Showing posts with label pH. Show all posts
Showing posts with label pH. Show all posts

Wednesday, April 26, 2017

The Ten Things Everyone Should Know about pH and ORP

Reprinted with permission from AquaMetrix Instruments

Here is a list of the ten things anyone in the business of measuring the pH or ORP of their process should know that will make his or her job more stress-free.

1. pH measurements are only good to 0.1 pH units.

Electrodes are funny things. They are the only electronic components that don’t even have specifications listed in their data sheets. One major figure of merit, the impedance of the glass electrode, is on the order of megaohms and can vary by a factor of two. Cross sensitivity to other ions (e.g. sodium), response time and differences between any two electrodes limit the accuracy of measurement. Expecting ac- curacy of greater than 0.1 pH units is

2. Speaking of accuracy... It is not the same as precision.

For a consistent process a pH probe can achieve precision of results to within 0.02 units but it’s accuracy will always be limited by variables such as calibration accuracy, high sodium content or careful routine calibration, however, will narrow the gap between the accuracy of readings closer to the lower level of precision.

3. ORP measurements are only good to ± 20 mV.

Once again the measurement of ORP might be characterized by a high precision but the accuracy of the reading is constrained by the dif culty of calibration, as explained in point 6, and the non-buffered calibration solutions that allow the ORP value of the calibration solutions to change over time. Whereas the buffered composition of pH calibration solutions insures that they will change minimally an ORP calibrations solution is a mixture of Fe2+ and Fe3+ salts. Just the addition of air to the mixture will increase the ORP of the mixture. So don’t look for “NIST traceable” on the label of an ORP calibration solution.

4. ORP measurements are relative.

The process electrode is nothing more than a platinum (or gold) band upon which oxidation (reduction) reactions take place. To complete the circuit, as in all potentiometric devices, is a
reference electrode. Usually that is the same Ag/AgCl electrode used in a pH probe so the REDOX potential that you read is the difference between the Pt band process electrode and the arbitrarily chosen reference electrode. What matters most with an ORP measurement is its change to an agreed upon standard.

5. pH calibration requires two points.

Calibration measures the response of an instrument as one changes the measurement variable in a known way. For pH measurements that measurement variable is the concentration of hydrogen ions. One calibrates a pH probe by drawing a line through points representing the response of a pH probe to more than one H+ ion concentrations (or pH values). Therefore calibration requires at least two points.

6. ORP calibration can only realistically be done with one point.

This sounds like a reversal of point 4 but it’s not. ORP is not a measure of any one species (e.g. H+ ions or oxygen molecules). It measures the collective REDOX potential of everything in the water. Furthermore calibration solutions, e.g. 200 mV Light’s solution and 600 mV Zobell’s solution are two completely different mixtures of reagents. Therefore all we can is choose one calibration solution and calibrate for it.

7. ORP measurements can be slow.

Stick an ORP probe in a calibration solution and you will get a steady reading with- in half a minute. Take the same probe and stick it in a glass of tap water and it might take 20 minutes for the reading to settle to the 200-300 mV that is typical of tap water. The response of the process electrodes to the REDOX reactions that take place on the surface of a Pt electrode depends on the speed of the many reactions that give the potential and the rate at which molecules diffuse through the water. The Fe2+ and Fe 3+ ions that comprise most of the ORP value in calibration solutions react very quickly with the Pt but the Cl- and dissolved oxygen that make up tap water react much more slowly. So the key to successful ORP measurement is patience.

8. pH measurements must be temperature compensated to be accurate.


A pH measurement is the determination of H+ ions in solution. Higher temperature causes the chemical activity to increase and the pH reading to increase accordingly. So we must remove the temperature effect by measuring it and using the well known Nernst equation to correct it for the reading at 250C. (The correction is quite simple. The pH value is proportional to temperature when the latter is an absolute value (i.e. in Kelvins).

9. ORP measurements are affected by temperature but are NOT corrected for it.

An ORP value simply reflects the ability of whatever is in the water to oxidize whatever contaminants are in the water. Of course oxidation speeds up at higher temperatures. But since ORP measures the rate of chemical reactions and not any one chemical species there is no need to correct it. However we can convert the temperature reading to the ORP that we would measure at 250 C so that we have a basis for comparing the chemistry of the process. That’s why we provide a temperature sensing thermistor or RTD with our differential ORP probes.

10. A differential probe properly cared for will last a long time but it won’t last forever.

Over time chemicals in the process make their way through the junction or salt bridge and into the pH 7 buffer that bathes the reference electrode. Manufacturers go to great length to minimize this contamination but they can only slow it down. Aquametrix differential probes allow the user to cheaply and quickly replenish both the pH 7 solution and the salt bridge so that our probes our industry leaders when it comes to probe lifetime. Nonetheless electrodes themselves lose their efficiency as the glass becomes contaminated and/or eroded by the process. However the good news that, with routine calibration and maintenance an Aquametrix differential probe can last for years in most environments. As the car ads say, “your mileage will vary” but rest assured there is no probe on the market that will outlast an Aquametrix differential probe... as long as you take good care of it.

Tuesday, September 27, 2016

Industrial pH Control Basics

pH sensor
pH sensor courtesy of HF Scientific
Analytical measurement and control of pH within a system is necessary for many processes common applications include food processing, wastewater treatment, pulp & paper production, HVAC, power generation, and chemical industries.

pH display
pH display
courtesy of HF Scientific 
To maintain the desired pH level in a solution a sensor is used to measure the pH value. If the pH is not at the desired set point, a reagent is applied to the solution. When a high alkaline level is detected in the solution, an acid is added to decrease the pH level. When a low alkaline level is detected in the solution a base is added to increase the pH level. In both cases the corrective ingredients are called reagents.

Accurately applying the correct amount of reagent to an acid or base solution can be challenging due to the logarithmic characteristics a pH reaction in a solution. Implementing a closed-loop control system maintains the pH level within a certain range and minimizes the degree to which the solution becomes acidic or alkaline.

An example of an automatic pH level control system is a water treatment process where lime softened water is maintained at a pH of 9 using carbon dioxide as a reagent. As the untreated water (or influent) enters the tank, the pH is continuously monitored by the pH sensor. The sensor is the feedback device to the controller where the setpoint is compared to the control value. If the values are not equal, the controller sends a signal to the control valve that applies carbon dioxide to the tank. The reagent is applied to the tank at varying rates to precisely control the pH level. With the pH level at 11 detected by the sensor, the controller commands the control valve to open and introduce more carbon dioxide. As the increased carbon dioxide mixes with the influent, the pH is lowered in a controlled manner. Reaching the setpoint, the carbon dioxide flow is minimized and the process is continually monitored for variation. The effluent is the treated water that is discharged out of the tank. The process continues to provide the lime softened water at the desired pH level.

Monday, March 21, 2016

The Ten Things Everyone Should Know about pH and ORP

pH ORP probe
pH ORP probe
(courtesy of AquaMetrix)
Reprinted with permission from AquaMetrix

1. pH measurements are only good to 0.1 pH units

Electrodes are funny things. They are the only electronic components that don’t even have specifications listed in their data sheets. One major figure of merit, the impedance of the glass electrode, is on the order of megahoms and can vary by a factor of two. Cross sensitivity to other ions (e.g. sodium), response time and differences between any two electrodes limit the accuracy of measurement. Expecting accuracy of greater than 0.1 pH units is unrealistic.

2. Speaking of accuracy... It is not the same as precision.

For a consistent process a pH probe can achieve precision of results to within 0.02 units but it’s accuracy will always be limited by variables such as calibration accuracy, high sodium content or Careful routine calibration, however, will narrow the gap between the accuracy of readings closer to the lower level of precision.

3. ORP measurements are only good to ± 20 mV. 

Once again the measurement of ORP might be characterized by a high precision but the accuracy of the reading is constrained by the difficulty of calibration, as explained in point 6, and the non-buffered calibration solutions that allow the ORP value of the calibration solutions to change over time. Whereas the buffered composition of pH calibration solutions insures that they will change minimally an ORP calibrations solution is a mixture of Fe2+ and Fe3+ salts. Just the addition of air to the mixture will increase the ORP of the mixture. So don’t look for “NIST traceable” on the label of an ORP calibration solution.

4. ORP measurements are relative.


The process electrode is nothing more than a platinum (or gold) band upon which oxidation (reduction) reactions take place. To complete the circuit, as in all potentiometric devices, is a reference electrode. Usually that is the same Ag/AgCl electrode used in a pH probe so the REDOX potential that you read is the difference between the Pt band process electrode and the arbitrarily chosen reference electrode. What matters most with an ORP measurement is its change to an agreed upon standard.

5. pH calibration requires two points.


Calibration measures the response of an instrument as one changes the measurement variable in a known way. For pH measurements that measurement variable is the concentration of hydrogen ions. One calibrates a pH probe by drawing a line through points representing the response of a pH probe to more than one H+ ion concentrations (or pH values). Therefore calibration requires at least two points.

6. ORP calibration can only realistically be done with one point.

This sounds like a reversal of point 4 but it’s not. ORP is not a measure of any one species (e.g. H+ ions or oxygen molecules). It measures the collective REDOX potential of everything in the water. Furthermore calibration solutions, e.g. 200 mV Light’s solution and 600 mV Zobell’s solution are two completely different mixtures of reagents. Therefore all we can is choose one calibration solution and calibrate for it.

7. ORP measurements can be slow.

Stick an ORP probe in a calibration solution and you will get a steady reading with- in half a minute. Take the same probe and stick it in a glass of tap water and it might take 20 minutes for the read-

ing to settle to the 200-300 mV that is typical of tap water. The response of the process electrodes to the REDOX reactions that take place on the surface of a Pt electrode depends on the speed of the many reactions that give the potential and the rate at which molecules diffuse through the water. The Fe2+ and Fe 3+ ions that comprise most of the ORP value in calibration solutions react very quickly with the Pt but the Cl- and dissolved oxygen that make up tap water react much more slowly. So the key to successful ORP measurement is patience.

8. pH measurements must be temperature compensated to be accurate.


A pH measurement is the determination of H+ ions in solution. Higher temperature causes the chemical activity to increase and the pH reading to increase accordingly. So we must remove the temperature effect by measuring it and using the well known Nernst equation to correct it for the reading at 250C. (The correction is quite simple. The pH value is proportional to temperature when the latter is an absolute value (i.e. in Kelvins).

9. ORP measurements are affected by temperature but are NOT corrected for it.

An ORP value simply reflects the ability of whatever is in the water to oxidize whatever contaminants are in the water. Of course oxidation speeds up at higher temperatures. But since ORP measures the rate of chemical reactions and not any one chemical species there is no need to correct it. However we can convert the temperature reading to the ORP that we would measure at 250 C so that we have a basis for comparing the chemistry of the process. That’s why we provide a temperature sensing thermistor or RTD with our differential ORP probes.

10. A differential probe properly cared for will last a long time but it won’t last forever.

Over time chemicals in the process make their way through the junction or salt bridge and into the pH 7 buffer that bathes the reference electrode. Manufacturers go to great length to minimize this contamination but they can only slow it down. Aquametrix differential probes allow the user to cheaply and quickly replenish both the pH 7 solution and the salt bridge so that our probes our industry leaders when it comes to probe lifetime. Nonetheless electrodes themselves lose their efficiency as the glass becomes contaminated and/or eroded by the process. However the good news that, with routine calibration and maintenance a differential probe can last for years in most environments.