S hp ph kh v hi trn cht hp ph rn

S hp ph kh v hi trn
cht hp ph rn
Bi:
unknown

S hp ph kh v hi trn cht hp ph rn
- S hp ph c nh gi bng lng kh hay hi (tnh theo mol) b hp ph trong mt
gam cht ca vt hp ph rn. Ngoi ra, ngi ta cn s dng i lng th tch iu
kin chun ca kh (hi) b hp ph trong mt gam vt hp ph rn,(V: xc nh c
t thc nghim, tnh bng cm3/g).
V = x.22400 (2.3)
Thng thng ng hp ph ng nhit c s dng nhiu. Da vo cc kt qu phn
tch s liu thc nghim, ngi ta chia thnh 5 dng ng hp ph ng nhit quan
trng nht.
Trng hp I, hp ph n lp, tun theo phng trnh hp ph ng nhit Langmuir.
Trng hp II, thng gp trong s hp ph vt l to thnh nhiu lp phn t cht b
hp ph trn b mt vt hp ph rn.Trng hp III t gp, n c trng cho s hp
ph m nhit hp ph bng hay nh hn nhit ngng t ca cht b hp ph.
(IV)(V)(III)(II)Trng hp IV, V tng ng vi s hp ph dng II v III c km theo
ngng t mao qun, n c trng cho h hp ph trn cc vt th xp

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S hp ph kh v hi trn cht hp ph rn

Phng trnh hp ph ng nhit Freundlich

Cc ng hp ph ng nhit c hai on thng: phn p sut p (hay nng C) thp

th hp ph t l bc nht vi p; v sau vng p cao dn th ng th chuyn
dn gn nh song song vi trc honh, c ngha l vng p sut thp hp ph t l
bc nht vi p, vng p sut cao m hp ph khng tng na l lc s hp ph bo
ha.
Nhn thy ng hp ph ng nhit gn vi dng mt nhnh ca ng parabol, do
Freundlich ngh phng trnh thc nghim:
x = k.p1 / n (2.4)

Trong x: hp ph; p: p sut kh cn bng trn cht hp ph; k, n : cc hng s. T

phng trnh (2.4) trn, ta c th rt ra phng trnh dng phng trnh ng thng:
1
logx = logk + n .logp (2.5)
Da vo s liu thc nghim, khi xy dng th vi trc tung: log x, trc honh: log
p, ta s xc nh c cc hng s k, 1/n. Vi th ny ta s d on c hp ph
nhng gi tr p cn thit.

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S hp ph kh v hi trn cht hp ph rn

Phng trnh Freundlich ch thch hp trong khong p sut trung bnh.

Dng phng trnh ny cng c th s dng trong trng hp hp ph cc cht trn b
mt phn chia lng-rn, lc p sut p c thay bng nng C.
So snh hai ng hp ph ng nhit hai nhit T1 v T2 , vi T1 < T2, ta thy
ng T2 nm di ng T1, iu chng t khi tng nhit th s hp ph gim.
Tuy nhin khi p (hay C) rt ln th hai ng u tim cn nhau, hp ph khng cn
ph thuc vo nhit .
Phng trnh hp ph ng nhit Langmuir
Khi thit lp phng trnh hp ph, Langmuir a ra cc gi nh sau :
+ B mt ng nht v nng lng.
+ Cc cht b hp ph hnh thnh mt lp n phn t.
+ S hp ph l thun nghch, c t c cn bng hp ph.
+ Tng tc gia cc phn t b hp ph c th b qua
Theo Langmuir, trn b mt cht hp ph rn c vng lc ha tr cha bo ha v vy ti
y s hnh thnh trung tm hp ph. Gi nh lc hp ph c bn knh tc dng nh, l
lc c bn cht gn ging vi lc ha tr, nn mi trung tm ch gi mt phn t cht b
hp ph v trn b mt to ra mt lp n phn t cht b hp ph. Cc phn t cht b
hp ph ny ch tng tc vi b mt cht hp ph, ch khng tng tc n cc phn
t khc.
Gi p l p sut kh, l phn b mt ti mt thi im no b phn t kh chim,
phn b mt cha b chim s l (1- ). s hp ph xy ra th cc phn t kh phi va
chm vo phn b mt cn trng, do tc hp ph t l thun vi p sut v phn
b mt cn trng : vhp = k1.p (1- )
Cn tc phn hp ph vphp s t l thun vi phn b mt b che ph: vphp = k2.
Khi cn bng hp ph c thnh lp: vhp = vphp
Ta s c: =
Nu t A =

k1.p
k2 + k1.p

k2
k1 ,

(2.6)

(A t l nghch vi hng s cn bng K, vi K =

k1
k2 ),

v nu xem =

x
xmax

, (tc l phn b mt hp ph ti mt thi im c tnh bng mc hp ph thi

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S hp ph kh v hi trn cht hp ph rn

im so vi mc hp ph cc i khi b mt b chim ht), ta suy ra phng trnh

p
Langmuir: x = xmax. 1 p = xmax. pmax
(2.7)
k

+p

Vi x : hp ph mt thi im no
xmax : l hp ph cc i
p : l p sut kh
A: i lng t l nghch vi hng s cn bng
Cc gi tr x, xm, p xc nh t thc nghim
p rt b, phng trnh c dng x = xmax. Ap (2.8)
ngha l x t l bc nht theo p trn h ta , ph hp vi dng ng thng t gc ta
ln
p rt ln, phng trnh c dng : x = xmax , trn h ta ta c mt ng song song
trc honh.

Phng trnh Langmuir phn nh kh trung thc gin hp ph, kh chnh xc i vi

nhiu mc ch thc t v l thuyt, tuy cha tht hon chnh, nhng n c xem l c
s cn thit hiu r tt c cc thuyt khc c xut sau .
Ta c th tm cc hng s trong phng trnh Langmuir bng cch chia hai v phng
trnh cho p c phng trnh ng thng.
p
x

A
xmax

1
xmax p

(2.9)

Da vo s liu thc nghim ca p v x, xy dng th vi trc tung l p/x, trc honh

l p ta s c mt ng tuyn tnh, t xc nh c gi tr ca xmax v A.
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S hp ph kh v hi trn cht hp ph rn

Phng trnh hp ph BET (Brunauer- Emmett- Teller)

Khi nghin cu s hp ph hi trn b mt rn, trong nhiu trng hp ngi ta thy
ng ng nhit hp ph c dng ch S. ng biu din cho thy sau khi t n
on nm ngang ng vi lc hp ph n phn t bo ha th hp ph cn tng
na, nh th phi c thm cc lp hp ph chng cht ln lp u tin. Trong trng
hp ny lp hp ph khng th l n phn t m l lp a phn t.
- Cc tc gi Brunauer - Emmett - Teller bng con ng nhit ng hc a ra
phng trnh hp ph ng nhit da trn cc quan im sau :
+ Hp ph vt l to thnh nhiu lp phn t chng ln nhau. Lp u tin ca cht b
hp ph hnh thnh do kt qu tng tc lc Van der Waals gia cht hp ph v cht b
hp ph, cc lp tip theo c hnh thnh do s ngng t kh.

+ Nhit hp ph lp th hai v cc lp tip theo th bng nhau v bng nhit ha lng

ca kh, trong khi nhit hp ph ca lp th nht th khc, l nhit to phc n, ln
hn nhit lng ca cc lp sau .
+ Cc phn t cht b hp ph ch tng tc vi phn t lp trc v lp sau m khng
tng tc vi phn t bn cnh.

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S hp ph kh v hi trn cht hp ph rn

Min to lp n phn t l t gc ta cho n im un A, t A tr i l s hp ph

a phn t.
- Phng trnh BET c dng :

V p0 p

1
Vm.C

C1 p
Vm.C . p0

(2.10)

Trong : po : p sut hi bo ha;

V: th tch kh hp ph p sut p
Vm : th tch kh b hp ph lp th I (n phn t)
1

C: tha s nng lng, c biu thc: C = e (qn q1). RT , vi qn l nhit ha lng, q1 l nhit
hp th kh trong lp n phn t
Khi C ln (q n = q 1 ) th phng trnh hp ph BET tng t nh phng trnh
Langmuir.
Phng trnh hp ph a phn t BET d dng chuyn sang dng tuyn tnh:
p / p0

V 1 p / p0

on bng

1
Vm.C

C1 p
Vm.C . p0 .

1
Vm.C ,

th

V p0 p

theo

p
p0 l

dc ca ng biu din bng

mt ng thng, ct trc tung mt

C1
Vm.C ,t

ta c th xc nh Vm v C.

Ngoi ra, bit Vm ta c th tnh c b mt vt hp ph So theo biu thc:

S0 =

Vm
V0 N.Wm

(2.11)

Trong N : s Avogadro
Wm : b mt chim bi mt phn t cht b hp ph lp n phn t
Vo : th tch 1 mol kh iu kin chun (22400 cm3/mol)
Thuyt hp ph BET c xem l thuyt u tin thnh cng m t qu trnh ng nhit
hp ph, s dng c nhiu trong thc t, d xut pht t nhng c s ca thuyt
Langmuir.

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