BI 7:

HP PH TRONG DUNG DCH TRN B CHT HP PH RN

MT
7.1. MC CH Kho st s hp ph acid acetic trong dung dch trn than hot tnh v thit lp cc ng ng nhit hp ph tng ng. 7.2. C S L THUYT V NGUYN TC Danh t hp ph dng m t hin tng trong mt cht no ( di dng phn t, nguyn t hay ion) c khuynh hng tp trung, cht cha trn b mt phn chia pha no . Trong trng hp cht hp ph rn, thng th cht c b mt ring (tng din tch trn 1 gam cht rn) rt ln, c gi tr vo khong 10 1000 m2/g. Cc cht hp ph rn thng dng l: than hot tnh, silicagel (SiO2), alumin (Al2O3), zeolit Trong s hp ph cc cht trn b mt cht hp ph rn, nguyn nhn ch yu ca s hp ph l do nng lng d b mt trn ranh gii phn chia pha rn kh hay rn lng. Cc lc tng tc trong hp ph ny c th l lc Van der Waals (hp ph vt l) hay cc lc gy nn do tng tc ha hc (hp ph ha hc) hay do c hai loi tng tc trn cng tc dng. Lng cht b hp ph trn b mt cht hp ph ty thc vo nhiu yu t nh: -

Bn cht ca cht hp ph v cht b hp ph. Nng ca cht tan. Nhit . Thc nghim th nghim nhit khng i, ta c th o c s mol cht b hp ph trn 1g cht hp ph rn ( ) cc nng cht tan khc nhau (C). ng biu din - C gi l ng ng nhit hp ph. Mt s phng trnh thc nghim v l thuyt c s dng biu th cc ng ng nhit hp ph: Freundlich, Langmuir, BET y l phng trnh thc nghim, p dng cho s hp ph cht kh hay cht ho tan trong dung dch = K. C1/n. Trong K v 1/n l nhng hng s khng c ngha vt l C l nng dung dch hp ph t cn bng

7.2.1. Phng trnh Freundlich

-

Vit di dng logarit log = 1/n logC + logK. Nh vy nu biu th log theo logC, ta s c 1 ng thng c h s gc 1/n v tung gc l logK. Phng trnh Freundlich thng thch hp khong nng (hay p sut) trung bnh, v nng thp thng t l thun vi C v nng cao thng t ti 1 tr s gii hn v do c lp vi C.

7.2.2. Phng trnh Langmuir: y l phng trnh l thuyt, p dng cho hp ph n lp:
=
kC = 1 + kC

Trong : - : che ph b mt - : s mol ti a cht b hp ph trn 1g cht rn sao cho cc phn t to thnh n lp. - k: hng s. C th vit li phng trnh trn di dng:
C C 1 = + k

Vy nu biu th C/ ta c 1 ng thng c h s gc 1/ v tung gc 1/k T phng trnh Langmuir, c th xc nh c b mt ring S0 ca cht hp ph theo cng thc: S0 = . N. A0 Trong N: s Avogadro = 6,023.1023. A0: din tch chim ch trung bnh ca 1 phn t cht b hp ph( khi hp ph gi l n lp). Chng hn vi CH3COOH, A0CH3COOH = 21 ( )2. 7.3. DNG C - HA CHT 7.3.1. Dng c: - Becher: 6 ci - Phu lc: 6 ci - Buret 25ml: 1 ci - Erlen 100ml: 5 ci - Pipet 10ml: 3 ci 7.3.2. Ha cht:

CH3COOH 0,2M Nc ct NaOH: 0.1N Phenolphtalein 1%

7.4. THC HNH - Dng acid acetic CH3COOH 0,2M v nc ct, pha long cc dung dch sau trong 6 bnh nn c nt nhm. Bnh 1 2 3 4 5 6 CH3COOH (ml) 50 40 30 20 10 5 Nc ct (ml) 0 10 20 30 40 45 - Lc u cc bnh va pha. - Dng cn phn tch cn 6 mu than hot tnh, mi mu 1g. - Cho vo mi bnh cha dung dch CH3COOH mt mu than, y nt lc mnh trong vi pht. yn 10 pht ri lc mnh vi pht. yn 30 pht xong em lc. - Ghi nhit th nghim. Nc qua lc nh phn bng dung dch NaOH 0,1N vi ch th phenolphtalein. - Vi bnh 1, 2, 3 nh phn 3 ln, mi ln 5 ml nc qua lc. - Vi bnh 4, 5 nh phn 3 ln, mi ln 10 ml nc qua lc. - Vi bnh 6 nh phn 2 ln, mi ln 20 ml nc qua lc. Lu : than hot tnh dng em ra li bng nc nng sau lc, sy ri cho vo chai thu hi li.

BI 4: HP PH NG NHIT V PHNG TRNH FRENDLICH I/ MC CH: Xc nh s hp ph axit axetic bi than hot tnh trong dung dch nc II/ KIN THC L THUYT: S hp ph cht khng in ly hoc cht in ly yu trn ranh gii phn chia pha rn lng thuc vo loi c tnh hp ph phn t v tun theo phng trnh Gibbs. Nu cht tan b hp ph mt lng ln hn dung mi th s hp ph gi l hp ph dng, cn ngc li l hp ph m. S hp ph ca cc cht hu c cng mt dy ng ng tun theo quy tc Traube: S hp ph gim vi s tng chiu di mch bi v vi s tng kch thc phn t tit din s dng ca cht hp ph hp ph b gim, cc phan t ln khng b ri vo l hp ca cht hp ph.

S hp ph trn ranh gii rn lng tun theo quy tc thng bng phn cc ca Rebindis: Cc cht b hp ph trn ranh gii phn chia pha ch xy ra trong trn hp nu do s c mt ca n lp b mt lm cho hiu s phn cc ca pha b gim . o s hp ph, ngi ta cho mt lng cn chnh xc cht hp ph vo cc th tch nh nhau ca dung dch ch b hp ph. Lng cht b hp ph c tnh nh l hiu s nng u v nng cn bng trong cc th tch nh nhau ca dung dch. Trong cc dung dch long, thng thng ngi ta khng tnh s hp ph ca dung mi. Theo cc d kin thc nghim xy dng th s ph thuc khi lng cht b hp ph vo nng cn bng ca n trong dung dch. S hp ph trn vt xp t dung dch long c m t bng phng trnh thc nghim Frenlich: X/m = k Cn Trong : X l s mol cht b hp ph (mol/l) m l khi lng cht hp ph (g) C l nng cn bng (mol/l hay mmol/l) k l hng s tng ng cho khi lng ca cht b hp ph nng cn bng. n l hng s (n = 0,1 0,5) tm hng s k v n th chuyn phng trnh trn thnh dng khc:
x lg x m lg = lgk + nlgC v tg = n = m lg C

Khi th ph thuc lg(x/m) vo lgC l ng thng nh hnh 6 TR LI CU HI : Cu 1: Hp ph l g? C my loi hp ph ?

-Hp ph l qu trnh cht cha cc phn t cht kh,lng hay cht ha tan ln b mt phn cch pha. B mt phn cch pha c th l kh- lng, khrn hay lng-lng, lng- rn *Phn loi hp ph:c 2 loi hp ph : l hp ph vt l v hp ph ha hc. Cu 2: Nhng thuyt no hc v hp ph? *C 3 thuyt hc v s hp ph - Thuyt hp ph ng nhit frendlich - thuyt ca Langmuir - Thuyt ca Bet Cu 3 : Gii thch cch tnh cc hng s k, n? -Gii thch cch tnh cc hng s n, K +Da vo th ph thuc gia Lg(x/m) v LgC ta bit c tg . Li c : tg = n. -Thay n vo phng trnh lg
x = lgK+n.lgC. Ta rt ra c K. m

Cu 4 : Nhng sai s no c th gp trong qu trnh th nghim? -Nhng sai s no c th gp trong qu trnh th nghim. + Sai s ch quan : sai s trong qu trnh cn, chun , ong, tnh ton kt qu. + Sai s khch quan : do dng c th nghim, ha cht V d : Chun l qu trnh i xc nh im tng ng, t im tng ng ta suy ra nng cht cn xc nh. Th nhng trong thc t ta khng th tm c ch th thay i mu ti im tng ng m ch c ch th thay i mu trc v sau im tng ng thi. Nh vy trong qu trnh chun tt yu phi xy ra sai s ch th.

III/ PHN THC NGHIM: 1/Dng c Bnh tam gic 250ml: Phu lc 100 ng ht 2,5,10,25ml Buret 25ml Giy lc 2/Ha cht CH3COOH 0,4N NaOH 0,1N Ch th Phenolftalein 3/Cch lm Cho vo 6 bnh tam gic theo t l: Bnh 1 2 3 CH3COOH 0,4N 50 40 30 Nc ct(ml) 0 10 20 Than hot tnh (g) 1 1 1 Lc mnh khong 30 pht, sau yn 15 3 ln ri ly kt qu trung bnh. Ch :Mi ln chun ly 10ml v cho thm 3 git phenolftalein, chun bng dung dch NaOH 0,1N n khi xut hin mu hng Kt qu th nghim c ghi vo bng sau: Bnh VNaOH 1 2 3
V
NaOH

:12 ci :6 ci :mi loi 1 ci :1 ci :1 hp :1 lt :1 lt :1 l

4 5 6 20 10 5 30 40 45 1 1 1 pht cho cn bng ri lc

dung dch vo 6 bnh khc. Chun mi bnh dung dch sau khi hp ph 2-

1 35.5 35,6 35,4 35,5

2 3 27,7 20 28 20,1 27,9 20 27,87 20,03

4 12,9 12,8 12,7 12,8

5 5,7 5,8 5,7 5,73

6 2,3 2,3 2,3 2,3

IV. X L KT QU TH NGHIM

Khi lng axit b hp ph c tnh theo cng thc sau: A=

C1 C 2 .V 1000 m

Trong :

C1 ,C2 l nng axt trc v sau khi hp ph. V:th tch dung dch ly ra hp ph(50ml) m:Khi lng vt b hp ph(than 1g)

Tnh ton ta c bng s liu sau:

C1 0,4 0,32 0,24 0,16 0,08 0,04

C2

0,3550

0,2787

0,2003

0,128

0,0573

0,023

0,045

0,0413

0,0397

0,032

0,0227

0,017

x .10 3 m
Lg(x/m)

2,25

2,065

1,985

1,6

1,135

0,85

-2.77

-2.69

-2.83

-2.8

-2.95

-3.07

LgC

-0.44

-0.56

-0.68

-0.9

-1.24

-1.64

 th ph thuc lg(x/m) vo lgC

-2.6 -1.8 -1.6 -1.4 -1.2 -1 -0.8 -0.6 -0.4 -0.2 -2.65 0

y = 0.3604x - 2.4858
Lg(x/m)

-2.7 -2.75 -2.8 -2.85 -2.9 -2.95 -3 -3.05 -3.1 (lgC,lgx/m) Linear ((lgC,lgx/m))

lgC

- Da vo th ta c: n=tg =0,3604 Lgk=-2,4858 k=3,27.10-3

NGHIN CU CN BNG HP PH TRN RANH GII PHA RN LNG T DUNG DCH I. Mc ch: Kho st s hp ph acid axetic trong dung dch trn than hot tnh v thit lp ng ng nhit tng ng. II. C s l thuyt: Trong bi ny chng ta nghin cu nh hng ca nng cht tan CH 3COOH ln hp ph ca n trn than hot tnh nhit khng i trong dung mi nc.Hp ph ca acid cacboxylic t dung dch nc thuc loi hp ph phn t v theo nhiu nghin cu n t ra l hp ph n lp. hp ph a ( mmol/g ) ln b mt than c th tnh t cng thc:

a=

C0 C .V .1000 m

C0, C l nng u v nng ti cn bng hp ph ca dung dch axit axetic ( mol/lit ).V l th tch dung dch trong xy ra s hp ph ( l ) v m l khi lng cht hp ph ( g ). Xc nh nng cht tan trc khi cho cht hp ph (C0 ) v nng sau khi t cn bng hp ph ( C ). T kt qu thc nghim dng th a = f (c ) ng ng nhit hp ph. III.Kt qu th nghim : 1.Lp ng ng nhit a = f(C): Bnh Vml axit C0 Vml NaOH 1 2 200 0.06 6.9 3 200 0.09 8.8 4 200 0.12 10.4 5 200 0.15 13.1 6 200 0.2 15.7

200
0.03 3.8

p dng cng thc C.V = C.V cho CH3COOH v NaOH 0.1N, ta tnh c C tng ng ca 100ml CH3COOH sau khi hp th than hot tnh nh sau: Bnh C Tnh a: 1 0.0038 2 0.0069 3 0.0088 4 0.0104 5 0.0131 6 0.0157

a = (C0 C).1000.V/m

Vi m = 3 g ; V = 100 ml = 0.1 l
Bnh a 1 0.873 2 1.77 3 2.707 4 3.653 5 4.563 6 6.143

V ng ng nhit hp ph a = f(C)

7 6 5 4 a 3 2 1 0 0 0.005 0.01 C 0.015 0.02 y = 445.44x - 1.0731 R2 = 0.9872

2. X l theo phng trnh Langmuir:

C/a = f(C) = y

C C 1 = + hay phng trnh c dng a a max ka max

Vy amax = 2.245.10-3 v k = -415 3. X l theo phng trnh Freundlich: lga = f(lgC) = y

y=

1 amax

x+

1 ka max

Vy theo th th 1/amax = 445.44 v 1/k.amax = -1.0731.

lg a = lg k +

1 1 lg C hay phng trnh c dng y = lg k + x n n

Vy theo th th 1/n = 445.44 v lgk =-1.0731 Suy ra n = 2.245.10-3 v k =0.0845