (Seiko Instruments,
Japan). A vacuum dry oven VOS-450D (Tokyo Rikakikai,
Japan) and a balance AT-201 (Mettler-Toledo, Switzerland) were
used for gravimetric analysis. All samples were weighed with
air-buoyancy correction in a room of controlled temperature
(25 1 C) and humidity (50 10%). Other operations were
performed in a room at 25 1 C.
2.2. Procedure of gravimetric analysis
One gram of the metal tellurium was washed with successive,
1 mol dm3 hydrochloric acid, water, and ethanol. The metal
was dried at 55 C for 30 min, cooled to the room temperature in
a silica gel desiccator, and weighed with 0.01 mg sensitivity. The

T. Suzuki, A. Hioki / Analytica Chimica Acta 555 (2006) 391394

392

metal was dissolved in 20 cm3 of 6.6 mol dm3 nitric acid, and
then the nitric acid was evaporated. After the residue (tellurium
nitrate) was dissolved in 30 cm3 of 4 mol dm3 hydrochloric
acid, hydrazinium solution (3 g of hydrazinium dichloride was
dissolved in 10 cm3 water) was added to precipitate elemental
tellurium. The precipitate was heated at 80 C for 1 h to digest
it and decompose the excess hydrazinium, cooled to the room
temperature, filtered out using a pre-weighed G4 glass filter crucible, and rinsed with successive, 0.1 mol dm3 hydrochloric
acid, water, and ethanol. The precipitated elemental tellurium
was dried at 80 C under vacuum (<2.7 kPa), cooled for 30 min
in a silica gel desiccator, and weighed. The procedure from
the drying to the weighing was repeated several times. The
filtrate and all rinsing solutions were evaporated, dissolved in
a nitric acid, and analysed with ICP-AES. Used glasswares
were rinsed with aqua regia to check the amount of mechanical loss of tellurium; the aqua regia was evaporated and the
residue was dissolved in a nitric acid, and similarly analysed with
ICP-AES.
For its conversion into tellurium oxide, the precipitated elemental tellurium was weighed into a porcelain crucible, heated
successively at 100 C for 30 min, at 300 C for 1 h, and at
600 C for 1 h in air,then cooled in a silica gel desiccator for 1 h,
and weighed. The procedure starting with the heating at 600 C
was repeated until a constant weight of tellurium oxide was
reached.
2.3. Procedure of impurity determination
One gram of the metal tellurium was washed with successive, 1 mol dm3 hydrochloric acid, water, and ethanol. The
metal was dried at 55 C for 30 min, cooled to the room temperature in a silica gel desiccator, and weighed with 0.01 mg
sensitivity. The metal was dissolved in 20 cm3 of 6.6 mol dm3
nitric acid, and then the nitric acid was evaporated. The resulting tellurium nitrate was dissolved in 30 cm3 of 4 mol dm3
hydrochloric acid, and diluted to 100 cm3 with water. Trace metals in the solution (1% (mass fraction) Te) were determined with
ICP-AES.

3. Results and discussion

3.1. Generic aspects of approach
In order to evaluate the purity of a high purity material,
the method by difference has been often utilized. Strictly
speaking, all elements except for the main constituent in the
Periodic Table should be quantified for the purpose of the
method. Since it is, however, impossible usually, we would
like to analyse the material by a technique using any property
of the main constituent. Gravimetric analysis is one of the
possible techniques; however, a weighing form is a key point
of the technique as well as the aspects of solubility error and
mechanical loss. In the present paper, the example of tellurium is
demonstrated.
3.2. Precipitate as elemental tellurium
Recovery of the tellurium was obtained together from the
precipitate, the element in the filtrate, all rinsing solutions, and
the element in the residue on the glassware. As shown in Table 1,
the last one, i.e., the mechanical loss of tellurium was negligible.
While the total recovery had a positive error, which was regarded
as significant compared to the repeatability of the measurements,
it seems that a cause of the positive error is oxidation of the elemental tellurium or occlusion of the solvent because impurities
were rarely found in the starting metal tellurium and the precipitated elemental tellurium (vide infra). Though the mass of
the precipitated elemental tellurium increased with the repetition number of the procedure of heating, cooling, and weighing
(Fig. 1) because of air oxidation, this effect could not explain the
positive error since it was negligibly small in a few repetitions.
Therefore if the recovered tellurium contained tellurium oxide,
the oxide would be formed at the precipitation before the first
repetition. Though sodium, calcium, and silicon in the precipitated elemental tellurium were detected with ICP-AES, those
contents were only a few mg/kg. On the other hand, sodium, calcium, and vanadium in the starting metal tellurium were detected
in the similar order of magnitude.

Table 1
Recovery as elemental tellurium
Te takena (g)

Precipitatea (g)

Te in filtrate and rinsing solution

(HCl and water) (mg)

Te in rinsing solution
(ethanol) (mg)

Te in residue on
glassware (mg)

Total recovery (%)

1.10150
1.09709
1.03701
0.99558
1.08001
1.19714
1.32770
1.15943
0.94455

1.10038
1.09623
1.03659
0.99491
1.07935
1.19606
1.32682
1.15862
0.94404

1.27
1.10
0.67
0.79
0.74
1.09
1.10
0.86
0.57

0.055
0.055
0.010
0.005
0.107
0.075
0.093
0.048
0.000

0.007
0.005
0.002
0.001
0.003
0.003
0.056
0.007
0.030

100.019
100.027
100.026
100.013
100.018
100.008
100.028
100.009
100.010

Average
Standard deviation
a

After air-buoyancy correction.

100.017
0.008

T. Suzuki, A. Hioki / Analytica Chimica Acta 555 (2006) 391394

Fig. 1. Dependency of the recovery of elemental tellurium on the repetition

number of drying at 80 C under vacuum for 1 h and cooling in a silica gel
desiccator for 30 min.

393

Fig. 2. Dependency of the recovery as tellurium oxide from precipitated elemental tellurium on heating time. Each identical symbol indicates a repetition
under the same condition.

3.3. Converting into tellurium oxide

Table 2 shows the recovery of tellurium oxide that was
obtained by oxidation of the elemental tellurium precipitated
by the procedure described in the Section 3.2. In this case,
the positive error caused by the oxidation of the elemental tellurium or the occlusion of the solvent should disappear. The
recovery of the tellurium oxide was, in fact, less than 100%
as an average, in spite of excessive recovery of the elemental tellurium that was the intermediate product to the tellurium
oxide. About 6 h heating was required until a constant mass
of the tellurium oxide was reached (Fig. 2), and the mass
was unchanged until at least 14 h heating. A heating condition was decided judging from the result of thermogravimetric
measurement, which indicated that it needed 550 C to convert elemental tellurium into tellurium oxide. When the tellurium oxide was measured by thermogravimetry during cooling
from 600 C to the room temperature, mass loss of 0.03 mg
for 16 mg tellurium oxide occurred. This fact suggested that
any adsorption on the tellurium oxide did not occur during the
cooling.

3.4. Quantication of the uncertainty through the whole

procedure
When the series of drying, cooling, and weighing of glass
filter crucible or porcelain crucible was repeated, there was a
random error of the order of 0.1 mg caused by adsorption of
water on its surface. That error was, however, compensated by
blank correction (Fig. 3a and b).
The loss to the filtrate and the rinsing solutions, the loss
caused by the residue left on the glassware, and the positive
error caused by the occlusion of the solvent were recognized
as possible components of systematic errors for elemental
tellurium. Since they were appropriately corrected for tellurium
oxide, the relative standard uncertainty of the measurement
as tellurium oxide was evaluated with the measurement
repeatability divided by 5 (0.0072%). The relative standard
uncertainties of the standard weight used and the linearity
of the balance were 0.0003% and 0.0002%, respectively.
The relative standard uncertainty from atomic weights was
calculated by the following equations according to uncertainty

Table 2
Recovery as tellurium oxide
Te takena (g)

Precipitatea (g) Te in filtrate and rinsing Te in rinsing solution Te in residue on Te taken from the TeO2 founda (g) Total recovery (%)
solution (HCl and water) (ethanol) (mg)
glassware (mg) precipitatea (g)
(mg)

1.22154
1.08001
1.19714
1.11216
1.03757

1.21976
1.07935
1.19606
1.11171
1.03693

Average
Standard deviation
a

After air-buoyancy correction.

1.75
0.74
1.09
1.23
1.33

0.000
0.107
0.075
0.000
0.000

0.049
0.003
0.003
0.018
0.009

1.21496
1.02834
1.13062
1.07124
1.01266

1.51921
1.28571
1.41396
1.33909
1.26577

99.973
99.978
99.994
100.013
100.000
99.992
0.016

394

T. Suzuki, A. Hioki / Analytica Chimica Acta 555 (2006) 391394

where X is the conversion factor when metal tellurium was

converted into tellurium oxide, each M is an atomic weight,
and each u is a standard uncertainty. IUPAC data [14] were
utilized for the atomic weights and their uncertainties. The
relative standard uncertainty of the conversion factor was
0.0043% from Eq. (2). Finally, combining all standard uncertainties, the expanded uncertainty for the purity of the metal
tellurium was estimated to be 0.017% using a coverage factor of
2.
4. Conclusions
Since gravimetric analysis is potentially one of the primary methods of measurement, it is sometimes useful for
purity evaluation of materials. However, weighing of only the
precipitate is often insufficient. In the present study it was
demonstrated about tellurium that comparison of different
weighing forms, solubility error and mechanical loss are important in order to attain an accurate purity evaluation with a low
uncertainty.
References

Fig. 3. (a) Effect of blank correction for porcelain crucibles. An abscissa indicates sequence of heating and weighing. Three crucibles are measured (three
series of plots with broken lines). Measured weights of the two crucibles are
corrected on the basis of measured weight of the other crucible (the middle
one). The two series of plots with solid lines resulted from the correction. (b)
Effect of blank correction for glass filter crucibles. The results of three crucibles
were treated in the same manner as (a).

propagation [13]:
MTe + 2MO
MTe






X 2
u(X)
1
X 2
=
u(MTe )2 +
u(MO )2
X
X
MTe
MO

X=

(1)

(2)

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