Oxidation Reduction Potential (ORP) DOC316.53.

01244
Direct Measurement Method Method 10228
–2000 to 2000 mV ORP electrode
Scope and application: For drinking water, wastewater and process water applications.

Test preparation

Instrument-specific information
This procedure is applicable to the meters and probes that are shown in Table 1.
Procedures for other meters and probes can be different.
Table 1 Instrument-specific information
Meter Probe
HQ1100 and HQ11d portable one input, pH/ORP Intellical MTC101 ORP
HQ4100, HQ2100 and HQ30d portable one input, multi-parameter Intellical MTC301 refillable ORP
HQ4200, HQ2200 and HQ40d portable two input, multi-parameter
HQ4300 portable three input, multi-parameter
HQ411d benchtop one input, pH/mV
HQ430d benchtop one input, multi-parameter
HQ440d benchtop two input, multi-parameter
Sension+ pH1 portable pH Sension+ 5045, 5048 or 5055 multi-parameter
Sension+ MM110 portable pH/ORP
Sension+ MM150 portable pH/ORP/EC
Sension+ pH3 lab pH Sension+ 5056 or 5057 single-parameter
Sension+ pH31 GLP lab pH
Sension+ MM340 lab two input, pH/mV/ISE
Sension+ MM374 lab two input, pH/mV/EC/ISE
Sension+ MM378 lab two input, pH/ISE/EC/DO

Before starting
Refer to the meter documentation for meter settings and operation. Refer to probe documentation for probe preparation,
maintenance and storage information.
Prepare the probe before initial use. Refer to probe documentation.
When an Intellical probe is connected to an HQ meter or an HQd meter, the meter automatically identifies the measurement
parameter and is prepared for use.
Do not dilute ORP/Redox standards and samples. Use a fresh ORP/Redox standard for calibration.
ZoBell’s redox potential is temperature dependent. The HQ/HQd calibration routine factors in this temperature dependency
allow accurate calibrations within the temperature range of 0 to 30 °C (32 to 86 °F). Light’s solution should be read at 25 °C
(77 °F). Custom ORP/Redox calibration solution values and temperature are user defined.
To significantly reduce the stabilization time for reducing-type samples, put the platinum disc in Reducing Solution for ORP
Electrodes for 3-10 minutes before the initial sample measurement.
Analyze the samples immediately. The samples cannot be preserved for later analysis.
Air bubbles under the sensor tip can cause slow response or measurement errors. To remove the bubbles, carefully shake
the probe.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.

1
 Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.
This procedure is specified for the HQ meters and HQd meters. The Sension+ meters can be used, but the menus and
navigation will be different.

Items to collect
Description Quantity

ORP/Redox Standard Solution 25 mL

Beaker (laboratory test) 1
Wash bottle with deionized water 1
Lint-free cloth 1

Sample collection
• Analyze the samples immediately. The samples cannot be preserved for later
analysis.
• Collect samples in clean glass or plastic bottles.

Test procedure

1. Rinse the probe with 2. Laboratory test: Put the 3. Push Read. A progress 4. When the value is stable,
deionized water. Dry the probe in a beaker that bar is shown. When the store or record the mV value
probe with a lint-free cloth. contains the solution. Do not measurement is stable, the and the temperature value.
let the probe touch the stir lock icon is shown.
bar, bottom or sides of the
container. Remove the air
bubbles from under the
probe tip. Stir the sample at
a slow to moderate rate.
Field test: Put the probe in
the sample. Move the probe
up and down to remove
bubbles from the probe tip.

Calculate standard hydrogen electrode (SHE)

To supply oxidation reduction (redox) potential measurements relative to the standard
hydrogen electrode (SHE), do the steps that follow:

1. Select the electrode potential (C) for the temperature of the solution measured. Refer
to Table 2.
2. Calculate the oxygen reduction potential of the sample relative to the SHE as follows:
ESHE = E0 + C
Where:
ESHE = oxygen reduction potential (ORP) of the sample relative to the SHE

2 Oxidation Reduction Potential, ORP (–2000 to 2000 mV)

 E0 = measured potential across the ORP electrode (mV)
C = potential across the reference electrode relative to the SHE
Table 2 Reference electrode potentials
Temperature Electrode potential (C) Temperature Electrode potential (C)
10 °C (50 °F) 221 mV 30 °C (86 °F) 204 mV
15 °C (59 °F) 216 mV 35 °C (95 °F) 200 mV
20 °C (68 °F) 213 mV 40 °C (104 °F) 196 mV
25 °C (77 °F) 208 mV

Interferences
Many factors limit the interpretation of ORP measurements in water. These factors
include irreversible reactions, electrode poisoning, multiple redox couples in the sample,
very small exchange currents and inert redox couples. ORP measurements in the field
can correlate poorly with ORP values calculated from the redox couples in the sample.
Because of these factors, the interpretation of ORP measurements will be specific to the
particular application.
Accuracy check
Standard solution method—Procedure A
Use one of the two standard solution methods to validate the test procedure and the
instrument.
Items to collect:
• Light's Solution ampule or 25 mL of ORP standard solution
• Beaker, 50-mL

1. Pour the content of the ampule in the beaker.

2. Immediately put the probe in the beaker.
3. Use the test procedure to measure the ORP of the solution.
4. Compare the expected result to the actual result. The potential should be
475 ± 10 mV or the specified ORP value.
Note: This potential is the standard reduction potential for Fe2+/Fe3+ with the reference
electrode potential subtracted. The solution is 0.01 M in both Fe2+ and Fe3+.

Standard solution method—Procedure B

DANGER
Chemical exposure hazard. Potassium Ferrocyanide and Potassium Ferricyanide are
toxic. Keep cyanide solutions at more than pH 11 to prevent exposure to hydrogen
cyanide gas. Dispose of reacted solutions according to local, state and federal
regulations.

Use either standard solution method to validate the test procedure and the instrument.
Items to collect:
• Potassium Ferrocyanide, 4.64 g
• Potassium Ferricyanide, 3.3 g
• Potassium Fluoride, 3.39 g
• 100-mL volumetric flask, Class A (2x)
• 150-mL beaker (2x)
• Deionized water, 200 mL

Oxidation Reduction Potential, ORP (–2000 to 2000 mV) 3

 1. Prepare Solution A (0.1 M Potassium Ferrocyanide and 0.05 M Potassium
Ferricyanide) as follows:
a. Put the items that follow in a 100-mL volumetric flask.
• 4.22 g reagent-grade K4Fe(CN)6•3H2O
• 1.65 g reagent-grade K3Fe(CN)6
b. Add 50 mL of deionized water to dissolve the solids. Mix well.
c. Dilute to the mark with deionized water. Mix well.
2. Prepare a Solution B (0.01 M Potassium Ferrocyanide, 0.05 M Potassium
Ferricyanide and 0.36 M Potassium Fluoride) as follows:
a. Put the items that follow in a 100-mL volumetric flask:
• 0.42 g reagent-grade K4Fe(CN)6•3H2O
• 1.65 g reagent-grade K3Fe(CN)6
• 3.39 g of reagent-grade KF•2H2O
b. Add 50-mL of deionized water to dissolve the solids. Mix well.
c. Dilute to the mark with deionized water. Mix well.
3. Put Solution A in a 150-mL beaker.
4. Use the test procedure to measure the solution. The reading should be approximately
234 mV.
5. Put Solution B in a 150-mL beaker.
6. Rinse the probe with deionized water. Dry the probe with a lint-free cloth.
7. Use the test procedure to measure the solution. The reading should be approximately
66 mV higher than Solution A.
8. Rinse the probe with deionized water. Dry the probe with a lint-free cloth.

Clean the probe

Clean the probe when:
• Drifting/inaccurate readings occur as a result of contamination on the sensing
element or incorrect storage conditions.
• Slow response time occurs as a result of contamination on the sensing element.
• The slope is out of range as a result of contamination on the sensing element.
For general contamination, complete the steps that follow.

1. Rinse the probe with deionized water. Blot dry with a lint-free cloth.
2. If harsh contaminants are attached to the probe, polish the probe tip with a soft cloth
or cotton swab to remove the contaminants.
3. Soak the probe in deionized water for 1 minute.

Summary of method
The ORP probe is a two-electrode probe that makes a potentiometric measurement. The
ORP electrode is an electron donor or electron acceptor, based on the test solution. A
reference electrode supplies a constant stable output for comparison. Platinum is used as
an indicating sensor and the potential is measured against the reference electrode,
usually Ag/AgCl.
Consumables and replacement items
HQ meters, HQd meters and probes

Description Unit Item no.

HQ1110 portable one input, pH/ORP meter each LEV015.53.1110A

HQ2100 portable one input, multi-parameter meter each LEV015.53.2100A

4 Oxidation Reduction Potential, ORP (–2000 to 2000 mV)

HQ meters, HQd meters and probes (continued)

Description Unit Item no.

HQ2200 portable two input, multi-parameter meter each LEV015.53.2200A

HQ4100 portable one input, multi-parameter meter each LEV015.53.4100A
HQ4200 portable two input, multi-parameter meter each LEV015.53.4200A
HQ4300 portable three input, multi-parameter meter each LEV015.53.4300A
HQ411d benchtop one input, pH/mV meter each HQ411D
HQ430d benchtop one input, multi-parameter meter each HQ430D
HQ440d benchtop two input, multi-parameter meter each HQ440D
Intellical ORP gel probe, standard with 1 m cable each MTC10101
Intellical ORP gel probe, standard with 3 m cable each MTC10103
Intellical ORP gel probe, rugged with 5 m cable each MTC10105
Intellical ORP gel probe, rugged with 10 m cable each MTC10110
Intellical ORP gel probe, rugged with 15 m cable each MTC10115
Intellical ORP gel probe, rugged with 30 m cable each MTC10130
Intellical ORP refillable probe, standard with 1 m cable each MTC30101
Intellical ORP refillable probe, standard with 3 m cable each MTC30103

Sension+ meters and probes

Description Unit Item no.

Sension+ pH3 lab pH meter each LPV2010T.97.002

Sension+ pH31 GLP lab pH meter each LPV2110T.97.002
Sension+ MM340 lab two input, pH/mV/ISE meter each LPV2200.97.0002
Sension+ MM374 lab two input, pH/mV/EC/ISE meter each LPV4110.97.0002
Sension+ MM378 lab two input, pH/ISE/EC/DO meter each LPV4130.97.0002
Sension+ 5045 multi-parameter probe each LZW5045.97.0002
Sension+ 5048 multi-parameter probe each LZW5048.97.0002
Sension+ 5056 single-parameter probe each LZW5056.97.0002
Sension+ 5057 single-parameter probe each LZW5057.97.0002

Optional reagents and apparatus

Description Unit Item no.

Beaker, polypropylene, 50 mL, low form each 108041

Beaker, 100 mL, polypropylene each 108042
Beaker, 150 mL, polypropylene each 108044
Beaker, 250 mL, polypropylene each 108046
Beaker, 400 mL, polypropylene each 108048
Beaker, 600 mL, polypropylene each 108052
Flask, volumetric, Class A, 100 mL each 1457442
Light's Solution, ampules, 20 mL 20/pkg 2612520
ORP Standard Solution, 200 mV 500 mL 25M2A1001-115

Oxidation Reduction Potential, ORP (–2000 to 2000 mV) 5

Optional reagents and apparatus (continued)
Description Unit Item no.

ORP Standard Solution, 600 mV 500 mL 25M2A1002-115

Probe clips, color-coded, for IntelliCAL probes 50/pkg 5818400
Probe, depth markers, rugged LDO probe only 10/pkg 5828610
Probe holder, 3 probes, for sensION+ benchtop meters each LZW9321.99
Probe stand, universal each 8508850

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© Hach Company/Hach Lange GmbH, 2007–2015, 2021. All rights reserved. 02/2021, Edition 9