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CHNG 2 KHUCH TN PHN T

Khuch tn: s chuyn ng ca mt cu t xc nh qua hn hp di tc dng ca gradient nng ca cu t khuch tn khuynh hng di chuyn cu t theo chiu sao cho cn bng c nng v trit tiu gradient. Khi gradient c duy tr bng mt ngun cung cp khng i cu t khuch tn ti u gi tr cao ca gradient di chuyn cu t n u gi tr thp ca nng th dng chuyn ng ca cu t khuch tn s lin tc c. Khuch tn phn t qua cc lp ng yn ca cht rn hay lu cht cc pha lu cht do khuy trn : khuch tn i lu. Khi hai pha chuyn ng tip xc vi nhau b mt tip xc pha to thnh hai lp phim (do ma st gia chng). Ch chuyn ng trong lp phim v trong dng c c trng khc nhau. nhau Lp phim lun trng thi chy tng cn gia dng chy th c th trng thi chy ri c trng truyn khi trong lp phim v trong dng khc nhau. Vn tc khuch tn trong lp phim << khuch tn trong dng d lp phim c b dy rt nh quyt nh i vi qu trnh khuch tn.

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2.1 KHUCH TN PHN T

2.1.1 So snh gia khuch tn v truyn nhit

ng lc: gradient nhit gradient nng . Dng nhit chuyn ng t im ny n im khc n khng li khong trng pha sau cng nh khng cn khng gian pha trc vn tc dng nhit khng c ngha > < khuch tn. Khuch tn l mt dng d vt ch ht c vn tc xc nh. h 1- Ch c mt cu t A trong hn hp truyn n hay i khi b mt tip xc pha v dng vt cht tng cng bng dng cu t A truyn i. V d hp thu mt cu t t pha kh vo pha lng. 2- Khuch tn ca cu t A trong hn hp bng v ngc chiu vi dng mol ca cu t B khng to nn dng chuyn ng mol tng cng. VD: chng ct v cho thy khng c s thay i th tch pha kh. Tuy nhin khi lng hay th tch tng cng ca pha lng thay h i v khi lng ring i mol l thay h i. i 3- Khuch tn ca A v B xy ra ngc chiu nhng vi thng lng mol khng bng nhau. Trng hp ny thng xy ra trong khuch tn cng vi phn ng ha hc tc cht, sn phm khuch tn n v i khi b mt xc tc. phn ng d th

2.1.1 Vn tc khuch tn
N: thng lng so vi mt v tr c nh trong khng gian. J: thng lng ca mt cu t so vi vn tc mol trung bnh ca tt c cc cu t. N quan trng trong vic p dng vo thit k thit b, J c trng cho bn cht ca cu t. [mol/(thi gian).(di gian) (din tch)]

nh lut Fick

J A = DAB

CA z

(2.1)

JA ca cu t A trong dung dch vi B : lng vt cht i qua mt n v din tch b mt trong mt n v thi gian t l vi gradient nng theo phng z. DAB : h s khu kh ch h tn t ca cu t A trong t cu t B; B 2 th nguyn l [chiu di] /[thi gian]. H s khuch tn l lng vt cht i qua mt n v din tch b mt thng gc vi phng khuch tn trong mt n v thi gian khi nng vt cht gim mt n v trn mt n v chiu di theo phng khuch tn.

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H s khuch tn: c trng l hc ca cht v mi trng xung quanh (nhit , p sut, nng , dung dch lng, kh hay rn v bn cht ca cc cu t khc); c trng cho tnh cht khuch tn ca cht trong mi trng. Thng lng mol ca A i qua mt phng c nh P l lng vt cht chuy yn ng g theo vn tc trung g bnh uM v l ng g vt cht do khuch tn phn t C C
N A = ( N A + NB ) C
A

DAB

(2.4)

H s khuch tn ca cu t A vo cu t B, hay ngc li cu t B vo cu t A l nh nhau.

DAB CA C = DBA B z z

(2.6) JA = JB

Nu CA + CB = const DAB = DBA ti mt nng v nhit cho trc. Tng qut, gradient nng , vn tc chuyn ng, thng lng khuch tn tn ti theo mi phng

2.1.3 Phng trnh lin tc

Phng trnh cn bng vt cht tng qut hay phng trnh lin tc Sut lng ra Sut lng vo + Vn tc tch t = Vn tc to thnh
( ux uy uz = 0 (2.13) + + + uy + uz + ) + ux x y z x y z t

Nu khi lng ring ca dung dch khng i,

Phng trnh dng lin tc (Continuity Equation) Xt cu t A

ux

ux uy uz + + =0 x y z

(2.14)

u y uz u A 2C 2C A 2C A + ) (2.16) + u y A + uz A + A ( x + + ) = M A DAB ( 2A + x y z x y z x y2 z2
ux C A C A C A C A 2C A 2CA 2CA + uy + uz + = DAB ( + + ) x y z t x2 y2 z2

Vi dung dch c khi lng ring khng i

Khi vn tc bng khng v khng c phn ng ha hc

C A 2CA 2CA 2CA ) = DAB ( + + t x2 y2 z2

(2.18)

nh lut Fick th hai

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2.2 KHUCH TN PHN T THEO MT CHIU

TRONG LU CHT NG YN HOC CHY DNG TRNG THI N NH
Khuch tn ch theo mt phng z:
NA CA NA 2 NA D C N + NB C = AB ln A C N A + NB z NA A 1 N A + NB C

(2.21)

2.2.1 Khuch tn phn t trong pha kh p dng nh lut kh l tng

CA p = A = yA C Pt

C =

Pt N = V RT

trong : pA - p sut ring phn ca cu t A Pt - p sut tng cng; yA - nng phn mol

1- A khuch tn n nh qua B khng khuch tn

;

VD: hp thu amoniac (A) trong hn hp vi khng kh (B) vo trong nc ch c amoniac ha tan vo nc trong pha kh xem nh ch c amoniac khuch tn qua khng kh khng khuch tn NA NB = 0; NA = const; = 1
NA =
Pt pA2 = pB2

DAB . Pt ln RTz Pt pA1

Pt pA2

N A + NB

(2.26)

Pt pA1 = pB1

NA =

pB2 pB1 = pA1 pA2 pBM = pB2 pB1

pB DAB Pt pA1 pA2 ln 2 RTz R z pB2 pB1 pB1

(2.27)

ln

pB2 pB1

NA =

DAB Pt ( pA1 pA2 ) RTzpBM

(2.29)

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2- Khuch tn n nh ng mol nghch chiu

;

VD: qu trnh chng ct

NA = NB = const

NA =

DAB ( pA1 pA2 ) RTz

(2.33)

3- Khuch tn n nh trong hn hp nhiu cu t s dng h s khuch tn hiu dng:

1 = DAm
i= A

DAi ( yi N A yA Ni )
N A yA
i= A

DAm

1 yA
i= B i DAi n

Ni

1
i= B i DAi n

y'

i= A

Ni

N A D AB Pt ln RTz N A

i= A n

i= A

N i Pt p A 2 N i Pt p A 1

V d 2.1: Oxygen (A) khuch tn qua monoxid carbon (B) khng khuch tn trng thi n nh. p sut tng cng l 1atm, nhit . p sut ring phn ca oxygen ti hai mt phng cch nhau 0,2 cm ln lt l 100 v 50 mmHg. H s khuch tn ca hn hp l 0,185/s. Tnh thng lng khuch tn ca oxygen theo mol/s. , cm2/s; ; Pt= 1atm; ; z=0,2cm , Vi DAB=0,185 R = 82,06 cm3atm/molK; pA1 = 100/760 = 0,137 atm; T=273K; pA2 = 50/760 =0,137 atm;

pB1 = 1 - 0,1317 = 0,8683 atm; pB2 = 1 0,0658 =0,9342 atm; pB1 pB2 0, 8683 0, 9342 p BM = = = 0, 901 atm pB1 0, 8683 ln ln 0, 9342 pB
NA DAB Pt 0,185 1, 0 ( 0,1317 0, 0658) = ( pA1 pA2 ) = 82, 06 273 0, 2 0, 901 RTz pBM
2

= 3,79106 mol/s.cm2

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H s khuch tn ca cht kh - Ph thuc: nhit , p sut, v bn cht ca cc cu t. - n v : cm2 /s Bng 2.1: H s khuch tn v s Sc cho cc cht kh trong khng kh v 1atm
Kh Acid acetic Aceton Amoniac Carbon dioxid Hi nc H s khuch tn DAB, cm2/s 0,106 0,082 0,215 0,137 0,219 Sc* 1,24 1,60 0,61 0,96 0,60

S Sc c tnh vi gi tr / ca khng kh tinh khit l 0,131 0 131 cm2/s - khng c s liu thc nghim, h s khuch tn gia hai kh A v B nhit T, p sut P c xc nh: theo thuyt ng hc cht kh
DAB = 1 1 1/ 2 ( + ) 1/ 3 1/ 3 2 M MB P( VA + VB ) A 4, 3 103 T3 / 2

H s khuch tn ca cht kh - H s khuch tn gia hai kh A v B nhit T, p sut P xc nh theo thuyt ng hc cht kh
DAB = 4, 3 103 T3 / 2
1/ 3 P( VA 1/ 3 2 + VB )

1 1 1/ 2 + ) M A MB

(2.36)

T - nhit tuyt i, K; P - p sut tuyt i, atm MA, MB - khi lng mol ca kh A v kh B, g/mol VA, VB - th tch mol ca kh A, kh B xc nh bng tng th tch nguyn t ca cc nguyn t to thnh phn t kh. kh Trng hp trong phn t c vng benzen, naptalen, anthracen th th tch tnh c phi tr i hng s cu trc. Bng 2.2: Th tch mol v th tch nguyn t ca mt s cht

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H s khuch tn ca cht kh V d 2.3: c tnh h s khuch tn ca hi etanol (A); qua khng kh (B) 1atm, 0oC Gii: dng (2.36) p (2 36) vi T = 273K; 273K Pt= 1 atm; t MA= 46,07; 46 07 MB= 29; 29 VA= 2(14,8) + 6(3,7) + 7,4 = 59,2cm3/mol; VB= 29,9/mol

DAB =

1 1 1/ 2 ( + ) 1/ 3 1 / 3 2 46, 07 29 1(15, 2 + 29, 9 )

4, 3 103 2733 / 2

2.2.2 Khuch tn phn t trong cht lng

NA =
N /( N A + N B ) x A2 NA D AB ( )tb ln A N A + NB z M N A /( N A + N B ) x A1

(2.21)

1 A khuch tn n nh qua B khng khuch tn 1NB = 0; NA = const;

xBM =

ln( xB2 /xB1 )

xB2 xB1

NA =

DAB ( )tb .( x A1 x A2 ) zxBM M

22 Khu Kh ch h tn n nh h ng mol l ngh hch h chi hiu NA = -NB = const;

NA = DAB DAB ( CA1 CA2 ) = ( )tb ( x A1 x A2 ) z z M

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NH Cl23 CO 2

H s khuch tn ca cht lng -H s khuch tn ca cht lng thay i ng k theo nng . Bng 2.3 cho mt s gi tr h s khuch tn trong cht lng
Dung chat chat NH3 CO2 Dung moi moi Nhiet o, o 0C 5 15 10 20
0,6 ' VA

Nong Nong o, mol/l 3,5 1,0 0 0

Nc Nc

He so so khuech khuech tan 2 5 cm /s.10 1,24 1,77 1,46 1,77

DAB =

7, 4 108 ( M B )0,5 T

, cm2 /s

- MB khi lng mol ca dung mi; T - nhit , K - nht ca dung dch, cP - VA th tch mol ca dung cht tnh theo bng 2.2 = 75,6 cho nc l dung cht

2.2.4 Khuch tn phn t trong dung dch gel sinh hc Tng tc v to ni trong khuch tn Phng trnh tnh h s khuch tn cho dung cht sinh hc H s khuch tn trong g dung g dch vi nc ca cc dung g cht sinh hc c phn t lng ln hn 1000 c th c c tnh gn ng theo phng trnh Polson hiu chnh nh sau
DAB = 9, 40 1010 T
(2.42)

( M A )1 / 3

: nht ca nc, c cP; MA- phn t lng; T - nhit , K. K

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2.23 Khuch tn phn t trong trong cht rn Khuch tn trong cht rn ra lm hai loi: khuch tn trong cht rn tun theo nh lut Fick v khng ph thuc ch yu vo cu trc thc t ca cht rn khuch tn trong cht rn xp ph thuc vo cu trc xp ca vt liu 1- Khuch tn trong cht rn tun theo nh lut Fick
dx A C + A ( N A + NB ) dz C th ng r t nh do c th b qua ( C A /C )( N A + N B ) N A = CDAB

Gi s C khng i cho khuch tn trong cht rn

NA =

DAB dCA dz

khuch tn qua mt lp cht rn iu kin n nh

NA = DAB ( C A1 C A2 ) z2 z1

khuch tn theo p phng g bn knh khuch tn theo phng bn knh qua tng hnh tr vi bn knh trong r1, bn knh ngoi r2 v chiu di L:
NA dC A = DAB 2rL dr
N A = DAB ( C A1 C A2 ) 2L ln( r2 / r1 )

H s khuch tn trong cht rn khng ph thuc vo p sut ca cht kh hoc lng bao quanh cht rn. V d, nu kh CO2 khuch tn qua mt lp cao su, DAB c lp vi pA l p sut ring phn ca CO2 ti b mt. Tuy nhin ha tan ca CO2 vo cht rn t l thun vi pA.

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ha tan ca dung cht kh A trong cht rn Biu din theo S, cm3 dung cht kh (0oC,1 atm)/cm3 cht rn.atm p sut ring phn ca A hay S = cm3(0oC,1 atm)/m3.atm
CA = S. pA mol/cm3 22400
CA = S. pA 22, 4

kmol/m3

V d 2.6/35 thm thu ca dung cht kh A trong cht rn thm thu PM,cm3 dung cht kh A (0oC, 1 atm) khuch tn trong mt giy qua mt n v tit din cm2 ca cht rn c b dy 1 d 1cm i tc t ng ca sai i bit p sut l 1 atm t
C A1 = 22400 SpA1
NA = DAB S( pA1 pA2 )

22400( z2 z1 )

22400( z2 z1 )

PM ( pA1 p A2 )

PM = DAB . S,

cm3 /( s.cm2 . atm/cm)

2- Khuch tn trong cht rn xp ph thuc vo cu trc a) Khuch tn ca cht lng qua cht rn xp

NA =

DAB ( C A1 C A2 ) ( z2 z1 )

Hnh 2.5: S cht rn xp tiu ti biu

- rng; DAB - h s khuch tn ca mui trong nc - h s hiu chnh on ng khuch tn ln hn vi cht rn tr thay i t 1,55.

H s khuch tn hiu dng:

DAe =

DAB cm2 /s

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b) Khuch tn ca cht kh qua cht rn xp

NA =

DAB ( C A1 C A2 ) ( 2 1 )
0,20 2,0

DAB ( pA1 pA2 ) RT( z2 z1 )

thay i theo nh sau:

0,40 1,75

0,60 1,65

2.3 KHUCH TN I LU
J A = ( DAB + N ) CA z

- N: h s khuch tn dng xoy, ph thuc vo cc tnh cht ca lu cht cng nh vn tc v v tr trong dng chuyn ng khng th ly tch phn trc tip xc nh thng lng cho mt sai bit nng cho trc

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