Problems With Determining Oxygen

Deficiencies in Ratios Used for Assessing

Spontaneous Combustion Activity
Darren Brady
Manager OHECC
Simtars
Department of Mines and Energy

Spontaneous Combustion Ratios
Several ratios commonly used to indicate spontaneous
combustion, compare products of oxidation with the
amount of oxygen consumed.
Spontaneous Combustion Ratios
These ratios are used to measure the intensity of any
oxidation of the coal that may be occurring. As the
coal gets hotter the oxidation reaction becomes more
efficient and more of the oxygen is converted to
products of oxidation, such as carbon monoxide and
carbon dioxide.
Spontaneous Combustion Ratios
Ratios such as Grahams, Youngs and Jones-
Tricketts all divide products of combustion by the
amount of oxygen consumed to give a quantifiable
measure of how much oxygen was used to generate
the amount of combustion products measured.
DC2.CAD
Oxygen Deficiency
Oxygen deficiency is the term given to the amount of
oxygen used (consumed/removed) from the inlet air
stream by any activity as it undergoes reactions and
interactions with the coal.
What Can Go Wrong?
More than one source of oxygen depletion
What Can Go Wrong?
Equation used for calculating the oxygen consumed
by any oxidation/absorption-adsorption
What Can Go Wrong?
The measurement technique
What Can Go Wrong?
Instrument inaccuracies
What Can Go Wrong?
Unreliable for samples where oxygen deficiencies are
less than 0.3%
More Than One Source of Oxygen Depletion
If there is more than one source of oxygen depletion
then these ratios will be under estimated as it
appears that more oxygen was used to produce the
products than was really the case
Equations
Grahams ratio is often expressed as



Where:
= Grahams ratio
= final carbon monoxide concentration (%)
= final nitrogen concentration (%)
= final oxygen concentration (%)
f f O N
CO
GR
f
2 2 265 . 0
100

=
GR
f CO
f N2
f O2
Equation 1
Equations
Enables calculation without actually knowing what the
initial gas concentrations were.
The denominator in Equation 1 is the oxygen
deficiency.
Initial Oxygen Calculation

f i N O 2 2 265 . 0 =
i O2
f N2
If initial gas entering an area has a fresh air ratio of
20.95% O2 to 79.02% N2 (20.95/79.02 = 0.265),
Equation 2 can be used to calculate the initial O2
concentration by using the amount of N2 determined
to be present in the sample
Where:
= initial oxygen concentration (%)
= final nitrogen concentration (%)
Equation 2
Initial Oxygen Calculation
Based on the assumption that nitrogen, being an inert
gas, will not be consumed or created.
Only valid for samples where the initial gas has the
same O2 to N2 ratio as fresh air and where N2 and Ar
results are combined (79.02%).
Eliminates most problems with dilution because the
measured N2 will also been diluted.



Oxygen Deficiency

f f O N OD 2 2 265 . 0 =
Where:
= oxygen deficiency (%)
= final nitrogen concentration (%)
= final oxygen concentration (%)
OD
f N2
f O2
Equation 3
The measured oxygen concentration in the sample is then
subtracted from the calculated initial oxygen to give the
oxygen deficiency
Equations
Problems when the oxygen deficiency is large.
Analysis is done on a percentage volume basis, if O2
is being consumed/removed and nothing replaces it,
the nitrogen concentration increases.
The elevated nitrogen concentration results in over
estimation of initial oxygen concentration and
therefore oxygen deficiency.
Equations

O
2

(%)
N
2
(+ Ar)
(%)
Initial O
2

(%) Eq 2
OD( %)
Eq 3
OD (%)
O
2
*(%)
2.3 81.8 21.7 19.4 18.65
9.2 80.4 21.3 12.1 11.75
15.7 83.1 22.0 6.3 5.25
8.1 89.1 23.6 15.5 12.85
*calculated assuming initial oxygen 20.95%.
Equations

GR
) (
f i O O
CO CO
GR
i f
2 2
100

=
Where:
= Grahams ratio
= final carbon monoxide concentration (%)
= initial carbon monoxide concentration (%)
= initial oxygen concentration (%)
= final oxygen concentration (%)
f CO
i O2
f O2
i CO
Equation 4
If initial gas results are available Grahams ratio is
often calculated using;
Equations
Used when a tube bundle sampling point located in
an intake
Problems with calibration or drift of the oxygen
analyser are negated as they are common to both
measurements.
Any dilution with seam gas between locations is seen
as oxygen deficiency and over estimates oxygen
deficiency.
Equations
Grahams ratio calculations using Equation 4
CH
4

(%)
O
2i

(%)
O
2f

(%)
CO
f

(%)
GR
0 20.95 20.8 0.0005 0.333
3% 20.95 20.8x0.97 =
20.18
0.0005x0.97
=0.00049
0.063
6% 20.95 20.8x0.94
= 19.55
0.0005x0.94
=0.00047
0.034
Equations
f i
i
f
O O
N
N
OD 2 2
2
2

|
|
.
|

\
|
=
OD= oxygen deficiency (%)
f N2 = final nitrogen concentration (%)
i N2 = initial nitrogen concentration (%)
i O2 = initial oxygen concentration (%)
f O2 = final oxygen concentration (%)


Where:
Equations
Where:
= Grahams ratio
= final carbon monoxide concentration (%)
= initial carbon monoxide concentration (%)
= final nitrogen concentration (%)
= initial nitrogen concentration (%)
= initial oxygen concentration (%)
= final oxygen concentration (%)
GR
f
i
f
i
i
f
O
N
N
O
N
N
CO CO
GR
i f
2
2
2
2
2
2
100

|
.
|

\
|

|
.
|

\
|

=
f CO
i CO
f N2
i N2
i O2
f O2
Equations
Grahams ratio calculations using Equation 6
CH
4
(%)
N
2f

(%)
O
2f

(%)
CO
f

(%)
GR
0 78.8 20.8 0.0005 0.55
3 78.8x0.97
=76.44
20.8x0.97
=20.18
0.0005x0.97
=0.00049
0.55
6 78.8x0.94
=74.07
20.8x0.94
=19.55
0.0005x0.94
=0.00047
0.55

Equations
The use of the fresh air N
2
concentration of 79.02%
includes 0.9% Ar in the amount and is used for
techniques that are unable to differentiate the two
gases.
If the two are reported separately, the fresh air ratio is
20.95% oxygen to 78.1% nitrogen
(20.95/78.1=0.268).


Equations


GC analysis determines Ar and N2 separately
Equations 1, 2 and 3 must be modified for GC results
Equations
Equation 1 becomes:
f f O N
CO
GR
f
2 2 268 . 0
100


=
Equation 7
Equations
Equation 2 becomes:
f i N O 2 2 268 . 0 = Equation 8
Equations
Equation 3 becomes:
f f O N OD 2 2 268 . 0 =
Equation 9
Equations
-0.4
-0.2
0
0.2
0.4
0.6
0.8
1
1.2
1.4
24/03/2006 0:00 13/05/2006 0:00 2/07/2006 0:00 21/08/2006 0:00 10/10/2006 0:00 29/11/2006 0:00 18/01/2007 0:00 9/03/2007 0:00 28/04/2007 0:00 17/06/2007 0:00
Oxygen Deficiency calculated using Nitrogen as 79.02%
Oxygen Deficiency calculated with Nitrogen as 78.1%
Measurement Technique
Tube bundle and real time systems dont measure N2
Its calculated by subtracting the sum of the measured
gases from 100.
GC actually measures N2
Influences which equation must be used


Real Time vs Tube Bundle Oxygen Measurements
20.3
20.4
20.5
20.6
20.7
20.8
20.9
21
21.1
21.2
21.3
16/ 07/ 2006 21: 36 17/ 07/ 2006 0: 00 17/ 07/ 2006 2: 24 17/ 07/ 2006 4: 48 17/ 07/ 2006 7: 12 17/ 07/ 2006 9: 36 17/ 07/ 2006 12: 00
Time
O
x
y
g
e
n

C
o
n
c
e
n
t
r
a
t
i
o
n
(
%
)





Realtime Tube
Real Time vs Tube Bundle Oxygen Deficiencies
-0.6
-0.5
-0.4
-0.3
-0.2
-0.1
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
16/ 07/ 2006 0: 00 16/ 07/ 2006 4: 48 16/ 07/ 2006 9: 36 16/ 07/ 2006 14: 24 16/ 07/ 2006 19: 12 17/ 07/ 2006 0: 00 17/ 07/ 2006 4: 48 17/ 07/ 2006 9: 36 17/ 07/ 2006 14: 24
O
x
y
g
e
n

D
e
f
i
c
i
e
n
c
y

(
%
)
Real Time Tube Bundle
Real Time vs Tube Bundle Grahams Ratio
-1
-0.8
-0.6
-0.4
-0.2
0
0.2
0.4
0.6
0.8
7/ 07/ 2006 0:00 7/ 07/ 2006 12:00 8/ 07/ 2006 0:00 8/ 07/ 2006 12:00 9/ 07/ 2006 0:00 9/ 07/ 2006 12:00 10/ 07/ 2006 0:00 10/ 07/ 2006 12:00 11/ 07/ 2006 0:00
Time
G
r
a
h
a
m
'
s

R
a
t
i
o
Real Time Tube
Fresh Air Oxygen as Measured by Tube Bundle
20.45
20.5
20.55
20.6
20.65
20.7
20.75
20.8
20.85
20.9
3/03/2007 0:00 4/03/2007 0:00 5/03/2007 0:00 6/03/2007 0:00 7/03/2007 0:00 8/03/2007 0:00 9/03/2007 0:00
%

O
x
y
g
e
n
Tube Bundle 1 Tube Bundle 2
Tube Bundle
Measurement of oxygen using paramagnetic
analysers is flow rate dependent so flows from all
tubes must be balanced.

Tube Bundle
Two locations with the same oxygen concentration
could read differently because more resistance in one
of the tubes results in a slower flow and subsequently
a lower reading than a location with the same
concentration but flowing through the instrument at a
faster rate.

Instrument Inaccuracies
Slight inaccuracies in all measurements no matter
how well the analysis is done and how good the
instrument performing the analysis is.
These slight variations can cause problems in
samples with no significant oxygen deficiency
whenever we get a slightly higher O2 (or slightly lower
N2 measurement by GC analysis), and apply the
known fresh air O2 to N2 ratio to determine the oxygen
deficiency.
Instrument Inaccuracies

O
2

(%)
N
2

(%)
Oxygen
Deficiency
(%)
20.61 76.63 -0.07
20.55 76.73 0.01
Instrument Inaccuracies
It can appear that oxygen has actually been created
(very unlikely underground).
Really indicates that the ratio has stayed the same.
Difference comes totally from the acceptable
inaccuracies (tolerance) of the measurement
technique.
Instrument Inaccuracies
Calibration gas suppliers certify each component as the
likely concentration within limits eg the O2 concentration in a
recently supplied certified calibration gas is 19.60.5%.
The true concentration may be as low as 19.1% or as high
as 20.1%.
When used to calibrate an instrument to 19.6% any
difference will result in all oxygen measurements being high
or low, but analytically acceptable.
A change in calibration gas can lead to a step change in
values measured by the sensor/instrument calibrated with
that gas.
Instrument Inaccuracies

Oxygen analysers, at best, are accurate to 1% of full
scale. Thus a measured value of 20.7% for O
2
would
be +/- 0.2%
A sample measured as: 10 ppm CO, 0.1% CO
2
,
20.7% O
2
and 79.2% N
2
(by difference) could thus
vary between 20.5% and 20.9% O
2
and conversely
N
2
would be between 79.4 and 79.0%
Thus Grahams Ratio would range between:
GR =100 x 0.001 / (0.265 x 79.4 - 20.5)
= 0.1 / (21.04 - 20.5)
= 0.1 / 0.54 = 0.18
and
GR = 0.001 x 100 / (0.265 x 79.0 -20.9)
= 0.1 / (20.94 - 20.9)
= 0.1 / 0.04 = 2.86

Instrument Inaccuracies
Oxygen Deficiencies Less Than 0.3%
When oxygen deficiencies are less than 0.3% the
variation between readings can significantly affect the
calculated ratios.
Oxygen Deficiencies Less Than 0.3%
Measured O
2
(%)
O
2
Def
(%)
CO
(%)
Grahams
Ratio
20.94 0.01 0.0003 3.00
20.92 0.03 0.0003 1.00
20.90 0.05 0.0003 0.60
20.88 0.07 0.0003 0.43
20.86 0.09 0.0003 0.33
20.84 0.11 0.0003 0.27
20.82 0.13 0.0003 0.23
20.80 0.15 0.0003 0.20
20.78 0.17 0.0003 0.18
20.76 0.19 0.0003 0.16
20.74 0.21 0.0003 0.14
20.72 0.23 0.0003 0.13
20.70 0.25 0.0003 0.12
20.68 0.27 0.0003 0.11
20.66 0.29 0.0003 0.10
20.64 0.31 0.0003 0.10
20.60 0.35 0.0003 0.09
20.58 0.37 0.0003 0.08

Conclusions
Despite the problems, ratios incorporating oxygen
deficiencies can still be useful but anyone doing
interpretation must be aware of all of these
implications.
Conclusions
Care must be taken when calculating oxygen
deficiencies to ensure that the calculation is correct
and representative for the sample and analysis
technique.
Conclusions
Interpretation of data is best done looking at trends
rather than one off samples. Even if the ratio is being
underestimated, any increase in intensity should
result in an increase in the trend although the rate of
change may not match the increase in intensity.