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Giáo Trình Hóa Keo Đ I Cương
Giáo Trình Hóa Keo Đ I Cương
I CNG
1 /15
S hp ph (Adsorption)
Cc cht hot ng b mt, cht khng hot ng b mt
* Cht hot ng b mt l cht cha b mt, c hp ph dng.
- Cht hot ng b mt c nhng tnh cht sau :
+ C sc cng b mt b hn ca dung mi: dd < dm
+ C tan tng i b, v nu khng nh th th n c xu hng tch ri khi b mt m tan su
vo trong cht lng.
- Cu trc phn t gm hai phn:
- Nhm a nc (phn cc) : -OH, -COOH, -NO2 , -NH2, -Cl .... Phn phn cc c momen lng
cc ln v d hydrat ha lm cho cht hot ng b mt c i lc ln vi nc v b ko vo pha lp
nc.
- Nhm k nc (khng phn cc): gc hydrocarbon -R, l phn k nc, l nguyn nhn lm cho
cht HBM c tan nh.
* Cht khng hot ng b mt l cht c xu hng ri khi b mt tan su vo dung dch, khi
hp ph m.
- Cht khng hot ng b mt c cc tnh cht sau :
+ C sc cng b mt ln hn ca dung mi, nh th qu trnh ri khi b mt mi l qu trnh nhit
ng hc t din ra. Kt qu l lun c dd > dm
+ C tan cao, v th cht mi c th ri khi b mt m tan su vo dung dch
- Cc cht in ly v c bn u l cht khng hot ng b mt, l cc acid, baz, mui. Phn t
ca chng khng c phn k nc, khi tan th in ly thnh nhng ion hydrat ha mnh.
2 /15
k1P
k1P k2
k
a
; K 1 , a: hp ph ti thi im t; am: hp ph cc i.
am
k2
=> a am.
KP
1 KP
Lga = lgb +
1
.lgP
n
3. Thuyt hp ph a phn t:
* Thuyt hp ph a phn t ca Polanyi:
* Thuyt hp ph a phn t ca BET:
P
1
C 1 P
.
V (P0 P) Vm.C Vm.C P0
V: Th tch cht b hp ph P.
P0: p sut hi bo ha.
Vm: Th tch kh trn lp n phn t.
3 /15
C d
.
RT dC
d
: c gi l hot ng b mt.
dC
: Sc cng b mt.
* Nu nng cht tan trong lp b mt > trong th tch dung dch:
C
d
0 => a>0: hp ph dng.
dC
d
0 => a<0: hp ph m.
dC
* Nu nng cht tan trong lp b mt = trong th tch dung dch th hp ph khng xy ra.
2. Qui tc Traube
Kh nng lm gim sc cng b mt ca cht HBM ph thuc vo chiu di ca hydrocarbon.
Trong hp cht hu c mch cacbon no, tnh hot ng tng 3,2 ln khi gc hirocacbon tng thm 1
nhm CH2.
Tuy nhin qui tc Traube ch ng cho trng hp dung mi l nc (mi trng rt phn cc).
4 /15
KC
1 KC
1
V.(C0 C)
m
Cc ion trong dung dch cht in ly l nhng phn t tch in, cho nn s hp ph cc ion l qu trnh d
ra s phn b li in tch. ng lc ca qu trnh l in trng trong khu vc lp b mt. V d nh
chuyn cc cation t th tch pha lng n ranh gii ca pha rn lm cho n c tch in dng hn.
tng tc tnh in cc ion tri du c ht n gn lp b mt phn chia hai pha v hnh thnh lp in k
S hp ph ion c tnh trao i, l s trao i gia ion ca lp in kp vi ion ca mi trng.
Dung dch cc cht in ly trong nc l dung dch thng gp nht trong thc t, phn ny ch yu ta kh
st s hp ph cc cht in ly trong nc.
Tnh chn lc ca s hp ph cht in ly
Cc ion cht in ly c hp ph u tin theo nhng tnh cht sau:
Mng tinh th hnh thnh bng lc ha hc nh th cng xy ra i vi cc ion ng hnh (ion c cng d
vi ion ang xt. V d: ngoi ion I , cc anion Cl , Br , CN , CSN ... cng c th b hp ph ln b m
tinh th AgI.
3. Hp ph trao i: c mt s c im sau:
- C tnh chn lc cao, ngha l s hp ph trao i ch xy ra vi nhng loi ion xc nh nh:
+ Cht hp ph acid (acidoid, nh SiO2, SnO2) c kh nng trao i vi cation.
+ Cht hp ph acid (acidoid, nh Fe2O3, Al2O3) c kh nng trao i anion.
+ Ngoi ra cn c cht hp ph lng tnh, ngha l trong iu kin xc nh no , loi cht hp ph ny
kh nng trao i c cation ln anion.
- Qu trnh hp ph khng phi lun lun thun nghch.
- S hp ph trao i c tc nh, nht l i vi cc qu trnh phi trao i cc ion nm su trong cht
ph.
+
- Nu s trao i din ra vi s tham gia ca ion H hay OH th pH ca mi trng s thay i.
6 /15
S khuch tn
Khuch tn l qu trnh t san bng nng trong h ( ha th ca mi cu t ng nht mi i
trong th tch h), tc l qu trnh chuyn cht t vng c nng ln n vng c nng nh. Q
trnh t xy ra trong h do nh hng ca chuyn ng nhit. Qu trnh khuch tn l bt thun nghch
tin hnh cho n khi nng hon ton ng u. Mc khng ng u c c trng bi grad
nng - l bin thin nng trn mt n v khong cch, n quyt nh mc v hng ca q
trnh khuch tn.
nh lut Fick I: Lng cht m chuyn qua tit din S (t vung gc vi chiu khuch tn), th t
thun vi S, vi khong thi gian khuch tn t v vi gradien nng theo khong cch (dC/dx).
dm D.
dC
.S.dt (p dng vi lng nh cht)
dx
dC
dx
2 -1
D: h s khuch tn (cm .s )
2
Trong iu kin chun (S = 1 cm , dt = 1 giy, dC/dx = 1) th D=m
H s khuch tn ph thuc vo tnh cht ht v mi trng phn tn.
Dng khuch tn i: i D.
dC dm
dx S.dt
nh lut Fick II: cho thy s bin i ca nng (C) theo thi gian (t) khi trong h khng thit
trng thi dng, p dng cho s khuch tn theo khng gian ba chiu.
dC
= D.C
dt
Phng trnh Einstein: cho thy s ph thuc ca D vo nhit tuyt i T, nht ca mi trng ph
tn , v kch thc ca ht r.
D
RT
T
R
k. ; k : hng s Boltzmann, R= 8,314J/mol.K
NB
B
T
kT
6 r
-5 2
Gi tr D trong cc h khc nhau nh sau: h dung dch phn t v ion c D10 cm /giy, cc h keo
-7
-9 2
10 - 10 cm /giy.
san bng nng hai pha ca mng. Hin tng gi l hin tng thm thu. Dng dung mi s ng
lu chuyn khi to c mt gradien p sut cn thit chng li p sut thy tnh tng ng gi l p s
thm thu .
Ni cch khc, p sut cn tc dng vo dung dch ngn dng thm thu gi l p sut thm thu ca
dung dch.
* i vi dung dch tht (dd l tng) p sut thm thu dd theo phng trnh Vant Ho
dd CRT
mRT
MV
m RT
RT
.
.
.N V
N
m
: nng ht (l s ht trong mt n v th tch, ht/lt)
.N.V
- V dung dch keo khng bn vng nhit ng nn khi lu nng ht c th b gim do hin tng k
t. Nh th p sut thm thu ca h keo thng b gim theo thi gian.
- Trong nhng iu kin ging nhau v nhit ng v nng khi lng, bao gi h keo cng c p sut n
hn nhiu so vi dung dch thc.
p sut thm thu ch ph thuc vo s ht ch khng ph thuc vo bn cht v kch thc ht.
Kt qu ny chng t nu kch thc ht cng nh, do cng c nhiu ht, th p sut thm thu cng l
Dung dch thc cha cc phn t c kch thc rt nh so vi dung dch keo nn bao gi cng c p s
thm thu ln hn h keo.
8 /15
1. Cc hin tng in ng hc
.
2. Cu to lp in kp
Ni chung lp in kp gm: lp ion quyt nh hiu th (ion to th) c c do s ion ha hay hp ph
bm trn b mt cht rn v loi ion ngc du (gi l ion nghch) c chuyn vo dung dch hay cn tn
trong dung dch.
(Trong dung dch keo cn c th c cc ion khc sao cho h trung ha in).
* C nhiu gi thuyt khc nhau v cu to ca lp in kp, nht l cu to ca lp ion ngh
Helmholtz a ra l thuyt u tin v lp in kp, xem nh mt t in phng. Qua nhiu nm, Go
Chapman, Stern, cng nhiu ngi khc dn hon thin l thuyt cng nh thc nghim kim chng
quan im.
- Theo quan im hin i c kim chng qua thc nghim, s xut hin lp ion quyt nh in th
do s hp ph chn lc mt trong cc ion c trong dung dch hoc l do cc phn t trn b mt rn ion ha
* u im:
- Gii thch c hin tng in ng hc (dung dch chia thnh 2 phn, 1 phn ln kt cht ch vi b m
rn trong in trng mnh, phn cn li chu tc ng ca s khuch tn v chuyn ng nhit).
- Th 0 gm 2 phn: th in ng hc v th tng t Helmolt.
* Nhc im:
- Thc t vic tnh ton gi tr th ln hn gi tr o c, c bit khi cc ion tin st b mt.
- Khng gii thch c hin tng i du in tch trn b mt ht keo.
10 /
15
11 /15
BI TP V CU HI
Bi 1: Xc nh b mt ring i vi cc ht sau:
-6
c dng khi lp phng vi cnh 10 m
-6
c dng khi cu vi ng knh 10 m
c dng khi tr vi ng cao v bn knh y bng 10
(p s: 6.10 6 m -1 ; 6.10 6 m -1 ; 4.10 6 m -1 )
-6
-4
Bi 2: Ngi ta nghin 1kg than ci thnh ht c ng knh 0,8.10 m. Khi lng ring ca than
2
-3
ci l 1,8.10 kg.m . Tnh b mt tng ca than ny?
(p s: 416,6 m 2 )
Bi 3: Tnh gi tr b mt ring ca kaolin c nghin thnh ht c dng khi cu ng knh
-5
3
-3
0,8.10 m, bit rng khi y khi lng ring ca kaolin l 2,5.10 kg.m v xem nh h n phn
-1
2 -1
tn. (Gi tr b mt ring tnh ra n v m , v m .kg
(p s: 7,5.10 5 m -1 75 m 2 .kg -1 )
Bi 4: Huyn ph t st trong nc gm cc ht dng khi cu, trong 80% ht c ng knh 10
5
-5
m, phn cn li l nhng ht c ng knh 5.10 m. Tnh b mt ring v phn tn ca h?
(p s: 5,24.10 5 m -1 ; 0,84.10 5 )
Bi 5: Xc nh s ht c to thnh khi phn tn 0,2 g thy ngn thnh cc ht dng khi cu c
-8
-3
ng knh 8.10 m. Bit khi lng ring ca thy ngn bng 13,54 g.cm .
(p s: 55.1011 ht)
-6 3
Bi 6: Bng phng php siu hin vi xc nh c trong th tch 2.10 m kh l si cha
-12
-3
80 tiu phn bi. Nng ca sol kh bng 1.10
kg.m , khi lng ring ca pha phn tn l
3
-3
2.10 kg.m . Tnh kch thc trung bnh ca ht, nu bit ht c dng khi lp phng?
(p s: 2,32.10-8 m)
-11 3
Bi 7: Bng phng php siu hin vi xc nh c 53 tiu phn du trong th tch 1,5.10 m sol
-5
-3
3
-3
kh. Bit nng ca sol kh l 2,1.10 kg.m , khi lng ring ca pha phn tn l 0,92.10 kg.m .
Cho rng cc tiu phn pha phn tn c dng khi cu, tnh bn knh trung bnh ca tiu phn?
(p s: 5,4.10 -7 m)
Bi 8: Di y l kt qu nghin cu s hp ph kh CO trn than hot tnh 273 K
P (mmHg) 100 200 300 400 500 600 700
3
V (cm ) 10,3 19,2 27,3 34,1 40,0 45,5 48,0
Tnh hng s cn bng hp ph v th tch kh CO b hp ph cc i trn than. Cho rng qu trnh
hp ph tun theo qui lut phng trnh hp ph ng nhit Langmuir.
(p s: 7,4.10-3 mmHg -1 ; 150 cm3 )
Bi 17: Sol AgI c iu ch t phn ng trao i gia AgNO 3 v lng d KI. Tip theo ngi ta
dng mt trong cc dung dch K2SO4 v (CH3COO)2Ca (c cng nng mol) lm keo t sol thu
c trn. Hi dung dch no trong s 2 dung dch trn s gy keo t mnh hn? V sao?
-6
Bi 18: Ngng keo t ca dung dch mui nhm sulfat i vi dung dch keo As 2S3 l 96.10
-3
-3
kmol.m . Hi cn bao nhiu ml dung dch mui nhm sulfat nng 0,01 kmol.m gy keo t
-1 3
10 m dung dch keo As2S3 ni trn?
Bi 19: Keo Fe(OH)3 c c do s thy phn khng hon ton mui st (III) clorur b keo t bng
cc dung dch sau: natri sulfur, natri clorur, bari clorur. Cht in ly no c tc dng keo t mnh hn?
V sao?
-5
-1
Bi 20: Tc ri ca ht thch anh trong nc l 2,5.10 m.s ; di ca ng cha huyn ph
-3
-2
ny l 0,2 m; hiu in th l 200 V; nht ca mi trng l 1.10 N.s.m v hng s in mi
ca h huyn ph ny l 80. Tnh th in ng hc ca ht thch anh trong h ny?
(p s: 35,2 mV)
-10 2 -1
Bi 21: Xc nh bn knh ht ca sol bc iodur, bit h s khuch tn ca h l 1,2. 10
m .s ;
-3
-2
nht ca mi trng l 10 N.s.m v nhit l 298 K.
(p s:1,82.10 -6 m)