Chng 7 CN BNG HO HC V CN BNG PHA

7.1. CN BNG HO HC : a s cc phn ng u xy ra theo 2 chiu v khi vn tc phn ng thun bng vn tc phn ng nghch, phn ng t trng thi cn bng. Ti y c phn ng thun ln phn ng nghch vn tip tc xy ra nn cn bng loi ny c gi l cn bng ng. V d, cn bng trong cc phn ng to thnh HI t H2 v I2 (hnh 7.1): H2 + I2
% [HI]

2 HI

100 80 60 40 20 20 40 60 80 100 t (ph)

Hnh 7.1. S to thnh (1) v phn hu (2) ca HI theo thi gian

7.2. HNG S CN BNG Xt phn ng thun nghch: aA + bB vn tc phn ng thun: vn tc phn ng nghch: eE + qQ Theo nh lut tc dng khi lng ta c:
a

v1 = k 1 [ ] [B ]
e q

v 2 = k 2 [E ] [Q ]

Khi phn ng t cn bng: v1 = v2 (G = 0), ta c:

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Suy ra:

k1 [] [B] = k 2 [E ] [Q ]
a b e

k1 [E ] [Q ] = k2 [ A ]a [B ]b
e

T l

k1 l mt hng s c gi l hng s cn bng, k hiu l KC k2

C

[E ]e [Q ]q = [A ]a [B ]b

(7-1)

KC l hng s cn bng tnh theo nng M (mol/l). Trong thc t ngi ta cn s dng cc loi hng s cn bng khc nh: cn bng tnh theo p sut KP, cn bng tnh theo nng mol phn KN, cn bng tnh theo s mol ca cc cht tham gia v to thnh trong phn ng Kn. Gia cc hng s cn bng ny c cc mi quan h sau:

K P = K C (RT )
vi

( 7-2)

e q E Q a b A B

trong n = (nE + nQ) - (nA + nB)

K P = K N P n
= NE NQ N
a A e q b

(7-3)

vi

NB

trong nng mol phn:

Ni =
KP

ni n A + n B + n E + nQ
P = Kn n i
e

(7-4)
q b

vi

n E nQ nA nB
a

trong : ni s mol ca cc cht P - p sut chung ca phn ng 71

Nu phn ng c n = 0 th cc hng s cn bng s bng nhau: KP = KC = KN = Kn. 7.3. S CHUYN DCH CN BNG. NGUYN L CHUYN DCH CN BNG LE CHATELIER 7.3.1. S chuyn dch cn bng Nh ni trn, cn bng ho hc l s cn bng ng. V d phn ng tng qut: aA + bB eE + qQ ang trng thi cn bng 1 (G1 = 0). Nu ta thay i ch mt trong cc thng s trng thi (P, C hoc T...) th cn bng s b ph v (G 0): phn ng s xy ra theo mt chiu (gi s chiu thun): aA + bB eE + qQ cho n khi thit lp c mt cn bng mi 2 (G2 = 0) tng ng vi iu kin mi. Vy s chuyn t mt trng thi cn bng ny sang mt trng thi cn bng khc di tc ng ca cc yu t iu kin phn ng c gi l s chuyn dch cn bng. 7.3.2. nh hng ca cc yu t iu kin phn ng n chuyn dch cn bng Ba yu t c nh hng ln nht n s chuyn dch cn bng l nng , nhit v p sut. 7.3.2.1. nh hng ca nng T biu thc tnh hng s cn bng theo nng :

[E ]e [Q ]q [A ]a [B ]b

Ta thy vi KC = const, nu tng [A] hoc [B] th cn bng s chuyn dch theo chiu t tri qua phi lm tng [E] v [Q] (lm gim [A] hoc [B]). Nu gim [A] hoc [B] th cn bng s chuyn dch theo chiu t phi qua tri lm gim [E] v [Q] (lm tng [A] hoc [B]).

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Nh vy, tng nng ca mt trong cc cht ca trng thi cn bng, cn bng s chuyn dch theo chiu lm gim cht . Gim nng ca mt trong cc cht ca trng thi cn bng, cn bng s chuyn dch theo chiu lm tng cht . 7.3.2.2. nh hng ca nhit Quan h gia entanpi t do v hng s cn bng c biu th qua cng thc:

G = -RTlnK hay H - TS = -RTlnK

Suy ra:

d ln K = dT RT

(7-5)

T biu thc trn ta nhn thy: Vi H > 0, nu T tng th K s gim. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm tng K (chiu t tri qua phi lm gim T). Vi H < 0, nu T tng th K s tng. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm gim K (chiu t phi qua tri lm gim T). Nh vy, nu phn ng ang trng thi cn bng m ta thay i nhit ca phn ng th cn bng s chuyn dch theo chiu chng li s thay i nhit . 7.3.2.3. nh hng ca p sut T biu thc: V T = const, ta c:

KP = KN Pn
d ln K N n = dP P

ta c: lnKP = lnKN + nlnP lnKN = lnKP - nlnP (7-6)

T biu thc trn ta nhn thy: Nu n > 0, khi P tng th KN tng. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm gim KN (chiu t phi qua tri lm gim P). Nu n < 0, khi P tng th KN gim. hng s cn bng khng i th cn bng phi chuyn dch theo chiu lm tng KN (chiu tri qua phi lm gim P). Nh vy, nu phn ng ang trng thi cn bng m ta thay i p sut chung ca phn ng th cn bng s chuyn dch theo chiu chng li s thay i p sut .

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7.3.3. Nguyn l chuyn dch cn bng Le Chatelier Nghin cu nh hng ca cc yu t n s chuyn dch cn bng phn ng, nm 1884 Le Chatelier da ra nguyn l chuyn dch cn bng: Mt h ang trng thi cn bng, nu ta thay i mt trong cc thng s trng thi ca h th cn bng s chuyn dch theo chiu chng li s thay i . 7.4. CN BNG PHA 7.4.1. Mt s khi nim c bn * Pha: Tp hp tt c cc phn ng th ca h c thnh phn,tnh cht vt l, ho hc ging nhau v c b mt phn chia vi cc phn khc ca h gi l pha. V d, h nc v nc l h c 2 pha trong mt pha l nc lng v mt pha l nc . H ny dc gi l h d th v c 2 pha; nc lng hoc nc l h ng th v ch c mt pha. * Cn bng pha: Cn bng trong cc h d th m khng xy ra phn ng ho hc gia cc cu t vi nhau nhng xy ra cc qu trnh bin i pha ca cc cu t c gi l cn bng pha. * Cu t: Phn hp thnh l nhng hp cht ho hc ng nht ca h c th tch ra v tn ti c lp bn ngoi h gi l cu t, c k hiu R. V d, dung dch mui n c 2 cu t l H2O v NaCl (cc ion Na+, Cl-... khng phi cu t ). * S cu t c lp: S nh nht cc cu t m t thnh phn ca tt c cc pha c trong h gi l s cu t c lp, c k hiu K. K=R-q S cu t c lp K c khi bng R nhng cng c khi khc R. Khi xt mt h m trong khng xy ra s chuyn i ho hc ( cc cu t khng tc dng vi nhau) ta

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c: R = K. Trong v d dung dch mui n trn y R = K = 2. Mt khc, nu xt h m trong xy cc tng tc ho hc th ta c R K. V d, i vi h phn ng: 2H2 + O2 = 2H2O ta c: R = 3, K c th l 1 hoc 2. K=R-1=3-1=2 v bt k mt cu t no ca h cng c th xc nh c bng 2 cu t kia. 7.4.2. Quy tc pha Gibbs Nh ta bit, s cn bng ca h ph thuc vo cc iu kin (nhit , p sut, nng ). S iu kin c th thay i mt cch c lp m khng lm thay i s pha v loi pha ca h c gi l s bc t do, c k hiu C. Nghin cu cn bng pha ca h d th, Gibbs da ra quy tc sau: Trong h cn bng, s lng pha f, s bc t do C v s cu t c lp K lin h vi nhau qua biu thc: C=K-+2 7.4.3. Cn bng pha trong h mt cu t Trong nghin cu cn bng pha ngi ta thng hay chn phng php th bng cch xy dng gin trng thi trn c s ca cc gi tr thc nghim. Gin trng thi c th xy dng cho mt hp cht bt k v n cho php xc nh iu kin bn ca pha hoc cn bng pha. Hnh 7.2 di y l gin trng thi ca nc. P mmHg 760 ............B......................... C lng (L) rn (R) 4,579 .................. O hi (H) A 0 t 0C
Hnh 7.2. Gin trng thi ca nc

(7-7)

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