Guia Escolha Adsorvente para DT - SUPELCO

Supelco Park 595 North Harrison Road Bellefonte, PA 16823-0048 USA Telephone 800-247-6628 814-359-3441 Fax 800-447-3044 814-359-3044
044 email: supelco@sial.com sigma-aldrich.com/supelco
Technical Report
A Tool for Selecting an Adsorbent for Thermal Desorption Applications
Research conducted by Jamie Brown, R&D, Co-author Bob Shirey, R&D
There are varieties of adsorbents used in the field of thermal desorption. Often choosing the right adsorbent can be difficult. The goal in selecting the proper adsorbent is to choose one that can retain a specific or group of analytes for a specified sample volume. However, just as important the adsorbent must also be able to release the analyte(s) during the desorption process. This report sheds some light on choosing the right adsorbent by demonstrating the relative differences between those most commonly used. Some of the adsorbents investigated in this research were Tenax TA, Carbotraps, Carboxens, Carbosieve, charcoals, and glass beads. The test probe for this research was a gas mix containing forty-three different analytes whose physical properties ranged from 50 to 260 in molecular weight and -30 to 215C in boiling point. The analytes in this mixture are a subset of the EPA Hazardous Pollutant list. EPA method TO-17 is the typical method you use to sample these analytes. We introduced this gas mixture to each of the adsorbents using the flash vaporization technique and then challenged each with various sampling volumes ranging from 0.2 to 100 liters. We thermally desorbed each of the adsorbents into a GC/MSD system.
Introduction
Our goal in performing this research was to develop a simple and easy to use tool for thermal desorption users. This tool demonstrates the relative difference between the adsorbents based on their capability to efficiently retain and release an analyte when challenged with various sample volumes. Several other conditions such as sampling flow rate, storage conditions, and the relative humidity of the sampled air can all influence the ability of an adsorbent to retain an analyte during the sampling process. This research covers only the sample volume aspect. The challenge we posed to each of the adsorbents was to spike a known quantity of a test mix onto the adsorbents. Then challenge the adsorbent by subjecting it to a constant flow of clean nitrogen until we obtained the desired volume. We then thermally desorbed the adsorbents into a GC system to determine what analytes remained (recovered) on the adsorbent after it we subjected it to the challenge volume. This was repeated for six different volumes of nitrogen. An analogy that depicts the challenge posed by this research is that of packed column chromatography. For this, we pack the adsorbent into a coiled column; we apply a carrier gas to carry the analytes from the injection port through the column to the detector at the opposite end. Essentially the same concepts exist here when sampling with a thermal desorption tube. The adsorbent is packed into an empty thermal desorption tube (very small column). The carrier gas for this research was nitrogen, but in the real world, it would be air. The Adsorbent Tube Injector serves as the injection port to introduce the gas mix into the nitrogen gas stream. The analytes migrate through the adsorbent bed where at some point in time, some of the analytes break-through whereas, others are retained by the adsorbent. Instead of having a detector at the end of the tube to analyze what broke-through, this research looks at what analytes the adsorbent retained. Thermal desorption of the tube releases the analytes in the GC/ MS system for detection.
Table of Contents
Abstract ................................................................................................. 1 Introduction ............................................................................................ 1 Experimental Details ............................................................................. 2 Sequence of Events .............................................................................. 5 Setting Up the Challenge Volume ........................................................ 6 The Analysis Matrix ............................................................................... 6 Calibration Procedures for the Analytical System ............................... 7 Calculating the Recovery of the First Desorption ................................ 7 Calculating the Recovery of the Second Desorption ........................... 7 Results: How to Use the Charts ........................................................... 7 General Guidelines for Interpreting the Trends ................................... 9 Using the Charts to Design a Multi-Bed Tube ..................................... 9 Discussion of the Results ................................................................... 10 Conclusion ........................................................................................... 10 Questions and Answers ...................................................................... 11 Acknowledgements ............................................................................. 11 References .......................................................................................... 11 Performance Charts ............................................................................ 12
We are committed to the success of our Customers, Employees and Shareholders t h r o u g h l e a d e r s h i p i n L i f e S c i e n c e , H i g h Te c h n o l o g y a n d S e r v i c e .
Experimental Details
Adsorbents Tested We tested twenty-four different adsorbents. Carboxen(s), Carbosieve S-III, and Carbopack(s) are exclusive to Supelco and have been used in the field of thermal desorption and purge and trap for years. We also chose adsorbents such as Tenax, silica gel, and glass beads because of their traditional use in the field of thermal desorption. Porapak, Chromosorb and HayeSep are also used in some thermal desorption applications. Coconut and petroleum charcoal predominately have been used for solvent desorption applications, but some uses of these materials do exist in thermal desorption applications. For this research, only one lot per adsorbent was tested. Table 1 shows the list of adsorbents tested and the physical properties of the adsorbents such as the mesh size, packing density, and bed weights. Analytes Used as the Test Probe The analytes chosen as test probes for this research are a subset of the EPA Hazardous Pollutant list, and are also common to many industrial hygiene sampling methods. We used a gas mix containing the 43 analytes listed in Table 2. This mix contained a broad spectrum of volatile organic analytes with physical properties that range from (50 to 260) in molecular weight, and (-30 to 215C) in boiling point. The gas mix is available as a Supelco stock product Catalog #500429. The concentration of each analyte in the gas mix is 1000ppb. We introduced a 20milliliter undiluted volume of this gas mix to each adsorbent. (Table 2 shows the calculated mass of each analyte contained in the 20mL volume). We chose the gas mix for several reasons. First, the analytes are in the gas phase to simulate a real world sample. Second, if we had used a liquid solvent mix, such as methanol, it could alter the results because it too may occupy the pore sites of the adsorbent. This could create a competition for sorption sites with the analytes of the test mix. Third, the use of a solvent would interfere in the detection of the very volatile analytes. This is due to the chromatographic conditions that we chose to optimize the transfer of the analytes to the capillary column.
Cryo-Focusing Trap The GERSTEL CIS 4 inlet was used to re-focus the analytes desorbed from the adsorbents. The injection port liner of the inlet contained two different materials to facilitate the retention of the very volatile analytes in the test mix. We used liquid nitrogen to cool the inlet liner to -150C during the desorption of the adsorbent tubes. We desorbed the inlet at 350C. We used a standard inlet liner (available from GERSTEL GC07540 10) and packed the inlet with the following adsorbents: Carbotrap C 20/40 mesh: 10mm bed length (25 milligrams) Glass Beads 60 mesh: 6mm bed length (25 milligrams) This inlet configuration was determined after we performed several experiments to optimize the chromatography of the gas mix. Figure 2 shoes an example of the chromatography achieved with this set-up. (Notice the resolution of the first five analytes).
Figure 2. The Results of the Test Gas Desorbed from a Carbotrap 300
The large CO2 is concentrated onto the refocusing trap during the process of the TDS A loading the adsorbent tube into the desorber oven.
Gas Chromatograph Supelco used a Hewlett Packard 6890 GC with a 5973 mass selective detector (Turbo Pump System) for the study. The capillary column was a 60 meter x 0.25mm ID, 3.0m film SPB-1 column. Other Equipment Used Supelcos prototype Adsorbent Tube Injector System served as the device to transfer the gas mix onto the adsorbent packed tubes. Dynatherm Model 60 Six-Tube Conditioner served as a means to condition the packed adsorbent tubes. A second unit served as a way to control the flow rate through multiple tubes simultaneously for the following volume challenges: 1, 2, 5, 10, 20, and 100 liters. Mettler Balance model AE100 served as a way to determine the actual bed-weights of each packed adsorbent tube. Table 3 shows the operating conditions for the equipment.
Analytical Equipment
Thermal Desorber GERSTEL loaned the thermal desorption unit used in this study to Supelco. The GERSTEL TDS A, shown in Figure 1, provided the means to automate the analysis of the adsorbents. The TDS A interfaces with the GERSTEL CIS4 Inlet that serves as the cryo-focusing trap for the desorption of the adsorbents.
Figure 1. GERSTEL TDS A Coupled to a HP6890GC/5973MSD
CO2
Table 1.
Physical Properties of Adsorbents

Pressure Drop (inches Weight of Adsorbent (mg) 379 275 297 308 258 291 227 226 239 402 399 416 254 217 290 143 204 188 151 171 826 380 283 250 Packing Density grams/cc 0.76 0.55 0.59 0.61 0.52 0.58 0.46 0.45 0.48 0.80 0.81 0.85 0.51 0.43 0.58 0.28 0.41 0.37 0.30 0.35 1.68 0.76 0.57 0.50
Adsorbent Name Carbosieve S-III Carboxen-563 Carboxen-564 Carboxen-569 Carboxen-1000 Carboxen 1001 Carboxen-1002 Carboxen-1003 Carboxen-1016 Carboxen-1018 Carbopack F Carbopack C Carbopack Y Carbopack B Carbopack X Tenax TA Tenax GR Porapak N Chromosorb 106 Hayesep D Glass Beads Silica Gel Grade 15 Coconut Charcoal Petroleum Charcoal
Adsorbent Class Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Carbon Molecular Sieves Graphitized Carbon Graphitized Carbon Graphitized Carbon Graphitized Carbon Graphitized Carbon Porous Polymer Porous Polymer Porous Polymer Porous Polymer Porous Polymer Other Other Other Other
Mesh Size 60/80 20/45 20/45 20/45 60/80 60/80 40/60 40/60 60/80 60/80 60/80 60/80 60/80 60/80 60/80 60/80 60/80 50/80 60/80 60/80 60/80 40/60 20/40 20/40
of water) @100mL/min
Conditioning Temp C 350 350 350 350 350 350 350 350 350 350 350 350 350 350 350 320 320 190 190 190 350 190 190 190
Desorption Surface Temp C Area m2/g 330 330 330 330 330 330 330 330 330 330 330 330 330 330 330 300 300 180 180 180 330 180 180 180 820 510 400 485 1200 500 1100 1000 75 700 5 10 24 100 240 35 24 250-350 750 795 <5 750 1070 1050
13.2 4.8 2.5 2.3 12.3 11.8 10.0 12.1 12.4 17.9 21.6 18.8 13.0 20.2 24.2 15.8 16.6 6.3 7.6 10.4 16.9 7.2 2.2 2.1
Packing density differs from free-fall density for it takes into account the particle to ID relationship of the specific inside diameter of the glass tube to the shape and mesh size of the adsorbent material. These values were determined from the actual lot number of the adsorbents tested in this research. The packing density can be used to calculate the approximate bed weight in a given volume of a 4-millimeter ID tube.
Table 2.
Analyte List
Calculated mass injected on tube per 20mL syringe volume
Quantifying Masses (M/Z) Analyte Halocarbon 12 Chloromethane Halocarbon 114 Vinyl chloride 1,3-Butadiene Bromomethane Chloroethane Halocarbon 11 Acrylonitrile 1,1-Dichloroethene Methylene chloride 3-Chloropropene Halocarbon 113 1,1-Dichloroethane cis-1,2-Dichloroethene Chloroform 1,2-Dichloroethane 1,1,1-Trichloroethane Benzene Carbon tetrachloride 1,2-Dichloropropane Trichloroethene cis-1,3-Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethene Chlorobenzene Ethylbenzene m & p-Xylene Styrene 1,1,2,2-Tetrachloroethane o-Xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene CAS# 75-71-8 74-87-3 76-14-2 75-01-4 106-99-0 74-83-9 75-00-3 75-69-4 107-13-1 75-35-4 75-09-2 107-05-1 76-13-1 75-34-3 156-59-2 67-66-3 107-06-2 71-55-6 71-43-2 56-23-5 78-87-5 79-01-6 10061-01-5 10061-02-6 79-00-5 108-88-3 106-93-4 127-18-4 108-90-7 100-41-4 108-38-3 (106-42-3) 100-42-5 79-34-5 95-47-6 622-96-8 108-67-8 95-63-6 541-73-1 106-46-7 95-50-1 120-82-1 87-68-3 M.W. 120.9 50.5 170.9 62.5 54.1 94.9 64.5 137.4 53.1 96.9 84.9 76.5 187.4 99.0 96.9 119.4 99.0 133.4 78.1 153.8 113.0 131.4 111.0 111.0 133.4 92.1 187.9 165.8 112.6 106.2 106.2 104.2 167.9 106.2 120.2 120.2 120.2 147.0 147.0 147.0 181.5 260.8 B.P. C -30 -24 4 -14 -5 4 12 24 77 32 40 45 47 57 60 61 84 74 80 77 97 87 112 112 114 111 132 121 132 136 139 145 146 144 162 165 168 173 173 181 213 215 Primary 85 50 85 62 39 94 64 101 53 61 84 41 151 63 61 83 62 97 78 117 63 95 75 75 97 91 107 166 112 91 91 104 83 91 105 105 105 146 146 146 180 225 Secondary 87 52 87 61 54 96 66 103 52 96,63 86,49 76 101 65,85 96,98 85 98 99,61 77 119 62,76 130,132 110 110 83,85 92 109,188 168,129 77,114 106 106 78 85,131 106 120 120 120 111,148 111,148 111,148 182 260
Elution Order SPB-1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31,32 33 34 35 36 37 38 39 40 41 42 43
ng/sample 99 41 140 51 44 78 53 112 43 79 69 63 153 81 79 98 81 109 64 126 92 107 91 91 109 75 154 136 92 87 174 85 137 87 98 98 98 120 120 120 148 213
Sequence of Events
Preparation of the Adsorbents We packed each of the adsorbents into a 4mm ID x 6mm OD x 178mm fritted glass tube, based on a fixed volume of 0.5cc. We constructed a 0.5cc vessel by cutting a 3.7cm length of tubing from a representative empty glass tube. We packed the adsorbent into the vessel and vibrated it to assure we obtained a consistent volume of the adsorbent. We then poured the contents of the 0.5cc vessel into the empty tube. We inserted a small plug of untreated glass wool on top of the adsorbent bed along with a small stainless steel clip to provide additional support to keep the adsorbent in place. We thermally conditioned each of the packed adsorbent tubes for eight hours with a continuous flow of clean nitrogen. Figure 3 illustrates the packed adsorbent tube. Table 1 lists the actual bed weights of each tube and the conditioning temperatures used for each adsorbent. Further details on our tube packing procedure can be found in the Questions & Answers section.
Figure 3. Drawing of the Packed Adsorbent Tube Depicting the Bed Length of Each Adsorbent
Adsorbent occupied a 3.7cm bed-length (0.5cc3 volume)
SS Clip Glass wool plug
Flow direction during the Challenge Flow direction during Desorption
Glass Frit Inlet of the tube
Table 3. Operating Conditions GERSTEL TDS A Parameters

GERSTEL MASter Software Sample Mode Flow Mode Transfer Temp Purge Time Initial Temp Initial Time Delay Time 1st Ramp Rate Final Temp Final Time 2nd Ramp Rate Final Temp Final Time Online Standard Solvent Venting 275C 1.00 min 25C 1.00 min 1.75 min 60C/min * * 0C -NA-NA-NA-
HP-6890 GC Parameters Oven Program

Initial Temp Each adsorbent was desorbed for a total of 6 minutes. To achieve this, the following conditions were used:
*Final Temp 180C 300C 330C *Final Time 3.5 min 1.5 min 1.0 min
Initial Hold
Ramp 1 Rate 1 Temp
Ramp 1 Hold Time Rate 2
Final Temp
Final Hold Time 8 min
35C 8.00 min 5C/min 100C
0 min 15C/min 230C
Capillary Column: 60 meter x 0.25mm ID, 3.0m film SPB-1 (Available from Supelco as a custom product).
Column Parameters Pressure Column Flow Avg. Velocity Set-Point 24.0psi 1.5mL/min 31cm/sec
HP-5973 MSD GERSTEL CIS-4 Inlet Parameters

GERSTEL MASter Software Cryo Cooling Equilib Time Initial Temp Initial Time 1st Ramp Rate Final Temp Final Time 2nd Ramp Rate Final Temp Final Time ON 0.2 min -150C 0.10 min 12C/sec 350C 3.00 min 0C -NA-NAHP Chemstation Inlet Screen Mode Inlet Pressure Total Flow Vent Flow Vent Pressure Until Purge flow to split vent @ Gas Saver Solvent Vent 26.7psi 14.0mL/min (Set-point) 20mL/min 26.9psi 0.00 min 10.0mL/min 0.01min Not used Scan Parameters Low Mass High Mass Threshold Em Voltage Sampling Rate 35amu 269amu 200 1576 23 MSD Temperature Zones MS Quad MS Source MS Interface Solvent Delay 150C 230C 230C 0.00 min
Adsorbent Tube Injector System

Parameters Block Temperature Glassware Transfer Gas Gas Flow Rate Transfer Time Transfer Volume Supply Pressure 65C 10mL Injection Glassware w/septa port Nitrogen 50mL/min 4 minutes 0.2 liters 50psig
Cryo-Focusing Trap CIS-4 Inlet Liner (Physical Data)

Inlet Liner Type Adsorbent Standard Liner with notch (GC07540 10) Carbotrap C* 20/40 mesh and Glass Beads 60 mesh (* adsorbent is at the notch) Untreated Glass Wool
Note: The actual adsorbent tube is not heated.
Glass Wool Type
Setting Up the Challenge Volume

The study looked at six different challenge volumes: 0.2, 1, 5, 10, 20, and 100 Liters. The 0.2-Liter volume simulates the small sample volume used in most purge and trap applications. The 1, 5 and 10 Liter volumes are typical sample volumes used in thermal desorption applications (1,2). The higher volumes of 20, and 100-Liters were chosen for two reasons. First, it will provide users additional information if they need to use larger sample volumes to increase detection limits by increasing their sample size (volume). Second, you can use these larger sample volumes to differentiate one adsorbent from another. An example of this would be a user that needs to obtain a 10 liter sample of analyte X. He/she can use the performance charts to compare the adsorbents and choose the one that has good recoveries that extend into 20 or 100-Liter range. By choosing the adsorbent that has capabilities beyond the desired sample volume, the user can safely assume they have chosen the appropriate adsorbent. Table 4 shows the challenge volume parameters used in this research. The challenge flow rate of 0.05 Liter/min was constant.
Figure 4. The Analysis Matrix

Series 1 Glass Beads Carbopack F Carbopack C Carbopack Y Carbopack B Carbopack X Series 2 Carboxen-563 Carboxen-564 Carboxen-569 Carboxen-1000 Carbosieve S-III Series 3 Coconut Charcoal Petroleum Charcoal Silica Gel Grade 15 Porapak N Chromosorb 106 HayeSep D Series 4 Carboxen-1001 Carboxen-1002 Carboxen-1003 Series 5 Tenax TA Tenax GR Carboxen-1016 Carboxen-1018
Challenge Volumes
Set 1 0.2 Liter Set 2 1 Liter Set 3 5 Liter Set 4 10 Liter Set 5 20 Liter Set 6 100 Liter
Table 4.
The Challenge Volume Parameters

Challenged Flow Rate (Liters/min) 0.05L/min 0.05L/min 0.05L/min 0.05L/min 0.05L/min 0.05L/min Challenge Time (hours) 4 min 20 min 100 min (1 hr 40 min) 200 min (3 hr 20 min) 400 min (6 hr 40 min) 2000 min (33 hr 20 min)
Challenge Volume (Liters) 0.2L 1L 5L 10L 20L 100L
Figure 5. Supelco Adsorbent Tube Injector System (spiking the test gas onto a tube)
The Analysis Matrix

With twenty-four different adsorbents to test, six different volumes for each adsorbent, and two desorptions of the same adsorbent, this matrix adds up to over 288 analysis excluding calibration and blank tubes. To minimize the effect of storage time on recovery, we conducted the analysis and prepping of the tubes in five series, as shown in Figure 4. This reduced the effect of storage time, since the analysis of the first tube to the last tube spanned less than 5 hours. Spiking the Test Gas Mix on the Tubes We introduced the 43 analyte gas mix onto each adsorbent packed tube by using the technique of flash vaporization. This was conducted by using a prototype device developed by Supelco that is presently named the Adsorbent Tube Injector System (See Figure 5). This device incorporates a Swagelok union fitted with vespel/graphite ferrules that connected the inlet of the tube to a glass injection chamber fitted with a septa port. A block of aluminum surrounds the glass injection chamber. This transfers the heat of the Multi-Blok Heater to the glassware. A continuous flow of clean nitrogen sweeps the injection chamber. We maintained the nitrogen flow rate for this research at 0.05L/ min using a constant flow controller. A 20mL syringe volume of the undiluted 43-analyte gas mix was injected into the septum port of the glassware while nitrogen swept the test mix onto the inlet of the tube that was at ambient temperature. After 4 minutes had elapsed, we removed the tube. The 0.2 Liter volume of nitrogen was enough to completely sweep the test mix onto the adsorbent contained in the tube.
However, for the other five volumes studied, we physically removed the tubes from the Adsorbent Tube Injector and placed them into one of the six-ports of a Dynatherm tube conditioner. We chose the Dynatherm Six-tube conditioner to provide the rest of the challenge volumes. The Six-tube conditioner has six individual ports that the flow rate can be controlled independently (See Figure 6). Each of the flow ports were set to deliver 0.05L/ min. (Only the pneumatic section of this device was used, at all times during the challenge volume the packed adsorbent tubes remained at ambient lab temperatures).
Figure 6. Dynatherm Six-Tube Conditioner with the Tubes In-Place During the Volume Challenge
Constructing the Calibration Curve Six analytical runs made up the single-point curve for each series. For each challenge volume (set) a Carbotrap 300 tube was spiked with the same 20mL syringe volume of the test mix and analyzed along with the adsorbents of that series. We copied the actual responses from the analysis directly into Microsoft Excel. We set up a spreadsheet template to perform all the recovery calculations. We averaged the analyte responses from these six calibration runs and divided them by 100 to calculate the average response factor for each analyte. We then considered the response factors as the model of 100% percent recovered. We created a separate calibration curve for each series of adsorbents tested. This procedure reduced the effect of detector drift over time, since the completion of the research took several months.
Calculating the Recovery of the First Desorption

We divided the analyte response from each adsorbent by the average response factor derived from the calibration curve (above) and multiplied it by 100%. The result was the percent recovered from the adsorbent. This freed up the Adsorbent Tube Injector to spike the next tube of the series by using the Dynatherm conditioner. After the desired challenge volume had elapsed, the tubes were removed and loaded into the TDS A thermal desorber. A sequence was set to analyze the tubes overnight. We analyzed each tube independently, and the results compared to a calibration curve. We identified the analytes using the primary and secondary quantitation ions of each analyte. The primary ion was used to determine the area response of each analyte. (See Table 2 for the primary and secondary ions used in this research.)
Calculating the Recovery of the Second Desorption

Each adsorbent tube was re-desorbed at the same temperature immediately following the primary desorption of each series of adsorbents. If we found any of the analytes from the test, then the recovery was determined. This information is important because if the analyte(s) can not be efficiently released from the adsorbent during the primary desorption then either the analyte is too strongly adsorbed or irreversibly adsorbed. The difference is that too strongly adsorbed means that adsorbent retains the analytes to the point that they are not efficiently released from the adsorbent during desorption and a portion of it can be observed in the second analysis. Where as, irreversible adsorption indicates the analyte can not be released from the adsorbent, and is not observed in the second analysis. Regardless of whether the adsorbent retains the analyte too strongly or irreversibly adsorbs it; the user should choose a different adsorbent for that analyte. In an effort to help users choose the right adsorbent the performance charts include this (*) symbol next to the analyte name if we observed more than 5% of that analyte in the second analysis. This allows users to quickly observe which analytes they should not sample with certain adsorbents.
Calibration Procedures for the Analytical System

It was not feasible to make syringe injections of liquid or gas standards directly onto the column for two reasons. First, the transfer line of the GERSTEL TDS A connects directly to the inlet by a fitting that replaces the septum port. Second, the large volume of the test mix could not be injected quantitatively. It is not practical to inject a 20mL syringe volume of the test gas directly on to a capillary column without altering the flow dynamics of the GC system. Therefore, the model we chose to determine the recovery was to spike the same 20mL syringe volume of the test mix onto a multibed Carbotrap 300 using the same technique as performed in the previous section. The gas mix was swept onto the Carbotrap 300 tube with a total volume of 0.2 Liters using with the Adsorbent Tube Injector. This was enough volume to sweep the entire gas mix onto the tube, but would not pose a challenge to the combined adsorbents of this multi-bed tube. With such a small sample transfer volume (200mL), no loss of any analyte was expected. We assumed 100% recovery from the Carbotrap 300. Figure 7 illustrates the flow direction we used to sample and desorb the collected analytes.
Results: How to Use the Charts Figure 7. Picture of the Carbotrap 300 Tube Used for the Calibration
Carbopack B
Challenge Flow Direction Desorption Flow Direction
Carbosieve S-III
Carbopack C
To simplify the use of the reams of data generated by this research we developed a simple scheme so users can visually see the recovery based on color rather than comparing multiple columns of numbers. We used the analogy of a traffic signal to display the results. The performance charts are color-coded, with Green indicating the recovery is greater than or equal to 80%. The Yellow indicates the recovery is between 21 and 79%. Red indicates the recovery is less than or equal to 20%. Using the feature of conditional formatting in the Excel program, we displayed the raw data by color instead of displaying the actual
values. This concept makes it easier to compare the adsorbents when you view the charts together. Recoveries of 80% or greater are typically considered acceptable in most thermal desorption methods. Recoveries between 21 and 79% indicates a significant amount of the analyte was recovered from the adsorbent, but warns the user that breakthrough occurred or that the analyte is too strongly retained. A recovery of less than 20% is simply not suitable for any sampling application. The performance charts allow the user to see the relative differences between the adsorbents and assists them in choosing an adsorbent that will retain the analytes of interest at a specific volume. You can also use these charts to choose a combination of adsorbents to construct a multi-bed tube, which can retain a
wide range of analytes. The performance charts illustrate that no one single adsorbent can retain and release the entire list of analytes. The best way to use the performance charts is to look for the trends of green color for the analytes of interest. As seen in the example chart below, the recoveries of most of the very volatile analytes are good. As the challenge volume increases, some of the recoveries decreased due to the analytes breaking through the adsorbent. In respect to this example (Carboxen-1000), when sampling for analytes that have higher boiling points, greater than Benzene, you should use a weaker adsorbent bed in front of this adsorbent. This is because the analytes are either too strongly adsorbed (denoted by the asterisk * symbol), or irreversibly adsorbed
Data pertinent to each adsorbent can be found here
Boiling Point Increases
Increasing Volume
Too Strongly Retained
When sampling for these analytesa weaker adsorbent should be placed in front of this adsorbent
General Guidelines for Interpreting the Trends
You should use the performance charts as a guideline when choosing an adsorbent. We list the analytes by their retention order from an SPB-1 capillary column. They are in the order of their boiling point, with the exception of Acrylonitrile and 1,2-Dichloroethane. (See Table 2) The adsorbents were desorbed at their maximum desorption temperature. (See Table 1) You should consider the effects of water when choosing an adsorbent, since we based this research on the challenge of dry nitrogen.
If the chart is Red and/or Yellow at the top and changes to Green then the adsorbent is capable of efficiently retaining and releasing the analytes with higher boiling points. As the boiling point of the analytes decrease, they begin to break-through the adsorbent. The Carbopack(s) and Porous Polymers are a good example of this trend. Place a stronger adsorbent behind this type of adsorbent to retain and release the low boilers.
Using the Charts to Design a Multi-Bed Tube

You can use the data from the charts to construct a multi-bed adsorbent tube. As the data illustrates there is no one adsorbent that will both retain and release the entire list of analytes. You can construct a multi-bed tube by placing a weaker adsorbent at the inlet followed by a stronger adsorbent. You can create two, three and four bed tubes. You can tailor the adsorbent configuration for the sampling application. The Carboxen(s)/Carbosieve S-III should always be used along with a weaker adsorbent if the environment to be sampled contains higher boiling point analytes. You can use a single or multi-bed tube packed with a Carbopack or a Porous Polymer and not include Carboxen(s)/Carbosieve, allowing the low boiling analytes to pass through the tube. For example, in many cases when using a liquid standard, it is often desirable to allow the solvent (i.e. Methanol) to pass through the adsorbent while the higher boiling point analytes are retained. The example below illustrates the trend to look for when designing a multi-bed tube. In this example, the goal is to choose a combination of three adsorbents that can retain the entire list of 43 analytes for a sample volume up to a 1-Liter. The large gray X(s) indicate those analytes that are retained by the absorbent bed that precede it. The black arrows illustrate those analytes that break-through the first bed, and are then retained by the second bed. Note, one of the analytes (indicated by black) actually break-through the second bed and is retained by the last bed. The gray arrows illustrate those analytes that break-through the second bed and are retained by the third (last) bed. The dotted black line denotes the 1-Liter volume.
Observing the Trend Left to Right - Across the Rows: (Increased volume per analyte) Starting at the 0.2-Liter volume, looking at one analyte: 1. If the row is solid Green across all six volumes then this adsorbent is a good choice for this analyte. 2. If the row starts Green and changes to Yellow and/or Red, then the analyte is breaking through the adsorbent. Note: When sampling, maintain a sample volume within the green limits. 3. If the row is Yellow or Red Choose another adsorbent. Observing the Trend Top to Bottom - Down the Columns: (Increased Boiling-point per analyte) Starting at the 0.2-Liter volume, looking at one volume: If the chart is green at the top and changes to Yellow, and/or Red then the adsorbent is capable of efficiently retaining and releasing the analytes with low boiling points. As the boiling point of the analytes increase, they become too strongly adsorbed (as indicated by the * symbol or are irreversibly adsorbed). The Carboxen(s) are a good example of this trend). Always place a weaker bed of adsorbent in front of this type of adsorbent to keep these analytes from reaching this adsorbent.
Carbopack B
Carbopack X
Carboxen-1018
First Bed
Second Bed
Third Bed
Weakest
Sampling Direction (In order of increasing adsorbent strength)
Strongest
Discussion of Results
The following comments are valid with respect to the analytes and conditions we used in this research. The comments may not hold true for other analytes and/or testing conditions. General Observations on Carboxen Adsorbents As expected the recovery was poor for those analytes with boiling points higher than Benzene. This is because the Carboxen(s) have small pores designed specifically to retain and release only the analytes with low boiling points. The Carboxen(s) should always be used with a weaker adsorbent bed placed in front. A bed of one or more of the Carbopack(s) or a Porous Polymer can be used so the higher boiling point analytes are kept from getting in contact with Carboxen. In the actual analysis, both Carbon Dioxide and Sulfur Dioxide were observed in most of the Carboxen adsorbent analyses (no Sulfur Dioxide was observed from the Carboxen-1016 or 1018). This is common to most carbon molecular sieves, and does not present a problem unless the user is trying to sample for these two analytes. Carboxen-1016 is a newly developed adsorbent by Supelco that demonstrates excellent performance across both a wide range of analytes and sample volumes. This can be observed by reviewing its performance chart. It is a good candidate for numerous thermal desorption applications. The recoveries of Trichloroethane were high (greater than 145%) for Carboxen-1000, 1002, 1003. This was most likely due to the dehydrohalogenation of 1,1,2,2-Tetrachloroethane. The corresponding recovery of 1,1,2,2-Tetrachloroethane from these same Carboxens was very low (less than10%). This situation would not occur if a multi-bed tube was used because a weaker adsorbent is placed in front of the Carboxen when sampling atmospheres containing 1,1,2,2-Tetrachloroethane. General Observations on the Carbosieve S-III It appears that the Carbosieve S-III performance was worse than other carbon molecular sieves. The pore shape of the Carbosieve is different from the Carboxens. Carbosieves have closed pores that may have been blocked by the analytes with high boiling points. This could have prevented some of the low boiling point analytes from reaching the available pore sites. Like the Carboxens, Carbosieve S-III must have a weaker bed of adsorbent, such as one of the Carbopacks or Porous Polymer, placed in front, to prevent the analytes with high boiling points from reaching the pores of this adsorbent during sampling. Carbosieve S-III also releases Carbon Dioxide during desorption, but not Sulfur Dioxide. General Observations on the Carbopack Adsorbents The performance charts illustrate the increasing strengths of the Carbopacks with Carbopack F being the weakest, followed by C, Y, B, and X in order of increasing strength. The range of the F, C, and Y would extend into higher boiling point analytes not investigated by this research. The recovery of the very volatile analytes from the Carbopack X extends beyond that of Carbopack B. The recovery of 1,3-Butadiene from Carbopack X extended well into 20-Liter challenge volume. This is significant because no other adsorbent in this research performed so well with this analyte. The Carbopack X closes the gap between the other Carbopack(s) and the Carboxen(s)/Carbosieve S-III in respect to its ability to
retain the analytes across the challenge volumes. However, Carbopack X should have a weaker adsorbent bed placed in front of it when sampling analytes with very high boiling points. All of the Carbopack(s) are virtually hydrophobic and are good choices when sampling in an environment where high humidity exists. General Observations on the Porous Polymers None of the porous polymers could retain the very volatile analytes. Both Tenax TA and Tenax GR performed well for those analytes that had boiling points higher than Benzene. The capabilities of Tenax TA and Tenax GR can be broadened if a bed of Carboxen is place after the Tenax. The Porapak N, Chromosorb 106, and HayeSep D all showed similar patterns with the recoveries of the mid to higher boilingpoint analytes. The background generated from these adsorbents caused problems with obtaining clean blanks. The analytical system had to be baked out to reduce the contamination level between each analysis. General Observation on the Charcoals It is common knowledge that charcoal itself is not a good adsorbent for thermal desorption for several reasons. The adsorptive strength of charcoal can be too strong and heat alone does not always cause the release of the analytes. This was apparent in this research. First, the recoveries of almost all the analytes from the first desorption were poor with the exception of a few very volatile analytes. Second, a significant amount of the analytes was also observed from the second re-desorption of the tube. The same trend was seen on both the coconut and petroleum based charcoals. However, there are applications where charcoal is and can be used as an adsorbent bed in multitube, to retain and release the very volatile analytes such as, Halocarbon 12 and Chloromethane. General Observations on Silica Gel Silica gel showed fair recovery of the very volatile analytes at the 0.2-Liter challenge. Silica gel should also have a weaker adsorbent bed placed in front of it when sampling analytes with high boiling points. Silica gel may have applications where Carbon Dioxide would interfere in the analysis of the very volatile analytes, since no Carbon Dioxide was observed in the analysis. General Observations on Glass Beads As expected the glass beads do not have the ability to retain many analytes. They have applications if used as the first bed in a multi-bed tube to prevent very high boilers to come in contact with a stronger adsorbent.
Conclusion
The result of this research provides the users of our adsorbents and thermal desorption tubes with a new tool for choosing an adsorbent(s) for their application. By using the colored performance charts, one can compare and choose an adsorbent or construct a multi-bed tube for a specific range of analytes across various sample volumes. There is no one adsorbent available that can both retain and release all the analytes. However, there is clear evidence that some of our new adsorbents such as, Carbopack X and Carboxen-1016 will benefit the field of thermal desorption.
10
Questions & Answers

Why were the adsorbents packed by bed-volume versus bed-weight?
Because the density range of the adsorbents tested varied significantly, packing the adsorbents at the same bed-weight was not feasible. For example, if we would have packed the adsorbents all at the same bed-weights, some of the adsorbents would have extended past the heated zone of the thermal desorber. Other tubes would have had too little adsorbent in the tube for the tests. The actual bed-weights and mesh size of each adsorbent can be seen in Table 1. The advantage of packing the tube by bed-volume for this research is that the bed-length of 3.7cm occupies about half of the average heated- zone of most thermal desorbers. This allows at least two different adsorbents to be packed in most thermal desorption tubes. By using the same bed-volume of adsorbent as conducted in this research, the user can expect similar performance from the adsorbents by using the colored charts.
Were any test analytes retained on the glass frit at the inlet of each tube?
No, not any of these analytes. We tested this by spiking the gas mix on to the empty fritted glass tubes and analyzed them right away. No significant quantity of any analyte was detected
Why was an Internal Standard not used?

An internal standard could not be used, because no one or group of analytes could have been retained on all the adsorbents. For example, there were only a few analytes retained on the glass beads. So if we had used a high boiling point analyte for the glass beads, the same analyte would not have been released from the Carboxen(s)/Carbosieve S-III. A separate internal standard would have been needed for each of the adsorbents, thus making the use of this technique not very helpful.
How can we assume 100% recovery from the Carbotrap 300 used for the calibration?
For this research, all we could do was assume 100% recovery. Other models could have been researched, but the important thing to keep in mind that performance charts are meant to illustrate the relative difference between the various adsorbents. We do not attempt to say the recoveries are absolute.
What mesh size were the adsorbents?

The mesh size of the adsorbent ranged from 20/40 mesh to 60/80 mesh. It is virtually impossible to acquire the adsorbents all at one mesh size.
Why was nitrogen used instead of air to challenge the tubes?

Nitrogen was used because of its purity compared to compressed air. If compressed air would have been used the adsorbents would have concentrated the slightest contaminants. Also there is a significant amount of water in most air systems, which would have required extensive efforts to reduce the moisture content.
Could the desorption temperature have an affect on recovery?

Yes, the desorption temperature could have both positive and negative affects on recovery. For this research, our attempt was to choose the highest temperature typically used.
What is the difference between Carbopacks and Carbotrap?

The only difference is the mesh size of the adsorbents. Carbotraps are 20/40 mesh, and Carbopacks are 40/60 mesh or smaller. The performance charts can also be used in comparing the Carbotrap adsorbents.
Why was 50mL/min chosen as the sampling flow rate?

The flow rate used during the challenges remained constant at 50mL/min. The US EPA TO-1 method (3) recommends that the linear flow velocity through an adsorbent tube be 50-500cm/ minute. Using Equation 1, the calculated linear velocity through a 4mm sampling tubes used in this study was 398cm/min). Equation 1
B=
p r2
B = linear velocity (cm/min) Q = flow rate (mL/min) p = 3.14 r2 = inside radius of the tube (cm)
References 1. Method 2549 Volatile Organic Compounds, NIOSH Manual of Analytical Methods Fourth edition 1996 2. Compendium of Methods for Determination of Toxic Organic Compounds in Ambient Air EPA TO-17 Determination of VOCs in Ambient Air Using Active Sampling onto Sorbent Tubes Second Edition 1997 3. Compendium of Methods for Determination of Toxic Organic Compounds in Ambient Air EPA TO-1 Determination of VOCs in Ambient Air Using Tenax Adsorption and GC/MS page TO-1 thru 9 Acknowledgement The author would like to thank GERSTEL for the use of their equipment for this research. The automated ability of TDS A eased the burden of method development for this research. Patents Carbosieve Adsorbent German Patent No 1935500. Patent Holder Badishe Anilin-&Soda-Fabrik Aktiengesellschaft. Carboxen-564 Adsorbent US pat. No. 4,839,331 Trademarks Celite Corp. - Chromosorb Crawford Fitting Co. - Swagelok Enka Research Institute Arhem - Tenax Gerstel GmbH - GERSTEL Hayes Separations Inc. - HayeSep Lab-Line - Multi-Blok Microsoft Corporation - Excel Sigma-Aldrich - Carbopack, Carbotrap, Carboxen Waters Associates. Inc. - Porapak
What does a 20mL syringe volume of the 1000ppb gas mix relate to in a real world sample?
The table below illustrates what the ppb concentration of the 20mL syringe volume would represent based on if the contents were released into the corresponding volumes. Example: If the 20mL syringe volume of the 1000ppb test gas mix were released into a 5-Liter sealed volume, the concentration of the gas mix would be diluted to 4ppb.
Challenge Volume 0.2 Liters 1 Liter 5 Liter 10 Liter 20 Liter 100 Liter What Concentration Does 20mL Gas Volume Represent 100ppb 20ppb 4ppb 2ppb 1ppb 0.2ppb
11
Carbopack F
(Graphitized Carbon Black) Surface Area: 5 m2/g Desorption Temperature: 330 C
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl chloride 1,3-Butadiene Bromomethane Chloroethane Halocarbon 11 Acrylonitrile 1,1-Dichloroethene Methylene chloride 3-Chloropropene Halocarbon 113 1,1-Dichloroethane cis-1,2-Dichloroethene Chloroform 1,2-Dichloroethane 1,1,1-Trichloroethane Benzene Carbon tetrachloride 1,2-Dichloropropane Trichloroethene cis-1,3-Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethene Chlorobenzene Ethylbenzene m & p-Xylene Styrene 1,1,2,2-Tetrachlorethane o-Xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene 0 0 0 0 0 0 0 0 113 0 0 0 0 0 0 0 1 0 2 0 3 6 3 23 6 117 25 127 123 117 108 119 109 107 106 105 108 114 112 114 129 120
Challenge Volume (Liters) 1 5 10

0 0 0 0 0 0 0 0 80 0 0 0 0 0 0 0 0 0 0 0 0 1 0 1 0 92 2 1 97 101 99 103 8 96 93 91 93 97 93 96 95 97 0 0 0 0 0 0 0 0 34 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 29 86 82 3 84 85 81 80 85 85 83 72 79 0 0 0 0 0 0 0 0 70 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 11 88 62 2 87 83 85 85 80 81 81 73 50
20
0 0 0 0 0 0 0 0 14 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 26 2 0 33 79 87 86 42 54 51 66 6
100
0 0 0 0 0 0 0 0 16 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 75 84 0 0 0 71 0
Performance Key Safe to use: Recovery is greater than 80% Caution: Recovery is between 21 to 79% Not Recommended: Recovery is less than 20% * indicates this analyte was strongly adsorbed
Carbopack C
0.2

0 0 0 0 0 0 0 0 68 0 0 0 0 0 0 0 0 0 0 0 0 1 0 2 0 103 2 44 106 104 98 102 9 95 95 94 96 97 97 97 101 99 0 0 0 0 0 0 0 0 33 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 66 95 96 0 92 84 87 88 87 85 86 84 85 0 0 0 0 0 0 0 0 54 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 6 92 87 0 90 87 89 90 87 86 86 85 84
20
0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 71 41 0 79 89 91 92 84 87 86 80 60
100
0 0 0 0 0 0 0 0 14 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 15 88 92 1 3 1 84 0
Carbopack Y
0.2

0 0 0 0 0 0 0 0 90 0 0 0 0 0 0 0 2 0 97 0 81 87 74 119 101 102 111 106 103 105 103 108 105 102 95 94 96 101 98 100 110 106 0 0 0 0 0 0 0 0 72 0 0 0 0 0 0 0 1 0 2 0 0 4 1 2 2 88 20 87 90 98 105 106 96 105 93 86 89 99 96 98 97 101 0 0 0 0 0 0 0 0 66 0 0 0 0 0 0 0 1 0 0 0 0 4 0 1 1 95 3 89 95 99 96 95 101 96 88 90 91 88 88 88 87 84
20
0 0 0 0 0 0 0 0 39 0 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0 99 2 92 101 105 100 98 108 100 92 95 95 90 90 90 86 83
100
0 0 0 0 0 0 0 0 40 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 23 1 0 75 105 108 105 2 106 96 96 97 96 94 95 92 91
Carbopack B
0.2

0 0 0 0 3 0 0 5 107 60 0 45 108 103 105 105 101 104 100 103 97 112 103 102 102 103 106 107 103 103 102 105 86 101 96 90 92 100 99 100 98 101 0 0 0 0 0 0 0 0 93 2 0 0 91 0 2 4 89 90 87 89 86 98 85 83 89 91 88 91 90 91 93 92 80 92 84 83 83 87 86 87 84 86 0 0 0 0 0 0 0 0 102 3 0 0 55 0 0 0 9 90 91 88 91 99 81 80 92 97 84 91 95 97 92 89 85 91 85 84 85 85 84 85 82 81
20
0 0 0 0 0 0 0 0 20 3 0 0 1 0 0 0 2 91 102 97 105 107 89 83 102 106 90 101 104 105 101 99 99 101 94 94 95 94 92 93 87 88
100
0 0 0 0 0 0 0 0 18 3 0 0 0 0 0 0 0 0 106 0 5 69 9 14 100 106 63 97 104 111 105 102 83 105 95 100 100 95 93 94 93 89
Carbopack X
0.2

133 0 103 31 97 0 114 106 110 108 114 87 107 102 103 77 100 100 99 87 97 122 88 70 98 101 86 105 102 100 93 93 71 92 72 68 60 84 78 83 58 68 0 0 98 1 90 0 0 94 102 96 43 70 90 92 92 71 90 88 90 80 89 109 80 72 88 100 71 95 99 94 87 83 69 87 73 68 56 81 77 80 50 67 0 0 101 1 99 0 0 100 109 103 1 60 97 100 99 69 107 102 98 93 99 120 86 77 96 96 77 94 95 97 89 85 72 88 68 66 57 75 69 73 49 61
20
0 0 32 2 118 0 0 112 122 120 0 47 102 114 113 69 112 105 105 96 107 121 92 79 102 105 72 99 103 103 94 90 71 93 73 70 61 78 74 78 49 62
100
0 0 0 2 0 0 0 0 114 9 0 0 97 45 65 1 91 98 104 86 106 124 68 54 94 101 60 94 98 101 100 92 77 99 78 73 64 79 78 77 51 67
* * * * * * *
Carboxen-563
(Carbon Molecular Sieve) Surface Area: 510 m2/g Desorption Temperature: 330 C
0.2

117 63 96 13 7 6 110 93 25 20 100 19 91 90 39 96 85 66 95 40 82 53 27 23 75 75 36 53 76 43 53 19 40 56 31 48 44 56 56 54 46 38 121 4 95 11 9 1 97 90 41 16 95 11 88 89 33 91 85 63 101 36 87 57 27 22 79 78 39 56 78 49 60 20 41 63 32 46 41 58 55 55 36 38 101 2 93 12 7 1 84 86 32 16 88 7 84 84 23 84 80 54 90 28 78 43 17 13 66 69 28 47 70 38 49 17 33 52 24 38 32 48 46 45 28 31
20
37 1 104 16 7 2 63 93 22 19 90 6 94 87 17 90 77 53 99 27 76 38 14 12 68 67 26 45 79 29 41 17 28 47 19 39 32 53 53 50 29 32
100
0 1 75 16 5 1 11 76 18 22 65 2 98 77 7 78 70 41 93 18 69 31 9 7 63 63 21 43 62 28 41 13 25 43 19 30 23 41 40 39 18 26
* * *
Carboxen-564
0.2

133 75 100 77 10 32 123 96 60 84 105 48 95 95 63 89 88 88 75 66 75 62 38 34 66 46 36 48 41 29 31 20 33 30 15 21 13 24 22 22 10 28 132 31 102 59 12 7 123 95 59 79 104 43 94 95 63 84 89 89 76 62 76 65 37 33 66 48 36 49 43 32 33 20 35 32 17 24 16 26 25 25 11 31 118 5 91 46 14 3 105 87 55 73 91 38 85 88 58 76 81 80 67 53 68 58 29 25 58 39 31 43 35 25 25 16 30 24 11 18 10 20 18 18 7 24
20
86 4 101 40 10 3 101 92 45 71 97 27 93 90 45 77 79 82 74 52 70 53 22 18 57 40 23 43 39 20 22 17 23 23 9 19 12 20 20 19 10 26
100
14 2 76 16 13 2 64 77 40 56 84 16 95 80 38 69 70 76 59 42 57 54 19 15 52 31 22 39 27 16 18 10 22 17 7 13 6 14 14 13 4 19
Carboxen-569
0.2

129 79 97 90 37 77 122 98 92 92 103 77 99 101 86 99 97 101 78 93 97 90 57 50 91 50 51 68 41 38 33 22 65 42 21 33 18 24 19 26 11 31 90 28 99 81 38 36 122 99 95 93 104 75 95 99 84 96 95 96 77 87 94 88 53 47 89 52 49 71 43 40 33 22 69 43 21 34 18 23 19 27 10 33 27 8 95 71 36 17 114 95 91 89 98 72 89 95 80 92 92 92 70 83 90 83 49 42 83 44 45 62 37 34 28 18 62 37 18 31 16 21 17 24 8 31
20
6 3 112 78 40 7 120 103 84 94 110 68 98 98 80 98 94 97 76 87 93 92 49 40 93 48 47 73 41 36 30 19 64 40 18 40 17 23 20 27 9 34
100
1 2 85 23 31 1 47 94 74 79 89 44 96 87 61 87 76 87 57 75 83 78 32 24 81 29 32 53 22 19 17 8 47 24 10 19 7 12 10 14 3 20
Carboxen-1000
0.2

128 90 98 102 44 79 126 97 99 118 106 84 94 99 95 97 113 86 85 40 84 146 40 32 68 50 19 59 42 24 22 18 9 20 7 9 5 15 13 13 3 8 129 9 99 93 44 20 129 99 100 121 108 84 91 98 96 95 112 84 86 35 85 147 39 31 67 47 19 57 39 23 21 17 9 19 6 9 5 14 13 12 3 7 123 4 93 82 52 6 118 94 99 113 100 85 86 95 94 92 107 81 81 37 82 140 42 35 69 49 18 57 42 27 24 19 13 18 8 11 6 16 14 14 3 9
20
126 4 97 71 45 2 106 95 88 116 98 79 95 99 94 97 125 87 82 37 79 149 34 26 67 44 13 60 38 19 18 13 7 16 5 8 4 12 12 11 3 7
100
1 3 88 7 35 2 68 93 80 106 93 56 94 89 83 90 106 80 77 32 75 146 28 21 66 41 14 56 33 17 17 12 8 15 5 7 3 11 11 10 2 6
* *
* * *
Carboxen-1001
0.2

130 86 89 92 53 79 117 103 96 103 104 90 103 104 95 103 99 99 90 95 99 110 62 52 98 61 58 84 49 45 42 30 69 55 30 44 24 28 21 33 10 31 57 18 138 86 48 34 114 104 111 103 111 91 104 104 96 105 101 99 87 95 97 107 60 52 97 57 55 82 45 39 32 22 68 44 23 37 19 22 17 26 9 23 6 9 110 88 57 15 107 109 88 107 107 89 101 105 90 103 95 96 80 91 90 98 51 43 85 59 45 77 47 42 34 24 55 43 23 35 19 21 16 23 8 21
20
3 5 111 76 53 7 104 108 95 105 110 86 101 104 90 103 96 96 82 92 95 105 51 43 91 52 46 75 42 37 28 19 54 36 16 28 14 17 13 20 7 18
100
1 2 126 16 49 2 24 133 89 90 84 130 100 120 88 117 94 96 82 92 95 95 61 54 94 53 55 78 42 37 28 19 76 39 19 33 17 19 14 20 9 19
* * * * * * * * * * *
Carboxen-1002
0.2

129 96 88 114 67 81 116 94 97 110 104 67 91 97 105 85 100 59 76 21 74 130 21 15 65 35 22 45 27 17 15 13 16 14 8 8 6 10 9 10 4 6 139 17 103 113 68 30 114 96 117 115 110 67 92 99 107 89 102 59 74 21 72 126 22 16 63 33 22 41 26 15 13 11 14 12 7 7 5 9 8 8 3 5 140 14 113 134 79 8 116 102 97 125 113 68 93 102 109 90 104 53 75 15 71 130 14 10 55 35 14 44 27 14 12 10 10 11 6 6 4 8 8 7 3 5
20
132 4 108 112 71 2 104 95 106 118 109 61 88 99 105 87 99 51 67 17 66 120 16 12 55 27 18 34 22 13 11 9 13 10 4 5 3 8 7 7 3 5
100
1 1 119 16 41 1 22 100 90 98 64 53 83 99 88 83 86 53 70 16 69 112 17 13 59 32 19 41 25 14 12 9 14 11 5 6 4 8 7 7 3 5
* * *
* * *
Carboxen-1003
0.2

131 76 89 89 56 58 111 97 98 120 103 56 93 95 101 85 97 62 84 28 77 139 18 12 65 48 19 59 40 26 23 19 17 22 13 13 8 16 14 15 5 9 138 6 98 97 57 9 103 96 112 119 104 53 94 94 100 86 98 62 82 28 76 136 18 12 63 46 20 57 38 23 18 15 16 17 10 11 7 13 12 12 5 7 129 3 109 103 69 1 93 101 95 126 104 55 93 97 101 88 98 59 84 24 74 135 15 9 59 51 17 60 42 26 19 17 13 15 11 12 7 15 14 13 5 8
20
126 2 104 90 62 1 81 95 116 124 101 46 97 97 106 90 107 58 80 21 75 145 12 7 62 36 15 46 30 16 13 10 13 12 4 6 3 9 8 8 3 5
100
2 1 119 21 61 1 4 98 88 101 48 28 86 91 82 72 82 51 72 18 66 115 9 6 48 38 14 49 31 18 14 11 10 13 6 7 4 9 8 8 3 5
* * * * * * *
* * *
Carboxen-1016
0.2

1 0 104 1 101 0 3 103 106 103 103 104 102 103 103 104 104 101 100 101 101 100 108 110 101 101 107 101 100 98 97 94 102 98 93 95 86 94 93 94 59 84 0 1 9 0 99 1 0 98 114 97 1 98 97 99 100 100 100 96 95 97 94 92 103 110 96 99 102 98 99 95 86 84 104 87 85 95 84 88 88 89 59 77 0 0 1 0 55 0 0 107 104 120 0 119 112 119 117 119 112 107 102 107 102 99 109 118 100 107 107 104 104 99 99 98 98 96 86 86 70 90 86 84 42 65
20
0 0 1 0 3 0 0 6 112 23 0 57 100 107 106 108 104 99 105 100 102 103 113 129 106 116 114 114 120 114 104 110 114 101 93 97 79 102 103 98 67 75
100
0 0 0 1 1 0 0 0 46 2 1 1 83 1 1 3 74 80 81 84 80 71 89 99 82 85 80 83 85 86 81 79 101 81 69 75 71 75 75 75 56 70
* *
Carboxen-1018
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl Chloride 1,3-Butadiene Bromomethane Ethyl Chloride Halocarbon 11 Acrylonitrile 1,1-Dichloroethylene Methylene Chloride 3-Chloropropylene Halocarbon 113 1,1 Dichloroethane cis-1,2 Dichloroethane Chloroform 1,2 Dichloroethane 1,1,1 Trichloroethane Benzene Carbon Tetrachloride 1,2-Dichloropropane Trichloroethylene cis-1,3 Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethylene Chlorobenzene Ethylbenzene m,p-Xylene Styrene 1,1,2,2-Tetrachlorethylene o-xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachloro-1,3-butadiene * 182 86 136 148 29 96 165 122 111 144 149 91 131 124 112 119 145 102 109 49 96 138 47 38 80 65 16 79 60 30 24 23 7 24 12 16 10 22 19 21 9 21

166 81 121 134 44 105 142 109 105 130 126 89 109 111 105 107 130 92 94 45 86 129 40 33 72 54 17 63 48 26 21 20 9 21 10 12 7 16 14 16 5 15 150 76 99 116 62 55 117 92 94 115 100 84 75 94 93 90 110 73 71 35 67 104 26 21 55 38 14 40 31 18 15 10 13 15 5 9 4 10 9 9 3 9 137 10 93 100 45 10 105 86 83 107 98 72 76 88 84 85 113 71 68 34 64 101 26 21 51 35 10 39 28 16 15 10 7 15 6 9 4 11 10 11 3 11
20
145 5 102 94 38 4 114 92 84 112 102 76 79 94 91 90 116 76 74 36 69 108 30 25 57 41 13 44 35 19 18 14 12 19 7 12 6 13 11 12 4 12
100
72 4 91 32 28 2 84 80 79 103 89 63 67 88 85 82 111 65 67 27 62 100 24 20 51 34 12 37 28 17 15 10 11 15 4 8 3 9 8 8 3 9
* *
* * * * * * *
* * * *
Carbosieve S-III
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl chloride 1,3-Butadiene Bromomethane Chloroethane Halocarbon 11 Acrylonitrile 1,1-Dichloroethene Methylene chloride 3-Chloropropene Halocarbon 113 1,1-Dichloroethane cis-1,2-Dichloroethene Chloroform 1,2-Dichloroethane 1,1,1-Trichloroethane Benzene Carbon tetrachloride 1,2-Dichloropropane Trichloroethene cis-1,3-Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethene Chlorobenzene Ethylbenzene m & p-Xylene Styrene 1,1,2,2-Tetrachlorethane o-Xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene * * 76 88 75 141 19 67 106 49 81 86 97 21 78 51 85 37 70 82 43 66 32 59 3 2 23 10 5 15 9 3 3 1 5 4 1 5 1 3 2 3 1 18

73 84 65 118 14 71 109 48 80 82 96 33 73 54 82 44 79 77 46 61 34 56 6 4 28 15 9 18 12 5 6 3 10 7 2 8 1 5 4 5 3 20 69 51 69 111 13 34 111 46 83 85 96 36 70 57 85 43 79 75 51 58 36 61 7 4 29 16 9 19 13 6 6 3 10 7 2 9 2 5 4 5 5 20 65 11 60 94 13 12 101 44 83 86 91 38 71 58 87 46 77 74 49 54 34 61 8 6 29 17 10 20 14 6 7 4 11 8 2 9 2 6 5 5 6 20
20
62 4 66 98 14 1 83 43 65 83 93 18 72 53 72 44 78 69 51 52 32 62 3 2 26 13 5 20 12 3 4 2 6 4 1 6 1 4 4 4 5 19
100
43 3 44 45 8 1 40 29 62 65 78 7 66 39 55 32 55 58 23 39 15 33 2 1 13 4 3 8 4 1 1 1 3 1 0 1 1 2 1 1 3 8
* *
TENAX TA
(Polymer) Surface Area: 35 m2/g Desorption Temperature: 300 C
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl Chloride 1,3-Butadiene Bromomethane Ethyl Chloride Halocarbon 11 Acrylonitrile 1,1-Dichloroethylene Methylene Chloride 3-Chloropropylene Halocarbon 113 1,1 Dichloroethane cis-1,2 Dichloroethane Chloroform 1,2 Dichloroethane 1,1,1 Trichloroethane Benzene Carbon Tetrachloride 1,2-Dichloropropane Trichloroethylene cis-1,3 Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethylene Chlorobenzene Ethylbenzene m,p-Xylene Styrene 1,1,2,2-Tetrachlorethylene o-xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachloro-1,3-butadiene 0 0 2 0 1 1 5 39 154 101 126 143 11 138 143 147 130 107 161 114 147 157 193 220 167 161 214 182 180 160 149 180 148 148 171 159 166 184 184 185 213 178

0 0 1 0 1 0 0 10 116 6 5 56 6 98 110 118 118 68 125 77 122 120 152 169 128 124 155 133 129 121 117 129 121 116 124 115 117 123 124 123 121 123 0 0 0 0 0 0 0 0 72 0 0 0 2 2 2 8 47 21 57 25 78 59 97 124 90 92 106 82 88 92 96 90 107 96 95 95 94 88 90 88 81 82 0 0 0 0 0 0 0 0 64 0 0 0 1 0 0 0 4 12 15 13 57 27 86 115 86 90 105 81 93 99 96 96 104 97 99 100 100 97 99 97 100 100
20
0 0 0 0 0 0 0 0 57 0 0 0 1 0 0 0 1 8 2 7 29 8 57 98 78 86 99 76 88 91 94 91 105 95 93 90 89 87 88 87 80 82
100
0 0 0 0 0 0 0 0 29 0 0 0 0 0 0 0 0 0 1 0 0 3 0 1 2 2 5 2 40 83 95 93 115 99 105 105 106 103 105 106 103 104
TENAX GR
( Polymer) Surface Area: 24 m2/g Desorption Temperature: 300 C
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl Chloride 1,3-Butadiene Bromomethane Ethyl Chloride Halocarbon 11 Acrylonitrile 1,1-Dichloroethylene Methylene Chloride 3-Chloropropylene Halocarbon 113 1,1 Dichloroethane cis-1,2 Dichloroethane Chloroform 1,2 Dichloroethane 1,1,1 Trichloroethane Benzene Carbon Tetrachloride 1,2-Dichloropropane Trichloroethylene cis-1,3 Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethylene Chlorobenzene Ethylbenzene m,p-Xylene Styrene 1,1,2,2-Tetrachlorethylene o-xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachloro-1,3-butadiene 1 2 3 3 17 8 54 53 146 121 150 139 25 136 138 143 126 131 156 126 141 151 181 207 159 159 204 182 175 157 149 178 148 148 169 155 164 184 187 189 226 195

0 0 1 0 2 1 2 11 111 20 21 89 10 102 113 116 109 83 120 86 115 114 142 161 121 125 150 132 134 126 118 130 123 118 130 120 124 132 131 132 132 130 0 0 0 0 0 0 0 1 87 1 1 2 3 6 14 17 79 27 82 27 91 79 100 116 90 92 104 82 92 95 94 89 103 95 95 95 94 89 91 90 86 86 0 0 0 0 0 0 0 0 93 0 0 1 2 1 3 2 25 13 41 13 79 61 98 116 91 94 110 88 97 101 97 97 103 98 101 101 102 100 101 100 111 107
20
0 0 0 0 0 0 0 0 89 0 0 0 1 1 2 1 8 8 17 7 64 37 91 109 94 98 110 93 97 98 98 94 109 98 102 98 98 95 95 95 87 89
100
0 0 0 0 0 0 0 0 91 0 0 0 0 0 1 0 1 1 2 1 2 6 4 23 17 46 47 23 84 94 99 93 110 100 101 103 104 100 103 102 115 103
Chromosorb 106
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl chloride 1,3-Butadiene Bromomethane Chloroethane Halocarbon 11 Acrylonitrile 1,1-Dichloroethene Methylene chloride 3-Chloropropene Halocarbon 113 1,1-Dichloroethane cis-1,2-Dichloroethene Chloroform 1,2-Dichloroethane 1,1,1-Trichloroethane Benzene Carbon tetrachloride 1,2-Dichloropropane Trichloroethene cis-1,3-Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethene Chlorobenzene Ethylbenzene m & p-Xylene Styrene 1,1,2,2-Tetrachlorethane o-Xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene * 1 13 101 5 65 17 109 104 64 86 105 118 86 107 103 101 109 96 94 90 99 83 103 111 89 84 92 80 82 83 83 56 87 83 66 72 70 62 62 61 51 45

0 7 1 0 5 0 0 52 28 46 43 105 95 109 108 107 111 104 108 99 111 95 122 135 108 106 119 100 104 110 121 79 112 123 67 70 68 64 63 67 50 46 0 7 0 0 4 0 0 0 7 1 0 1 53 40 39 68 77 76 76 65 82 59 84 92 82 82 82 81 83 89 86 58 83 80 69 67 66 66 65 64 50 45 0 10 0 0 4 0 0 0 4 1 0 0 5 1 1 9 61 70 77 57 102 61 112 126 104 104 105 95 97 93 93 72 95 91 82 79 75 77 77 74 52 47
20
0 5 0 0 4 0 1 0 12 1 1 0 1 0 1 1 3 30 68 16 106 40 114 128 112 111 113 102 105 105 106 78 104 103 99 95 90 97 94 93 69 64
100
0 5 0 0 4 0 1 0 5 0 0 0 0 0 0 0 0 0 3 0 1 4 4 38 47 76 39 48 80 89 91 67 89 88 93 92 89 87 86 85 71 66
* * * * * * * * * * * *
Porapak N
0.2

0 0 2 0 5 0 0 33 91 66 92 105 79 95 95 93 94 88 88 88 92 85 100 113 88 86 97 83 83 84 94 85 94 96 96 89 86 95 95 94 80 80 0 0 0 0 4 0 0 1 74 1 1 16 62 86 89 93 94 91 91 92 93 89 103 114 92 90 100 90 89 91 95 90 95 95 91 91 91 90 90 90 81 80 0 0 0 0 4 0 0 0 72 0 0 0 10 18 21 77 95 90 93 75 93 91 104 116 96 97 105 97 96 94 94 91 99 94 94 93 93 92 92 91 83 82
20
0 0 0 0 4 0 0 0 71 0 1 0 2 1 0 13 81 48 67 19 109 94 124 136 114 107 125 112 108 105 111 110 109 111 113 107 107 116 113 114 99 99
100
0 0 0 0 3 0 0 0 11 0 0 0 0 0 0 0 0 1 0 0 37 1 58 109 95 92 102 77 93 91 92 87 95 92 91 90 89 93 92 91 83 81
HayeSep D
0.2

0 0 1 0 0 0 0 92 62 81 98 108 97 103 103 102 102 100 102 97 103 95 116 130 103 100 114 98 99 98 103 87 106 104 108 101 102 107 105 107 98 88 0 0 0 0 3 0 0 0 30 0 1 1 102 100 96 105 104 103 104 97 104 93 119 133 107 106 118 106 105 104 110 98 110 110 109 104 103 112 107 109 99 95 0 1 0 0 6 0 0 0 21 1 1 0 15 1 0 36 103 104 108 76 106 71 118 131 112 108 123 108 109 107 112 91 111 112 113 108 108 116 114 115 109 107
20
0 1 0 0 0 0 0 0 34 1 5 0 1 0 0 1 7 77 103 43 105 55 116 128 110 108 121 106 108 104 112 92 109 112 114 109 107 120 116 118 102 98
100
0 0 0 0 0 0 0 0 22 0 2 0 0 0 0 0 0 0 2 0 3 0 13 103 104 100 111 86 102 101 105 80 102 104 106 101 101 110 107 107 102 95
* *
Glass Beads
Surface Area: <5 m2/g Desorption Temperature: 330 C
0.2

0 0 0 0 0 0 0 0 74 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 3 29 60 73 1 2 2 24 5 0 0 0 0 0 0 0 0 15 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 2 3 2 0 3 6 14 23 2 3 3 12 4 0 0 0 0 0 0 0 0 11 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 11 22 1 1 1 9 2
20
0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 5 0 0 0 2 0
100
0 0 0 0 0 0 0 0 7 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 5 0 0 0 2 0
Silica Gel
Surface Area: 750 m2/g Desorption Temperature: 180 C
0.2

0 8 8 4 27 110 95 22 72 139 93 58 79 79 90 79 90 36 84 65 82 83 47 20 80 76 81 80 73 62 62 53 75 60 47 46 43 66 64 60 52 43 0 0 0 15 6 1 67 0 71 64 99 22 79 52 95 74 95 9 91 22 82 90 34 10 86 75 88 90 77 69 72 62 78 71 54 45 43 77 74 71 50 50 0 0 0 18 2 0 14 0 75 23 4 9 4 13 93 36 101 1 99 1 86 98 19 4 97 79 94 97 79 79 76 62 76 73 57 52 49 77 76 72 53 52
20
0 0 0 17 1 0 3 0 57 6 1 9 0 2 33 3 90 0 105 0 75 95 7 2 86 77 83 109 77 47 43 37 56 40 25 21 21 53 50 43 25 23
100
0 0 0 0 1 0 2 0 63 0 0 9 0 0 0 0 60 0 79 0 68 1 1 1 77 79 74 10 76 72 68 47 71 66 52 47 44 68 66 63 52 52
* * *
* * *
Coconut Charcoal
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl chloride 1,3-Butadiene Bromomethane Chloroethane Halocarbon 11 Acrylonitrile 1,1-Dichloroethene Methylene chloride 3-Chloropropene Halocarbon 113 1,1-Dichloroethane cis-1,2-Dichloroethene Chloroform 1,2-Dichloroethane 1,1,1-Trichloroethane Benzene Carbon tetrachloride 1,2-Dichloropropane Trichloroethene cis-1,3-Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethene Chlorobenzene Ethylbenzene m & p-Xylene Styrene 1,1,2,2-Tetrachlorethane o-Xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene * * * 90 117 57 82 0 3 66 48 42 42 63 23 22 29 25 26 22 21 5 21 7 10 3 2 5 1 2 1 0 0 0 0 1 0 0 0 1 0 0 1 3 1

95 71 64 95 0 20 76 53 56 51 73 38 27 38 37 33 28 25 9 22 12 15 8 6 8 2 5 3 1 1 0 1 2 1 0 0 1 0 0 0 4 2 110 3 64 87 52 1 74 53 60 50 76 36 30 38 37 35 29 26 9 23 12 15 9 7 9 2 5 3 1 1 0 1 2 1 0 0 0 0 0 0 3 2 74 1 59 62 48 1 58 50 59 47 72 33 32 37 36 35 29 27 10 24 12 15 9 7 10 2 6 3 1 1 0 1 3 1 0 0 0 0 0 0 2 1
20
29 3 53 29 42 1 44 46 62 44 67 32 31 35 35 34 27 25 11 23 12 14 9 7 10 2 6 3 1 1 0 1 3 1 0 0 0 0 0 0 2 1
100
0 11 21 2 16 1 1 21 44 23 14 14 20 21 21 21 18 17 7 15 8 11 6 5 7 1 4 2 1 0 0 0 2 0 0 0 0 0 0 0 1 1
* * * * * * * * * * * * * *
Petroleum Charcoal
0.2
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 Halocarbon 12 Chloromethane Halocarbon 114 Vinyl chloride 1,3-Butadiene Bromomethane Chloroethane Halocarbon 11 Acrylonitrile 1,1-Dichloroethene Methylene chloride 3-Chloropropene Halocarbon 113 1,1-Dichloroethane cis-1,2-Dichloroethene Chloroform 1,2-Dichloroethane 1,1,1-Trichloroethane Benzene Carbon tetrachloride 1,2-Dichloropropane Trichloroethene cis-1,3-Dichloropropene trans-1,3-Dichloropropene 1,1,2-Trichloroethane Toluene 1,2-Dibromoethane Tetrachloroethene Chlorobenzene Ethylbenzene m & p-Xylene Styrene 1,1,2,2-Tetrachlorethane o-Xylene 4-Ethyltoluene 1,3,5-Trimethylbenzene 1,2,4-Trimethylbenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene * 96 119 65 85 30 43 85 57 51 42 68 40 24 35 29 32 27 21 7 21 9 9 6 5 8 2 5 3 2 1 1 1 4 1 1 1 1 1 1 1 2 1

120 93 66 93 44 56 99 63 69 55 79 54 30 45 43 39 33 27 10 25 14 13 12 10 10 3 8 4 2 1 1 1 4 1 1 1 1 1 1 1 2 2 114 10 79 85 45 25 104 69 72 58 77 52 34 47 45 42 34 28 11 28 14 15 13 11 11 3 9 4 2 1 1 1 4 1 0 0 0 1 0 1 2 1 84 5 69 63 40 6 80 60 66 52 78 45 34 44 42 41 33 28 11 27 14 14 13 10 11 3 8 4 2 1 1 1 4 1 0 0 0 1 1 1 1 1
20
36 2 65 34 34 1 64 58 72 52 76 45 37 46 45 43 34 29 12 28 15 16 14 11 12 4 9 4 3 2 1 2 4 1 0 0 0 1 1 1 1 1
100
0 0 24 0 14 0 1 25 46 26 21 22 26 26 28 27 22 21 9 20 10 11 10 7 9 2 6 3 1 1 0 1 2 1 0 0 0 0 0 0 0 0
* * * * * * * * * * * * * * * * * *
For expert answers to your questions contact our Technical Service Department: Phone 800-359-3041, 814-359-3041 Fax 800-359-3044, 814-359-5468 E-mail techservice@sial.com To download Supelco's free technical literature visit us at sigma-aldrich.com/supelco-literature
sigma-aldrich.com/supelco
Order/Customer Service 800-247-6628, 800-325-3010 Fax 800-325-5052 E-mail supelco@sial.com Technical Service 800-359-3041, 814-359-3041 Fax 800-359-3044, 814-359-5468 E-mail techservice@sial.com
SUPELCO l Supelco Park, 595 North Harrison Road, Bellefonte, PA 16823-0048 l 814-359-3441 We are committed to the success of our Customers, Employees and Shareholders through leadership in Life Science, High Technology and Service.
The SIGMA-ALDRICH Family

T402025 EQF 2001 Sigma-Aldrich Co. Printed in USA. Supelco brand products are sold through Sigma-Aldrich, Inc. Sigma-Aldrich, Inc. warrants that its products conform to the information contained in this and other Sigma-Aldrich publications. Purchaser must determine the suitability of the product(s) for their particular use. Additional terms and conditions may apply. Please see reverse side of the invoice or packing slip.

Guia Escolha Adsorvente para DT - SUPELCO

Enviado por

Dados do documento

Descrição original:

Título original

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Guia Escolha Adsorvente para DT - SUPELCO

Enviado por

Direitos autorais:

Formatos disponíveis

Supelco Park 595 North Harrison Road Bellefonte, PA 16823-0048 USA Telephone 800-247-6628 814-359-3441 Fax 800-447-3044 814-359-3044

044 email: supelco@sial.com sigma-aldrich.com/supelco

We are committed to the success of our Customers, Employees and Shareholders t h r o u g h l e a d e r s h i p i n L i f e S c i e n c e , H i g h Te c h n o l o g y a n d S e r v i c e .

Figure 1. GERSTEL TDS A Coupled to a HP6890GC/5973MSD

Physical Properties of Adsorbents

Elution Order SPB-1 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31,32 33 34 35 36 37 38 39 40 41 42 43

SS Clip Glass wool plug

Flow direction during the Challenge Flow direction during Desorption

Glass Frit Inlet of the tube

Table 3. Operating Conditions GERSTEL TDS A Parameters

HP-6890 GC Parameters Oven Program

Ramp 1 Rate 1 Temp

Ramp 1 Hold Time Rate 2

Final Hold Time 8 min

35C 8.00 min 5C/min 100C

0 min 15C/min 230C

HP-5973 MSD GERSTEL CIS-4 Inlet Parameters

Adsorbent Tube Injector System

Cryo-Focusing Trap CIS-4 Inlet Liner (Physical Data)

Note: The actual adsorbent tube is not heated.

Glass Wool Type

Setting Up the Challenge Volume

Figure 4. The Analysis Matrix

The Challenge Volume Parameters

Challenge Volume (Liters) 0.2L 1L 5L 10L 20L 100L

The Analysis Matrix

Calculating the Recovery of the First Desorption

Calculating the Recovery of the Second Desorption

Calibration Procedures for the Analytical System

Challenge Flow Direction Desorption Flow Direction

Data pertinent to each adsorbent can be found here

Boiling Point Increases

Too Strongly Retained

General Guidelines for Interpreting the Trends

Using the Charts to Design a Multi-Bed Tube

Sampling Direction (In order of increasing adsorbent strength)

Questions & Answers

Why was an Internal Standard not used?

What mesh size were the adsorbents?

Why was nitrogen used instead of air to challenge the tubes?

Could the desorption temperature have an affect on recovery?

What is the difference between Carbopacks and Carbotrap?

Why was 50mL/min chosen as the sampling flow rate?

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10

Challenge Volume (Liters) 1 5 10