NHIT NG HC CC HIN TNG B MT

1.

Khi nim chung

Xt vng ranh gii pha ngn cch I v II c tit din As. V s ph thuc ca nng cu t 1 theo khong cch thng gc vi b mt Hnh 1:

Gi nng b mt '1 l lng tha cu t 1 so vi trong V'I v V'II : 1As = n1 C1IVI C1IIVII 1.1. Nng b mt V tr y" . S thay i nng b mt l: (1)

(i i) = (CiII CiI )( y y)

(2)

Clng Chi 0, chn v tr mt phng phn chia lm cho = 0, v ch c mt cu t hin din. Theo (1), ta thy v tr ny, hai vng bng nhau. Khi C II C Ij = 0, xt (2), j khng b nh hng v tr mt phng phn chia. j

1.2.

Nng lng t do v entropy b mt YS AS = Y niI .Yi I niII .Yi II

Yi I v Yi II l cc i lng mol ring phn thng thng trong pha I v II.
niI v niII l s mol trong pha th tch I v II.

Cc nh ngha Y = G,S b mt: (3)

1.3.

Sc cng b mt
1/18

 G = A S

T , P , ni

(4)

Vi phn ton phn

dG = SdT + VdP + dAS + idni (5)

Trong qu trnh tng b mt mt lng dAS T, P = const, ni = const theo nh ngha nng lng t do b mt (3), ta c, kt hp vi Gi I = Gi II = i :

tng dniI + dniII c trng cho bin thin s mol cu t i trong cc pha th tch. y chnh l cu t cho vo pha b mt trc c nng b mt bng 0. Vy: v
dniI + dniII = idAS

GS dAS = dAS i dniI + dniII

GSdAS = dAS + i i dAS = GS ii (6) (7) (8) (9)

Vi phn (6): d = dGS idi idi dGS = SSdT + idi Thay (8) vo (7): d = SSdT idi y l phng trnh c bn ca sc cng b mt do Gibbs tm ra.

2.

Ranh gii pha lng-hi 2.1. H mt cu t Sc cng b mt trong khng kh c P = 1 atm . Th d: thc(C2H5OH) o(C2H5OH) dS = SSdT = 22,75 0,3 = 22,27 0,1 20oC dyne/cm (10)

H mt cu t khng c nng b mt nn: Nhit hp ph trong mt n v b mt hnh thnh mt cch thun nghch khi lng lng v lng hi khng i v TSS = const, trong : SS =
d dT

(11)

Nu din tch b mt b mt i (bt thun nghch) P = const, V = const, ngha l cng i km vi sc cng b mt khng c ly i th nhit s ta ra, HS s l: HS = GS + TSS = T
d dT

(12)

Sc cng b mt ca cc cht lng tinh khit c thay i tng t nhau theo T : Phng trnh thc nghim : = 0 (1 Tr )
11 9

2/18

Tr l nhit rt gn =

T , vi Tc nhit ti hn. Tc

0 l hng s thc nghim , l sc cng b mt ca cht lng siu lnh gi thuyt 0oK. 0 lin quan n cc tnh cht khc ca cht lng. Theo (13), entropy b mt l: SS =
11 0 (1 Tr )2 9 9 Tc

(14)

0 SS 0

khi T Tc

2.2.

H 2 cu t

C hai loi ranh gii gia hai pha lu cht trong h hai cu t: ranh gii pha lng-hi tng t vi ranh gii ca h mt cu t. - ranh gii lng-lng gia hai cu t khng tan ln Trng hp u, nhit v thnh phn lng l hai thng s c lp v c mt nng b mt. (9) tr thnh: d = SSdT 2d2 trong , ta chn 1 = 0 v k hiu 2(1) = 2. Cng theo nh ngha entropy b mt phi tng ng vi 1 = 0. Chn x2 ca cht lng l bin thnh phn c lp, do :
d2 = S2dT + V2dP + 2 dx2 x 2 T , P

(15)

(16)

p sut c xc nh bng cc tnh cht ca pha th tch v l p sut hi cn bng ca h. C th vit (16) dng: d2
2 P S2 V2 dT + x dx2 T x2 , bh 2 T , bh

(17)

Kt hp vi (15): d

2 P S S 2 S2 + 2V2 dT 2 x dx2 (18) T x2 , bh 2 T , bh

Entropy mol ring phn v th tch mol ring phn l tnh cho cht tan trong pha lng (v x2 ly cho dung dch).

3/18

 i lng trong ngoc c th xem nh l tng entropy trn mt n v b mt T x2 tng ln khi V= const.

S hng u tin Ss l entropy ca b mt to nn v 2 S2 l entropy ca 2 mol cu t 2 v trc y n hin din trong pha th tch. Khi ly i 2 mol cu t 2 l ly i th tch 2 S2 s c b li bng hi : V
S P chnh l ca qu trnh bay hi, V T

i lng th ba l entropy qu trnh bay hi cn thit b p cho th tch 2V2 .

Theo quan im trn, nhit hp th trong s tng b mt, thun nghch trn mt n v din tch khi th tch khng i l T i vi h hai cu t cng nh trong h mt cu T x2 t. Ngc li, hiu ng nhit ca s ph v bt thun nghch b mt lng-hi khi th tch khng i l:

H hai cu t kh nng xc nh nng da vo s bin thin ca theo thnh phn dung dch.
T (18) 1 = 2 x x 2 T ,bh 2 T
1

(19)

S dng fugat nh l bin c lp s cho dng phng trnh n gin hn, tin li v P ring phn c th s dng nh fugat P thp.

2 =

1 RT

ln f 2
T

(20)

Trong dung dch l tng fugat t l vi phn mol: 2 =

1 RT ln x 2

dd l tng

(21)

p dng (20) cho dung dch nc-ru etylic

Bng 1. Sc cng b mt v nng b mt ca dung dch 25oC.

x2 1,00 0,90 0,80 0,70 0,60 0,50

, dyne/cm 21,93 22,59 23,26 23,93 24,67 25,43

logP2, mm 1,771 1,722 1,679 1,639 1,600 1,565

210-13, pht/cm2 14,0 16,5 17,5 20,4 23,0

21010, mol/cm2 2,32 2,74 2,91 3,39 3,82

4/18

0,40 0,30 0,25 0,20 0,15 0,12 0,10 0,064 0,04 0,02 0,00

26,43 27,60 28,49 29,97 32,20 34,42 36,72 42,13 47,86

1,529 1,492 1,467 1,428 1,372 1,316 1,256 1,097 0,908 0,602

29,5 33,5 37,8 40,3 42,3 42,2 40,7 37,2 32,2 26,8

4,90 5,56 6,28 6,69 7,02 7,01 6,76 6,18 5,35 4,45

2.3.

H a cu t

B mt lng-hi ca mt h c nhiu hn hai cu t c cng tnh cht nh ni. Hiu ng nhit th tng t. S nng b mt th tng ln. Vi h k cu t, phng trnh (9) cho:
k P d = S s i (1) S i Vi dT T xi ,bh i =2

k i =2

i (1)

RTd ln f i

(22)

S bin thin ca theo T chnh l i lng entropy (trong du ngoc). c (k 1) nng b mt th fugat (hay hot ) ca (k 1) cu t cht tan phi c xc nh trong k dung dch khc nhau vi thnh phn dung dch c khc nhau va v cng nhit . S khc bit thnh phn ny s cho ta (k 1) phng trnh c dng nh phng trnh (22) nhng khng c s hng u, v dT = 0. Gii h phng trnh trn tm cc nng b mt.
3. Quan im nhit ng v tnh cht b mt

Xt b mt phng.
5/18

Tu i kin P = const hay V = const Bin thin dG v F ca qu trnh: dG = SdT + VdP + dAS + idni F = SdT PdV + dAS + idni Cc phng trnh trn p dng cho ton h, k c pha th tch. Nhc li : i vi vi phn ton phn dZ = L(x,y)dx + M(x,y)dy Z th L(x,y) = v M(x,y) = x y v
Vy:
Z y x

(5) (23)

L 2Z M = = y xy x

S A S
S A S
-

= T P , AS , ni T , P , ni
= T V , AS , ni T ,V , ni

(24)

(25)

Lu s khc bit khi gi cho P v V khng i. i vi b mt lng-hi c th duy tr c hai pha, khng th thay i T khi P = const, phng trnh (24) khng p dng c. Phng trnh (25) vi iu kin V = const, p dng c:

S T A S

T ,V ,ni

l nhit hp thu trong qu trnh thun nghch, din tch b mt tng mt n v T = const, V = const v ni = const.

H mt cu t: kt qu tng t pt (11)
SS =

d dT

H hai cu t: t pt (25) c th thy mi quan h gia nhit hp thu vi T ni nh pt (18)

2 P d = S S 2 S 2 + 2V2 dT 2 x T x2 ,bh 2
S A S
-

dx 2 (18) T ,bh

= (25) T V , AS , ni T ,V ,ni

Cng c th tm li c kt qu trc y v nng b mt trong h lng-hi 2 cu t nh sau:

6/18

 n 2
-

= 2 T ,V , AS ,n1 AS

T ,V ,n1 ,n2

(26)

S tn ti cu t 2 ph thuc:
o T,P o B mt o Bn cht pha th tch.

Nh vy n2 = f (2, AS) T phng trnh vi phn ring phn dng:

V P T P , = V T V P T

( (

) )

2 A S

n2 AS ,T ,V ,n 2 1 = n2 T ,V ,n1 ,n2 2 A,T ,V ,n 1

S tng ca n2 theo b mt 2, T, V v n1 khng i chnh l 2 nh ngha trc y. a kt qu ny vo phng trnh (26) v o ngc

n2

, ta c: (27)

n 2
3.1.

= 2 2 n T ,V , AS ,n1 2

A,T ,V ,n1

Ranh gii pha lng-lng, 2 cu t

C s khc bit gia b mt phn chia pha lng-lng (gia hai cu t khng tan ln nh benzen v nc) v b mt lng-hi. Thnh phn ca mi pha ph thuc T, P v cn bng vi pha cn li.

Khi P = const, o s bin i ca theo T, p dng (24) c th tnh c lng entropy hp th:
S A S = T P , AS , ni T , P , n1

(24)

tnh cho 1 n v din tch b mt tng ln P = const, T v ni = const. phn mol khng i V pha th tch l rt ln, gi thnh phn khng i ca ton h s tng b mt do chuyn vt cht gia pha th tch v vng b trong mi pha th tch. mt.

Cc hiu ng nhit gn vi s thay i din tch b mt u c lin quan n T S A v H A S S

7/18

 H A S

= T T , P , ni T , P , ni = T , P , ni P T , AS , ni

(28)

T (5), ta c th vit:
V A S

(29)

cho thy th tch tng trn mt n v din tch b mt T, P, ni = const.

3.2. Ranh gii pha lng-lng, 3 cu t

Thm mt cht tan th 3 vo h cha 2 cht lng khng tan ln nhau lp th ba, gi l n3, l nng cu t 3 trong mt pha.
= 3 n 3 T , P , AS , n1 , n2 AS T , P ,n1 ,n2 , n3

bin c

Nu gi T, P v lng ca hai cht lng kia khng i, t (5) ta c: (30)

Tin hnh tng t nh vi (26), (27) cho h hai cu t c b mt lng-hi ( b qua cc ch s T, P, n1, n2) ta c:

3 A S n3
v thay vo (30):

n3 AS 3 = n3 3 A S
3 n 3 3 AS

(30)

n = 3 n A 3 AS S
n trong 3 A S
4.

(31)

l nng b mt ca cu t 3. 3

Cc b mt cong 4.1. p sut trong cc git v bong bng

p sut bn trong P' ca mt git th ln hn p sut bn ngoi P0. Chuyn mt th tch dV cht lng t pha th tch vo bn trong git cht lng i hi mt cng l (P' Po)dV
P

bng vi cng tng b mt mt lng dAS V dV v dAS = 4r2dr = 8rdr

2 dAS = dV r

v thu c phng trnh Laplace:

8/18

P' Po =
P

2 r
P

(32)

1 1 Khi mt cong mt cu: P' Po = + r r 1 2

vi r1, r2 l cc bn knh chnh khc mt cong.

4.2. Khuynh hng ph v b mt cong

1958 Thompson p sut hi trn git nh > git ln > trn mt phng ca cng cht lng, tnh cht ca cc vt cht d bay hi phn tn cao. Theo quan im nhit ng, bin thin nng lng t do: dG = SdT + VdP + dAS + idni (5) p dng cho cc mt phng hiu chnh cho mt cong vi iu kin sc cng b mt khng thay i theo cong ranh gii pha trong h khng lm thay i p sut bn ngoi. (5)

Mt cu nm hon ton trong mt h th tha iu kin th hai ny. Ch : Ha th i( P ) trong (5) lin quan n qu trnh chuyn cht qua mt phng nn khng lm thay i AS.

i( P ) = n i T , P, A

,n j

Vi git hnh cu, As = f(V,ni ) Cng b mt dAS ph thuc dni Khi mt cu t i thay i s mol dni th th tch bin i: dV =

V dn
i

vi ht cu: dAS = 2dV = r

2Vi dni r
2Vi r
dni

Kt hp vi (5), ta c: dG = SdT + VdP +

(P) i

(33)

Khuynh hng ra i ca cu t th i khi git biu din bng o hm ca nng lng t do trong (33) theo ni :
G 2V i = = i( P ) + i n r i T , P ,n j

Vy ha th ca git tng ln so vi trn mt phng:

9/18

i i( P ) =

2Vi r

(34)

Nu p sut khng cao lm s dng fugat thay cho p sut hi

ln fi fi
(P)

2Vi rRT

(35)

Nu b mt li hng v pha hi, fugat gim

cn i du ca r trong (34) v (35) .

Nu mt cong mt cu th thay

1 1 2 bng + r r1 r2

vi r1 v r2 l cc bn knh chnh khc ca mt cong.

Vi b mt hnh tr, bn knh ng tr l r1 ,

cn r2 = . Phng trnh Kelvin Sc cng b mt chnh lch P 2 bn mt cong 2 Mt cu : P' Po = r

P

1 1 Khi mt cong mt cu: P= P' Po = + r r 2 1

P

Vic chuyn cht lng t mt phng thnh git i hi tiu th nng lng to b mt nng lng t do b mt tng ln:

Khi bn knh git tng t r r + dr Din tch b mt tng t 4r2 4(r + dr)2 tc l 8rdr tng nng lng t do b mt l 8rdr Qu trnh ny chuyn dn mol cht lng t b mt phng c p sut hi l Po thnh git lng c p sut hi P tng nng lng t do l Vy V
RT ln
dnRT ln dnRT ln Pr Po

Pr = 8rdr Po

dn = 4r2 dr /M
Pr 2M 2 V = = r Po r
ln fi fi
(P)

Tng ng pt (35)

2Vi rRT

vi l khi lng ring cht lng

V l th tch mol
10/18

Th d R= 10-5cm 10
-6 -7

Pr /Po 1,01 1,1 3,0

10
5.1

5. Mng mng ca 1 cu t khng ha tan S hp ph kh

o lng kh b hp ph: s mol nS hay th tch kh V iu kin tiu chun cho mt lng xc nh cht rn. ng ng nhit hp ph cho mi quan h gia th tch b hp ph vi p sut hi ca kh.

Hnh 5. ng ng nhit hp ph ca Argon trn rutile 85oK.

Nhit hp ph vi phn (hay ring phn) H cn c gi l nhit hp ph ng hng (isosteric) v n gn lin vi mt lp ph b mt xc nh, k hiu qst . Hnh 6 ng cong qst ca qu trnh hp ph din bin theo th tch hp ph Argon/rutile.

Gi tr qst thay i nhanh di lp n phn t cho thy c th b mt rn khng ng nht. Ch : nhit hp ph mol ring phn nhanh chng t n nhit ha hi ca cht lng khi m lp n phn t hon thnh.

11/18

 Nhit hp ph, tng t nh nhit ha hi ca cht lng, c th thu c bng cch ly o hm theo T ca p sut hp ph:

q H P = st = TV T nS TV

(43)

Gi s hi l kh l tng:
q ln P = st 2 RT T n S
5.2 Entropy ca kh b hp ph

(44)

Entropy mol ring phn ca mt kh b hp ph l o hm theo T ca nng lng t do hp ph, so vi entropy ca kh trng thi chun ca n. S = (RT ln f ) + S o T

(45)

trong , nng lng t do tnh bng fugat ca kh cn bng hp ph xp x bng p sut kh.
Ly vi phn (45), suy ra c qst : qst Rlnf + So T

S =

(46)

i vi kh l tng trong qu trnh hp ph t kh cn bng. (So -Rlnf ) l entropy p sut cn bng

qst l entropy mol ring phn T

Hnh 7. Entropy mol ring phn ca argon trn rutile - Nu c nhit lng k nhy, c th o nhit dung mol ring phn ca cht b hp ph. Nhit dung thng o trn cht rn thun tu sau o trn cht rn khi tng dn lng cht kh b hp ph trn . T tnh s bin thin entropy mol ring phn theo nhit bng h thc:
S S (T2 ) = S S (T1 ) +

T2

T1

CS d ln T

12/18

6. Mng n phn t Cc phng php nghin cu n lp khng tan:

1. p sut mng (p sut b mt): l gim sc cng b mt do n lp. do n lp to lc gin chng li lc tng tc co li ca b mt sch
= o o sc cng b mt ca cht lng tinh khit sc cng ca b mt c mng.

(36)

Gi A l din tch b mt, tnh bng: 2/phn t /v phn t n gin m2/mg /v phn t phc tp

ng cong -A c xem tng ng vi ng cong P-V ca khi vt cht 3 th nguyn:

Lp mng dy10-7cm c = 1dyne cm-1 tng ng vi p sut th tch 107dyne cm-3, hay 10 atm.

Cn Langmuir Adam o trc tip ng cong -A ca lp mng n lp khng tan :

Hnh 8 . Nguyn tc ca cn b mt Langmuir

Hnh 9. Cn b mt 2. nht b mt : l s thay i nht do lp mng n phn t. nht b mt thay i theo trng thi vt l ca mng. a s mng khng tan c nht b mt khong 10-3 -1 poise b mt. nht ca mng dy 10-7cm tng ng vi nht th tch khong 104-107 poise. o nht bng pp dao ng vng (bn) platin trn b mt.
13/18

3. Knh hin vi in t: chiu chm tia nguyn t kim loi vo lp mng c mang ln cht nn bng collodion o b dy lp mng. o b rng x ca phn b mt khng c mng che ph, tnh c b dy lp mng l x tan

Hnh 10. Nguyn tc knh hin vi in t kho st n lp.

6.1 Tnh cht vt l mng n phn t

Ty thuc vo : - Lc tng tc gia cc phn t trong mng - Kh nng ion ha. - Nhit . C 3 loi mng n phn t: - Mng ngng t (rn): cc phn t nm st nhau, thng gc vi b mt. - Mng tri rng ra chim din tch ln hn mng ngng t, to trng thi gin-nh-cht-lng. - Mng kh hay hi: cc phn t tch ri ra, chuyn ng c lp.
MNG KH

- Mng kh l tng to nn khi cc phn t c kch thc b, khng c tng tc nhau. - nh lut kh l tng hai chiu
A= kT

ng cong = f (A) T = const l 1 hyperbol. - Mng kh l tng hai chiu thu c khi b mt rng v p sut thp. - Dung dch cht hot ng b mt long c tng tc cht tan - cht tan khng ng k
gim sc cng b mt t l vi nng = o bC vi b l hng s p sut b mt = bC

d = b dC
C d T pt Gibbs = . RT dC

= / RT (mol cm-2) A= kT (nu A tnh bng cm2/pt) A= 1,38T (nu A tnh bng 2/pt)
14/18

(k = hng s Bolzmann, 1,38.10-16) Th d : Mng kh ca dung dch cetyl trimetyl ammonium bromua c xc nh th = f (A)

Hnh 11. ng cong -A dung dch cetyl trimetyl ammonium bromua Nhn xt : nc - Phn t trong lp mng b ion ha thnh C16H33N(CH3)3+ y nhau trong trong pha
tng i ln

- i vi 1 din tch b mt xc nh
phn t du chen vo gia dy hydrocarbon trit tiu tng tc ni phn t D/N > K/N

- ranh gii K/N :

c tng tc trong mch bng lc y tnh in ng cong = f (A) xp x ng A= kT

- ranh gii D/N :

c tng tc trong mch < lc y tnh in A > kT

* Cc acid bo v ru c mch C 12 to mng kh khng l tng T phng, c A < kT , nht l P cao v b mt b.

MNG NGNG T

Gm cc acid palmitic, stearic v cc acid bo no mch di hn to nn T phng. Do tng tc gia cc mch hydrocarbon mnh nn cc phn t trong mng to thnh mng hay thnh o trn b mt. p sut b mt rt b.

15/18

Hnh 12. Mng ngng t Th d: Acid stearic tri trn b mt dung dch HCl long c p sut b mt tng nhanh A khong 252/pt (ng vi tng tc cc nhm nh chc). ng cong -A rt dc A = 20,52/pt (s co mnh hn v gi cht mch hydrocarbon) din tch chim ch o c l 18,52

Hnh 11. ng cong -A dung dch acid stearic

MNG GIN

Acid oleic to mng gin hn acid no stearic ( gi tr ln hn)v:

- Lin kt i lm tng tc mch hydrocarbon yu hn. - Khi b mt ln cc phn t acid oleic tch ri nhau - Mch hydrocarbon c khuynh hng nm ngang vi nhm cha lin kt i a nc tip xc vi nc.
Khi nn lp mng acid oleic s a lin kt i khi b mt mch hydrocarbon thng gc b mt.

Hnh 12. Mng gin ca acid oleic

16/18

Hnh 13. ng cong -A ca acid oleic

Vi acid myristic, s bin thin ca -A trong khong rng cho thy:

Hnh 13. ng cong -A dung dch acid myristic trn b mt HCl N/10 - Khi A > 8002/pt lp mng kh - A = 502/pt mng gin tun theo pt trng thi (- o)(A -Ao) = kT - Khong cn li l cc trng thi trung gian.
6.2 Cc yu t nh hng mng n phn t

Lc tng tc gia cc phn t ph thuc cu hnh v s nh hng phn t mng . to mng gin cn cc yu t sau:
Cc nhm u mch cng knh ngn cn s co mch v s tng tc mch hydrocarbon C hn 1 nhm phn cc: acid bo cha no, hydroxy-acid. Cn c p sut mng thng sc ht gia nhm phn cc th 2 v dung dch trc khi cc phn t nh hng thng gc. C hn mt mch hydrocarbon nh hng theo cc hng khc nhau t phn phn cc ca phn t : ester, glyceride C mch hydrocarbon cong :

- acid brasidic(trans-CH3(CH2)7CH=CH(CH2)11COOH)
c mch hydrocarbon thng to mng ngng t

- acid crucic (cis-CH3(CH2)7CH=CH(CH2)11COOH)

c mch hydrocarbon cong to mng gin C mch hydrocarbon phn nhnh.
17/18

Khi mng n lp b ion ha, cn phi ch bn cht v pH ca cht nn : - n lp acid bo tri trn cht nn kim nhm carboxyl b ion ha v y nhau to mng kh hay mng gin nhit thp. - n lp acid bo tri trn cht nn kim cho thm cht in ly tan trong kim, Ca2+ to x phng canxi khng tan to mng ngng t.
6.3 S bay hi qua mng 1. S tn tr nc

- hn ch lng nc mt mt t cc h v bn cha do bay hi Ph b mt nc bng n lp khng tan (ru cetyl) lm gim tc bay hi 40%. - Cc n lp phi tha yu cu :

Hn ch ti a s thm thu : mng st cht. T tri trn b mt (do gi, ma) Oxy khuch tn d dng qua n lp.

- n lp to nn t dng lng hay dang bt.

2. n lp trn cc git:

- hn ch s bay hi git nc nh lm kt khi cc ht mn trong khai thc qung( ph mng bo v khng tan. - Phn tn 1 t ru cetyl trong nc ( lm tng i sng git hng ngn ln. - Cc m my m bi, khi, nhatrong thnh ph chm phn tn l do s thnh lp n lp.

18/18