Determination of Sulfuric Acid and Oleum Concentration

Relevant for: Chemical industry / Sulfuric acid production

Sulfuric acid is widely used in the chemical industry, plastics industry and petrochemistry, for the
production of phosphoric acid as a starting material for fertilizers, in the metal industry (e.g. in
etching baths), and in accumulators.

Dissolving sulfur trioxide, SO3, in concentrated sulfuric

acid results in a fuming solution called oleum (or
"fuming sulfuric acid"). Oleum is used in the chemical
industry, for example for the production of
intermediate materials or chemical fibers.

2.2. Conventional: Titration - a tedious method

The conventional method for determination of sulfuric

acid concentration is titration. However, titration is not
only time-consuming and hazardous, but also includes
a range of error prone operation steps even for skilled
1. Quality control in sulfuric acid production laboratory staff.

The titration of sulfuric acid or oleum is carried out

Sulfuric acid (H2SO4) is a high production volume with a base, commonly sodium hydroxide, NaOH. The
chemical and plays an important role in various acid sample has to be diluted prior to titration - a time-
industries. Sulfuric acid is a colorless and odorless consuming and hazardous operation. The accuracy of
oily liquid which is highly hygroscopic. Depending on the results is influenced by several factors such as the
its concentration the acid is used for different skill of the operator, the quality of the standard base
purposes. solution, the precision of the burettes, the quality of
The production of sulfuric acid proceeds in several the indicator used, etc. In routine analysis accuracies
steps starting from sulfur dioxide SO2. The biggest of 0.1 % w/w to 0.5 % w/w H2SO4 can be attained.
industry in need for sulfuric acid is the fertilizer
2.3. The alternative: Density or density and
production (approx. 50–60 % of the total H2SO4 sound velocity measurement
production volume). The acid is also needed for the
manufacturing of various goods and chemicals (e.g. Anton Paar offers instruments for sulfuric acid as well
hydrochloric and nitric acid, synthetic fibers, as oleum measurements where concentration
pigments). Other applications include the pickling monitoring and quality control are needed.
process to remove impurities from metals, the
recovery of metals and the application as electrolyte in Anton Paar instruments not only ensure safety for the
storage batteries. operator but also high quality results: they are easy to
use and operator independent. Neither sample
2. Concentration determination preparation (e.g. dilution) nor additional chemicals are
needed. A reliable density and/or sound velocity result
2.1. General is shown quickly and the conversion into
concentration is performed automatically.
Concentration determination for quality control and
subsequently adjustment of process parameters is The density and sound velocity characteristics of
important in the production stage when concentrated sulfuric acid/oleum over the concentration range of
sulfuric acid containing dissolved sulfur trioxide (SO 3) 0 % to 114 % w/w H2SO4 and 0 to 65 % w/w free SO3
is diluted with water to the desired concentration. (oleum) show that in some ranges the concentration

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can be determined from the density result, and in Table 5: Concentration range and required accuracy determine the
suitability of the measuring instrument
other ranges from the sound velocity result. Figure 1
Sulfuric Acid
graphically demonstrates that density measurement is Instrument Accuracy [g/cm³]
[% w/w]
absolutely sufficient in the concentration range from
0 % to 90 % H2SO4, but concentrations above 90 % DMA 35
need an additional parameter for clear concentration DMA 35 Ampere 0 - 90 ±0.001 g/cm³
DMA 35 Ex
determination. Based on these findings, the
measuring method "Sulfuric Acid & Oleum" was DMA 501 0 - 90 ±0.001 g/cm³
defined for DSA M, allowing the fast and accurate
determination of sulfuric acid and oleum samples of DMA 1001 0 - 90 ±0.0001 g/cm³
any concentration.
DMA 4100 M 0 - 90 ±0.0001 g/cm³

DMA 4500 M 0 - 90 ±0.00005 g/cm³

DMA 5000 M 0 - 90 ±0.000007 g/cm³

0 – 114

DSA 5000 M (0 % - 100 % ±0.000007 g/cm³

sulfuric acid: 0 % -
65 % oleum)

3. Safe, fast, and reliable measurements

3.1. Filling sulfuric acid and oleum into DSA M

Only a small volume of approximately 3 mL sample is

required, no sample preparation is needed. The
Figure 1: Density and sound velocity characteristics of sulfuric
acid and oleum sample is filled into the DSA 5000 M measuring cells
by using a glass syringe or via an external peristaltic
Depending on required accuracy and acid pump.
concentration, several Anton Paar density meters
offer themselves. Tip: Inserting the glass tip of the syringe directly into
 The portable DMA 35 Ampere density meter is the inlet adapter of DSA 5000 M may result in the
the ideal solution for sulfuric acid measurements fracture of the tip due to applied inappropriate
pressure. Do not insert the syringe directly into a
in the concentration range 0 %w/w to 90%w/w.
Teflon adapter, use a small piece of viton hose
 DMA 35 & DMA 35 Ex portable density meters between the syringe and DSA 5000 M instead (see
for quick density checks in the lab or for Figure 2).
measurements directly from tanks or vessels in
the field. DMA 35 Ex is intrinsically safe for the
use in hazardous areas.
 DMA 501 and DMA 1001 stand-alone benchtop
density meters for reliable analyses.
 DMA 4100/4500/5000 M laboratory instruments
for quality control of raw, intermediate and final
products.
 DSA 5000 M laboratory density and sound
velocity meter for highly accurate concentration
determination of sulfuric acid and oleum across
the whole concentration range.

Table 5 summarizes the density meters suitable for

Figure 2: Filling DSA 5000 M with a glass syringe
the respective concentration ranges.

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3.2. Titration versus DSA 5000 M results 3.2.4. 20 % w/w Oleum

3.2.1. General remarks Table 3: Comparison of titration and DSA 5000 M results, incl.
mean value and standard deviation (s.d.); sample: 20 % w/w oleum
Number of
The following measurements were carried out in order Titration DSA 5000 M
measurement
to compare DSA 5000 M results with values obtained
by titration (Table 1 to Table 4). For this purpose Sulfuric Sulfuric
Oleum Oleum
different concentrations of H2SO4 and oleum were Acid Acid
[% w/w] [% w/w]
[% w/w] [% w/w]
measured.
1 104.67 20.75 104.54 20.18
The measurement results show a very good
agreement between titration and DSA 5000 M. 2 104.65 20.68 104.54 20.19
Furthermore it should be marked that the standard
3 104.61 20.48 104.54 20.19
deviation of titration results is constantly higher than of
DSA 5000 M measurements. 4 104.64 20.61 104.54 20.19

3.2.2. 50 % w/w Sulfuric acid mean value 104.64 20.62 104.54 20.19

Table 1: Comparison of titration and DSA 5000 M results, incl. s.d. 0.03 0.10 0.00 0.01
mean value and standard deviation (s.d.); sample: 50 % w/w
sulfuric acid
3.2.5. 50 % w/w Oleum
Number of
Titration DSA 5000 M Table 4: Comparison of titration and DSA 5000 M results, incl.
measurement
mean value and standard deviation (s.d.); sample: 50 % w/w oleum
Sulfuric Acid Sulfuric Acid Number of
[% w/w] [% w/w] Titration DSA 5000 M
measurement

1 47.92 47.88 Sulfuric Sulfuric

Oleum Oleum
Acid Acid
2 47.95 47.88 [% w/w] [% w/w]
[% w/w] [% w/w]

3 47.81 47.88 1 111.31 50.24 111.23 49.90

mean value 47.89 47.88 2 111.28 50.12 111.23 49.90

s.d. 0.07 0.00 3 111.34 50.40 - -

mean value 111.31 50.26 111.23 49.90

3.2.3. 96 % w/w Sulfuric acid
s.d. 0.03 0.14 0.00 0.00
Table 2: Comparison of titration and DSA 5000 M results, incl.
mean value and standard deviation (s.d.); sample: 96 % w/w
sulfuric acid 4. Safety issues

Number of 4.1. Protective devices

Titration DSA 5000 M
measurement
Sulfuric acid and oleum cause very strong reactions:
Sulfuric Acid Sulfuric Acid
[% w/w] [% w/w] They destroy all kinds of tissue and fabric on contact.
It is essential to observe all safety regulations
1 96.15 96.00 regarding the handling, cleaning, rinsing of the
samples and waste liquids. Avoid contact with the
2 96.15 96.00
substance: Prevent skin/eye contact by using of
3 96.07 96.00 impervious gloves, clothing, boots, apron, and eye
goggles.
4 96.23 96.00

mean value 96.15 96.00 4.2. Dilution of sulfuric acid

Diluting with water must be performed with caution as
s.d. 0.07 0.00
this extremely exothermal reaction generates a large

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amount of heat. The concentrated acid is always • The temperature is exactly controlled by an
added to water and not the other way around. integrated Peltier thermostat.
• DSA 5000 M has a rugged construction, requires
4.3. Storage only small space in the lab and can also be
operated on the production floor.
Sulfuric acid should be safely stored in glass vessels
6. Process instruments from Anton Paar
or bottles.
Anton Paar also provides process measuring systems
4.4. Cleaning for the determination of sulfuric acid and oleum
concentration. These density and sound velocity
Never flush out oleum or concentrated sulfuric acid transducers work according to the same
with water. Always start the cleaning procedure with measurement principle as the DSA 5000 M bench-top
an acid which is weaker than the previously filled one. analyzer.
Follow the sequence, given in Figure 3, before
cleaning with water.

Figure 3: Cleaning liquid sequence for oleum and sulfuric acid

5. At a glance: Oleum analysis safe and accurate

with DSA 5000 M

• DSA 5000 M provides measuring results

unmatched in accuracy, independent of the
operator, and enables to optimize product quality
immediately.
• The automated measuring procedure is highly
reliable, and avoids operating errors that are
possible with e.g. titration.
• A measurement takes only 3 minutes. The
conversion to concentration units is automatically
carried out.
Contact Anton Paar GmbH
• The instrument can be connected to your
Laboratory Information Management System Tel: +43 316 257-0
(LIMS) using the Anton Paar software LIMS density@anton-paar.com
Bridge. www.anton-paar.com

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