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How to test ORP?

Monday, May 28, 2018 9:05 PM

How to test Oxidation-Reduction Potential (ORP)?

Oxidation-Reduction Potential (ORP) is measured by inserting an ORP sensor into water. This can be either a handheld sensor or it can be built into a system. The meter then reads the electrical potential (voltage) from the sensor, and it may apply a correction or offset before reporting the value. The reported values, which can be positive or negative, are usually reported in millivolts (mV).

Anatomy of an ORP sensor

ORP sensors work by measuring the electrical potential (voltage) between two electrodes in contact with water. Both electrodes are often contained in a single unit called a combination electrode. One electrode is called the indicator electrode, and it is usually made of platinum (other materials such as gold or graphite are also sometimes used).

The other electrode is called the reference electrode. The reference electrode is usually made of silver and silver chloride (Ag/AgCl electrodes), although electrodes made of mercury and mercury chloride (called “calomel electrodes”) are sometimes used. This electrode contains a filling solution containing potassium chloride.

Electrons from the water interact with both electrodes, creating a voltage between them that is read by the meter.


The Standard Hydrogen Electrode (SHE)

The voltage created between the two electrodes actually depends on the type of reference electrode. For example, for the same water, a higher voltage will be read when using a Ag/AgCl electrode than when using a calomel electrode[1]. Because of this, it is sometimes useful to report an ORP reading that has been adjusted to correspond to a standard reference electrode called the Standard Hydrogen Electrode (SHE). SHE ORP values are comparable to a quantity called Eh, which describes the theoretical ORP of the solution and has the same scale as SHE ORP measurements.

The SHE requires bubbling hydrogen gas through a strong acid solution, so it is not practical for routine laboratory or field use. This reference electrode produces a voltage that is about 200 mV higher than what is produced using the Ag/AgCl electrode. When converting a Ag/AgCl ORP value to SHE, +200 mV is added to the Ag/AgCl ORP number.

Technical note: The actual mV value added when reporting an ORP value in reference to the SHE may depend on the concentration of the filling solution[1].

 

ORP Standard Solutions and Calibration

Because the meter reads the ORP voltage directly from the sensor, a calibration is not necessarily required. However, because the response of the sensor can degrade over time, it is sometimes desirable to test the sensor using a standard solution to verify that it is giving the correct response, such as within +/-10 mV[2]. Two common ORP standard solutions are Zobell’s solution and Light’s solution. At 25°C, Zobell’s solution has an ORP of approximately +228 mV when measured using a Ag/AgCl reference electrode, and Light’s solution has an ORP of approximately +475 mV under the same conditions[1].

Caption: Typical ORP values (in mV) of Zobell’s and Light’s solutions for the three types of reference electrodes[1]

 

Calomel

Ag/AgCl

SHE

Zobell’s

+183

+228

+428

Light’s

+430

+475

+675

 

Technical note: The actual ORP values of Zobell’s and Light’s solutions depend on temperature and the concentration of the filling solution[1,2].

 

The testing with the standard solution can also be used to adjust the actual measured reading so that it matches the value of the standard. This is accomplished by adding an offset to the actual measured mV reading (the offset is the difference between the ideal mV reading and actual mV reading for the standard). This can be thought of as a type of calibration, and most meters can be set up to add the offset automatically.

An offset can also be applied in other situations. For example, a user may want the ORP sensor to read a certain mV value when certain chemical conditions are reached, such as a specific combination of pH and chlorine concentration in a water disinfection application. This technique may be used to make ORP readings consistent between different ORP sensors, or a new offset may be calculated when an old electrode is replaced with a new one.

Reporting ORP Measurements

ORP measurements are most often reported in mV values relative to the reference electrode used. Most often, the Ag/AgCl reference electrode is used, so values are usually reported based on measurements with this electrode. Calomel electrodes are less common because they contain mercury, so calomel ORP values are relatively uncommon.

Sometimes, however, values are reported relative to the SHE. As explained above, these values are approximately 200 mV higher than values for the Ag/AgCl electrode.

When ORP values are reported, the reference electrode that the values are based on should also be reported in order to avoid confusion. If values are seen where the reference electrode is not specified, they are usually assumed to be reported relative to the Ag/AgCl electrode.

Conclusion

ORP is a common, simple and straightforward measurement that provides a quick indication of how oxidizing or reducing a water is. The reading provided by the meter depends on the condition of the sensor, any offset value provided during calibration, and the type of reference electrode used, so care must be taken in interpreting the results. Nonetheless, ORP is especially useful for providing either a quick snapshot of the oxidation/reduction state of a solution or for monitoring its changes over time.

 

References

[1] American Public Health Association (APHA) (2005) Standard methods for examination of water and wastewater, 21st edn. APHA, AWWA, WPCF, Washington.

[2] U.S. Environmental Protection Agency (2017) Field measurement of oxidation reduction potential (ORP). SESDPROC-113-R2.

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What is ORP (Oxidatio-Reduction Potential)

Monday, March 12, 2018 8:55 PM

What is Oxidation-Reduction Potential (ORP)?

Oxidation-reduction potential (ORP) or redox is a measurement that indicates how oxidizing or reducing a liquid is. For example, water may be moderately oxidizing (such as aerated water), strongly oxidizing (such as chlorinated water or hydrogen peroxide solution), or reducing (such as an environment where anaerobic microbes are active). In short, ORP is a measure of the cleanliness of the water and its ability to break down contaminants. This measurement has a variety of applications, such as checking for safe sanitation of drinking water or monitoring fluid for the suitability for anaerobic microbial processes.



What are oxidation and reduction?

Oxidation and reduction are related chemical processes that refer to the exchange of electrons in a reaction. Oxidation refers to when a chemical loses electrons. Reduction refers to when a chemical gains electrons, so reduction is the opposite of oxidation. Both oxidation and reduction can happen in the same reaction, which is why reactions involving oxidation and reduction are often called redox reactions.

As an example, let’s look at the reaction of oxygen gas with hydrogen gas to form water:

O2 + 2H2  -- 2H2O

If we look closer at the water molecule,  writing it as (H+)2(O-2), it can be viewed as a combination of two ions, O-2 and H+, that have electrical charges because they gained or lost electrons:

2H+ + O-2  -- (H+)2(O-2)

Electrons have a negative charge, so the oxygen atom in the water molecule gained two electrons to end up with a −2 charge:

O + 2e- -- O-2

In the above reaction, the oxygen atom was reduced because it gained electrons.

Each of the two hydrogen atoms in the water molecule lost an electron to end up with a +1 charge:

H2 -- 2H+ + 2e-

In this reaction, the hydrogen atoms were oxidized because they each lost an electron.

Reaction

Oxidation or Reduction?

O + 2e- -- O-2

The oxygen atom gains electrons.

The oxygen atom is reduced.

H -- H+ + e-

The hydrogen atom loses an electron.

The hydrogen atom is oxidized.

O2 + 2H2 --2H2O

The oxygen atoms are reduced.

The hydrogen atoms are oxidized.

 

In the reaction of oxygen and hydrogen gas to form water, the oxygen accepts electrons from the hydrogen, so we can say that the hydrogen is oxidized by the oxygen. Likewise, we canalso say that the oxygen is reduced by the hydrogen.

Some common oxidation processes include decomposition of organic matter and conversion of iron to rust (iron oxide).



Electrons and the ORP scale

From the above discussion, one might guess where the word “oxidize” comes from. Oxygen gas is very good at accepting electrons from other atoms, and this is indeed the most common type of oxidation process that occurs in the environment. From this, we might also suppose that an environment that contains oxygen gas is an oxidizing environment. In such an environment, iron will turn to rust, and aerobic respiration can occur.

One might also guess that a reducing environment is an environment without oxygen gas. Such an environment often includes dissolved gases that are products of anaerobic activity, such as methane, hydrogen sulfide, and hydrogen.

Chemicals (such as oxygen) that accept electrons from other compounds are called oxidizing agents, and substances (such as methane or hydrogen) that give up electrons are called reducing agents.

The degree to which a fluid is oxidizing or reducing (represented by ORP) depends on the presence and strength of various oxidizing and reducing agents. ORP can also be thought of as representing the availability of electrons. Because reducing agents give up electrons, a reducing environment is one where electrons are relatively available. In contrast, an oxidizing environment is one where electrons are relatively unavailable.

ORP is expressed as an electrical potential (a voltage). Generally speaking, a reducing environment is indicated by a negative reading, and an oxidizing environment is indicated by a positive reading. The most common unit for expressing ORP is the millivolt (mV), and most meters can read values ranging from -1000 mV to +1000 mV. The more extreme the negative or positive value, the more reducing or oxidizing the fluid is.

orp_range


Different oxidation-reduction processes and conditions have different ORP values, with aerobic conditions having higher ORP values and anaerobic conditions having lower ORP values. \

 

Applications of ORP measurement

One of the biggest applications of ORP is in water disinfection. Municipal drinking water supplies, for example, use strong oxidizers such as chlorine to kill bacteria and other microbes and to prevent their growth in water supply lines. Higher ORP values are associated with higher concentrations of the disinfectant, so ORP is used to monitor and control disinfectant levels in water supplies. In swimming pools and spas, disinfectants are used to kill microbes that may transmit diseases. In outdoor swimming pools and cooling towers, disinfectants are also used to prevent the growth of algae.

ORP is also used for monitoring and control of many oxidation-reduction reactions in industrial processes. For example, in automated industrial systems, ORP is often used to maintain a slight excess of oxidizing chemicals such as chlorine, hydrogen peroxide and ozone, or reducing chemicals such as sulfur dioxide and sodium sulfite.

In wastewater treatment, ORP is used to determine the types of microbial processes that are occurring and to help operators manage the treatment system by promoting or preventing certain reactions. For example, ORP may be controlled in various parts of a system to digest organic matter, remove nitrate or phosphorus, and control odors.

Because low values of ORP indicate anaerobic conditions, ORP can be used to detect anaerobic microbial activity in the environment, such as in the water column or in sediment. ORP can also be used to indicate soil saturation, which makes it useful for mapping wetlands[1].

In other environmental applications, ORP measurements can be viewed as an extension of the dissolved oxygen (DO) scale[1]. DO meters can cover the range of aerobic conditions, but they cannot indicate how reducing an anaerobic environment is. The ORP scale, on the other hand, covers a wide range of reducing conditions. Because of this, ORP can provide insight into the chemistry of anaerobic environments, such as the types of microbial processes in sediments or reactions involving pollutants in contaminated aquifers.

ORP can also be used in conjunction with membrane DO sensors to identify conditions where the DO measurements may be faulty[1]. Under anaerobic conditions, membrane-type DO sensors may give false readings if sulfides are present. If the ORP measurement indicates anaerobic conditions, then positive DO measurements taken from these types of sensors should be considered suspect.

Conclusion

ORP is a fast and inexpensive measurement of the oxidizing and reducing conditions in an environment or system. This makes ORP measurement suitable for a wide range of industrial and environmental applications where oxidizing and reducing conditions vary. ORP is especially useful for routine or continuous monitoring situations where slower and more expensive chemical tests would not be as practical.

References

 [1] U.S. Environmental Protection Agency (2017) Field measurement of oxidation reduction potential (ORP). SESDPROC-113-R2.

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