A-124

2012 IEEE International Conference on Condition Monitoring and Diagnosis

23-27 September 2012, Bali, Indonesia

Solubility Study of Different Gases in Mineral and

Ester-based Transformer Oils
A. Mller, M. Jovalekic and S. Tenbohlen
Institute of Power Transmission and High Voltage Technology
University of Stuttgart
Stuttgart, Germany
esters, as well as silicone oils. In this contribution, different
insulating fluids are analysed:

AbstractThe paper presents a comparison of gas solubility of

different mineral oils as well as ester-based transformer
insulating fluids. The maximum gas solubility of different gases,
e.g. ambient air, nitrogen or fault gas is determined. Also, the
solubility of a gas mixture in transformer oil is analysed. In
addition, the experimental values are compared to calculated
values derived from engineering standards.

Two mineral oils (Nynas Nytro Lyra X and Shell Diala

DX) based on mainly naphthenic compounds, both
inhibited.

One natural ester (Cooper Power Systems Envirotemp

FR3) based on vegetable oil with additives. This
kind of oil typically is a triglyceride. It has a high flash
point compared to mineral oil (330 C) and is
biodegradable. The lower oxidative stability has to be
considered and thus it is necessary to use it in
hermetically sealed transformers.

One synthetic ester (M&I Materials Ltd Midel 7131).

It is a synthetically produced pentaerythritol based
ester. As with natural esters, it has a high flash point
and is biodegradable. Because of its molecular
structure it has good oxidation stability.

One fully synthetic silicone fluid (Wacker Silicones

Powersil Fluid TR 50). Silicone fluids are inorganic
substances with high thermal and oxidation stability.

Keywords: DGA; gas solubility; mineral oil; natural ester;

synthetic ester; silicone oil;

I.

INTRODUCTION

To ensure a safe and secure operation of transformers

various diagnosis techniques are used. Especially, the wellestablished dissolved gas analysis (DGA) can provide
important information about faults inside a transformer. The
paper presents a comparison of gas solubility of different
mineral as well as ester-based transformer insulating oils. Also,
the solubility of a gas mixture in transformer oil is analysed.
With the introduction of alternative insulating liquids and
their increasing application in power transformers, these liquids
are examined in many publications regarding their physical
properties, dielectric strength and their influence on diagnostic
measurements. Gas solubility concerns the design of
hermetically sealed transformers, but also the dissolved gas in
oil analysis [1, 2, 3]. For mineral oil, it is possible to calculate
the gas solubility according to ASTM D2779 [4]. This standard
has its roots in the aerospace industry. One motivation of this
work is to check if the assumptions and boundary conditions
for solubility calculations are also valid for alternative
insulating fluids.

Table I shows the densities at 20 C and the viscosities at

40 C of the analysed insulating fluids. All data are taken from
the corresponding datasheet. Both mineral oils have similar
values for density and viscosity. For the non-mineral oils,
densities differ a bit, but viscosities are higher. This fact
influences the gas solubility as shown in the following.
TABLE I.

ANALYSED ISULATING FLUIDS

Another aspect is the mutual influence on the solubility of

dissolved fault gases and air gases. The consequence can be
noticed in the amount of dissolved gas in free breathing and
nitrogen blanketed transformers versus hermetically sealed
transformers without any gas contact. This information can be
useful for considering pressure and temperature variations,
which influence the dissolved gas analysis.
II.

Insulating fluid

ANALYSED INSULATING FLUIDS

Commonly used insulating fluids are based on a mixture of

paraffinic and naphthenic mineral oils. Alternative dielectric
fluids for power transformers are mainly natural and synthetic

978-1-4673-1018-5/12/$31.00 2012 IEEE

DENITIES AT 20 C AND VISCOSITIES AT 40 C OF THE

937

Density (kg/dm)

Viscosity (mm/s)

Nytro Lyra X

0.875

9.3

Diala DX

0.878

8.0

Environtemp FR3

0.921

32.0

Midel 7131

0.97

28.0

Powersil Fluid TR 50

0.96

40.0

III.

tank, e.g. free breathing or nitrogen blanket. For measurement

of the maximum solubility of nitrogen, the volumetric method
is used. The maximum solubility is measured at room
temperature, approx. 25 C, and at 90 C. Table II shows the
maximum solubility of nitrogen for the analysed insulating
fluids.

MEASUREMENT EQUIPMENT AND APPROACH

To determine the dissolved gases in oil and the maximum

gas solubility two methods are used. On the one hand,
concentrations are measured using gas chromatography. On the
other, the concentrations are calculated using the measured
volume of gas which dissolves in the oils. The second method
is mainly used for higher temperatures, because the sample
preparation for the gas chromatograph (GC) takes longer time
in which the samples would cool down and thus invalidate the
results.

TABLE II.

Max. solubility of nitrogen in %

Insulating fluid

A. Gas chromatography
Measurements are performed according to IEC 60567 [5]
using a GC linked with a headspace sampler. In a small vial
(volume 20 ml), 10 ml of sample oil is in contact with a
headspace volume. To prepare these sample vials a glove box
with an argon atmosphere is used. After 30 min of shaking in
the headspace sampler at 70 C gas equilibrium between
dissolved gases in the oil and the headspace is reached.
Afterwards the gas sample is automatically injected in the GC.

25 C

90 C

Nytro Lyra X

8.5

11.0

Diala DX

9.0

11.1

Environtemp FR3

7.0

9.3

Midel 7131

7.4

9.2

Powersil Fluid TR 50

13.9

14.7

Nitrogen solubility increases with increasing temperature.

The absolute values are different for the oils, but the
temperature dependent change is similar. Silicone oil behaves
different with almost double the solubility. Also, the maximum
solubility of nitrogen correlates with the density of the
observed fluids. However, a better dependency on viscosity can
be seen (in comparison to Table I). A lower viscosity leads to
higher nitrogen solubility and vice versa [3], except for silicone
oil.

In the GCs columns, the injected gas mix is separated to its

components. Concentration of the individual gas components
are measured by two detectors: a flame ionization detector
(FID) and a thermal conductivity detector (TCD). The FID
measures combustible gases with high accuracy. The TCD can
measure all gases with a different thermal conductivity than the
carrier gas. A methanizer is used to convert CO and CO2 to
methane and thus these gases can be detected more precisely in
the FID. Typically, 11 fault gases are measured: H2, CH4,
C2H2, C2H4, C2H6, C3H6, C3H8, CO, CO2, O2 and N2. After the
analysis, it is possible to calculate the fault gas concentration in
oil using the Ostwald-coefficients. The unit of concentration is
l/l. Also ppm (v/v) (parts per million, volumetric) as unit is
quite common.

To verify the concentrations, values derived from literature

[2] are used. Therefore, the values for mineral and silicone oil
may differ from oils used in this contribution. Also, the authors
investigated air instead of nitrogen. Nevertheless, the
characteristics and concentration values (sum of O2 and N2) of
the fluids are comparable.

For the analysis in this contribution a Siemens Sichromat

2/8 GC (2 columns in independent ovens, FID, TCD,
methanizer, argon as carrier gas) with a Hewlett Packard HP
7694 headspace sampler is used.

TABLE III.

B. Volumetric method
To get the maximum concentration values of single gases at
a specific temperature the volumetric method is used. Hereby,
degassed oil is filled in several 100 ml syringes. In each
syringe a defined volume of gas is injected, e.g. 8.5 %, 9.0 %
and 9.5 % of the oil filling. For temperature control, the
syringes are heated in an oven. After two days in the oven and
periodic shaking the gas dissolves. The maximum gas
concentration of the analysed oil is between the last syringe
with completely dissolved gas and the first syringe with a small
gas bubble. For each concentration value, two measurements
were performed. Regarding the accuracy of this method, such a
manual approach cannot have the same performance as a gas
chromatograph. The uncertainty is +/- 0.25 % absolute.
IV.

MAXIMUM SOLUBILITY OF NITROGEN AT DIFFERENT

TEMPERATURES AND ATMOSPHERIC PRESSURE

SOLUBILITY OF AIR IN MINERAL AND NON-MINERAL OILS AT

20 C [2]
Solubility of air in l/l at 20 C

Insulating fluid

Density
(kg/dm)

O2

N2

CO2

Mineral oil

0.8783

33480

64760

577

FR3

0.9210

21995

49613

647

Midel

0.9197

21705

45268

555

Silicone

0.9645

54938

113078

763

B. Hydrogen
Hydrogen is a common fault gas. Typically, at all faults
both thermal and electrical, hydrogen is produced in high
quantity. For measurement of the maximum solubility of
hydrogen the gas chromatograph is used. The maximum
solubility is measured at room temperature, approx. 25 C,
only. Table IV shows the maximum solubility of hydrogen for
the analysed insulating fluids.

MAXIMUM SOLUBILITY OF SINGLE GASES

A. Nitrogen
On many transformers, nitrogen is the gas with the highest
concentration dissolved in the insulating fluid. However, it
depends on the sealing principle of the transformer conservator

938

TABLE IV.

MAXIMUM SOLUBILITY OF HYDROGEN AT 25 C

Insulating fluid

A second possibility to calculate the k-factor is shown

based on the assumption that all gases have the same k-factor at
700 K. The equation is not valid for gases like methane or
ethylene. Subsequently, the k-factor k has to be corrected to the
density d of the fluid using (1):

Max. solubility of hydrogen

in % at 25 C

Nytro Lyra X

5.15

Diala DX

4.49

Environtemp FR3

3.68

Midel 7131

4.35

7.7k (0.98  d ) 



This contribution uses the k-factors from Fig. 1 at 25 C

with a density correction according to (1). In a next step, the
Bunsen coefficient B is calculated using (2):

Hydrogen has a smaller maximum solubility compared to

nitrogen. It can be seen that fluids with a higher viscosity have
a lower maximum solubility. Maximum solubility values for
hydrogen only apply to nearly complete degassed fluids
(dissolved air content < 1 %).
V.

kd

2697( p  pv )

k

T



where p is the pressure of the gas in MPa (here: 0.103 MPa,

atmospheric pressure), pv is the vapour pressure of the liquid at
a specified temperature in MPa (neglected in this context) and
T is the temperature in K. The solubility of the gas G in ppm
by weight is calculated afterwards using (3):

GAS SOLUBILITY CALCULATION

The maximum solubility of gases in transformer insulating

fluids can also be calculated besides experimental
determination. The ASTM D-2779 standard shows a method to
estimate the equilibrium solubility of several common gases
[4]. The method only includes petroleum fractions with
densities in the range from 0.63 to 0.90 kg/dm at 15 C. Thus,
the method is not verified for non-mineral insulating fluids.

1

A. Calculation
For the calculation, two parameters are needed: the density
of the insulating fluid and the Ostwald coefficient (which
depends on gas type and temperature). Fig. 1 shows the
Ostwald coefficient (k-factor) needed for several gases at
different temperatures. The solid lines indicate measured
values whereas the dashed lines are interpolated.

BM g
T  288.6
d 1  0.000595
G
 
1.21
d

0.0224

where Mg is the molecular weight of the gas in g/mol and d

is the density of the liquid in kg/dm. The factors are empirical
ascertained constants. To adjust the value of the solubility G
from ppm by weight to ppm by volume (4) is used [6]:

mg
d
l

22400
G G
Mg
l
kg



In (4) the assumption is made that gases show ideal

behaviour i.e. 1 mol gas has the volume of 22.4 l at standard
conditions.
B. Results
Table V shows the results from the maximum solubility
calculation as well as the measurement results.
TABLE V.
Insulating
fluid
Nytro Lyra X

Diala DX
Environtemp
FR3
Midel 7131

Figure 1. Solubility of gases in petroleum liquids [4]

939

RESULTS OF MAXIMUM SOLUBILITY CALCULATION AT 25 C

Gas

Max. solubility at 25 C in l/l

Calculation

Measurement

Fault in %

H2

43413

51500

15.7

N2

69460

85000

18.3

H2

38168

44900

15.0

N2

61069

90000

32.1

H2

23941

36800

34.9

N2

38305

70000

45.3

H2

3739

43500

91.4

N2

5983

74000

91.9

The fault evaluation percentage is based on measured

values. For mineral oil, there are slight deviations between
theoretical and measured value for nitrogen as well as
hydrogen. For esters, especially the synthetic ester, the error is
huge. The reasons are the higher densities over 0.9 kg/dm.
Therefore, the empirical constants of the standard do not fit any
more. For silicone oil, the error would be even higher due to a
higher density and much higher solubility (see Table II and
Table III).
VI.

VII. CONCLUSION
In this contribution, the gas solubility values for different
mineral, ester based as well as silicone insulating fluids are
presented. With a temperature rise from 25 C to 90 C the
nitrogen solubility increases round about 2 %. For example, in
a transformer with 50000 l oil filling this leads to a gas
exchange of about 1 m. Silicone oil behaves different with
twice the solubility compared to mineral oils. The measured
values are comparable to those from literature. At room
temperature, hydrogen is less soluble than nitrogen.

MAXIMUM SOLUBILITY OF A GAS MIXTURE

These values were also calculated using ASTM D2779

standard. The results are satisfactory for the mineral oils. For
alternative insulating fluids the calculation did not fit and for
these classes of materials new constants are needed.

The maximum solubility of a gas mixture consisting of

hydrogen and ambient air (for the mineral oils) or nitrogen (for
the non-mineral fluids) is measured. The samples are prepared
by using gastight syringes filled with degassed oil. A gas
mixture is injected with different proportions of H2 and air
respectively N2. In the process, one gas is abundantly available
and the other gas is dosed according to the desired
concentration. Afterwards the syringe is shaking for at least
1 hour. The maximum solubility is measured at room
temperature, using the gas chromatograph. CO2 from ambient
air and argon from glove box atmosphere are neglected.

In the last experiment, the solubility of a gas mixture at

room temperature is ascertained. Air or nitrogen saturated oils
can dissolve only small amounts of fault gases compared to
degassed oils. Therefore, the transformer conservator tank
sealing principle is of crucial importance for fault gas limit
concentrations.
REFERENCES

Fig. 2 illustrates the result. Each data point in the diagram is

the average of at least two measurements. The x-axis shows the
concentration of air or N2 in % without H2 (maximum
solubility of air), the y-axis the concentration of H2 in %
without air or N2 (maximum solubility of hydrogen).

[1]

[2]
[3]

[4]

[5]

[6]

Figure 2. Solubility of a gas mixture from hydrogen and N2 / air at 25 C

In the area below the curves it is possible to dissolve more

gas in the corresponding insulating fluid. Above the curves,
additional gas could not be solved and bubbles would rise. This
behaviour strongly depends on the insulating fluid and on the
conservator sealing principle. For example, a transformer with
completely degassed oil can dissolve more hydrogen (and other
fault gasses as well) compared to an air saturated oil, which
would allow to dissolve only H2 in the range of 1000 l/l. Once
again, it is noted, that the scaling of both axes is in % (1 % =
10 000 l/l).

940

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