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Forewarned is Forearmed: Error and risk minimization in process analysis – Part 3

Forewarned is Forearmed: Error and risk minimization in process analysis – Part 3

In the course of life, each of us learns to trust our gut feelings or our experiences to avoid situations that seem dangerous or risky. You quite literally sense potential dangers with an uneasy feeling. Who hasn’t painfully learned that touching a hot stove top isn’t a good idea? Or who voluntarily goes outside during a tornado?

While humans can rely on their intuition and learned patterns to avoid dangers or use protective strategies, this is far more complicated with electronic systems or machines. All components of a system must be in a permanently safe state. Failures and malfunctions of individual components can have devastating consequences for production processes and the safety of the operators.

An example of this is the Seveso disaster in 1976, in which highly toxic dioxin TCDD escaped as a result of an uncontrolled reaction, and sustainably poisoned flora and fauna. With regard to other major chemical accidents, the European Seveso III Directive then came into force in 2012 to control major accident hazards to prevent major accidents.

Have you read Part 1 and Part 2 of our «Advantages of PAT (Process Analytical Technology)» series? If not, find them here!

Recognize, master, and avoid errors

Process engineering systems that are operated continuously contain countless components that can wear out or fail during their life cycle. However, if the measuring, control, or regulating circuit is affected, failures can cause immense damage. Under no circumstances should humans nor the environment be exposed to any kind of danger. For this reason, the functional safety of the components must be guaranteed, and their risk and hazard potential must be analyzed in detail.

The service life of mechanical components can be evaluated by observing mechanical wear and tear. However, the aging behavior of electronic components is difficult to assess. A unit of measure that makes risk reduction and thus functional safety quantifiable is the so-called «Safety Integrity Level» (SIL). 

The following procedure is followed:

  1.   Risk analysis
  2.   Realization of risk reduction
  3.   Evidence that the realized risk reduction corresponds at least to the required risk reduction

«Process analysis systems are part of the entire safety cycle of a manufacturing plant and therefore only one component whose risk of malfunctions and failures must be considered in an assessment.»

Risk assessmentA process is considered safe if the current risk has been reduced below the level of the tolerable risk. If safety is ensured by technical measures, one speaks of functional safety.

Significance for process analysis systems

Errors can happen anywhere, and can never be completely excluded. To minimize possible errors, it is therefore necessary to estimate the risk of occurrence and the damage to be expected from it as part of a risk analysis. A distinction must be made here between systematic and random errors.

Systematic errors are potentially avoidable and are caused, for example, by software errors or configuration deficiencies. Accordingly, they already exist during or prior to commissioning.

In contrast, random errors are potentially difficult to avoid because they occur arbitrarily. Nevertheless, the error rate or failure probability can be determined statistically and experimentally.

Random errors usually result from the hardware and occur during operation. Ultimately, systematic errors should be avoided, and random errors should be mastered to ensure trouble-free functionality.

Process analysis systems are the link between manual laboratory analysis and the industrial process. In applications where continuous and fully automatic monitoring of critical parameters is required, process analyzers are indispensable. Due to the different analysis conditions in the laboratory and directly in the process, there are some challenges when transferring the measurement technology from the lab to the process. The decisive factors are the working and environmental conditions (e.g., high temperatures, corrosive atmospheres, moisture, dust, or potentially explosive environments) which the process analyzers have to meet regarding their design, construction materials, and reliability of the components. The analyzer automatically and continuously transmits system and diagnostic data to prevent hardware or software components from failing through preventive measures. This significantly reduces the chance of random errors occurring.

General process analyzer setup

a) Analyzer Setup

Process analyzers have been specially developed for use in harsh and aggressive industrial environments. The IP66 protected housing is divided into two parts, and consists of separate wet and electronic parts. The electronics part contains all components relevant to control and operate the process analyzer. Modular components like burettes, valves, pumps, sampling systems, titration vessels, and electrodes can be found in the analyzer wet part. Representative samples can thus be taken from the process measuring point several meters away. The analysis procedure, the methods to be used, and method calculations are freely programmable.

A touchscreen with intuitive menu navigation allows easy operation, so that production processes can be optimized at any time. The course of the measurement is graphically represented and documented over the entire determination, so that the analysis process is completely controlled. The measurement results can be generated 24/7 and allow close and fully automatic monitoring of the process. Limits, alarms, or results are reliably transferred to the process control system.

When operating the analyzer, there is a risk that software errors can lead to failures. In order to recognize this with foresight, the system delivers self-diagnostic procedures as soon as it is powered on and also during operation. This includes, e.g., checking pumps and burettes, checking for leaks, or checking the communication between the I/O controller, the human interface, and the respective analysis module.

b) Sensors

The central component of a process analyzer is the measurement technique in use. In the case of sensors or electrodes, there are several requirements such as chemical resistance, ease of maintenance, robustness, or precision which they must meet. The safety-related risk arises from the possibility if measurement sensors fail due to aging, or if they become damaged and subsequently deliver incorrect measurement results.

Failure of the electrode, contamination, or damage must be reported immediately. With online analysis systems, the analysis is performed in an external measuring cell. In addition, recurring calibration and conditioning routines are predefined and are performed automatically. The status of the electrode is continuously monitored by the system.

Between measurements, the electrode is immersed in a membrane-friendly storage solution that prevents drying out and at the same time regenerates the swelling layer. The electrode is therefore always ready for use and does not have to be removed from the process for maintenance. This enables reliable process control even under harsh industrial conditions.

c) Analysis

Process analyzers must be able to handle samples for analysis over a wide concentration range (from % down to trace levels) without causing carry-over or cross-sensitivity issues. In many cases, different samples from several measuring points are determined in parallel in one system using different analysis techniques. The sample preparation (e.g., filtering, diluting, or wet chemical digestion) must be just as reliable and smooth as the fully automatic transfer of results to the process control system so that a quick response is possible.

Potential dangers for the entire system can be caused by incorrect measurement results. In order to minimize the risk, a detector is used to notify the system of the presence of sample in the vessel. The testing of the initial potential of the analysis or titration curves / color development in photometric measurements are diagnostic data that are continuously recorded and interpreted. Results can be verified by reference analysis or their plausibility can be clarified using standard and check solutions.

Detect errors before they arise

The risk assessment procedures that are carried out in the context of a SIL classification for process engineering plants are ultimately based on mathematical calculations. However, in the 24/7 operation of a plant, random errors can never be completely excluded. Residual risk always remains. Therefore, the importance of preventive maintenance activities is growing immensely in order to avoid hardware and software failures during operation.

A regular check of the process analyzer and its diagnostic data is the basic requirement for permanent, trouble-free operation. With tailor-made maintenance and service concepts, the analyzer is supported by certified service engineers over the entire life cycle. Regular maintenance plans, application support, calibration, or performance certificates, repairs, and original spare parts as well as proper commissioning are just a few examples.

Advantages of preventive maintenance from Metrohm Process Analytics

  • Preservation of your investment
  • Minimized risk of failure
  • Reliable measurement results
  • Calculable costs
  • Original spare parts
  • Fast repair
  • Remote Support

In addition, transparent communication between the process control system and the analyzer is also relevant in the context of digitalization. The collection of performance data from the analyzer to assess the state of the control system is only one component. The continuous monitoring of relevant system components enables conclusions to be drawn about any necessary maintenance work, which ideally should be carried out at regular intervals. The question arises as to how the collected data is interpreted and how quickly it is necessary to intervene. Software care packages help to test the software according to the manufacturer’s specifications, to perform data backup and software maintenance.

«Remote support is particularly important in times when you cannot always be on site.»

In real emergency situations in which rapid error analysis is required, manufacturers can easily support the operator remotely using remote maintenance solutions. The system availability is increased, expensive failures and downtimes are avoided, and the optimal performance of the analyzer is ensured.

Read what our customers have to say!

We have supported customers even in the most unlikely of places⁠—from the production floor to the desert and even on active ships!

Post written by Dr. Kerstin Dreblow, Product Manager Wet Chemical Process Analyzers, Deutsche Metrohm Prozessanalytik (Germany).

Frequently asked questions in Karl Fischer titration – Part 2

Frequently asked questions in Karl Fischer titration – Part 2

Since I started working at Metrohm more than 15 years ago, I have received many questions about Karl Fischer titration. Some of those questions have been asked repeatedly from several people in different locations around the world. Therefore, I have chosen 20 of the most frequent questions received over the years concerning Karl Fischer equipment and arranged them into three categories: instrument preparation and handling, titration troubleshooting, and the oven technique. Part 1 covered instrument preparation and handling, and Part 2 will now focus on titration troubleshooting and the KF oven technique.

Summary of questions in the FAQ (click to go directly to each question):

Titration troubleshooting

1.  If the drift value is 0, does this mean that the titration cell is over-titrated?

A drift of zero can be a sign that the cell might be over-titrated. In combination with the mV signal (lower than end-point criteria) and the color of the working medium (darker yellow than usual), it is a clear indicator for over-titration. However, volumetric titrations sometimes exhibit a zero drift for a short time without being over-titrated. If you have a real excess of iodine in the titration cell, the result of the next determination will most likely be erroneous. Therefore, over-titration should be avoided. There are various possible reasons for over-titration, like the sample itself (e.g., oxidizing agents which generate iodine from the working medium), the electrode (coating or invisible depositions on the Pt pins/rings), the reagent, and method parameters (e.g., the titration is rate too high), to name just a few.

2.  Should I discard the Karl Fischer reagent immediately if it turns brown?

Different factors can cause over-titration, however, the reagent is not always the reason behind this issue. The indicator electrode can also be the reason for overshooting the endpoint. In this case, regular cleaning of the electrode can prevent over-titration (see also questions 7 to 9 from Part 1 in this series on cleaning).

A low stirring speed also increases the risk of over-titration, so make sure the solution is well mixed. Depending on the type of reagent, the parameters of the titration need to be adjusted. Especially if you use two-component reagents, I recommend decreasing the speed of the titrant addition to avoid over-titration. Over-titration has an influence on the result, especially if the degree of over-titration changes from one determination to the next. So over-titration should always be avoided to guarantee correct results.

3.  What is drift correction, and when should I use it?

I recommend using the drift correction in coulometric KF titration only. You can also use it in volumetric titration, but here the drift level is normally not as stable as for coulometric titrations. This can result in variations in the results. A stabilization time can reduce such an effect. However, compared to the absolute water amounts in volumetry, the influence of drift is usually negligible.

4.  My results are negative. What does a negative water content mean?

Negative values do occur if you have a high start drift and a sample with a very low water content. In this case, the value for drift correction can be higher than the absolute water content of the sample, resulting in a negative water content.

If possible, use a larger sample size to increase the amount of water added to the titration cell with the sample. Furthermore, you should try to reduce the drift value in general. Perhaps the molecular sieve or the septum need to be replaced. You can also use a stabilizing time to make sure the drift is stable before analyzing the sample.

Karl Fischer oven

5.  My samples are not soluble. What can I do?

In case the sample does not dissolve in KF reagents and additional solvents do not increase the solubility of the sample, then gas extraction or the oven technique could be the perfect solution.

The sample is weighed in a headspace vial and closed with a septum cap. Then the vial is placed in the oven and heated to a predefined temperature, leading the sample to release its water. At the same time, a double hollow needle pierces through the septum. A dry carrier gas, usually nitrogen or dried air, flows into the sample vial. Taking the water of the sample with it, the carrier gas flows into the titration cell where the water content determination takes place.

6.  Can all types of samples be analyzed with the oven method?

Many samples can be analyzed with the oven. Whether an application actually works for a sample strongly depends on the sample itself. Of course, there are samples that are not suitable for the oven method, e.g., samples that decompose before releasing the water or that release their water at higher temperatures than the maximum oven temperature.

7.  How do I find the optimal oven temperature for water extraction?

Depending on the instrument used, you can run a temperature gradient of 2 °C/min. This means it is possible to heat a sample from 50 to 250 °C within 100 minutes. The software will then display a curve of water release against temperature (see graph).

From such a curve, the optimal temperature can be determined. Different peaks may show blank, adherent water, different kinds of bound water, or even decomposition of the sample.

This example curve shows the water release of a sample as it has been heated between 130 and 200 °C. At higher temperatures, the drift decreases to a stable and low level.

Generally, you should choose a temperature after the last water release peak (where the drift returns to the base level) but approximately 20 °C below decomposition temperature. Decomposition can be recognized by increasing drift, smoke, or a color change of the sample. In this example, there are no signs of decomposition up to an oven temperature of 250 °C. Therefore, the optimal oven temperature for this sample is 230 °C (250 °C – 20 °C).

In case the instrument you use does not offer the option to run a temperature gradient, you can manually increase the temperature and measure the sample at different temperatures. In an Excel spreadsheet, you can display the curve plotting released water against temperature. If there is a plateau (i.e., a temperature range where you find reproducible water contents), you have found the optimal oven temperature.

8.  What is the highest possible water content that can be measured with a Karl Fischer oven?

Very often, the oven is used in combination with a coulometric titrator. The coulometric titration cell used in an oven system is filled with 150 mL of reagent. Theoretically, this amount of reagent allows for the determination of 1500 mg of water. However, this amount is too high to be determined in one titration and it would lead to very long titration times and negative effects on the results. We recommend that the water content of a single sample (in a vial) should not be higher than 10 mg, ideally around 1000–2000 µg water. For samples with water contents in the higher percentage range, you should consider the combination with a volumetric titrator.

9.  What is the maximum sample size that can be used with the oven? If I use too much sample, will the needle be blocked?

The standard vial for the oven method has a volume of approximately 9 mL. However, we do not recommend filling the vial completely. Do not fill more than 5–6 mL of sample in a vial. We offer the possibility to customize our oven systems, allowing you to use your own vials. Please contact your local Metrohm agency for more information on customized oven systems.

For liquid samples, we recommend using a long needle to lead the gas through the sample. Solid samples and especially samples that melt during analysis require a short needle. The tip of the needle is positioned above the sample material to avoid needle blockage.

Additionally, you should use a «relative blank value», i.e., taking only the remaining air volume into account for blank subtraction. You can find more information about the relative blank and how to calculate it in Application Note AN-K-048.

10.  What is the detection limit of the oven method, and how much sample is required to analyze a sample with 10 ppm (mg/L) water content?

We recommend having at least 50 µg of water in the sample, if analyzed with coulometry. However, if conditions are absolutely perfect (i.e., very low and stable drift plus perfect blank determination), it is possible to determine even lower water contents, down to 20 µg of absolute water. For a sample with a water content of < 10 ppm (mg/L), this would correspond to a sample size of at least 2 g.

11.  How do I verify an oven method?

For the verification of an oven system, you can use a certified water standard for oven systems. With such a standard, you can check the reproducibility and the recovery. There are a few types of standards available for different temperature ranges.

I hope this collected information helps you to answer some of your most burning KF questions. If you have further unanswered questions, do not hesitate to contact your local Metrohm distributor or check out our selection of webinars.

Automate thermal sample preparation

It’s easy with an oven sample changer from Metrohm!

Post written by Michael Margreth, Sr. Product Specialist Titration (Karl Fischer Titration) at Metrohm International Headquarters, Herisau, Switzerland.

Making a better beer with chemistry

Making a better beer with chemistry

Lager or ale? Pale ale or stout? Specialty beer, or basic draft? This week, to celebrate the International Beer Day on Friday, August 7th, I have chosen to write about a subject near and dear to me: how to make a better beer! Like many others, at the beginning of my adult life, I enjoyed the beverage without giving much thought to the vast array of styles and how they differed, beyond the obvious visual and gustatory senses. However, as a chemist with many chemist friends, I was introduced at several points to the world of homebrewing. Eventually, I succumbed.

Back in 2014, my husband and I bought all of the accessories to brew 25 liters (~6.5 gallons) of our own beer at a time. The entire process is controlled by us, from designing a recipe and milling the grains to sanitizing and bottling the finished product. We enjoy being able to develop the exact bitterness, sweetness, mouthfeel, and alcohol content for each batch we brew.

Over the years we have become more serious about this hobby by optimizing the procedure and making various improvements to the setup – including building our own temperature-controlled fermentation fridge managed by software. However, without an automated system, we occasionally run into issues with reproducibility between batches when using the same recipe. This is an issue that every brewer can relate to, no matter the size of their operation.

Working for Metrohm since 2013 has allowed me to have access to different analytical instrumentation in order to check certain quality attributes (e.g., strike water composition, mash pH, bitterness). However, Metrohm can provide much more to those working in the brewing industry. Keep reading to discover how we have improved analysis at the largest brewery in Switzerland.

Are you looking for applications in alcoholic beverages? Check out this selection of FREE Application Notes from Metrohm:

Lagers vs. Ales

There are two primary classes of beer: lagers and ales. The major contrast between the two is the type of yeast used for the fermentation process. Lagers must be fermented at colder temperatures, which lends crisp flavors and low ester formation. However, colder processes take longer, and so fermentation steps can last for some months. Ales have a much more sweet and fruity palate of flavors and are much easier to create than lagers, as the fermentation takes place at warmer temperatures and happens at a much faster rate.

Comparison between the fermentation of lagers and ales.

Diving a bit deeper, there are several styles of beer, from light pilsners and pale ales to porters and black imperial stouts. The variety of colors and flavors depend mostly on the grains used during the mash, which is the initial process of soaking the milled grains at a specific temperature (or range) to modify the starches and sugars for the yeast to be able to digest. The strain of yeast also contributes to the final flavor, whether it is dry, fruity, or even sour. Taking good care of the yeast is one of the most important parts of creating a great tasting beer.

Brewing terminology

  • Malting: process of germinating and kilning barley to produce usable sugars in the grain
  • Milling: act of grinding the grains to increase surface area and optimize extraction of sugars
  • Mashing: releasing malt sugars by soaking the milled grains in (hot) water, providing wort
  • Wort: the solution of extracted grain sugars
  • Lautering: process of clarifying wort after mashing
  • Sparging: rinsing the used grains to extract the last amount of malt sugars
  • Boiling: clarified wort is boiled, accomplishing sterilization (hops are added in this step)
  • Cooling: wort must be cooled well below body temperature (37 °C) as quickly as possible to avoid infection
  • Pitching: prepared yeast (dry or slurry) is added to the cooled brewed wort, oxygen is introduced
  • Fermenting: the process whereby yeast consumes simple sugars and excretes ethanol and CO2 as major products

Ingredients for a proper beer

These days, beer can contain several different ingredients and still adhere to a style. Barley, oats, wheat, rye, fruit, honey, spices, hops, yeast, water, and more are all components of our contemporary beer culture. However, in Bavaria during the 1500’s, the rules were much more strict. A purity law known as the Reinheitsgebot (1516) stated that beer must only be produced with water, barley, and hops. Any other adjuncts were not allowed, which meant that other grains such as rye and wheat were forbidden to be used in the brewing process. We all know how seriously the Germans take their beer – you only need to visit the Oktoberfest once to understand!

Determination of the bitterness compounds in hops, known as «alpha acids», can be easily determined with Metrohm instrumentation. Check out our brochure for more information:

You may have noticed that yeast was not one of the few ingredients mentioned in the purity law, however it was still essential for the brewing process. The yeast was just harvested at the end of each batch and added into the next, and its propagation from the fermentation process always ensured there was enough at the end each time. Ensuring the health of the yeast is integral to fermentation and the quality of the final product. With proper nutrients, oxygen levels, stable temperatures, and a supply of simple digestible sugars, alcohol contents up to 25% (and even beyond) can be achieved with some yeast strains without distillation (through heating or freezing, as for eisbocks).

Improved quality with analytical testing

Good beers do not make themselves. For larger brewing operations, which rely on consistency in quality and flavor between large batch volumes as well as across different countries, comprehensive analytical testing is the key to success.

Metrohm is well-equipped for this task, offering many solutions for breweries large and small.

Don’t take it from me – listen to one of our customers, Jules Wyss, manager of the Quality Assurance laboratory at Feldschlösschen brewery, the largest brewery in Switzerland.

«I have decided to go with Metrohm, because they are the only ones who are up to such a job at all. They share with us their huge know-how.

I can’t think of any other supplier who would have been able to help me in the same way

Jules Wyss

Manager Quality Assurance Laboratory, Feldschlösschen Getränke AG

Previous solutions failed

For a long time, Jules determined the quality parameters in his beer samples using separate analysis systems: a titrator, HPLC system, alcohol measuring device, and a density meter. These separate measurements involved a huge amount of work: not only the analyses themselves, but also the documentation and archiving of the results all had to be handled separately. Furthermore, Jules often had to contend with unreliable results – depending on the measurement procedure, he had to analyze one sample up to three times in order to obtain an accurate result.

A tailor-made system for Feldschlösschen

Jules’ close collaboration with Metrohm has produced a system that takes care of the majority of the necessary measurements. According to Jules, the system can determine around 90% of the parameters he needs to measure. Jules’ new analysis system combines various analysis techniques: ion chromatography and titration from Metrohm as well as alcohol, density, and color measurement from another manufacturer. They are all controlled by the tiamo titration software. This means that bitterness, citric acid, pH value, alcohol content, density, and color can all be determined by executing a single method in tiamo.

Measurement of the overall water quality as well as downstream analysis of the sanitization process on the bottling line is also possible with Metrohm’s line of Process Analysis instrumentation.

Integrated analytical systems with automated capabilities allow for a «plug and play» determination of a variety of quality parameters for QA/QC analysts in the brewing industry. Sample analysis is streamlined and simplified, and throughput is increased via the automation of time-consuming preparative and data collection steps, which also reduces the chance of human error.

Something to celebrate: The Metrohm 6-pack (2018)

In 2018, Metrohm celebrated its 75 year Jubilee. At this time, I decided to combine my experience as a laboratory analyst as well as a marketing manager to brew a series of six different styles of beer for the company, as a giveaway for customers of our Metrohm Process Analytics brand, for whom I worked at the time. Each batch was brewed to contain precisely 7.5% ABV (alcohol by volume), to resonate with the 75 year anniversary. The array of ales was designed to appeal to a broad audience, featuring a stout, porter, brown ale, red ale, hefeweizen, and an India pale ale (IPA). Each style requires different actions especially during the mashing process, based on the type of grains used and the desired outcome (e.g., flavor balance, mouthfeel, alcohol content).

Bespoke bottle caps featuring the Metrohm logo.
The 6 styles of beers brewed as a special customer giveaway to celebrate the Metrohm 75 year Jubilee.

Using a Metrohm Ion Chromatograph, I analyzed my home tap water for concentrations of major cations and anions to ensure no extra salts were needed to adjust it prior to mashing. After some of the beers were prepared, I tested my colleagues at Metrohm International Headquarters in the IC department, to see if they could determine the difference between two bottles with different ingredients:

Overlaid chromatograms from IC organic acid analysis highlighting the differences between 2 styles of the Metrohm 75 year Jubilee beers.

The IC analysis of organic acids and anions showed a clear difference between the beers, allowing them to determine which sample corresponded to which style, since I did not label them prior to shipping the bottles for analysis. As the milk stout contained added lactose, this peak was very pronounced and a perfect indicator to use.

Metrohm ion chromatography, along with titration, NIRS, and other techniques, allows for reliable, comprehensive beer analysis for all.

In conclusion, I wish you a very happy International Beer Day this Friday. Hopefully this article has illuminated the various ways that beer and other alcoholic beverages can be analytically tested for quality control parameters and more  fast, easy, and reliably with Metrohm instrumentation.

For more information about the beer quality parameters measured at Feldschlösschen brewery, take a look at our article: «In the kingdom of beer The largest brewery in Switzerland gets a made-to-measure system». Cheers!

Read the full article:

«In the kingdom of beer – The largest brewery in Switzerland gets a made-to-measure system»

Post written by Dr. Alyson Lanciki, Scientific Editor (and «chief brewing officer») at Metrohm International Headquarters, Herisau, Switzerland.

Frequently asked questions in Karl Fischer titration – Part 1

Frequently asked questions in Karl Fischer titration – Part 1

Since I started working at Metrohm more than 15 years ago, I have received many questions about Karl Fischer titration. Some of those questions have been asked repeatedly from several people in different locations around the world. Therefore, I have chosen 20 of the most frequent questions received over the years concerning Karl Fischer equipment and arranged them into three categories: instrument preparation and handling, titration troubleshooting, and the oven technique. Part 1 will cover instrument preparation and handling, and Part 2 will cover the other two topics.

Summary of questions in the FAQ (click to go directly to each question):

Instrument preparation and handling

1.  How can I check if the electrode is working correctly?

I recommend carrying out a volumetric or coulometric Karl Fischer titration using a certified water standard as sample. In volumetry, you can carry out a threefold titer determination followed by a determination of a different standard. Then, you can calculate the recovery of the water content determination of the standard.

To check a coulometric system, carry out a threefold determination with a certified water standard and calculate the recovery. If the recovery is between 97–103%, this indicated that the system, including the electrode, is working fine.

The color of the working medium is an additional indicator as to whether the indication is working properly.

Pale yellow is perfect, whereas dark yellow or even pale brown suggests indication problems. If this happens, then the indicator electrode should be cleaned.

Check out questions 7 and 8 for tips on the cleaning of the indicator electrode.

2.  How long can an electrode be stored in KF reagent?

Karl Fischer electrodes are made from glass and platinum. Therefore, the KF reagent does not affect the electrode. It can be stored in reagent as long as you want.

3.  Can the molecular sieve be dried and reused, or should it be replaced?

The molecular sieve can of course be dried and reused. I recommend drying it for at least 24 hours at a temperature between 200–300 °C. Afterwards, let it cool down in a desiccator and then transfer it into a glass bottle with an airtight seal for storage. 

4.  How long does conditioning normally take?

Conditioning of a freshly filled titration vessel normally takes around 2–4 minutes for volumetry, depending on the reaction speed (type of reagent), and around 15–30 minutes for coulometry. In combination with an oven, it might take a bit longer to reach a stable drift owing to the constant gas flow. I recommend stabilizing the entire oven system for at least 1 hour before the first titration.

Between single measurements in the same working medium, conditioning takes approximately 1–2 minutes. Take care that the original drift level is reached again.

5.  When conditioning, many bubbles form in the coulometric titration cell with a very high drift, also when using fresh reagent. What could be the reason for this effect?

At the anode, the generator electrode produces iodine from the iodide-containing reagent. The bubbles you see at the cathode are the result of the reduction of H+ ions to hydrogen gas.

After opening the titration cell or after filling it with fresh reagent, the conditioning step removes any moisture brought into the system, avoiding a bias in the water content determination of the sample. Removing the water results in an increased drift level. During conditioning, the aforementioned H2 is generated. The gas bubbles are therefore completely normal and not a cause for concern. Generally, the following rule applies: The more moisture present in the titration vessel, the higher the drift value will be, and the more hydrogen will form.

6.  What is the best frequency to clean the Karl Fischer equipment?

There is no strict rule as to when you should clean the KF equipment. The cleaning intervals strongly depend on the type and the amount of sample added to the titration cell. Poor solubility and contamination of the indicator electrode (deposition layer on its surface) or memory effects due to large amounts of sample can be good reasons for cleaning the equipment.

The drift can be a good indicator as well. In case you observe higher and unstable drift values, I would recommend cleaning the titration cell or at least refilling the working medium.

7.  How do I clean the Karl Fischer equipment?

For a mounted titration vessel, it can be as simple as rinsing with alcohol. For an intense cleaning, the vessel should be removed from the titrator. Water, solvents like methanol, or cleaning agents are fine to clean the KF equipment. Even concentrated nitric acid can be used as an oxidizing agent, e.g. in case of contaminated indicator electrodes or coulometric generator electrodes.

All of these options are fine, but keep in mind that the last cleaning step should always be rinsing with alcohol followed by proper drying in a drying oven or with a hair dryer at max. 50 °C to remove as much adherent water as possible.

You should never use ketones (e.g., acetone) to clean Karl Fischer equipment, as they react with methanol. This reaction releases water. If there are still traces of ketones left in the titration cell after cleaning, they will react with the methanol in the KF reagent and might cause the drift to be too high to start any titration.

8.  Is it also possible to use a cleaning agent like «CIF» or toothpaste to clean the double Pt electrode?

Normally, rinsing with alcoholic solvents and polishing with paper tissue should be enough to clean the indicator electrode. You may also use detergents, toothpaste, or the polishing set offered by Metrohm! Just make sure that you rinse the electrode properly after the cleaning process to remove all traces of your chosen cleaning agent before using the electrode again.

Cleaning instructions can also be found in our video about metal and KF electrode maintenance:

9.  How do I clean a generator electrode with a diaphragm?

After removing the generator electrode from the titration vessel, dispose the catholyte solution, then rinse the electrode with water. Place the generator electrode upright (e.g., in an Erlenmeyer flask) and cover the connector with the protection cap to prevent corrosion. Fill the generator electrode with some milliliters of concentrated nitric acid, and let the acid flow through the diaphragm. Then fill the cathode compartment with water, and again allow the liquid to flow through the diaphragm. Repeat the rinsing step with water several times to make sure that all traces of nitric acid are washed out of the diaphragm.

Please note that the nitric acid treatment can be left out if the level of contamination does not require it.

Finally, pour some methanol into the generator electrode to remove the water. Repeat this step a few times to remove all traces of water. The last step is properly drying the electrode in a drying oven or with a hair dryer at max. 50 °C. After this cleaning procedure, the electrode is as good as new and can be used again for titrations.

Keep on the lookout for our next installment in this two-part series, or subscribe to the blog below so you’re sure not to miss it! In Part 2, I will cover the topics of KF titration troubleshooting and the Karl Fischer oven technique.

Post written by Michael Margreth, Sr. Product Specialist Titration (Karl Fischer Titration) at Metrohm International Headquarters, Herisau, Switzerland.

The role of process automation in an interconnected world – Part 2

The role of process automation in an interconnected world – Part 2

The following scenario sounds like a fictional dystopian narrative, but it is a lived reality. A catastrophe, much like the current COVID-19 crisis, is dramatically impacting society. The normality, as was known before, has suddenly changed: streets are swept empty, shops are closed, and manufacturing is reduced or at a complete standstill. But what happens to safety-related systems, e.g. in the pharmaceutical or food industry, which must not stand still and are designed in such a way that they cannot fail? How can the risk of breakdowns and downtimes be minimized? Or in the event of failure, how can the damage to people and the environment be limited or, in general, the operational sequence maintained?

Digitalization: curse or blessing? 

When considering process engineering plants, one is repeatedly confronted with buzzwords such as «Industry 4.0», «digitalization», «digital transformation», «IoT», «smart manufacturing», etc. The topic is often discussed controversially and often it is about an either-or dichotomy: either man or the machine and the associated fears. No matter what name you give to digitalization, each term here has one thing in common: intelligently networking separate locations and processes in industrial production using modern information and communication technologies. Process automation is a small but important building block that needs attention. Data can only be consistently recorded, forwarded, and reproduced with robust and reliable measurement technology.

For some time already, topics including sensors, automation, and process control have been discussed in the process industry (PAT) with the aim of reducing downtimes and optimizing the use of resources. However, it is not just about the pure collection of data, but also about their meaningful interpretation and integration into the QM system. Only a consequent assessment and evaluation can lead to a significant increase in efficiency and optimization.

This represents a real opportunity to maintain production processes with reduced manpower in times of crisis. Relevant analyses are automatically and fully transferred to the process. This enables high availability and rapid intervention, as well as the assurance of high quality requirements for both process security and process optimization. In addition, online monitoring of all system components and preventive maintenance activities effectively counteracts a failure.

Digitally networked production plants

Even though digitalization is relatively well-established in the private sector under the catchphrase «smart home», in many production areas the topic is still very much in its infancy. In order to intelligently network different processes, high demands are made. Process analysis systems make a major contribution to the analysis of critical parameters. Forwarding the data to the control room is crucial for process control and optimization. In order to correspond to the state-of-the-art, process analysis systems must meet the following requirements:

Transparent communication / operational maintenance

Processes must be continuously monitored and plant safety guaranteed. Downtimes are associated with high expenditure and costs and therefore cannot be tolerated. In order to effectively minimize the risk of failures, device-specific diagnostic data must be continuously transmitted as part of the self-check, or failures must be prevented with the help of preventive maintenance activities. Ideally, the response must be quick, and faults remedied without having to shut down the system (even remotely).

Future-proof automation

If you consider how many years (or even decades) process plants are in operation, it is self-explanatory that extensions and optimizations must be possible within their lifetime. This includes both the implementation of state-of-the-art analyzers and the communication between the systems.

Redundant systems

In order to prevent faults from endangering the entire system operation, redundancy concepts are generally used.

Practical example: Smart concepts for fermentation processes

Fermenters or bioreactors are used in a wide variety of industries to cultivate microorganisms or cells. Bacteria, yeasts, mammalian cells, or their components serve as important active ingredients in pharmaeuticals or as basic chemicals in the chemical industry. In addition, there are also degradation processes in wastewater treatment assisted by using bioreactors. Brewing kettles in beer production can also be considered as a kind of bioreactor. In order to meet the high requirements for a corresponding product yield and the maintenance of the ideal conditions for proper metabolism, critical parameters have to be checked closely, and often.

The conditions must be optimally adapted to those of the organism’s natural habitat. In addition to the pH value and temperature, this also includes the composition of the matrix, the turbidity, or the content of O2 and CO2. The creation of optimal environmental conditions is crucial for a successful cultivation of the organisms. The smallest deviations have devastating consequences for their survival, and can cause significant economic damage.

As a rule, many of the parameters mentioned are measured directly in the medium using inline probes and sensors. However, their application has a major disadvantage. Mechanical loads (e.g., glass breakage) or solids can lead to rapid material wear and contaminated batches, resulting in high operational costs. With the advent of ​​smart technologies, online analysis systems and maintenance-free sensors have become indispensable to ensure the survival of the microorganisms. In this way, reliably measured values ​​are delivered around the clock, and it is ensured that these are transferred directly to all common process control systems or integrated into existing QM systems.

Rather than manual offline measurement in a separate laboratory, the analysis is moved to an external measuring cell. The sample stream is fed to the analysis system by suction with peristaltic pumps or bypass lines. Online analysis not only enables the possibility of 24/7 operation and thus a close control of the critical parameters, but also the combination of different analysis methods and the determination of further parameters. This means that several parameters as well as multiple measuring points can be monitored with one system.

The heart of the analysis systems is the intelligent sensor technology, whose robustness is crucial for the reliable generation of measured values.

pH measurement as a vital key parameter in bioreactors

Knowledge of the exact pH value is crucial for the product yield, especially in fermentation processes. The activity of the organism and its metabolism are directly dependent on the pH value. The ideal conditions for optimal cell growth and proper metabolism are within a limited pH tolerance range, which must be continuously monitored and adjusted with the help of highly accurate sensors.

However, the exact measurement of the pH value is subject to a number of chemical, physical, and mechanical influencing factors, which means that the determination with conventional inline sensors is often too imprecise and can lead to expensive failures for users. For example, compliance with hygiene measures is of fundamental importance in the pharmaceutical and food industries. Pipelines in the production are cleaned with solutions at elevated temperatures. Fixed sensors that are exposed to these solutions see detrimental effects: significantly reduced lifespan, sensitivity, and accuracy.

Intelligent and maintenance-free pH electrodes

Glass electrodes are most commonly used for pH measurement because they are still by far the most resistant, versatile, and reliable solution. However, in many cases changes due to aging processes or contamination in the diaphragm remain undetected. Glass breakage also poses a high risk, because it may result in the entire production batch being discarded.

The aging of the pH-sensitive glass relates to the change in the hydration layer, which becomes thicker as time goes on. The consequence is a sluggish response, drift effects, or a decrease in slope. In this case, calibration or adjustment with suitable buffer solutions is necessary. Especially if there are no empirical values ​​available, short intervals are recommended, which significantly increase the effort for maintenance work.

With online process analyzers, the measurement is transferred from the process to an external measuring cell. This enables a long-lasting pH measurement to be achieved with an accuracy that is not possible with classic inline probes.

In many process solutions, measurement with process sensors takes place directly in the medium. This inevitably means that the calibration and maintenance of electrodes is particularly challenging in places that are difficult to access, leading to expensive maintenance work and downtimes. Regular calibration of the electrodes is recommended, especially when used under extreme conditions or on the edge of the defined specifications.

If the measurement is carried out with online process analyzers, then calibration, adjustment and cleaning are carried out fully automatically. The system continuously monitors the condition of the electrode. Between measurements, the electrode is immersed in a membrane-friendly storage solution that avoids drying out, and at the same time prevents the hydration layer from swelling further as it does not contain alkali ions. The electrode is always ready for use and does not have to be removed from the process for maintenance work.

The 2026 pH Analyzer from Metrohm Process Analytics is a fully automatic analysis system, e.g., for determining the pH value as an individual process parameter.

Maintenance and digitalization

In addition to the automatic monitoring of critical process parameters, transparent communication between the system and the analyzer also plays a decisive role in terms of maintenance measures. The collection of vital data from the analyzer to assess the state of the system is only one component. The continuous monitoring of relevant system components enables conclusions to be drawn about any necessary maintenance work. For example, routine checks on the condition of the electrodes (slope / zero point check, possibly automatic calibration) are carried out regularly during the analysis process. Based on the data, calibration and cleaning processes are performed fully automatically, which allow robust measurement even at measuring points that are difficult to access or in aggressive process media. This means that the operator is outside the danger zone, which contributes to increased safety.

Summary

The linking of production processes with digital technology holds a particularly large potential and contributes to the economic security of companies. In addition, the pressure is growing steadily for companies to face the demands of digitalization in production. As an example, in the area of ​​fermentation processes, the survival of the microorganisms is ensured by closely monitoring relevant parameters. Intelligent systems increase the degree of automation and can make the process along the entire value chain more efficient.

Find out in the next installment how functional safety concepts help to act before a worst case scenario comes true where errors occur and systems fail.

Want to learn more about the history of process analysis technology at Metrohm? Check out our previous blog posts:

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Post written by Dr. Kerstin Dreblow, Product Manager Wet Chemical Process Analyzers, Deutsche Metrohm Prozessanalytik (Germany).