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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.

Trace metal analysis with solid-state electrodes – Part 2

Trace metal analysis with solid-state electrodes – Part 2

In the second part of our series on «heavy metal» analysis with solid-state electrodes, the focus lies on the scTRACE Gold electrode. Gold electrodes have been used in electrochemistry for decades. However, the scTRACE Gold has a very special design. Originally developed to improve the voltammetric determination of arsenic, the electrode has also proven to be suitable for the determination of a number of other elements, such as copper, iron, lead, and even the toxic chromium(VI).

How does it work?

The working electrode is a gold micro-wire (Fig. 1), which is thinner than a human hair. This special form of electrode leads to a very short initial preparation time. Different from other gold electrodes, the scTRACE Gold is ready for use within a few minutes.

Another advantage of this electrode is that it comes with the reference and the auxiliary electrode printed on the rear side of the sensor (Fig. 2). That does not only save on costs for the two additional electrodes required in a voltammetric system, it also makes maintenance for the reference electrode obsolete.

Figure 1. Close-up view of the gold micro-wire working electrode on the scTRACE Gold.

Figure 2. Close-up view of the reference and auxiliary electrode on the rear side of the scTRACE Gold.

Applications

The high level of sensitivity and a straightforward setup makes voltammetry a valuable tool in drinking water analysis.

Availability of clean drinking water is one of the major concerns of the 21st century. Besides microbiological contaminations, such as bacteria and viruses, the presence of heavy metals in drinking water can be a health risk. The first step in providing clean water is to identify contaminants, since health-threatening concentrations of heavy metals are not visible. For many heavy metals, limit values in drinking water are specified by authorities like the U.S. Environmental Protection Agency (EPA) or the European Commission. Water quality laboratories often use ICP (inductively coupled plasma) to monitor metal concentrations in drinking water.

Voltammetry is one of the few analysis techniques which offers a comparable sensitivity. Needing only basic infrastructure and low running costs, voltammetry is a viable alternative to monitor some key elements. In the following sections, some selected application examples are shown which demonstrate the capabilities of the scTrace Gold electrode in water analysis.

Arsenic in drinking water

Arsenic gained some global notoriety when water wells were built in Bangladesh to avoid diseases caused by microbiological contaminations in the surface water. Rather than suffering from cholera or hepatitis, people were instead afflicted with chronic arsenic poisoning.

It would be somewhat careless to believe that arsenic is only a problem in less developed countries. Actually, arsenic can be found nearly everywhere in the earth’s crust. Though as Paracelsus already knew, «the concentration makes the poison».

Therefore, the crucial question is how much of this arsenic finds its way into the water table. The WHO (World Health Organization) recommends a concentration of 10 µg/L arsenic as the maximum level in water that is intended for human consumption. This figure is also the legal limit in many countries.

Want to know more about arsenic? Then download our free article: «Arsenic – The multipurpose poison».

The voltammetric determination of the limit value of 10 µg/L shows a recovery of about 92% (n = 10 determinations) with a relative standard deviation of 6.5%. With a detection limit of 1 µg/L, which is one tenth of the legal limit, voltammetry using the scTRACE Gold electrode offers a reliable and cost-effective way of monitoring the arsenic content of drinking water.

For more information, download our free application note AN-V-210: Total arsenic in mineral water – Straightforward determination by voltammetry on a gold microwire electrode.

The scTRACE Gold electrode can be used with the 884 Professional VA as well as with the 946 Portable VA Analyzer. The 884 Professional VA is designed for laboratory use. The system is extremely flexible and can be adapted to user requirements. The modular setup also allows a later extension of the instrument from manual to fully automated.

As the name says, the 946 Portable VA Analyzer is intended for mobile use. It allows for on-site determination, directly at the sample source.

Copper in surface water

Under normal circumstances, copper in drinking water is not a problem. The legal limits are comparably high, WHO recommends a maximum concentration of 2 mg/L. An example from the field illustrates where the determination of copper in water can nevertheless be advisable.

The production of distilled alcoholic beverages (e.g., gin, whiskey, brandy, schnapps) involves single or multiple distillation of the raw material, which is done in copper stills. Cleaning out the copper apparatus and draining the rinsing water to a river can contaminate the environment with copper.

Although regulatory limits in effluents are usually higher than in drinking water, the copper limits can still be exceeded if the water is not treated properly prior to discharge. Since pollution from this cleaning is not a continuous process but only occurs periodically, it is difficult to detect and even harder to confirm, especially in less accessible areas.

Here, mobile voltammetry using the scTRACE Gold with the 946 Portable VA Analyzer can make a valuable contribution to the protection of the environment due to the reliable determination of low concentrations of copper.

For a concentration of 5 µg/L, the mean recovery of 10 determinations is approximately 107%, with a relative standard deviation of 2%. Concentrations down to 0.5 µg/L copper in the water can be determined directly at the point of sampling. This allows immediate re-sampling in case of suspicious results, and can furthermore help to locate the source of the pollution. In this way, chances increase to identify the source and hold the responsible entity accountable.

For more information, download our free application note AN-V-213: Copper in drinking water – Straightforward determination by voltammetry using a gold microwire electrode.

Iron in water

According to WHO, iron does not pose a health concern in levels typically found in drinking water. In contrast, it is an essential element for human nutrition. Nevertheless, many countries specify a maximum contaminant level between 200 µg/L and 300 µg/L.

The reason is simply that higher concentrations have a negative effect on the taste of the water, and will stain laundry and sanitary appliances. 

With a detection limit of 10 µg/L, the voltammetric determination of iron offers a straightforward method for monitoring the iron concentration of the water supply. The recovery of a voltammetric determination of 20 µg/L Fe is in the range of 91% (n = 10 determinations) with a relative standard deviation of 1%.

For more information, download our free application note AN-V-216: Iron in drinking water – Straightforward determination by voltammetry using a gold microwire electrode (DHN method).

What’s next?

In part two of this series, I introduced the scTRACE Gold electrode which I will also continue to discuss in Part 3. In the next installment, I will focus on applications which are carried out after electrochemical modification of the gold micro-wire.

Post written by Barbara ZumbrägelProduct Manager VA/CVS 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.

History of Metrohm IC – Part 1

History of Metrohm IC – Part 1

Ion chromatography (IC) has been a part of the Metrohm portfolio of analytical chemical instrumentation since 1987, and in that span of 33 years, several new and exciting developments have been introduced challenging the limits of what IC can do. From simple setups for academic laboratories, to hyphenated techniques (e.g., IC-ICP-MS) broadening the capabilities of chemical analysis – we’ve done it! This week, I would like to begin to unveil the history of this analytical method at Metrohm and how it has changed over the intervening decades.

«The mid-1980‘s. Our mission: develop an affordable ion chromatograph with a minimal footprint, simple to use, providing outstanding measurements.»

Walter Terzer, R&D Ion Chromatography, Metrohm AG

«The 690 Ion Chromatograph was engineered for people without a PhD in chemistry, too. And it was so rugged that quite a few 690 IC’s are used even today. Most importantly: At the time, it cost only half as much as our competitor’s product!»

Dr. Markus Läubli, R&D Ion Chromatography, Metrohm AG

The beginning: 1980’s

Ion chromatography was added to the Metrohm portfolio in 1987, broadening our span of techniques, which at the time only included titration, meters, voltammetry, and the Rancimat. IC, already a couple of years on the market, was seen on one hand as a very interesting method, but on the other hand also as a very complex and expensive technology.

The increasing viability of IC for previously typical titration applications guided Metrohm to focus on this method.

The Metrohm 636 Titroprocessor.

Development of the conductivity detector

Conductivity is the most common detection technique used with ion chromatography. Conductivity is the inherent sum parameter of all ions in aqueous solution. As ion chromatography is performed using aqueous solutions such as eluents (i.e. the mobile phase) and samples, conductivity is the essential detection mode.

You can see how this is measured in the video below. Other detection techniques can be used as well, but typically are applicable only in special cases.

The modernized, compact, and intelligent Metrohm IC Conductivity Detector.

In the early 1980s, the method of IC began to compete for market share with titration. Based on positive experiences with the amperometric detector (641 VA Detector, introduced in 1980, and originally sold as an HPLC detector) and Metrohm’s competence in conductivity measurement, this led to the idea to develop a conductivity detector in a similar manner. A prerequisite for the project was the availability of separation columns (stationary phase) which allowed analysts to reach detection limits of 1 mg/L (or lower) of the standard anions.

The Metrohm 641 VA Detector.

In 1984, a test was run on an initial setup consisting of a single-piston HPLC pump, a 6-port injector, commercially available IC separation columns, a conductivity detector, and a chart recorder (586 Labograph). This test proved that the 1 mg/L limit could be reached, and thus the project of developing an official Metrohm conductivity detector began.

At that time, chemical suppression introduced by Small, Stevens, and Baumann [1] was patented and not available. However, non-suppressed conductivity detection described by Gjerde, Schmuckler, and Fritz [2] was seen as a viable alternative. When measurement of low concentrations of ions in solution was necessary, the very small chromatographic peaks plus the high conductivity background from the mobile phase (eluent) created a challenge, and special requirements for the conductivity detector had to be taken into account. The most critical of these was the temperature coefficient of the conductivity, which is typically around 2%/°C. This requires maintaining an extremely stable temperature during the measurement.

During the initial development phase it was found that, aside from bulk measurement, platinum was not the best material for electrodes in a flow-through cell. However, stainless steel worked perfectly. The measuring cell still needed to be insulated, however, insulation alone was not sufficient. Active thermostating was required to achieve a temperature stability of better than 0.01 °C. That stability was measured with a thermocouple, and recorded on the Labograph. Later on, with more sophisticated tools the stability was determined to be better than 0.001 °C.

Even after all of this hard work, the initial system baseline stability was still not good enough. As it turned out, several components of the IC system needed to be thermally stabilized. Additionally, the different brand of HPLC pump was not optimal for the development of the Metrohm ion chromatograph.

The Metrohm 690 Ion Chromatograph.

The first decision was to put the conductivity detector project to the side, and start building an ion chromatograph. Thus, the first Metrohm IC (the 690 Ion Chromatograph) was developed. The 690 IC consisted of: a foam polymer housing for perfect thermal insulation, the electronic and detector block, as well as a pulse dampener, a sample injector, and separation column. All capillary connections consisted of HPLC capillaries at the time (made from stainless steel). The inadequate HPLC pump was replaced and upgraded with a Metrohm IC Pump, and the Labograph was almost immediately followed by an integrator, which completed the IC system.

Despite the general consensus in the 1980s that ion chromatography was only robust while using metal-free instruments, Metrohm was able to run anion, cation, and ion-exclusion chromatography on stainless steel-based systems. Even determinations of heavy metals were performed without issues.

Conductivity detection with «electronic suppression»

A drawback of non-suppressed IC is the relatively high inherent baseline noise, due to high conductivity levels from the mobile phase. Parameters which add to this baseline noise include temperature induced fluctuations, pump noise, and electronic noise.

The temperature influence on baseline noise was minimized thanks to the near perfect thermal stabilization of the detector. The quality of the high pressure pump is important to stabilize the baseline, however, under standard running conditions it does not add much to the baseline noise. Finally, after optimizing these points, it was clear that the electronic noise was the most important parameter on which to focus. Each electronic component influences temperature fluctuations and also adds some amount of noise.

Internal view of the Metrohm 690 IC. The conductivity detector is highlighted.

The thermostated detector block consisted of an aluminum block for thermostating, a built-in measuring cell, and an electronic preamplifier. This preamplifier guaranteed that the measured analog conductivity signal was insensitive to external fields when guided to the main electronics.

Auto Zero function for background compensation purposes during measurement.

The Auto Zero function measured the actual conductivity at initialization of the function and was subtracted from the signal throughout the chromatogram. This can be called background compensation. The «electronic suppression» designation is given due to an electronic setup which additionally reduced the electronic noise. The idea behind this is as simple as it was effective. The electronics were set to measure the actual conductivity signal as well as the measured background conductivity through two parallel paths with identical electronic components. Subtraction of the two signals was done just prior to the output to the external A/D converter. Under an assumption that the same components should add the same noise and exhibit similar thermal behavior, both signals are influenced in the same manner. Therefore, the noise level was minimized even further.

Additionally, the apparent noise level was improved using the optimal output window (called «Full-scale») in units of [µS/cm]. The Metrohm Application Note AN-C-032 describes this effect. At that time, this noise level of approximately 2 nS/cm was similar to or better than analyses performed with chemical suppression.

Separation column developments

At market launch in late 1987, Metrohm offered a total of six IC separation columns: two suitable for anions, one for monovalent cations, one for divalent cations, and one for organic acids (ion-exclusion). At that time, the group of Prof. Dr. Schomburg (Institut für Kohlenforschung, Mühlheim/Ruhr, DE) studied the preparation of HPLC phases by coating polymer materials on to e.g. silica. One of the phases used was poly(butadiene/maleic acid) on a silica material, which was found to be able to separate mono- and divalent cations in a single isocratic run. Metrohm acquired the technology and started column production in Herisau, Switzerland.

The so-called «Schomburg column» or later «Super-Sep Cation column» was the very first column on the market allowing the simultaneous separation of alkali and alkaline earth metal cations. Even the current Metrosep C 4 and Metrosep C 6 columns’ roots date back to the Schomburg column.

Data handling capabilities

In the first months on the market, only the Labograph (a chart recorder) was available for the new IC. This was of course not really acceptable. Nevertheless, results achieved by cutting out and physically weighing the peaks were quite correct. The first integrator (Shimadzu C-R5A) was a tabletop integrator with LCD display (2 lines), storage capabilities (2 chromatograms in the instrument, and 5 chromatograms per external card), and a thermo-printer for documentation.

Top: Metrohm 690 Ion Chromatograph with Labograph on the left, and separation columns in the foreground.
Bottom: Metrohm 690 Ion Chromatograph with the Shimadzu C-R5A tabletop integrator on the left.

In 1991, the first PC-based data acquisition and handling software (714 IC-Metrodata) was developed, consisting of a data acquisition box and the DOS-based integration software. Five years later in 1996, the software of the 714 IC-Metrodata was updated to a Windows version. Then in 2000, the new IC Net software was released together with the 762 IC Interface and 771 IC Compact interface for both data acquisition and remote control capabilities.

The 690 IC featuring the 714 IC-Metrodata, ushering scientists into a new era of peak integration possibilities.

What’s next?

Stay tuned for the next installment in this series, covering the 1990s and early 2000s. During this time, Metrohm developed modular IC, the Metrohm Suppressor Module (MSM), as well as some outstanding separation columns. Subscribe to the blog below so you don’t miss out!

Download our free Monograph for more information

Practical Ion Chromatography – An Introduction

References

[1] Small, H.; Stevens, T.S.; W.C. Baumann. Novel ion exchange chromatographic method using conductimetric detection. Anal. Chem. 1975, 47 (11), 1801–1809. https://doi.org/10.1021/ac60361a017

[2]  Gjerde, D. T.; Fritz, J. S.; Schmuckler, G. Anion Chromatography with Low-Conductivity Eluents. J. Chromatogr. A 1979, 186, 509–519. https://doi.org/10.1016/S0021-9673(00)95271-3

Post written by Dr. Markus Läubli, Manager Marketing Support IC 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.