4l 1nkM4L u5OkP1lON

Thermal desorption is the heat-stimulated release of gases or vapors previously adsorbed on the interior walls of the system 1bey moy bove
beeo oJsotbeJ oo tbe cbombet sotfoce wblle lt wos exposeJ to tbe eovltoomeot ooJ tbeo slowly teleoseJ os tbe pomp temoveJ qos ftom tbe
cbombet Altetootlvely tbey moy bove teocbeJ tbe looet sotfoce by Jlffosloo ftom wltblo ot petmeotloo ftom tbe ootslJe 1be tote of
Jesotptloo ls o fooctloo of tbe molecolot bloJloq eoetqy tbe tempetotote of tbe sotfoce ooJ tbe sotfoce covetoqe Cos ls boooJ oo sotfoces by
physlsorpLlon and chemlsorpLlon hyslsorbed molecules are bonded Lo Lhe surface by weak van der Waals forces of energy 40 M!/(kgmole)
AdsorpLlon aL energles greaLer Lhan Lhls value ls known as chemlsorpLlon
Weakly physlsorbed molecules are removed qulckly from solld surfaces aL amblenL LemperaLure and do noL hlnder pumplng Chemlsorbed parLlcles
desorb slowly unless exLernal energy ls provlded ln Lhe form of phonons phoLons or charged parLlcles 1he effecLs of readsorpLlon musL be lncluded
ln real vacuum sysLems when deLermlnlng Lhe neL or measured Lhermal desorpLlon raLe lf readsorpLlon ls slgnlflcanL Lhe Lrue ouLgasslng raLe wlll
be much hlgher Lhan Lhe measured ouLgasslng raLe
uesorpLlon WlLhouL 8eadsorpLlon
2eroOrder uesorption
urfaces covered wlLh mulLllayers of molecules such as waLer vapor wlll desorb aL a consLanL raLe 3
n molecular surface denslLy
Lv Lhe laLenL heaL of vaporlzaLlon L 40600 M!/(kgmol) or 97 kcal/gmol for waLer
a a consLanL (L descrlbes Lhe raLe aL whlch molecules deparL from a surface saLuraLed wlLh large quanLlLles of va
1his process is co//ed tero order desorption
llrsL Crder uesorpLlon
When Lhe surface coverage becomes less Lhan one monolayer molecules LhaL do noL dlsssoclaLe on adsorpLlon deparL wlLhouL reLurn aL a raLe
proporLlonal Lo Lhelr surface concenLraLlon 1hls can be expressed maLhemaLlcally
uesorpLlon wlLh a raLe dC(L)/dL whlch ls proporLlonal Lo Lhe concenLraLlon of aLoms or molecules on Lhe surface C ls called flrsLorder desorpLlon
1hls ls a descrlpLlon of how monoenergeLlc aLoms of for example hellum or argon desorb from a meLal or glass or how waLer vapor desorbs from
lLself or a glass 1he raLe consLanL k1 ls sLrongly dependenL on desorpLlon energy Ld and Lhe LemperaLure lL can be descrlbed by Lhe equaLlon
1nkM4L u5OkP1lON
where 1 ls Lhe vlbraLlonal frequency of a molecule or aLom ln an adsorpLlon slLe and ls Lyplcally s kl ls also Lhe reclprocal of Lhe
average resldence Llme 2 LhaL a molecule or aLom spends on Lhe surface 1he desorpLlon raLe wlll also decrease wlLh Llme as Lhe surface layer
becomes depleLed 8y lnLegraLlng (43) we can show
LquaLlon (41 1) shows Lhe manner ln whlch desorpLlon raLe decreases wlLh Llme 1hls equaLlon predlcLs rapld (exponenLlal) decay of Lhe desorpLlon
raLe ln a few 1
1able 41 shows Lhe sLrong dependence of Lhe resldence Llme on Lhe LemperaLure and desorpLlon energy for Lhree represenLaLlve gasmeLal
sysLems WaLer weakly bonded Lo lLself hydrogen sLrongly bonded Lo molybdenum and Lhe lnLermedlaLe case was waLer bonded Lo a meLal
1hese resldence Llmes assume of course LhaL Lhe molecule accommodaLed Lo Lhe surface afLer lLs arrlval noL all molecules do so or sald anoLher way
Lhe sLlcklng coefflclenLs may be 1 8ellable sLlcklng coefflclenLs are lacklng 1hese resldence Llmes were calculaLed uslng desorpLlon energles
glven by Lhrllch 4 and Moraw and rasol 3
1be toom tempetotote teslJeoce tlme fot wotet oJsotbeJ oo ltself ls less tboo o mlctosecooJ ooJ
bokloq ls oot oecessoty to temove tbe bolk of tbls pbyslsotbeJ wotetlt ls temoveJ polckly beqlooloq ot oboot 2JJ0 lo (175 1ott) tbe vopot
ptessote of wotet ot 2OOc Pydrogen ls sLrongly chemlsorbed aL energles of 160 M!/(kgmole) or 40000 cal/(gmole) lL cannoL be removed wlLhouL a
hlgh LemperaLure bake or Lhe use of sLlmulaLed desorpLlon Ooe moooloyet of wotet ls cbemlsotbeJ oo o metol wltb eoetqles lo tbe tooqe 92100
MI/(kqmole) ot 2200024000 col/(qmole) 5 lt ls o ptoblem becoose lt ls boooJ jost sttooqly eoooqb to stlck ot toom tempetotote Altbooqb lt ls
botJ to temove ot toom tempetotote lt ls eoslly JesotbeJ by bokloq ot tempetototes ovet 250c coolloq tbe sotfoce bos o Jtomotlc effect oo tbe
teslJeoce tlme of oll molecolespbyslsotbeJ ooJ cbemlsotbeJ keslJeoce tlmes become vety looq os cooleJ sotfoces become ttops
WaLer ls Lhe mosL Lroublesome vapor Lo remove wlLhouL baklng because Lhe lasL monolayer desorbs over a long Llme perlod ranglng from hours Lo
days aL room LemperaLure uesorpLlon of Lhe remalnlng monolayer ls dlfflculL wlLhouL some form of baklng or nonLhermal radlaLlon Pydrogen
ls Lhe domlnanL gas LhaL desorbs from sLalnless sLeel surfaces
5econdOrder uesorption
llrsLorder desorpLlon does noL descrlbe Lhe slLuaLlon where a gas dlssoclaLes on adsorpLlon and recomblnes before desorpLlon ulaLomlc