Mc lc:

1.1. Bi cnh - Lch s

1.2. Cc l thuyt

1.2.1. Thuyt Langmuir

1.2.2. L thuyt hp ph

1.2.3. Quy trnh nghin cu hp ph ng nhit

1.3. Khi nim L thuyt BET

1.4. Cc phng trnh nghin cu BET

1.4.1. Xy dng ng ng nhit hp ph

1.4.2. M hnh Langmuir

1.4.3. M hnh Frienlich

1.5. Gii thiu mt s my s dng phng php BET

1.5.1. Model Micromeritics TriStar II Plus o hp ph vt l t ng

1.5.2. Micromeritics Gemini VII 2390 Phn tch dng din tch b mt

1.6. Hnh nh lin quan

1.7. ng dng

1.8. Ti liu tham kho

 1.1. Bi cnh - Lch s [1], [2]

c ch trng pht trin vo nm 1938.

Nm 1938, Stephen Brunauer , Paul Hugh Emmett , v Edward Teller xut bn

bi bo u tin v l thuyt BET trong Tp ch ca Hip hi Ha hc M.

Trong thc t ngi ta thy c nhiu dng ng ng nhit hp ph khc vi

ng ng nhit Fruendlich hay Langmuir. Cc nh khoa hc Brunauer,
Emmett v Teller tm ra l thuyt gii thch v mi quan h nh lng
chng di dng phng trnh ng nhit BET. [5]

1.2. Cc l thuyt

1.2.1. Thuyt Langmuir [3]

Cc phng trnh Langmuir (cn c gi l ng nhit Langmuir, phng

trnh hp ph Langmuir hoc phng trnh Hill - Langmuir) hp ph cc phn
t trn mt b mt vng chc o p sut kh hoc s tp trung ca n trn b
mt rn nhit c nh. Phng trnh c pht trin bi Irving Langmuir
nm 1916.

1.2.2. L thuyt hp ph [7]

Hp ph trong ha hc l qu trnh xy ra khi mt cht kh hay cht lng b ht

trn b mt mt cht rn xp. Cht kh hay hi c gi l cht b hp ph
 (adsorbent), cht rn xp dng ht kh hay hi gi l cht hp ph
(adsorbate) v nhng kh khng b hp ph gi l kh tr. Qu trnh ngc li
ca hp ph gi l qu trnh gii hp ph hay nh hp ph.

Trong qu trnh hp ph c to ra mt nhit lng, gi l nhit hp ph. B mt

cng ln tc xp ca cht hp ph cng cao th nhit hp ph to ra cng
ln.

C 2 qu trnh hp ph: hp ph vt l v hp ph ha hc.

Gia hp ph vt l v hp ph ha hc tht ra kh phn bit, c khi n tin

hnh song song, c khi ch c giai on hp ph vt l tu thuc tnh cht ca
b mt ca cht hp ph v cht b hp ph, tu thuc vo iu kin qu trnh
(nhit , p sut... )

1.2.3. Quy trnh nghin cu hp ph ng nhit [6]

Cc khi nim c bn:

Hp ph l hin tng tch lu cht trn b mt phn cch pha.

Lu : Phn bit qu trnh hp ph v qu trnh hp th.

Cht hp ph: l cht thu ht phn t (ion) ln b mt.

Cht b hp ph: l cht c tch lu trn b mt phn cch pha (thng kho
st l rn - lng).

ng hc hp ph l din bin nng cht b hp ph (cn li trong dung

dch) theo thi gian. ng cong biu din nng theo thi gian c gi l
ng ng hc hp ph.

ng ng nhit hp ph biu din s ph thuc dung lng hp ph theo

nng cn bng mt nhit xc nh.
 Dung lng hp ph l lng cht b hp ph trn mt n v cht hp ph ti
thi im cn bng.

Nghin cu hp ph:

Bao gm 2 ni dung: (1) kho st ng hc hp ph v (2) xy dng ng

ng nhit hp ph.

Kho st ng hc hp ph:

Vic kho st ng hc hp ph gip chng ta nh gi c tc qu trnh

hp ph l nhanh hay chm, xc nh c thi gian t cn bng lm th
nghim xy dng ng ng nhit hp ph.

Quy trnh thc nghim:

Tu theo c im ca h hp ph m ta c th tin hnh theo quy trnh 1 hay 2.

Quy trnh 1: Ly 1 L dung dch, khuy u (c th bng my khuy t hoc

khuy c), thm m (g) cht hp ph v tip tc khuy trong 10 pht (mc ch
l b mt cht hp ph thm t hon ton). Sau thm V (ml) dung dch
cht hp ph gc v bt u tnh gi. Sau cc thi im 5, 10, 20, 40, 60, 120,
180 pht ly mu v lc nhanh qua giy lc 0,45 um (tt nht l lc bng thit
b lc cm tay). S lng mu ly khong 7 10 (lu phi xc nh nng
ti thi im ban u (mu s 0), mu ny cn ly lp li 2 3 ln). Mu sau
lc c bo qun bng cht bo qun tng ng.

Khi lng cht hp ph m v th tch cht gc V phi c tnh ton trc khi
lm th nghim c nng mong mun. Yu cu i vi chn m v V l:
phi hn ch c sai s trong qu trnh phn tch, o c; hiu xut hp ph
khi cn bng t khong 30 70 %.

Thi gian ly mu c th thay i tu theo bn cht (cch tt nht la chn

thi gian ly mu l tham kho cc nghin cu cng loi c thc hin).
Xc nh thi gian cn bng: Qu trnh hp ph coi nh t cn bng khi ta c 3
s liu st nhau dao ng quanh 1 con s (hay sai lch gia 2 s liu cui cng
khng qu 2%).

Quy trnh 2: Trong quy trnh ny, s lng bnh phn ng (thng s dng bnh
tam gic c nt cao su) bng vi s lng mu ly (7- 10). Vi mi bnh ta cho
th tch dung dch v lng cht hp ph v cht b hp ph l nh nhau. Cc
bc th nghim c thc hin tng t quy trnh 1. Sau mi thi im, mt
bnh c ly ra lc.

ng ng hc hp ph:

Biu din bin thin nng trn th C t v xc nh thi gian t cn

bng.

1.3. Khi nim L thuyt BET

BET (Brunauer Emmett - Teller) l thuyt nhm gii thch hp ph vt l

ca phn t kh trn mt b mt vng chc v l c s cho k thut phn tch quan
trng o din tch b mt ring ca vt liu. [2]

L thuyt BET cho rng s hp ph kh, hi trn b mt cht rn l hp ph vt l,

giai on p sut thp th tun theo quy lut nh ca phng trnh ng nhit
hp ph ca Langmuir, nu tng p sut th s din ra qu trnh hp ph a lp khi
p sut tin ti bng p sut hi bo ha trn b mt rn th c th xy ra hin
tng ngng t trong cc mao qun hp ph. Nh vy theo BET cc phn t cht
hp ph khng chuyn ng t do trn b mt v khng tng tc vi nhau,
nhng im khc nhau c th hnh thnh nhiu lp hp ph nhng tng b mt l
khng i. thit lp phng trnh ng nhit BET ngi ta tha nhn gi
thuyt ca Langmuir v b sung thm mt s iu: [5]
 Enthanpy ca cc phn t khng thuc lp th nht u bng nhau v bng
enthanpy ha lng.

S lp hp ph tr nn v cng ln p sut bo ha.

1.4. Cc phng trnh nghin cu BET [6]

1.4.1. Xy dng ng ng nhit hp ph:

Quy trnh thc nghim:

xy dng ng ng nhit hp ph, ta tin hnh th nghim vi 7- 10 nng

ban u (C0) cht b hp ph khc nhau, cng 1 nng cht hp th. Cc iu
kin khc (pH, nhit , lc ion, th tch, tc khuy nh nhau trong mi th
nghim. Qu trnh hp ph vi mi nng ban u c tin hnh qu thi gian
cn bng hp ph (khong 5 10 % m bo hp ph t cn bng). Sau khi
t cn bng, cc mu c lc xc nh nng cn li (ch a hp ph) sau
khi cn bng.

ng ng nhit hp ph:

Gi: V l th tch dung dch phn ng.

m l khi lng cht hp ph.

C0 l nng cht hp ph ban u.

Ccb l nng ti thi im cn bng.

Dung lng hp ph c tnh nh sau:

Nh vy, vi mi nng ban u C 0 ta s c mt dung lng hp ph ng vi

nng cn bng tng ng, biu din s ph thuc ca dung lng hp ph vo
nng cn bng ta thu c hg th c dng nh sau:
X l s liu thc nghim:

S liu thc nghim c th c x l theo mt s m hnh hp ph ng nhit.

Hai m hnh ph bin c s dng l: m hnh Langmuir v m hnh Frienlich.

1.4.2. M hnh Langmuir:

Trong : : dung lng hp ph ng vi nng C.

m: dung lng hp ph cc i n lp.

C: nng cht b hp ph lc cn bng.

Km: hng s cn bng hp ph.

xc nh m, Km trong phng trnh Langmuir ta tuyn tnh ho phng trnh

trn thnh:

T cc s liu nng cht b hp ph thi im ban u v thi im cn bng,

lng cht hp ph ta tnh c cc thng s trong bng sau:

S th nghim Ccb 1/Ccb 1/

1
2

N

Biu din s ph thuc 1/T theo 1/C cb. ng thu c s l mt ng thng vi

giao im vi trc tung l 1/ T m, dc ca ng thng l 1/ T mKm. T ta xc
nh c cc thng s trong phng trnh Langmuir.
1.4.3. M hnh Frienlich:

Trong : : dung lng hp ph ti thi im cn bng.

C: l nng cht b hp ph trong dung dch trng thi cn bng g/l.

K: l hng s ng nhit Freundlich.

n: h s m ng nhit Freundlich, (n >1).

xc nh K, n trong phng trnh Frienlich, ta tuyn tnh ho phng trnh trn

thnh:

ln() = ln(K) + ln(C)/n

T cc s liu kho st ta tnh ton c nh bng s liu sau:

S th nghim Ccb Ln(Ccb) Ln( )

1
2

N

Biu din s ph thuc ln() theo ln(Ccb) ta s thu c mt ng thng. T

dc ca ng thng ta xc nh c n, t giao im vi trc tung ta xc nh
c K.

M hnh no m t tt hn qu trnh hp ph?

tr li cu hi ny thng thng ta da vo cc gi tr h s tng quan R 2 ca

cc ng tuyn tnh, R2 cng gn 1 th m hnh tng ng tt hn.

Nhng lu khi lm th nghim

S hp ph chu nh hng bi nhit , pH, mi trng (lc ion, cht hp ph
cnh tranh). Nn khi tin hnh th nghim ta cn o (theo di cc yu t ny). Cc
thng s ny cn n nh trong sut th nghim.

1.5. Gii thiu mt s my s dng phng php BET

1.5.1. Model Micromeritics TriStar II Plus o hp ph vt l t ng [8]

c tnh k thut:
Thit b phn tch din tch b mt v l xp: ba cng mu, l thit b phn tch
hp ph vt l t ng hon ton vi chc nng c lin tc, chi ph vn hnh
thp, ng thi phn tch cng lc 03 mu xc nh din tch b mt ring
(Specific Surface Area) v phn b kch thc l (pore size distribution ) t 17
n 5000 Angstroms. Bnh phn tch c ch to t thp khng g chng chu n
mn v nng cao kh nng qun l kh.C th nng cp ln tnh nng o din tch
b mt xung thp n 0.001m2/g vi ty chn s dng kh Krypton . Kt hp vi
phn mm nn d liu tng tc MicroActive. Giao din iu khin c nng
cao vi cc ch bo thi gian thc v lch bo tr h thng. Gi bao gm h
thng bm chn khng vi chn khng cao, in p 100-230 volt, 50/60 Hz.

Cc kh phn tch: N2, Kr, O2, Ar, CO2, CO, Butane hoc bt k kh khng n mn
no khc.

Cc c tnh ni bt ca h thng phn tch:

Phn tch c lp v ng thi 3 mu

Hon thnh phn tch BET 5 im trong 20 pht

Hiu chun cm bin p sut ph hp chun NIST

o din tch b mt xung n 0.01 m2/g s dng kh Nit

C nhiu ch cho th tch trng: nhp vo, o, tnh ton

Cc ch p sut bo ha: nhp vo, o hoc ghi lin tc

C 6 cng chun b mu ring bit s dng (xem phn di)

Cng ngh o ng nhit c cp bn quyn duy tr mc dung dch lm

lnh trong ng mu ln n 24 gi phn tch lin tc khng cn ngi gim
st
 M un bm chn khng phn t turbo bao gm bm ht chn khng cao
turbo tch hp vi bm mng th

K thut DFT i cho php xc nh cc tnh cht ca Cacbon l nh

Cc k thut phn tch/bo co thc hin c trn my

Din tch b mt n im BET Din tch b mt a im BET

Hp ph ng nhit (isotherm) Gii hp ph ng nhit (isotherm)

Din tch b mt Langmuir Th tch l xp va BJH mesopore

Din tch v th tch l nh Tng th tch l xp

th DeBoer t-plot & cc loi khc Phng php MP

Chun ng nhit th s

th t s f-Ratio Nhit ca hp ph

ng nhit Freundlich & Temkin L thuyt hm mt

Cc ng nhit chun Horvath-Kawazoe

Dubinin-Radushkevich Dubinin-Astakhov

Chi tit cc ty chn v tm lc

Xp chng th (bao gm c d liu nn)

Cc c tnh ca phn mm:

Tng thch h iu hnh Microsoft Windows.

Chia s a mng v my tnh mng.

Chc nng chnh sa d liu trn mn hnh v xut d liu nh dng n

gin.

iu khin ti a 4 thit b t mt my tnh.

 Model ASAP 2020 o Hp Ph Vt L T ng.

1.5.2. Micromeritics Gemini VII 2390 Phn tch dng din tch b mt [9]

Micromeritics Gemini VII 2390 Series phn tch din tch b mt nhanh chng v
ng tin cy xc nh din tch b mt chnh xc. Chi ph thp, tc cao, s dng
n gin, tin cy cao, chc chn v ginh c v tr quan trng trong cc
phng th nghim nghin cu v kim sot cht lng trn ton th gii. Xc nh
BET n v a lp trn cc khu vc b mt Langmuir, tng khi lng l, v cc
phng php phn tch vi m.

Kh nng c o

Thit k ca Gemini cung cp kh nng c o ch c cc sn phm t tin

hn. Nhiu tnh nng li thi vn c trong cng c tch truyn thng tnh c
loi b thng qua ch t chi. iu ny cung cp mt cng c o lng chnh
xc hn v n nh hn chnh xc hn, do cung cp kh nng c o. V d,
s dng nit, cc my Gemini c kh nng thc hin cc php o trn vt liu vi
din tch b mt rt thp, khi m cng c tng t s yu cu s dng Krypton
nhng Krypton khng ch t hn m o ng nhit krypton i hi p lc thp
hn v yu cu thnh phn b sung trong cng c o lng nhng p lc thp
hn. Nu khng c yu cu b sung, my Gemini gi v chi ph vn hnh vn cn
thp.

Cc phin bn Windows d dng lm theo nhng ci t v kim tra xc

minh h thng m bo hiu sut ti u v tin cy cao.

Cho php o din tch b mt thp m khng i hi krypton.

Cc u im

Chi ph thp

Hot ng hon ton t ng

Thng lng cao - ln n bn my Geminis c th hot ng vi 1 my tnh

C kh nng o din tch b mt ca vt liu kch thc nh

La chn ch phn tch (qut hoc cn bng)

Khng c li nhit khuch tn

Thit k bng thp khng g

1.6. Hnh nh lin quan [4]

+ T th ng hp ph ng nhit BET ca N 2 trn gm xp, ti p/po = 0 th
lng N2 hp ph ca vt liu ch khong 0,15 cm 3/g nhng khi p/po tng t 0,85
n 1 th lng N2 hp ph ca vt liu tng t bin t 0,7 n 3,1 cm3/g.

Tuy nhin, cng t th ng hp ph ng nhit BET ca N 2 trn gm xp c

gn CNT, ti p/po = 0 th lng N2 hp ph ca vt liu l 2 cm3/g vy khi p/po
tng t 0,85 n1 th lng N2 hp ph ca vt liu tng t bin t 12 n 47
cm3/g. Nh vy, sau khi gn CNT, lng N2 hp ph ca vt liu tng ~ 17 ln.

+ Ngoi ra kt qu o din tch b mt ca vt liu gm xp c gn ng nano

cacbon theo BET din tch tng ln ~ 16 ln (12,6 m 2/g) so vi vt liu gm xp
khi cha gn ng nano cacbon (0,8 m2/g).

+ Khng ch vy, t th biu din din tch b mt ri ng ca gm xp, i vi

cc mao qun c ng knh t 1 - 5 nm th din tch ln nht l ~ 0,13 m 2/g.nm
nhng cng t th ca gm xp gn CNT, vi cc mao qun c ng knh
t 1 5 nm th din tch l ~ 1,7 m 2/g.nm. Nh vy, din tch b mt ring ca
cc mao qun t 1 5 nm l cc mao qun c kh nng tt hp ph cc ion kim
loi nng tng ~ 13 ln. iu ny ng ngha vi kh nng hp ph ca gm
xp sau khi gn CNT tng ln nhiu.

1.7. ng dng [2]

- Xc nh din tch b mt bn trong ca nhiu vt liu rn xp:

+ Xc nh cc b mt bn trong ca xi mng dn

+ Xc nh kh nng hp ph cao ca than hot tnh (bng cch cho hp ph kh

Nit lng).

1.8. Ti liu tham kho

[1] Determination of the surface area by the BET mothod Ngun:

http://www.scribd.com/doc/202902584/080425-Tobias-BET

[2] http://en.wikipedia.org/wiki/BET_theory

[3] http://en.wikipedia.org/wiki/Langmuir_equation

[4] Nguyn Tun Nam Nghin cu ch to, c trng cu trc vt liu ng nano
cacbon trn gm v ng dng x l asen trong nc b nhim. Ngun:
dl.vnu.edu.vn/bitstream/11126/.../01050000959.pdf
[5] L Xun Hi AMH CN Qu Trnh & Thit B

[6] Cao Th H, V Ngc Duy Quy trnh nghin cu hp ph ng nhit.

[7] http://vi.wikipedia.org/wiki/H%E1%BA%A5p_ph%E1%BB%A5

[8] http://khoatri.com/1/model-asap-2020--do-hap-phu-vat-ly-tu-dong.aspx?
langId=Vi

[9] http://www.azonano.com/equipment-details.aspx?EquipID=294