Titration

So you need to measure the amount of sodium chloride in your food products. While we have written about this topic previously in other posts and addressed some of the approaches used to test for % sodium chloride (including the use of hand-held salt meters) we have found that it is a more common practice to use an automatic titrator to accomplish this task.  In fact we think it is the preferred instrument and method of choice.  To be sure there are pros and cons to using different methods but we still find that titration is accepted as the primary method for getting the most accurate results.

How it's used

Although salt meters using the conductive method are faster (3 seconds vs. 2 to 3 mintues) and can be employed quickly in a production line process, titrators can also be implemented in the same testing environment with modest effort.  Additionally and regardless of how the tests were performed on the production line, titrators are generally put to work in the Quality Control/Quality Assurance Lab as a final check against periodic production line testing.

Supporting the use of titration as an accepted method includes some well known documented techniques including Mohr's and Volhard's methods making titration a recognized and trusted approach.

What's next...

Once you have made the decsion to use titration as the testing method it's just a matter of knowing:

• What items you need

• How to prep your sample

• How to setup the titrator

Luckily we have already thought about this and put together a list of 8 items your going to need.  We also created an application-note providing step-by-step instructions for you to follow to conduct a titration.

Many companies produce the foods we eat.  Do you ever wonder why or how they test for salt during the production process?

Salt which is made up of 40% sodium and 60% Chloride is an important ingredient found in food.  While salt can make food taste better, control color, and maintain food texture, it is also considered a health-risk factor (mostly due to the sodium).  Measuring and controlling the levels of salt between the extremes is a constant battle.  Producers of processed foods generally have the biggest need for identifying and controlling salt levels to address not only the taste, color, and texture of foods but also to address some of the healthier eating lifestyles more and more consumers are demanding.

For these reasons it is paramount that salt is measured accurately.  So how do we do that?

Food comes in a variety of forms.  Solid, Liquids, pastes, creams, pieces, chunks, wafers, crackers, gooey, sauces, liquids with chunks in them...let's see what else..Anyway, you get the idea.  There are a lot of ways food can be produced and consumed!

So what device or devices can we use to measure the salt found in these numerous forms of processed foods?

Well, there are a number of "salt meters" out there that can measure salt.  However, not all salt meters can measure the particular salt you are looking for in the same way.  In fact some "salt meters" can only measure salt under certain conditions and or in certain substances like water or sea water.  For this reason it is important to first consider what your going to be testing.  For example, If your food sample includes "food stuff particles" that you can grind into a paste form, then you can probably use a salt meter that utilizes the conductivity method.  On the other hand if you have a brine that you immerse food into and your only concerned with the liquid then perhaps a different salt meter will work.  

The point is this.  The form of the food at the instant you are going to perform the test is key.  Many types of foods can be formed into pastes and diluted with water.  If the food you need to test is like this then a simple salt meter utilizing the conductivity method may be able to perform the test to your satisfaction.  I say may because % salt levels and other accuracy factors may require that you use an entirely different method of titration known as silver nitrate titration instead.

Salt Meter vs. Titration?

A brief explanation and description of the two measurement approaches:

The Mohr method, also known as a silver nitrate titration method, utilizes the characteristics of silver nitrate that reacts with chloride ions to measure the salinity %. 

Conversley, some of the more popular salt meters emloy the electric conductivity method.  Both methods measure the salinity but operate on different measurement principles.  However, by creating a conversion table between the two testing methods, correlation between the set of results can be seen.

Aside from the measurement capabilities of each approach there are pros and cons to each.

While each method has benefits we have recently found through some informal surveying that some food processors are choosing to use both methods.  These companies are finding that it is easier to use the hand held devices and perform quick spot checks on the production line.  If any problems are identified on the production line then further verification and testing can be performed using the titration approach.  Some think using this collaborative approach is ideal.

ALSO READ OUR MOST RECENT UPDATES TO THIS BLOG POST : Salt related posts

Most operators who measure moisture using a Volumetric Karl Fischer Titrator tend to have difficulty in 3 areas.   Unlike Coulometric Karl Fischer Titrators where the equipment setup and reagents are fairly straight forward, Volumetric Karl Fischer Titrators differ greatly.  Understanding how a Volumetric Karl Fischer Titrator differs and how the equipment functions is not only paramount in terms of knowing how to operate the instrument it is critical if you want to obtain accurate and repeatable results.

8 out of 10 questions we receive usually fall into one of these 3 problem areas:

1. What REAGENTS should I use for testing my samples?  Titrants, Composites, Solvents?

2. "TITER VALUE" ..Who, What, Where, Why and How?

3. "SAMPLE SIZE" ..How much do I need or should I use? 

Although these 3 areas at first may seem problematic and unrelated they are not.  In this 9-minute presentation we will explain why the burette size matters, how to calculate a correct sample size and explain how the volumetric titrator reagent strengths work.  Tying all three areas together will hopefully not only clear up some of the mysteries surrounding Volumetric Karl Fischer Titration but also empower operators with choices for conducting tests under varied conditions.  And, oh yes, obtain accurate and repeatable results every time.    Important note:1 ppm = 0.001 mg/g; 1 mg/g = 1000 ppm.

In this presentation we discuss the basic Karl Fischer Water Standards and talk about some of their uses for both Coulometric and Volumetric Karl Fischer Titration.  We also describe some of the related problems that can be identified and overcome by using Karl Fischer Water Standards.

• Karl Fischer Water Standards
• Why we use them
• Coulometric Karl Fischer
• Volumetric Karl Fischer 

Simply put, drift is background moisture that the Karl Fisher titrator is detecting.  What is background moisture?  Well, it is moisture that the Karl Fisher titrator (specifically the detector electrode) is detecting inside the vessel -that’s not coming from your sample.  Drift or "background moisture" can be the result of having the titration vessel sitting idle for some time where moisture has slowly infiltrated and accumulated inside the vessel, or it may be the result of a leak that is allowing a small amount of moisture to enter the vessel continually.  Although we might like to think that the Karl Fisher titrator vessel is air-tight/moisture-tight, it is not.  Depending on how well the vessel is sealed there may be a little or there may be a lot of background moisture interference.  All Karl Fisher titrators deal with the drift issue.  Unfortunately drift cannot be completely eliminated but the good news is that it can be reduced, measured, isolated, and discarded from your test results.

Before a single test is run on a Karl Fisher titrator it must go into a “ready” mode.   But before the titrator can go into a “ready” mode it most likely will go through a “pre-titration” mode.  During the “pre-titration” mode excess drift (moisture) is detected and removed by the reagent inside the vessel.  A “ready” mode ideally will occur when the drift being measured is low and steady/stable – usually below .1 micro grams per second.  Once the drift becomes low and stable the Karl Fisher Titrator records the drift level and goes into a “ready” mode and will allow the operator to introduce a sample into the vessel.  Upon completion of the test the Karl Fisher titrator adds up all of the moisture detected over the duration of the test and subtracts out the known drift level that was also measured during the test.  This process of knowing what the drift was before the test allows the Karl Fisher Titrator to then determine and backout the drift -leaving only the moisture detected from the sample as your result.

There are multiple methods of moisture determination, including loss on drying, Karl Fischer titration, piezoelectric sorption, spectroscopy, and chilled mirrors among others. However, it is advantageous to use Karl Fischer (KF) titration in moisture analysis for the following reasons:

1. It is highly accurate and precise (Part Per Million Accuracy).
2. KF is specific to water determination. This specification is different from the other popular moisture analysis method, loss on drying (LOD), because LOD can detect the loss of any volatile substance. However, this specification is advantageous because it allows KF titration to work independent from volatile substances present in the sample
3. The process does not require large samples, which is typically truer with Loss on Drying where more sample is required to achieve higher accuracy and repeatability - which introduces another entirely different problem.
4. It does not require much time to perform an analysis since the samples are easy to prepare and the analysis itself is short in duration.
5. The method has a nearly unlimited measurement range (from 1ppm to 100%).
6. Karl Fischer titration can determine the moisture content of a sample in any state, whether it is a solid, liquid, or gas.

We hope the above advantages show some of the benefits that Karl Fischer titrators can provide.  Even today with technological advancements Karl Fisher Titration remains very popular not only because of the advantages we mention, but also because it is widely accepted as a standard for moisture detection and measurement.  

This is a popular question for most operators using a coulometric Karl Fischer titrator.  So let's get started.  There are two things to consider.  First, you have the chemical limitations of the reagents themselves.  Second, you have the user/operator variable. Sometimes changing the reagent has more to do with the condition of the reagent sitting in the vessel.  How full is the vessel after running numerous test? How long has the reagent been sitting in the vessel? How messy is the reagent and sample residue inside the vessel? Sometimes the user may simply want to replace the reagents because they look dirty/messy or their vessel is too full from adding samples during previous tests.

Setting aside those factors just mentioned, if we look at the reagents themselves and their capacity to measure moisture, we can come up with a general guideline as follows:

Note:  This example describes a Coulometric Karl Fischer Titrator with dual reagent setup (using Anolyte and Catholyte)

1.  In general and with regard to reagent brand, 100mL of Anolyte (AKA Anode- the reagent used in the vessel) reagent analyzes up to 1gram (1 million micro grams) of water.  20mL of Catholyte (AKA Cathode- the reagent used in the generator electrode/inner buret) reagent analyzes up to 1gram (1 million micro grams) of water.  The relationship according to the amount of water each reagent can analyze has a relationship of 100mL Anolyte to 20mL Catholyte – a 20% relationship of catholyte to anolyte.

2.  Anolyte is commonly purchased in 500ml bottles, Catholyte is commonly purchased in10x5mL ampules.

3.  A typical coulometric Karl Fischer titrator Vessel is charged with 75mL of anolyte and 1ea 5mL catholyte ampule.  Based on the 20% relationship it says that 3x5mL catholyte ampules would be used with each 75mL vessel charge of Anolyte.

4.  A 500mL bottle of Anolyte can charge the Coulometric Karl Fischer titrator vessel 6.6 times (round to 6 times to account for spillage).  3x5mL Catholyte ampules per charge of the vessel times 6 charges of the vessel = 18x5mL catholyte ampules.

Typically users do not expire the entire useful life of the reagents moisture measuring capability because of some of the factors I mentioned initially.  Another factor that I have to mention is that ambient moisture will require the coulometric Karl Fischer Titrator to maintain a dry vessel.  This process of keeping or getting the vessel in a ready to go mode can use some of the reagents useful life.  e.g. it’s not counting the moisture in your samples but that of the outside ambient moisture – for the most part this should be a small amount, but something to keep in mind and know about.

So, with all of this information, the question you may have is how long will my reagents last?  Well, that depends.  But, if you want to continue using the math we have already discussed, then, 1 charge of the vessel (75mL of anolyte with 3x5mL catholyte ampules) can measure 750,000 micro grams of water.

And, for those of you who think in Parts Per Million (PPM) you can translate into the  following:

PPM = micro grams of H2O detected / Your Sample Size (in grams)

A simple method is to run a water standard through the Karl Fischer Titrator like a normal direct injection test. Depending on the water standard you use, the result should equal a pre-determined level of moisture plus or minus a margin for error. These water standards are certified by the manufacturer (a certificate is included) to equal a precise level of moisture.

We use Hydranal water standards. There are two kinds we typically use for coulometric Karl Fischer Titrators.

1) 0.1 normal

2) 1.0 normal.

The 0.1 normal administered at about 1mL should result in 100ppm (Parts Per Million) of moisture when measured. The acceptable result for this standard for the Karl Fischer titrator is +/- 10%. So your Karl Fischer Titrator should produce a reading between 90ppm and 110ppm to be in the acceptable range. If it is, you know your Karl Fischer Titrator is performing correctly.

For the 1.0 normal everything is the same except the standard should result in 1,000ppm and your acceptable range is smaller at +/-3%. So your Karl Fischer Titrator should produce a reading between 970ppm and 1,030ppm.

We get this question a lot.  "How do you go about testing for moisture if the sample is in liquid form?..What about solid form?"

Well basically, moisture testing using the karl fischer method is a standard in the industry that measures down to the Parts per million (PPM) level.  The theoretical accuracy is down to 1 part per million level.  I say theoretical because usually any variance is due to atmospheric conditions and operator repeatability.  Specifically, and for this example, “coulometric” Karl Ficsher is best when you are using a small sample and expect and are trying to measure less than 1% (1%moisture =10,000PPM) of water (moisture/humidity) in your sample.  [Note: there is a volumetric Karl Fischer method vs. coulometric Karl Fisher method but for this discussion I am speaking from the coulometric Karl Fischer standpoint]

With this in mind,

A. If you are testing a liquid sample you only have to use the karl fischer titrator and directly inject the liquid sample with a syringe (usually around 1mL) into the vessel.

B. If you are testing a solid sample (that cannot be “broken down sufficiently with solvents like Xylene for example) you will use both the karl Fischer AND an evaporator oven.  The evaporator oven heats up the sample (usually the sample size is less than 1gram…we typically might use 1/10th of a gram..but then again we might use 3 grams -it really depends on how much moisture you expect to find). The evaporator is connected with a nitrogen gas source that is used to deliver the moisture via a heater tube on the evaporator into the titration vessel.

To see an actual demonstration of the Karl Fischer Titrator and the evaporator oven during an actual test please view the video below and watch the short 2 to 3 minute video.

To be sure there are many more things I could mention but this is a high level summary of the two approaches.

Hope this helps.

Most people know about Karl Fisher as a method for determining moisture content.  After that there seems to be confusion when the words “Coulometric” and “Volumetric” are mentioned.  It goes something like this:

Novice: “Hi, I need to test for moisture and I need a Karl Fisher Titrator.  Can you tell me how much it costs?”

Expert: “O.K., do you need a Coulometric or Volumetric Karl Fisher Titrator?”

Novice: “uh what?”

Expert: “Well you see there are two kinds of Karl Fisher Titrators.  Depending on your sample size and the amount of moisture you expect to find -it may not only be advantageous but necessary to use a Coulometric vs. a Volumetric..and or vice versa.”

Novice: “I see.”  So how do I know what kind of Karl Fisher I need?

Expert: “Generally speaking, if you are working with small samples (0 to a few grams) AND the expected moisture is low (around 1% or less) you probably want to use a Coulometric Karl Fisher.  On the other hand, if your sample size is larger AND you expect to find a lot of moisture in the 2%+ range then you probably should consider a Volumetric Karl Fisher Titrator.”

Novice: “Do they both report moisture results the same way? You know, accuracy, resolution, repeatability?”

Expert: “Yes they do.  Both Volumetric and Coulometric Karl Fisher Titrators report moisture results in either Parts Per Million (PPM) or %.

Novice: “So then what makes them different?”

Expert: “Coulomeric Karl Fisher Titrators use a reagent called an Anolyte.  This Anolyte is 100% self contained and requires only an electrical current to cause a reaction where the Anolyte releases iodine.  It is this “iodine” that “neutralizes” the moisture inside the vessel.  A typical Coulometric Karl Fisher Titration Vessel can hold about 75mL of Anolyte.  The amount of Anolyte inside the vessel can only “release” so much iodine and therefore can only neutralize and measure a finite amount of moisture.  In this case using the 75mL as the example the reagent can only neutralize and measure 750,000 micro grams of moisture (water/H2O).  Now compare this to a Volumetric Karl Fisher and the game changes.  The Volumetric Karl Fisher method does not use a single self-contained Anolyte reagent that reacts to an electrical current.  Instead, the Volumetric titration is performed by “dripping” in IODINE at an precise amount into the titration vessel where there is a SOLVENT solution present in the vessel.

Novice: “How does the Volumetric Titrator “Drip in” IODINE into the vessel where the SOLVENT is located?”

Expert:”Good question.  It uses a buret that has a piston that moves up and down pulling The IODINE solution from a source bottle into and filling the buret and then pushing it out through tubing and into the vessel. ”

Novice: “Is there another name for this “IODINE solution”?  How do I get it?

Expert: “Another good question.  “This IODINE solution” is what makes the volumetric method so versatile when measuring larger amounts of moisture via Karl Fisher Titration.  The Iodine solution can come in two forms and with differing strengths.”

Novice:” Two forms?  Different strengths? Huh?

Expert: ” Yes, the two forms are referred to as “One-Component” and “Two-Component”.”

Expert: “The “One-Component” Iodine solution is referred to as Composite or Titer.  The Composite can come in 3 strengths; 1 (1mL of composition can consume 1mg or 1,000micro grams of water), 2 (1mL of composition can consume 2mg or 2,000micro grams of water) and 5 (1mL of composition can consume 5mg or 5,000micro grams of water).  We refer to these compositions as Composition-1 (aka Comp1), Composition-2 (aka Comp2), and Composition-5 (aka Comp5).

Novice: Differing Strengths.  Hmmm.  So for every 1mL you “drip in” it will consume, neutralize and measure the corresponding amount of moisture depending on the Composition strength.

Expert: “That’s right.  So for example if you use a Volumetric Karl Fisher Titrator with a 20mL buret you could conceivably introduce in one push of the piston that’s inside the buret, 20mLs of Composition.  If your using Comp5 you would be able to consume, neutralize and measure 20mL x 5,000 micro grams =100,000 micro grams of water.   Most Composition are sold in 500mL bottles.  So each bottle has the capacity to consume, neutralize and measure 2,500,000 micro grams of water.

Novice: “That’s a lot of water measuring capability!”

Expert: “Yes it is.”

This is a simple example and there are other factors to be considered for sure.  We thought this brief example would help those just getting started and trying to understand the basic comparison between Coulometic Karl Fisher and Volumetric Karl Fisher.