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Physical Adsorption

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Chapter2

PhysicalAdsorption

The literature pertaining to the sorption of gases by solids is now so vast that it is

impossible for any, except those who are specialists in the experimental technique,

rightlytoappraisethework,whichhasbeendone,ortounderstandthemaintheoretical

problemswhichrequireelucidation.J.E.LennardJones,19321

Adsorptionisthephenomenonmarkedbyanincreaseindensityofafluidnearthe

surface,forourpurposes,ofasolid.*Inthecaseofgasadsorption,thishappenswhen

moleculesofthegasoccasiontothevicinityofthesurfaceandundergoaninteraction

with it, temporarily departing from the gas phase. Molecules in this new condensed

phase formed at the surface remain for a period of time, and then return to the gas

phase.Thedurationofthisstaydependsonthenatureoftheadsorbingsurfaceandthe

adsorptive gas, the number of gas molecules that strike the surface and their kinetic

energy (or collectively, their temperature), and other factors (such as capillary forces,

surfaceheterogeneities,etc.).Adsorptionisbynatureasurfacephenomenon,governed

bytheuniquepropertiesofbulkmaterialsthatexistonlyatthesurfaceduetobonding

deficiencies.

Adsorptionmayalsooccuratthesurfaceofaliquid,orevenbetweentwosolids.

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landscape, dotted with wells of varying depths corresponding to adsorption sites (a

simplifiedrepresentationisshowninFigure2.1).Asinglegasmoleculeincidentonthe

surface collides in one of two fundamental ways: elastically, where no energy is

exchanged, or inelastically, where the gas molecule may gain or lose energy. In the

former case, the molecule is likely to reflect back into the gas phase, the system

remainingunchanged.Ifthemoleculelackstheenergytoescapethesurfacepotential

well, it becomes adsorbed for some time and later returns to the gas phase. Inelastic

collisions are likelier to lead to adsorption. Shallow potential wells in this energy

landscape correspond to weak interactions, for example by van der Waals forces, and

thetrappedmoleculemaydiffusefromwelltowellacrossthesurfacebeforeacquiring

the energy to return to the gas phase. In other cases, deeper wells may exist which

correspondtostrongerinteractions,asinchemicalbondingwhereanactivationenergy

is overcome and electrons are transferred between the surface and the adsorbed

Figure2.1.Apotentialenergylandscapeforadsorptionofadiatomicmoleculeonaperiodic

twodimensionalsurface.Thedepthoftheenergywellisshowninthezaxis.

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molecule.Thiskindofwellishardertoescape,thechemicallyboundmoleculerequiring

a much greater increase in energy to return to the gas phase. In some systems,

adsorptionisaccompaniedbyabsorption,wheretheadsorbedspeciespenetratesinto

thesolid.Thisprocessisgovernedbythelawsofdiffusion,amuchslowermechanism,

andcanbereadilydifferentiatedfromadsorptionbyexperimentalmeans.

Intheabsenceofchemicaladsorption(chemisorption)andpenetrationintothebulk

ofthesolidphase(absorption),onlytheweakphysicaladsorption(physisorption)case

remains. The forces that bring about physisorption are predominantly the attractive

dispersion forces (named so for their frequency dependent properties resembling

optical dispersion) and shortrange repulsive forces. In addition, electrostatic

(Coulombic)forcesareresponsiblefortheadsorptionofpolarmolecules,orbysurfaces

with a permanent dipole. Altogether, these forces are called van der Waals forces,

namedaftertheDutchphysicistJohannesDiderikvanderWaals.

2.1

VanderWaalsForces

Anearlyandprofoundlysimpledescriptionofmatter,theideallawcanbeelegantly

derivedbymyriadapproaches,fromkinetictheorytostatisticalmechanics.Firststated

bymileClapeyronin1834,itcombinesBoyleslaw(PV=constant)andCharlesslaw

(stating the linear relationship between volume and temperature) and is commonly

expressedintermsofAvogadrosnumber,n:

Equation2.1

16

Thissimpleequationdescribesthemacroscopicstateofathreedimensionalgasof

noninteracting,volumelesspointparticles.Thegasconstant,R,isthefundamentallink

between microscopic energy and macroscopic temperature. While satisfactory for

describing common gases at low pressures and high temperatures, it is ineffective for

real gases over a wide temperature and pressure regime. A better approximation was

determined by van der Waals, combining two important observations:2 a) the volume

excludedbythefinitesizeofrealgasparticlesmustbesubtracted,andb)anattractive

force between molecules effects adecreased pressure. The suggestion of an excluded

real gas volume was made earlier by Bernoulli and Herapath, and confirmed

experimentally by Henri Victor Regnault, but the attractive interactions between

moleculeswastheimportantcontributionbyvanderWaals.Thechangeinpressuredue

to intermolecular forces is taken to be proportional to the square of the molecular

density,givingthevanderWaalsequationofstate:

Equation2.2

Atthetime,vanderWaalswasadamantthatnorepulsiveforcesexistedbetween

what he reasoned were hard sphere gas particles. Interestingly, it was James Clerk

MaxwellwhocompletedandpopularizedvanderWaals(thenobscure)workinNature3

and also who later correctly supposed that molecules do not in fact have a hard

sphere nature. Nevertheless, the sum of the attractive and repulsive forces between

atomsormoleculesarenowcollectivelyreferredtoasvanderWaalsforces.Forces

17

betweenanyelectricallyneutralatomsormolecules(therebyexcludingcovalent,ionic,

and hydrogen bonding) conventionally fall into this category. Together, these include:

Keesom forces (between permanent multipoles), Debye forces (between a permanent

multipole and an induced multipole), London dispersion forces (between two induced

multipoles),andthePaulirepulsiveforce.

2.1.1 IntermolecularPotentials

Inhistime,therangeofvanderWaalsattractiveinteractionwaspredictedtobeof

molecular scale but the form of the potential as a function of distance, U(r), was

unknown. There was unified acceptance that the attraction potential fell off with

distance as r, with > 2 (the value for that of gravitation), but the value of was

activelydebated.

In parallel with the effort to determine this potential, a noteworthy advance in the

generaldescriptionofequationofstatewasthevirialexpansionbyH.K.Onnes:4

Equation2.3

Perhapsmostimportantly,thisdescriptionsignifiedarealizationoftheunlikelihood

that all gases could be accurately described by a simple closed form of equation.

Additionally, the second virial coefficient, B(T), by its nature a firstneighbor term of

interaction, sheds insight on the attractive potential between molecules. A major

breakthrough followed, culminating in the theory now attributed to Sir John Edward

LennardJones, an English theoretical physicist. His description of the potential energy

18

betweentwointeractingnonpolarmoleculesused=6andarepulsivetermoforder

12:5,6

Equation2.4

TheresultconstitutesabalancebetweenthelongerrangeattractivevanderWaals

potential (of order r6) with the shortrange repulsive potential arising from electron

orbital overlap (of order r12), described by the Pauli exclusion principle, and is also

referredtoasa612potential.Itapproximatesempiricaldataforsimplesystemswith

gratifying accuracy, and has the added advantage that it is computationally efficient

since r12 is easily calculated as r6 squared, an important consideration in its time. A

representativeplotofthispotentialisshowninFigure2.2.

Figure2.2.TheLennardJones612potential,scaledinunitsofU0,thedepthofthewell.The

equilibriumdistancebetweentheinteractingspeciesisr=r0.

19

Atfardistances(r>>r0),themagnitudeoftheinteractionpotentialisnegligible.Ifthe

speciesbecomespontaneouslyclosertogether(e.g.,astheresultofrandomcollision),it

isfavorableforthemtoremainataspecificdistanceapart,namelyr=r0.Atveryshort

distance,thePaulirepulsiontermdominatesandthesystemisunfavorable.

Anumberofsimilarpotentialformsaroseshortlyafterward(usingvariousformsfor

thePaulirepulsiontermsuchasanexponentialorotherpowerofordernear12),and

anearlytriumphofthesemodelswasaccuratelyfittingthesecondvirialcoefficientof

simplegases,suchasheliumforwhichtheequilibriumHeHedistancewascalculatedto

ber0=2.9in1931.Thisvalueremainsaccuratewithin2%today.

Coincidentally,LennardJonesworkwasoriginallyundertakentoattempttoexplain

apuzzlingobservationmadeduringvolumetricadsorptionmeasurementsofhydrogen

onnickel,7,8showingtwodistinctcharacteristicbindingpotentialsassociatedwith

differenttemperatureregimes.Thiswouldleadtothefirstexplanationofthe

differentiablenatureofadsorptionatlowandhightemperature(nowreferredto

separatelyasphysisorptionandchemisorption,respectively).Asaresultofitssuccess,

theLennardJonesinverseseventhpowerforce(fromtheinversesixthpowerpotential)

becamethebackboneofadsorptiontheory.

2.1.2 DispersionForces

Ther6LennardJonespotentialwasderivedfromfirstprinciplesandfirstexplained

correctly by the German physicist Fritz London;9, 10 hence, the attractive force that

occursbetweenneutral,nonpolarmoleculesiscalledtheLondondispersionforce.It

isaweak,longrange,nonspecificintermolecularinteractionarisingfromtheinduced

20

polarizationbetweentwospecies,resultingintheformationofinstantaneouselectrical

multipole moments that attract each other. Arising by rapid, quantum induced

fluctuations of the electron density within a molecule or atom (the reason they were

coined as dispersiveforces by London), the force is stronger between larger species

due to those species increased polarizability. The key to the correct explanation of

dispersion forces is in quantum mechanics; without the uncertainty principle (and the

fundamental quantummechanical property of zeropoint energy), two spherically

symmetric species with no permanent multipole could not influence a force on each

otherandwouldremainintheirclassicalrestposition.Thesubjectofdispersionforcesis

importanttomanyfields,andathoroughoverviewoftheirmoderntheorycanbefound

elsewhere.11

Thephysisorptionofnonpolarmoleculesoratomsonanonpolarsurface(aswellas

their liquefaction) occurs exclusively by dispersion forces. Dispersion forces are also

essential for explaining the total attractive forces between multipolar molecules (e.g.,

H2) for which typical static models of intermolecular forces (e.g., Keesom or Debye

forces)accountforonlyafractionoftheactualattractiveforce.Theexistenceofnoble

liquids (liquefied noble gases) is a fundamental verification of dispersion forces since

there is no other attractive intermolecular force between noble gas atoms that could

otherwiseexplaintheircondensation.

2.1.3 ModernTheoryofPhysicalAdsorption

Despite their correctexplanation over 80 years ago, dispersion forces are not well

simulated by typical computational methods, such as densityfunctional theory which

21

cannot accurately treat longrange interactions in weakly bound systems.12 The first

principles methods that are dependable are computationally intensive and are often

foregoneforempiricalpotentialssuchasaLennardJonespotentialasdescribedinthe

previous section.13,

14

physisorptivematerialshasbeenmuchlessthanthatforchemisorptivematerials,and

wasnotacomponentoftheworkdescribedinthisthesis.

22

2.2

GasSolidAdsorptionModels

A thermodynamic understanding of adsorption can be achieved by describing a

simplified system, and a small subset of important models will be discussed. The

constituentchemicalspeciesofthesimplestsystemareapuresolid,indexedass,anda

singlecomponent adsorptive gas, indexed as a in the adsorbed phase, g in the gas

phase,orxifitisambiguous.Thesystemisheldatfixedtemperatureandpressure.We

startwiththefollowingdescription:

(i)

theadsorptivedensity,x,iszerowithinanduptothesurfaceofamaterial,

(ii)

distancefromthesurface,and

(iii)

atdistancefromthesurface,xisequaltothebulkgasdensity,g.

Figure2.3.Asimplifiedrepresentationofagassolidadsorptionsystem(left)andanon

adsorbingreferencesystemofthesamevolume(right).Adsorptivedensity(green)isplotted

asafunctionofr.

23

AschematicofthissystemisshowninFigure2.3(left).Thefunctionalformofthe

densificationatthesorbentsurface,andthethicknessof theadsorptionlayerarenot

preciselyknown.However,theadsorbedamountcanbedefinedasthequantityexisting

inmuchhigherdensitynearthesurface,andiseasilydiscernedwhencomparedtothe

reference case of a nonadsorptive container, shown in Figure 2.3 (right). We may

assume that the gas pressure, Pg, is equal to the total hydrostatic pressure, P, of the

systematequilibrium,whichisconsistentwithordinaryexperimentalconditions.

2.2.1 MonolayerAdsorption

Thesimplestrepresentationofanadsorbedphaseisasanidealgas,constrainedtoa

twodimensionalmonolayerwherethereisnointeractionbetweenadsorbedmolecules:

Equation2.5

Here,PaisthespreadingpressureoftheadsorptionlayerandAaisitsareaofcoverage.

In the system described, the surface area for adsorption is fixed, as well as the

temperature.Ifwetakethespreadingpressureasproportionaltothatofthegasphase

inequilibriumwithit,wefindthattheamountadsorbedisalinearfunctionofpressure:

Equation2.6

This relationship, called Henrys law, is the simplest description of adsorption, and

applies to systems at low relative occupancy. When occupancy increases, the

relationshipbetweenthepressuresoftheadsorbedphaseandthegasphasebecomes

unknown,andamoregeneraltreatmentisnecessary.

24

thevanderWaalsequationofstatetotwodimensions:

Equation2.7

Forsimplicity,itisconvenienttodefineafractionalcoverageofthesurfaceavailablefor

adsorption,,asthenumberofadsorbedmoleculespersurfacesite,aunitlessfraction

thatcanalsobeexpressedintermsofrelativesurfacearea:

Equation2.8

Withthisdefinition,andamoreelegantdescriptionofthespreadingpressureofthevan

derWaalstwodimensionalphase,theHilldeBoerequationisderived:

Equation2.9

This equation has been shown to be accurate for certain systems, up to a maximum

coverage of = 0.5.15 Ultimately though, treatment of the adsorbed phase without

referencetoitsinteractionwiththesurfaceencountersdifficulties.

Amoreinsightfulapproachistotreatadsorptionanddesorptionaskineticprocesses

dependent on an interaction potential with the surface, also seen as an energy of

adsorption.Indynamicequilibrium,theexchangeofmassbetweentheadsorptionlayer

andthebulkgasphasecanbetreatedbykinetictheory;atafixedpressure,therateof

25

coverage.Thisequilibriumcanbedescribedbythefollowingscheme:

(mathematical) product of the concentrations of the reactants, ci, and a reaction

constant,K(T):

Equation2.10

Equation2.11

Correspondingly,forthereverse(desorption)reaction:

We can assume that the number of adsorption sites is fixed, so the concentration of

adsorbed molecules and empty adsorption sites is complementary. To satisfy

equilibrium, we set Equations 2.10 and 2.11 equal and express them in terms of the

fractionaloccupancy,recognizedasequivalenttoca:

1

Equation2.12

Arrheniustypeequation:

26

Equation2.13

Theratiooftheadsorptionanddesorptionconstantsis:

Ifthegasphaseisassumedtobeideal,itsconcentrationisproportionaltopressure,P.

Secondly, if we assume that the energy of the adsorbed molecule, Ea, is the same at

every site, and the change in energy upon adsorption, E, is independent of surface

coverage,theresultisLangmuirsisothermequation:

Equation2.14

TheLangmuirisotherm,inthecontextofitsinherentassumptions,isapplicableoverthe

entire range of . Plots of multiple Langmuir isotherms with varying energies of

adsorption are shown in Figure 2.4 (right). In the limit of low pressure, the Langmuir

isothermisequivalenttoHenryslaw:

lim

Equation2.15

TheplotsinFigure2.4showthetemperatureandenergydependenceoftheLangmuir

isotherm equation. With increasing temperature, the Henrys law region is marked by

moregradualuptake,asimilartrendasfordecreasingenergyofadsorption;bothtrends

areconsistentwithexperiment(insystemsreferredtoasexhibitingtypeIisotherms).

27

Figure2.4.Langmuirisothermsshowingthedependenceofadsorptionsiteoccupancywith

pressure,varyingtemperature(left)andenergyofadsorption(right).

Althoughitenjoysquantitativesuccessincharacterizingadsorptioninlimitedrangesof

pressure for certain systems, conformity of experimental systems to the Langmuir

equationisnotpredictable,anddoesnotnecessarilycoincidewithknownpropertiesof

the system (such as expected homogeneity of adsorption sites, or known adsorbate

adsorbate interactions).16 No system has been found which can be characterized by a

single Langmuir equation with satisfactory accuracy across an arbitrary range of

pressure and temperature.15 Langmuirs model assumes: 1) the adsorption sites are

identical,2)theenergyofadsorptionisindependentofsiteoccupancy,and3)boththe

two and threedimensional phases of the adsorptive are well approximated as ideal

gases. Numerous methods have been suggested to modify the Langmuir model to

generalizeitsassumptionsforapplicationtorealsystems.

28

characteristic energies, one possibility is to superimpose a set of Langmuir equations,

eachcorrespondingtoadifferenttypeofsite.ThisgeneralizedLangmuirequationcan

bewrittenas:

1

Equation2.16

The weight of each component isotherm, i, corresponds to the fraction of sites with

the energy Ei. This form of Langmuirs equation is applicable across a wide range of

experimental systems, and can lend insight into the heterogeneity of the adsorbent

surfaceandtherangeofitscharacteristicbingingenergies.Itstreatmentofadsorption

sitesasbelongingtoatwodimensionalmonolayercanbemadecompletelygeneral;

theadsorptionlayercanbeunderstoodasanysetofequallyaccessiblesiteswithinthe

adsorption volume, assuming the volume of gas remains constant as site occupancy

increases(anassumptionthatisvalidwhena>>g).Theapplicationofthisequation

forhighpressureadsorptioninmicroporousmaterialsisdiscussedinSection2.4.6.

2.2.2 MultilayerAdsorption

ApracticalshortcomingofLangmuirsmodelisindeterminingthesurfaceareaavailable

for adsorption. Typically, fitting experimental adsorption data to a Langmuir equation

results in an overestimation of the surface area.16 The tendency of experimental

isotherms toward a nonzero slope in the region beyond the knee indicates that

29

homogeneous adsorption sites at the sorbent surface, and a secondary phase

correspondingtoadsorptioninlayersbeyondthesurfaceoftheadsorbent.

An adaptation of Langmuirs model can be made which accounts for multiple,

distinctlayersofadsorption.Acharacteristicofadsorptioninamultilayersystemisthat

each layer corresponds to a different effective surface, and thus a different energy of

adsorption.Thedistinctionbetweenthemultilayerclassofsystemsandageneralized

monolayer system (such as in Equation 2.16) lies in the description of the adsorbent

surface; even a perfectly homogeneous surface is susceptible to a multiple layers of

adsorption, an important consideration at temperatures and pressures near the

saturation point. Brunauer, Emmett, and Teller successfully adapted the Langmuir

model to multilayer adsorption by introducing a number of simplifying assumptions.17

Most importantly, 1) the second, third, and ith layers have the same energy of

adsorption, notably that of liquefaction, and 2) the number of layers as the pressure

approaches the saturation pressure, P0, tends to infinity and the adsorbed phase

becomesaliquid.Theirequation,calledtheBETequation,canbederivedbyextending

Equation 2.12 to i layers, where the rate of evaporation and condensation between

adjacentlayersissetequal.Theirsummationleadstoasimpleresult:

1

Equation2.17

30

If the Arrhenius preexponential factors A1/A2 and A2/Al (from Equation 2.13) are

approximatelyequal,atypicalassumption,16theparametercBETcanbewritten:

Equation2.18

Thechangeinenergyuponadsorptioninanyofthelayersbeyondthesurfacelayeris

takenastheenergyofliquefaction,andthedifferenceintheexponentinEquation2.18

is referred to as the net molar energy of adsorption. Strictly within BET theory, no

allowanceismadeforadsorbateadsorbateinteractionsordifferentadsorptionenergies

atthesurface,assumptionsthatpreventtheBETmodelfrombeingappliedtogeneral

systemsandacrosslargepressurerangesofadsorption.

TheBETequationwasspecificallydevelopedforcharacterizingadsorptioninagas

solidsystemnearthesaturationpointoftheadsorptivegasforthepracticalpurposeof

determiningthesurfaceareaofthesolidadsorbent.Despiteitsnarrowsetofdefining

assumptions, its applicability to experimental systems is remarkably widespread. As a

result, it is the most widely applied of all adsorption models, even for systems with

knowninsufficienciestomeettherequiredassumptions.Nitrogenadsorptionat77Kup

to P0 = 101 kPa has become an essential characterization technique for porous

materials, and the BET model is commonly applied to determine the surface available

foradsorption,calledtheBETsurfacearea.Evenformicroporousadsorbentswherethe

BET assumptions are highly inadequate, this is the most common method for

determinationofspecificsurfacearea,anditsdeficienciesaretypicallyassumedtobe

similarbetweencomparablematerials.

31

adsorption data to Equation 2.17 and determining the monolayer capacity, nsites.

Typically, N2 adsorption data are plotted in the form of the linearizedBET equation, a

rearrangementofEquation2.17:

1

1

1

Equation2.19

The BET variable, BBET, is plotted as a function of P/P0 and if the data are satisfyingly

linear,theslopeandinterceptareusedtodeterminensiteswhichisproportionaltothe

surfaceareaasstatedinEquation2.8(usingAsites=16.22)16.Inpractice,thelinearityof

theBETplotofa nitrogenisothermat77Kmaybelimitedtoa smallrangeofpartial

pressure.Anacceptedstrategyistofitthelowpressuredatauptoandincludingapoint

referred to as point B, the end of the characteristic knee and the start of the linear

regioninaTypeIIisotherm.15,16

2.2.3 PoreFillingModels

TheLangmuirmodel,anditssuccessiveadaptations,weredevelopedinreferenceto

anidealizedsurfacewhichdidnothaveanyconsiderationsformicrostructure,suchas

the presence of narrow micropores, which significantly change the justifiability of the

assumptions of monolayer and multilayer adsorption. While numerous advances have

32

been made in adsorption theory since the BET model, a notable contribution was by

Dubininandcollaboratorstodevelopaporefillingtheoryofadsorption.Theirsuccessat

overcoming the inadequacies of layer theories at explaining nitrogen adsorption in

highlymicroporousmedia,especiallyactivatedcarbons,ishighlyrelevant.TheDubinin

Radushkevich(DR)equation,describingthefractionalporeoccupancypore,isstatedas:

W

W

Equation2.20

analogous way as the Langmuir or BET equation for determining surface area. Its

similaritiestoBETanalysesarediscussedinAppendixD.

33

2.2.4 GibbsSurfaceExcess

Measurements of adsorption near or above the critical point, either by volumetric

(successivegasexpansionsintoanaccuratelyknownvolumecontainingtheadsorbent)

orgravimetric(gasexpansionsintoanenclosedmicrobalancecontainingtheadsorbent)

methods, have the simple shortcoming that they cannot directly determine the

adsorbed amount. This is readily apparent at high pressures where it is observed that

the measured uptake amount increases up to a maximum and then decreases with

increasing pressure. This is fundamentally inconsistent with the Langmuir model of

adsorption,whichpredictsamonotonicallyincreasingadsorptionquantityasafunction

of pressure. The reason for the discrepancy can be traced to the finite volume of the

adsorbedphase,showninFigure2.3.Thefreegasvolumedisplacedbytheadsorbed

phasewouldhavecontainedanamountofgasgivenbythebulkgasdensityeveninthe

absence of adsorption. Therefore, this amount is necessarily excluded from the

measured adsorption amount since the gas density, measured remotely, must be

subtractedfromintheentirevoidvolume,suchthatadsorptioniszerointhereference

statewhichdoesnothaveanyadsorptionsurface.

In the landmark paper of early thermodynamics, On the Equilibrium of

Heterogeneous Substances,18 Josiah Willard Gibbs gave a simple geometrical

explanationoftheexcessquantityadsorbedattheinterfacebetweentwobulkphases,

summarizedforthegassolidcaseinFigure2.5.Theabsoluteadsorbedamount,shown

inpurple,issubdividedintotwoconstituents:referencemoleculesshowninlightblue,

existingwithintheadsorbedlayerbutcorrespondingtothedensityofthebulkgasfar

34

from the surface, and excess molecules shown in dark blue, the measured quantity of

adsorption. The Gibbs definition of excess adsorption, ne, as a function of absolute

adsorption,na,is:

Equation2.21

Any measurement of gas density far from the surface cannot account for the

existence of the reference molecules near the surface; these would be present in the

reference system. The excess quantity, the amount in the densified layer that is in

excessofthebulkgasdensity,istheexperimentallyaccessiblevalue.Itissimpletoshow

thattheexcessuptakeisapproximatelyequaltotheabsolutequantityatlowpressures.

As the bulk gas density increases, the difference between excess and absolute

adsorptionincreases.Astatemaybereachedathighpressure,P3inFigure2.5,where

theincreaseinadsorptiondensityisequaltotheincreaseinbulkgasdensity,andthus

the excess quantity reaches a maximum. This point is referred to as the Gibbs excess

maximum. Beyond this pressure, the excess quantity may plateau or decline, a

phenomenonreadilyapparentinthehighpressuredatapresentedinthisthesis.

35

VsVadsVg

P1

P2

P3

P4

P5

Figure2.5.TheGibbsexcessadsorptionisplottedasafunctionofpressure(center).A

microscopicrepresentationoftheexcess(lightblue),reference(darkblue),andabsolute

(combined)quantitiesisshownatfivepressures,P1P5.Thebulkgasdensity(gray)isa

functionofthepressure,anddepictedasaregularpatternforclarity.Thevolumeofthe

adsorbedphase,unknownexperimentally,isshowninpurple(top).

36

2.3

AdsorptionThermodynamics

2.3.1 GibbsFreeEnergy

Adsorptionisaspontaneousprocessandmustthereforebecharacterizedbyadecrease

inthetotalfreeenergyofthesystem.Whenagasmolecule(oratom)isadsorbedona

surface,ittransitionsfromthefreegas(withthreedegreesoftranslationalfreedom)to

the adsorbed film (with two degrees of translational freedom) and therefore loses

translational entropy. Unless the adsorbed state is characterized by a very large

additionalentropy(perhapsfromvibrations),itfollowsthatadsorptionmustalwaysbe

exothermic(Hads<0)since:

Equation2.22

constanttemperatureandpressure,thevariablesheldconstantduringequilibriumgas

adsorptionmeasurements.Thechemicalpotentialineachphaseisdefinedas:

,

Equation2.23

We have assumed that the thermodynamic properties of the solid surface remain

unchangeduponadsorption,anapproximationthatservesuswellforthispurpose.Let

us assume that the system is held in a constant temperature bath, and we have

37

adsorbentsurfacebyaddingdngmoleculesofgas.Theadsorbedphaseandthebulkgas

phase are not in equilibrium, and will proceed to transfer matter in the direction of

lower free energy, resulting in adsorption. When equilibrium is reached, the chemical

potentialofthegasphaseandtheadsorbedphaseareequal,since:

0

Equation2.24

Determining the change in chemical potential, or the Gibbs free energy, of the

adsorptive species as the system evolves toward equilibrium is essential to a

fundamental understanding of adsorptive systems for energy storage or other

engineering applications. We develop this understanding through the experimentally

accessiblecomponentsoftheGibbsfreeenergy:HadsandSads.

2.3.2 EntropyofAdsorption

WetakethetotalderivativeofbothsidesofEquation2.24,andrearrangetoarriveat

theclassicClausiusClapeyronrelation:

Equation2.25

where:

,

38

The specific volume of the free gas is usually much greater than that of the adsorbed

gas,andarobust19approximationsimplifiestherelation:

Equation2.26

Werearrangetoderivethecommonequationforchangeinentropyuponadsorption:

S

Equation2.27

2.3.3 EnthalpyofAdsorption

Atequilibrium,thecorrespondingchangeinenthalpyuponadsorptionis:

H

Equation2.28

Werefertothisasthecommonenthalpyofadsorption.Tosimplifyfurther,wemust

specifytheequationofstateofthebulkgasphase.Theidealgaslawiscommonlyused,

a suitable equation of state in limited temperature and pressure regimes for typical

gases(thelimitationsofwhichareinvestigatedinSection2.4.1).Foranidealgas:

Equation2.29

39

ThisisoftenrearrangedinthevantHoffform:

ln

1

Equation2.30

Theisostericheatofadsorption,acommonlyreportedthermodynamicquantity,isgiven

apositivevalue:*

ln

1

Equation2.31

Foradsorptionattemperaturesorpressuresoutsidetheidealgasregime,thedensityof

thebulkgasphaseisnoteasilysimplified,andweusethemoregeneralrelationship:

q

Equation2.32

If the excess adsorption, ne, is substituted for the absolute quantity in the equations

above,theresultiscalledtheisoexcessheatofadsorption:

q

Equation2.33

Itistypicaltoreporttheisostericenthalpyofadsorptioninthiswayaswell,andforourpurpose,

increasingenthalpyreferstotheincreaseinmagnitudeoftheenthalpy,ormostspecifically,the

increaseintheheatofadsorption.

40

It is common to include the ideal gas assumption in the isoexcess method since the

assumptionsarevalidinsimilarregimesoftemperatureandpressure,giving:

ln

1

Equation2.34

For cases where the adsorptive is in a regime far from ideality, it is sometimes

necessary to use a better approximation for the change in molar volume specified in

Equation 2.26. For example, gaseous methane at high pressures and nearambient

temperatures (nearcritical) has a molar volume approaching that of liquid methane.

Therefore,amoregeneralequationmustbeused,andherewesuggesttoapproximate

themolarvolumeoftheadsorbedphaseasthatoftheadsorptiveliquidat0.1MPa,vliq:

Equation2.35

Thisgivesthefollowingequationsfortheisostericandisoexcessheatofadsorption:

q

Equation2.36

Equation2.37

41

Insummary:

Assumptions:

IsoexcessMethod(

IsostericMethod

ln

1

IdealGas

ln

1

Eq.2.31

Eq.2.32

Eq.2.33

S

NonidealGas

Eq.2.34

NonidealGas

ln

1

ln

1

Eq.2.36

Eq.2.37

The Henrys law value of the isosteric enthalpy of adsorption, H0, is calculated by

extrapolationoftheadsorptionenthalpytozerouptake:

H

lim

Equation2.38

42

A common technique for determining the enthalpy of adsorption in the ideal gas

approximationistoplotlnPasafunctionofT1,avantHoffplot,andtofindtheslope

ofthelinealongeachisostere(correspondingtoafixedvalueofn).Ifthedataarelinear

in a certainrange of T 1, theenthalpy of adsorption is determined tobe temperature

independentinthatrange,correspondingtotheaveragetemperature:

2

Equation2.39

Iftheslopeisnonlinear,asubsetofthedatabetweentwotemperatures,T1andT2,is

foundwheretheslopeisapproximatelylinear.Adifferenceof10Kisconsideredtobe

acceptableformostpurposes.15Insidethiswindow,theaveragetemperatureis:

2

1

Equation2.40

withintherangeoftemperaturescollected.

43

2.4

ThermodynamicCalculationsfromExperimentalData

Simplicityandaccuracyaredesiredinsolvingthethermodynamicrelationsderived

inSection2.3forcalculatingtheentropyandenthalpyofadsorptionfromexperimental

data. The limitations of the two most commonly applied simplifications, the ideal gas

andisoexcessassumptions,arediscussedinSections2.4.12.

The primary obstacles to a completely assumptionless derivation of the

thermodynamicquantitiesofinterestaretwofold.Mostimportantly,boththeisosteric

and isoexcess treatments require tabulations of the equilibrium pressure, or ln P, at

fixedvaluesofuptake,naorne.Experimentally,itispossibletocontrolPandmeasure

the amount adsorbed, but exceedingly difficult to fix the adsorbed quantity and

measure the equilibrium pressure. Therefore, a fitting equation is often used to

interpolatethemeasuredvalues.Theinterpolationofadsorptiondataisverysensitive

tothefittingmethodchosen,andsmalldeviationsfromthetruevaluecausesignificant

errors in thermodynamic calculations.2022 Sections 2.4.36 discuss the use of the data

with and without a fitting equation, and compare the results across three types of

modelindependent fitting equations in an effort to determine the most accurate

methodologyforcalculatingthermodynamicquantitiesofadsorption.

Secondly,thedeterminationoftheabsolutequantityofadsorptionrequiresamodel

which defines the volume of the adsorbed phase as a function of pressure and

temperatureinthesystem.Numerousmethodshavebeensuggestedtodefineit,anda

successfulmodelispresentedinSection2.5.

44

Thedatausedforthecomparisonsismethaneadsorptiononsuperactivatedcarbon

MSC30, a standard carbon material whose properties are thoroughly discussed in

Chapters46.Itisawellcharacterizedmaterialwithtraditionalsorbentpropertiesanda

largesurfacearea(givingalargesignaltonoiseratioinmeasurementsofitsadsorption

uptake).Thedatasetconsistsof13isothermsbetween238521K,andspanspressures

between0.059MPa,asshowninFigure2.6.

Figure2.6.EquilibriumadsorptionisothermsofmethaneonMSC30between238521K,the

testdataforthermodynamiccalculationsofadsorption.

45

2.4.1 IdealGasAssumption

Theidealgaslawisdefinedbytwomainapproximations:thatthegasmoleculesdo

notinteractorhaveinherentvolume.Inthelimitofzeropressure,allgasestendtoward

ideality since they are dilute enough that interactions are improbable and the total

volumeofthesystemisapproximatelyunchangedbyincludingthemoleculesinit.For

hydrogen, the ideal gas law holds approximately true for a large pressure and

temperatureregimearoundambient;forexample,theerrorindensityisonly6%even

at 10 MPa and 298 K (see Figure 2.7a). However, at low temperatures and high

pressures that are desired in many adsorption applications, nonideality of the gas

phaseisstrikinglyapparentformostcommongases.Figure2.7bshowsthedensityof

methane as a function of pressure at various temperatures of interest for storage

applications. The very significant nonideality of both hydrogen and methane is

apparent at room temperature and elevated pressures. In addition, each gas shows

significant nonideality in their respective low temperature regimes of interest for

storage applications, even at low pressures. This is an issue for most adsorptive gases

sincethelatentheatofphysicaladsorptionisveryclosetothatofliquefaction.

ThevanderWaalsequationofstatepredictsadensityforhydrogenandmethane

thatisgenerallyanacceptableapproximationofthetruedensityatpressuresupto10

MPa,asshowninFigure2.8.Forhydrogenat77K,theerrorindensityislessthan0.4%

between 05 MPa, an acceptable figure for isosteric heat calculations, and much

improvedcomparedtothe4.5%errorintheidealgasdensity.

46

Ultimately, real gases exhibit properties that cannot be accurately modeled in our

pressureandtemperatureregimeofinterestbyanysimplemeans.Themostaccurate

pure fluid model available at this time is the 32term modified BenedictWebbRubin

(mBWR) equation of state.23 For this work, we refer to the mBWR model, as

implementedbytheREFPROPstandardreferencedatabase,24astherealgasequation

ofstate.

Figure2.7.Acomparisonofidealgasdensity(dottedlines)to(a)hydrogenand(b)methane

atvarioustemperatures,andpressuresupto100MPa.

Figure2.8.Acomparisonoftheidealgas,vanderWaals(vdW)gas,andreal(mBWR)gas

densityofmethaneandhydrogenat298Kbetween0100MPa.

47

2.4.2 IsoexcessAssumption

For thermodynamic or other calculations from experimental adsorption data at

sufficiently low pressures, such as in determining BET surface area, the measured

(excess)quantityofadsorption(fromEquation2.21)sufficesforapproximatingthetotal

adsorptionamount.However,thisassumptionquicklybecomesinvalidevenatrelatively

modest pressures and especially at low temperatures where the gas density is high

comparedtothedensityoftheadsorbedlayer.20,21

Nevertheless, the simplest approach to thermodynamic calculations using

experimentalisothermdataistoproceedwiththemeasuredexcessuptakequantity,ne,

in place of the absolute adsorption quantity, na. Since the volume of adsorption is

fundamentally unknown, a model is required to determine the absolute adsorption

amount, a task that is beyond the scope of many adsorption studies. This shortcut is

valid in the low coverage limit since, from Equation 2.21, if the pressure of the gas

approacheszero:

lim

lim

Equation2.41

ThisapproachcanthereforebeeffectiveforapproximatingtheHenryslawvalue

of the isosteric enthalpy of adsorption. However, it leads to significant errors in

determining the dependence of the enthalpy on uptake (discussed further in Section

2.4.35)andanyisoexcessenthalpyofadsorptionvaluescalculatedatcoverageshigher

thanne/nmax=0.5shouldonlybeacceptedwithgreatcaution.

48

2.4.3 CalculationsWithoutFitting

Controlling the pressure of experimental measurements is possible, but it proves

very difficult to perform experiments at specific fixed quantities of uptake. By

coincidence, such as in a large data set like the one used in this comparison, it may

happen that numerous data points lie at similar values of excess adsorption, and

analysis of the isostericenthalpy ofadsorption may be performed without fitting. The

vantHoffplotofthesecoincidentallyalignedpointsisshowninFigure2.9.

Figure2.9.ThevantHoffplotofthe(unfitted)methaneuptakedataatparticularvaluesof

excessadsorptiononMSC30.Thedashedcoloredlines,frombluetoorange,indicatethe

temperaturesoftheisothermsfrom238521K,respectively.

49

Figure2.10.Theaverageisoexcessenthalpyofadsorptioncalculatedovertheentire

temperaturerangeofdatashowninFigure2.9,238521K.

Sincetheexperimentalquantityisexcessadsorption,theisoexcessmethodmustbe

used; the resulting isoexcess enthalpy of adsorption is shown in Figure 2.10. This

methodisseverelylimitedsinceitreliesonthestatisticalprobabilityoftwodatapoints

lying on the same isostere in the vant Hoff plot. This likelihood is dramatically less at

high uptake where only low temperature data are available, and requires intense

experimental effort to be accurate. The fixed values of ne are necessarily

approximated (in this case, 0.05 mmol g1) and the absolute adsorbed amount is not

used, resulting in a significant, unphysical divergence at high values of uptake.

Nonetheless, without any fitting equation or model, we achieve an acceptable

determination of the Henrys law value of the enthalpy of methane adsorption on

MSC30(asanaverageovertheentiretemperaturerange):15kJmol1atTavg=310K.

50

2.4.4 LinearInterpolation

A primitive method for fitting the experimental adsorption data is by linear

interpolation. This method does not require any fitting equation and is the simplest

approach to determining values of P at specific fixed values of ne to be used in the

isoexcessmethod.TheMSC30datasetfittedbylinearinterpolationandtheresulting

vantHoffplotisshowninFigure2.11.Thedataareoftenapparentlylinearforanalysis

acrosstheentirerangeofne,butarelimitedtothevaluesofnewheretherearemultiple

measured points (favoring the measurements at low uptake and low temperature).

Additionally,athighvaluesofnetheisoexcessapproximationbecomesinvalid,orne

na,anderrorsbecomelargerasneincreases.

Tocalculatetheenthalpyofadsorption,theisoexcessmethodisusedbecausethe

absolute adsorption is unknown; the results are shown in Figure 2.12. The average

enthalpyofadsorptionovertheentiredataset(whereTavg=310K)isplottedatthetop.

The temperature dependent results are plotted at top, middle, and bottom, using

windowsofsizes3,5,and7temperatures,respectively.Thecolorsfrombluetoorange

represent the average temperatures of each window, from low to high. Two

observationsmaybemade:thereisnosignificanttrendofthetemperaturedependence

ofthedata,andincreasingthewindowsizehastheeffectofdecreasingoutliersbutnot

elucidatinganyfurtherinsightintothethermodynamicsofadsorptioninthissystem.As

before,theenthalpyofadsorptiondivergesathighvaluesofuptakewheretheisoexcess

approximationisinvalid(ne>10)andcannotberegardedasaccurate.

51

Figure2.11.Linearinterpolationoftheexperimental(excess)uptakedataofmethaneon

MSC30(top),andthecorrespondingvantHoffplotshowingtherelativelinearityofthedata

evenusingthisprimitivefittingtechnique(bottom).Thecoloredlines,frombluetoorange,

indicatethetemperaturesofthemeasurementsfrom238521K,respectively.

52

Figure2.12.IsoexcessenthalpyofadsorptionofmethaneonMSC30,usinglinear

interpolationfitsand3(top),5(middle),and7(bottom)temperaturewindows.A

calculationoveralldata(asingle13temperaturewindow)isalsoshown(dashedblack).

53

2.4.5 VirialTypeFittingEquation

Numerous equations have been suggested to fit experimental adsorption data for

thermodynamic calculations. The most common is to fit the data with a model

independentvirialtypeequation25andproceedwiththeGibbsexcessquantities,ne,as

directlyfitted.Theadvantagestothismethodarethatthenumberoffittingparameters

iseasilyadjustedtosuitthedata.Thefittingequationhastheform:

ln

Equation2.42

squaresfittingalgorithm.TheexperimentaldataofmethaneadsorptiononMSC30are

shown in Figure 2.13, fitted using first, third, and fifth order terms (with 4, 8, and 12

independentparameters,respectively).Itcanbeobservedthatthedataareverypoorly

fitted beyond the Gibbs excess maximum and cannot be used. In addition, as the

numberoffittingparametersisincreased,awellknownlimitationofpolynomialfitting

occurs:acurvatureisintroducedbetweendatapoints.However,theisoexcessmethod

is never employed beyond the Gibbs excess maximum, and an analogous plot of

optimized fits of only selected data is shown in Figure 2.14. The data are well

approximated even for i = 1, but some improvement is gained for i = 3. There is no

significantimprovementbyaddingparameterstoi=5.Thedataarewellfittedatlow

temperaturesupto~4MPaandatallpressuresforisothermsatandabove340K.

The enthalpy of adsorption is calculated by the isoexcess method, using:

54

ln

1

Equation2.43

Thefunctionalformoftheenthalpyisthatofanithorderpolynomial.Therefore,ifonly

firstorderparametersareused,theenthalpywillbeastraightline(asshowninFigure

2.15).Thisisacceptableforsomepurposes,butallowslittlepotentialinsighttothetrue

dependenceoftheenthalpyonuptake.Afitusinghigherordertermsmaybepreferred

for that reason. Nevertheless, in this comparison, third order terms do not lend any

significant contribution to the analysis (see Figure 2.16). The Henrys law value of the

enthalpycalculatedinEquation2.43is:

H

lim

Equation2.44

ThefitsofselectdatagivevaluesoftheHenryslawenthalpyintherangeof13.5

17.5kJmol1.Sincetheparametersareconstantwithtemperature,itisnotpossibleto

determinethetemperaturedependenceoftheisoexcessenthalpywithasinglefitting

equation, and it is often assumed to be negligible. If a moving window method is

employed, a temperature dependence is accessible, but does not yield any significant

trends in this case (for windows of 3 temperatures, with i = 1 or i = 3) as shown in

Figures 2.1516. All calculations show an increasing isoexcess enthalpy of adsorption

exceptforsmallwindowsofisothermsusingonlyfirstorderfits,andoverall,thisfitting

methodologyisunsatisfactoryforanalyzingmethaneadsorptiononMSC30.

55

Figure2.13.First(top),third(middle),andfifthorder(bottom)virialequationfitsof

methaneadsorptionuptakeonMSC30between238521K,fittingthecompletedataset

includingtheuptakebeyondtheGibbsexcessmaximum.

56

Figure2.14.First(top),third(middle),andfifthorder(bottom)virialequationfitsof

methaneadsorptionuptakeonMSC30between238521K,fittingonlythedatabelowthe

Gibbsexcessmaximum.

57

Figure2.15.Isoexcessenthalpyofadsorption,usingfirstordervirialequationfitsand3

temperaturewindows.Alsoshownistheresultforafirstordervirialequationfitusingthe

entiredataset,a13temperature(13T)singlewindow.Thecalculatedenthalpiesare

comparedtothoseforageneralizedLangmuirfit(giveninSection2.5).

Figure2.16.Isoexcessenthalpyofadsorption,usingthirdordervirialequationfitsand3

temperaturewindows.Alsoshownistheresultforathirdordervirialequationfitusingthe

entiredataset,a13temperature(13T)singlewindow.Thecalculatedenthalpiesare

comparedtothoseforageneralizedLangmuirfit(giveninSection2.5).

58

2.4.6 GeneralizedLangmuirFittingEquation

A major limitation of the virialtype equation is that it does not accurately

interpolatethedataathighadsorptionuptakeinthenearorsupercriticalregimewhere

themaximuminGibbsexcessisaprominentfeatureofthedata.Anotherapproachisto

incorporatetheGibbsdefinition(Equation2.21)ofadsorptionintothefittingequation,

whichcanbedoneinamodelindependentway.

An effective strategy is to choose a functional form for na that is monotonically

increasing with pressure, consistent with the physical nature of adsorption.20 The

Langmuir isotherm is one example, although others have been suggested (e.g.,

LangmuirFreundlich,21 Unilan,22 and Toth26 equations). If an arbitrary number of

Langmuir isotherms are superpositioned, referred to as a generalizedLangmuir

equation,thenumberofindependentfittingparameterscanbeeasilytunedtosuitthe

data. Langmuir was the first to generalize his equation for a heterogeneous surface

consistingofnumerousdifferentadsorptionsitesofdifferentcharacteristicenergies.27

ImplementingthegeneralizedLangmuirmodel(Equation2.16)inamodelindependent

way,absoluteadsorptiontakestheform:

,

1

Equation2.45

The volume of adsorption in the Gibbs equation also has a pressure dependence

that is fundamentally unknown, but which is generally accepted to be monotonically

59

equation,simplifyingthefinalequationandkeepingthenumberofparameterslow:

,

Equation2.46

Theexcessadsorptiondataarethenfittedto:

,

Equation2.47

TheKiareequivalenttotheequilibriumconstantsofadsorptionintheclassicalLangmuir

model, but are not required to have physical meaning for this purpose. They can be

taken as constant with pressure, but having a dependence on temperature similar to

Equation2.13:

Equation2.48

Thefittingparameters(cn,cV,i,Ci,andEi)areconstants.Iftheidealgaslawappliesto

thepressureandtemperatureregimeofinterest,theequationsimplifies:

,

Equation2.49

60

Figure2.17.DoubleLangmuirfitofmethaneuptakeonMSC30usingtheidealgaslaw.

TheexperimentaldatafittedbyadoubleLangmuirisotherm(i=2)withtheidealgas

assumptionareshowninFigure2.17.Forallbutthehighestpressures,thedataarewell

approximatedbythismethod.Thecurvatureoftheinterpolationbetweenpoints,even

near or at the Gibbs excess maximum, is representative of the physical nature of the

system, and the extrapolation to high pressures shows much improved behavior

compared to the previous fitting methods. A limitation of the ideal gas assumption is

thattheexcessuptakeisothermscannotcrossathighpressure,thelowesttemperature

data decreasing proportionally with pressure. This is not consistent with experimental

results where it frequently occurs that low temperature data falls significantly below

highertemperaturedataatthesamepressure.Thisphenomenonisentirelyduetonon

idealgasinteractionsfromanonlinearchangeingasdensity,andcanbeaccountedfor

by using the more general form of the excess adsorption (Equation 2.47). Data fitted

using 1, 2, and 3 superimposed Langmuir isotherms (with 4, 7, and 10 independent

parameters,respectively)andusingthemBWRgasdensityareshowninFigure2.18.

61

Figure2.18.Single(top),double(middle),andtriple(bottom)Langmuirequationfitsof

methaneadsorptionuptakeonMSC30between238521K.

62

preferredmethodinthisstudy.ThetripleLangmuirfitisnotsignificantlyimprovedto

justifytheadditionof3independentfittingparameters.Theextrapolationofthedatato

highpressuresshowsbehaviorconsistentwithotherexperimentalresultsofhydrogen

andmethaneadsorptionatlowtemperature.

2.5

GeneralizedLangmuirHighPressureAdsorptionModel

To understand the true thermodynamic quantities of adsorption from

absolute adsorption amount as a function of pressure. The necessary variable that

remains unknown is the volume of the adsorption layer and numerous methods have

beensuggestedtoestimateit.Typicalmethodsincludefixingthevolumeofadsorption

asthetotalporevolumeofthesorbentmaterial,20usingavolumeproportionaltothe

surface area (assuming fixed thickness),28 or deriving the volume by assuming the

adsorbed layer is at liquid density.29 Some approaches are specific to graphitelike

carbonmaterials,suchastheOnoKondomodel.30, 31Themostgeneralapproachisto

let the adsorption volume be an independent parameter of the fitting equation of

choice,equivalenttotheparametercVinthemodelindependenttreatmentabove.

The generalizedLangmuir equation20 (as shown in Section 2.4.6) and numerous

others(e.g.,LangmuirFreundlich,21Unilan,22andToth26equations)havebeenshownto

be suitable fitting equations for determining absolute adsorption from excess uptake

isothermssincetheyaremonotonicallyincreasingandcontainarelativelysmallnumber

63

offittingparameterstoachieveasatisfactoryfittotheexperimentaldata.Weconsider

the following fitting equation for Gibbs excess adsorption as a function of pressure,

identicalinformtothemodelindependentequationabove(Equation2.47):

1

Equation2.50

yieldssatisfyingresultsacrossanumberofmaterialsinsupercriticaladsorptionstudies

ofbothmethaneandhydrogen(wheretheregimebeyondtheexcessmaximumiswell

characterized),givingthereducedequation:

,

Equation2.51

We have found that the assumption that the total adsorption volume scales

proportionallywithsiteoccupancyisrobust,andthisfittingequationhasbeenshownto

besuccessfulforbothcarbonaceous(seeChapter6)andMOFmaterials.20Wereferto

thismethodasthedoubleLangmuirmethod,andiftheabsolutequantityofadsorption

is held constant, it yields the true isosteric quantities of adsorption. The absolute

quantity,fromtheGibbsdefinition,is:

,

Equation2.52

64

Thefractionalsiteoccupancy,alsocalledthesurfacecoverage,is:

,

Equation2.53

LeastsquaresfitsofmethaneuptakeonMSC30tothedoubleLangmuirequationare

shown in Figure 2.19, the fitted excess adsorption (left) and calculated absolute

adsorption (right) at all temperatures measured. The goodness of fit is satisfactory

acrosstheentirerangeoftemperatureandpressure,witharesidualsumofsquaresless

than0.04mmolg1perdatapoint.TheoptimalfittingparametersforMSC30aregiven

inTable5.2,andtheirrelationtothematerialspropertiesisdiscussedinSection5.2.3.

Figure2.19.DoubleLangmuirequationfitsofmethaneadsorptionuptakeonMSC30

between238521K,showingcalculatedexcessuptake(left)andcalculatedabsoluteuptake

(right)assolidlines,andthemeasuredexcessuptakedataasfilleddiamonds(leftandright).

To derive the isosteric enthalpy from the generalized Langmuir equation, the

derivativeofpressurewithrespecttotemperatureisdecomposedasfollows:

65

Equation2.54

FromEquations2.5053,therespectivecomponentsofthederivativearegivenby:

1

1

2

1

2

1

2

Thesearecombinedtofindtheisostericenthalpyofadsorption,inEquations2.3137:

P

X Y Z

Equation2.55

TheisostericenthalpyofadsorptionofmethaneonMSC30isshowninFigure2.20,

using the ideal gas law to approximate the density in the gas phase. The results are

consistent with reported results for numerous sorbent systems and show a physically

insightful dependence of the isosteric enthalpy on both uptake and temperature. The

Henrys law value is between 14.515.5 kJ mol1, consistent with the isoexcess results

66

calculated without a fitting equation (the best approximate of the Henrys law value),

andtheenthalpydeclineswithuptaketo14kJmol1.Duetotheidealgasdependence

ofthedensitywithpressure,theenthalpyreachesaplateauathighvaluesofuptake.

When the real gas data is used, the calculation of isosteric enthalpy changes

significantlyathighpressures,asshowninFigure2.21. Nonidealityofmethaneinthe

gasphaseissubstantialundertheseconditionsandmustbetakenintoaccountforthe

most accurate description of adsorption thermodynamics in MSC30, and was also

necessary when extended to other systems. The tendency of the isosteric heat to a

constantvalueathighuptake32iscommonlyreportedasevidenceofpropercalculation

procedures20,21;howeveraplateauwasnotobservedwhenidealgasassumptionswere

Figure2.20.Isostericenthalpyofadsorption,usingadoubleLangmuirfitwiththeidealgas

assumption(Equation2.31).

67

Figure2.21.Isostericenthalpyofadsorption,usingdoubleLangmuirfits:(left)withtheideal

gasassumption(Equation2.31),and(right)withtherealgasdensity(Equation2.32),both

employingthetypicalmolarvolumeassumption.

Figure2.22.Isostericenthalpyofadsorption,usingdoubleLangmuirfitsandrealgasdensity:

(left)withthetypicalmolarvolumeassumption(Equation2.32),and(right)withthe

suggestedliquidmethaneapproximation(Equation2.36).

68

omitted from the calculations in this study. We suggest that a general exception be

madeforadsorptioninthesignificantlynonidealgasregimewherethereisnoreason

tosuggestthattheisostericenthalpyofadsorptionwouldpersisttoaplateauvalue.

Secondly, the change in molar volume on adsorption must also be carefully

consideredathighpressureforcertainadsorptives,wherethemolarvolumeinthegas

phaseapproachesthatofitsliquid.Thisisnotthecaseacrossawidetemperatureand

pressure regime for hydrogen, for example, but is highly relevant to methane even at

temperaturesnearambient.FormethaneadsorptiononMSC30inthisstudy,theusual

approximation, treating the adsorbed phase volume as negligible compared to that of

thegasphase,holdsinthelowpressurelimitbutbecomesinvalidbeyond1MPa.The

differenceinisostericheatcalculatedwithorwithouttheapproximationis>1%beyond

1 MPa, as shown in Figure 2.22. To approximate the molar volume of the adsorbed

phase,wesuggesttousethatofliquidmethane(seeEquations2.3637),afixedvalue

that can be easily determined and which is seen as a reasonable approximation in

numerous gassolid adsorption systems. Specifically for methane, we use va = vliq = 38

mLmol1,thevalueforpuremethaneat111.5Kand0.1MPa.Forourdataofmethane

on MSC30, the difference between the molar volume of the gas and the adsorbed

phasesbecomessignificantatalltemperaturessincevais530%themagnitudeofvgat

10 MPa. The variationof the liquid molar volume with temperatureand pressure was

considered;thedensityalongthevaporizationlineis~20%,andsocanbeconsidereda

negligible complication within the error of the proposed assumption. A fixed molar

volumeoftheadsorbedphasewasusedthroughoutalltemperaturesandpressures.

69

2.6

Conclusions

In summary, the method used to determine the uptake and temperature

dependenceoftheisosteric(orisoexcess)enthalpyofadsorptionofmethaneonMSC

30 had a significant effect on the results. The virialtype fitting method has the

advantage that with few parameters, one can fit experimental isotherm data over a

large range of P and T in many systems. The best fits to Equation 2.42 are found for

systems with a weakly temperature dependent isosteric heat. For high temperatures

(near the critical temperature and above) and up to modest pressures, this equation

often suffices with only 24 parameters (i = 01). However, application of this fitting

proceduretomoderatelyhigh(definedasnearcritical)pressuresorlowtemperatures

(where a Gibbs excess maximum is encountered) lends substantial error to the

interpolated results even with the addition of many parameters. In every case

implementing the isoexcess assumption, the enthalpy diverged at high uptake where

theassumptionisfundamentallyinvalid.Itissimpletoshowthatsincene<na,theslope

of the excess isosteres in the vant Hoff plot will be more negative than that of the

correct absolute isosteres (since the pressure necessary to achieve a given state of

uptake will be underestimated), effecting a perceived increase in the calculated

enthalpyofadsorption.Pitfallssuchasthesearecommonlyignored,orthedatabeyond

moderate quantities of surface coverage are discarded. In any case, the isosteric

enthalpy is not accessible for high pressures using this method, and quantities

calculated using excess uptake data must be referred to as isoexcess quantities to

distinguishthemfromtrueisostericvaluesbasedonabsoluteadsorption.33

70

AdoubleLangmuirtypeequationwithabuiltindefinitionofGibbssurfaceexcesswasa

suitablefittingequationofmethaneuptakeonMSC30inthemodelindependentcase,

andcouldalsobeusedasamodeltodeterminetheabsolutequantityofadsorptionand

toperformatrueisostericenthalpyanalysis.Inboththeisoexcessandabsoluteresults,

the enthalpy of adsorption showed physically justifiable characteristics, and gave a

Henryslawvalueclosesttothatforamodelfreeanalysisofthelowpressuredata.All

simplifyingapproximationswithinthederivationoftheisostericenthalpyofadsorption

werefoundtobeextremelylimitedinvalidityformethaneadsorptionwithinapressure

and temperature range close to ambient. Therefore, real gas equation of state data

must be used and a simple approximation of the finitemolar volume of the adsorbed

phasewasproposed.

2.7References

(1)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

J.E.LennardJones,'Processesofadsorptionanddiffusiononsolidsurfaces',Trans.FaradaySoc.,

28,333359(1932).

J.D.vanderWaals,'Overdecontinuiteitvandengasenvloeistoftoestand',thesis,Leiden

(1873).

J.C.Maxwell,'Onthedynamicalevidenceofthemolecularconstitutionofbodies',Nature,11,

357359(1875).

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