The Theory of pH Measurement What is the exact meaning of the term pH? pH as a term was coined by Sorensen in 1909.

He described the concentration of hydrogen ion as a logarithmic scale which he called Pondus Hydrogeni or the exponent of hydrogen. pH is a quantitative unit of measure which describes the degree of acidity or alkalinity of a substance. It is measured on a scale of 0 to 14. The term pH is derived from p the mathematical symbol of the negative logarithm, and H the chemical symbol of Hydrogen. The formal definition of pH is the negative logarithm of the hydrogen ion concentration i.e. pH = -log10[H]+ In practice it is the hydrogen ion activity which is measured rather than its concentration. How are pH values measured? pH is a potentiometric measurement where the electrode used produces an electrical signal which the pH meter converts to a pH reading The signal produced and measured is a voltage and since voltage is a potential difference, two potentials are needed to make a measurement: 1. The sensing electrode provides a potential proportional to the logarithm of the hydrogen ion activity in the sample. 2. The reference electrode ideally provides a stable and consistent potential independent of the activity of the sample. The potential difference between the reference and sensing electrode is measured by the meter and converted into a pH value. How does a pH meter measure the response of a pH electrode? The potential difference developed between the reference electrode and sensing electrode is dependant on the activity of the hydrogen ions in solution. For an ideal electrode the response is defined by the Nernst equation: E = Eo 2.3 (RT/nF) log aH+ where: E = total potential (in mV) developed between the sensing and reference electrode Eo = standard potential of the electrode at aH+ = 1 mol/l R = Gas constant T = temperature K n = valency of ion F = Faraday constant aH+ = activity of the hydrogen ion in solution

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The term 2.3RT/nF is referred to as the Nernst slope. For an ideal electrode the slope at 25C is 59.16 mV per decade change in hydrogen ion activity (see Figure 1).
450 350 250 Electrode potential (mV) 150 50 -5 0 -1 5 0 -2 5 0 -3 5 0 -4 5 0 pH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 A s ym m e tr y P o in t (E o ) S lo p e = 5 9 .1 6 m V /p H

Figure 1. Slope of an ideal electrode @ 25C In practice the response of a real electrode does not exactly follow that predicted by the Nernst equation and must be compensated for. During calibration the meter determines the actual slope and asymmetry potential for the electrode in use and then matches the pH meter to the correct characteristics of the electrode in use. What does the term asymmetry potential mean? For an ideal electrode the potential difference between the reference and measuring electrode is 0mV at pH 7. As the ideal electrode doesnt exist the deviation of a few mV at pH 7 that is found with real electrodes is called the asymmetry potential, Eo. In practical terms it is a measure of the performance of the reference electrode - if the result is outside of +/- 15mV this is indicative of problems with the reference electrode such as contaminated electrolyte or reference element poisoning. What are the acceptable ranges for the slope and asymmetry potential of a pH electrode? For an ideal electrode the theoretical slope is -59.16 mV/pH and the asymmetry potential at pH 7 is 0 mV. In practice, a range of -55 mV/pH to -60 mV/pH (or 95 102%) and an asymmetry potential of +/- 15 mV is acceptable. What is a combination electrode? All pH sensors consist of a measuring glass electrode and reference electrode. A combination electrode is an electrode which contains both the reference and measuring electrode in the one body. What is the function of the reference electrode? The reference electrode provides a constant potential regardless of the composition of the solution it is placed in. The voltage difference between the reference and measuring

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electrodes is a function of the pH value of a solution. Common reference systems in use are Silver/Silver chloride/ (Ag/AgCl) and Mercury/Calomel (Hg2Cl2). The Silver/Silver Chloride reference is far the most frequently employed because it has universal applicability, a wide operating temperature range and is relatively non-toxic. What does the term resistance mean in relation to pH electrodes, and why is it important? This is a measure of the electrical resistance of the measuring electrode of a pH electrode. It is influenced by the chemical composition of the glass, its thickness and shape. The resistance of pH membrane glass is important as it increases with decreasing temperature. A change in resistance leads to a change in electrode response, in particular the higher the resistance of the membrane the slower the electrode response is. This can result in an electrode not being useable at a particular temperature. For example, electrodes designed for low alkaline error at high temperatures are generally of higher than normal resistance and should not be used at all at low temperatures. For this reason manufacturers specify temperature ranges in which their electrodes can be used with confidence. What exactly is the function of the diaphragm on a pH electrode, and why is it important? The diaphragm on a pH electrode allows a flow of electrolyte from the reference solution into the solution being measured. This completes the electrical circuit between the reference and sensing electrode and gives the potential difference which is measured by the pH meter. The type of diaphragm used will influence the outflow of electrolyte into the sample, which will in turn effect the response speed of the electrode. The common diaphragm types are listed below along with their inherent properties. For most common applications a platinum diaphragm is the one of choice. Diaphragm Type Platinum Ceramic Resistance (approx.) 0.5 k 1 k Outflow rate KCl @ 25C 0.1ml/hr 0.05ml/hr sat. Application Normal applications or extremes of conductivity For general measurements in aqueous solutions where conductivity is greater than 500s/cm. Unsuitable for high salt content. Non-aqueous, high salt, poorly conducting solutions that require easy cleaning (pastes/emulsions) etc; low ionic strength. Low maintenance gel filled electrodes

Ground Joint or 0.2 k Sleeve

0.5 2ml/hr

Annular Gap

0.1 k

N/A

Why does the glass bulb at the bottom of electrodes come in a variety of shapes?

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The glass membrane on pH electrodes comes in a variety of different shapes based on the fitness for purpose of the electrode. The most common membrane shapes in use today are outlined below: Membrane type Sphere Dome Flat Cylinder Spear Cone Shape Property Low resistance High resistance, shock proof, easy clean High resistance, shock proof, easy clean Medium resistance, shock proof Application Common applications Automatic applications cleaning

pH measurement on surfaces (e.g. skin, paper) Fermenter electrodes

High resistance, shock Suitable for sticking in proof semi-solid media (e.g. cheese, meat) Low resistance, robust, Universally applicable easy clean

In practice there is a trade-off between the speed of response of the electrode and its ruggedness, thus the application the electrode is being selected for will govern the choice of membrane design. The classical sphere shaped membrane offers low electrical resistance due to its large surface area but is relatively fragile. The cone shaped membrane is seen as a universal design as it is robust, of medium resistance and is easy to clean. What is the difference between the various types of membrane glass for pH electrodes? As pH is measured in a wide variety of solutions at varying temperatures it is not possible to formulate a single pH membrane glass which can give accurate and reliable pH measurements in all conditions. For this reason different types of membrane glass have been developed to give good performance in a variety of measurement conditions. The most common membrane glass types found in Schott electrodes are as outlined below: Membrane glass type L H S Properties Suitable for wide application area, has low impedance and thus gives rapid response time over wide temperature range Optimised for use in alkaline range and high temperature applications up to 135C. Also has very low alkaline error (Na+ error). This type will bear rapid temperature changes. In hot alkaline

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solutions it has very constant measuring values and fast response time Offers fast response time in drinking water, service water and sewage, and also suitable for general applications

If the wrong membrane type is selected for a particular application it may be rendered unusable without any obvious signs of change. Does temperature have any effect on pH measurement? What practical steps can I take to reduce the effects of temperature on pH measurement? Does Automatic Temperature Compensation (ATC) compensates for sample measurements taken at different temperatures? What does ATC actually do? The subject of the above questions is comprehensively covered in the technical paper entitled The Effects of Temperature on pH Measurement published by J. J. Barron, C. Ashton. & L. Geary of the Reagecon Technical Services team. It includes details of practical remedial actions which can be taken to reduce or eliminate these effects. What does the term junction potential mean? This is the portion of the total observed potential difference between the measuring and reference electrode that is formed at the liquid / liquid junction between the reference electrode filling solution and the test sample. The contribution of the liquid junction potential to the measured potential should be kept as small and as constant as possible. This can be achieved by careful selection of electrode, and good probe maintenance. What affect does junction potential have on pH readings? The flow rate of electrolyte from the reference electrode into the sample is affected by the design of the electrode diaphragm. Low or irregular flow rates may cause variation in the liquid junction potential which will result in erroneous readings. This is why it is important to select the correct electrode for the application of interest. What is meant by the response time of an electrode, and why is it important? The response time of an electrode is the length of time necessary to get a stable reading when the electrode is moved from one solution to another of different pH or temperature. Response time is dependent on the electrode type, the measuring sample, temperature, the magnitude and direction of concentration change and the presence of interfering substances. A slow response time can be indicative of the incorrect selection of electrode for the intended application. Good Measurement Practice

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Reagecon manufacture a large number of different types of pH buffers. What is the difference between these types of buffer and what are they used for? Reagecon manufactures the most comprehensive range of pH buffers in the world which are designed to suit all end user requirements. The most popular pH buffer types manufactured are outlined below: Buffer type pH buffer @ 20C pH buffer @ 25C Technical Buffers Professional Range Buffer capsules Description Value assigned at 20C to 0.01pH units Value assigned at 25C to 0.01pH units Manufactured in accordance with DIN 19266 and tested at 25C to 0.02pH units Value assigned at 20C as per N.I.S.T and at 25C as per DIN 19266 Value assigned at 25C to 0.02pH units

All of these buffers are manufactured to exacting specifications and are supplied with detailed Certificates of Analysis which shows traceability to a N.I.S.T. SRM. In addition to the type of buffer, different pack options are available to suit all needs: Pack option 500ml, 1L & 5L Colour Coded Buffers Twin Neck Bottle Bag In Box Buffer Capsules Uses/Advantages Suitable for wide range of uses Ease of identification Ideal for field work as there is no need for a separate measuring container. Also avoids possibility of contaminating bulk solution Available in 5L or 10L size, ideal for large volume users Ideal for users who perform calibration infrequently or where storage is an issue

Does it make any difference which pH buffer I use to calibrate my pH meter? Most modern pH meters are supplied with the facility for automatic buffer recognition. The manufacturer will have programmed in a pH versus temperature profile into memory for a specific type of buffer such as DIN or NIST (see table below) DIN 19266 buffers @25C 1.679 0.010 3.776 0.010 4.005 0.010 6.865 .0.010 7.413 0.010 9.180 0.010 10.012 0.010 12.454 0.050
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NIST buffers @ 20C 1.677 0.010 3.788 0.010 4.001 0.010 6.879 0.010 7.429 0.010 9.225 0.010 10.062 0.010 12.627 0.050

If a different buffer to that specified by the manufacturer is used for calibration this will result in calibration errors. If you have any doubt on the best buffers to use for your pH meter then the Reagecon Technical Services team will be happy to advise you. Should I stir my sample when taking a pH measurement? It is not strictly necessary to stir samples for pH measurement. Although stirring the solution ensures a quicker response, if the buffer solutions are stirred, then the sample should also be stirred. It is important that the stirring is carried out at the same speed for both samples and buffers. By stirring at a uniform rate this ensures a representative sample measurement is obtained (this is particularly important for colloidal or particulate samples) and also improves electrode response time. Electrodes with ceramic diaphragms suffer from interference under stirring. The platinum diaphragm on the other hand does not suffer from this interference and is thus the diaphragm of choice for most common applications. What value pH buffers should I use to calibrate my pH meter? For proper calibration, buffer solutions of carefully selected accuracy and pH range are required. The calibration should be performed using two buffers whose values bracket the expected value of the samples being measured. In practice many pH meters are equipped with auto buffer recognition - this requires the use of the buffer values specified by the meter manufacturer. It is essential that the difference between the two calibration buffers should be no more than 2 3 pH units apart. This represents 2 3 decades of difference in pH value (i.e. a 100 to 1,000 times increase in H+ ion concentration). What practical steps should be performed when calibrating a pH meter? When carrying out the calibration the following points should all be borne in mind Electrodes should never be allowed to run dry because this will create static charges on the glass membrane resulting in a very sluggish response. Cleaning of the electrode between buffers and sample or from sample to sample should be carried out by a jet of water from a wash bottle, followed by careful rinsing with the buffer or sample to be measured. For very accurate work it is recommended to repeat the zero calibration after slope adjustment.

Why should control standards be used when measuring pH? For confidence in pH measurement control standard should be run regularly as a check on the functioning of the measurement system. If a control sample is run after calibration and the expected result obtained this will give the user a 99% confidence level in the calibration of the meter, and any results obtained for subsequent sample measurements. In a situation where multiple users are performing pH measurements the use of a control sample will provide confidence in the results being obtained from the different operators. The control buffer selected for use should be within the calibration range of the meter. What do I need to do to check that my pH meter is functioning correctly?

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To have full confidence in your pH measurements it is essential that you can demonstrate that each component of the measuring system is functioning to specification. If any component of the measurement system does not meet this requirement, questionable results will be obtained. For pH measurement, the following must be verified: The pH meters ability to correctly process both pH and temperature inputs correctly The pH electrodes ability to generate the correct output signal The temperature sensors ability to generate the correct output signal Routine calibration using pH buffers will not demonstrate all of the above, this is why annual calibration should be performed. What does annual calibration involve? To fully demonstrate that all components of the pH measuring system are functioning correctly, the following steps should be performed: Certified, traceable electrical simulators and standards should be used to verify that the pH meter is processing input signals correctly. The performance of the temperature probes should be compared to a certified reference thermometer The pH meter and electrode should be calibrated using certified, traceable pH buffers. The correct performance of the pH electrode should be verified using certified, traceable control standards. For most pH users it is not practical to purchase and maintain a certified traceable pH simulator, as it is expensive. Reagecons Technical Services Department can provide a calibration service to customers that meets all their requirements, be it Instrument Calibration or Validation. What is the difference between Instrument Calibration and Validation, and which one do I need? It is a regulatory requirement for pharmaceutical companies to perform Instrument Validation on new equipment, and regular Requalification on existing equipment. In brief, Instrument Validation is a fully documented process that ensures the instrument is working correctly. It demonstrates that the measuring instrument is working correctly and hence has no detrimental effect on the quality of the analytical results. For industries which are not as heavily regulated annual calibration (as previously described) would be sufficient to demonstrate that the instrument is working correctly. Reagecons Technical Services Department has developed calibration and validation protocols for a wide range of pH instruments. This service can be performed at the customers premises, or alternatively the instrument can be sent to Reagecon for calibration in our purpose-built Metrology Laboratory. Electrode Selection My pH electrode has a hole with a detachable cover at the top of the glass section. What is the purpose of this hole?

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This hole serves two purposes - to allow replacement of the electrolyte and also to allow pressure to be equalised during measurement. If the hole is covered during measurement then the electrolyte will not be able to travel through the electrode's diaphragm into the sample thus the electrode accuracy and responsiveness will be reduced. Some electrodes have a hole at the top for replacing the electrolyte, but others dont. Why is this? This electrode contains the electrolyte in a gel format. It is non-refillable, and thus is low maintenance. Gel filled electrodes are less accurate than liquid filled electrodes due to a slower response resulting from liquid potentials. In addition, if the electrolyte becomes poisoned it cannot be changed, and the electrode must be replaced. What applications should gel filled electrodes be used for? Gel filled electrodes are generally supplied with plastic bodies. They are thus more rugged than liquid filled glass electrodes, hence they are commonly used with portable meters. Measuring the pH of water from a water purification system can be problematic. Why is this? The objective of a water purification system is to produce a finished product of low ionic strength. This also means that there is low hydrogen ion concentration present, which can result in slow response times and inaccurate pH results if using a general-purpose pH electrode. The problem can be overcome by selecting an electrode that has the following characteristics: A diaphragm with a high outflow rate of electrolyte. An A glass membrane (gives a short response time in low ionic strength media). The Schott Blueline 13 electrode combines both of these features in a laboratory electrode and is thus ideal for this application. What is the alkaline error in pH measurement? In strongly alkaline solutions measurement errors can appear due to a contribution to the potential from alkali ions - Lithium (Li+) and Sodium (Na+) ions in addition to that of the hydrogen ions. Na+ and Li+ ions interact with the glass membrane and can partially or completely replace the H+ ions present. The resulting low hydrogen ion activity results in the observed pH reading being more basic than the true value. This effect occurs in solutions with a pH value > 11 and increases with increasing temperature. The magnitude of the alkali error depends on the concentration of the interfering ion with respect to the H+ ion concentration. Membrane glasses with large alkali errors have only a short service life in the presence of high concentrations of alkali metal ions How can the pH of a strong alkaline solution be measured accurately? If you need to perform measurements in solutions containing high concentrations of alkali metal ions it is advisable to use a special membrane glass type (e.g. Schott membrane type H used in the H62 electrode) when the pH value exceeds pH 11.

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How can the pH of a non-aqueous liquid be measured? The pH scale is defined in terms of hydrogen ion activity in aqueous solution and is not therefore strictly applicable to pH measurement in non-aqueous systems. If measurements are to be performed in non-aqueous liquids, there are several problems which may be encountered. The low ionic strength and low conductivity of some nonaqueous solvents may result in high noise or drift. In addition, the glass membrane of the pH electrode may become dehydrated from immersion in the non-aqueous solvent and thus lose its ability to respond to H+ ions. The ideal way to minimize these effects is to use a separate reference and measuring electrode with an auxiliary salt bridge containing a non-aqueous electrolyte filling solution .If this is not available a standard pH electrode may be used providing the following steps are performed: Select an electrode with a low resistance membrane and a free flowing diaphragm such as the Schott Blueline 13. Use an electrode containing a non-aqueous filling solution (such as saturated Lithium Chloride in Ethanol for non-polar solvents or Lithium Chloride in Glacial Acetic Acid for polar solvents). Soak the electrode in the non-aqueous solvent for ten minutes after standardisation and before use in the sample. Between successive measurements, the electrode should be rinsed with the nonaqueous solvent used to dissolve the sample. If the reading begins to drift after considerable time in a non-aqueous solvent, the pH glass bulb must be rehydrated by immersion in an aqueous buffer.

What working life can I expect from a pH electrode? The working life of a pH electrode is heavily dependant on the application, and how it is maintained. A well-maintained pH electrode will function for 6 to 24 months in most typical applications. However, the life span of an electrode will be greatly reduced by exposure to high temperatures, high process pressure, or by exposure to aggressive media (such as HF or very caustic applications) which can result in damage to the membrane or reference system. As the membrane on a pH electrode ages the speed of response reduces decreases until it becomes unacceptably slow. Care & Maintenance How should I store my pH electrodes when not in use? Why should I store electrodes in Electrode Storage Solution? How should I clean my pH electrode? How should I clean my electrode between pH measurements? How can pH electrodes be rejuvenated?

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What does the term drift mean in relation to pH measurement, and why should I be concerned about it? The subject of the above questions is comprehensively covered in the technical paper entitled Care, Maintenance and Fault Diagnosis for pH Electrodes published by J. J. Barron, C. Ashton. & L. Geary of the Reagecon Technical Services team. It includes details of practical remedial actions which can be taken to improve the accuracy of pH measurements and extend the working life of pH electrodes. What is the minimum level of filling solution to use in a refillable pH electrode? The filling solution level must be higher than the sample level to maintain a uniform flow of filling solution. A level of at least 2cm above sample height is recommended.

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