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GIO TRNH
HO KEO
(Dng cho ngnh Nng Lm Ng nghip)
H NI 2006
LI NI U
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CHNG I
KHI NIM V CC H KEO
H keo l mt h phn tn, nhng cht phn tn phn b dng cc ht nh c kch
thc ln hn nhng phn t v ion n gin, gi l cc ht keo. Tuy nhin, cc ht keo vn
khng b giy lc gi li, chng ch b gi li bi cc mng t bo sinh vt.
Do cht phn tn dng cc ht keo nn h keo c nhng c im khc vi cc h
phn tn khc.
I. Cch phn loi cc h phn tn
1. Theo kch thc ht phn tn
Da vo kch thc hoc ng knh ca ht phn tn, cc h phn tn c chia lm
3 loi chnh sau:
H phn tn phn t:
Trong h, cht phn tn dng nhng phn t rt nh, kch thc nh hn 10-7cm,
chng l nhng phn t v ion n gin. Cc h phn tn phn t c gi l dung dch tht
hay dung dch thuc loi h ng th v c nghin cu nhiu. V d: cc dung dch phn
t v in ly.
H phn tn keo
Gm cc ht phn tn c kch thc 10-7 n 10-4cm, gi l cc ht keo1. H phn tn
keo thng c gi l h keo hoc son (sol).
V d: keo AgI, keo Protit.. trong nc.
Trong cc dung dch long, mi phn t protit cng nh phn t polyme khc x s
nh 1 ht c kch thc ht keo. Mi ht keo khc ni chung gm hng nghn n hng trm
phn t, ion n gin to thnh.
So vi phn t, ion n gin th ht keo c kch thc ln hn, nhng chng ta khng
nhn thy bng mt thng. quan st c cc ht keo c bit l cc ht c kch thc
khong 10-7cm ngi ta dng knh siu hin vi in t. Vy h keo l h phn tn siu vi d
th, trong ht phn tn c kch thc khong t 10-7 n 10-4cm. Cc h keo l i tng
nghin cu ca ho keo.
H phn tn th
Gm cc ht c kch thc ln hn 10-4cm, thng gi l h th.
Ni chung h th l h vi d th khng bn vng. Chng hn, trong mi trng lng c
ht phn tn rn kch thc ln hn 10-4cm, th ht c th s nhanh chng lng xung hoc
ni nn trn b mt lng (tu theo khi lng ring ca ht v ca mi trng) ngha l tch
khi mi trng ca h.
Trong h th c 2 loi quan h quan trng l huyn ph v nh tng.
Huyn ph l h th gm cc ht rn phn b trong mi trng lng nh: nc ph
sa Nh tng l h th gm cc ht hoc git lng phn b trong mi trng lng nh: cc
ht du m trong nc. Trong nhiu trng hp phi thm cht lm bn vo huyn ph v
nh tng cc h phn tn bn vng.
Cc huyn ph v nh tng dng trong thc t l nhng h vi d th tng i bn.
Cc h c bn cht ca h keo nn c th coi l cc h keo khi nghin cu v s dng.
Ho keo cng nghin cu cc h vi d th c tnh bn. Trong gio trnh ny chng ta
coi h th c tnh bn v h keo u thuc loi h vi d th.
Mt s ngi s dng khong 10-7 n 10-5cm, nhng hin ti khng c quy nh cht ch no.
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l h bn keo, c tnh cht b mt trung gian gia h keo a lu v h keo ght lu nhng h
bn keo rt gn vi h keo ght lu.
II. Nhng c im ca h phn tn keo
1. B mt d th
B mt phn chia cc pha ca h d th gi l b mt d th ca h. i vi mt h
phn tn d th, th b mt d th ca h tnh bng tng din tch b mt cc ht phn tn. Kch
thc ht cng nh th b mt d th S ca h cng ln. V d:
Phn chia 1cm3 mt cht rn thnh cc ht hnh lp phng cnh l. Nu l = 1cm, th
ch c 1 ht, din tch b mt ca n l 6cm2. Nu l = 10-4cm, th s c 1012 ht, tng
din tch b mt cc ht l S=6.104cm2. Nu l = 10-7cm, th s c 1021 ht, tng din tch b
mt cc ht l S=6.107cm2.
R rng l cng vi mt lng cht phn tn dng ht th kch thc ht cng nh,
s ht cng nhiu, tng din tch b mt cc ht cng ln. Khi kch thc ht bng 10-7cm th
b mt d th ca h rt ln xem bng I.1.
Bng I.1: S bin thin din tch b mt ca mt h ng vi 1cm3 lp phng, cht
phn tn, khi chia thnh cc ht hnh lp phng c kch thc gim dn.
Kch thc ca
ht hnh lp phng
cnh l(cm)
1
10-1
10-2
10-3
10-4
10-5
10-6
10-7
S ht n
1
103
106
109
1012
1015
1018
1021
Th tch 1
ht (cm3)
1
10-3
10-6
10-9
10-12
10-15
10-18
10-21
Din tch b
mt 1 ht s
(cm2)
6
6. 10-2
6. 10-4
6. 10-6
6. 10-8
6. 10-10
6. 10-12
6. 10-14
Nu phn chia cht phn tn thnh nhng phn t rt nh, kch thc khong 10-8cm
th S=0. Nhng phn t l cc phn t v ion n gin, chng khng c b mt ngn cch
vi mi trng ca h.
2. B mt ring v phn tn
B mt ring ca h phn tn l tng din tch b mt ca cc ht, ng vi 1 n v th
tch cht phn tn nghin nh:
S
(1.1)
V
S: tng din tch b mt ca cc ht
V: th tch cht phn tn nghin nh
Sr: b mt ring
n gin cho tnh ton ngi ta cho ht c hai dng l hnh lp phng v hnh
cu, chng hn:
H gm n ht hnh lp phng cnh l th
Sr =
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S 6nl 2 6
= 3 =
(1.1a)
V
l
nl
nhng ht hnh cu bn knh r th
S
n4r 2 3
Sr = =
=
(1.1b)
4 3 r
V
n r
3
i vi cht phn tn nghin th vic xc nh khi lng n gin hn so vi vic
xc nh th tch, nn b mt ring c tnh bng tng din tch b mt ca cc ht, ng vi
1 n v khi lng cht phn tn nghin nh:
S
S 'r =
(1.2)
m
m: khi lng cht phn tn nghin
Sr: b mt ring tnh theo khi lng (th nguyn l cm2g-1, m2g-1)
Thay th m= .V, vi l khi lng ring ca ht vo cng thc I.2 v tnh ton
tng t nh trn s c cc cng thc tnh Sr khi ht dng hnh lp phng.
6
S 'r =
(1.2a)
l
v khi ht dng hnh cu
3
S 'r =
(1.2b)
r
Hnh cu l dng ph bin ca ht keo, nn cng thc 1.2b thng c ng dng
V d: Nghin SiO2 thnh cc ht hnh cu bn knh r = 10-5cm. Tnh b mt ring ca
SiO2? Bit khi lng ring ca SiO2 l = 2,7g.cm-3
Gii:
p dung cng thc 1.2b:
3
Sr =
= 1,11.10 5 cm 2 g 1 = 11,1m 2 g 1
5
2,7.10
T cng thc I.1a v I.1b suy ra
k
Sr =
(1.3)
d
v tng t, qua cc cng thc 1.2a v 1.2b chng ta c:
k
S 'r =
(1.4)
d
k: hng s ph thuc hnh dng ht
d: kch thc ca ht, d = l nu ht hnh lp phng cnh l v d = r nu ht hnh
cu bn knh r.
Vy b mt ring t l nghch vi kch thc ht phn tn. H keo gm cc phn tn
kch thc nh (10-7 10-4cm) l h c b mt ring cc i hoc c b mt ring rt pht
trin. y l c im c bn ca h keo. so snh b mt d th ca cc h ngi ta da
vo b mt ring. Nu cng lng cht phn tn th h keo l h c b mt ring rt pht trin,
do c b mt d th rt ln. Theo quan im ca nhit ng hc th s c mt ca mt b
mt phn cch ln gn lin vi s c mt ca mt nng lng b mt ng k iu nh
hng rt nhiu n cc tnh cht ha keo ca h nh tnh hp ph, tnh cht in, tnh bn,
tnh ng t.
Sr =
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ri
ai%: thnh phn phn trm khi lng ca cp ht i so vi tng khi lng ca
cc cp ht
ri : bn knh trung bnh ca ht cp i
3 a % b% c %
3 0,45
0,35
0,20
+
+
+
+
= 134,14m 2 .g 1
5
6
7
r2
r3 2,65 10
2,5.10
2.10
r1
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v=
2 ( 0 ) 2
r g
9
(1.6)
Gii:
p dng cng thc I.6:
v=
2(2,7 1,0) 3 2
(10 ) .980 = 3,219.10 2 cm.s 1
9 0,0115
A
h
B
Hnh I.1: S sa lng
ca ht phn tn
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h
t
(I.7)
h
2 ( 0 ) t
(I.8)
hoc
r=k
h
t
(I.9)
vi
9
2( 0 ) g
i vi h phn tn c th mt nhit xc nh, th k l mt hng s nn vic xc
nh kch thc ht cn li l vic o cao h m ht sa lng trong thi gian t.
Trong cc h n phn tn, tc sa lng cc ht bng nhau, s phn lp s xy ra sau
mt thi gian xc nh. Cui cng trong h ch c lp mi trng trong sut pha trn v lp
cc ht sa lng pha di.
Trong h a phn tn, tc sa lng cc ht c kch thc khc nhau, khng bng
nhau, nn bin gii phn cch 2 lp nh trn khng r rt. Sau mt thi gian nht nh,
nhng cao khc nhau chng ta rt c cc cp ht khc nhau ra khi h.
Cn lu rng, phng trnh I.8 ch cho php xc nh kch thc ca ht sa lng hnh
cu hoc dng hnh cu, khng b sonvat ho v ht sa lng l ht n hay ht c thn.
Phng php phn tch sa lng xc nh kch thc ht phn tn ch p dng vi
cc h huyn ph. i vi h c phn tn cao nh h keo, do tc sa lng ca ht rt nh
nn phi s dng my ly tm hay siu ly tm sa lng ht.
Cch phn chia cp ht, tu thuc vo yu cu nghin cu v kh nng cho php ca
phng php phn cp. Cn nh rng, mi cp ht l mt h a phn tn hp. Mt h a phn
tn hp cng c th coi l h n phn tn, bn knh ca ht l r . V d:
H phn tn gm 4 loi ht: loi 1 c r = 10-6cm chim 10%, loi 2 c r = 2.10-6cm
chim 25%, loi 3 c r = 3.10-6cm chim 35% v loi 4 c r = 4.10-6cm chim 30% khi
lng ca tt c cc cp ht, nu coi l h n phn tn th bn knh ht l r = 2,26.10 6 cm
k=
2. Mc a phn tn
c mt s phng php biu th mc a phn tn ca cc h keo, sau y l
phng php biu th bng a phn tn ca h.
Cc ht keo c coi l nhng phn t ln tng t cc phn t cht cao phn t. Do
chng ta phn bit khi lng trung bnh s M n v khi lng trung bnh khi M w ca ht.
Khi lng trung bnh s hoc khi lng trung bnh theo s lng ht thng gi tt
l khi lng trung bnh ca ht, tnh theo cng thc:
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Mn =
n M
n
i
(I.10)
ni : s ht i trong h
Mi: khi lng 1 ht i
Tr s M n tnh c t cc phng php cho php xc nh nng cht phn tn.
Khi lng trung bnh khi hoc khi lng trung bnh tnh theo khi lng ca ht
tnh theo cng thc.
ni M i2
(I.11)
Mw =
wi
wi: khi lng ca tt c cc ht i
Tr s M w c suy ra t cc phng php cho php xc nh kch thc ht.
Lun thy M w > M n , nu l cc phn t n gin th M n = M w
a phn tn ca h tnh bng t s gia khi lng trung bnh khi v khi lng
trung bnh s ca cc ht.
M
= w
(I.12)
Mn
: a phn tn
Nu = 1 hoc M n = M w th h l n phn tn, thng thy h gm nhng phn
t n gin.
Nu >1 hoc M w > M n th h l a phn tn. Khi >>1 th mc a phn tn ca
h rt rng, l h gm cc ht rt khc nhau v kch thc hoc khi lng.
V d: C 2 h a phn tn A v B gm cc ht c khi lng nh sau (quy c 1 n
v khi lng y bng 103vC cho ph hp vi cc ht, khi lng ht ny l 100n v):
H A gm 100 ht, khi lng mi ht l 1 n v v 1 ht khi lng 100 n v.
H B gm 100 ht, khi lng ca mi ht l 1 n v v 100 ht khi lng mi ht
l 100 n v.
Hy tnh a phn tn ca mi h?
Gii:
p dng cc cng thc I.11; I.10 v I.12 i vi h A:
Mw =
(100 12 ) + (1 100 2 )
= 50,5 n v
(100 1) + (1 100)
Mn =
(100 1) + (1 100)
= 1,99 n v
100 + 1
50,5
25,37
1,99
v i vi h B:
Mw =
Mn =
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99
1,96
50,5
nc ra
mng thm tch
h keo
nc vo
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10
Cho h keo vo mt bnh thm tch, nhng pha di bnh c bt bng mt mng
thm tch. c im ca mng thm tch l ch cho cc phn t v ion n gin i qua, cc ht
keo khng i qua c. C bnh trn c t trong mt chu nc sch c dng chy xem
hnh I.2. Cc ion ca cht in ly khuch tn qua mng thm tch t h keo vo nc v b
nc cun i. Cui cng trong bnh thm tch ch cn li l h keo. tng tc qu trnh
v hiu qu tinh ch, ngi ta t bnh thm tch trong in trng ca dng in mt chiu.
l nguyn tc ca phng php in thm tch tinh ch keo.
Ngoi phng php thm tch cn c th dng phng php siu lc.
Thc cht l s lc dung dch keo qua cc mng lc c bit, mng lc c cc l nh
vi kch thc xc nh. Cc ion v phn t nh lt qua mng lc, cn cc ht keo k c phn
t cht polyme b gi li trn phu lc. Bng cch chn cc mng c l thch hp, phng
php siu lc chng nhng cho php tnh ch cc h keo m cn tch ring c cc ht keo
theo kch thc ca chng.
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11
CU HI V BI TP CHNG 1
1. Cch phn loi cc h phn tn? Phn bit cc h: huyn ph v nh tng, keo ght lu
v keo a lu? Cho v d.
2. Hy chng t rng kch thc ht phn tn cng nh th b mt d th cng ln.
3. B mt ring v phn tn? Cng thc tnh b mt ring theo kch thc ht?
4. c im ca h phn tn keo?
5. Phn bit h n phn tn vi h a phn tn? Cp ht v nguyn tc phng php phn
tch sa lng?
6. a phn tn ca h? Phng php tnh?
7. Nguyn tc cc phng php iu ch v tinh ch cc h keo?
8. Mt dung dch protit X. B mt ring ca protit l 8,24.104 m2g-1, khi lng ring ca
ht l = 1,1616g cm-3. Tnh bn knh trung bnh r ca cc ht protit X trong dung dch?
Tr li: 3,13.10-5cm
9. Mt loi t st c khi lng ring l =2,68g.cm-3 c nghin thnh 3 cp ht: cp 1
c r1 = 2,5.10 6 cm chim 45%, cp 2 c r2 = 4,6.10 5 cm chim 28%, cp 3 c
r3 = 1,8.10 4 cm chim 27% khi lng tt c cc cp ht. Tnh b mt ring ca loi t st
nghin trn.
Tr li: 20,91m2.g-1
10. Trong th tch ca mt h keo Ag c 0,105g Ag. Gi s ht dng hnh lp phng c
di cnh l 2.10-6cm. Tnh
a/ S ht keo v nng mol ht ca h
b/ B mt d th ca ht
Khi lng ring ca Ag l 1,05g.cm-3
Tr li: 1,25.1015ht, 2,083.10-9mol ht.l-1; 3m2
11. Tnh thi gian cn thit ht SiO2 bn knh 5.10-4cm lng trong nc ct 250C, nht
0,01poa, c 50cm? Bit khi lng ring ca SiO2 l 2,6g.cm-3 v ca nc l 0,982g.cm-3.
Tr li: 94,69 pht
12. Mt hn hp gm 0,5mol cht A khi lng phn t A l 100.000 v 0,5 mol cht B khi
lng phn t ca B l 200.000. Tnh khi lng trung bnh s v khi lng trung bnh khi
ca phn t.
Tr li: 150.000 v 167.000
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12
CHNG II
TNH CHT NG HC PHN T
V S KHUCH TN NH SNG CA CC H KEO
M
A
x
Hnh II.1. S tng trng chuyn ng Brao ca mt ht t A n B.
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13
(II.2)
D: h s khuch tn ca h
2. S khuch tn
Nu trong h c hin tng khng ng u v mt hay nng ht phn tn th c
s di chuyn cc ht t vng nng cao ti vng nng thp hn ( san bng nng ),
chng ta ni l c s khuych tn.
nh lut Fich I (Fick1) v s khuych tn phn t dng cng thc nh sau:
dm = D
dC
Sdt
dx
(II.3)
dC
= 1 , S = 1 , t = 1 th m = D. Vy, h s khuch tn l lng cht chuyn
dx
qua mt n v thit din thng trong mt n v thi gian khi grdien nng bng -1.
Trong h CGS th th nguyn ca D l cm2.s-1
Theo Anhstanh:
RT
(II.5)
D=
.
N0B
Nu
RT
1
.
N 0 6
(II.6)
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14
n gin th ht keo c kch thc ln hn, di trung bnh bnh phng rt nh, nn kh
nng khuch tn ca h keo nh hn nhiu so vi cc dung dch phn t.
- Bit h s khuch tn D s tnh c bn knh r ca ht, l cch xc nh kch
thc ht phn tn bng phng php o h s khuch tn.
Trong th nghim, da vo cc phng php xc nh nng , s tnh c D theo
cng thc (II.4)
Bit khi lng ring v bn knh r ca ht, tnh c khi lng M ca 1mol ht
phn tn.
4
(II.7)
M = r 3 N 0
3
Do c th da vo h s khuch tn ca dung dch cao phn t tm khi lng
phn t cht polyme, nu chp nhn rng phn t polyme dng ht hnh cu trong dung
dch.
3. p sut thm thu
Tnh ng hc phn t l nguyn nhn gy ra hin tng thm thu v p sut thm
thu ca cc dung dch v cc h keo
p sut thm thu l p sut thy tnh nn ln mng bn thm c tc dng lm ngng
s thm thu gia dung mi nguyn cht v dung dch
p sut thm thu cc dung dch phn t long, theo Vanhp(Vant Hoff) c biu
th bng phng trnh:
m
(II.8)
P = RTC = RT
M
(II.9)
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15
P RT
=
+ Bm
m M
(II.10)
m 0,082.298.10
=
= 19.997
P
0,01222
M
Na+
Cl-
Na+
cl-Cl-
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16
(1)
(1)
(2)
n Na+
Rn-
(nc1)
(c1)
Na+
(c2)
Cl-
(c2)
Rn
(3)
Na+ Cl-
(2)
Na+
Cl-
(c2-x)
(c2-x)
Hnh II.3: S phn b cc ion 2 bn mng thm tch (3), h keo (1) v dung dch
tht (2):
a. trng thi u
b. trng thi sau khi thm tch
Lc u nng cc ion thm tch (Na+,Cl -) v ion khng thm tch (Rn-) phn b
2 bn mng nh trnh by hnh II.3a. Sau c s khuch tn cc ion thm tch qua mng
(3). Do nh hng ca ion keo, lng ion Na+v Cl- khuc tn d dng t h (2)sang h (1).
Gi x l lng ion (tnh theo nng ) Na+ hoc Cl- chuyn t dung dch tht vo
dung dch keo th nng ion trong mi h c biu din hnh II.3b.
Theo quan im ng hc th tc khuch tn cc ion thm tch ca h t l thun
vi nng ca chng trong h .
Tc khuch tn cc ion Na+ v Cl- t h (1) sang h (2) l :
v12 = k (C Na + .C u ) (1)
v tc khuch tn cc ion Na+ v Cl- t h (2) sang h (1) l :
v 21 = k (C Na + .C u ) ( 2 ) )
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17
vi k l hng s tc .
Khi v12 = v 21 th hnh thnh cn bng mng nnan, l trng thi cn bng ca s
khuch tn cc ion thm tch gia h keo v dung dch tht tip xc vi nhau qua mng thm
tch. Khi :
k (C Na + .C Cn 1 ) (1) = k (C Na + + .C Cn 1 ) ( 2 )
(C Na + .C Cn 1 ) (1) = (C Na + .C Cn 1 ) ( 2)
II.12
Thay nng cc ion Na+v Cl- bit hnh II.3b vo cng thc II.10 s tm c:
x=
C 22
nC1 + C 2
II.13
Suy ra:
n 2 C 21 + 2nC1C 2 + 2C 2 2
nC1 + 2C 2
2nC1C 2 + 2C 2
(C 2 x) + (C 2 x) =
nC1 + 2C 2
(C Na + + .C Cl ) (1) > (C Na + + .C Cl ) ( 2)
(II.14)
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18
du
dx
II.15
f: lc ma st .
S: din tch tip xc gia 2 lp lng
du
: gradien tc gia cc lp theo hng x thng gc vi trc y
dx
: h s t l c gi l nht
Trong h CGS th nguyn ca l yn.cm-2s, c tn l poa, cn trong h SI th th
nguyn cat l N.m-2.s, 1N.m-2s = 10 poa,.
nht ca cc h keo
S chy ca son khc vi cht lng nguyn cht v dung dch tht ch, trong mi
trng ca h c nhng ht keo m kch thc ln hn rt nhiu so vi cc phn t n gin.
Cc ht keo chon khng gian ca cht lng, lm cho cc phn t trong s chy lc i v lm
tng gradien tc trung bnh gia cc lp, do nht ca h keo cao hn nht ca
mi trng.
Theo Anhstanh th nht ca h keo ph thuc vo th tch v hnh dng ht keo,
nu l ht keo rn dng hnh cu th:
= o(1 + 2,5 )
(II.16)
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19
(II.17)
r
C
C
i vi dung dch cao phn t long th r tnh theo phng trnh:
(II.18)
r=KMC
K: hng s, c trng cho mt dy ng ng cao phn t trong mt dung mi xc
nh.
M: khi lng phn t ca cao phn t
C: nng , tnh theo s mol c bn trong 1lt ( l s mol mt xch polyme c
trong 1 lt dung dch, v d: 1mol c bn ca polybutadien bng 54g)
Da vo phng trnh II.18 tnh c M, nhng ch p dng khi mch ngn hay di
nhng phi l cao phn t cng, ngha l gi c dng ko di hoc dng hnh que hi cong.
Cng theo phng trnh II.18 th nht rt gn r/C=KM khng ph thuc nng . Nhng
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20
thc t nht rt gn ca dung dch cao phn t ph thuc nng theo phng trnh bc
nht:
= [ ] + aC
(II.19)
C
a: hng s
S ph thuc phn nh tng tc ln nhau gia cc phn t cht cao phn t trong
dung dch.
xc nh M ngi ta thng s dng phng trnh sau:
(II.20)
[] =K.M
K: hng s i vi mt dy ng ng cao phn t trong mt dung mi xc nh
: hng s, c trng cho tnh mm do ca mch.
Nu =1 th phng trnh II.20 tr thnh phng trnh II.18, nu =0,5 th mch cao
phn t mm do. Nhng nu =0 th cao phn t dng ht hnh cu, nht ca dung dch
khng ph thuc kch thc hoc M ca cht cao phn t. Thc t thng thy rng: 0<<1.
Dung mi nh hng nhiu n hnh dng cao phn t trong dung dch. mt dung
mi thch hp th cao phn t c th dng mch m ko di, nhng mt dung mi khc th
c th cun li. V nguyn tc, cao phn t cng d tan vo dung mi th n cng d sonvat
ho, mch cao phn t m ko di, nht dung dch cng ln. Trong dung mi khng ph
hp, cao phn t tan t, tnh sonvat ca n km, phn t cao phn t d cun li v cun cng
cht th nht ca dung dch cng nh.
nht ca cc dung dch tinh bt, prott c lin quan n cc qu trnh ch bin thc
phm
II. S khuch tn nh sng ca h keo.
Tnh cht quang hc ca mt h phn tn phn nh quan h nhiu mt gia cu to ca
h v nh sng ti nh: tnh cht mi trng, nng v kch thc ht, hnh dng v trng
thi b mt ca ht phn tn, di sng ca tia ti, phng gia tia ti v v tr quan st
Trong gio trnh ny, chng ta b qua cc hiu ng quang hc do mi trng gy ra
m ch tp trung nghin cu tnh cht quang hc ca h bt ngun t quan h gia nng ,
kch thc ht v di sng ca tia ti. Quan h y biu th cho bn cht ca hin tng
quang hc cc h keo, l s khuch tn nh sng (light cattering)
nh sng i qua h keo s b hp th mt phn v mt phn b khuch tn. Tu theo
quan h gia kch thc ca ht v bc sng ca tia ti, s c cc hin tng khc nhau:
i vi dung dch tht, cc phn t ca cht tan c kch thc rt nh hn so vi bc
sng ca nh sng ti, nn nh sng d dng truyn qua, tt nhin b hp th mt phn tu
thuc vo bn cht ca dung dch. Hin tng quang hc ny c trnh by cc gio
trnh Vt l.
Nu > th nh sng ti b phn x - xem hnh II.5. Hin tng ny thng xy ra
cc h th.
Nu th nh sng ti b ht ht theo mi phng, ht tr thnh ngun sng th
cp, l s khuch tn nh sng - xem hnh II.6
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21
Tia ti
Tia l
Tia
cc tia
phn x
>
Hnh II.5: hin tng
phn x nh sng
h keo
di sng Tinan
S
I =k
n 2
II.21
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22
Cx =
C 0 h0
hx
tia l
tia l
(2)
II.22
tia ti
(1)
(1)
h keo
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23
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24
CU HI V BI TP CHNG 2
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25
CHNG III
NNG LNG B MT. S HP PH
hp cht ion > hp cht phn cc > hp cht khng phn cc.
cht rn > cht lng.
Bng III.1: Sc cng b mt ca mt s cht lng v cht rn trn gii hn vi khng kh
Tn cht
Hydro(lng)
Oxy(lng)
te tylic(lng)
Hecxan(lng)
tylic(lng)
Clorofooc(lng)
t(0C)
-252
-198
20
20
20
20
103 (N.m-1)
2
17
17
18,5
21,6
27,1
Tn cht
Bezen (lng)
Nc (lng)
Thu ngn (lng)
Thic (lng)
PbF2 (rn)
Ba504 (rn)
t(0C)
20
20
20
920
920
25
103 (N.m-1)
28,9
72,75
485
510
900
1250
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26
103 (N.m-1)
75,64
74,22
73,49
72,75
71,97
69,58
66,18
62,61
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27
III. 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:
G=
n
S
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(III.2)
28
hoc
G=
n
m
(III.3)
Gmax
Ccb
Sp
Sr
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.=
G
G max
(III.5)
29
ph b mt ca than:
130.10 4
=
= 43,33%
300.10 4
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:
(III.6)
kh=(x-y)C=kp.y
hoc
y
C
=
x kh
(III.7)
+C
kp
y
G
v t
=
x Gmax
kh
=a
kp
nn c phng trnh:
C
(III.8)
a+C
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
G = Gmax
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30
Gmax
.C = k .C
a
(III.9 )
(2)
G = Gmax
M
(1)
C1
C2
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31
1
lg C + lg k
n
1
v k.
n
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:
p
1 (c 1) p
=
+
(III.10)
v( p 0 p) v.c v m cp 0
Lp th v s ph thuc ca lgG vo lgC, dng y = ax+b, s tnh c
(C 0 C )V
m
(III.11)
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.
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32
dng.
ph ca TiO2:
1,972
=
.100% = 25,28%
7,8
Ion b hp ph y l ion C12H25SO-4, chng t b mt ht TiO2 mang in tch
4. S hp ph trn b mt lng
Nc l cht lng c sc cng b mt ln. Cc cht ho tan c th b hp ph ln b
mt lng lm gim sc cng b mt ca nc.
Quan h gia lng cht b hp ph (G) trong lp b mt, nng cht tan trong dung
dch (C) v sc cng b mt () ca dung dch theo phng trnh:
G=
C d
.
RT dC
(III.11)
G: hp ph (mol.cm-2)
d
: bin thin sc cng b mt ca dung dch.
dC
Phng trnh III.11 gi l phng trnh hp ph Gip (Gibbs). Da vo phng trnh
chng ta phn bit 2 trng hp sau:
d
>0 th G<0, l hp ph m, nng cht tan trong lp b mt nh hn
Khi
dC
trong th tch dung dch. Nhng cht tan nh th gi l nhng cht khng hot ng b mt.
(1)
(2)
(1)
(2)
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33
b
benzen
nc
c
d
Hnh III.4: S v s sp xp nh hng cc phn t cht hot ng b mt:
a v b: ranh gii khng kh v pha lng
c v d: ranh gii gia 2 pha lng
Trong dung dch nc cht hot ng b mt b hp ph sp xp nh hng nh sau:
phn phn cc hng vo nc (mi trng phn cc), phn khng phn cc hng vo
khng kh (mi trng khng phn cc). Tu theo nng dung dch m lp b mt c th
cha bo ho - xem hnh III.4a, hoc bo ho - xem hnh III.4b. Tng t, cc phn t cht
hot ng b mt sp xp nh hng b mt 2 pha lng c phn cc rt khc nhau l
H2O v C6H6 xem hnh III.4c v III.4d. (Ch : H2O c sc cng b mt ln hn so vi
C6H6).
lp hp ph bo ho cc phn t cht hot ng b mt xp kht nhau to thnh
mng b mt che ph b mt dung dch.
Mch cc bon cng di, tnh ght nc ca cc phn t cht hot ng b mt cng
tng, chng cng c khuynh hng tp trung trn b mt, sc cng b mt ca dung dch cng
gim. l c s l thuyt ca quy tc Trao b (Traube): Kh nng b hp ph ca mt dy
ng ng cc hp cht hu c phn cc trn b mt nc tng vi s tng di mch cc
bon. V vy phng trnh Gp rt ph hp vi cc cht hot ng b mt m phn t c mch
cc bon ln (cc cht tng i t tan).
Ch : ngi ta gi nhng cht hot ng b mt nh: C17H35COONa, C12H25SO4Na,
C16H33N(CH3)3NBr, l cc cht hot ng b mt ion ho, nhng ion C17H35COO-,
C12H25SO4- v C16H33C(CH3)3N+ l nhng anion v cation hot ng b mt.
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34
LK
T
RK
RL
L
R
RK = RL + LK .cos
(III.12)
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35
P0
ln
2V
P
=
P0
RTr
(III.13)
1
r . .h.g
2
(III.14)
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36
1
.r.h v
2
1
2
0 = 0 r.h0
T c cng thc:
=0
.h
0 h0
(III.15)
V d: 200C, khi nhng mt ng mao qun thy tinh vo benzen th ct cht lng
dng ln n hx =5cm, cn khi nhng vo nc th ct nc dng ln n h = 11,3cm. Tnh
sc cng b mt ca benzen nhit trn?
Bit:
Gii:
p dng cng thc III.14
0,899 5
= 72,75
= 29,02dyn.cm 1 = 29,02.10 3 N .m 1
0,997 11,3
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37
CU HI V BI TP CHNG 3
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38
CHNG IV
TNH CHT IN CA CC H KEO
+
+
+
+
+
+
++
+ +
mAgI
++
+ ++
+
+
+
+
+
+
tng khuch tn
tng hp ph
ion quyt nh th
nhn keo
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39
Nhn keo
Nhn keo do rt nhiu phn t, nguyn t hoc ion n gin tp hp li, cng c
trng hp do s chia nh ca ht ln hn. Nhn keo c th c cu to tinh th hoc v nh
hnh, nhng l phn vt cht n nh, hu nh khng c bin i trong cc qu trnh bin
ng ca h phn tn.
Lp in kp.
Lp in kp gm hai lp tch in ngc du nhau, nhng cu to phc tp v lun
lun bin i di tc ng bn ngoi (mi trng, pH, lc ion, nhit .). Lp in kp
c hnh thnh ch yu do s hp ph.
V d 1. Bng phn ng trong dung dch ca AgNO3 vi KI khi cho d lng ca mt
trong hai cht, chng ta s nhn c cc h keo dng AgI v keo m AgI.
Phn ng trao i:
KNO3 + AgI
AgNO3 + KI
To ra cht kh tan AgI, nhng phn t ny tp hp vi nhau thnh nhiu ht nh AgI.
Nu d AgNO3 th cc ht keo dng AgI c to thnh - xem hnh IV.1 cng thc cu to
nh sau:
{ [mAgI ] nAg
nhn
keo
( n x ) NO 3
tng hp
ph
x+
xNO 3
tng khuch
tn
ion keo
ht keo hoc mi xen keo
Ht nh AgI l nhn keo, hp ph chn lc i vi cc ion Ag+, mt s ion i (I-) ko
theo, to thnh ion keo. Lp ion i xung quanh ion keo c gi l tng khuch tn. Tng
hp ph v tng khuch tn tch in ngc du nhau hp thnh lp in kp b mt ht
keo. Ion Ag+ c gi l ion quyt nh th, ion keo mang in(+) nn gi l ht keo dng.
Nu d KI th cc ht nh AgI hp ph chn lc i vi ion I- to ra ht keo m AgI,
cng thc cu to nh sau:
{[mAgI] nI- (n-x) K+ }x-xK+
Trng hp ny ion I- c gi l ion quyt nh th.
Nu s mol AgNO3 v KI va phn ng vi nhau th trong h ch c rt nhiu ht
nh AgI ( c kch thc ca ht keo), chng s kt dnh vi nhau thnh cc ht ln hn v sa
lng. V th ngi ta gi ion Ag+ hoc AgNO3 v ion I- hoc KI l nhng cht lm bn cho
cc h keo AgI.
Tc dng lm bn cho h phn tn c th l cht v c, cht hu c, cng c th l
dung mi hoc cc iu kin v pH, v nhit ca h. Ngi ta hay lm bn keo ght lu
c phn tn cao bng cht prtit nh: gelatin, albumin
Tng hp ph c cu to dy c tng i n nh t khi b bin i bi ngoi cnh.
Trong tng hp ph cc ion quyt nh th gn cht vi b mt nhn keo, c mt s ion i
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40
{[ mFe (OH )
]nFeO + ( n x )Cl
x+
xCl
{[mAl (OH ) ]
3
xAl ( OH ) +2
yAl ( OH ) 2 O
zA
Khi x > y th ion Al (OH ) +2 l ion quyt nh th, c ht keo dng Al(OH)3, trong
tng khuch tn gm z ion A trong a s l anion. Khi y > x th ion Al(OH)2O- l ion quyt
nh th, c ht keo m Al(OH)3, trong tng khuch tn a s l cation.
Do trng thi cn bng (*) ph thuc pH mi trng nn du in tch hat keo
Al(OH)3 s thay i khi pH mi trng bin i.
Ngoi nguyn nhn do hp ph ion nhng cng c trng hp ht phn tn mang in
do b mt c nhm chc c kh nng in ly, do b mt hp ph nhng phn t cha cc
nhm chc c kh nng ion ho. nhng trng hp y s phn chia nhn keo vi lp in
kp khng r rng.
Keo t c thnh phn phc tp, bao gm keo dng, keo m, keo lng tnh. Nhng
keo t phn ln l keo m, v b mt ht thng c hin tng in ly ra ion H+
III. Lp in kp v in th b mt ca ht keo.
1. Cu to lp in kp.
Trong dung dch in ly b mt rn tch in xut hin mt lp in kp gm: lp
in tch b mt ca b mt rn v lp ion i c mt s l thuyt v lp in kp bt
ngun t nhng quan nim khc nhau v cu to lp ion i. Sau y l nhng ni dung chnh
ca thuyt Hemhn, thuyt Guy- Sepmen v thuyt Stc.
Thuyt Hemhn (Helm holtz)
Lp in kp cu to theo kiu mt t in phng. Cc ion i nh nhng in tch
im, ch c tng tc tnh in vi b mt rn v cch b mt rn mt khong 0, gi l b
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41
0 =
(IV.1)
: mt in tch b mt
: hng s in mi ca mi trng
0: b dy lp in kp
in th bin i tuyn tnh theo b dy ca lp in kp - xem hnh IV.2b.
+
+
+
+
cht +
rn +
+
+
+
+
+
+
+
0
a
d
Hnh IV.3: S bin i th b mt theo
khong cch (thuyt Guy Sepmen)
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42
(IV.3)
z F
Ci = Ci 0 exp i
(IV.4)
RT
v tnh c mt in tch () ca dung dch ti x (tnh bng tng i s in tch ca cc
cation v anion:
z i F
RT
Theo phng trnh Poaxng (Poisson):
= z i Ci F = F zi Ci 0 exp
2 =
(IV.5)
(IV.6)
4
4
z F
F z i Ci 0 exp - i
=
=
(IV.7)
x
RT
T Guy v Sepmen thit lp c quan h ca in th b mt vi khong
cch x hoc cng thc v in th b mt ca lp in kp nh sau:
= 0 .e
x
d
(IV.8)
: in th b mt ti x tnh t b mt rn
0: in th b mt Hemhon.
d: b dy lp in kp (ln hn b dy lp in kp Hemhon).
khi dung dch ch c cht in ly tr(2) .
Bin lun cng thc IV.1:
- B dy lp in kp s l 0 khi x 0, th =0
- B dy lp in kp x=d th =0/e
- Khi x- th = 0.
Chng ta nhn thy: lp in kp kiu Hemhn ch l mt trng hp c bit ca
lp in kp Guy Sepmen.
(2) Trong thnh phn cht in ly tr khng cha ion c th xy dng li tinh th ca b mt rn.
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43
e
(3)
(2)
(1)
x
d3
d2
d1
1
Ci zi2
2
(IV.10)
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44
(1)
e
0
d
'0
d'
e
(2)
-0
Hnh IV.5: S bin i th b mt:
(1) ca lp Guy Sepmen
(2) ca lp Stc
Thuyt Stc.
Tc gi b sung thm cho thuyt Guy v Sepmen rng: b mt trt ca ht phn
tn ngoi lc ht tnh in, cc ion i cn c th c lc hp ph (lc tng tc phn t) vi
b mt rn. Trn c s nghin cu hin tng i du in tch b mt trong dung dch
cht in ly.
Chng hn khi b mt rn tch in dng th tng i ca n l cc ion m, b dy
lp in kp l d. Nu trong dung dch c nhng ion m ho tr cao nh SO42-, PO43- th lc
ion ca dung dch tng c th rt ln v d 0 th mt lp in kp th 2 xut hin, c b dy
lp l d. Du in tch v in th b mt i t dng thnh m - xem hnh IV.5.
Cc ion ho tr cng cao th ni chung cng km hydrrat ho, chng tng tc tnh
in mnh hn vi b mt rn v c th b hp ph (bi lc tng tc phn t), dn n s
qu in tch, do c hin tng i du in tch b mt rn. Lp in kp th 1 l lp
in kp Guy - Sepmen, lp in kp th 2 c gi l lp in kp Stc.
Lp in kp Stc l s m rng lp in kp khuch tn Guy - Sepmen cho trng
hp i du in tch b mt trong dung dch in ly. Trng hp ny t xy ra, thng ch
xut hin cc dung dch c lc ion ln v nhiu ion ho tr cao. Ion hu c ho tr thp
cng rt d b hp ph nn n c th gy ra hin tng i du in tch cc b mt.
2. in th b mt ca ht keo.
Gm th nhit ng v th in ng
Th nhit ng
Th nhit ng xut hin b mt ca nhn keo v mi trng. in th ny tng
t in th in cc, l bc nhy th gia hai pha l kim loi (pha rn) v dung dch
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45
(IV.12)
1
Ci z i2
1
3
2
(3)
(2)
(1)
x
d3
d2
d1
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46
4 v
u
(IV.13)
h
t
(IV.14)
4 h
. .( 300 ) 2
u t
(IV.16)
150
= 3v.cm 1 , h = 2,4cm, t = 20 x60 = 1200s.
30
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47
XM + + M + ' XM + ' + M +
(a)
XA + A ' XA ' + A
(b)
XM + + H + XH + + M +
(d)
XA + OH XOH + A
(e)
M-+
A
A-
+ H+
H-+
A
A-
+ M+
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48
(G1 ) (C 2 ) (G 2 ) (C1 )
y: G1 v G2 l hp ph ca ionit i vi ion M1 v vi ion M2 , C1 v C2 l cc
nng ca ion M1 v ca ion M2 trong dung dch.
Biu thc quan h gia hp th (G) ca ionit vi nng ion trao i (C) trong
dung dch khi phn ng trng thi cn bng v ho tr (z) cc ion , c thit lp, c
th gi l phng trnh hp ph trao i:
G1
z1
C1
z1
(IV.9)
=K 1
1
G2 z 2
C 2 z2
z1 v z2 l ho tr ln lt ca M1 v M2
K l hng s cn bng i vi 1 ionit xc nh v 1 dung dch xc nh (v ion trao i
v nng ca n) mt nhit khng i.
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49
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50
CU HI V BI TP CHNG 4
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51
CHNG V
TNH BN CA CC H KEO V S KEO T
1
v
= =
k h
=
r2 t
(V.1)
v: tc sa lng
r: bn knh ht phn tn
h: cao m ht sa lng c trong thi gian t
k: hng s i s mt h phn tn xc nh, nhit khng i
Vy:
- Tnh bn ng hc t l nghch vi kch thc ht phn tn. Kch thc ht cng ln,
tnh bn ng hc ca ht cng nh.
- Tnh bn ng hc cho bit thi gian sa lng () ca ht. l thi gian ht sa
lng c 1cm. Thi gian sa lng cng di th tnh bn ng hc cng cao xem bng V.1.
Bng V.1: Thi gian sa lng ca cc ht SiO2 (khi lng ring 2,7gcm-3) trong nc
(=0,0115poa, khi lng ring 1g.cm-3).
Bn knh ht r (cm)
Tc sa lng (cm. s-1)
Thi gian sa lng
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10-3
3,2. 10-2
31 giy
10-5
3,2. 10-4
52 phht
10-5
3,2. 10-6
86,6 gi
10-6
3,2. 10-8
360 ngy
10-7
3,2. 10-10
Hng chc nm
52
(2)
T
(3)
d
2d
(1)
h
Hnh V.1: ng cong th ht (1), th y (2)
v th tng hp (3) bin i theo
khong cch gia cc ht (l)
Th ht .
Mt cch gn ng ngi ta coi th ht h ca 1 ht keo l tng lc ht ca cc phn
t to nn ht. Do th ht gia cc ht c du m, c lp vi cht in ly ca mi trng.
Th ht xut hin ngay t khi cc ht cn xa nhau (trong 1 phm vi xc nh) tng dn theo
hm lu tha ca khong cch l gia 2 ht:
A
h = n
(V.2)
l
y A l hng s ca th ht, n l cc s nguyn dng chng hn khi l = 10-4 th n
= 2, khi l t 4.10-4 n 5.10-4cm th n = 3, khi l tng ln na th n = 6.
Th y.
Khi cc ht keo mang in cng du s y nhau c bn cht ca lc Culng. Th y
c du dng, xut hin khi cc ht gn nhau, c bit khi c s chm ln nhau ca 2 lp in
kp (trong tng khuch tn). Th y ph thuc vo in th b mt o ca ht (trong
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53
r
2
2
0
ln( 1 + e
l
d
(V.3)
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54
Cn =
C .V
Vk + V
(V.5)
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55
i vi keo As2S3
Cn
58
51
49,5
50
MgCl2
MgSO4
CaCl2
BaCl2
0,72
0,81
0,65
0,69
AlCl3
Al(NO3)3
1
Al2(SO4)3
2
Ce(NO3)3
0,093
0,095
0,096
Cn
trung bnh
52
0,72
Cn (mM.l-1)
Cht in ly
i vi keo Fe(OH)3
Cn
NaCl
KCl
1
BaCl2
2
KBr
KI
16,00
K2SO4
MnSO4
K2Cr2O7
0,205
0,22
0,195
Cn
trung bnh
9,25
9,00
9,65
11,3
12,50
1,207
0,091
0,08
i vi ion gy keo t cng ho tr, ion no hydrat ho cng mnh (bn knh hydrat
cng ln) cng in trng ca n cng nh, tc dng gy keo t ca n cng km. i
vi cc ion kim loi kim, tc dng gy keo t ca chng tng dn nh sau:
Li+, Na+, K+, Cs+
do bn knh hydrat ca ion gim dn theo dy .
V d: cc h keo m As2S3, AgI b keo t bi cc ion Na+; Ca2+; Al3+;, v cc h
keo dng Fe(OH)3, Al(OH)3 b keo t bi cc ion Cl-; SO42-; ngng keo t ca cc ion
Na+; Ca2+; Al3+; i vi keo m As2S3, AgI v ca cc ion Cl-; SO42-;i vi keo dng
Fe(OH)3 , Al(OH)3 c nu bng V.2 v bng V.3.
Cc quy tc trn ch ph hp vi cc ion v c khng phn ng ho hc vi ht keo,
cn cc ion hu c khng thuc cc quy tc trn. i vi h keo ca cng mt cht phn tn
nhng khc nhau v nng , v cch iu ch th ngng keo t c th khc nhau. Cn c
chun ho khng ch nng , kch thc ht, cp ht m c cch thm dn dung dch in
ly gy keo t, tc khuy; lc, th gi tr Cn mi n nh.
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56
i vi keo AgI
Cn
Cn
trung bnh
LiNO3
Na NO3
K NO3
165
140
136
147
Mg(NO3)2
CaCl2
Ba(NO3)2
2,6
2,4
2,26
Al(NO3)3
Ce(NO3)3
0,067
Cht in ly
0,064
Cn (mM.l-1)
i vi keo Al(OH)3
Cn
Cn
trung bnh
NaCl
KCl
43,5
46
45
2,42
K2SO4
K2Cr2O7
K2CrO4
0,3
0,63
0,69
0,51
0.068
K3[Fe(CN)6]
K4[Fe(CN)6]
0,08
0,053
0,08
0,053
Cht in ly
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57
S keo t
khng keo t
khng keo t
keo t hon ton
keo t hon ton
khng keo t
khng keo t
keo t hon ton
Du in tch ht keo
m
m
khng tch in
khng tch in
dng
dng
khng tch in
1
1
1
2
Cn = C1 + C2 = C1 + C2 = ....
2
2
3
3
C1v C2: ngng t ca cht in ly 1 v 2 khi gy keo t ring.
Tc dng gim kh nng gy keo t ca cc ion.
y s gp cc ion gy keo t c tnh cht khc nhau (v ho tr, v bn knh
hydrat), chng lm yu kh nng gy ng t keo hay chng i khng nhau. V d: s i
khng gia Li+ v Mg2+, gia Li+ v Ba2+. Do ngng keo t tng hp Cn ln hn ngng
keo t Ci ca mi cht in ly vi t l s dng trong hn hp.
1
1
1
2
C n > C1 + C 2 ;
C n > C1 + C 2 ...
2
2
3
3
V d: gy keo t keo m As2S3 ngi ta c ngng keo t ca LiCl l C1, ca
BaCl2 l C2, ca MgCl2 l C3. Nu trn LiCl v BaCl2 cng gy keo t keo m As2S3, hay trn
LiCl v MgCl2 cng lm keo t keo , th ngng keo t tng hp Cn trong trng hp th
nht v Cn trong trng hp th 2 l:
1
1
C n = C1 + 1,3C 2 ,
C 'n = C1 + 2C3
4
4
Tc dng tng cng kh nng gy keo t ca cc cht in ly.
Trng hp ny t xy ra gia cc ion v c n gin, thng thy xut hin vi cc
ion phc, c bit l hp cht hu c a din tch c mch ln. C th tnh k nc ca gc
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58
(2)
(1)
C2
(3)
C1
C1
C1
C1
4. S keo t tng h.
S keo t tng h y bao gm s keo t mt h keo bng mt h keo c in tch
tri du hoc mt h keo a lu hoc mt dung dch cht bn keo.
Hai keo tri du: trn 2 h keo c in tch tri du c th to nn s keo t. Chnh
tng tc tnh in gia chng lm cho 2 keo tri du tp hp v sa lng nhanh hn.
Chng hn trn keo dng Fe(OH)3 bn vi keo m As2S3 bn vi mt t l thch hp
th s keo t c 2 keo. Khi lng cha ca 1 trong 2 cht keo qu ln c th to nn s keo t
bt thng.
Nc ph sa (gm cc ht keo hoc ht th mang in m) c lm trong bi phn
nhm Al2(SO4)3.K2SO4.24H2O (to ra ht keo dng). cng l s keo t tng h.
Gia keo a lu v keo ght lu
H keo ght lu km bn. H keo a lu bn
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59
Hp ph
n
Ht a lu
Ht ght lu
Ht ght lu c a lu
HnhV.3: S v c ch bo v keo ght lu bng keo a lu
Tc dng lm tng tnh bn cho keo ght lu bng keo a lu c gi l tc dng bo
v ca keo a lu. Nh hin tng trn m nhiu ht v c vn rt kh phn b trong c th
sinh vt (nh cc hp cht Fe3+, PO43-..) nh cc cht hu c (thng l protit) bo v m
chng xm nhp, phn b c trong c th sinh vt. Nhiu ht st, ht keo t cng
c cc hp cht hu c thch hp bo v khng b kt ta, m khng b phn tn trong
cc mi trng lng.
Tc dng bo v ca cht cao phn t l ch c a lu ngha l to iu kin cho
ht sonvt ha nhng cng c th gi cho th in ng cao hoc cn tr khng cho cc ht
li gn nhau n khong cch m lc ht tc dng mnh. Cui cng cng c th v chuyn
ng nhit ca cc phn t cht cao phn t ln v s y nhau gia chng mnh nn ht keo
kh li gn nhau. Do m h thm bn vng.
Keo c bo v c th sy kh v sau li c th ha tan vo dung mi c thnh
son.
n
+
Ht a lu
Hp ph
Ht ght lu
Ht a lu c ght lu ho
HnhV.4: S v c ch lm keo t nhy cm
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60
gii thch? Bit rng albumin l keo a nc. Coi khi lng ring ca h keo Fe2O3 l
1g.cm-3.
Gii:
- Khi lng cht phn tn Fe2O3 l 0,1g
- Khi lng 1 ht keo Fe2O3:
4
m = (10 5 ) 3 .3,6 = 1,5.10 14 g
3
- S lng ht keo Fe203 trong 10 ml h keo :
0,1
n=
= 6,66.1012 ht
1,5 10 4
- S phn t (ht keo) albumin:
1,5.10 3 6,02.23 23
n' =
= 2,55.1016
35.400
- T s:
n' 2,55.1016
=
= 2,6.10 3
n 6,66.1012
Vy 1 ht keo hp ph khong 2500 phn t albumin, ngha l albumin bao bc
ht Fe2O3. Ht keo c bo v bn, kh b keo t.
V d 2: ly 1,5mg albumin trn pha thnh 1 lt dung dch albumin, cho 1 git (bng
1
ml) dung dch vo 10ml h ko Fe2031% (nh v d 1) th hin tng keo t xy ra
25
rt nhanh bi NaCl. Gii thch?
Gii:
- S phn t albumin trong 1 git dung dch:
1
1
2,55.1016
= 1,02.1012
1000 25
- Trong 10 ml h keo Fe203c 6,66.1012 ht keo
- T s:
S ht keo Fe203
6,66.1012
=
=6,5
S ht albumin
1,02.1012
Ngha l albumin to iu kin cho cc ht keo FeO3 tp hp, kt dnh vi nhau, do
s keo t xy ra d dng khi thm NaCl vo.
Gia keo u lu v cht bn keo.
Cht bn keo thuc loi cht hot ng b mt trong c cht hot ng b mt
anion nh C12H25S04Na v cht hot ng b mt anion nh C12H25(CH3)3NBr
Trong dung dch nc chng c kh nng in ly ra anion hot ng b mt, v d:
C12 H 25 S 0 4 Na
C12 H 25 S 0 4 + Na +
hoc cation hot ng b mt, v d:
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61
++
++ ++
+
++ ++
++
++
++ ++
+
++ ++
++
+ n
Ht k nc
Hp ph
Hnh V.5. S v s hp ph ca
ht keo (+) Fe2O3 i vi cc anion
C12H25SO4- :
a: Hp ph n lp (k nc ho)
b: Hp ph 2 lp (i du in)
++
++ ++
+
++ ++
++
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62
(1)
(3)
(2)
CA
CB
(1).
(a)
(b)
+
(c)
(d)
63
v=
d n
= k ( n)2
dt
(V.7)
= kdt
( n) 2
vi iu kin t1 = 0 th tng s ht trong h bng n0 v t2=t th tng s ht trong h bng n,
s nhn c:
1
1
= kt
n n0
hay:
n0
n =
(V.8)
1 + kn0t
Phng trnh V.8 cho php xc nh: c bao nhiu ht cc loi tn ti trong h, sau cc
phn ng (a,b,c,d) xy ra trong khong thi gian t.
S dng thi gian l thigian bn keo t hoc thi gian keo t mt na, l khong
thi gian s ht ca h trong mt n v th tch ch cn mt na, ngha l khi:
n
n = 0
(V.9)
n
Thay t bng v phng trnh V.9, vo phng trnh V.8 th c cc phng trnh:
n
n0
n = 0 =
(V.10)
2 1 + kn0
1
(V.11)
kn 0
1
vo phng trnh V.8, chng ta thy tng s ht keo cn c trong h
Thay k =
n0
sau thi gian t l:
n
(V.12)
n = 0
t
1+
Theo phng trnh V.12: bit n0, bit n cc thi im t kho st, chng ta tnh
c thi gian bn keo t . Trong vng keo t nhanh, i vi mi h keo, l mt hng s.
iu rt ph hp vi l thuyt ng hc phn t. Mt khc, nu bit c gi tr v gi
tr n0 th tnh c n sau thi gian t. Thc t cho thy, kt qu tnh c theo phng trnh
V.12; trng hp vi nhng o m thc nghim xem bng V.5.
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64
Bng V.5: S ht keo vng (Au) sau thi gian, theo l thuyt v theo thc nghim.
Sau thi gian t (s)
S ht keo 10-8 trong 1 cm3
- Thc nghim
- Tnh c
270
390
450
570
8438
8438
5,3
5,8
4,1
4,0
3,5
3,5
2,6
2,7
H phn tn keo
gy keo t
pepti ho
Nu lm gim in th , lm tng tnh k nc . Thc y qu trnh keo t th
ngc li, lm tng in th , tng tnh a dung mi s thc y qu trnh keo tn (pepti
ho).
Khuy lc, tng nhit c tc dng ph v nhng lin kt gia cc ht bng tc
ng c hc, nhit hc lm keo tn, nhng l keo tn tm thi. Khi cc yu t y khng
cn, keo li ng t tr li.
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65
Cc tc ng ho l nh: pha long (ra bng nc), thay i ion gy keo t, thay cc
ion ho tr cao bng cc ion ho tr thp hn, mc hydrat ho cao hn c tc dng m
rng b dy lp in kp (d) lm tng in th . Lin kt cc ht trong trng thi ng t yu
dn, khi th y vt tri th ht cc ht phn tn tr li, h keo ti xut hin.
Keo tn bng cht in ly l s thm cht in ly m mt trong cc ion ca n c th
xy dng mng li tinh th ca pha phn tn hoc b hp ph ln b mt ht. V d: kt ta
Fe(OH)3 c th keo tn bng FeCl3 do to ra keo Fe(OH)3, cng thc cu to ht keo nh
sau:
3+
(3n x )Cl
x+
xCl
Ion Fe3+l ion quyt nh th. Nguyn nhn hin tng nh sau: sau khi b cc ht th
Fe(OH)3 hp ph, cc ion Fe3+ c tc dng phn chia hoc phn tn cc ht thnh nhng
ht keo. y l mt v d v iu ch keo bng phng php phn tn, ngi ta gi FeCl3 l
cht phn tn hoc cht keo tn.
Tc dng bo v ca cc cht cao phn t in ly i vi keo ght lu, s to lp hp
ph th 2 ca ion hot ng b mt trn b mt ht ght lu cng c coi l yu t lm
tng kh nng pepti ho.
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66
CU HI V BI TP CHNG 5
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67
CHNG VI
H KEO A LU V H BN KEO
C5
C3
C4
C2
C1
Hnh VI.1: S quay ca cc mt xch
trong mch polyme. Gc
ha tr l -
chuyn t v tr cn bng ny sang mt v tr cn bng khc, cn phi tiu ph mt
nng lng Eo c trng cho hng ro th nng ca s quay. Gi tr Eo cng ln th v tr
E0
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68
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69
nh, chng xut hin v t tan d theo kiu tp hp ca cc phn t nh cc cht lng
nguyn nht. Mc d cc tp hp c tnh cht thng k nhng v mch cacbon di v dung
dch c nht cao nn thi gian tn ti ca cc mixen cng lu hn so vi nhng tp hp
ca cc phn t nh.
Trong trng hp dung moi khng thch hp cho cht polyme phn tn, nu chng ta
dng cc bin php vt l, ha hc phn tn cng thu c cc h keo. cc h keo
bn vng tp hp th bt buc phi dng cht lm bn. y l bn php c dng nhiu
trong cng ngh iu ch cao su, sn, cream lm thuc .
3. Nhit ng hc v s ha tan polyme
Trong dung mi thch hp, s ha tan polyme l mt qu trnh t din.
Phng trnh nhit ng hc cho s ha tan nh sau:
G = H - TS
(VI.4)
trong s ha tan polyme, th tch h khng i nn c th p dung phng trnh:
F = U - TS
(VI.5)
Qu trnh ha tan d theo c ch no cng phi theo chiu gim nng lng t do
ng nhit ng p (G < 0) hoc gim nng lng t do ng nhit ng tch (F < 0 ) ca
h.
Qu trnh ha tan l qu trnh tng entropy (S > 0) v s trn ln lun km theo s
tng entropy. Theo tnh ton th s ho tan polyme vo dung mi gy ra bin i entropy l
Sp, c gi tr nm gia bin i entropy ca s ha tan cc phn t nh (S) v s phn b
cc ht keo ght lu vo mi trng (Sk):
Sk < Sp < S
Ngha l tnh v trt t ca cc phn t polyme trong dung dch ch km cc phn t
trong dung dch phn t, nhng ln hn rt nhiu so vi cc ht keo ght lu trong cc h
keo. iu cng thy c nh nhit ng thng k. Nu biu din xc sut trng thi nhit
ng trc ha tan l Wt v sau ha tan l Ws th chng ta c phng trnh phn nh bin
thin entrropy trong qu trnh ho tan polyme nh sau:
S = S2 S1 = k(lnWs ln Wt )
W
S = k ln s > 0
(VI.6)
Wt
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70
khi ha tan trong dung mi phn cc (v d: H2O), s nhm ion ha v phn cc rt nhiu,
nn s hidrat ha rt mnh, nhit ha tan ln v S tng nhanh lm cho G cng nh, qu
trnh ha tan cng d tin hnh.
4. S trng ca polyme.
Trng l giai on u ca s ha tan polyme. l s khc nhau c bn so vi s
ha tan nhng cht phn t nh.
S trng l qu trnh polyme hp th dung mi lm cho khi lng ca polyme tng,
th tch ca n cng tng, tnh cht c l ca polyme thay i, nhng tnh ng th ca n vn
c duy tr.
Cc polyme thng trng thi v nh hnh, sp xp khng c kht, li c chuyn
ng nhit ca cc mt xch, nn gia cc mch polyme tn ti nhng khe h m cc phn t
dung mi c th lt qua. Lc u ch c s khuch tn ca dung mi vo polyme, lm yu lc
lin kt gia cc phn t, khi cc lin kt b t th phn t polyme s khuch tn vo mi
trng to thnh dung dch.
Tc trng khng ch ph thuc khi lng mol ca polyme m cn ph thuc tnh
mm do ca cc mt xch trong phn t. Cc polyme mch cng t trng, cn cc polyme
loi hnh cu hu nh khng trng. V d: glucogen bt, M = 800.000, dng hnh cu khng
trng trong nc. Do lc tng tc gia cc ht hnh cu nh nn s ha tan d dng m
khng qua giai on trng.
Trong thc t khng c ranh gii r rt gia s trng v s ha tan. Khng phi kt
thc s trng bao gi cng l s ha tan. Thng thng th n mt th tch xc nh, s
trng dng li v h c hai pha: pha dung dch bo ha polyme v pha thch (gn rn) l pha
bo ha dung mi trong polyme. l s trng hn ch. Cng c khi s trng hn ch
chuyn thnh s trng khng hn ch (s ha tan) khi thay i iu kin th nghim. V d:
gelatin v aga, trng hn ch nc lnh nhng trng khng hn ch nc nng.
trng
trng ca polyme c tnh theo phng trnh
m m0
=
(VI.7)
m0
m0: khi lng polyme trc khi trng (g)
m: khi lng polyme sau khi trng (g)
Kho st s bin i trng theo thi gian t chng ta c phng trnh:
d
= k ( max t )
(VI.8)
dt
max: trng gii hn (cc i)
t: trng thi im t
k: hng s tc trng (ph thuc bn cht polyme, duung mi, nhit )
Gii phng trnh VI.8 s c:
max
1
k = ln
(VI.9)
t max t
chnh gi tr k cho bit tc trng trong nhng iu kin xc nh.
Ngoi bn cht polyme th hnh dng ht polyme cng nh hng ln ti hng s tc
trng.
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p sut trng
S trng gn lin vi s tng th tch do to nn p sut trng P:
(VI.10)
P=PoCk
C: lng polyme kh trong thch trng thu c
k: hng s, thng thy k 3
Khi C = 1 th P = Po , c th chuyn phng trnh VI.10 thnh phng trnh:
lnP = lnPo + klnC
(VI.11)
COOH
R
COO- H+
+ H2O
CH
NH2
CH
NH+3 OH-
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COOH
R
COOH
+
+ H
CH
CH
NH2
NH3
lc protit mang in dng.
Trong mi trng baz(chnh xc l mi trng c pH cao hn im ng in) th
protit c tng tc:
COOH
R
COO+ OH-
CH
+ H2O
CH
NH2
NH2
y protit mang in m.
Mi protit c mt c tnh in khc nhau. i vi protit c nhiu nhm COOH th
tnh axit tri, n thng mang in m, protit c nhiu nhm NH2 th tnh baz tri, n
thng mang in tch dng. Tuy nhin in tch ca n cn ph thuc pH mi trng nh
thy trn . C gi tr pH mi trng m b mt protit khng mang in hoc trng thi
ng in. Gi tr pH ng vi trng thi ng in gi l im ng in. Mi protit c mt
im ng in ring- xem bng VI.1, pH thp hn im ng in keo protit mang in
dng, pH cao hn im ng in keo protit mang in m.
Protit l keo a nc lng tnh, s tch in b mt ca n nh hng nhiu n tnh
cht ca dung dch protit.
Bng VI.1. im ng inca mt s protit.
Tn protit
Casein
Gelatin
Albumin(trng)
Globulin
Zein(ng)
Hemoglobin
Gliadin(la m)
im ng in (pH)
4,6
4,7
4,8
5,4
6,2
6,7
7,1
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(P,D)
im ng in
66
pH
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b
a
Hnh VI.2- S dng cc mixen bn keo trong mi trng nc
(mi trng phn cc)
a: Dng cu
b: Dng tm
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Ti hn
Ct
C
Hnh VI.3: S ph thuc ca dn in ng
lng ca kali lat vo nng dung
dch
Chnh nng ti hn l ranh gii phn bit hai tnh cht khc nhau c bn trong mt
h: khi l dung dch tht, khi l dung dch keo ty thuc vo nng cht phn tn ( cng
chnh l mt trong cc l do khin ta gi cc dung dch cht hot ng b mt l dung dch
bn keo).
Nng ti hn mixen Ct ph thuc vo bn cht cht bn keo v iu kin bn ngoi
(nhit , nng cht in ly, khi lng ring ca dung dch ). Thc t thy rng :
Mch cacbon cng ln th Ct cng nh, do tan ca cht bn keo gim. Vi cng
mch cacbon nhng hp cht cha no c Ct ln hn so vi hp cht no, hp cht c nhm ion
ha gia mch c Ct ln hn so vi hp cht c nhm ion ha u mch. Trong mt dy
ng ng ca cc cht bn keo Ct gim theo s tng ca mch cacbon, tng t nh quy tc
Trao b v s hp ph dng ca cc axit bo trn b mt dung dch.
C th xc nh Ct ca mt cht bn keo bng cch o dn in ng lng , do
ti gi tr Ct dn in ng lng v nhiu tnh cht khc ca dung dch bn keo gim t
ngt.
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S ha tan keo:
cc cht hu c khng phn cc nh benzen, heptan, du ha, cc phm mu
khng tan trong nc. Tuy nhin khi c mt x phng nng C > Ct th cc cht hu c
s chui vo trong lng mixen x phng. Hin tng d gi l s ha tan keo.
X phng trong mi trng khng phn cc s c kh nng ha tan nc vo du m
l s ha tan keo nghch. Hin tng c ngha rt ln trong cng nghip thc phm.
Bng VI.2. Nng ti hn mixen Ct (milimol. l-1) ca mt s hp cht 250Ctrong nc.
Tn cht hot ng b mt
Cc cht hot ng b mt anion
Natri dodecyl sunfat
Natri tetradecyl sunfat
Natri hexadecyl sunfat
Natri octadecyl sunfat
Cc cht hot ng b mt cation
Dodecyl trrimetyl amoin bzomua
Tetradcyl trimetylamoni bzomua
Cetyltrimetylamoni bzomua.
Octadecyltrimetyl amoni bromua
X phng no v cha no
Kali stearat
Kali oleat
Ct
C12H25SO4Na
C14H29SO4Na
C16H33SO4Na
C18H37SO4Na
8,00
2,0
0,6
0,18
C12H25(CH3)3 NBr
C14H29(CH3)3 NBr
C16H33(CH3)3 NBr
C18H37(CH3)3 NBr
10,0
3,0
1,5
0,25
C17 H35COOK
C17 H33COOK
0,45
1,5
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Lnh vc ng dng:
3 n 6
7 n 9
Thm t
8 n 1
13 n 15
Ty ra
15 n 18
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cch gia cc ht khng ln, d xy ra s kt dnh v sa lng (nu khi lng ring ca cht
phn tn ln) hoc sa ni (khi khi lng ring ca mi trng ln hn). Tnh bn tp hp
ca nh tng m c km, ph thuc vo cht lm bn hay cht nh ho.
Cht nh ho a nc tri, tan vo nc tt hn, n xc tin cho qu trnh ho to
nh tng D/N, cn cht nh ho a du hn th xc tin qu trnh nh ho to nh tng loi
N/D. Nh cht nh ho c th to nn cc nh tng c nng rt cao (trn 90% th tch h
l cht phn tn ).
2. Cht nh ho.
Cht nh ho l cht c tc dng lm bn nh tng. Trong a s trng hp cht nh
ho l cc cht bn keo hoc mt s cc cht khc (c th l cht v c) c trong phn t phn
a du k nc v phn a nc k du.
D
N
(a)
D
D
N
N
(c)
(b)
(d)
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Lng
Kh
Cht to bt
H nh VI.6: S cu to bt
Cht to bt hp ph trn 2 mng ca lp cht lng xem hnh VI.6.
y chng ta ch cp n h thng bt (c ngha trong ngnh sn xut v i
sng) Bt bao gm cc t bo kh a dng to nn cu trc xp t ong. H thng bt tuy c
din tch b mt ln, nhng nng lng b mt l cc tiu bt tn ti c. Tho mn quy
tc th trn 1 cnh lng ca bt lun lun c 3 mng to nn vi nhau mt gc 1200 v
mt im ch c th to 4 cnh i qua. Cc bt kh sp xp st nhau lm cho bt c tnh bn
vng c hc no .
Bt sau khi hnh thnh s b ph hu. H c cht to bt c sc cng b mt nh,
nhng khi to thnh, h nhn nng lng ( tng s lng ht bt). Do s c qu trnh
t din theo chiu gim nng lng, theo cch mng cht lng khng ngng chy dn theo
chiu sc ht ca trng lc. V th mng mng dn. Cho n khi dy ca mng bt nh
hn 10-5 cm th mu sc (do s khuch tn nh sng) ca mng thay i hn. T a sc
chuyn thnh khng sc (khng cn tnh khuch tn nh sng) v sau bt v
Vy h thng bt khng c tnh bn ng hc, cn tnh bn tp hp rt ph thuc bn
cht v nng cht to bt. Cc cht to bt c khnng to thnh cc mng b mt bo ha
v to dung dch c nht cao s tng tnh bn c hc cho bt.
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Cng ngh to bt c s dng nhiu trong k thut: to mng xp, tuyn ni, ch
to bia v nc gii kht, to ch phm cu ho Tuy nhin s to bt cng gy nn nhiu
tr ngi cho h nh: ngn cn s bay hi trong ni chng, to ra h d th Trng hp y
cn thm vo cht chng to bt. V d: ru (nh ru amylic, octylic c dng nhiu) v
ete thng thng.
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CU HI V BI TP CHNG 6
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83
CHNG VII
S TO CU TH. H PHN TN MI TRNG KH
V0
a
V2
V1
b
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1
= 0,278cm 3
3,6
0,278
=
= 0,00278 hoc 0,278%
100
V0 =
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5. Mt s tnh cht ca cu th
Hin tng sol gel thun nghch
Mt tnh cht c bit ca trng thi cu th l tnh sol gel thun nghch. l kh
nng ca h khi cu th b ph v bi mt lc c hc no , li c th t phc hi cu
th trong mt thi gian, ngha l c trng thi cn bng:
sol (keo) gel
khi lc thi tc ng, trong nhng iu kin xc nh (nhit , pH).
Tnh cht sol gel thun nghch l khi nim chung ch s bin i thun nghch ca
keo gel v keo thch. l v lin kt gia cc ht khi to cu th thuc loi lin kt yu
(v d: lc tng tc phn t, lc do lin kt hydro).
Hin tng sol gel thun nghch thng gp trong t nhin, trong cng ngh, trong
c th sng. Mt s loi t st c tnh sol gel thun nghch, iu c li trc nhng tc
ng ca hin tng ng t, s khoan rung, s h cc rung Trong k thut khoan ging,
khi mun ht b t ngi ta bin gen thnh son, nhng khi mun nh hnh thnh ging
th phi ho rn thnh ging bng cch chuyn son vo; nhng phi nhanh to thnh gen. Khi
pha sn l lc to son nhng khi sn ln b mt th phi to gen sn khng b chy tri. S
ng vn x phng bng dung dch NaCl nng cao c th lm cho x phng gelatin ho
tc l to thch khun hoc ng bnh.
Hin tng teo v trng.
Hin tng teo l kh nng t gim kch thc gel (nhng vn gi nguyn dng
ban u ca n) lm thot mi trng phn tn ra khi cc nguyn t cu th. Nguyn nhn l
do lc u trong s to cu th, gia cc nguyn t cu th s im tip xc cn kh t. Dn
dn do s sp xp li cc ht (nh chuyn ng nhit) s im tip xc tng ln, cu th b
nn li, y mt phn mi trng ra ngoi.
Ngc vi hin tng teo l hin tng trng: Cu th teo li ht mi trng phn
tn.
Cc cu th c th tnh teo v tnh trng
II. H phn tn mi trng kh.
1. c im.
H phn tn keo v th trong mi trng kh gi l sol kh hoc aerosol.
Aerosol l h rt long, phn tn thp, a phn tn cao, mi trng c nht
rt nh. Tng tc gia ht phn tn v mi trng khng ng k nn lp in kp b mt
ht khng hnh thnh. Trong h chuyn ng Brao rt mnh, s sa lng rt nhanh so vi h
phn tn trong mi trng lng.
Aerosol gm sng m, khi, bi v loi hn hp gia chng vi nhau. Sng m l
h gm cc git lng phn tn trong mi trng kh. Khi l h cc ht rn phn tn trong mi
trng kh. Bi thuc loi khi nhng ht rn y ln hn so vi ht rn trong khi. Nu
khi l kh thi cng nghip th l h phn tn phc tp gm cc ht rn, ht lng, bi v
kh thi.
Trong aerosol ngi ta chp nhn kch thc cc ht nh sau: khi gm cc ht kch
thc khong 10-7 n 10-3cm. Bi gm cc ht khong 10-3. Sng m gm cc ht c kch
thc khong 10-5n 10-3 cm.
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5.10-5
10-410-3
10-310-2
10-410-3
5.10-6
10-510-4
10-510-2
5.10-410-4
Du in tch
-
Aerosol
SiO2
P2O5
NaCl
Than
Tinh bt
Du in tch
+
+
+
+
+
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88
chuyn dch v pha ngun sng, do lc ny pha sau ht c hm nng bi cc tia khc x
trong ht mnh hn so vi pha trc ht.
Nhit di, nhit sa lng, quang di l nhng hin tng lin quan n tnh ng hc phn
t ch c trng cho h aerosol.
Cc ht c chuyn ng Brao rt mnh, nhng nht cu mi trng rt nh v kch
thc ht li th, nn h aerosol khng bn vng, d sa lng. Ht c kch thc ln th tc
sa lng ln, cc ht nh th chuyn ng rt mnh nn d v chm vo nhau v lin kt li
thnh nhng ht ln hn. V th h aerosol c nng cao thi gian keo t mt na rt nh,
cc h aerosol long th thi gian keo t mt na rt ln.
Vy aerosol long l h rt bn. Cc ht c kch thc ht 10-5 n 10-4cm c nng
cao nht cao 18km trong kh quyn, chng l lng t 3 n 22 ngy lm tng rt
mnh tnh c ca kh quyn.
C th ph v aerosol bng cch thay i tc v chiu ca dng aerosol bng cch
lc, bng tc dng sng siu m. thm mm ngng t, tc dng ca in trng
Aerosol t nhin c ngha ln trong thin vn, trong nng nghip. Chng l mt yu
t quyt nh n ch ma, kh hu, thi tit. Cc hin tng ma tuyt, phng in khi
ging t, cu vng l do h aerosol trong kh quyn. H aerosol sinh ra do kh thi cng
nghip gy nhim mi trng nn cn phi c khc phc.
III. Bt v tnh cht ca n.
Bt l h phn tn th trong mi trng kh , ggn vi tinha cht ca aerosol. Do kch
thc ht ln nn h khng c tnh bn ng hc. Do mt ht ln nn khi lng ring ca
bt rt ln hn so vi aerosol.
Kch thc ht bt rt khc nhau ph thuc vo phng php iu ch v mc ch s
dng. Sau y l kch thc ht mt s bt dng trong cng ngh thc phm.
Tn loi bt
Cc oxyt kim loi
BaSO4 (to thnh do kt ta)
BaSO4 (to thnh do nghin)
Cao lanh
Tinh bt go
Tinh bt ng
Tinh bt khoai ty
Bt m loi tt
Bt m loi trung bnh
Kakao
ng knh ht 104cm
0,1 n 1,0
1 n 5
5 n 20
2 n 20
6 n 10
15 n 25
100 n 150
50 n 200
200 n 800
100 n 200
S ha bi ca bt.
Khi c gi, cc ht tch khi bt v tr thnh bi tr l lng trong khng kh gi l s
ha bi ca bt.
u tin l s trt ca cc hat, khi tc gi ti mt gi tr no th ht nhy ma
v tch khi b mt (rt mnh nhng im nh cao ca bt). S trt, s nhy ma lm cho
cc ht va p vo nhau theo kiu dy chuyn, c ht ri xung, c ht bay ln v to bi
trong mi trng kh.
S ha bi ph thuc vo tc gi, kch thc, dng ht, dnh ca bt, nhit
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Tc gi cng ln, kch thc ht cng nh, ht dng hnh cu, b mt ng nht,
nht v dnh thp th tc ha bi cng ln.
V d: vi tc gi 10.m.s-1 th ch cc ht ct kch thc nh hn 0,1mm nhy ma,
cn cc ht ln hn ch c chuyn ng ln trt trn b mt ct.
Khi m ca ht tng th tc ha bi gim. m lm tng dnh ht, bi sc
cng b mt ca nc ln. ng thi m cn to iu kin cho cc ht tch in hoc trung
ha in. Ni chung m lm cho cc ht bt tch in, lm tng dnh gia cc ht, lm
cn tr s ha bi ca chng.
S to cu th.
Lng nc thm vo bt tng s chuyn bt kh thnh bt nho v thnh h cu th
(gel hoch thch) c xp khc nhau, tnh lu n khc nhau ph thuc vo bn cht ca
bt. Cu th to thnh trong iu kin tnh ng nhit. Nu c ngoi lc tc ng th cu th
khng hnh thnh, dng chy trong h chuyn h thnh lyosol. dng bt nho hay cu th
th nht ca h rt cao, nhng khi tr thnh h phn tn trong mi trng lng th h c
nhng tnh cht ca h phn tn th.
Tc dng to vin kh cho bt
y l tc dng ngc vi s ha bi v s to sol ca bt. mi loi bt xc nh,
vi dnh thch hp, khi c ly tm th cc ht bt kt dnh vo nhau, to nn dng hnh
cu rt d hnh thnh. Nu tc ly tm qu ln hoc qu nh th s to vin rt km.
S nghin cht phn tn thnh bt v s to vin bt c dng nhiu trong sn xut
v i sng.
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CU HI V BI TP CHNG 7
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PH LC
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K hiu
g
R
T
N0
-2
Gi tr
9,8m.s
8,314J.mol-1-1
0,0.82.l.atm.mol-1.-1
t0(C) + 273
6,02.1023
3,1416
92
MC LC
Li ni u
Chng I: Khi nim v cc h keo ...........................................................................................2
I. Cch phn loi cc h phn tn ...........................................................................................2
1. Theo kch thc ht phn tn .........................................................................................2
2. Theo trng thi tp hp pha ca h.................................................................................3
3. Theo cng tng tc gi ht phn tn v mi trng ca h. .................................3
II. Nhng c im ca h phn tn keo. ...............................................................................4
1. B mt d th...................................................................................................................4
2. B mt ring v phn tn ...........................................................................................4
III. Khi nim v h a phn tn ............................................................................................6
1. Cp ht............................................................................................................................6
2. Mc a phn tn ........................................................................................................8
IV. iu ch v tinh ch cc h keo .....................................................................................10
1. iu ch........................................................................................................................10
2. Tinh ch keo .................................................................................................................10
Cu hi v bi tp: ....................................................................................................................12
Chng II: Tnh cht ng hc phn t v s khuch tn nh sng ca cc h keo................13
I. Tnh ng hc phn t ......................................................................................................13
1. Chuyn ng Brao (Brown) .........................................................................................13
2. S khuch tn ...............................................................................................................14
3. p sut thm thu .........................................................................................................15
4. Cn bng mng nnan (Donnan) ...............................................................................16
5. nht .........................................................................................................................18
II. S khuch tn nh sng ca h keo. ...............................................................................21
Cu hi v bi tp .....................................................................................................................25
Chng III: Nng lng b mt. S hp ph ...........................................................................26
I. Nng lng b mt v sc cng b mt. ...........................................................................26
II. Khuynh hng gim din tch b mt ca h. .................................................................27
III. S hp ph. .....................................................................................................................28
1. Mt s khi nim c bn ..............................................................................................28
2. hp ph v ph...................................................................................................28
3. S hp ph trn b mt rn...........................................................................................30
4. S hp ph trn b mt lng.........................................................................................33
IV. S thm t v s ngng t mao qun...........................................................................35
1. S thm t. .................................................................................................................35
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