pH Measurement

pH measurement is used in a wide variety of applications: agriculture, wastewater treatment, industrial processes, environmental monitoring, and in research and development. pH is a measure of the acidity or alkalinity of a solution. The pH value states the relative quantity of hydrogen ions (H+) contained in a solution. The greater the concentration of H+ the more acidic the solution and the lower the pH. In this relationship, pH is defined as the negative logarithm of hydrogen activity. A standard pH measuring system consists of three elements: 1. pH electrode 2. temperature compensation element 3. pH meter or controller Definition of pH The pH value of a solution is the negative log of its hydrogen ion activity (), which is the product of hydrogen ion concentration [H+] and the activity coefficient of hydrogen (H+) at that concentration. pH = -log = -log H+[H+] In pure water and in dilute solutions, the H+ activity can be considered the same as the H+ concentration. pH = -log gH+[H+] = -log [H+] The pH of a solution measures the degree of acidity or alkalinity relative to the ionization of water. Pure water dissociates to yield 10-7 M of [H+] and [OH-] at 25C; thus, the pH of water is 7 minus the point of neutrality. pHwater = -log [H+] = -log 10-7 = 7 Most pH readings range from 0 to 14. Solutions with a higher [H +] than water (pH less than 7) are acidic; solutions with a lower [H+] than water (pH greater than 7) are basic or alkaline.

pH Measurement Measuring pH involves comparing the potential of solutions with unknown [H+] to a known reference potential. pH meters convert the voltage ratio between a reference half-cell and a sensing half-cell to pH values. Today, most electrodes are combination electrodes with both the reference and sensing half-cells in the same body. Reference Half-Cells contain a conductor (usually silver with a silver chloride coating) immersed in a solution with known [H+]. The potential between this internal conductor and the known solution is constant, providing a stable reference potential. Sensing Half-Cells (measuring half-cells) are made of a nonconducting glass (or epoxy) tube sealed to a conductive glass membrane. Like the reference half-cell, the sensing half-cell also contains a conductor immersed in a buffered electrolyte solution, ensuring constant voltages on the inner surface of the glass membrane and the sensing conductor. When the pH electrode is immersed in the solution to be measured, a potential is established on the surface of the sensing glass membrane. If the unknown solution is neutral, the sum of fixed voltages on the inner surface of the glass membrane and on the sensing conductor approximately balances the voltage on the outer surface of the glass membrane and the reference half-cell. This results in a total potential difference of 0 mV and a pH value of 7. In acidic or alkaline solutions, the voltage on the outer membrane surface changes proportionally to changes in [H+]. The pH meter detects the change in potential and determines [H+] of the unknown by the Nernst equation:
E = E + 2.3RT unknown [H+] log nF internal [H+]

where: E = total potential difference (measured in mV) E = reference potential

R = gas constant T = temperature in Kelvin n = number of electrons F = Faraday's constant [H+] = hydrogen ion concentration

pH Systems
A successful pH reading is dependent upon all components of the system being operational. Problems with any one of the three: meter, electrode, or buffer will yield poor readings. Meters: A pH meter is a sophisticated volt meter capable of reading small millivolt changes from the pH electrode system. The meter is seldom the source of problems for pH measurements. Today pH meters have temperature compensation (either manual or automatic) to correct for variations in slope caused by changes in temperature. Microprocessor technology has created many new convenience features for pH measurement; autobuffer recognition, calculated slope and % efficiency, log tables for concentration of ions, and more. Electrodes: A pH electrode consists of two half cells; an indicating electrode and a reference electrode. Most applications today use a combination electrode with both half cells in one body. Over 90% of pH measurement problems are related to the improper use, storage, or selection of electrodes. Buffers: These solutions of known pH value allow the used to adjust the system to read accurate measurements. For best accuracy:

Standardization should be performed with fresh buffer solutions. Buffers used should frame the range of pH for the samples being tested. Buffers should be at the same temperature as the samples. (For example: if all your samples are at 50C, warm your buffers to 50C using a beaker in a water bath.)

Buffer values are dependent upon temperature. The following table lists the NIST values of pH buffers at various temperatures.

pH Temperature Compensation

The pH of any solution is a function of its temperature. Voltage output from the electrode changes linearly in relationship to changes in pH, and the temperature of the solution determines the slope of the graph. One pH unit corresponds to 59.16 mV at 25C, the standard voltage and temperature to which all calibrations are referenced. The electrode voltage decreases to 54.20 mV/pH unit at 0.0C and increases to 74.04 mV/pH unit at 100.0C (see graph).
Typical pH electrode response Since pH values are temperature dependent, pH as a function of temperature applications require some form of temperature compensation to ensure standardized pH values. Meters and controllers with automatic temperature compensation (ATC) receive a continuous signal from a temperature element and automatically correct the pH value based on the temperature of the solution. Manual temperature compensation requires the user to enter the temperature. ATC is considered to be more practical for most pH applications.

pH Electrode Selection Guide

The Electrode Pair Sensing and reference half-cell electrodes must be used together to complete the pH circuit. Most of the electrodes in our catalog are combination electrodes that house both half-cells in a single probe.
Sensing Half-Cells

Sensing half-cells are the measuring portion of the electrode system and contain the pH-sensitive membrane. Glass vs ISFET Sensors The glass membrane or bulb of an electrode is constructed for use in specific conditions. Different types of glass membranes can strengthen the electrode, expand its temperature range, or prevent sodium error at high pH values.

General-purpose glass: various pH ranges, temperatures to 212F (100C). Blue glass: pH 0-13, temperatures to 230F (110C)

Amber glass: pH 0-14, temperatures to 230F (110C), low sodium (Na+) error (In solutions with high Na+ concentrations, Na+ can be misread as H+ at pH 12 and higher.)

Cole-Parmer also offers solid-state ISFET (ion-specific field effect transistor) electrodes. The nonglass measuring surface won't break and wipes clean for dry storageexcellent for use in the food industry. Epoxy vs Glass Body Epoxy-body electrodes are impact resistant and ideal for rough handling, but should not be used at higher temperatures or for inorganics. Glass-body electrodes withstand high temperatures and highly corrosive materials or solvents.

Epoxy-body electrode

Glass-body electrode

Reference Half-Cells

Reference half-cells provide the reference potential needed for pH measurement. Our selection of electrodes includes a variety of reference cell options: Single- vs Double-Junction In combination electrodes, the reference junction allows H+ ions to pass freely between the reference and sensing half-cells to complete the electrical circuit. Economical single-junction electrodes are ideal for general-purpose applications. Use

double-junction electrodes with solutions that contain sulfides, heavy metals, or Tris buffers to prevent contamination of the reference cell. Although most reference cells feature a H+-permeable glass junction, electrodes with reference junctions made of PTFE are also availableuse with solutions that may clog conventional glass junctions. Silver/Silver Chloride (Ag/AgCl) vs Calomel (Hg/Hg2Cl2) Ag/AgCl is the most common internal element, suitable for almost all applications [temp limit: 176F (80C)]. Hg/Hg2Cl2 is recommended for use in solutions containing proteins, organics, or heavy metals that could react with silver and clog the reference junction [temp limit: 158F (70C)]. Refillable vs Sealed Refillable electrodes have ports that allow you to refill the reference chamber with reference solutionthey are economical and long-lasting. Sealed electrodes are rugged and require virtually no maintenance; however, they must be replaced when the fill-solution level is low.

pH Measurement FAQs

1. If I order a pH meter, what accessories do I need to use with it?

2. My coworker is using an ORP electrode to measure the same solution as I, but our readings are not even close. Could there be something wrong with my electrode? 3. Can I measure the pH of a gas? 4. How should I store my electrode? 5. What is the difference between a combination electrode and a sensing electrode with a reference cell? 6. How does one take soil pH measurements?

7. Why is a double junction electrode better than a single junction electrode? 8. Is automatic temperature compensation (ATC) really necessary? 9. When do you use a half cell? 10. How often should I calibrate my pH meter? 11. How can you unclog a pH electrode? How can you restore a dry pH electrode? 12. How far can my pH electrode be from my meter? What if it is too far? 13. How do I extend the ATC wire on my industrial pH electrodes? 14. What is dead band? 15. If measuring samples across the entire pH range, what slope should be used? 16. What is the difference between blue glass and amber glass, and what does that have to do with pH measurement? 1. If I order a pH meter, what accessories do I need to use with it? You need a pH electrode and at least two pH buffers, one at pH 7 and the other at either pH 4 or 10. Go to Top 2. My coworker is using an ORP electrode to measure the same solution as I, but our readings are not even close. Could there be something wrong with my electrode? No. Because ORP is a relative measurement, it is almost impossible to compare two ORP electrodes directly. ORP electrodes come equipped with bands made up of platinum, gold, or hydrogen, for example. Each band type will give you a different reading in the same solution. Even if the electrodes are of the same band type, the leak rate through the reference junction will affect your readings. Instead, simply measure two solutions and note the difference between the two electrodes. Once again, the difference between two solutions should compare. You should be looking for a change of state, rather than an absolute measurement. You can check your electrode using pH buffer and quinhydrone.

Go to Top 3. Can I measure the pH of a gas? The only way to measure the pH of a gas is to dissolve it into distilled water and measure the mixture. Technically, the pH of the distilled water/gas mixture will be that of the gas. Go to Top 4. How should I store my electrode? The best solution for electrode storage is 4M KCL. pH 4 buffer, pH 7 buffer, or tap water are also acceptable. Never store your electrode in distilled water. Go to Top 5. What is the difference between a combination electrode and a sensing electrode with a reference cell? A combination electrode is more convenient and requires a smaller sample container and volume. The sensing electrode with reference cell combination allows you to select the reference cell most compatible with your solution. You can select the double junction, calomel, or ROSS SURE FLOW half cell. You will probably get better life from this combination, and can replace each cell individually. Go to Top 6. How does one take soil pH measurements? Use our soil electrodes EW-05992-62 or EW-05992-60. Prepare the sample by combining a 5 g soil sample with 5 g of distilled water, mixing thoroughly, and allowing the mixture to settle for 10 minutes. Carefully insert probe so bulb is in the soil part and the junction is in the supernatant. Allow reading to stabilize. Go to Top 7. Why is a double junction electrode better than a single junction electrode? A double junction electrode is less likely to become clogged because the second junction is located higher up in the probe out of contact with the fluid. Go to Top

8. Is automatic temperature compensation (ATC) really necessary? The necessity of ATC depends on the required accuracy of a pH reading. pH readings vary with temperature. For example, a sample with a pH of 7 at 25C, may have a pH of 7.08 at 5C and a pH of 6.98 at 60C. Go to Top 9. When do you use a half cell? When you are measuring a pressurized flow in a stream or pipe. The reference half cell would be mounted upstream, the measuring electrode would be mounted down stream. Go to Top 10. How often should I calibrate my pH meter? Before each use or set of uses. Go to Top 11. How can you unclog a pH electrode? How can you restore a dry pH electrode? First check the interior wire. If corrosion is evident, replace the electrode. If not, then soak the electrode in pH 4 buffer solution at 50 degrees C for 2-4 hours. Restore a dry electrode by soaking it in tap water after rinsing out the refill chamber with distilled water and refilling with the proper solution. Go to Top 12. How far can my pH electrode be from my meter? What if it is too far? 200 feet (61 meters) is the maximum distance an electrode can be from a pH meter. If the distance is greater, you will need a transmitter. Use either a 4 to 20 mA transmitter (make sure your pH meter accepts 4 to 20 mA signal) or purchase an industrial electrode with a built-in transmitter. A transmitter will allow you to use your electrode up to 1000 feet (305 meters) from your meter provided you are not in a noisy environment. Go to Top

13. How do I extend the ATC wire on my industrial pH electrodes? You can extend the ATC wire with copper wire or a special extension cable. Go to Top 14. What is dead band? When the input is varied to a device until a detectable output charge is observed then the input is varied in the opposite direction until a detectable output charge is seen, the increment through which the input signal is varied is the deadband. Go to Top 15. If measuring the entire range of pH what slope should be used? The upper end or pH 10 buffer. Go to Top 16. What is the difference between blue glass and amber glass, and what does that have to do with pH measurement? The valance of Na+ is much larger than H+. Amber glass has a smaller pore size thus possibly discriminating between H+ and Na+ allowing only the smaller H+ to enter the greatly eliminating Na+ interference.

pH/ORP Control Systems Selection Guide

Cole-Parmer is committed to providing the most innovative solutions for your pH control applications. If you are controlling wastewater effluent, run-off, or any other industrial process, we can help. Technical Help Cole-Parmer supports its products before and after the sale. For help selecting, installing, or troubleshooting pH control components, call our Application Specialists at 800-323-4340. They are available from 7:00 A.M. to 7:00 P.M. (CST) to answer all of your technical questions. Common Terms
Typical pH Neutralization System In this typical system for pH control, the pH of the effluent stream is maintained constant by the regulated delivery of acid or base to the system, depending upon the variation in pH. The controller measures the pH and activates the proper pump to add the needed reagent to the system. If the pH rises, it activates the acid pump, if the pH falls, it activates the base pump. The pH is measured by the electrode immersed in the well-stirred solution. The signal may be sent to the recorder by means of an optional transmitter.

ATC is an abbreviation for "automatic temperature compensation". The temperature of a system is rarely fixed and pH electrodes respond differently at different temperatures, resulting in erroneous measurements and improper control. ATC, designed into most controllers, references all readings to a single temperature when used with an ATC element. ATC elements are often built into pH electrodes or can be mounted externally.

Dead Band refers to the span of input signal (pH or mV) variation that produces no change in output. A nonzero dead band prevents pumps from cycling on and off rapidly. This is especially useful when the the measured value of the system is very close to the setpoint. Some controllers offer an adjustable dead band. On/Off Control is the simplest and most economical but least precise control method. Here, a pump set at a fixed flow rate is simply turned on and off. Preamplifier boosts the power supplied to a pH electrode. Recommended for applications with over 150 ft of distance between controller and electrode.

Proportional Control gives an output that corresponds to the difference between setpoint and measured pH. This can take the form of a pulse whose frequency increases as more chemical additive is required, or as a 4-20 mA signal where increased amperage corresponds to more chemical feed demand.

How to Build a Control System Proper control of pH involves more than just a controllermany other devices are used to ensure that pH is measured correctly, that a long term record is kept, and that chemical is added and mixed. To build a complete control system you will need the following items, depending upon your application needs.
pH/ORP Controllers

We offer a wide range of pH/ORP controllers. Select controllers with on/off control for simple applications or with proportional control to minimize pH deviation. Controllers with flow assemblies, recorders, or ion concentration are also available We have a model for virtually every application.

Industrial pH Electrodes

We offer single and double junction combination electrodes in a variety of mounting configurations, ATC elements, and materials of construction. Ideal for continuous monitoring, the thicker glass bulb on an industrial electrode makes it more durable for permanent mounting.

Metering Pumps

Pumps are a necessary component of any pH control system. When selecting a suitable pump, keep in mind the required flow rate, compatibility of the pumps control input with the pH controller output, as well as the chemical compatibility of the pumps wetted materials. We offer a wide range of pH/ORP pump control systems to work with your application (see link below).

Recorders and Dataloggers

Many regulatory agencies require that pH levels be maintained within certain boundaries and that these levels be verified with a log. Many of the controllers we offer have a current or voltage recorder output. Some controllers even have a built-in recorder or datalogger.

Mixers

Use a mixer to blend chemicals in your system. Proper mixing can help you maintain a stable pH throughout your process.

How to Store, Clean, and Recondition pH Electrodes

Introduction Taking care of your pH electrodes will ensure proper functioning, as well as enhance their longevity. Read the following primer on the best methods for storing, cleaning, and reconditioning electrodes: Storing Electrodes For best results, always keep the pH bulb wet, preferably in a storage solution or in pH 4.01 buffer with 1/100 part of saturated potassium chloride (KCl) added. Other pH buffers or tap water are acceptable storage media, but avoid storing in distilled water because it will deplete the hydration layer of refillable electrodes, and decrease the life of nonrefillable electrodes. The electrolyte level in the outer cavity should be kept above the level of the solution measured. An electrode storage bottle can be used for short- or long-term storage.

To reuse the storage bottle included with the electrode, slide the cap and then the Oring onto the electrode, insert the electrode midway into the bottle containing storage solution (or a 50:50 mixture of 4 M potassium chloride and pH 4 standard buffer), and gently screw on cap. Close the fill hole on liquid-filled units. (Insertion directly into the cap/bottle assembly with the cap/O-ring in place may cause harm to the electrode by damaging the junction or it may develop pressure and cause storage liquid to flow into the electrode.) KCl and pH 4 buffer provide good conditions for mold to grow. To prevent mold from growing in storage solutions, use up to 4% of sodium benzoate or azide in the reference fill and storage solutions. If the electrode has not been hydrated (i.e. placed in solution for more than one hour), allow the electrode to soak in a buffer (preferably pH 4) prior to standardization or measurement. This will help optimize and re-establish the thin hydration layer on the sensing bulb, which is critical to pH measurement. NOTE: Electrodes should not be stored for a period longer than six months. Electrode stock should be rotated accordingly. Cleaning Electrodes Mechanically intact electrodes with no broken parts can often be restored to normal performance by one of the following procedures:

General Cleaning: Soak the electrode in 1:10 dilution of household laundry bleach in a 0.1 to 0.5% liquid detergent solution in hot water with vigorous stirring for 15 minutes. Place junction under warm, running tap water for 15 seconds. Drain/refill the reference chamber. Soak the electrode in storage solution for at least 10 minutes. Salt Deposits: Dissolve the deposit by immersing the electrode in 0.1 M HCl for five minutes, followed by immersion in 0.1 M NaOH for five minutes, and thorough rinsing with distilled water. Oil/Grease Films: Wash electrode pH bulb in mild detergent or methanol. Rinse electrode tip with distilled water. Clogged Reference Junction: Heat a diluted KCl solution to 60 to 80oC. Place the reference portion of the pH electrode into the heated KCl solution for approximately 10 minutes. Allow the electrode to cool while immersed in unheated KCl solution.

Protein Deposits: Dissolve the deposit by immersing the electrode in a 1% pepsin solution with a background of 0.1 M HCl for five minutes, followed by thorough rinsing with distilled water. Air Bubbles: If air bubbles appear in the electrode (especially with microelectrode and narrow test tube electrodes), open up the fill hole, grab the cable of the probe about 18" from the connection to the electrode, and spin in a circular motion over your head (like a helicopter) for about a minute. The centrifugal force should force the air bubble to the fill hole/top of the electrode.

After any of these special cleaning procedures, remember to drain/refill the reference chamber, if refillable. Soak the electrode in storage solution for at least 10 minutes prior to use. If these steps fail to restore normal electrode response, replace the electrode. Reconditioning Electrodes Older electrodes, or electrodes that have been stored dry, may need to be "reconditioned". Recondition an electrode by soaking it in pH 4.01 buffer or electrode storage solution for at least 30 minutes. Here are other tips for reconditioning or reviving an electrode: Often electrodes are used in applications that require regular cleaning of the electrode or reference. These applications usually involve very hard waters (with high scale content), dirty samples like soil slurries, viscous materials, or samples with high oil and protein content. As with any procedure involving strong chemicals, please wear appropriate safety apparel and goggles, and provide adequate ventilation. These procedures are not recommended for persons unfamiliar with, or unable to use, safe techniques involving these chemicals: detergents, HCl (hydrochloric acid), NaOH (sodium hydroxide). Method 1: Soak the electrode in a 0.4 M of HCl (hydrochloric acid) for 10 minutes, then rinse the electrode with deionized or distilled water. This should remove any organic protein from the glass electrode and the surface of the reference electrode. Method 2: Soak the electrode in a 3.8 or 4.0 M KCl (potassium chloride) solution heated to 50oC for one hour. Allow the KCl solution to cool down to room temperature, then rinse the electrode with deionized or distilled water. This will open and clean the reference electrode of all contaminants. Method 3: Soak the electrode in a 4.01 pH buffer solution, heated to 50oC for one

hour. Allow the buffer to cool down to room temperature, then rinse the electrode with deionized or distilled water. This will open and clean the reference electrode. Method 4: After each use, rinse the electrode in 0.5 N or 1% HCl. If you have a buildup of oil or protein contaminants, try soaking the electrode in a warm detergent and water solution. Degreasing dishwashing detergents or stain-removing prewash pretreatments are ideal for this (any brand will work). An overnight soak may be needed if buildup is heavy. Then rinse the electrode in deionized or distilled water and soak for 10 minutes in 1% HCl. Rinse the electrode again in deionized or distilled water and then calibrate using pH buffers. If the electrode calibrates to buffers, it can be used in tests. When the electrode cannot be calibrated, even after attempts to clean it, it must be replaced. Method 5: For protein removal, soak the electrode in a contact lens enzymatic cleaner solution overnight. The enzymes will remove proteins from glass and plastic.

Troubleshooting pH Electrodes
Getting the optimal performance from your pH electrodes is important. Several factors can influence an electrodes functionality, including drifting readings, slow response times, and environmental influences. Find out how to determine what may be affecting your electrodeand what you can do about it. DRIFTING READINGS Drifting readings can occur if you are using a gel-filled electrode under the following conditions: when measuring a relatively large volume of sample, measuring samples at slightly colder temperatures, or testing fairly clean water. For reference, read the following article: http://www.coleparmer.com/techinfo/techinfo.asp?htmlfile=pHPureWater.htm Here are some reasons you could be experiencing "drift" and tips to overcome it: Gel-filled electrodes leak solution at a much slower rate than liquid-filled electrodes and will take longer to stabilize. This slower response can be perceived as "drift". Use a liquid-filled or refillable electrode instead or allow longer time for reading to stabilize. When measuring a 500-mL sample (especially with a gel-filled electrode), your readings will take longer to reach equilibrium ("drift") than if you used a smaller volume of sample, say 100 or 200 mL. Use a smaller sample size.

 When measuring samples that are fairly clean, CO2 can cause the pH to change as the sample is mixed and allowed to sit and react with the air. Again this appears as drift, but it is actually the CO2 changing the pH of your sample. Generally, plastic electrodes are not as good as glass electrodes. Electrodes with built-in temperature sensors aren't as good or dont respond as fast as separate pH and temperature electrodes. Use glass refillable electrodes or electrodes without ATC. If you are using plasticware (beakers), and especially if you are using a magnetic stir plate and stir bar, you may experience a drift or change in the reading due to static charge that was affecting the reference potential of the electrode. Use a glass vessel, especially if you use a magnetic stirrer. If the body and gel inside of your electrode is at room temperature (22C or about 72F) and you insert your electrode into a water sample that is 10C (about 50F), your electrode will drift until it reaches the same temperature as your sample. Allow the temperature of your electrode and sample to equilibrate before taking a reading. Also, always record the temperature in addition to your pH reading. SLOW RESPONSE TIMES Consider the following possible sources for slow response times: Plastic gel-filled (non-refillable) electrodes are often preferred for their low cost and low maintenance; however they are much slower to respond than more expensive liquid-filled, glass refillable electrodes. Properly functioning new gel-filled electrodes will go from pH 7 to pH 4 in no more than 60 to 90 seconds. A glass refillable electrode may take about half that time. As electrodes age (especially gel-filled electrodes), they respond more slowly. Single-junction electrodes used with incompatible samples may yield a very slow response after a short time because the electrode may have become irreversibly clogged. Use a double-junction electrode to prevent similar clogging in the future. Consider your response time during standardization with pH calibration standard buffers. In some circumstances, it is normal if your electrode is quick to respond during calibration, but slower to respond in your sample. Electrodes that are dirty or have dried out will give a sluggish response. If rinsing with clean water isn't enough, warm, soapy water works well for most organics, while low concentrations of acids work well for most inorganic material. After cleaning, a period of soaking to rehydrate the glass sensing bulb may be necessarywarm pH 4 buffer works well and is easy to confirm when hydration is complete as the pH reading will be constant.

 Using plastic beakers during calibration or measurement. The odds of encountering a slow response seem to increase when using a magnetic stirrer to mix solutions. The spinning/friction of the stir bar in a plastic beaker often causes the pH electrode to perform oddly. Turn off or slow down your stirrer and switch to a glass beaker. Removing and reinserting the electrode from the solution may also help. ENVIRONMENTAL FACTORS Static Electricity Interference Using a plastic beaker while stirring with a magnetic stir bar can create a static charge, thus offsetting the reference potential and resulting in erratic pH readings. Switch to a glass vessel or stop the stirring and remove the electrode from the stirrer. Static charge can also occur in industrial applications with plastic pipes. Electromagnetic Noise Wiring between the electrode and the controller may cause eletromagnetic noise. Fix the problem by: If the signal is not preamplified, the distance between the electrode and the controller must be kept to an absolute minimum, preferably less than 20 feet. Under no circumstances should the cable for an unamplified signal be spliced. All wiring connections must be kept clean and dry. The electrode wires and any other low-voltage wiring must be physically isolated in a separate conduit at least six inches from any AC power lines. Failure to do so will result in unstable, and inaccurate readings.

Tips for pH Buffer Use

These solutions of known pH value allow the user to adjust the system to read accurate measurements. For best accuracy:

Standardization should be performed with fresh buffer solutions. Buffers used should frame the range of pH for the samples being tested.

Buffers should be at the same temperature as the samples. (For example; if all your samples are at 50C, warm your buffers to 50C using a beaker in a water bath.) Buffer values are dependent upon temperature. The following table lists the NIST values of pH buffers at various temperatures. Table of NIST Values of pH Buffers at Various Temperatures

Temperature (C) 0 10 20 25 30 40 50 60 70 80 90

4.01 Buffer 0.05M Potassium Acid Phithalate 4.00 pH 4.00 pH 4.00 pH 4.01 pH 4.02 pH 4.04 pH 4.06 pH 4.09 pH 4.13 pH 4.16 pH 4.21 pH

6.86 Buffer 0.025M KH2PO4 0.025M Na2HPO4 6.98 pH 6.92 pH 6.88 pH 6.86 pH 6.85 pH 6.84 pH 6.83 pH 6.84 pH 6.85 pH 6.86 pH 6.88 pH

9.18 Buffer 0.01M Borax 9.46 pH 9.33 pH 9.22 pH 9.18 pH 9.14 pH 9.07 pH 9.01 pH 8.96 pH 8.92 pH 8.88 pH 8.85 pH

Typical Problems in Industrial pH Measurement & Control

Reprinted with permission of Eutech Instruments Electrical Interference Relay Hunting Limit and Proportional Control In-Line Calibration Current Transmission4/20 mA pH Measurement in Liquids with Hydrofluoric Acid Alarm Function Prevention of Chemical Wastage ORP Measurements Manual Temperature Compensation

Monitoring the quality of water is one of many important aspects in environmental control. With the increasing growth in human population, water for human consumption has become scarce and increasingly polluted. There are many parameters that define the quality of water but the most important of these is probably pH. Electrical Interference pH is a deceptively simple measurement. However, there are many factors that need to be taken into account for a reliable reading. The most important characteristic of pH electrodes is it's very high impedance, of the order of 109 ohms. This is compounded by noisy factory environments and by long distances between the electrode and the controller. A typical pH measuring device would be normally configured to operate in the single ended mode, also known as the asymmetrical mode. This means that the reference electrode would be connected to the ground potential of the amplifier. This configuration works very well as long as the environment is electronically noise-free. This is not the situation in an industrial environment. It is very commonly seen that the readings on a pH controller suddenly fluctuates, even to over-range or under-range condition. This situation arises, when for example, the mixing motor is switched on. An old leaky motor might inject some electrical interference of 1 to 2 volts into the liquid whose pH is monitored. This noise being a common signal, is picked up by both the pH and the reference electrodes. Since in the asymmetrical mode, the reference electrode is grounded, the electrical noise is present only on the pH electrode. This noise would be amplified along with the pH signal and thus the fluctuating readings. If the electrical noise was from a DC source, typically like those in an electroplating tank, the problem would not be fluctuating readings mostly stable but incorrect values.
More Details or Order Online: A simple way to solve this problem would be to reconfigure the input to floating differential mode. In other words, not to Eutech Instruments pH ground the reference electrode. Therefore, the electrical 2000 1/2 DIN PI disturbance will be present equally on both the pH and controller reference electrodes. It therefore becomes a common mode signal and hence can be rejected very easily by the operational amplifier. However, this brings in the necessity to use an additional grounding electrode commonly referred to as potential matching pin.

Relay Hunting

Hunting of the relays around the set point is a very common problem faced in the industry. This may even lead to the breakdown of expensive dosing pumps and solenoids at times. Let us look at what causes this problem. Let us assume that in atypical case, a low set point of 6 pH has been set. It would mean that when the pH drops to a value below 6, the caustic dosing pump starts. The addition of caustic solution would start to increase the pH. When the pH reaches 6, the pump would stop. The mixing pump would still continue operating and hence the pH would drop back below 6. This would start the cycle all over again and so on. This results in the hunting of the relay around the set point. A simple way to overcome this problem would be allowing the pump to continue to dose even beyond the set point, say until 6.5 pH in the above example. In such a situation, when dosing pump stops, the pH might drop to probably 6.2 pH which is still above the set point and hence hunting is prevented. This extra band that has been introduced is known as the hysteresis band. In modern day controllers, independent and adjustable hysteresis bands are available for the high and low set points. Limit and Proportional Control The function of a pH controller would be mainly to monitor the pH and activate the pumps if the pH value goes out of the set points, and dose the respective chemicals which would bring the pH back within limits. The manner in which this corrective action takes can be in two ways, namely limit control and proportional control. Limit control is a coarse method since it keeps the relays on permanently if the pH is out of limits. The dosing of the chemical would not be regulated based on the deviation of the pH from the set point but at a steady and fixed rate. This would causeovershoot and undershoot of the process and hence the control will not be smooth. In applications where fine control is required like those in food or pharmaceutical applications which usually operate within a narrow band, a limit control would not be acceptable. The best option would be to switch to 'Proportional Control'. This, as the name suggests, would offer a control action which is proportional to the deviation of the pH value from the set point. In other words, the further the pH value from the set point, the longer the dosing. As the pH approaches the set point, the dosing reduces and finally stops when the pH reaches the set point. There are two methods of applying 'proportional control', Pulse Length and Pulse Frequency. In the pulse length mode of operation, the total time of the pulse can be fixed by the user typically anywhere between point 0.5 and 20 seconds. The 'ON' time of the pulse would vary depending on the deviation of the pH from the set point. The

further away the pH, the longer the 'ON' time and hence, the higher the dosing. As the pH approaches the set point, the 'ON' time and hence dosing keep reducing. In the Pulse Frequency mode of operation, the frequency can be set by the user typically anywhere between 60 and 120 pulses per minute. The frequency of the pulse would vary depending on the deviation of the pH from the set point. The further away from the pH from the set point, higher the frequency, hence higher dosing. As the pH approaches the set point, the frequency and the dosing reduces. In-Line Calibration In most of the industrial applications, the pH controller would be calibrated at the beginning of the process. As the process progresses, bleed samples would be taken and analyzed separately in the laboratory. At times, it is noticed that there is a mismatch between lab results and the readings on the controller. This might have come about due to the soiling of pH electrode being used in an aggressive environment which might also be a long process running a few days in some cases. In order to correct this problem, the electrode may have to be taken out of the process tank which means halting the process. This may not be acceptable in most cases. A simple way to overcome this problem would be to provide a facility of a one-point calibration which can be done on-line. This does not affect the original slope of the calibration but offsets the line. alpha-pH1000 controller allows one-point on-line calibration to be done without having to disassemble the electrode housing. Current Transmission4/20 mA In most industries these days, it is essential to have a hard copy of the parameter that is monitored over the entire time frame of the process. The easiest and most economical way of achieving this would be to connect up the controller to a chart recorder. It is therefore necessary for the controller to have a 4/20 mA transmission capability. Most present day controllers come with this facility built in. However, there are only a few which offer many features in this mode. Conventionally, in the controllers, 4 mA would correspond to 0 pH and 20 mA to 14 pH. When such a device is connected to a 1/4 DIN panel mounted chart recorder, the pH value can be constantly monitored. If the process requires a stringent control and is also operating within a narrow band of set points, say 1 pH; the recording on the chart paper will not be well resolved. This is due to the fact that in the conventional controller the range of 14 pH is distributed over 16 mA. It can therefore be seen for a 1 pH variation, the current varies only by 1.15 mA approximately. This on the chart paper would be a movement across a width of less than 1/2 cm for the recorder

mentioned above It is clear from this example that recording would not be well resolved and hence would not be of much use. An easy and economical solution to the problem would be to have a controller with 'zoom' facility for the current output. This in simple terms would mean that the user should have the facility to fix the pH values he wants to the 4 and 20 mA output. Let us consider a process operating within 1 pH band say 6 and 7 pH. If it was possible to se the controller to deliver 4 mA at 6 pH and 20 mA at 7 pH, it can be seen that we now have the entire 16 mA over just 1 pH band. This has now given us a 'zoom' of almost 14 times. It would be an added advantage if this 'zoom' band could be set anywhere on the entire pH scale. pH Measurement in Liquids with Hydrofluoric Acid In certain processes Hydrofluoric (HF) is bound to be present. Typical cases would be like those in glass industries. pH measurements in such situations poses a problem. Since conventional pH electrodes are themselves made of glass, especially the 'bulb', in a short span of time depending on the concentration of the HF, the electrode dies. Most often the solution to this problem would be using electrodes made of high HF resistance glass. This, as one may see does not totally eliminate the problem. Logically, the best solution would be to use a material that is not attacked by HF. Antimony electrode, which is basically an ORP electrode can be used here. The solution is not as simple as it sounds. This is due to the fact that the property of the glass electrode is very different from that of the Antimony electrode. Therefore these electrodes cannot just be swapped, one in place of the other. The alpha-pH1000 controller has the facility to switch from one to another and in that process change internally all the settings associated with the type of electrode, either glass or Antimony. This method, though not the best, is still a good and economical way to measure pH in HF environment. Alarm Function Most of the mid-range controllers these days come with a separate relay for the 'alarm' function. This relay generally activates if the measured parameter is out of either of the set points. What this means is that in the event there is a control action taking place, the alarm relay is also active and hence the alarming device be it a siren or a flashing light. As a result of this, generally there is not much attention given when the lights starts to flash or the siren starts to hoot. Invariably there is a reset switch wired up externally, which will be operated to stop the noise. We see therefore in such situations, the alarm device is looked at as a nuisance rather than a facility. How could we better utilize this feature.

Let us look at a practical situation. Assume that the low set point is fixed at 6 pH. When the pH drops to a value below 6, the set point relay gets activated and hence the chemical dosing starts. Under normal circumstances, the alarm relay also would have got activated and as long as the alarm condition exists, the siren keeps hooting. If by experience one would know how long it would take for the dosing action to correct the situation, say 2 minutes in this example, it would be great advantage if one could set a delay time of 2 minutes for the alarm relay to function. What this means in reality is that once the set point is exceeded, only the dosing pump starts and the alarm relay circuit starts the counter. If in 2minutes the problem did not get corrected, which may be due to airlock in the pump or empty chemical tank, then the alarm relay activates and therefore the siren or the flashing light This would be more meaningful. Prevention of Chemical Wastage In certain industries it becomes essential to monitor two parameters simultaneously and carry out corrective action based on one parameter first followed by the other. pH and ORP measurements would be a good example in 'electroplating' and 'swimming pool'. The pH is first adjusted to a specific level and then the ORP control is done. Thepractical problem one would face here is that the pH and ORP are independent. While the pH is being corrected, the ORP gets affected and vice versa. If it were possible to HOLD the ORP controller while the pH is being corrected and let it start the control only when the pH is within the acceptable limits, then that would result in a large saving of the chemicals. If this control process could be carried out automatically, it would be an added advantage. ORP Measurements ORP or Redox is the oxidation-reduction potential usually measured in millivolts. This is not a specific ion measurement since all the ions present in the liquid will contribute to the ORP potential. It can be seen therefore that in areas like wastewater treatment, the ORP in actual millivolt would not make much meaning. Instead if it was possible for the controller to measure the millivolt and display it as a relative percentage, then the transition from one state to another can be more easily seen. For this to be possible, the controller should be capable of operating in what is known as the ORP % mode, which is available in the alpha-pH1000 controller. The user can calibrate the unit with two liquids whose relative toxic levels are known and then use it to measure and control the ORP % value of the water being processed. Manual Temperature Compensation There are many instances where a temperature probe is not being used. This typically would be when there is no large variation in temperature of the process. It is still

necessary to apply a compensation for correcting for the effect of temperature if the process temperature is going to be anything other than 25C. Most of the controllers these days have the facility of Manual Temperature Compensation (MTC). The drawback however in most of them is that there is only one setting for the MTC. If for example, the MTC is set to 40C and measurement is being carried out, the compensation corresponding to 40C would be applied. If now the user decides to carry out a calibration, care should be taken to reset the MTC to 25C. If this step is forgotten, then calibration would be wrong. This error may not be very high in case of pH measurements. However in Conductivity and Resistivity measurements, assuming that the temperature coefficient of the liquid is around 2% perC, the error for a 15C variation could be as high as 30%. This would in no way be acceptable. A simple solution to this problem is by providing two settings for the MTC namely one for Process temperature and another for the Calibration. This way the controller can apply the correct compensation based on the mode, 'measurement' or 'calibration', in which it is operating.

Laboratory pH Electrodes
Use laboratory electrodes with pH meters to intermittently test the pH of a solution. Electrodes feature glass or epoxy bodies and come in either combination or half-cell styles. Laboratory electrodes are further categorized according to fermentation, general purpose laboratory, specialty, and ion-selective applications.

Fermentation electrodes resemble industrial electrodes because they can be used continuously for several days. Fermentation electrodes are rugged, can be hooked up to some pH controllers, and are either autoclavable or in-situ-sterilizable. Ion-selective electrodes determine the concentration of specific ions. We offer solid state, gas sensing, and liquid membrane electrodes. Application Guide We offer a variety of laboratory electrodes for your general-purpose and specialty laboratory applications. The "Application Guide" below provides information to help you find the electrode that best fits your application. Carefully choose the electrode best suited for your application to ensure accurate pH measurements. The guide only offers suggestions call our Application Specialists for more specific recommendations or clarification. Use the guide below to help select the electrode that best fits your application, or call our Application Specialists for more specific recommendations or clarification.

Biological samples, proteins, and tris buffer Calomel (Hg/Hg2Cl2) or double-junction Pharmaceuticals Calomel (Hg/Hg2Cl2) or double-junction Hydrofluoric acid Antimony or HF electrode Low ionic strength samples, acid rain, boiler feed water and distilled water Sure-Flow or ISFET (Ion specific field effect transistor) Drinking water Standard Ag/AgCl with single-junction Waste water Double-junction Solutions with heavy metals Double-junction

Soil samples Soil electrode or double-junction pH>9 and high Na+ Amber glass bulb, Ag/AgCl High or rapidly changing temperatures Ross Fruits, cheese, and meat Spear-tip, Ag/AgCl, or ISFET Flat surfaces, paper, skin Flat-surface Nonaqueous samples, solvents, and alcohols Sure-Flow or double-junction Viscous samples, slurries, emulsions and oils, paints and inks Sure-Flow, double-junction, or ISFET

pH Electrode Care
Electrode Calibration Since glass pH electrodes measure H+ concentration relative to their reference halfcells, they must be calibrated periodically to ensure accurate, repeatable measurements. Our wide selection of commercial pH calibration buffers include

solutions standardized against NIST-certified pH references for calibrating meters with resolution up to 0.001 pH. Although calibration against one pH reference buffer (one-point calibration) typically ensures accurate pH measurement, frequent two-point or even three-point calibrations ensure the most reliable results. Make sure your pH system includes calibration buffers for a range of pH values. Conditioning pH electrodes are shipped with the electrodes moist. Prior to using your electrode for the first time, follow these three steps to condition your electrode: 1. Remove the protective cap or rubber boot from the bottom of the sensor and rinse the electrode with distilled or deionized water. 2. Place the electrode in a beaker containing one of the liquids listed below (in order of ionic ability to condition the electrode). Soak for 20 minutes. o 3.8 M or 4.0 M KCL o 4.0 pH buffer o 7.0 pH buffer Note: Never condition a pH electrode in distilled or deionized waterlong term exposure to pure water will damage the special glass membrane. 3. After conditioning the sensor for 20 minutes, rinse the electrode with distilled or deionized water. The electrode is now ready for calibration and to measure pH. Handling Electrodes should be rinsed between samples with distilled or deionized water. Never wipe an electrodewiping can cause erroneous readings due to static charges. Blot the end of the electrode with lint-free paper to remove excess water. Refillable Electrodes The filling solution in refillable electrodes should be filled up to, but not past, the refill hole. Make sure the refill hole is left open when measuring to ensure that the fill solution flows properly through the reference junction. Storage

Always keep your pH electrode moist. We recommend that you store your electrode in a solution of 4 M KCl. If 4 M KCl is not available, use a pH 4 or 7 buffer solution. DO NOT store electrode in distilled or deionized waterthis will cause ions to leach out of the glass bulb and render your electrode useless. After storage, you may notice white KCl crystals forming outside your electrode. This will not interfere with measurements. Simply rinse the electrode and blot dry before use. Protective Rubber Boot Most electrodes are shipped with a protective rubber boot over the glass bulb to help prevent cracking or scratching. Remove the rubber boot before using your electrode. Keep your electrode in long-term storage with the boot onjust fill the boot with enough 4 M KCl solution to cover the glass bulb and replenish as needed to keep the bulb moist.