Manometric Gas Sorption Analyzers - LabSolutions

Hiden Isochema IMI SeriesManometric Gas Sorption Analyzerswww.hidenisochema.com

About Hiden IsochemaHiden Isochema is a world leader in the design andmanufacture of sorption instruments for research,development and production applications in surfacechemistry and materials science.We have been producing sorption measurementsystems since 1992 when Hiden Analytical first beganmanufacturing the Intelligent Gravimetric Analyzer (IGA).Following a decade of continued success, Hiden Isochemawas formed as a wholly-owned subsidiary of Hiden Analyticalin order to further specialize in the development andmanufacture of sorption-specific instrumentation.Since then, we have expanded our product range toinclude unique climate control and manometricsorption systems, and we continue to strengthen ourreputation for delivering high quality and versatileinstrumentation while providing industry-leading levelsof technical support.

IMI Series OverviewPowerful Tools for Sorption ScienceThe IMI series offers a multifunctional platform for the study of physisorption, chemisorption and gas absorption by materials,from entry level manometric analyzers to advanced multistream dynamic flow systems with integrated mass spectrometry.These versatile instruments satisfy the demands of a diverse range of applications, from surface area determination to highpressure studies, from gas storage and separation to high pressure catalysis.The key features of the IMI series include:Fully upgradable modular designStatic and dynamic operational mode optionsAutomatic switching between static and multistream operationMulti-gas control providing programmable sorbate selectionVersatile instrument control from standard methods to complete user defined experimentsAdaptive analysis software including end point detection for sorption processes,reaction kinetics and sample pretreatmentFull integration of mass spectrometers from Hiden’s quadrupole rangeenabling synchronized instrument control and data acquisition

Principles of OperationStatic ModeThe manometric gas sorption measurements performedby IMI systems utilize a change in pressure within a fixedvolume to determine the amount of gas sorbed or desorbedby a sample.ValveHelium GasWorking GasValveUpon pressurization, the number of moles of gas, n m , in anIMI system of volume, V, is given by the real gas law,Dosing Volume V 1n m = pVZRT(1)PressureSensorValveValveDuring a sorption experiment, an aliquot of gas is deliveredfrom a dosing volume, V 1 , to the reactor volume, V 2 , byopening a separating valve. In the absence of sorption,the instantaneous pressure drop from the initial dosingpressure, p 1 , to the final pressure, p 2 , is given by thefollowing molar balance,V 2ReactorVolumep 1V 1= p 2(V 1 +V 2)ZRT ZRT(2)Figure 1 A schematic diagram of an IMI manometric sorptionanalyzerA drop in pressure beyond p 2 indicates that sorption hasoccurred. The amount of gas sorbed, Δn m , is then calculatedfrom the final equilibrium pressure, p 3 ,∇n m = p V 1 1 _ p 3(V 1 +V 2)ZRT ZRT(3)For a high quality measurement, p x and V x must be knownaccurately and, in Eq. (3), the temperature, T, is assumed tobe constant. Since the sample held inside V 2 is often at asignificantly different temperature to V 1 , the temperaturedifferential must be accounted for by modifying Eq. (3)appropriately.pp 1p 2p 3PressurizationStabilizationDosingSorptionA full gas sorption isotherm can be determined bysequentially dosing gas and recording the equilibrium uptakeat various pressures. The reversal of the process results inthe measurement of the corresponding desorption isotherm.tFigure 2 A schematic plot of a single dosing step, showingpressure as a function of time during a manometric sorptionmeasurement

Principles of OperationDynamic ModeReactor SealThermocoupleSampleTemperatureControl ZoneIn addition to static mode operation, IMI systems equippedwith Mass Flow Controllers (MFCs) can also functionin dynamic (flowing) mode for the measurement ofTemperature Programmed Desorption (TPD), and theperformance of gas mixture and exchange experiments.In a typical TPD experiment, a sample is loaded with gasin-situ at an elevated temperature and pressure. The sampleis then cooled, before a linear thermal ramp is used to drivethe desorption process, which is performed into an inertcarrier gas stream. The active species can then be detectedand quantified using an integrated quadrupole massspectrometer or by observing a change in the composition ofthe gas flowing through an outlet MFC. The amount ofdesorbed gas can then be calculated by integrating the massspectrometer, or flow composition, signal to give,t 1n tot = ∫n(t)dtt 0(4)Gas InletSampleGas OutletFigure 3 A layout drawing of the standard IMI reactor, indicatingthe reactor gas flow path for dynamic (flow) experimentswhere n tot is the total number of moles of desorbed gas, n(t)is the number of moles of gas desorbed as a function of time,and t 0 and t 1 are the start and end times of the experiment.Furthermore, the characteristic temperature of desorptioncan be determined from the peak positions in a TPDspectrum, while activation energies can be calculated fromthe shift in the peak position as a function of the appliedtemperature ramp rate.Mass FlowControllerPressureSensorOptional MassSpectrometerHelium GasMass FlowControllerWorking GasMass FlowControllerSample TemperatureControl ZoneFigure 4 A schematic diagram of an IMI dynamic (flow) systemVacuumSystem

Standard IMI SystemsThe IMI series consists of a number of standard instrument configurations, each of which is optimized for a specific applicationor research area, as shown in the diagrams below. Additionally, the modular design makes it straightforward to retrospectivelyupgrade each IMI system in order to satisfy your future research needs.Static Gas Delivery LinesStatic Gas Delivery LinesIMI-HTPIMI-PSIDosing VolumeVacuumSystemDosing VolumeVacuumSystemReactorVolumeThermostatReactorVolumeLN 2 DewarLN 2AutorefillIMI-HTP:For hydrogen storage studiesIMI-PSI:For nanoporous materialsStatic Gas Delivery LinesGas Delivery LinesOptional MassSpectrometerSCF ReservoirIMI-NRGIMI-FLOWSupercriticalFluid (SCF)CompressorDosing VolumeReactorVolumeVacuumSystemDosing VolumeReactorVolumeVacuumSystemThermostatThermostatIMI-NRG:For energy and environmental researchIMI-FLOW:For dynamic flow studiesLegendGas lineMass flowHigh range pressure sensorAutomatic diaphragm valveOptional componentcontrollerLow range pressure sensorBursting disc

IMI ApplicationsAll IMI systems can be used to study physisorptionand chemisorption, as well as the absorption of gases bymaterials. Time-dependent measurements allow theobservation of sorption kinetics, while equilibrium uptakedetermination at different temperatures can be used for thecalculation of sorption enthalpies.In addition, each model in the IMI range has been optimizedfor specific application areas:High accuracy hydrogen storage material analyzerHydrogen StorageMethane Storage•Metal and Complex HydridesEnthalpy of Formation/Decomposition DeterminationExtended pressure sorption analysis system for nanoporous mediaPorous Material Characterization•Specific Surface Area (BET) DeterminationPore Size Distribution Calculation(Micro) Porosity and Free Volume MeasurementConfined Fluid and Capillary Condensation AnalysisVersatile sorption analyzer for energy and environmental scienceCarbon Capture and StorageShale Gas and Coal Bed MethaneGeological CO 2 SequestrationGas Solubility in Ionic Liquids• Oxygen StorageState-of-the-art dynamic flow and thermal desorption systemGas Separation and PurificationIsotope Exchange (SSITKA)•Breakthrough Curve DeterminationHigh Pressure Catalysis and Catalyst DeactivationTemperature Programmed Studies (TPR/TPO/TPD)IMI-HTPIMI-PSIIMI-NRGIMI-FLOW

IMI-HTPHigh Accuracy Hydrogen Storage Material AnalyzerThe IMI-HTP is designed primarily for the investigation ofnovel hydrogen storage materials using Sieverts’ Method upto pressures of 200 bar. It offers highly automated sorptionmeasurement procedures, as well as full control over allexperimental parameters. This flexibility enables fullyprogrammable operation throughout the entire measurementpressure range, with the sample temperature controllablefrom ambient up to 773 K. Optional cryocooling can extendthis range down to cryogenic temperatures.The system hardware, including the stainless steelconstruction, all-metal seals, and oil-free vacuum degassingcapability, is specified to meet the challenging demands ofhigh pressure hydrogen operation, while the reactor featurespermanent overpressure protection to satisfy the mostrigorous safety requirements.The instrument’s inherent flexibility allows users tocharacterize the fundamental properties of hydrogen storagematerials by determining PCT (Pressure-Composition-Temperature) relations, kinetic rates of absorption anddesorption, and van ’t Hoff plots for the calculation of sorptionenthalpies. Applied experiments, such as cyclic thermal andpressure stability testing, can then be used to assess thepotential of a material to suit real-world applications.H2 pressure / mbar600005000040000300002000010000333 K343 K353 K363 K373 K383 K00 0.2 0.4 0.6 0.8 1 1.2 1.4Hydrogen content / Weight %ModelKey FeatureMax. PressureApplicationsIMI-HTPSub-μg Hydrogen SorptionResolution100 / 200 barPCT MeasurementsEnergy Gas StorageMetal HydridesSorption Enthalpy DeterminationFigure 5 Desorption isotherms for the LaNi 5 -H system,measured at six temperatures using an IMI-HTP hydrogenstorage material analyzer

IMI-PSIExtended Pressure Sorption Analysis System for Nanoporous MediaThe IMI-PSI is specifically designed for the investigation ofgas sorption by nanoporous materials, at both low(cryogenic) and elevated temperatures. It allows theadsorption behaviour of porous solids to be characterized atthe temperatures and pressures relevant for gas storage, gasseparation and other sorption-based technologies. Thesystem can also be used to determine the surface area andother pore structure characteristics of nanoporous materials.Operation is available up to 200 bar, and an additional highaccuracy 1 bar pressure range is also included as standard.This provides optimum resolution at the sub-ambientpressure conditions required for the study of gas-solidsurface interactions.Supplied with an immersion reactor and high performanceDewar, the IMI-PSI provides optimal thermal stability atcryogenic temperatures, which is a crucial factor for highaccuracy measurement. The IMIwin software features arange of data fitting functions, including BET analysis for thedetermination of the specific surface area, and DA and HKanalysis for the characterization of the pore size distribution.An automated Dewar refill device is also available, whichallows extended periods of operation at cryogenictemperatures. This option further increases the degree ofinstrument automation, allowing longer unattendedmeasurement times.Uptake (wt %. d.b.)3.532.521.51BET Surface Area AnalysisBET area = 79.56 +/- 0.24 m 2 /gp/n(p 0 -p)16141210864ModelKey FeatureMax. PressureApplicationsIMI-PSI77 K Liquid Nitrogen ImmersionReactor (1 cm 3 )100 / 200 barPorous Materials0.50200 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40p/p 00 0.05 0.10 0.15 0.20 0.25 0.30 0.35BET Surface AreaPore Size Distribution AnalysisIsotherm Hysteresisp/p 0Figure 6 BET analysis of the specific surface area of theBAM-PM-104 Standard Reference Material measured on anIMI-PSI, using nitrogen adsorption at 77 K. The inset shows theBET plot, with the fit performed using the relative pressure range,p/p 0 = 0.08 to 0.3

IMI-NRGVersatile Sorption Analyzer for Energy and Environmental ScienceThe IMI-NRG provides a fully integrated system for energyand environmental science research. It has been developedspecifically for the characterization of materials for gasseparation, capture and storage applications, which havemany potential uses in this field, including the storage ofenergy gases, and CO 2 capture and sequestration.High pressure operation to 200 bar is offered asstandard with a high accuracy pressure sensor for thefull measurement range. The IMI-NRG comes complete withan integral supercritical fluid (SCF) compressor, which allowsthe study of CO 2 adsorption at elevated temperatures acrossthe entire pressure range into the supercritical phase, usingonly a standard gas cylinder.The IMI-NRG incorporates superior thermostatting andenhanced anti-condensation protection, due to the sensitivityof CO 2 adsorption measurements to temperaturefluctuations, particularly in the near-critical region. A largecapacity sample reactor is also available, which allows theperformance of sensitive measurements on bulkier samplesor those exhibiting relatively low gas uptakes.11ModelIMI-NRG10Uptake (wt %. d.b.)9876543210300 K308 K313 K318 K323 K328 K333 K0 10000 20000 30000 40000 50000 60000Pressure (mbar)Key FeatureMax. PressureApplicationsSupercritical Fluid (SCF)Compressor200 barCarbon Capture and StorageGeological CO 2 /CH 4Gas Solubility in Ionic LiquidsOxygen StorageFigure 7 Reversible methane sorption isotherms measured on acommercial activated carbon (Filtrasorb F-400) in an IMI-NRG witha large sample reactor between room temperature and 333 K.Adsorption is shown with a solid line while desorption is dashed

IMI-FLOWState-of-the-Art Dynamic Flow and Thermal Desorption AnalyzerH2 desorption rate / μg min -13.532.521.510.5Hydrogen SignalSample Temperature600550500450400350300250200Temperature / KThe IMI-FLOW combines the static mode measurementcapabilities of the full IMI range with unique dynamic (flowing)mode operation, allowing the performance of TemperatureProgrammed Desorption (TPD) as well as mixed gasexperiments. High performance MFCs are used to regulatethe flow of gas, while the integrated sample reactor heatingsystem allows the precise control of the applied linearthermal ramp rates. Optional liquid nitrogen cryocoolingallows the performance of TPD from cryogenic temperatures.01502 4 6 8 10 12 14 16 18 20 22 24Time / minFigure 8 A thermal desorption (TPD) spectrum showingthe amount of hydrogen released from a 3 mg Pd samplehydrogenated in-situ at an elevated temperature and pressure inan IMI-FLOW. The hydrogen signal was determined using anoptional dynamic sampling mass spectrometerIn the IMI-FLOW, thermal desorption is performed into aninert carrier gas stream and detected using a downstreamMFC or an optional integrated quadrupole massspectrometer. The design of the instrument incorporatesa low volume gas pathway for both a rapid response andmaximum sensitivity. The addition of a dynamic samplingquadrupole mass spectrometer for evolved gas analysis,combined with multiple flow streams, also allows theperformance of gas mixture and exchange experiments.The versatile and integrated nature of the IMI-FLOW, whichallows direct control of a close-coupled mass spectrometerfrom the IMIwin software suite, makes it a unique andsophisticated analysis system.CH4 flow / ml min -1 CO2 flow / ml min -15040302010030 35 40 45 50 55604020030 35 40 45 50 55Time / min6420-2-4-6-8Displaced CH 4 / mlModelKey FeatureMax. PressureApplicationsIMI-FLOWDynamic Gas Flow Control & IntegratedMass Spectrometer Compatibility100 / 200 barGas SeparationBreakthrough CurvesTPR/TPO/TPDCatalysis / SSITKAFigure 9 Dynamic flow experiment designed to determine thenature of selective adsorption of CO 2 over CH 4 . The inlet and outletCO 2 flows are shown above, while CH 4 flow/displacement andtemperature are shown below. See Hiden Isochema ApplicationNote 129 for more information

Reactor OptionsLarge Capacity Sample ReactorThis custom-designed reactor offers additional samplecapacity of up to 10 cm 3 , and therefore provides IMI systemswith the flexibility to investigate either low density samples,upscaled production methods or materials exhibiting onlymodest uptakes. Volume displacers are also available toaccommodate smaller samples. The large capacity samplereactor is fully compatible with the enhanced anticondensationprotection and liquid nitrogen cryocoolingoptions, and comes equipped with a 773 K integral heater asstandard.Removable ReactorThe removable reactor allows IMI systems to be used inconjunction with existing laboratory inert environmenthandling facilities. The reactor is designed to be easilydetached and transferred into a glovebox, in which airor moisture sensitive samples can be safely loaded orunloaded. The removable reactor comes complete with anintegral heater for sample degassing and temperaturecontrol.Cryocooling SystemLiquid nitrogen cryocooling provides accurate control at lowtemperatures for the standard, large capacity and removablereactors. The cryocooling system feeds liquid nitrogen to thereactor while the integrated heater allows the temperature tobe regulated and controlled precisely throughout the fulloperating temperature range. The circulation of the liquidnitrogen is driven by a dedicated pumping unit, which isconveniently mounted in the standard IMI mobile cart.

System AccessoriesSupercritical Fluid CompressorThe supercritical fluid compressor is an integrated systemthat delivers high pressure feed gas to an IMI sorptionanalyzer from a low pressure supply. The system isprincipally designed to deliver supercritical fluids, suchas carbon dioxide or ethane, at pressures above thoseof standard gas cylinders. Automatically controlled by theIMIwin software, the compressor continuously replenishes ahigh pressure reservoir to maintain the maximum supplypressure. Oil-free operation ensures the compressor systemdelivers high purity gas to the instrument without risk ofsample contamination.Detachable Sample Loading GloveboxThe detachable glovebox allows air or moisture sensitivesamples to be loaded and unloaded from an IMI system,under an inert atmosphere, in laboratories without dedicatedglovebox facilities. The glovebox is sealed onto the reactorflange and purged with dry inert gas from an external supply.It is mounted on a dedicated trolley and supplied completewith resealable storage and transfer vessels and a sparesample holder to enable rapid interchange.Expansion VolumesFor further flexibility, IMI systems may be fitted with a numberof expansion vessels to enlarge the dosing volume andhence provide different aliquot delivery capabilities. Thisprovides greater flexibility in the development of experimentalmethodology and allows the anticipated pressure changedue to sorption to be varied according to specific researchneeds. Up to four additional vessels can be included,providing up to 16 different dosing volume permutations,each of which may be automatically selected through theIMIwin software.

Customer SupportHiden Isochema believes that scientific and technical supportis as important as your custom, and counts customersatisfaction as the most important measure of excellence.User training and continued application-focused support arevital services that we consider to be integral to our products.Our field engineers offer a wealth of technical experience,while our PhD-qualified applications team offer both apractical and scientific perspective in order to provide youwith the very best in product support and customer service.This knowledge base, combined with our proactiveapproach, makes Hiden Isochema the respected leader inthe industry.As part of this commitment, we offer:•all instruments•on demand••Comprehensive 12 month warranties onOn-site installation, commissioning and trainingAdvanced or bespoke user training coursesLifetime technical support and free softwareupgrades for academic usersA 24 hour response time to scientific andtechnical support enquiriesHiden Isochema Quality and SafetyTo ensure the highest standards of safety, product andservice provision, Hiden Isochema is fully compliant witha number of key safety and quality codes:ISO 9001:2008 (BSI) Quality Standard••European Union Pressure Equipment Directive PED 97/23/ECEuropean Union Electromagnetic Compatibility and ElectronicSafety Directives 87/336/EEC and 73/23/ECDQ/IQ/OQ procedures (full certification supplied upon request)

Need More Information?Contact us now: info@hidenisochema.comor via www.hidenisochema.com

Technical Specifications:SystemConstructionWetted components:ManifoldsValve diaphragmsPressure transducer diaphragmsAll metalStainless steel (316L)ElgiloyHastelloy C276Typical Species Energy gases: Hydrogen, deuterium, methane, ethane, etheneAtmospheric/environmental gases: Nitrogen, oxygen, carbon dioxide, carbon monoxideNoble gases:Helium, neon, argon, krypton, xenonSupercritical fluids:Carbon dioxide, ethane, xenonSample Reactors Maximum bulk sample volume: ~1 cm 3 (Standard, Immersion, Removable Reactors)~10 cm 3 (Large Capacity Reactor)Construction material:Stainless steel (316L)Internal sample holder:Gold-plated copper (stainless steel available on request)Reactor seal:Cajon VCROverpressure protection:Permanent (electron beam welded nickel foil burst disc)Temperature Measurement range: 77 – 773 KTemperature sensors:Platinum Resistance Thermometer (Pt100) or Type-K thermocoupleAccuracy:± 1 K (Type-K) or ± 0.1 K (Pt100)Typical regulation accuracy:± 0.1 KCabinet regulation accuracy:± 0.1 KPressure Maximum operating pressure: 100 bar (optionally 200 bar)Typical accuracy:± 0.05 % of rangeTransducer ranges:2, 10, 100 mbar1, 10, 100, 200 barBase vacuum:< 10 -6 mbar with turbomolecular vacuum pumpCompressibility correction accuracy: 0.1 % (NIST fluid properties database)Sorption measurement resolution: < 1 μmolDynamic Gas FlowControl(IMI-FLOW)Control method:Thermal mass flow controlNumber of gas inlets: Up to 8Typical switching time:1 – 3 seconds for specified compositionMaximum flow rate: 1000 ml min -1Mass Spectrometer(IMI-FLOW)Coupling method:Heated stainless steel or Quartz Inert Capillary (QIC) inletAtomic mass range: 1 – 200 a.m.u. (standard)1 – 50 a.m.u (optimized for light gas detection)Detector:Dual Faraday/electron multiplierIt is Hiden Isochema’s policy to continually improve product performance and therefore specifications are subject to change.Hiden IsochemaAdvancing Sorption AnalysisHiden Isochema LtdTel: +44 (0) 1925 244 678Fax: +44 (0) 1925 244 664Email: info@hidenisochema.comWeb: www.hidenisochema.com