51935-88 Electrodos PDF
51935-88 Electrodos PDF
51935-88 Electrodos PDF
51935-88
Gel-filled pH Electrode
Models 51935-00, 51935-11, 51935-22
© Hach Company, 1999-2005. All rights reserved. Printed in China te/dk 03/03 2ed
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Table of Contents
Specifications..................................................................................5
Safety Precautions..........................................................................7
Section 5 Troubleshooting.....................................................25
Electrode Service Request Questionnaire ..................................29
Glossary .........................................................................................31
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4
Specifications
Specifications are subject to change without notice.
Electrode Type
pH combination with temperature probe
Range
0-14 pH units
Isopotential Point
7.00 ±0.5 pH units (0 ±29 mV)
Electrode Resistance
250 Mohms at 25 °C (new)
Slope
-58 ±3 mV at 25 °C
Temperature Range
Routine Use—0 to 45 °C (32 to 113 °F)
Occasional Use—0 to 100 °C (32 to 212 °F)
Storage
-40 to 50 °C (-40 to 122 °F)
Reference Half Cell
Ag/AgCl
Dimensions
Tip Diameter—12 mm (0.472 inches)
Total Length—152.4 mm (6 inches)
Cable Length—0.91 m (36 inches)
Cable Connector
• sension 5-pin Connector (Cat. No. 51935-00)
• Hach One® Meter Series BNC & 3.5 mm Phone Connector
(Cat. No. 51935-11)
• EC Series BNC & DIN Connector (Cat. No. 51935-22)
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Safety Precautions
Please read this entire manual before unpacking, setting up, or
operating this instrument. Pay particular attention to all danger
and caution statements. Failure to do so could result in serious
injury to the operator or damage to the equipment.
To ensure the protection provided by this equipment is not
impaired, do not use or install this equipment in any manner
other than that which is specified in this manual.
Precautionary Labels
Read all labels and tags attached to the instrument. Personal
injury or damage to the instrument could occur if not observed.
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Section 1 Introduction
9
Introduction, continued
The sension Gel-filled pH Electrode uses a silver/silver chloride
reference element with a glass frit junction and a full-range pH
glass that can be used in a wide variety of applications,
especially at extreme levels of pH. If using the sension System,
the meter will automatically account for buffer temperatures
during calibration and factor the information into the reported
pH. The Auto Buffer Recognition/Auto Temperature
Compensation calibration program built into sension meters
contains accurate pH profiles for buffers of pH 4.01, 6.86, 7.00,
and 10.01 at temperatures from 0 to 60 °C.
Reference
END VIEW
Temperature
Sensor
10
Introduction, continued
temperature and ionic strength of the aqueous solution, etc.
This hydrated layer affects the sensing properties of the bulb
(charge transfer, and ion transport). A dry bulb will not
function.
To ensure the full development of the hydrated layer, electrodes
should be conditioned for several minutes in a solution
comparable to the sample in terms of pH and ionic strength.
Normal Conditioning
(For routine measurements in samples of moderate to high
conductivity, approximately 150 µS and greater):
11
Introduction, continued
• Use calibration standards and samples that are at the same
temperature to improve accuracy.
• Use fresh calibration standards to achieve greater accuracy.
• Thoroughly rinse and blot the electrode dry between
sample measurements or rinse with small volumes of
sample or deionized water.
• Measure samples within a short period of time after
collecting. Weakly buffered alkaline solutions can absorb
carbon dioxide causing downward drift of pH readings.
Cover samples if necessary.
• A multi-point calibration will ensure more accurate
measurements than a single point calibration.
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Section 2 Applications
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14
pH, Water and Wastewater (above 150 µS/cm)
pH mV setup
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pH, Water and Wastewater, continued
cal
0
16
pH, Water and Wastewater, continued
READ READ
enter enter
READ
enter
OR
10. After the last 11. The display will 12. Rinse the
calibration point has show Store?. Press electrode with
stabilized and the ENTER to store the deionized water
display reads calibration or EXIT to followed by a small
Standard 3?, press leave the calibration amount of sample and
EXIT. mode without storing blot dry.
Note: For a three-point the values.
calibration, repeat steps
9-10 with an additional
buffer.
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pH, Water and Wastewater, continued
OR
Accuracy Check
Checking Electrode Response
An electrode is responding properly if its calibration slope is
58±3 mV per pH unit.
Checking Calibration Accuracy
Returning the electrode to a calibration buffer and determining
the pH provides a good test of the system. Rinse and
recondition the electrode before measuring subsequent
samples.
Checking the Precision of the Sample Reading
When practical, measure the pH of the sample several times and
report the average pH. sension2 meters will store and calculate
the average of up to 99 readings.
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pH, Water and Wastewater, continued
Method Performance
Precision
In a single lab using an ASTM Substitute Wastewater Standard,
specification number D5905-96, and two electrodes with a
single sension2, a single operator obtained a standard
deviation of 0.005 pH. Each electrode was exposed to seven test
solutions with no rinsing in between and with a default
stability of 0.5 mV/min.
Interferences
Sodium error may occur in samples with pH 12 or higher. See
Section 4.2 on page 24.
Summary of Method
Water with relatively high conductivity typically has a fairly
high buffer capacity. Slight pH changes due to absorption of
carbon dioxide are usually not significant. If the sample
conductivity is not known and high accuracy is desired, use the
Platinum Series pH Electrode and follow either the Low Ionic
Strength or high purity method.
The sension Gel-filled pH Electrode responds to the hydrogen
ion concentration (activity) by developing an electrical
potential. At a constant temperature, this potential varies
linearly with the pH of the solution being measured.
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pH, Water and Wastewater, continued
REQUIRED REAGENTS AND APPARATUS
Quantity Required
Description Per Test Unit Cat. No.
Gel-filled pH Elect. w/Temp., 5-pin ..1 ..............each ...51935-00
Gel-filled pH Elect. w/Temp., BNC & 3.5mm1 .each ... 51935-11
Gel-filled pH Elect. w/Temp., BNC & DIN1.......each ...51935-22
sension2 Portable pH/ISE Meter/w/elect.1 ......each ...51725-10
sension1 Portable pH/mV Meter/w/elect.1......each ... 51700-11
OPTIONAL REAGENTS
Buffer, Powder Pillow
pH 4.01, color-coded red............................. 15/pkg...... 22269-95
pH 6.86 .......................................................... 15/pkg...... 14098-95
pH 7.00, color-coded yellow....................... 15/pkg.......22270-95
pH 10.00, color-coded blue......................... 15/pkg.......22271-95
Singlet pH Solution, pH 7 and 10 ..... 10 each/pkg...... 27698-20
Singlet pH Solution, pH 4 and 7....... 10 each/pkg...... 27699-20
Singlet pH Solution, pH 4 ........................... 20/pkg.......27700-20
Singlet pH Solution, pH 7 ........................... 20/pkg.......27701-20
Singlet pH Solution, pH 10 ......................... 20/pkg.......27702-20
Singlet pH Solution,Rinse Solution ........... 20/pkg.......27703-20
Buffer Solution, pH 4 (red) ........................ 500 mL...... 22834-49
Buffer Solution, pH 7 (yellow) .................. 500 mL ...... 22835-49
Buffer Solution, pH 10 (blue)..................... 500 mL ...... 22836-49
pH Storage Solution Powder Pillows......... 20/pkg...... 26573-64
Water, deionized..................................................4 L...........272-56
OPTIONAL APPARATUS
Sample Bottles
General Purpose with Screw-cap,
polypropylene, 500-mL................................ each.......27581-10
Cleaned and Certified, HDPE,
for EPA reporting, 500-mL .......................... each.......27582-10
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Section 3 Electrode Maintenance
The sension™ Gel-filled pH Electrode has been designed to give
trouble-free use, but requires careful handling to extend
longevity. This section presents methods of storing and
cleaning the electrode.
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Electrode Maintenance, continued
2-minute period. Rinse with deionized water. Soak in deionized
water for at least 15 minutes.
Oils and fats—Immerse the electrode tip in a detergent solution
such as Alconox™. Use a soft brush or ultrasonic bath if
necessary. Avoid scratching the glass bulb.
Organic films—Use an appropriate solvent, such as methanol or
acetone.
Note: Keep the cable and connector away from dirt, abrasives, and harsh
solvents.
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Section 4 pH Electrode
Characteristics
4.1 Theory of Operation
pH is a measure of the hydrogen ion activity in a solution and
is defined as: -log10 aH+ where aH+ is the activity of the
hydrogen ion. The 0-14 range of pH measurement is the
measurement of a difference in hydrogen ion concentration of
100,000,000,000,000 (1 x 1014). This means that at pH 0, the
hydrogen ion concentration is 1 x 1014 times greater than at
pH 14. This also means that the hydroxyl ion concentration at
pH 14 is 1 x 1014 times greater than at pH 0.
When the hydrogen and hydroxyl ions are present in equal
numbers (the neutral point), the pH is 7. pH values from 0 to 7
are termed acidic and those from 7 to 14 are termed basic. It is
important to note that a pH change of one unit (for instance
from pH 6 to pH 7) is a factor-of-10 change in hydrogen ion
concentration.
The glass membrane of a pH electrode responds to the
hydrogen ion activity by developing an electrical potential at
the glass/liquid interface. At a constant temperature, this
potential varies linearly with the pH of the solution being
measured. The change in potential per pH unit is termed the
slope of the electrode. The slope of the electrode increases
linearly with temperature.
The potential inside the pH glass bulb is fixed by the filling
solution, and the reference electrode potential is constant.
For these reasons, any change in the potential of the electrode
system at a given temperature will be due to any change in the
pH of the solution being measured.
Effects of temperature on pH measurements depend on the
reference electrode used, pH of the solution within the pH
electrode and pH of the test solution. At a certain pH,
temperature will have no effect on the potential of the electrode
system. This is known as the isopotential point. Also, at some
pH level, the system will exhibit no potential. This is known as
the zero potential point. Both the isopotential point and the
zero potential point are features designed into electrodes. Hach
electrodes are designed so the isopotential and zero potential
points are at pH 7 to minimize temperature effects at this
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Section 4, continued
calibration point. At 25 °C, an electrode performing at 100%
efficiency will decrease by 59.2 mV for every unit increase
in pH.
4.2 Sodium Error Interferences
Sodium error occurs at elevated pH values when sodium ions in
the sample solution are incorrectly sensed as hydrogen ions by
the glass pH bulb. Below pH 12, sodium error is negligible.
The pH sensing bulbs can be optimized for different
applications by altering glass composition. This electrode has
been designed using a research-grade, full-range glass that is
less susceptible to sodium ion error. Accurate pH values (less
than 0.1 pH error) will be achieved at up to 100 mM Na+
concentrations in the range of 12 to 13 pH units, and up to
50 mM both at 25 °C in samples of pH 14.
In a single lab, using a sample group of three pH sensing
half-cells, in a controlled test versus a Standard Hydrogen
Electrode, the following results were obtained:
Table 1 Sodium Ion Error
pH [Na+] Error
12.1 0.00 M 0.00
12.1 0.01 M 0.01
12.1 0.05 M 0.02
12.1 0.10 0.03
12.5 0.00 M 0.02
12.5 0.01 M 0.02
12.5 0.05 M 0.03
12.5 0.10 0.05
13.7 0.00 M 0.04
13.7 0.01 M 0.06
13.7 0.05 M 0.07
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Section 5 Troubleshooting
Symptom Cause Remedy
No Electrode is improperly Check connection.
response connected to meter.
If a two-channel meter, is Reconnect the electrode to
the electrode connected to the desired channel or
the displayed channel? change the displayed
(A shorting cap on a channel channel on the meter.
input will show ZERO on
the display.)
Connector is dirty or wet. 1. Inspect both male and
female connector.
2. Clean with mild
solvents such as
alcohol or acetone.
3. Clean and dry with a
lint-free cloth or
compressed air.
Reference junction is Immerse in hot water or an
blocked. ultrasonic bath for several
minutes.
pH sensing bulb and Submerge the probe
reference junction are not in deeper into the sample.
contact with the sample.
Cable contains kinks, breaks, Replace or repair
loose connectors, etc. electrode.
The meter is broken. 1. Try another electrode.
2. Try the other channel.
3. Check and replace
batteries, if necessary.
4. Put shorting caps on
and see if meter
‘zeros’.
The meter is not set up to Select the appropriate
read the appropriate connector from the meter
connector. setup menu (5-pin on
sension meters).
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Troubleshooting, continued
Symptom Cause Remedy
Out-of- See “No response”, above. See “No response”, above.
range
The bulb may be broken. Replace bulb.
response
Erratic Electrode is not plugged-in Plug electrode into meter
response to selected meter channel. channel.
Extreme external electrical Install a shorting cap on
fields are present. (The pH the unused meter terminal.
cable, though shielded, can Do not use stirrers in low
act as an antenna.) ionic strength solutions.
Avoid static electricity,
nearby pumps, power
supplies, etc.
pH sensing bulb and Submerge the probe
reference junction are not in deeper into the sample.
contact with the sample.
The sample chemistry is None.
changing.
The pH of a LIS solution is Use LIS Chamber
changing due to CO2 uptake. Accessory.
The bulb is cracked, If dirty, clean according to
discolored, or contaminated. Section 3.2 on page 21.
If cracked, discard
electrode.
The sample container is Use a clean sample
contaminated. container.
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Troubleshooting, continued
Symptom Cause Remedy
Low slope Bulb is old. Replace electrode.
Bulb is dirty. Clean according to Section
3.2 on page 21.
Standards are inaccurate. Make sure standards were
entered into meter
correctly.
Use only NIST traceable
buffers.
Use fresh buffers.
Change buffers frequently.
History of harsh usage. Replace electrode.
Cracked bulb. Replace electrode.
High slope Buffers are incorrect. Use appropriate buffers.
Incorrect measurement or Follow procedures
calibration technique. described in SECTION 2 on
page 13.
Temperature variations in Keep sample and standards
standards. at same temperature.
Standards contaminated. Prepare fresh standards.
High offset Leakage pathway results in Return electrode under
stray voltage via internal warranty.
electrical short.
Reference gel has become Submerge in hot water or
diluted or junction is an ultrasonic bath to
plugged by a clogged frit. attempt to unclog the frit.
Replace electrode if no
improvement occurs.
Cracked bulb. Replace electrode.
Sluggish Sample is cold and of low Wait patiently.
response ionic strength.
Improper conditioning. Condition according to
Section 1.3 on page 10.
Bulb, guard, and electrode Clean according to Section
stem are dirty. 3.2 on page 21.
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Electrode Service Request
Questionnaire
1. What model of meter is the electrode being used with?
15. Did you use a low range method for Low Ionic Strength
and high purity water samples with conductivity below
150 µ/cm?
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Glossary
Acid—a chemical compound that contributes hydrogen ions
(H+) to an aqueous solution or causes the pH to be less than 7.0.
Buffer—
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Glossary, continued
regardless of solution composition. The sensing half-cell
develops a potential proportional to solution composition.
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Glossary, continued
Ion—An atom, group of atoms or molecule that is electrically
charged as the result of gaining or losing electrons. An ion
resulting from the gain of electrons becomes negative (anion),
while an ion resulting from the loss of electrons becomes
positive (cation).
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Glossary, continued
Sensing half-cell—Provides a voltage proportional to the
concentration of a specific ion in solution.
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General Information
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How To Order
By Telephone: By Mail:
6:30 a.m. to 5:00 p.m. MST Hach Company
Monday through Friday P.O. Box 389
(800) 227-HACH Loveland, CO 80539-0389
(800-227-4224) U.S.A.
By FAX: (970) 669-2932
International Customers
Hach maintains a worldwide network of dealers and
distributors. To locate the representative nearest you, send
E-mail to intl@hach. com or contact:
In Canada, Latin America, Africa, Asia, Pacific Rim:
Telephone: (970) 669-3050; FAX: (970) 669-2932
In Europe, the Middle East, or Mediterranean Africa:
HACH Company, c/o Dr. Bruno Lange GmbH
Willstätterstr. 11
D-40549 Düsseldorf, Germany
Telephone: +49/[0]211.52.88.0
Fax: +49/[0]211.52.88.231
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Repair Service
Authorization must be obtained from Hach Company before
sending any items for repair. Please contact the HACH Service
Center serving your location.
In the United States:
Hach Company
100 Dayton Avenue
Ames, Iowa 50010
(800) 227-4224 (U.S.A. only)
Telephone: (515) 232-2533
FAX: (515) 232-1276
In Canada:
Hach Sales & Service Canada Ltd.
1313 Border Street, Unit 34
Winnipeg, Manitoba
R3H 0X4
(800) 665-7635 (Canada only)
Telephone: (204) 632-5598
FAX: (204) 694-5134
E-mail: canada@hach.com
In Latin America, the Caribbean, the Far East,
the Indian Subcontinent, Africa, Europe, or the Middle East:
Hach Company World Headquarters
P.O. Box 389
Loveland, Colorado, 80539-0389
U.S.A.
Telephone: (970) 669-3050
FAX: (970) 669-2932
E-mail: intl@hach.com
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Warranty
Hach warrants most products against defective materials or
workmanship for at least one year from the date of shipment;
longer warranties may apply to some items.
HACH WARRANTS TO THE ORIGINAL BUYER THAT HACH
PRODUCTS WILL CONFORM TO ANY EXPRESS WRITTEN
WARRANTY GIVEN BY HACH TO THE BUYER. EXCEPT AS
EXPRESSLY SET FORTH IN THE PRECEDING SENTENCE,
HACH MAKES NO WARRANTY OF ANY KIND WHATSOEVER
WITH RESPECT TO ANY PRODUCTS. HACH EXPRESSLY
DISCLAIMS ANY WARRANTIES IMPLIED BY LAW,
INCLUDING BUT NOT BINDING TO ANY WARRANTY OF
MERCHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE.
LIMITATION OF REMEDIES: Hach shall, at its option, replace
or repair nonconforming products or refund all amounts paid
by the buyer. THIS IS THE EXCLUSIVE REMEDY FOR ANY
BREACH OF WARRANTY.
LIMITATION OF DAMAGES: IN NO EVENT SHALL HACH BE
LIABLE FOR ANY INCIDENTAL OR CONSEQUENTIAL
DAMAGES OF ANY KIND FOR BREACH OF ANY WARRANTY,
NEGLIGENCE, ON THE BASIS OF STRICT LIABILITY, OR
OTHERWISE.
This warranty applies only to Hach products purchased and
delivered in the United States.
Catalog descriptions, pictures and specification, although
accurate to the best of our knowledge, are not a guarantee or
warranty.
For a complete description of Hach Company’s warranty policy,
request a copy of our Terms and Conditions of Sale for U.S.
Sales from our Customer Service Department.
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