D e l i v e r i n g t h e To o l s f o r S c i e n c e

Checking pH Electrode Functionality

T here are many different industries that rely on the use of a pH
meter to make decisions about a process. Calibration is an
important function that must be done routinely to standardize the
How to calculate a pH Electrode Slope Percentage
1) Read the mV potential generated by an electrode in calibration
buffer.
electrode in face of its ever-changing characteristic. That is, when 2) Determine the mV potential being generated per pH unit.
the meter is calibrated it is done to compensate for the changes 3) Divide this number by the theoretical maximum (59.16 mV/pH
that have taken place to the electrode since the previous calibration. unit @ 25oC) and multiply by 100.
There are many influences, including aging, temperature, coatings
Example:
and chemicals used, that will affect the probe characteristic. So the
pH electrode generated –15 mV in pH 7.01 buffer and +160 mV in
question becomes, what is typical and how do you check it?
pH 4.01 buffer.
A pH meter is a very sensitive voltmeter. When a pH probe is placed
160 mV – (-15 mV) = 175 mV
into a solution, an mV potential is generated in response to the
175mv/3 = 58.33 mV/pH unit
hydrogen ion concentration [H+]. The theoretical voltage generated
58.33/59.16 x 100 = 98.6% slope
can be determined by the Nerst equation. Theoretically at 25oC,
Generally a slope between 90 and 105% is acceptable.
a pH 7.0 solution will generate 0 mV and there will be a 59.16
Offset value (pH 7.01) should always fall between +/- 25 mV
mV change for each pH unit. So at pH 4.0, +177.48 mV will be
generated while at pH 10.0, with a lower H+ concentration relative Some pH meters are now manufactured with indicators that give
to pH 7.0, a potential of -177.48 mV will be generated. Again, feedback on probe condition. Hanna Instruments has incorporated
this is theoretical and does not represent the real world behavior. algorithms into meters that
In fact, a new pH electrode will generate between +/- 10 mV in look at the slope and the offset
pH 7.0 and will have a slope percentage between 95 and 105%. value of the user of potential
The slope percentage is determined by dividing the actual voltage probe problems. Meters with
generated by the theoretical and then multiplied by 100. the Cal-Check feature have
indicators that include the
The following two examples show electrodes with different
overall probe condition, when
characteristics, where the voltage generated was measured with
to clean the electrode, and on
a pH meter.
some models when the buffer
Example 1: An electrode in pH 7.0 buffer generates +15 mV. is contaminated.
When placed in pH 4.0 buffer it generates +175 mV. The net The image here shows an
difference between the two buffers is +160 mV, which is then example of two pH probes
divided by +177.48 mV. The result, 0.901, is then multiplied by that have acceptable slope
100 to give a slope percentage of 90.1%. percentages but different offset
values. No other manufacturer
Example 2: An electrode in pH 7.0 buffer generated -45 mV
of pH meters distributed in
while in pH 4.0 it generated +115 mV. The net difference is 160
the U.S. would have caught
mV and, as seen from example 1, equates to a 90.1% slope.
the offset error. The electrode condition bar gives an easily read
Example 2 is a prime example of how a probe can be calibrated but indication of electrode health.
not be operating with an acceptable probe characteristic. That is, a
Featured Products
slope of 90% is acceptable but the offset of -45mV is not. An offset
Exclusive Hanna Cal-Check is available on Hanna meters HI 4221
shift can be the result of a build-up of dirt on the probe. This will
and HI 4222.
affect the response time. Also, if the coating comes off with use
then the characteristic will change and the calibration will no longer Supplied with glass body pH electrode, temperature probe, 12V
be valid. Typically, the offset should fall within +/-25 mV and the DC adapter, pH 4 & 7 buffer solutions, electrode refilling solution,
slope should be between 85 and 105%. The greater the accuracy electrode holder and instructions.
needed the closer the readings should be to the theoretical. Extract from article by Paul Fabsits, Hanna Instruments
Paula’s Pointers
Follow these tips to get the best from your electrode.
Background Reading
1. Use correct electrode storage solution to ensure minimum electrode response time. This text provides the coverage
2. Clean electrode to prevent drift and slow response times. Remember excessive cleaning may and practice needed to build
impair performance and shorten electrode life. a solid foundation in the
3. Remove the fill hole cover during calibration and measurement. Cover the fill hole overnight and mathematical concepts used
during storage. in laboratory sciences. The
4. Filling solution level must be higher than the sample level. convenient workbook design
5. Rinse to prevent contamination by carry-over on the electrodes. Do not wipe the pH electrode includes practice problems
glass bulb, as static will result in slow or drifty response. that help users focus
6. Stir all buffers and samples at a uniform rate. Prevent heat transfer by using a piece of insulating on areas they want to
material between the stir plate and beaker. strengthen, such as
7. Do not re-use buffers and standards and ensure they are within the expiration date before use. solutions, dilutions, pH
8. Calibrate at least once a day with 2 or 3 buffers that bracket the expected sample range. and graphing. Z700681 Essential Laboratory Mathematics

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Labware Listens 5 6
Down Time
Electrode cleaning and storage solutions 4 7 1 Number puzzles first appeared in
7 5 newspapers in the late 19th century in
he Sigma-Aldrich Technical Service teams are
T frequently asked to recommend pH electrode cleaning
and storage solutions. However, we did not offer a
7 9
8
2

1 3
the form of magic squares that relied on
arithmetic to solve. Soon after a Suduko
like puzzle appeared. Unlike the Magic
Square, Suduko is a logic based puzzle
simple solution within our product range. Recognizing 3 6 7 4 where the objective is to complete the
this demand, we are now able to offer a full range of pH grid so that each column, row and each
3 1 6 5 2 3x3 square contains the digits 1 to 9.
electrode cleaning and storage solutions. No matter what The completed puzzles are a form of
5 3 4 6
test samples you are using we have a cleaning solution Latin square with the addition of no
5 9 repetitions in the 3x3 square.
for you.

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