S hp ph. 1. Mt s khi nim c bn S hp ph. l hin tng b mt nhm thu ht cht b hp ph ln b mt cht hp ph, lm gim sc cng b mt ca cht hp ph.

. Ngc vi s hp ph , qu trnh i ra ca cht hp ph khi b mt cht hp ph gi l s gii hp hoc phn hp. Khi tc hp ph bng tc phn hp th s hp ph trng thi cn bng. Hp ph vt l v hp ph ho hc. Da vo bn cht ca lc hp ph, ngi ta phn bit hp ph vt l v hp ph ho hc. Hp ph vt l gy ra bi lc vt l (lc tng tc phn t ), cn hp ph ho hc gy ra bi lc ho hc(lc ca lin kt ho hc). V d: s hp ph ca than hot tnh i vi cc phn t kh hoc hi CO2, C2H5OH, H2O(gi l hp ph phn t) l hp ph vt l, nhng s hp ph ca cht rn AgI i vi Ag+ trong dung dch l hp ph ho hc v n kin ton cu trc b mt mng tinh th hp cht ho hc AgI. Do lc hp ph yu, nn hp ph vt l c tnh thun nghch. Khi nhit tng lc tng tc phn t gim nn hp ph vt l gim. V vy hp ph vt l thng tin hnh nhit thp (thp hn nhit si ca cht b hp ph ). Hp ph vt l c th l hp ph n lp hoc n phn t, cng c th l a lp hoc a phn t. Hp ph ho hc c bn cht ca mt phn ng ho hc, nn hp ph ho hc c tnh bt thun nghch (rt kh thc hin s phn hp). Khi nhit cng tng, tc phn ng ho hc tng, nn hp ph ho hc tng. Do hp ph ho hc thng xy ra nhit cao. Nhit hp ph. S hp ph pht nhit, nhit hp ph vt l rt nh, nhit hp ph ho hc ln; tng ng hiu ng nhit ca phn ng ho hc. Tuy nhin ranh gii gia hp ph vt l v hp ph ho hc ch l tng i. c bit khi cht hp ph l nhng ion hu c th hp ph vt l v hp ph ho hc thng xy ra ng thi. Ion hu c d b hp ph bi cc b mt phn cc, b mt c in tch ngc du, cng c trng hp b mt mang in tch cng du th c th do lc tng tc phn t ln hn lc y tnh in. Tnh chn lc nh hng. S hp ph c tnh chn lc v nh hng theo quy tc nh sau: Nhng cht c tnh cht tng t nhau d hp ph vo nhau. Nhng phn c tnh phn cc nh nhau hoc gn ging nhau s hng vo nhau. Nu l hp ph ho hc i vi cc ion, th ion b hp trc phi l ion c trong thnh

phn cu to tinh th b mt, sau l nhng ion tng t c kh nng hon thnh cu to mng li tinh th b mt. Th t hp ph i vi cc ion y theo s u tin cho ion c in trng ln hn (in tch ln, sonvat ho t hn). V d: cht rn AgI hp ph mnh i vi I khi trong dung dch c KI, nhng cng c kh nng hp ph ion Cl (hoc SCN) khi trong dung dch c NaCl hoc NaSCN 2. hp ph v ph hp ph ca mt cht hp ph l lng cht b hp ph(mol, milimol) b hp ph trn mt n v din tch hoc trn mt n v khi lng cht hp ph khi c trng thi cn bng hp ph, mt nhit xc nh. Thng k hiu hp ph l G: S n G = (III.2) Trng i hc Nng nghip H Ni Gio trnh Ho keo 29 http://www.ebook.edu.vn 29 hoc

n: s mol hay s milimol cht b hp ph S: din tch b mt (m2 , cm2 ) m: khi lng cht hp ph (g) nhit khng i, hp ph ca mt cp cht hp ph v cht b hp ph ph thuc vo bn cht cp cht y, b mt cht hp ph, nng (hoc p sut) ca cht b hp ph. Khi tng nng cht b hp ph th hp ph tng n cc i v khng i cho d nng cht b hp ph tip tc tng xem hnh III.1.

Vy : hp ph cc i Gmax l hp ph ti a ca cht hp ph ng vi nng cn bng xc nh ca cht b hp ph, mt nhit xc nh. ph hoc ph b mt l t s gia din tch b mt cht hp ph hp ph v tng din tch b mt ca cht hp ph , thng tnh theo phn trm:

Sr: b mt ring. Sp: din tch b mt ca cht hp ph hp ph : ph. Khong xc nh ca ph: Khi 0 < <100% th xy ra hp ph n lp khng hon ton, khi >100% th c hp ph a lp v khi =100% th xy ra hp ph n lp hon ton. Quan h gia ph vi hp ph theo cng thc.

(III.4) % 100 . r p S S = max . G G Sr Sp = = (III.5) m n G = (III.3) Ccb C

G Gmax 0 Hnh III.1: S ph thuc ca hp ph G vo nng cn bng Ccb (mol.l -1 ) ca cht b hp ph Trng i hc Nng nghip H Ni Gio trnh Ho keo 30 http://www.ebook.edu.vn 30 Din tch b mt hp ph c lin h vi hp ph: Sp = G.No.So, y So gi l ph c bn hoc ph nguyn t, l din tch ti thiu ca mt phn t hoc mt ion chim ch b mt cht hp ph. V d: 10g mt loi than ci c b mt ring l Sr =300m2 .g-1 hp ph c 0,46g ru C2H5OH, 250 C. Tnh ph ca loi than ny i vi C2H5OH? Bit rng So(C2H5OH)= 21,62 ,1=10-8 cm. Gii hp ph ca than: Din tch b mt ca 1g than hp ph:

ph b mt ca than:

Trng hp ny xy ra hp ph n lp khng hon ton. 3. S hp ph trn b mt rn. Cc cht rn c sc cng b mt rt ln so vi cht lng v cht kh ho lng. Do b mt cht rn d hp ph cc phn t ca cht lng v cht kh. Sau y l mt s phng trnh hp ph ng nhit cho php xc nh hp ph. Phng trnh hp ph ng nhit Lang mua (Langmur). Tc gi gi thit rng: hp ph vt l trn b mt rn l hp ph n lp, b mt cht hp ph ng nht v nng lng, do nhit hp ph mi im l nh nhau. Trong mt h kn ng nhit, mt cht rn hp ph tip xc vi mt cht kh c nng C. Nu tng s im c kh nng hp ph trn mt cm2 b mt cht hp ph l x, trong y im hp ph nng cht b hp ph l C, s im cn li cha hp ph l: x-y th tc hp ph (Vh) t l thun vi s x-y v nng C:

Vh= kh(x-y)C. Tc phn hp (Vp) t l thun vi y: Vp= kp.y. Khi c cn bng hp ph th Vh=Vp , nn: kh=(x-y)C=kp.y hoc

(III.6)

khv kp: cc hng s ca tc hp ph v tc phn hp. Do t s : (III.8) max Ca CGG + = Phng trnh (III.8) c gi l phng trnh hp ph ng nhit Lang mua. Phng trnh III.8 cho bit quan h gia hp ph v nng cn bng ca cht b hp ph , trong 1 . 001 , 0 10 46 46 , 0 = = g mol x G 1 2 4 16 23 . 10 . 130 10 . 10 . 02 , 6 001 , 0 = = g cm x S p max G G x y =a k k p h = v t nn c phng trnh: % 33 , 43 10 . 300 10 . 130 4 4

== C k k C x y p h + = (III.7) Trng i hc Nng nghip H Ni Gio trnh Ho keo 31 http://www.ebook.edu.vn 31 Gmax v a l cc hng s ph thuc nhit i vi mt cp cht hp ph v cht b hp ph xc nh, G v Gmax tnh theo mol. g-1 v C tnh theo mol. l -1 Phng trnh hp ph ng nhit Lang mua ch ph hp vi thc nghim trong hai trng hp sau: Khi nng cht b hp ph rt nh th C<<a, nn G t l vi C

ng ng nhit hp ph c dng tuyn tnh. Khi nng cht b hp ph rt ln th C >> a, nn G = Gmax, ng ng nhit hp ph l ng song song so vi trc honh. ng vi khong nng trung bnh (t C1 n C2 ) cc ng ng nhit hp ph

Lang mua khng ph hp vi ng cong thc nghim - xem hnh III.2. Trn hnh III.2 trnh by cc ng ng nhit hp ph Lang mua, ng cong thc nghim MN ch ph hp vi phng trnh III.9. Mt khc, nhit thp c th c trng hp hp ph n gii hn Gmax, nhng s hp ph vn tip tc khi tng nng cht b hp ph. Nhng hn ch bt ngun t nhng gi thit gn ng ban u ca tc gi. Thc t b mt cht hp ph khng hon ton ng nht v hp ph vt l khng ch n lp m c th a lp. Phng trnh hp ph ng nhit Lang mua cho s hp ph n lp khng ch p dng i vi cht kh m c dung dch phn t long. Phng trnh hp ph ng nhit Frendlich (Freundlich). Trng hp nng cht b hp ph c gi tr trung bnh ngi ta s dung phng trnh hp ph ng nhit Frendlich:

G: hp ph ( tnh theo mol.g-1 ) x: s mol cht b hp ph m: khi lng cht hp ph (g) C: nng cn bng hp ph (mol.l -1 ) k v n: cc hng s i vi mt cp cht hp ph v cht b hp ph, n>1. n Ck m x G 1 . . = = (III.9) CkC a GG.. max = = (III.9 ) Hnh III.2: Cc ng ng nhit hp ph Lang mua:(1) v (2) G = Gmax G = Gmax C M (1) N (2) (2) G

C1 C2 Trng i hc Nng nghip H Ni Gio trnh Ho keo 32 http://www.ebook.edu.vn 32 Hng s k chnh l hp ph ng vi nng C = 1 Cc hng s k v n d xc nh bng thc nghim da vo cng thc:

Lp th v s ph thuc ca lgG vo lgC, dng y = ax+b, s tnh c n 1 v k. Phng trnh III.9, khng p dng khi nng cht b hp ph ln, v n ch l b xung cho phng trnh hp ph ng nhit Lang mua. Thc t thy rng s hp ph ca than hot tnh i vi cht hu c trong nc ph hp vi phng trnh III.9. Trong dung dch nc than hot tnh (b mt khng phn cc) hp ph rt mnh nhiu cht hu c v chng km phn cc hn nc. Phng trnh BET l phng trnh hp ph ng nhit ca 3 tc gi l Brunaoe, Emt v Tenle, c dng nh sau: vm: th tch kh b hp ph khi ton b b mt cht hp ph b ph 1 lp n phn t c kht. v: th tch tng cng ca kh b hp ph p mt cn bng p po: p sut hi bo ho ca cht b hp ph cng nhit vi nhit xy ra hp ph c: hng s ph thuc nhit Bit vm c th tnh c din tch b mt cht hp ph. Phng trnh BET l phng trnh hp ph vt l a lp ca cht hp ph rn i vi cht kh. Phng trnh c p dng xc nh b mt ring ca cht xc tc v cht hp ph rn. V d: che ph 1g silicagel (SiO2.H2O) bng mt lp n phn t cn th tch kh nit l vm =129ml ( 1atm v 00 C). Tnh din tch b mt ca silicagel, nu ph c bn ca nit l 16,22 . Gii: Phng trnh hp ph trong dung dch. Trong thc nghim, vic xc nh hp ph ca cht hp ph rn trong dung dch phn t v dung dch in ly nhit khng i, da vo phng trnh: G: hp ph (mol.g-1 ) C0 v C: nng u v nng cn bng (mol.l

-1 ) ca dung dch cht b hp ph. V: th tch (l) dung dch trong xy ra hp ph. m: khi lng (g) cht hp ph. (III.10) )1( . 1 ) ( 0 0 cp v pc cvppv p m += 1 2 2 8 23 3 . 7 , 561 ) 10 .( 2 , 16 . 10 . 02 , 6 . 4 , 22 10 . 129 = = g m Sr (III.11) )(0 m VCCG = kC n G lg lg 1 lg + =Trng i hc Nng nghip H Ni Gio trnh Ho keo 33 http://www.ebook.edu.vn 33 V d: Cho 5g bt TiO2vo 100ml dung dch Natri Dodecylsunfat vit tt l NaDS (C12H25SO4Na) nng 0,002M. Sau mt th