Humidity Extremes

Alphasense Application Note AAN 106
AAN 106 HUMIDITY EXTREMES: DRYING OUT AND

WATER ABSORPTION
Alphasense electrochemical toxic gas sensors are low power devices with excellent
resolution, dynamic range and selectivity. These electrochemical cells contain
sulfuric acid electrolyte for ionic transport. See Application Note AAN 0104 for an
explanation of their operation.
This aqueous acid electrolyte will lose water in low humidities and gain water in high
humidities. This Application Note explains why Alphasense toxic gas sensors are
specified to operate in the humidity range of 15 to 90% rh and describes sensor
performance after drying out or absorbing water.
The Thermodynamics
Mixtures of water and sulfuric acid have been used for decades to generate a known
water vapour pressure, also called the “equilibrium relative humidity” (erh). As the
sulfuric acid concentration increases the water vapour pressure over the liquid
mixture decreases, eventually reaching zero percent rh in concentrated sulfuric acid.
Figure 1 below shows how the equilibrium relative humidity decreases as the sulfuric
acid concentration increases. The erh is only slightly dependent on the temperature,
as Figure 1 shows.
100
90
0C
80
25C
70
60 50C
%rh
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90
% H2SO4
Figure 1. Equilibrium relative humidity (erh) of sulfuric acid and water mixtures.
Alphasense toxic gas sensors start out with a concentration of 5 M sulfuric acid
corresponding to 60% equilibrium relative humidity at 20°C. If you expose a gas
sensor to humidity less than 60% rh then this relative humidity difference will force
the sensor to lose water by evaporation. Likewise, if you place the sensor in humidity
above 60% rh then the sensor will absorb water.
In dry atmospheres the water/sulfuric acid electrolyte will lose water and become
more concentrated so the electrolyte erh will decrease and eventually equal the
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relative humidity of its environment. The sensor stabilises to its local relative
humidity environment.
Conversely, in very high humidities the electrolyte will absorb water and increase its
erh. The danger is that if it absorbs too much water then the sensor cannot contain
the extra electrolyte which can sometimes be two or three times the initial electrolyte
volume, causing sensor leakage.
Figure 2 shows how an H2S-A1 sensor loses weight in low humidities and gains
weight in high humidities at 20C.
0.4
0.3
0.2
95%rh
Weight Gain / Loss (g)
0.1
75% rh
-0.1
25% rh
-0.2
0% rh
-0.3
-0.4
2 4 6 8 10 12 14 16 18 20 22 24 26 28
Time/ Days
Figure 2. Sensor weight gain/ loss when subjected to humidity extremes.
The Kinetics
How fast does this happen? Figure 3 shows the rate of weight loss (i.e. water loss
from the electrolyte) for an H2S-A1 sensor for 50 days when exposed to 0%rh air at
20°C. The sensor reaches a stable weight after 25 to 30 days. Note that sensors
with larger gas diffusion holes reach their equilibrium weight in only 10 days while
sensors with smaller holes take much longer. The rate of water loss is proportional to
the hole area (not hole diameter). Note that sensors with large diffusion holes have
high nA/ ppm sensitivity (i.e. are high resolution sensors) and sensors with small
diffusion holes have lower nA/ppm sensitivity, with high range and lower sensitivity.

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0.35
0.3
7.5 mm hole
0.25
3.8 mm
Weight Loss/ g
0.2
2.5 mm hole
0.15
0.1
0.05
0
0 5 10 15 20 25 30 35 40 45 50 55
Time/ Days
Figure 3. Weight loss for Alphasense H2S-A sensors in 0% rh. Increasing hole size
speeds up water loss rate.
What else influences the rate of water loss or water absorption?

• Temperature affects the rate of water loss. At higher temperatures water
evaporates or absorbs faster.
• Hole size influences the rate of water loss. Sensors with high range and low
sensitivity will dry out slower because they have a smaller gas diffusion barrier
hole.
• Rate of airflow across the sensor does not affect the rate of water/water gain.
• Sensors with chemical filters lose or gain water at the same rate as sensors
without chemical filters.
Weight loss and weight gains are reversible: if you allow a sensor to stabilise in very
dry air, then it will regain weight when you place it back in a moist environment.
Performance Changes
Alphasense Technical Group has studied the effects of water loss and gain on
sensor performance.
Water Absorption
Sensor performance does not change as the sensor absorbs water. The sensor will
appear to be normal with standard response time, sensitivity and zero current, but if it
continues to absorb water above 90% rh then the sensor will leak – this is associated
with either a large reduction in sensitivity or a very high zero current. In these cases
the sensor has been used outside of warranted performance.

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Performance Change During Dehydration

Dehydration is a more common problem. This complex problem has been modelled
and the effects are mostly understood. During dehydration the sensor goes through
two, possibly three mechanisms of water loss.
1 In the first 5 to 20 days the sensor rapidly loses water by evaporation.

2 Eventually the sensor has lost enough water that the equilibrium relative
humditity approaches the ambient relative humidity and the sensor remains
stable. If the sensor is used within rh specification then the sensor
performance is stable and the instrument/ detector should be recalibrated at
the ambient rh where it will remain stable.
3 If the sensor is used in atmospheres less than 15% rh (see Figure 7 below)
the electrolyte cannot dehydrate to match the ambient relative humidity and
will continue to lose water until there is inadequate electrolyte to transport
ions between the electrodes– this sensor will fail, although it can be
recovered by storing in a moist atmosphere (less than 90% rh).
Figures 4, 5, 6 and 7 show the response time (t90) and sensitivity for CO and
H2S sensors.
5 0
4 5
4 0
Response t90/ sec
3 5
C O -B F
3 0
2 5 C O -A F
2 0
C O -B F
C O -A F
1 5
1 0
0 5 1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5
T im e / D a y s
Figure 4. Increasing response time of CO sensors when losing water at low rh.
1 8
1 7
1 6
Response t90 /sec
1 5
1 4
1 3
1 2
0 5 1 0 1 5 2 0 2 5 3 0 3 5
T im e /D a y s
Figure 5. Response time (t90) stays constant for H2S sensors when losing
water at 0% rh.

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1 1 0
1 0 0
% initial sensitivity
9 0
8 0
7 0
6 0
0 5 1 0 1 5 2 0 2 5 3 0
T im e / D a y s
Figure 6. Sensitivity for CO sensors remains constant during dehydration at 0%rh.
1 20
1 10
Sensitivity nA/ppm (CO)
1 00
C O -B F
90
80
70
C O -A F
60
50
0 5 10 15 20 25 30 3 5
T im e /D a y s
Figure 7. Sensitivity decreases for H2S sensors during phase 1 when

dehydrated at 0%rh.
The critical points to note about these graphs are:

• CO sensor sensitivity is stable during both phases 1 and 2 of dehydration.
• H2S sensitivity decreases during phase one of dehydration but stabilises during
phase two.
• CO sensor response time increases from typically 20-25 seconds to 30-40
seconds during stage one but will eventually stabilise if the humidity is greater
than 15% rh. H2S sensors appear not to change their response time even
during drying out.
Other properties such as noise and zero current are not affected by dehydration or
water absorption.

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Recovery
If a sensor has been exposed for a long period to an ambient humidity significantly
different than the equilibrium relative humidity of about 60% rh then its properties
may change. However, this is reversible and if exposed to a high humidity after
dehydration or a low humidity after water adsorption, then the sensor will return to its
original state. Operation for extended periods outside the 15-90% rh range will
invalidate the warranty.
Figure 8 shows a group of CO-AF sensors increasing their weight after being
dehydrated for a long period at low humidity. The rate of water absorption after
dehydration is at about the same rate as the rate of water loss during dehydration.
5 .8
5 .7 5
5 .7
Day 13
Weight/ g
Day 10
5 .6 5
5 .6
5 .5 5
D ay 1
5 .5
D a te
Figure 8. Weight gain of CO-AF sensors during rehydration after dehydration at 0%

rh.
Failure Analysis
A simple way to check for excessive dehydration or water absorption is to weigh the
sensor. Although each sensor is not weighed by Alphasense, we weigh a sample of
every sensor batch and can tell you the mean batch weight when manufactured. If
the sensor weight is more than ±250 mg from the original weight then the sensor will
either show performance change if dried out or potential leakage if used in high
humidities. Contact Alphasense Technical Sales for batch weights.
Case Cracking in Extreme Conditions

The polymer used in Alphasense toxic sensors is polycarbonate. This engineering
plastic shows excellent strength and impact resistance, but if the sensors are
exposed to temperatures below -30C, then cracking may occur. This is outside the
specified environmental conditions; contact Alphasense if you suspect that your
sensor has been exposed to temperature and humidity extremes, outside of the
specified ranges.

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Conclusions
• Toxic gas sensors will lose weight (dehydrate) or gain weight when exposed to
humidities significantly away from the equilibrium relative humidity of 60% rh.
• Sensors absorbing water at high humidities (>90% rh) for long periods may leak.
• Sensors exposed to humidities greater than 15% rh but less than 60% rh will lose
water but then stabilise within 5 to 25 days, depending on the sensor type and
ambient temperature.
• When CO sensors dehydrate, the sensitivity remains constant but the response
time slows.
• When H2S sensors dehydrate, the sensitivity initially decreases before stabilising
but the response time remains constant.
• Sensors that have dehydrated will gain water and return to their original
performance if stored in a high humidity (<90% rh) environment for 5 to 25 days.
• Sensors that have gained water but have not leaked (between 60% and 90% rh)
will lose water when exposed to a low humidity (between 15% and 60% rh)
environment.
• Short-term excursions into very low or very high humidities are permissible.
Figure 3 shows the rate that sensors lose water when exposed to zero relative
humidity.
• If a sensor is exposed to a long-term ambient relative humidity far away from 60%
rh, then allow the sensor to stabilise for about 25 to 30 days, then check
calibration.

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Alphasense Application Note AAN 106

AAN 106 HUMIDITY EXTREMES: DRYING OUT AND

Figure 2. Sensor weight gain/ loss when subjected to humidity extremes.

© Alphasense Ltd Page 2 of 7 Issue 12

What else influences the rate of water loss or water absorption?

© Alphasense Ltd Page 3 of 7 Issue 12

Performance Change During Dehydration

1 In the first 5 to 20 days the sensor rapidly loses water by evaporation.

© Alphasense Ltd Page 4 of 7 Issue 12

Figure 6. Sensitivity for CO sensors remains constant during dehydration at 0%rh.

Figure 7. Sensitivity decreases for H2S sensors during phase 1 when

The critical points to note about these graphs are:

© Alphasense Ltd Page 5 of 7 Issue 12

Figure 8. Weight gain of CO-AF sensors during rehydration after dehydration at 0%

Case Cracking in Extreme Conditions

© Alphasense Ltd Page 6 of 7 Issue 12

© Alphasense Ltd Page 7 of 7 Issue 12

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