New IGC Application Spaces for High Temperature Measurements

Foreign.

Hello everyone and thank you for joining us for today's service Measurement Systems webinar being hosted as part of our one week online Festival of Inverse Gas Chromatography, ITC Sea Week. Thank you everyone for joining us today and I hope you have enjoyed the other educational session and research resources we've been releasing throughout IGCSEA week. Today we'll be exploring the topic New IGC Application Spaces for High Temperature Measurement and we're very lucky to have with us Dr. Annette Condor who is Surface Measurement Systems Lead Specialist on Inverse Gas Chromatography. As with all of our educational events, you will have an opportunity to have any questions asked and answered by Annette Condor in the live Q and A session at the end of that presentation. To take part in this, there are two very simple ways you can either submit your questions in writing in the questions panel and then I will ask Annette the question when we come to the Q and A session, or if you have a bit of an extended question or a two part, three part question you'd like to ask yourself, please just select the correct icon to raise your hand when they come to the Q and A and I will let you know when you can unmute your microphone and engage Dr. Condor directly with your question. So before I pass over, I just thought I'd give you all a quick background for the presenter today. So Annette Condor is the IGCSEA Product Manager and Product Specialist of Surface measurement systems. Since 2005, Anne has been working on gas chromatographic techniques and she studied in chemical she studied chemical engineering at the University of Ammonia, Hungary where she receives her Master's in Chemical Engineering accredited by the British Institution of Chemical Engineers and she received a PhD in chemistry and environmental science. Sorry, she received a PhD in chemistry and Environmental Science. She published several research works in peer reviewed journals, collaborating with research groups from around the world and her research interests lie in areas of surface characterization of different solid materials and improvements to the inverse gas chromatographic technique. We're very lucky to have Annette here today with us as she really is one of the world's leading authorities on inverse gas chromatography, both the technique and its instrumentations. So without further ado, I will hand over to Dr. Condor to begin our presentation.

Hi John and hi everyone. Good morning, good afternoon, whichever is the time, at your location. Thank you John for that nice introduction and today I will show you some applications, especially at high temperature range and the overview of my presentation is on the slides. First I will show you a study on Zeolite an adsorption study and then another study where we investigated temperature effect on surface energy in case of zeolite and graphite. And then I will show you another study on diffusion coefficient. And at the end of my presentation I will show you the high temperature SCA system and a couple details of this device. The first study is an adsorption study on zeolite sample. And in this study we determined the Bt aromatic hydrocarbons adsorption isotherms at different temperature on zeolite sample. The Btex compounds are the benzene, ethylbenzane, tolane and silane adsorptive molecules. And the adsorbent was in this study was degusa Da YF20 hydrophobe zeolite. It was a de illuminated zeolite. The specific surface area of this zeolite is 657 meters square per gram. What we determined with the nitrogen volumetric system and for the IGC measurements we crashed this zeolite and then fractionated with a set of standard sieves and then selected a specific fraction which was from 200 to 500 microns. And we packed from this fraction into a glass column 274.5 precisely. And we used a 4 milli ID column. And first we determined the surface energy at 150 Celsius degree. And on this side you can see the surface energy profile and the surface energy distribution. You can see that the dispersive component of this zeolite is very uniform energetically. There's not too many difference in the dispersive energy size. Although we measured relatively heterogeneous specific surface energy which can be related to the inhomogeneous surface modification of this cellulite because it was partially deluminated and probably this caused this significant decreases in the specific surface energy. And we measured various specific surface energy sites on this surface. After we characterized the surface, we measured those aromatic hydrocarbons adsorption isotherms at different temperatures. On this slide you can see an example. It's a orthostorption isotherms at different temperature. So from 170 Celsius up to 250 Celsius degree. And from the adsorptionizer terms we determine the Henry constants for all the different aromatic hydrocarbons. And we plotted the Henry constant against the temperature. But you can see on the right graph. And also we compared the different Henry constant of the aromatic hydrocarbons with other zeolites with other adsorbents. And on this graph you can see the comparison in case of Benzene So you can see the in what we measured Henry constants for benzene on this zeolite is the black dots. Filled dots and there's a straight line also represent the trend of these dots. And you can see that the Henry constants of benzene on this cell line is higher compared with other adsorbent. And based on the results we can say that this zeolulide has an excellent absorption capacity for benzene. It's much better than the four A zeolite or sepiolite for example. This study was published in the journal Chromatography. So if you are interested in this study, we are happy to share this paper with you. Just let us know at the end of the presentation. On the next slide I will show you some results on the temperature effect measurements. So we determined the temperature effect on surface energy in case of zeolite 13x and graphite. A natural graphite sample on the first graph shows the zellide 13x results at 300, 350 and 400 Celsius degree. At 350 the dispersive surface energy profile consists of quite uniform. Although at 400 Celsius it shows some degree of heterogeneity. And also what you can see that it increasing with the temperature. So the surface energy level of this zolite is increasing with the temperature. So the temperature has an effect on the surface energetics of this zeolite 13x which can affect the adsorption behavior and the adsorption capacity of some molecules. On this slide you can see the natural graphite surface energetics at different temperatures 100 and 120 Celsius. And this sample seems doesn't affected by the temperature much, so the surface energy doesn't change with the temperature. And we used a natural graphite anode powder which was supplied by Sigma Aldrich. And there's also different types of graphite. So not just natural graphite but there's synthetic graphite or composite graphite. All these graphite produced differently and what is also important fact that the raw material is different. So in case of the natural graphite the raw material is a graphite or in case of the synthetic graphite the raw material is a petroleum coke or coal. It's known that raw material and the processing way are of a solid has an effect on the surface properties of the final product. And unfortunately I can't show you data on the synthetic graphite but I can tell that it's a completely different surface energy than the natural graphite. So we saw that the natural graphite has a quite uniform surface energy profile and it doesn't change with the temperature. Synthetic graphite has a different energy levels due to the production process, the raw material and some other factors as well. On the next couple slides I will show you some diffusion coefficient data by a PONS injection using IGCSE system. So we implemented into the analyzer. So for the diffusion coefficients calculation and for the application panel, we use this publication basis which because this publication describes very well the diffusion coefficients calculation by inverse gas chromatography. And the diffusion coefficients calculation is really based on the one dental equation. And it's a little bit simplified because you can see that the red line become almost zero. So where you can work with IGC at the linear velocity range, this component, the longitudinal diffusion component become very, very small and zero. So this component is excluded from the 1dmter equation. But the other parameters are in there. The diffusion measurement based on the different flow rate and IGC is an appropriate tool to measure transport diffusion. Since the experiments are performed in the flowing system and under concentration gradients and for example in FCC process diffusion is supported by flow and concentration gradient. Same kind of diffusion. What we can measure with inverse gas chromatography in our software, the IGCSEanalyzer software now has its application panel where you can directly and automatically calculate the diffusion coefficients. And the panel looks like this. And I just show you now a data when we use this application. So the two samples, they were two microporous catalysts. Then we measured cyclohexane and Tulane and diffusion coefficients at two different temperatures, 250 and 300 Celsius. The carrier flow rate was varied from f5 to 32. So we injected cycloxin and tolling several times. And we use different flow rates in each case. Then we determined the diffusion coefficients and we performed three runs. You can see the relative standard deviation of the experiments are quite good. And here's the graphical demonstration of the results. So you can see the two different samples. Blue is the sample one and orange is the sample two. And the two probe cyclohexane and Tulane at two different temperatures. You can see that the blue blocks so that on the sample one, the diffusion coefficients of the two different probes at the two different temperature doesn't change much with the temperature. But on the sample too, the temperature has a significant effect on the diffusion coefficients in case of both probes. So in case of cyclohosine and Tulane as well. So sample 2 has that the surface of the sample 2 is not that stable. The different temperatures. So that's why the diffusion coefficients also changing the temperature. We presented this result and other study in this case study what you received on Monday with the package or you can still download that application note package. This also was in that support documents and if you are interested diffusion analysis we recommend this case study and we can share with you the method setup and all the details. So as I promised, the last couple slides contains the higher temperature SCA details, some parameters, same hardware with a little modification. So our high temperature SVA has a temperature range from 30 to 500 Celsius. The stability of the set point all over the temperature range is less than 0.5. And it has mass flow controllers with flow rates from zero to hundred milliliters per minute. And we added a safety feature because 500 Celsius is quite high. So we added the safety features to the instruments. There's an integrated warning system to prevent exposure to heat elements of the system. And just a little bit detailed picture about the oven. It's a sematograph. So we collaborated with the German company to design this high temperature oven. And it has a direct column heating which is really efficient. And it's important when you measure thermodynamic parameters because the temperature has to be very stable along the column. And also during the whole experiment the temperature has to be stable. So this oven has the excellent stability. It's less than 0.5 Celsius in the whole temperature range from 30 to 500. We can provide the system with different inner diameter columns. The column material can be quartz, stalinized glass or stainless steel. And again we have also a cutoff switch for safety reasons. Here's the specs. The summary Temperature ranges from 30 to 500. The temperature control accuracy is 0.1 Celsius and the oven temperature control accuracy range. So at low temperature around 30 Celsius, it's just point Celsius the stability. But at the highest temperatures we can get very very good stability is 0.5 Celsius. So along the whole range is less than 0.5. The system still has an automated injection system. The flow range is quite wide and it's stable. Also we tested so from 0 to 100 milliliter per minute you can set a reference flow and it's automatically controlled and generated during the experiment which is important for the diffusion coefficients measurements. The temperature stability also important. But temperature stability is more important for surface energy and adsorption measurements versus thermodynamic parameters measured. So that's our high temperature SCA and basically where high temperature STA can be used, you can use to characterize different solid surfaces. You can measure the temperature effect and especially the temperature effect on surface properties of adsorbents which has a strong adsorption properties. It can be used to determine processing performance diffusion coefficients measurements and also you can measure homogeneity studies on cutlass carbon graphite samples. So that's all I wanted to share with you today. And if you are really interested in high temperature assay or if you want to measure properties at high temperature, please contact with us. We are happy to assist you and also if you have any questions, I'm happy to answer them. Thank you for your attention and the floor is yours.

Thank you Annette. That was a great presentation. Yes, we have a few questions in already. So just a quick reminder before we dive into those. If you would like to ask a question based on the presentation you just saw or on anything IGC related, which Annette can answer, please submit these in writing in the questions panel or raise your hand and we can come around to you to let you know when you can unmute your microphone and ask your question in person. So the first question we have is which range in isotherms was used for the calculation of Henry's constant in the CLI study?

Yes. So basically we used all the measured isotherms. So at each temperature we measured the adsorption isotherm. So from 170, I think the smallest one was 150Celsius and we went up to 250Celsius. And at each temperature we determine the Henley constant. And on this graph on the right, right side you can see the Henry constant at different temperatures. So you can see it was I think 423 was the smallest temperature. What we used in case of the benzene and the Tulane for the other solvents. For the other aromatic hydrocarbons the smallest temperature was 170 and we went up to 250 Celsius. So the Henry constant. Yeah, yeah, the Henry constant was met. Determined at each temperature for each. Its option is terms.

Thank you. I have a question here. Do you have any examples related to activated carbon showing the surface energy profile?

Yeah, we measured the activated carbons but I can't show you right now because I didn't prepare any data on activated carbon. But yeah, we do have. So we can share with you whoever asked. So just drop us an email and then we can yeah. Show you data on activated carbon.

Yeah, we'll follow up with that question after this session. Just to kind of Address that query in a bit more detail fashion. Another question here. Is it possible to measure the surface area of a zeolite with the IGC technique? And what's the recommended sample amount for the zeolite samples?

Yeah, it's a good question. Unfortunately we can't measure high surface area with IGC technique due to technical limitation due to the pulse injection. Actually the pulse injection has its own limitations. So we can't really inject impulse huge amount of solvents which would saturate a surface of this zeolite which has a quite high surface area like almost 700 meters square per gram. We determine the maximum surface area what we can determine with pulse injection. It's around 120 meters square per gram. That's what we can accurately determine because in that case we have measured data points in the whole BT range higher surface area. It happened that the was determined but in that case just a few data points was in the PT range. So unfortunately with pulse injection you can measure this high surface area although it's possible with frontal injections what we are working on to add to the instrument but it's almost the same like the dbs. So with dbs, with our other procedure product you can measure high surface area because there's a constant concentration of the. The organic vapor or water and it. It helps you to saturate the surface with the probe. So at the moment unfortunately you can't measure and yeah, you, I. I don't have recommendation for the mask but yeah, we are working on energy and if you have DVs you can use that or other technique.

A bit of an interesting question here I think more practical side of IDC and they ask the column being used in the IDC SCA is a tube with different diameters, 2, 3, 4 millimeters etc. Whereas the analytical GC which is they understand as a different purpose is just. But that uses a capillary coiled column and they were wondering in your opinion, if you were to use a capillary coiled column in an itc will it have any effect on the accuracy of the end results as the retention may be greater than a normal column?

Yeah, it's a. Interesting question and yeah, it's a good one as well. So in case of an antico gc the columns, capillary columns are quite long and that column contains a lot of solid relatively large because along the column the different compounds need to be separated and basically there's a lot of surface also in that capillary column for this reason to help the separation of the different compounds. So at the end you will detect them separately in case of IGC measurements. When you investigate your solid surface, when basically which is in the column is your sample of interest, it's not necessary to have that huge surface or that big surface area. And that's why we use a different type of columns. Even though when during my PhD studies we used a U shaped column for IGC measurements, we haven't had to pack fully those columns. So like in case of this daylight we also just used two 274 milligrams. So I don't think that it would be useful or necessary because that would increase the measurement time. And also it's not suitable the capillary column to our IGC. But maybe other home builders IGCs you could. But I don't think that is. It's a practical thing.

Thank you. Another question here and they ask the experiment with high temperature is above the boiling point of some probe molecules like cyclohexane, toluene. Does this cause any issues when it comes to vapor? And.

No, we inject everything in a vapor phase. So like IGC SES has a vapor phase injections like a headspace injection for an intercogc. So we already inject everything in vapor phase. So the injection injector port it doesn't affect or this doesn't affect the injections. So yeah, in this case.

Another kind of a practical question about the high temperature IGC is someone asks if they were using the original IGC SCA with a 150 temperature range, is it possible to upgrade that system to a 500 temperature range without changing the whole system?

We are working on this. To solve this upgrade, I recommend this person to contact with the local sales or our direct sales people. Yeah, we can negotiate this. Yeah, at the moment we don't really offer but because it has mainly the same base. But yeah, it's under discussion. So let's contact with our dialect salespeople and then we can discuss. But actually the instrument has to be shipped back definitely. So. So maybe the cost wise it wouldn't really worse to them because it would be like buying the same instrument. So I don't know. Yeah, yeah, contact with the salespeople and then we can negotiate or we can discuss.

Great. And then last question here. What types of tube are suitable for measurement with this technique? Is it the. I think they're inquiring especially is does the material have an effect? Does it have to be a specific type of material you're using?

So for high temperatures so if the Temperature is above 200, we recommend the quartz column which is stable at high temperature and won't break like the glass. So we recommend the quartz column or the stainless still a tube. We tested this column so there's no any effects, I mean with the probes or anything. So you can use any of these columns. Maybe it's just me, but you were breaking up so I couldn't hear the last question.

No, no, I just muted while I was pulling up the question. Okay, so they've asked, apart from the common organic vapor, is it possible to use some other vapors such as fragrances like pinine or limonene? Is there any limitation about the minimum vapor pressure when doing this?

There's a slight limitation, but I used limonene in igcse and I use or linalool some fragrances because during my PhD I was working with fragrances and flavor compounds and then we purchased the igcsea. So we did a couple experiments using IGCSEA system and then we could really measure pregnancies and fibers. Yeah, yeah, contact with us and we can assist, we can help you because you need a couple of parameters to enter into the database and yeah, we can help you with that, but it's possible. And what is the benefits really with IGC you can inject much, much smaller concentrations with igcsea due to the vapor phase injection than what we could inject with a normal syringe GC system. So IGC system when we use the syringe, because the smallest syringe for automated injections, I think it's a 5 microliter, I think it's for Agilent. But that with vapor phase injection you can inject much more smaller amount, smaller moles than what basically you can inject in a liquid phase with the 5 micron microliters range. So yeah, you can do fragments, flavors, you can do so many nasty stuff.

All right, thank you. We have another question, but I think, I think this is one that I can cover for the audience. The question is asked if there's any other resources that they can consult to learn more about the technique. And I can say yes, there are plenty of techniques. Our website gives a detailed explanation and exploration of this technique and there is also a huge library of application notes available for download on our website in the download section. And furthermore, we have a YouTube page which has both introductory videos describing the technique as well as a range of webinars and workshops going into everything from the basics of the technique and introduction to the technique to involved applications of the technique in different markets and then furthermore to this our members of our team are always more than happy to schedule a call or have a meeting with you to kind of explain the, explain the technique in a bit more detail and go through your kind of thoughts and questions about the, the method. So yeah, so that I hope that answers your question.

Yes, yeah I confirm. Yeah, we are always happy to arrange a meeting, discuss specific questions, applications. So we have a quite big scientific team with a lot of experts. So yeah, just contact with us if you can't find that specific elsewhere on our websites or on our documents.

And another question that's just come in, Annette, they ask is it possible to measure MOF materials with itc and if the preheating temperature will affect the structure or stability of the mof, is it going to change the surface energy as well?

It's a great question and the answer yes and no. So in more detail. So yes, you can measure MAFS. There's a customer who measures MOFs and it's possible they published a couple papers on MOFs and I don't know, maybe they already investigated this temperature, the preconditioning effect, the pre treatment temperature effect. I don't know. Is there any studies out there I haven't done yet so far this kind of study? Yeah, but it's a very interesting application or study which could be done on this instrument. Very, very informative kind of study because MOFs are really, yeah at the moment huge interest on MOFS materials. But yeah, you can measure with IGC of course and we can share the link of that publications which studied MOFS material. So yeah, contact with us and then we can share more information on this.

Well, I think that's all the questions we have for now. We're coming up near the end of our time so I think we're going to leave it there. So once again a huge thank you for being with us today for not only for answering all the questions and giving us a brilliant insight into this new product we're working on, but also just for assistance for being kind of the central force in organizing ITC to kind of promote this technique for the scientific community.

Oh, thank you John, thank you and also thank you for your a huge amount of help on this and thank you for the. Yeah, the audience. Without you, without the community, we couldn't arrange this, we could just touch with each other. Yeah, thank you, thank you for taking time and thank you for your attention again.

So yeah, and for myself, thank you again to our audience and to our speaker and of course, IGCSEA Week is not yet over. We have one final and possibly our most exciting release coming tomorrow. This is our IGC Zork and Science Directory 2019 edition for IGC. Now, if you're ever in need of historical references and studies to inform new research or to build a hypothesis, or for whatever reason, you may need to look back and acquire industry sorted and application sorted studies in the ICC space, we are slowly working our way through the years to give you a cataloged glossary of all studies published related to inverse Gas Chromatography and the ICCSEA and the 2019 edition for the ID seal being released tomorrow. So please keep a lookout in your inbox and you'll be sent a link to download this free of charge. So keep an eye out for that around lunchtime tomorrow. So that brings us to the end of today's session. I'd love to say thank you again to everyone who attended and for supporting both this session, the IGC Week event, and the IGC technique in general. So once again, thank you to Annette and our attendees and wherever you are, have an enjoyable remainder of your day. Thank you.