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Redox microelectrode manual

Redox microelectrode manual

TABLE OF CONTENTS
Overview.................................................................... 2
Getting started........................................................... 2
1. Unpacking a new electrode .............................................. 3
2. mounting of the electrode and reference ......................... 3
3. Connecting the redox electrode........................................ 3
4. Calibration........................................................................ 3

Measurements........................................................... 4

the same solution, the Redox


electrode tip will develop an
electric potential relative to the
reference electrode which
reflects the tendency of the
solution to release or take up
electrons; also called the
Oxidation-Reduction Potential
(ORP).

Overview
The Unisense REDOX
microelectrode is a miniaturized
platinum electrode designed for
research applications within
environmental sciences, and
related areas.

This manual covers the Unisense


redox microelectrodes with or
without internal reference
electrode

With tip diameters down to


below 50 microns, the Unisense
REDOX microelectrode allows
measurements of redox potential
with a very high spatial
resolution.

RD10 (outer tip diameter <20


m - for fine scale
measurements)
RD25 (outer tip diameter 2030m)
RD50 (outer tip diameter 4060m)
RD100 (outer tip diameter 90110m)
RD500 (outer tip diameter 400600m)
RD-spec - Redox
microelectrodes with customer
specified specifications

Mounting of the electrode .................................................... 4


Reverting the redox potential to the
hydrogen scale ..................................................................... 4
Electrical noise ..................................................................... 5

Cleaning the electrode .............................................. 5


Advanced redox electrodes ...................................... 5

Thus the redox microelectrode


must be used in combination
with a reference electrode (e.g.
Unisense REF) and connected to
a high-impedance millivoltmeter. The Unisense REDOX
microelectrode can be used for
measurements in salinities from
0 to full ocean strength.

Storage and maintenance......................................... 5


References ................................................................. 6
Trouble shooting........................................................ 6

Figure 1. Shows the redox electrode and


a (external) reference electrode

The Unisense REDOX microelectrodes are miniaturized redox


platinum electrodes. When the
electrode tip is immersed in an
aqueous solution and connected
via a high-impedance millivoltmeter to a reference electrode
(see figur 1 and 2) immersed in
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Getting started
The signal from the redox
electrode is read on a high
impedance milivolt meter like
the Unisense PHM210. Therefore

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WARNING
Do not let the
microelectrode
tip touch
anything during
handling it is
very fragile.

Redox microelectrode manual

Redox microelectrode manual

submerged sufficiently in the


medium to cover the liquid junction during all measurements

the redox electrode must be


connected to a millivoltmeter
like the Unisense PHM210 during
measurements.

In the following, we assume that


you use a Unisense PHM210
millivoltmeter with your redox
electrode otherwise perform
analogous steps with the
millivoltmeter in question.

1. Unpacking a new
electrode
WARNING
Do not remove seal and
protective plastic tube before the
following steps (1-4 are
successfully completed

3. Connecting the redox


electrode

Replacement of electrodes
Unisense will replace electrodes
that have been damaged during
shipment provided that:

Connect the Unisense REDOX


microelectrode to the input
terminal of a high-impedance
millivoltmeter and the reference
electrode to the Ref/Ground
terminal.

The electrodes were tested


right upon receipt according to
the delivery note and the
manual
The seal is still intact.

The electrodes are returned

to Unisense for inspection

The electrodes are correctly


packed for return to Unisense
according to the note included
in the electrode box.

4. Calibration
Prepare quinhydrone redox
buffer solutions:
Mix 1 l of buffer solution (pH 4
or pH 7) with 10 g of
quinhydrone. Crystals of
quinhydrone should be present
indicating that the solution is
saturated. Quinhydrone is a
mixture of equal amounts (molar
basis) of hydrochinone and
quinone.

When receiving a new


microelectrode remove the
shock-absorbing grey plastic net.

2. Mounting the electrode


and reference
Secure the Unisense REDOX
microelectrode in a holder with
its tip immersed in a buffer
solution. Also place the tip of a
reference electrode (e.g.
Unisense REF5000) in the same
solution.
A Unisense REDOX electrode
with internal reference has to be

As redox electrodes directly


reflects the potential to be
measured, the calibration is
linear and in principle only 1
point calibration is needed
However, 2 points should be
measured to ascertain valid
electrode function.
Response time is up to 10
seconds

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Construction of
the electrode
with an internal
reference
involves
creation of a
liquid junction
approximately 3
cm from the
electrode tip.
During
measurements
this liquid
junction has to
be submersed in
the sample in
order to
complete the
measurement
circuit

micromanipulator MM-33
(MM33-2 or MMS) The Unisense
REDOX microelectrode tip is
surprisingly flexible and may
bend slightly to find its way
around physical obstacles. But
coarse lateral movements of the
electrode when its tip is in
contact with a solid substrate
may easily cause the tip to
break.

If you use a strip chart recorder


or other data acquisition device,
connect this to the output
connections of the milivoltmeter. Expose both reference
electrode and the Unisense
REDOX microelectrode tip to
quinhydrone redox buffers (pH 4
and 7). Record the signal sizes
on the display of the
millivoltmeter and/or your data
collection. The obtained
potentials will depend on the
actual temperature and on the
type of reference used. The
difference between the potential
obtained in quinhydrone redox
buffer 4 and quinhydrone redox
buffer 7 by using any reference
electrode should be between 170
and 185 mV. If the difference in
the obtained potential is not
within this range, clean the
electrode.

Due to the small size of the


microelectrode tip and to the
steep-ness of redox gradients in
many environments, even a
displacement of the electrode tip
of few microns may change its
immediate redox environment.
Therefore measurements should
be performed only in a stabilized
set-up fixed on a sturdy table
free of moving or vibrating
devices like the Unisense LS18
lab stand.

Reverting the redox


potential to the hydrogen
scale

If the electrode functions


according to the above
description, carefully remove the
seal and the protective plastic
tube before making
measurements.

As the redox potential measured


will depend on the type of
reference electrode used,
reference is normally made to
the hydrogen scale when redox
potentials are reported. The
reference potential of
quinhydrone redox buffers using
a standard hydrogen reference
electrode is as follows

Measurements
Mounting of the electrode
During measurements the redox
electrode should be properly
mounted in a stable set-up. We
recommend the Unisense lab
stand LS18 and the Unisense

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pH 4
buffer

pH7
buffer

IMPORTANT
As the Redox
microelectrode
is sensitive to
temperature, it
is necessary to
perform
calibration at
the same temperature as your
measurements

Redox microelectrode manual

Redox microelectrode manual

20

470

295

25

462

285

30

454

275

shipping. The room in which the


redox microelectrode is stored
should be dry and not too hot
(10-30C).

Cleaning the
electrode
The electrode can by cleaned by
immersing it in nitric acid (1+1)
Keep the electrode in the nitric
acid solution for about 30
minutes and allow it to cool and
rinse with water afterwards.

If another reference than the


standard hydrogen electrode is
used an offset is introduced and
must be compensated for. If, for
example, a potential of 44 mV
was obtained in quinhydrone
redox buffer pH 7, and the
temperature is 25 C then use
(285 mV- 44mV) = 241 mV as
offset.

Advanced redox
electrodes
Unisense can construct redox
electrodes for customer
requested applications at
additional costs. The most
frequently construction options
are described at our web page
under redox electrode
specifications

Electrical noise
As well as the physical size, the
electrical current generated by
the high-impedance
microelectrode is very small.
Although the Unisense REDOX
microelectrodes are very
resistant to electrical noise from
the environment, electrical fields
may interfere with the electrode
signal. Minimize this by
switching off unnecessary
electrical/mechanical equipment
and by not touching electrode or
wires during operation.

http://www.unisense.com/support/rd_spec.h
tml

The options include for instance


customer specified dimensions,
pressure tolerance, internal
reference and cable length. If
your specifications for a special
redox electrode are not
described at our web page
please contact sales@unisense.com
for further options and prices.

On suspicion of electrode
damage, repeat calibration and
consult Trouble-shooting.

Their Use in Microbial Ecology, p.


293-352. In K. C. Marshall (ed.),
Advances in Microbial Ecology, vol.
9. Plenum, New York.

References
WARNING
Always
introduce and
retract the
redox
microelectrode
axially using a
micromanipulator and a stable
stand when
measuring in
solid or
semisolid
substrate like
sediment,
tissue, biofilms,
microbial mats
etc.

Revsbech, N. P., and B. B.


Jrgensen. 1986. Microelectrodes:

Trouble shooting
Problem:

Drift in the calibration potential values

Possible cause:

Contamination of the platinum surface

Solution:

Clean the electrode tip as described above

Problem:

Sensitivity of the REDOX microelectrode is low or


the signal is unstable (1).

Possible cause:

Contamination of the platinum surface.

Solution:

Clean the electrode tip as described above.

Problem:

Sensitivity of the REDOX microelectrode is low or


the signal is unstable (2)

Possible cause:

Reference electrode is malfunctioning.

Solution:

Repair or change reference electrode.

Storage and
maintenance

Temperature
Keep good track of the
temperature, as the electrode
signal is very dependent on
temperature.

Store the electrode in the


protective plastic tube used for
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If you encounter
other problems
and need
scientific/technic
al assistance,
please contact
sales@unisense.com

for on-line
support (we will
answer you
within one
workday)