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Karl Fischer Over Titration and 7 things you should know about it

By Hank Levi on Wed, May 02, 2012 @ 06:30 PM

We have all seen it.  We’re running a test to see how much moisture is in our sample when inexplicably the liquid inside the Karl Fischer vessel starts to turn from a normal light-yellow color to a dark burnt-red looking color.  Sometimes the titrator screen will inform us of the problem with a digital readout stating the dreaded

OVER-TITRATION!” 

kfbeforestart resized 600describe the imagedescribe the imagedescribe the image

 

Sometimes the digital readout says nothing at all.  In either case the operator knows something has gone wrong because the Karl Fischer Titrator is no longer giving moisture results.  A panic to figure out the problem and get testing underway again becomes the immediate priority. 

But where do you start?  

As it turns out “over-titration” is probably one of the top 2 or 3 complaints or issues we hear about from operators.    So what is causing this problem to occur?  How can we determine the source of this problem, fix it, and more importantly how can we avoid it?

 
This is a critical question for operators and managers working in a production or QC environment who are concerned with keeping their Karl Fischer Titrator 100% “in-service”, day-in and day-out.   Having the ability to identify the problem correctly so appropriate measures can be taken quickly is very important.

 
So how do we approach the problem of “over-titration”?   By knowing the facts.  Having a clear understanding of the process can help operators correct the problem faster when time is of the essence.  

Important facts you should know about over-titration:  
  1. Over-titration is a state where there is more iodine present in the vessel than water (general definition).
  2. When over-titration occurs the vessel will become very dark as a result of the abundance of iodine present inside the vessel.
  3. The reagent inside the vessel should normally have a light-yellow color absent a very dark sample such as oil.
  4. The Karl Fischer Titrator always attempts to maintain an equilibrium where only enough iodine is introduced to counter and neutralize the water present inside the vessel.
  5. During a single titration test there should only be enough iodine introduced to counter and neutralize the amount of water present inside the titration vessel during that test – no more, no less.
  6. Any incident that interferes with the final amount of iodine introduced during the titration test can lead to dis-equilibrium and result in more iodine being introduced than necessary.
    Important facts you should know about Karl Fischer Titrator Glassware:  
  1. The Karl Fischer Vessel and Glassware is composed of the following
    1. Vessel (coulometric and volumetric)
    2. Generator Electrode (coulometric only) - The Generator Electrode is a precision electrode designed to deliver an electrical current inside the vessel to the reagent – causing the reagent to produce iodine
    3. Titration nozzle (volumetric only) - The titration nozzle delivers precise amounts of iodine (composite or titrant) via a burette driven mechanism using a piston
    4. Detector Electrode (coulometric and volumetric) - The detector electrode has a sole purpose and probably the most important role in continuously monitoring and determining the conductivity levels within the titration vessel.
  So what are the causes that can lead to over-titration? 

✓ A damaged Detector Electrode

✓ A "Tricked" or "Fooled" Detector Electrode (no joke)

Since coulometric and volumetric Karl Fischer Titrators handle the delivery of iodine differently it’s worth describing the two methods separately.  

A Word About Coulometric Karl Fischer Titration:

In a coulometric system the reagent is a complete system where it is designed to release iodine when the generator electrode delivers an electrical current to it.  So what causes the generator electrode to deliver too much current causing the over production of iodine?  Another way to say it is, “who or what” is telling the generator electrode to continue to generate a current when it’s not needed?  

   
The detector electrode!  So why would the detector electrode do this?   describe the image
Without getting into too much of the electronics the detector electrode is designed to “detect” conductivity in the vessel.  Depending on the amount of conductivity detected the detector electrode will send a message to the titrator telling it to continue producing a current - enough to release the appropriate amount of iodine to counter and neutralize the water present in the vessel.  As long as this process is working during a titration an eventual endpoint will be found and a result will be produced.  


So it’s really a problem of misinformation. If the Karl Fischer Titrator is not getting the right information from the detector electrode then over-titration is possible. 

The problems we see that can effect the proper functioning of the detector electrode include:  
  1. The electrode cable.  If the cable becomes cracked or breaks it can cause a situation where the message to the titrator is to continue producing a current – continually.  In this case the vessel will become very dark and in most cases the titrator will not even know it is in an over-titration state.  The generator electrode will simply continue to produce a current, turning the vessel very dark.  There will be no other warning or notice from the titrator for the operator to see.
  2. Cracked electrode.  Sometimes mishandling or even a stirrer bar bouncing around inside the vessel can cause a tiny crack near the bottom of the detector electrode that cannot be seen with the naked eye.  These cracks can allow small amounts of reagent inside the electrode enough where errors in detection will begin to occur.  What ensues is an unstable drift that jumps around giving the titrator a misreading. The jumping around and unstable drift may be picked up by the titrator and an error stating “OVER TITRATION” may be seen on the screen of the titrator.
  3. Cable connectors.  Sometimes the connectors on the titrator itself can become dirty, wet and corroded.  Also, some electrodes use multi-plug designs that can also become dirty, wet and corroded.   These connectors if not clean and dry can lead to a similar misreading similar to a cracked electrode where the drift begins to jump around and become unstable.  The titrator may also state that there is “OVER TITRATION” when this occurs.

Find more Coulometric Karl Fischer Titrator information 

A "Tricked" or "Fooled" Detector Electrode you say?describe the image

If it’s determined that the problem is not the detector electrode then we need to look at the stirring action inside the vessel.  If the iodine being released is not mixing well because the stirrer is off or set too low, then the detector electrode will not realize there is iodine already released inside the vessel.  This will cause the detector electrode to continue telling the titrator to produce more current via the generator electrode up to the point where the detector electrode senses a reduction in the conductivity level inside the vessel.  Conductivity only reduces as the iodine interacts with the water.  So it is important for the detector electrode to sense the true and most accurate “mix or state” of iodine and water during the titration process.  If it does not know the true state of the mix it will be fooled into telling the titrator to keep going – causing OVER TITRATION.        

A Word About Volumetric Karl Fischer Titration:

   
describe the imageIn a volumetric system the reagent setup is different where a composite or titrant is introduced via a burette piston through a titration nozzle.  The amount of composite or titrant delivered is based upon the commands of the titrator.  The command from the titrator to the burette and piston that push out the “iodine” through the titration nozzle is, yes, given by the detector electrode.  For the purposes of this discussion the difference between the coulometric and volumetric setup is that the delivery of iodine is different.   But the same problem can occur where the iodine does not mix well and therefore trick the detector electrode in to thinking there is not enough iodine present inside the vessel to counter and neutralize the water.  Since both coulometric and volumetric Karl Fischer Titrators use detector electrodes the problems mentioned earlier about the detector electrode will hold true with volumetric titrators also.  

Learn more about Volumetric Karl Fischer Titration 

 

 7 Thoughts (DOs and DON'Ts) on Problem Solving and Prevention:  

1.  Don’t abuse the detector electrode!  Be very careful with the detector electrode and do not handle it unnecessarily.  Small bumps (clanks) here and there can lead to a crack.   Do you really need to remove the detector thinking dragonelectrode from the vessel all the time?
2.  Don’t turn up the titrator’s stirrer speed to high.  This will only cause the stirrer bar to bounce around uncontrollably and possibly hit and damage the detector electrode (crack).
3.  Do inspect all connections and connectors on the detector electrode cable and Karl Fischer Titrator to ensure they are dry and clean.
4.  Do be careful with the detector electrode cable.  Try not to bend it unnecessarily.
5.  Do make sure there is enough stirring action inside the vessel to mix the iodine around effectively.  A small vortex should be visible.  But not too fast to cause the stir bar to bounce around.
6.  Do introduce some moisture - Sometimes when you are in an over-titration situation and the vessel is already very dark you can introduce a little moisture to bring the vessel back to equilibrium.  This sometimes works and immediately the vessel turns from a dark burnt-red color to a light-yellow.
7.  Do have a spare detector electrode on hand.  This little electrode seems to get over looked but plays a huge role inside the Karl Fischer Titrator vessel.

Created on 05/02/12 at 18:10:44

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How to use a titrator to measure % sodium chloride in food products

By Hank Levi on Sun, Dec 18, 2011 @ 03:57 PM

Automatic Titrator

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.

                                 

                                         Created on 12/18/11 at 12:16:27  

 

                                           Created on 12/18/11 at 13:00:41

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How to test for Salt during food production

By Hank Levi on Mon, Oct 31, 2011 @ 12:53 PM

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

Examples by Manufacturing Type

Frozen Vegetable Processor

The salt content of the blanching water is important for maintaining the bright colors of vegetables

A Condiment Manufacturer

Testing Sauces and dressings

A Cheese Maker

Measure the salinity of saltwater that the cheese is soaked in

A Potato Chips Manufacturer

Checking for salt sprinkled on fried potato slices

A fresh Cut Fruit Processor

Use a 2% saline solution with a small amount of ascorbic acid to prevent discoloration of fruits

A Deli Food Supplier

Measure foods with a salt meter vs. by taste

A Canned Food Manufacturing Plant

Measure the brine for canned tuna

A Pickles Manufacturer

Measure the salinity of the brine for salt-packed products

A Cold Cut Meat Manufacturer

Measure salt concentration of ham and deli slices

A Baker

Measure and monitor the salinity of bread dough to around 1%-2%

 

 

 

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?

describe the image               Titrator

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 %. 

Created on 10/31/11 at 10:37:41

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.

Created on 10/31/11 at 10:41:32  

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

 
 Pro's and Con's

 

Salt Meter

Titration

 Measurement Range

Less..maybe

More

 Accuracy

Less

 More

 Ease of Use

More

 Less

 Time to test

Less

 More

 Cost

 Less

 More

 

 

 

 

 

 

 

 

 

 

 

 

 

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.smiley2

 

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

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I'm Having Problems with my Volumetric Karl Fischer Titrator

By Hank Levi on Fri, Jul 29, 2011 @ 11:55 AM

Most operators who measure moisture Volumetric Karl Fischer Titratorusing 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? 

Learn more about Volumetric Karl Fischer Titration

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.

Created on 07/29/11 at 11:54:29

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Karl Fischer Titration and Water Standard Presentation

By Hank Levi on Tue, Jun 28, 2011 @ 10:43 AM

Kf waterstandard presentation resized 600In 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.

Learn more about Karl Fischer Titration

Find more Coulometric Karl Fischer Titrator information

Learn more about Volumetric Karl Fischer Titration

 

Created on 06/28/11 at 10:48:28
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Karl Fisher Titration and drift

By Hank Levi on Fri, Jun 03, 2011 @ 12:36 PM

karl fisher driftSimply 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.

Find more Coulometric Karl Fischer Titrator information

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.

Learn more about Volumetric Karl Fischer Titration

 

 Created on 06/03/11 at 12:38:02

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Here are 6 Advantages Karl Fischer Titration offers when measuring moisture

By Hank Levi on Thu, Jun 02, 2011 @ 11:12 AM

Karl FisherThere 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.  Learn more about Karl Fischer Titration

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Karl Fischer Titrators; How much reagent do I need?

By Hank Levi on Fri, May 20, 2011 @ 02:48 PM

This is a popular question for most operators using a coulometricKarl Fisher Reagents 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.

Learn more about Karl Fischer Titration

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)

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Calibrating Karl Fisher Titrators using water standards

By Hank Levi on Fri, May 20, 2011 @ 02:33 PM

“Calibrating” a Karl Fischer titrator is somewhat of a misnomer.MKC520 Karl Fisher Titrator What most operators are attempting to do is determine whether their Karl Fisher titrator is measuring moisture accurately.

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.

Learn more about the Karl Fischer 710 Series

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.

Find more Coulometric Karl Fischer Titrator information

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.

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Karl Fisher Titration can be used to measure solid and liquid samples

By Hank Levi on Wed, May 11, 2011 @ 01:19 PM

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.

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