Giáo Trình Hóa Lý Kỹ Thuật

TRNG AI HOC A LAT
GIAO TRNH
HOA LY
DUNG CHO SINH VIEN NGANH MOI TRNG
TRAN KIM CNG - 2002
Giao trnh Hoa ly dung cho SV nganh Moi trng Phan I. ONG HOA HOC. CHNG I. MOT SO KHAI NIEM C BAN.
I. Toc o cua phan ng hoa hoc:
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1. nh ngha: Toc o cua phan ng hoa hoc la bien thien nong o cua mot chat a cho (chat tham gia phan ng hoac san pham phan ng) trong mot n v thi gian. 2. Cac cach bieu dien toc o phan ng: a. Bieu dien toc o phan ng theo nong o cua chat tham gia phan ng : Xet phan ng : A 1 + A 2 sp thi iem t1, thi iem t2, Ta co: v =
_
C1,A1
C 1,A 2
C 2 , A 1 C 2 ,A 2
(I-2). t 2 t1 t t S d co dau tr ang trc (I-1,2) la v khi t2 > t1 th C 2 ,A < C1,A , cung nh C 2 ,A <
A1 A2
C 2 ,A1 C1,A1 t 2 t1
) = C
(I-1), v =
C 2 ,A 2 C1,A 2
) = C
C 1,A 2 .
Tom lai, v =
_
C A i t
(I-3).
_
Khi t 0 th toc o trung bnh ( v ) se tien en toc o thc (v), tc la
v=
dC A i dt
(I-4).
b. Bieu dien toc o phan ng theo nong o cua chat san pham phan ng:
/ / + A2 Xet phan ng: A 1 + A 2 A 1
thi iem t1, thi iem t2, Ta co: v =

_
C1,A/ C1,A 1
1
/ 2
C2 ,A / C2,A/
1 1
C 2 ,A / C 1,A / t 2 t1
C A /
i
C A / t
(I-5), v =
C 2 ,A / C1,A /
2
t 2 t1
C A / t
(I-6).
Tom lai, v =
( I-7 ).
Tng t nh tren, ta suy ra: v =
dC A /
i
dt
(I-8).
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng c. Ket luan:
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v=m
C dC (I-9) va v = m (I-10). t dt
Chu y: Dau tr ang trc cac bieu thc tren neu bieu dien theo chat tham gia phan ng; dau cong ang trc cac bieu thc tren neu bieu dien theo chat san pham phan ng. d. Ghi chu:
/ / / / Gia s ta co phan ng: 1A 1 + 2 A 2 +L 1A 1 + 2 A 2 +L
th v =
/ 1 dC A 2 1 dC A1 1 dC A 2 1 dC A1/ = =L= / = / = L (I-11). 1 dt 2 dt 1 dt 2 dt
II. S phan loai ong hoc cac phan ng hoa hoc:
Ve phng dien ong hoc, ngi ta chia cac phan ng hoa hoc theo phan t so hoac theo bac phan ng. 1. Phan t so cua phan ng: a. nh ngha: + Phan t so cua phan ng la so phan t tng tac cung mot luc vi nhau va do tng tac o ma gay nen phan ng. + Theo phan t so, ngi ta chia cac phan ng thanh phan ng n phan t, lng phan t va tam phan t, tuy theo so phan t tham gia vao moi tac ong hoa hoc c ban. b. Phan ng n phan t: + nh ngha: la phan ng n gian xay ra ch do mot phan t, trong o s bien oi hoa hoc cua mot phan t la mot tac ong hoa hoc c ban. + V du: I 2 2I ; sp + Phng trnh ong hoc: Xet phan ng: A sp , ta co: v = k.C A o, CA la nong o chat A. c. Phan ng lng phan t: + nh ngha: la phan ng trong o tng tac hoa hoc xay ra la do s va cham ong thi gia hai phan t cung dang hoac khac dang. + V du: 2 HI H 2 + I 2 ; CH 3 COOC 2 H 5 + NaOH CH 3 COONa + C 2 H 5 OH (I-12), trong o k la hang so toc
A + B sp ; 2 A sp
+ Phng trnh ong hoc: - Xet phan ng: A + B sp , ta co: v = k.C A .C B (I-13). Thac s Tran Kim Cng Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng - Xet phan ng: 2A sp , ta co: v = k.C 2 A (I-14). d. Phan ng tam phan t:
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+ nh ngha: la phan ng trong o tng tac hoa hoc xay ra la do va cham ong thi gia ba phan t cung mot luc. + V du: 2 CO + Cl 2 2 COCl ; A + B +C sp ; 2 A + B sp . + Phng trnh ong hoc: - Xet phan ng: A + B + C sp , ta co: v = k.C A .C B .C C (I-15). - Xet phan ng: 2A + B sp , ta co: v = k.C 2 A .C B (I-16). e. Ghi chu: + S va cham ong thi gia ba phan t cung mot luc a co xac suat rat be va v vay, phan ng tam phan t a la rat hiem. Trong thc te, ngi ta cha phat hien c nhng phan ng co phan t so ln hn ba. + oi vi nhng phan ng ma trong phng trnh phan ng ch ra rang trong phan ng co mot so phan t ln hn ba tham gia th qua trnh thc te xay ra bang con ng phc tap (gom nhieu giai oan - nhieu tac ong hoa hoc c ban) gom hai hoac nhieu hn hai giai oan noi tiep nhau, trong moi giai oan o, tng tac hoa hoc ch xay ra la do va cham cua hai, hoac hiem hn, cua ba phan t. V du: Phan ng: 2 NO + 2 H 2 N 2 + 2 H 2 O xay ra theo hai giai oan sau: 2 NO + H 2 N 2 O + H 2 O (cham); N 2 O + H 2 N 2 + H 2 O (nhanh). 2. Bac phan ng: a. nh ngha: + Bac cua phan ng hoa hoc hay goi tat la bac phan ng la tong so cac he so luy tha cua nong o trong phng trnh bieu dien s phu thuoc cua toc o phan ng vao nong o cua cac chat phan ng . + Theo bac phan ng, ngi ta chia cac phan ng hoa hoc ra lam phan ng bac mot, bac hai, bac ba, bac khong va bac phan so. b. Phan ng bac mot: + nh ngha: Phan ng bac mot la phan ng trong o s phu thuoc cua toc o phan ng vao nong o c mo ta bang phng trnh: v = k.C (I-17), trong o C la nong o cua chat au (chat tham gia phan ng). + V du: - Xet phan ng: A sp , ta co: v = k.C A (I-18). - Xet phan ng: A + B (rat d) sp, ta co: v = k.C A .C B = k / .C A (I-19).
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng
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V B rat d nen nong o chat B thay oi khong ang ke theo thi gian , tc la: C B C 0,B = const , va v vay, toc o phan ng ch phu thuoc vao nong o chat A. c. Phan ng bac hai: + nh ngha: Phan ng bac 2 la phan ng trong o s phu thuoc cua toc o phan ng vao nong o c mo ta bang phng trnh: v = k. C A . C B (I-20) hoac
v = k. C 2 A (I-21), trong o CA, CB la nong o cua chat tham gia phan ng A, B.

+ V du: - Xet phan ng: A + B sp , ta co: v = k. C A . C B . - Xet phan ng: 2A sp , ta co: v = k. C 2 A . - Xet phan ng: A + B + C (rat d) sp, ta co: v = k.CA.CB.CC = k/.CA.CB . d. Phan ng bac ba: + nh ngha: Phan ng bac ba la phan ng trong o s phu thuoc cua toc o phan ng vao nong o c mo ta bang phng trnh sau: v = k . C A . C B . C C (I-22) hoac v = k. C 2 A . C B (I-23), trong o CA, CB va CC la nong o cua chat tham gia phan ng A, B va C. + V du: - Xet phan ng: A + B + C sp , ta co: v = k. C A . C B . C C . - Xet phan ng: 2A + B sp, ta co: v = k. C 2 A .C B . e. Phan ng bac khong: + nh ngha: Phan ng bac khong la phan ng ma toc o phan ng khong phu thuoc vao nong o cua cac chat tham gia phan ng. Phng trnh ong hoc cua phan ng bac khong co dang: v = k = const (I-24). + V du: A (rat d) +B (rat d) sp, ta co: v = k . C A . C B = k ( a x )( b x ) , trong o a, b la nong o ban au cua A, B tng ng, x la o giam nong o cua A cung nh B. V x<< a, b nen a x a ; b x b va v vay, ta co: v k. a. b = k / = const . f. Phan ng bac phan so: + nh ngha: Phan ng bac phan so la phan ng phc tap, xay ra qua nhieu giai oan trung gian. + V du: H 2 ( k ) + Br2 ( k ) 2 HBr ( k ) , la phan ng day chuyen, xay ra qua nhieu giai oan va no tuan theo phng trnh ong hoc phc tap sau ay:
1
dC HBr dt
2 k. C H 2 . C Br 2 = C 1 + k / . HBr C Br2
(I-25).
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 3. S khac nhau gia phan t so va bac phan ng:
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+ T nhng nh ngha tren ve phan t so va bac phan ng, mi au, ta co the ngh rang phan t so va bac phan ng ch la mot v chung co gia tr trung nhau (phng trnh ong hoc bieu th nh nhau). Tuy nhien, s trung nhau o ch co chang la mot so phan ng hoa hoc n gian; noi chung, trong a so cac phan ng hoa hoc, phan t so va bac phan ng co nhng gia tr khac nhau. Bac phan ng co the la mot phan so, co the bang khong; trong khi o, phan t so ch la nhng so nguyen mot, hai, ba. + V du: Xet phan ng tam phan t: A + B + C sp thi iem t =0, nong o: a b c thi iem t = t, nong o: a-x b-x c-x - Neu a, b vac khong khac nhau nhieu th v =k(a-x)(b-x)(c-x) (I-26) va v vay, phan ng tren la phan ng bac ba. - Neu a,b << c th x << c va v vay, v k(a-x)(b-x)c =k/(a-x)(b-x) (I-27). Nh vay, phan ng tren bay gi la phan ng bac hai. - Neu a << b,c th x << b,c va v vay, v k(a-x)bc = k//(a-x) (I-28). Nh vay, phan ng tren bay gi la phan ng bac mot. Nh vay, oi vi phan ng tam phan t va xet, bac phan ng co the la bac ba, cung co the la bac hai va cung co the la bac mot. + Tom lai, hai khai niem phan t so va bac phan ng la hai khai niem hoan toan khac nhau. Phan loai phan ng theo phan t so la da vao c che cua phan ng; con phan loai theo bac phan ng la da vao ac iem ong hoc cua phan ng, tc la toc o phan ng thc te phu thuoc vao nong o nh the nao, dang ham nao?
III. Phng trnh ong hoc va hang so toc o cua phan ng hoa hoc:
1. Phng trnh ong hoc cua phan ng: + nh ngha: phng trnh ong hoc cua phan ng la phng trnh bieu dien s phu thuoc cua toc o phan ng vao nong o cua cac chat phan ng. + nh luat tac dung khoi lng: oi vi nhng phan ng n gian ve phng dien ong hoc, nhiet o khong oi, toc o phan ng ty le thuan vi tch so nong o cua cac chat phan ng trong nhng trng hp n gian nhat, moi mot nong o co luy tha bang he so ty lng cua chat trong phng trnh phan ng.
/ / / / A1 + 2 A2 +L, ta co phng trnh V du: xet phan ng: 1A 1 + 2 A 2 +L 1
ong hoc cua phan ng nh sau: v = . C Aii = . C A11 . C A22 .L (I-29). i =1
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 2. Hang so toc o cua phan ng hoa hoc:
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+ nh ngha: Hang so k trong phng trnh bieu dien s phu thuoc cua toc o phan ng vao nong o cac chat phan ng (phng trnh ong hoc cua phan ng) la hang so toc o cua phan ng. + Khi nong o cac chat phan ng eu bang 1 n v th v =k va v vay, hang so toc o k con c goi la toc o rieng cua phan ng. + k khong phu thuoc vao nong o cua cac chat phan ng nhng phu thuoc vao ban chat cua cac chat phan ng, vao dang, lng va ban chat cua chat xuc tac, vao nhiet o, ... + k co th nguyen va th nguyen cua k phu thuoc vao phng trnh ong hoc cua phan ng. V du: - oi vi phan ng bac 1, th nguyen cua k la thi gian -1. - oi vi phan ng bac 2, th nguyen cua k la thi gian -1.nong o -1.
Thac s Tran Kim Cng
Khoa hoa hoc
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CHNG II. ONG HOC CUA MOT SO PHAN NG HOA HOC.

I. Phan ng mot chieu bac mot:
1. Mot so v du:
CH 3 N 2 CH 3 C 2 H 6 + N 2 ; N 2 O 5 N 2 O 4 + O 2 ; A sp
2. Phng trnh ong hoc:
k Xet phan ng dang tong quat: A sp
1 2
t =0 t =t
a a -x
Trong o x la o giam cua nong o chat A sau thi gian phan ng la t va k la hang so toc o cua phan ng. Ta co phng trnh ong hoc dang vi phan cua phan ng tren nh sau:
v=
d(a x ) dx = = k (a x ) (II-1). Lay tch phan phng trnh (II-1), ta c: dt dt
dang tch phan cua phan ng mot chieu bac 1; k co th nguyen la thi gian -1. T phng trnh (II-2), ta suy ra: a x = a. e kt (II-3). T phng trnh (II-2), ta suy ra: ln(a -x) = lna - kt (II-4). T phng trnh nay, ta suy ra o th bieu dien s phu thuoc cua ln(a -x) vao t la mot ng thang i xuong. T phng trnh (II-3), ta suy ra o th bieu dien s phu thuoc cua a -x vao t la mot ng cong i xuong. Khi a-x = a/2 th t = t1/2 ( t1/2 c goi la thi gian na phan ng hay con goi la 1 0,693 = const (II-5). Nh vay, t 1 / 2 cua phan ng chu k ban huy) va t 1/ 2 = ln 2 = k k mot chieu bac1 khong phu thuoc vao nong o va la mot hang so oi vi mot phan ng nhat nh, tai mot nhiet o nhat nh.
II. Phan ng mot chieu bac hai:
1 a k = ln (II-2). Phng trnh (II-2) nay c goi la phng trnh ong hoc t ax
1. Mot so v du:
CH 3 COOC 2 H 5 + NaOH CH 3 COONa + C 2 H 5 OH;2HI H 2 + I 2 A + B sp;2A sp

2. Phng trnh ong hoc: a. Trng hp nong o ban au cua cac chat khac nhau:
k sp Xet phan ng: A + B
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng t=0 t=t ieu kien: a b. Ta co phng trnh ong hoc dang vi phan cua phan ng tren la: a b
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a-x b-x
v=
d ( a x) d ( b x) dx = = = k.(a x)( b x) (II-6). dt dt dt
Phan li bien so va lay tch phan phng trnh (II-6) nay, ta c:
1 b ( a x) ln (II-7). ay la phng trnh ong hoc dang tch phan t ( a b ) a ( b x) cua phan ng mot chieu bac 2 khi nong o ban au cua hai chat khac nhau. b. Trng hp nong o ban au cua cac chat giong nhau: k=
k sp Xet phan ng: A + B
t=0 t=t
a-x b-x
dx = k (a x) 2 (II-8). ay la dt phng trnh ong hoc dang vi phan cua phan ng mot chieu bac 2 khi nong o ban au cua cac chat giong nhau. T phng trnh nay, neu lay tch phan th ta c:
ieu kien: a = b. V vay, a-x = b-x nen ta co: v =
1 1 1 k= (II-9). ay la phng trnh ong hoc dang tch phan cua phan t a x a ng mot chieu bac 2 khi nong o ban au cua cac chat giong nhau.T phng trnh nay, ta suy ra th nguyen cua k la thi gian-1.nong o -1. Cung t phng trnh nay, ta 1 1 = kt + (II-10).T phng trnh (II-10), ta suy ra o th bieu dien suy ra: ax a 1 s phu thuoc cua vao t la mot ng thang i len. ax
T (II-9), ta suy ra: t 1/ 2 =
1 (II-11). ka
III. Phan ng mot chieu bac ba:
1. Mot so v du:
2 NO + O 2 2 NO 2 ;2 NO + Cl 2 2 NOCl;2 NO + 2H 2 N 2 + 2H 2 O A + B + C sp;2A + B sp
2. Phng trnh ong hoc: Co nhieu trng hp xay ra nhng sau ay ta ch xet 2 trng hp:
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng a. Ca ba chat tham gia phan ng co nong o ban au giong nhau:
k sp Xet phan ng: A + B + C
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t=0 t=t
a b a-x b-x c-x
ieu kien: a=b=c; do o, ta co: a-x = b-x = c-x; va v vay, ta co:
d ( a x ) dx = = k ( a x ) 3 (II-12). ay la phng trnh ong hoc dang vi dt dt 1 1 1 2 (II-13). Phng phan. Lay tch phan phng trnh nay, ta c: k = 2 2 t ( a x) a trnh (II-13) nay la phng trnh ong hoc dang tch phan cua phan ng mot chieu bac 3 khi nong o ban au cua 3 chat giong nhau. v=
Th nguyen cua k la thi gian-1.nong o-2 . T phng trnh (II-13), ta suy ra:
1 1 = 2 kt + 2 (II-14). T phng trnh 2 ( a x) a
nay, ta suy ra o th bieu dien s phu thuoc cua len. T (II-13), ta suy ra: t 1/ 2 =
1 vao t la mot ng thang i ( a x) 2
3 (II-15). 2 ka 2
b. Ca ba chat tham gia phan ng co nong o ban au khac nhau:

k sp Xet phan ng: A + B + C
t=0 t=t
a b
a-x b-x c-x
ieu kien: a b c a ; do o, ta co: a x b x c x a x ; va v vay, dx = k (a x)( b x)(c x) (II-16). Phan li bien so va lay tch phan phng ta co: v = dt trnh nay (phng trnh ong hoc dang vi phan), ta c:
1 1 1 1 a b c (II-17). ln ln ln k= + + t ( a b)( a c) a x ( b a )( b c) b x ( c a )(c b) c x ay la phng trnh ong hoc dang tch phan cua phan ng 1 chieu bac 3 khi nong o ban au cua 3 chat khac nhau.
IV. Phan ng mot chieu bac khong:
1. Cac v du: C4H9COOC5H11 (rat d)+H2O (rat d) C4H9COOH+C5H11OH A (rat d)+ B (rat d) sp. Thac s Tran Kim Cng Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 2. Phng trnh ong hoc: Xet phan ng: A (rat d)+B (rat d)sp t=0 t=t a a-x b b-x
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ieu kien: x << a, b. Ta co phng trnh ong hoc dang vi phan la:
d ( a x) d ( b x) dx = = = k (a x)( b x) kab = k / (II-18). Lay tch dt dt dt x / phan phng trnh nay, ta c: x = k / t hay k = (II-19). ay la phng trnh ong t hoc dang tch phan cua phan ng mot chieu bac khong. v=
V. Phan ng mot chieu bac n:
k sp Xet phan ng: A + B + L
t=0 t=t
...
a-x b-x ...
Ta ch xet khi a=b=... nen a - x = b - x = ... Phng trnh ong hoc dang vi dx = k (a x) n (II-20). phan trong trng hp nay la: v = dt
1 a Vi n =1, ta co: k = ln (II-21). t ax

Vi n 1, ta co: k =
1 1 1 n 1 (II-22). ay la phng trnh n 1 t ( n 1) (a x) a
ong hoc dang tch phan cua phan ng mot chieu bac n (n1) khi nong o ban au 1 1 = ( n 1) kt + n 1 cua cac chat giong nhau. T phng trnh nay, ta suy ra: n 1 ( a x) a 1 (II-23). T phng trnh nay, ta suy ra o th bieu dien s phu thuoc cua ( a x ) n 1 vao t la mot ng thang i len. T (II-22), ta suy ra: t 1/ 2 = Chu y: khi n =1 th t 1/ 2 = 0,693 / k . Th nguyen cua k la thi gian-1.nong o-(n-1).
VI. Cac phng phap xac nh bac phan ng:
2 n 1 1 (II-24). k ( n 1)a n 1
e xac nh bac phan ng, ngi ta co the dung nhieu phng phap khac nhau. Du phng phap nay hay phng phap khac, tat ca eu c xac nh da vao thc nghiem. Co nhieu phng phap khac nhau e xac nh bac phan ng, sau ay chung ta ch xet 1 so phng phap (vi nong o ban au cua cac chat giong nhau): Thac s Tran Kim Cng Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 1. Phng phap the:
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Xac nh nong o cua mot chat nao o cac thi iem khac nhau, roi em the cac d kien thc nghiem thu c vao phng trnh ong hoc dang tch phan (bieu thc tnh k) cua phan ng bac mot, bac hai,... e xem xem phng trnh nao cho ta gia tr hang so toc o k khong oi (xap x bang nhau) th bac phan ng chnh la bac ng vi phng trnh o. a. Phng phap o th th nhat: Nh chung ta a biet cac phan tren, cac phan ng co bac phan ng khac nhau co dang ham f(C) phu thuoc vao thi gian t khac nhau; nen trong phng phap o th th nhat nay, ngi ta bieu dien s phu thuoc cua ham f(C) vao t bang o th e xem xem dang ham nao cua nong o co ng bieu dien la mot ng thang va t o suy ra bac phan ng. V du: + Neu phan ng nghien cu la phan ng bac nhat th ta co:
1 a k = ln ln( a x ) = ln a kt . t ax
Bang thc nghiem, ta xac nh c a va cac x cac t khac nhau va t o, ta ve c o th bieu dien s phu thuoc cua ln(a-x) vao t se co ng bieu dien la mot ng thang, co dang nh tren H.II.1. + Neu phan ng nghien cu la phan ng bac 2 th ta co:
1 1 1 1 1 k= ( ) = kt + . Nh vay, ng bieu dien s phu thuoc cua t ax a ax a
1 vao t la mot ng thang, co dang nh tren H.II.2. ax

+ Neu phan ng nghien cu la phan ng bac ba th ta co:
1 1 1 1 1 2 = 2 kt + 2 . Nh vay, ng bieu dien s phu 2 2 a 2t (a x) (a x) a 1 thuoc cua vao t la mot ng thang, co dang nh tren H.II.3. (a x) 2 k=
ln(a-x)
1 a-x
1 (a-x)2
H.II.1: o th f(C) -t H.II.2: o th f(C) - t H.II.3: o th f(C) - t cua phan ng bac 1 . cua phan ng bac 2 . cua phan ng bac 3. Thac s Tran Kim Cng Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng b. Phng phap o th th 2:
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Khi theo doi s phu thuoc cua nong o mot chat tham gia phan ng nao o vao thi gian, ta thu c o th co dang nh tren H.II.4.
C C1 C2 1 t1 t 2 2 t
H.II.4: o th bieu dien s phu thuoc cua nong o (C) vao thi gian (t).
dC = kC n = tg (II-25). T phng trnh (II-25), ta co: dt n n tg 1 = kC 1 va tg 2 = kC 2

Nh ta a biet,
C tg 1 1 = tg 2 C2
T o th,
tg 1 tg 2 lg tg1 lg tg 2 n= = C1 lg C1 lg C 2 lg C2 lg
ta xac nh
(II-26).
c: C1 , C 2 , 1 , 2 nen
ta
suy
ra
c:
lg C1 ,lg C 2 ,lg tg 1 ,lg tg 2 va thay vao phng trnh (II-26), ta suy ra c n.

c. Phng phap toc o au: Bang thc nghiem, ta xac nh c toc o au (vo) cua phan ng; t o, ta xac nh c bac phan ng nh sau:
v=
dx = k ( a x ) n v o = ka n (II-27). dt
Ta lam 2 th nghiem: Th nghiem 1: vi nong o au la a1, ta xac nh c v0,1. Th nghiem 2: vi nong o au la a2, ta xac nh c v0,2. Ta co: v 0 ,1 = ka va v 0 , 2 = ka
n 1
n 2
lg v 0 , 2 lg v 0 ,1 a v 2 = 0,2 n = (IIlg a 2 lg a 1 v 0 ,1 a1
n
28). d. Phng phap da vao thi gian na phan ng: Ta lam nhieu th nghiem vi cac gia tr nong o ban au a khac nhau ma van thay t1/2 co gia tr xap x bang nhau th ta co the ket luan phan ng nghien cu la
Thac s Tran Kim Cng
Khoa hoa hoc
- 14 -
phan ng bac 1, v nh ta a biet la ch co phan ng bac 1 mi co thi gian na phan 0,693 ng la mot hang so, khong phu thuoc vao nong o ban au ( t1/ 2 = = const ). k Trong trng hp chung, khi n 1 th nh ta a biet t 1/ 2 Muon xac nh n, ta phai lam hai th nghiem sau: Th nghiem 1: vi nong o ban au la a1, ta xac nh c t1/2,1. Th nghiem 2: vi nong o ban au la a2, ta xac nh c t1/2,2.
n 1
2 n 1 1 = . (n 1) ka n 1
t1/ 2 ,1 a 2 = T o, ta suy ra: t1 / 2 , 2 a 1

VII. Phan ng thuan nghch:
n = 1+
lg t1/ 2 ,1 lg t1/ 2 , 2 (II-29). lg a 2 lg a1
1. Nguyen l ve tnh oc lap cua cac phan ng: a. Noi dung cua nguyen l ve tnh oc lap cua cac phan ng: Neu trong he ong thi xay ra nhng phan ng hoa hoc khac nhau th moi mot phan ng eu tuan theo ung nh luat tac dung khoi lng va dien bien oc lap oi vi nhau. S bien thien chung cua toan he phan ng bang tong tat ca cac bien thien oc lap o. Nguyen l nay ap dung tot cho cac phan ng thuan nghch, phan ng song song, phan ng noi tiep, b. Ap dung nguyen l ve tnh oc lap cua cac phan ng cho phan ng thuan nghch: + nh ngha phan ng thuan nghch: la phan ng dien ra ong thi theo ca hai chieu, ngha la phan ng c cau tao bi hai phan ng khac nhau dien ra ong thi theo hai chieu ngc nhau. + Bay gi, ta xet phan ng thuan nghch sau ay:
A1 + A2
k1 k2
A1
+ A2
Tai thi iem t, oi vi phan ng thuan, ta co: v t = k 1 . C A 1 . C A 2 va oi vi phan ng nghch, ta co: v n = k 2 . C A / . C A / . Theo nguyen l ve tnh oc lap cua cac
1 2
phan ng, ta co toc o cua toan bo phan ng thuan nghch tren la:
v = vt vn = k1 . CA1 . CA 2 k 2 . CA / . CA / (II-30). 1 2
phng trnh tren, v la toc o chung cua phan ng thuan nghch, vt va vn la toc o cua phan ng thuan va nghch tng ng, k1 va k2 la hang so toc o cua phan / / ng thuan va nghch tng ng, C A1 , C A 2 , C A / , C A / la nong o cua A 1 , A 2 , A 1 ,A 2
1 2
tng ng thi iem t.
Thac s Tran Kim Cng
Khoa hoa hoc
- 15 -
nhiet o khong oi, sau mot thi gian phan ng nhat nh nao o th toc o phan ng thuan bang toc o phan ng nghch, tc la vt=vn; luc o, ngi ta noi rang phan ng ang trang thai can bang (Can lu y rang can bang hoa hoc la can bang ong, tc la phan ng van dien ra theo ca hai chieu nhng toc o bang nhau.). Khi CA / . CA / k 1 2 o, ta co: K = 1 = (II-31), K c goi la hang so can bang. k 2 CA1 . CA 2 Chu y: * Trong ong hoa hoc, ngi ta con s dung ai lng K/ =1/K =k2/k1. * oi vi mot phan ng nao o co k1>>k2 th vt >>vn va luc o, ta co the coi: v v t = k 1 . C A 1 . C A 2 , co ngha la phan ng c coi la phan ng mot chieu. 2. Phan ng thuan nghch bac 1 (bac 1-1): a. Cac v du:
NH4SCN
Xet phan ng:
A k1 k2
(NH 2 )2 CS ;
A B
b. ong hoc cua phan ng thuan nghch bac 1-1:
t=0 t=t
a a -x
b b +x
dx 2 dx1 = k 2 ( b + x ) (II-33), trong o: x1 = k 1 ( a x ) (II-32) va v n = dt dt va x2 la phan nong o chat A b mat i do A bien thanh B va phan nong o chat B b mat i do B bien thanh A tng ng.
Ta co: v t =
2 phng trnh tren, ta suy ra: dx1 dx 2 dx = k1 (a x) k 2 (b + x ) = k1 a k 2 b (k1 + k 2 ) x v = vt vn = = dt dt k1 a k 2 b = (k1 + k 2 ) k + k x (II-34). ay la phng trnh ong hoc dang vi phan cua 2 1
phan ng thuan nghch bac 1-1.
k 1a k 2 b dx = , ta co: = ( k 1 + k 2 )( x ) (II-35). Lay tch phan phng k1 + k 2 dt 1 trnh nay, ta c: k 1 + k 2 = ln (II-36). ay la phng trnh ong hoc dang t x tch phan cua phan ng thuan nghch bac 1-1.
at V k1/k2=K nen ta suy ra: =
Ka b (II-37). K+1
Khoa hoa hoc
Thac s Tran Kim Cng
- 16 -
k 1 b + x cb = (II-38) va khi biet k 2 a xcb c K, ta se xac nh c . Biet va bang thc nghiem, ta xac nh c x thi iem t, ta se xac nh c k1 +k2. Biet k1 +k2 va k1 /k2, ta se xac nh c k1 va k2.
Bang thc nghiem, ta se xac nh c: K =
VIII. Phan ng song song:
1. nh ngha va cac v du: a. nh ngha: Phan ng song song la phan ng ma t cac chat tham gia phan ng xay ra ong thi theo nhieu hng khac nhau e tao ra cac san pham khac nhau. b. Cac v du: + Phan ng nhiet phan kaliclorat:
KCl KClO 3 KCl + KClO 4 + O2
+ Phng trnh phan ng song song dang tong quat:

A
+
...
B1 + ... B2 + ... Bn + ...
2. ong hoc cua phan ng song song mot chieu bac 1: a. ong hoc cua phan ng song song mot chieu bac 1 n gian nhat: Xet phan ng:
k1 A k2
t=0 t=t a a -x
B C
0 0 x1 x2
vA B =
dx dx1 = k 1 ( a x ) ( II-39 ); v A C = 2 = k 2 ( a x ) (II-40). dt dt
Phng trnh ong hoc dang vi phan cua phan ng song song tren la:
Thac s Tran Kim Cng
Khoa hoa hoc
- 17 -
dx dx1 dx 2 = + = k 1 ( a x ) + k 2 ( a x ) = ( k 1 + k 2 )( a x ) (II-41). Lay tch phan dt dt dt 1 a (II-42). ay la phng trnh ong hoc phng trnh tren, ta c: k 1 + k 2 = ln t ax dang tch phan cua phan ng song song tren. T phng trnh nay, ta suy ra:
a x = a. e ( k 1 + k 2 ) t (II-43).
T cac phng trnh (II-39,43), ta co: dx1 = k 1 . a. e ( k 1 + k 2 ) . dt (II-44). Lay tch ak 1 1 e ( k 1 + k 2 ) t (II-45). phan phng trnh nay, ta c: x1 = k1 + k 2
Tng t, t cac phng trnh (II-40,43), ta cung tm c:
x2 =
ak 2 1 e ( k 1 + k 2 ) t k1 + k 2
cac phng
(II-46). trnh (II-45,46), ta suy ra: x1: x 2 = k 1: k 2 (II-47)
T va x1, t = =
ak 2 ak 1 (II-48); x 2 ,t = = (II-49). k1 + k 2 k1 + k 2
b. ong hoc cua phan ng song song mot chieu bac 1 dang tong quat:
k1 X1 k2 X 2 kn Xn
t=0
0 0
M
0 t=t a-x x1 x2
M
xn Ta co phng trnh ong hoc dang vi phan cua phan ng tren la: dx dx1 dx 2 dx = + +L+ n = dt dt dt dt 50). Lay tch phan phng trnh nay, ta c: Thac s Tran Kim Cng Khoa hoa hoc d xi
i =1 n
dt
= ( k 1 + k 2 +L+ k n )( a x ) =
k (a x) (IIi i =1

k i .t a 1 i =1 ln k = a x = a . e (II-51) (II-52). i t a x i =1
n
n
- 18 -
Tng t nh muc 2.8.2.a, ta tm c cac bieu thc sau ay (II-53):
k i .t ak 1 ak x1 = n 1 e i =1 , x 2 = n 2 ki ki
n
i =1
i =1
n k i .t k i .t . 1 e i =1 , va x = ak n 1 e i =1 n n ki
i =1
T cac phng trnh tren, ta suy ra: k1: k2: ...: kn=x1:x2:...:xn (II-54). 3. Ghi chu: + T viec khao sat cac loai phan ng song song khac nhau tren, ta thay rang ty le nong o cua cac chat san pham trong cac hng khac nhau cua phan ng song song co gia tr khong oi, khong phu thuoc vao thi gian, mac du hang so toc o phan ng cua chung la khac nhau. + oi vi phan ng song song, phan ng rieng re nao dien ra vi toc o ln nhat, phan ng o se quyet nh tnh chat va toc o cua toan bo phan ng song song.
IX. Phan ng noi tiep:
1. nh ngha va cac v du: a. nh ngha: Phan ng noi tiep la phan ng ma t cac chat tham gia phan ng khong bien oi trc tiep thanh san pham cuoi cung ma hnh thanh lan lt mot hoac nhieu chat trung gian. b. Cac v du: + Phan ng xa phong hoa dietylphtalat bang kiem:
C 6 H 4 ( COOC 2 H 5 ) 2 + NaOH C 6H 4 ( COONa ) COOC 2 H 5 + C 2 H 5OH C 6 H 4 ( COONa )COOC 2 H 5 + NaOH C 6 H 4 ( COONa ) 2 + C 2 H 5OH
+ Phng trnh tong quat cua phan ng noi tiep la:
k1 k2 k3 kn A +L X Y L A / +L
va co the trong giai oan nao o cua phan ng tren la phan ng thuan nghch. 2. ong hoc cua phan ng noi tiep mot chieu bac mot dang n gian nhat:
1 2 B C Xet phan ng: A
t=0 t=t
0 z
a -x y = x - z
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng Ta co:
- 19 -
dC A dx = = k 1 ( a x ) (II-55), dt dt 56)
va
dC B dy d ( x z) = = = k 1 ( a x) k 2 ( x z) (IIdt dt dt
dC C dz = = k 2 ( x z) (II-57). dt dt
Ta can biet rang:
dC A dC B dC C + + =0 dt dt dt dC dC B dC C dx dy dz A = + (II 59)hay = + (II 60) dt dt dt dt dt dt a. Xac nh s phu thuoc cua nong o tng chat A, B va C vao thi gian: C A + C B + C C = a (II 58)
+ Tm CA: T phng trnh (II-55), lay tch phan, ta c: C A = a x = a. e k 1t (II-61). + Tm CC = z: T cac phng trnh (II-57,61),ta suy ra:
dz = k 2 ( x z) = k 2 . a (1 e k 1t ) k 2 z (II-62). dt
Giai phng trnh vi phan tuyen tnh cap mot khong thuan nhat nay, ta c:
k2 k1 C C = z = a 1 e k 1t + e k 2 t (II-63). k 2 k1 k 2 k1
+ Tm CB: T cac phng trnh (II58,61,63),ta suy ra: C B = y = 64). b. o th cua phan ng noi tiep: + Bieu thc tnh tmax va CB max:
k 1a e k 1 t e k 2 t (IIk 2 k1
t max
k1 k2 k 2 k 1 k1 k2 ln k 1 ln k 2 = = (II-65); C B max = a (II-66). k k1 k 2 k1 k 2 2 ln

T
+ Bang bien thien: 0 a
t max
CA
C At max
Thac s Tran Kim Cng
Khoa hoa hoc
- 20 -
CB CC
0 0
C B max
C Ct max
0 a
+ o th cua phan ng noi tiep tren co dang nh H.II.5.
C a
CA M CB
*
CC
t max
H.II.5: o th cua phan ng noi tiep bieu dien s phu thuoc cua CA, CB va CC vao t. c. Chu y: Trong mot day nhng phan ng noi tiep, neu co mot phan ng nao o cham nhat so vi cac phan ng khac th toc o phan ng o se quyet nh toc o cua toan bo phan ng.
Thac s Tran Kim Cng
Khoa hoa hoc
- 21 -
CHNG III. LY THUYET VE CAC QUA TRNH S CAP.

I. Anh hng cua nhiet o en toc o phan ng:
1. Qui tac Vanthoff (Vanhop): Nh chung ta a biet, khi tang nhiet o th toc o phan ng hoa hoc cung tang len; s tang o, noi chung, la rat ln. e bieu th s phu thuoc cua toc o phan ng vao nhiet o, Vanhop a a ra qui tac gan ung la: Khi tang nhiet o them 10o th toc o phan ng tang t 2 en 4 lan, k 0 tc la = T + 10 = 2 4 , trong o la he so nhiet o cua toc o phan ng, kT
k T , k T + 10 0 la hang so toc o T o, T+10 o tng ng.

Qui tac Vanhop ch la qui tac gan ung va cung ch ap dung c trong mot khoang nhiet o nhat nh; con trong khoang nhiet o ln hoac nhiet o cao, qui tac Vanhop khong ap dung c na. 2. Phng trnh Arrhenius (Areniuyt): Bieu thc pho bien va chnh xac hn thng c dung e bieu th anh hng cua nhiet o en toc o phan ng la phng trnh Areniuyt. S thiet lap phng trnh Areniuyt la da vao nhiet ong hoc nh sau:
U ln K C = oi vi qua trnh ang tch, ta co: (III-1). 2 T V RT

oi vi qua trnh ang ap, ta co:
H ln K P (III-2). = T P RT 2
k1 (III-3) (k1 k2 va k2 la hang so toc o cua phan ng thuan va nghch tng ng), H, U la hieu ng nhiet ang ap, hieu ng nhiet ang tch tng ng, R la hang so kh, T la nhiet o tuyet oi.
Trong o K (KP hoac KC) la hang so can bang cua phan ng va K = Neu coi hieu ng nhiet la hieu cua hai mc nang lng E1 va E2 th, t cac phng d ln k 1 d ln k 2 E E = 12 22 (III-4). T phng trnh (III-4), trnh (III-1,2,3), ta co: dT dT RT RT d ln k 2 E d ln k 1 E = 22 + C (III-6). = 12 + C (III-5) va ta suy ra: dT dT RT RT Bang thc nghiem, ngi ta a tm c C trong hai phng trnh tren bang khong d ln k 1 E = 12 (III-7) va va v vay, cac phng trnh o c viet lai nh sau: dT RT
Thac s Tran Kim Cng
Khoa hoa hoc
- 22 -
d ln k 2 E = 22 (III-8). T cac phng trnh nay, ta co the viet thanh mot phng dT RT d ln k E = trnh dang chung la: (III-9). dT RT 2
Phng trnh (III-9) la phng trnh Areniuyt dang th nhat - dang vi phan. No bieu th s phu thuoc cua hang so toc o k cua phan ng vao nhiet o T. E co th nguyen cua nang lng va Areniuyt goi no la nang lng hoat hoa. E1 goi la nang lng hoat hoa cua phan ng thuan va E2 goi la nang lng hoat hoa cua phan ng nghch. Neu lay tch phan phng trnh (III-9), vi s chap nhan E la mot hang so, khong phu thuoc vao nhiet o ( mot khoang nhiet o nhat nh), th ta c: E +B ln k = RT (III-10). Phng trnh (III-10) cung la phng trnh Areniuyt dang th hai - dang tch phan. T phng trnh (III-10), ta thay rang neu ta bieu dien s phu thuoc cua lnk vao 1/T th ng bieu dien la mot ng thang nh tren H.III.1.
lnk
C
O 1/T
H.III.1: S phu thuoc cua lnk vao 1/T. T o th H.III.1, ta suy ra c: B = OC va 11).
E = tg E = R. tg (IIIR
Nh vay, bang thc nghiem, ta co the de dang xac nh c nang lng hoat hoa cua phan ng. T phng trnh (III-10), neu ta at B=lnA th ta co:
E + ln A k = A . e RT (III-12). Phng trnh nay cung la mot dang cua RT phng trnh Areniuyt.
ln k =
T phng trnh (III-12), ta rut ra mot vai nhan xet sau: + Neu T = const th: - Khi E ln th k se be, ngha la toc o phan ng se be. Ngc lai, khi E be th k se ln, ngha la toc o phan ng se ln. ieu o co ngha la nhiet o khong oi, nhng phan ng co nang lng hoat hoa ln se xay ra kho khan va cham; neu nang lng hoat hoa qua ln th thc te phan Thac s Tran Kim Cng Khoa hoa hoc
- 23 -
ng hoa hoc khong xay ra. Ngc lai, nhng phan ng co nang lng hoat hoa be se xay ra de dang va nhanh. - Khi E ln, e phan ng co the xay ra, ngha la e co toc o u ln, th phai thc hien phan ng nhiet o cao. - oi vi nhng phan ng co nang lng hoat hoa bang nhau, phan ng nao c tien hanh nhiet o cao hn se xay ra vi toc o ln hn. + Hang so toc o phan ng va do o, toc o phan ng se thay oi manh theo nhiet o oi vi cac phan ng co nang lng hoat hoa ln. Ngc lai, cac phan ng co nang lng hoat hoa be se co toc o phan ng thay oi rat t theo nhiet o. + ai lng E trong trng hp phan ng n gian, xay ra theo mot giai oan, la nang lng d toi thieu so vi nang lng trung bnh cua cac phan t nhiet o T a cho ma cac phan t phan ng can phai co e tng tac gia chung co the co hieu qua(xem H.III.2).
Nang lng
III
E1
E2
II
Tien trnh phan ng
H.III.2: S o bieu dien hang rao nang lng cua phan ng hoa hoc.
II. Thuyet va cham hoat ong va thuyet phc chat hoat ong:
1. Thuyet va cham hoat ong: + Quan iem cua thuyet va cham: e phan ng hoa hoc xay ra, cac phan t tham gia phan ng, trc het, phai va cham vi nhau. Tuy nhien khong phai va cham nao cung dan en phan ng ma ch nhng va cham gia cac phan t co nang lng ln hn hoac bang nang lng hoat hoa va phai co nh hng thch hp oi vi nhau mi co hieu qua. + Bieu toan hoc cua thuyet va cham: Tren c s quan iem tren va tren c s l thuyet ong hoc phan t, thuyet va cham a thiet lap c cong thc cua mnh nh sau:
k = p.Z o .e E / RT (III-13), trong o p la tha so nh hng khong gian ac trng

cho s nh hng thuan li, p thng co gia tr t 1 en 10-10 va Zo la tha so trc luy tha (bang hang so).
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 2. Thuyet phc chat hoat ong:
- 24 -
+ Quan iem cua thuyet nay la phan ng hoa hoc xay ra la nh s hnh thanh t cac tieu phan tham gia phan ng mot to hp tam thitrang thai chuyen tiep-goi la phc chat hoat ong. V du:
chat au
A +B
K*
phc chat trung gian
(AB)*
kp
san pham phan ng
C +D
Phc chat hoat ong khong phai la mot hp chat hoa hoc ben ma no ch la mot trang thai chuyen tiep cua cac tieu phan trong luc phan ng, co mc nang lng cao; do o, no khong ben, de b phan huy e tao thanh san pham phan ng hoac chat au.
+ Bieu thc toan hoc cua thuyet phc hoat ong: k pu = .
kT S / R E / RT e .e (III-14). h
Thac s Tran Kim Cng
Khoa hoa hoc
- 25 -
CHNG IV. PHAN NG QUANG HOA, PHAN NG DAY CHUYEN
VA KHAI NIEM VE XUC TAC.

I. Phan ng quang hoa:
1. Khai niem:
Phan ng quang hoa la phan ng xay ra di tac dung cua anh sang. Noi chnh xac hn, phan ng quang hoa la phan ng xay ra, trong o nang lng can cho s dien bien cua phan ng hoac can cho s kch thch phan ng c a vao he phan ng di dang nhng dao ong ien t nh anh sang trong thay, tia t ngoai, tia hong ngoai, ... V du: Cac phan ng tong hp nh hidroclorua, phosgen, ... Phan ng phan huy H2O2, AgCl, AgBr, ... Cac phan ng oxi hoa, quang hp, ... Cac hien tng mat mau cua cac chat mau.
2. Mot so nh luat c ban cua phan ng quang hoa: a. nh luat Grothuss - Draper:
Ch nhng bc xa nao c hap thu bi he phan ng mi co the gay nen s bien oi hoa hoc. Tuy vay, cung can hieu rang, mac du phan ng quang hoa ch xay ra khi chat phan ng hap thu cac bc xa nhng khong phai he co s hap thu bc xa la co s bien oi hoa hoc. Trong nhieu trng hp, mot phan hoac toan bo bc xa bien thanh nhiet, ngha la nang lng bc xa ch lam tang chuyen ong nhiet cua cac phan t hap thu bc xa ma thoi. ieu o co ngha la, neu noi nhng bc xa b hap thu eu gay nen phan ng la khong ung. b. nh luat Bunsen - Roscoe: Tac dung hoa hoc cua bc xa ty le thuan vi tch so cua cng o anh sang (I) va thi gian (t) cua no. nh luat Bunsen - Roscoe ch gan ung, v khong phai tat ca nang lng b hap thu eu cung cap cho qua trnh hoa hoc. c. nh luat ng lng quang hoa cua Einstein (Anhstanh): nh luat nay la nh luat tong quat va quan trong nhat oi vi phan ng quang hoa. nh luat nay phat bieu nh sau: e phan ng c trong mot phan ng quang hoa, moi phan t chat phai hap thu mot lng t bc xa a gay nen phan ng. Mot mol chat khi chu s bien oi trong phan ng quang hoa se nhan mot nang . 23 ), h la lng la: = N . h. (jun/mol) (IV-1), trong o: N la so Avogadro ( 6,0210 . 34 jun.giay) va la tan so cua bc xa b hap thu. hang so Planck ( = 6,2210 Ma = c / (XI-2), trong o: c la toc o anh sang ( 310 . 10 cm/giay) va la o dai
Thac s Tran Kim Cng Khoa hoa hoc
- 26 -
cua song anh sang (tnh bang n v cm). Nhng thng ngi ta hay bieu th o dai cua song anh sang bang n v angstron, ngha la 10-8 cm, nen phng trnh (IV-2) c viet la: = 10 8 . c / (IV-3). T cac phng trnh (IV-1,3), ta suy ra:
E=
N. h. c N . h. c 8 .108 (cal/mol) (IV-5). .10 (jun/mol) (IV-4) E = 4,184.
a cac gia tr N, h va c vao phng trnh (IV-5), sau khi bien oi, ta c: 2,6859 5 .10 (kcal/mol) (IV- 6), trong o: tnh bang n v Ao (angstron). E= T phng trnh nay, ta thay rang nang lng do phan t hap thu phu thuoc vao o dai song cua dao ong ien t va ty le nghch vi no. Dao ong ien t co o dai song ngan nhat se co nang lng ln nhat va co hoat ong hoa hoc manh nhat.
3. Hieu suat lng t:
Thc nghiem ch ra rang, trong nhieu trng hp, so phan t a phan ng trong phan ng quang hoa khong bang so lng t b hap thu. V vay, e ac trng cho phan ng quang hoa, ngi ta a ra khai niem hieu suat lng t ( ). Hieu suat lng t la ty so gia so phan t cua chat a phan ng va so lng t anh sang b hap thu, tc la:
so phan t cua chat a phan ng = so ln g t anh sang a b hap thu
Tuy thuoc vao o ln cua hieu suat lng t ma ngi ta chia cac phan ng quang hoa ra thanh 4 loai sau ay: + Cac phan ng trong o =1, v du: s tao thanh bromciclohexan, s phan huy H2S trong dung dch benzen, ... + Cac phan ng trong o <1, v du: s tao thanh hexabrombenzen, s phan huy amoniac, ... + Cac phan ng trong o >1, v du: s tao thanh hidrobrmua, s phan huy nitdioxit, ... + Cac phan ng trong o >>1, v du: phan ng tao thanh hidroclorua t hidro va clo, phan ng clo hoa metan, ... Theo nh luat ng lng quang hoa th hieu suat lng t phai bang 1. Tuy vay, s sai lech cua hieu suat lng t so vi 1 khong co ngha la nh luat ng lng quang hoa khong ung. Qua thc nghiem, ngi ta thay rang phan ng quang hoa c tao thanh t cac phan ng s cap va thng tiep theo la cac phan ng th cap. Nguyen nhan cua s sai lech co the giai thch nh sau:
Thac s Tran Kim Cng
Khoa hoa hoc
- 27 -
Trong phan ng quang hoa s cap, moi phan t b bien oi la do s hap thu trc tiep mot lng t bc xa (v vay, =1). Nhng sau o thng con xay ra phan ng th cap; phan ng nay khong can nhan nang lng bc xa. Cac san pham cua phan ng s cap se tiep tuc phan ng vi cac chat phan ng (v vay, >1). Trong nhng trng hp nhng bc xa do nhng phan t chat phan ng hap thu b tieu dung mot phan vao nhng qua trnh phu nao o (v du: khi va cham, nang lng d cua phan t c truyen sang phan t cua mot chat khac) hoac chung c nhng phan t cua cac chat khac cha trong he hap thu th <1.
Nh vay, cac sai lech eu do nhng qua trnh th cap gay ra; con nhng qua trnh s cap do s hap thu nang lng bc xa gay ra th c mo ta ung bang nh luat ng lng quang hoa.
II. Phan ng day chuyen:
1. Khai niem: a. nh ngha phan ng day chuyen:
Phan ng day chuyen la phan ng ma khi co s hoat ong hoa (kch thch) mot tieu phan nao o trong he phan ng th lam cho khong nhng tieu phan o tham gia vao phan ng ma ca mot loat nhng tieu phan khac cung lan lt tham gia vao phan ng. b. V du ve phan ng day chuyen: Phan ng tong hp hydroclorua t hydro va clo la phan ng day chuyen co c che nh sau:
h Cl 2 2Cl
( sinh mach )
( phat trien mach )
Cl + H 2 HCl + H H + Cl2 HCl + Cl

----------------------------
2Cl Cl 2
( ngat mach )
Theo s o tren, ta co the chia phan ng day chuyen thanh 3 nhom phan ng sau ay: + Phan ng s cap (qua trnh sinh mach) hnh thanh nhng trung tam hoat ong (nguyen t, goc t do, ...). + Phan ng th cap (qua trnh phat trien mach) xay ra gia nhng trung tam hoat ong vi phan t chat tham gia phan ng va hnh thanh nhng trung tam hoat ong mi, lam cho phan ng tien trien t chu k nay sang chu k khac, tao thanh mach phan ng. + Nhom phan ng th ba lam mat cac trung tam hoat ong dan en s cat mach phan ng (qua trnh ngat mach).
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng c. Phan loai phan ng day chuyen:
- 28 -
Ngi ta chia cac phan ng day chuyen thanh 2 loai sau ay: + Phan ng day chuyen khong phan nhanh: la phan ng trong o moi tieu phan hoat ong khi tham gia bien oi sinh ra khong qua mot tieu phan hoat ong mi. Phan ng tong hp hydroclorua t clo va hydro la phan ng day chuyen khong phan nhanh. + Phan ng day chuyen phan nhanh: la phan ng trong o t mot tieu phan hoat ong sinh ra 2, 3, ... tieu phan hoat ong mi. V du ve phan ng day chuyen phan nhanh: phan ng tong hp nc t hidro va oxi xay ra theo c che sau ay:
H 2 2H H + O 2 HO + O HO + H 2 H 2 O + H
O + H 2 HO + H
2H H 2
2. ac iem cua phan ng day chuyen:
So vi cac phan ng hoa hoc thong thng, phan ng day chuyen co nhng ac iem khac biet la: + Mot trong nhng ac iem quan trong nhat cua phan ng day chuyen, co anh hng en toc o phan ng, la o dai mach, ngha la so nhng phan t cua mot chat au a phan ng nh mot tac dung sinh mach. Ve ieu nay, cac phan ng co the khac nhau trong nhng gii han rat rong va o dai mach co the phu thuoc nhieu vao ieu kien dien bien cua phan ng. Co nhng phan ng o dai mach rat be, ch khoang hai hoac ba mat xch; nhng cung co nhng phan ng co o dai mach at ti hang nghn va hn the na mat xch.
o dai mach cua mot phan ng phu thuoc vao quan he gia so tieu phan hoat ong c hnh thanh trong mot n v thi gian va so tieu phan o dung vao viec hnh thanh cac san pham phan ng va cac qua trnh khac; noi cach khac, o dai mach phu thuoc vao quan he gia so mach sinh ra trong mot n v thi gian va so mach mat i trong cung khoang thi gian o.
+ Toc o phan ng day chuyen phu thuoc vao kch thc, hnh dang va chat lieu lam bnh phan ng. Cac tieu phan hoat ong co the b tieu ph vao cac tng tac phu. Trong so cac tng tac nay, s va cham vi thanh bnh hoac vi cac phan t tr trong bnh co mot vai tro ac biet quan trong. V trong cac va cham o, cac phan t hoat ong thng mat nang lng d cua chung va tr thanh cac phan t khong hoat ong va v vay, trong nhng qua trnh o, ngi ta thay co xay ra s ngat mach. S ngat mach o lam
Thac s Tran Kim Cng
Khoa hoa hoc
- 29 -
giam kha nang phat trien xa hn cua phan ng va trong nhng trng hp khong thuan li th ieu o co the lam dng han phan ng lai. + Phan ng day chuyen rat nhay vi s co mat cua chat la. Ch can co dau vet cua chat la la co the lam tang hay giam toc o phan ng. + Vi nhng phan ng no theo c che day chuyen co ton tai mot gii han ap suat va qua trnh no ch xay ra trong vung gii han ap suat o. Neu ap suat cao hn hoac thap hn gii han o th khong xay ra s no.
3. ong hoc cua phan ng day chuyen: a. ong hoc cua phan ng day chuyen khong phan nhanh:
Phan ng day chuyen khong phan nhanh la phan ng phc tap, chat au va san pham phan ng b tieu thu va tao thanh trong cac qua trnh phat trien mach. Do o, toc o phan ng day chuyen tnh theo mot cau t nao o bang toc o cua giai oan phat trien mach, trong o cau t nghien cu b tieu thu hoac c tao thanh. V vay, neu co mot mat xch gom hai phan ng th cap, trong o moi phan ng eu co s tieu thu chat au va tao thanh san pham, ngha la:
k1 k2 R1 + A1 R R1 + B2 , trong o: R1 va R 2 + B1 ; R 2 + A 2 2 la cac dC A1 dC B1 = = k 1 . C R . C A1 (IV-7) va goc t do, th ta co: 1 dt dt dC A 2 dC B2 = = k 2 . C R . C A 2 (IV-8). 2 dt dt
Muon viet phng trnh vi phan cho nong o goc t do, ta phai ke en toc o cua phan ng sinh mach (vsm=vo) va toc o cua phan ng ngat mach ( v ngm = v R ).
i
Bnh thng, phan ng sinh mach se tao ra mot trong cac goc t do nao o e tham gia vao phan ng day chuyen, v du: R1 .
Neu k hieu v R va v R la toc o mat goc t do R 1 va R 2 th ta co:
1 2
dC R
1
dt dC R dt
2
= v o k 1 .C A1 .C R + k 2 .C A 2 .C R v R (IV-9) va
1 2 1
= k 1 . C A1 . C R k 2 . C A 2 . C R v R (IV-10).
1 2 2
V cac goc t do la cac tieu phan trung gian rat hoat ong nen trong toan bo qua trnh phan ng, nong o cua chung c xem nh dng, ngha la: nen v o = v R + v R (IV-11).
1 2
dC R
1
dt
dC R dt
=0
Thac s Tran Kim Cng
Khoa hoa hoc
- 30 -
Nh vay, trong che o dng, toc o ngat mach bang toc o sinh mach; v vay, neu xem ngat mach ch do mat mot trong cac goc t do th phng trnh (IV-11) se la v o = v R (IV-12).
i
k3 Rikh) th ta co: v o = k 3 .C R (IV+ Xet trng hp ngat mach bac 1 (tc la R i

i
v 13) va vp = k i o C A i (IV-14) (theo cac phng trnh (IV-7,8 ,13)). k3

k3 R i 2 ) th ta co: v o = 2k 3 .C 2 + Xet trng hp ngat mach bac 2 (tc la 2 R ( i R
i
IV-15) va vp = k i C Ai
vo (IV-16) (theo cac phng trnh (IV-7,8,15)). 2k 3
+ Neu ta chia toc o cua phan ng day chuyen cho toc o cua phan ng ngat mach hoac sinh mach th ta se thu c o dai mach ( )cua phan ng day chuyen khong phan nhanh la: - Trng hp 1: ngat mach bac 1, ta co: = - Trng hp 2: ngat mach bac 2, ta co: =
ki C A i (IV-17). k3
ki 2k 3 .v o
C A i (IV-18).
+ Sau ay la mot so v du ve viec tnh toc o cua phan ng day chuyen khong phan nhanh: - V du 1: Chng minh rang phan ng: Cl 2 + HCOOH sp , tuan theo phng trnh dC HCOOH = k. C Cl 2 . C HCOOH , biet rang c che cua phan ng nh sau: ong hoc sau: dt
,k 0 Cl 2 h 2 Cl
(sinh mach)
k1 Cl + HCOOH HCl + HOOC k2 HOOC + Cl 2 HCl + CO 2 + Cl
(phat trien mach) (ngat mach)
k3 Cl + thanh bnh Cl hap phu
Giai: V ngat mach bac 1 oi vi Cl nen ki=k1 va C A i = C HCOOH va v v o = k o .C Cl 2 nen ta co:vp = k i

k o .C Cl 2 k .k vo C Ai = k 1 C HCOOH = k. C Cl 2 . C HCOOH , trong o:k = o 1 . k3 k3 k3
- V du 2: Chng minh phng trnh ong hoc cua phan ng clo hoa C2Cl4 trong CCl4 dC C2 Cl4 /2 = k. C 3 la Cl 2 , biet rang c che cua phan ng la: dt
Thac s Tran Kim Cng
Khoa hoa hoc

,k 0 Cl 2 h 2Cl
k1 Cl + C 2 Cl 4 C 2 Cl 5 k2 C 2 Cl 5 + Cl 2 C 2 Cl 6 + Cl k3 2C 2 Cl 5 C 2 Cl 6 + C 2 Cl 4
- 31 -
(sinh mach) (phat trien mach) (ngat mach)
Giai:
V ngat mach bac 2 oi vi C 2 Cl 5 nen ki=k2 va C A i = C Cl 2 va v v o = k o .C Cl 2 nen
vp
k o .C Cl 2 ko vo /2 = k i C Ai = k 2 C Cl 2 = k. C 3 Cl 2 , trong o: k = k 2 2k 3 2k 3 2k 3
b. ong hoc cua phan ng day chuyen phan nhanh:
1/ 2
Phng trnh ong hoc thng dung e mo ta cho phan ng day chuyen phan dn = v o + .n (IV-19), trong o: n la nong o tong cong cua cac goc nhanh la: v = dt t do, vo la toc o sinh mach, .n la hieu gia toc o sinh nhanh va toc o ngat mach. Neu ca hai qua trnh sinh nhanh va ngat mach eu la phan ng bac 1 oi vi nong o goc t do th toc o cua chung co the viet di dang f.n va q.n . Khi o, ta dn = v 0 + ( f q ) n = v 0 ( q f )n (IV-20). co: dt + Neu q > f th he phan ng se co trang thai nong o dng cua goc t do sau mot thi gian nao o, nen ta co: n d =
v0 (IV-21). Ta thay rang neu f = 0 th nd = vo/q (IVqf
22). Neu so sanh 2 phng trnh (IV-21) va (IV-22) th ta se thay rang nong o dng cua phan ng day chuyen khong phan nhanh nho hn nong o dng cua phan ng day chuyen phan nhanh. + Neu q < f th f -q=>0 va lay tch phan phng trnh (IV-19) tren, ta c:
v 0 t e 1 (IV-23). T phng trnh nay, ta thay rang n tang nhanh theo thi gian va se co nguy c dan en s no. n=
+ ac iem ac trng cua phan ng day chuyen phan nhanh la co hai che o dien bien rat khac nhau nh sau: - Neu toc o cua phan ng ngat mach ln hn toc o cua qua trnh sinh nhanh th se co che o dng va trong a so cac trng hp, toc o phan ng nho en mc khong the o c. - Neu toc o cua qua trnh sinh nhanh ln hn toc o cua phan ng ngat mach th toc o phan ng se tang len khong ngng va se ket thuc bang s no. + Ta co the ieu khien chut t mot trong nhng thong so quyet nh en toc o cua phan ng ngat mach va toc o cua qua trnh sinh nhanh nh ap suat, nhiet o, thanh
- 32 -
phan hon hp, kch thc, hnh dang va trang thai bnh phan ng, ... Hien tng thay oi chut t cac thong so co the chuyen t trang thai dng (xay ra cham) sang trang thai no (xay ra nhanh) hoac ngc lai trong ong hoa hoc goi la hien tng ti han hay gii han (xem H.IV.1).
P
gii han no th ba
vung khong nogii
vung no han no th hai gii han no th nhat T
H.IV.1: Gii han no cua phan ng day chuyen phan nhanh.

nh phng trnh ong hoc cua phan ng phc tap:
III. Nguyen ly nong o on nh va viec ap dung nguyen ly nay trong viec xac
1. Noi dung cua nguyen l nong o on nh (hay con goi la nguyen l nong o dng):
Nong o chat trung gian (goc t do, phc chat hoat ong, ...) sau mot thi gian phan ng c on nh, tc la ao ham cua nong o cua no theo thi gian bang khong.
2. Ap dung nguyen l nong o dng trong viec xac nh phng trnh ong hoc cua phan ng phc tap:
V du: cho phan ng tong hp hidrobromua xay ra theo c che sau:

k1 k2 Br2 2 Br , Br + H 2 HBr + H k3 k4 H + Br2 HBr + Br , H + HBr H 2 + Br k5 2 Br Br2
1/ 2 dC HBr k . C H 2 . C Br2 = Hay chng minh: . C dt 1 + k / . HBr C Br2
Giai: + Theo c che phan ng, ta co:
dC HBr = k 2 . C H 2 . C Br + k 3 . C Br2 . C H k 4 . C HBr . C H (a) dt

+ Ap dung nguyen l nong o dng oi vi H va Br , ta co:
Thac s Tran Kim Cng
Khoa hoa hoc
- 33 -
dC H dt
va
= 0 = k 2 . C H 2 . C Br k 3 . C Br2 . C H k 4 . C HBr . C H (b) = 0 = 2 k 1 . C Br2 k 2 . C H 2 . C Br + k 3 . C Br2 . C H + k 4 . C HBr . C H 2 k 5 . C 2 (c) Br
dC Br dt
+ T cac phng trnh ( a, b, c), ta suy ra:
dC HBr dt
k 2k 2 1 k5 = k 1+ 4 k3
/ va k =
1/ 2 /2 . C H 2 . C1 Br2
/2 k. C H 2 . C 1 Br2 = , trong o: / C HBr 1+ k . C Br2
C HBr C Br2
k k = 2k 2 1 k5
1/ 2
k4 (ieu phai chng minh). k3
IV. Khai niem ve xuc tac:
1. nh ngha:
Xuc tac la hien tng thay oi toc o phan ng gay ra do tac dung cua mot so chat goi la chat xuc tac. Chat c goi la chat xuc tac khi chat nay sau khi tham gia vao qua trnh phan ng th cuoi cung khong b thay oi ve lng cung nh ve chat. Chat xuc tac lam tang toc o phan ng goi la chat xuc tac dng va thng goi la chat xuc tac. Chat xuc tac lam giam toc o phan ng goi la chat xuc tac am va thng goi la chat c che. Co mot so chat, du lng rat be, khi co mat trong he phan ng th lam giam hoac mat kha nang hoat ong cua chat xuc tac, goi la chat au oc xuc tac. Ngc lai, co mot so chat, khi co mat trong he th lam tang hoat tnh cua chat xuc tac, goi la chat kch thch hay con goi la chat mang. Ngi ta chia cac phan ng xuc tac thanh phan ng xuc tac ong the va phan ng xuc tac d the. Phan ng xuc tac ong the la phan ng trong o chat xuc tac nam cung pha vi cac chat tham gia phan ng. Chat xuc tac cho loai phan ng nay thng la cac dung dch acid, baz, muoi cua kim loai chuyen tiep. V du: phan ng iod hoa aceton nh xuc tac acid. Phan ng xuc tac d the la phan ng trong o chat xuc tac nam khac pha vi cac chat tham gia phan ng. Chat xuc tac cho loai phan ng nay thng la chat ran (thng la kim loai va oxit kim loai) va phan ng se xay ra tren be mat chat xuc tac.
- 34 -
Ngoai ra, con co loai phan ng xuc tac men, trong o men la chat xuc tac.
2. ac iem cua hien tng xuc tac:
+ Co tnh chon loc cao: moi chat xuc tac thng ch xuc tac cho mot phan ng nhat nh hoac mot loai phan ng nhat nh. + Chat xuc tac lam tang toc o phan ng ch khong lam dch chuyen can bang hoa hoc, tc la chat xuc tac lam tang toc o phan ng thuan bao nhieu lan th cung lam tang toc o phan ng nghch bay nhieu lan. + Chat xuc tac lam tang toc o phan ng cua nhng phan ng von d co kha nang xay ra mac du het sc cham ch khong gay nen phan ng, tc la chat xuc tac lam giam nang lng hoat hoa cua phan ng ch khong lam thay oi trang thai au va trang thai cuoi ( G khong oi).
Thac s Tran Kim Cng
Khoa hoa hoc
- 35 -
* BAI TAP ONG HOA HOC *

BAI 1: Hang so can bang cua phan ng thuan nghch sau ay:
A k1 k2 B
la 10, con hang so toc o cua phan ng thuan k1 = 0,2 sec-1.

Hay xac nh thi gian e CA = CB, biet rang ban au ch co A. GIAI:
Ta co: k 1 + k 2 = ln
1 t
; K = k1/k2 =10 va k1 = 0,2 sec-1 k2 = 0,02 sec-1 . x
K. a b 10a 0 = 10a / 11 . V CA = CB nen ta suy ra: a - x = x a - x = = K +1 10 + 1 1 10a / 11 ln 3,63 (sec). x =a/2. Ta suy ra: t = 0,2 + 0,02 10a / 11 a / 2 =
-------------------------------------------k k B C , co cac thong so ac trng sau BAI 2: Cho phan ng noi tiep: A
1 2
ay:
Khi nong o chat B at cc ai th chat A la 25% la 85 sec.

Hay tnh k1 va k2. GIAI:
CA = 4,5 ; con thi gian e o bien oi CB
+ Nh chung ta a biet, C At max
k k 2 k1 k k 2 k1 = a. 1 (a), C B max = a. 1 (b) va k2 k2
k1
k2
a 1 k 1 = ln (c). t ax
+ T cac phng trnh (a, b) va bai ra, ta co:
C At max C B max
k2 = 4,5 (d). k1
+ Theo bai ra, khi t= 85 sec th x = 25%.a nen t phng trnh (c), ta co:
k1 =
1 a 3,3810 ln . 3 (sec-1) (e). 85 a 0,25. a

------------------------------------------------
+ T cac phng trnh (d, e), ta suy ra: k2 = 15,21.10-3 sec-1.
Thac s Tran Kim Cng
Khoa hoa hoc
- 36 -
BAI 3: Cho hang so toc o cua phan ng xa phong hoa etylacetat bang xut nhiet
o lam th nghiem la 3 l/mol.phut.
Tnh thi gian e xa phong hoa c 50% etylacetat nhiet o o, neu tron 1 1 M vi ... lt dung dch CH3COOC2H5 20
1. 1 lt dung dch NaOH 3. 1 lt dung dch NaOH
1 1 M. 2.1 lt dung dch NaOH M. 10 20
1 1 M. 4. 4 lt dung dch NaOH M. 25 20

1 1 M. 6. 2 lt dung dch NaOH M. 40 15
GIAI:
5. 0,5 lt dung dch NaOH
+ Cong thc tnh:
1 1 1 (a) (khi nong o ban au cua cac chat giong nhau); k a x a 1 b( a x) ln t= (b)(khi nong o ban au cua cac chat khac nhau). k ( a b) a ( b x) t=
+ Tnh toan: Goi a va b la nong o ban au cua xut va etylacetat; theo bai ra, ta co: x = 50%.b. 1. Ap dung cong thc (a), ta tnh c: t 13,33 phut (=13 phut 20 giay). 2. Ap dung cong thc (b), ta tnh c: t5,41 phut. 3. Ap dung cong thc (b), ta tnh c: t19,18 phut. 4. Ap dung cong thc (b), ta tnh c: t6,22 phut. 5. Ap dung cong thc (b), ta tnh c: t20,8 phut. 6. Ap dung cong thc (a), ta tnh c: t=20 phut. ----------------------------------
BAI 4: Cho phan ng song song sau:

k1 k2 A k3 k4 B C D E
Thac s Tran Kim Cng
Khoa hoa hoc
- 37 -
thi iem t bang 10 giay, C A , C B , C C , C D , C E tng ng la 0,5 mol/l, 0,03 mol/l, 0,02 mol/l, 0,3 mol/l, 0,15 mol/l. Biet ban au, nong o cac chat B, C, D, E eu bang khong.
Hay tnh k 1 , k 2 , k 3 va k 4 theo n v phut-1. GIAI:
+ Cong thc:
1 C k1 + k 2 + k 3 + k 4 = ln oA t CA C oA = C A + C B + C C + C D + C E k1 : k 2 : k 3 : k 4 = C B : C C : C D : C E
+ Tnh toan: thay cac d kien bai ra vao cac cong thc tren; sau o, giai he cac phng trnh, ta tnh c k 1 , k 2 , k 3 va k 4 tng ng la 0,2496 phut-1, 0,1664 phut-1, 2,496 phut-1 va 1,248 phut-1. ---------------------------------------------
BAI 5: Nong o cac chat A, B va C trong dung dch X eu la a mol/l. Sau 1000
giay, mot na lng chat A a phan ng.
Neu phan ng xay ra trong dung dch X la phan ng bac mot, bac hai, bac ba va bac khong th sau 2000 giay se con lai bao nhieu % chat A so vi ban au? GIAI:
Ta xet cac loai phan ng bac 1, 2, 3 va 0 (s dung phng trnh ong hoc dang tch phan khi nong o ban au cua cac chat giong nhau) th ta se thu c ap so tng ng vi phan ng bac1, 2, 3 va 0 la 25%, 33,33%, 37,8% va 0%. -----------------------------------------------
BAI 6: Cho phan ng nhiet phan kh N2O5 xay ra theo c che sau:
N2O 5 k1 NO 2 + NO 3 k2
k3 NO 2 + NO + O 2 NO 2 + NO 3 k4 3NO 2 NO + N 2 O 5
Hay ap dung nguyen l nong o dng oi vi NO3 va NO e tm phng trnh tnh toc o cua phan ng co c che tren. AP SO:
dC N 2 O5 dt
2k 1 . k 3 C N 2 O5 . k2 + k3
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng Phan II. IEN HOA HOC. CHNG V. DUNG DCH CAC CHAT IEN GIAI.
I. Tnh chat chung cua dung dch:
- 38 -
1. o giam ap suat tng oi cua dung moi tren dung dch so vi dung moi nguyen chat la:
P1o P1 o = N 2 (V-1), trong o P1 va P1 la ap suat hi bao hoa cua dung moi tinh o P1
khiet va cua dung moi tren dung dch tng ng, N2 la nong o phan mol cua chat tan trong dung dch.
2. o tang nhiet o soi va o ha nhiet o ong ac cua dung dch so vi dung moi nguyen chat la: TS =TS -TSo =ES .m2 (V-2), T=To -T =E.m2 (V-3), trong o TS () la o tang nhiet o soi (o ha nhiet o ong ac), TS va TSo la nhiet o soi cua dung dch va dung moi tng ng, T va To la nhiet o ong ac cua dung dch va dung moi tng ng, ES va E la hang so nghiem soi va nghiem lanh tng ng, m2 la nong o molan cua chat tan trong dung dch. 3. Ap suat tham thau cua dung dch la: =C2.RT (V-4), C2= n2 /V, trong o la ap suat tham thau, n2 la so mol chat tan, V la the tch dung dch, C2 la nong o mol cua chat tan, R la hang so kh va T la nhiet o tuyet oi.
II. Dung dch cac chat ien giai:
1. Tnh chat cua dung dch cac chat ien giai:
+ o dan ien kha cao do trong dung dch co cac ion t do. + oi vi dung dch cac chat ien giai, ta co cac he thc sau:
P= P1o P1 =i.P1o.N2 (V-5); TS ()=i.ES ().m2 (V-6); =i.C2.RT (V-7), trong o: i 1 va khi dung dch vo cung loang th i la 1 so nguyen n gian 2, 3, 4, con bnh thng i la so thap phan. 2. Thuyet Areniuyt ve s ien li: + Cac phan t chat tan trong cac dung dch chat ien giai chu s phan li thanh nhng ion dng (cation) va ion am (anion). Cac ion nay se tham gia vao s dan ien.
+ S phan li c coi nh la 1 phan ng hoa hoc, tuan theo nh luat tac dung khoi lng nh nhng phan ng hoa hoc khac.
Thac s Tran Kim Cng
Khoa hoa hoc

[ H+ ] [ A- ] [ HA ]
- 39 -
V du: HA
H+ +
A ,K=
, K la hang so phan li
+ Cac chat ien giai trong dung dch co o phan li nhat nh tuy thuoc vao tnh chat cua chung. o phan li c nh ngha la t so gia so phan t a phan li n' va tong so phan t luc au n, tc la = n'/n (01). Thuyet Areniuyt giai thch c s sai lech gia dung dch noi chung va dung dch cac chat ien giai la: do s phan li cua cac phan t chat tan ma lam cho so tieu phan thc te trong dung dch chat ien giai tang len so vi khi khong co s phan li va v vay, o giam ap suat hi tng oi cua dung moi tren dung dch tang len, o ha nhiet o ong ac, o tang nhiet o soi va ap suat tham thau tang len. Moi lien he gia he so ang trng i va o phan li nh sau: i=1+ ( -1) (V8), trong o la so ion do 1 phan t phan li ra.
V du:* Dung dch NaCl loang co i=1+1(2-1)= 2.
* Dung dch K3PO4 loang co i=1+1(4-1)= 4.

III. o dan ien cua dung dch chat ien giai:
+ Khi co dong ien 1 chieu i qua chat dan ien loai 2, lng ien c chuyen ve cac ien cc la nh cac ion t do. Nhng ion dng (cation) chuyen ve ien cc am (catod), con nhng ion tch ien am (anion) chuyen ve ien cc dng (anod). + ien tr trong dung dch chat ien giai (R) cung giong nh trong bat k chat dan ien nao phu thuoc vao ban chat cua chat dan ien, tiet dien ngang va chieu dai cua no, tc la R=.l/s, trong o la ien tr rieng cua chat dan ien phu thuoc vao ban chat cua no, l la chieu dai va s la tiet dien ngang (xem H.V.1).
l S
dung dch chat ien giai
H.V.1: S o ien tr cua dung dch chat ien giai. Khi l=1cm va s=1cm2 th R=. Nh vay, ien tr rieng la ien tr cua 1 chat dan ien co chieu dai 1cm va co tiet dien ngang la 1 cm 2. + Trong ien hoa, ngi ta thng anh gia tnh chat dan ien cua chat dan ien bang ai lng nghch ao cua ien tr rieng va c goi la o dan ien rieng ().
Thac s Tran Kim Cng
Khoa hoa hoc

1 (V-9), o dan ien rieng co th nguyen la -1.cm-1.
- 40 -
+ S phu thuoc cua o dan ien rieng vao nong o dung dch nh sau: = const..C (V-10) va o th -C se la mot ng cong co cc ai co dang nh tren H.V.2.
H.V.2: o th -C
H.V.3: o th -C
H.V.4: o th -C1/2.
+ e tien li hn trong viec nghien cu, ngi ta thng s dung cai goi la o dan ien ng lng. o dan ien ng lng lien he vi o dan ien rieng theo he thc:
=1000 /C (V-11), trong o C la nong o ng lng. Th nguyen cua o dan ien ng lng la -1.cm2.lg-1.
o dan ien ng lng phu thuoc vao nong o dung dch (xem H.V.3). Khi nong o dung dch giam th o dan o dan ien ng lng tang. Vi s pha loang dung dch, o dan ien se tang len en 1 gia tr gii han nao o. Gia tr gii han cua o dan ien ng lng goi la o dan ien khi pha loang vo cung va c k hieu la hay o. Khi C0 th 1, ngha la chat ien giai phan li hoan toan, luc o ta co o. Ngc lai, khi C tang th giam, do o giam. S phu thuoc cua o dan ien ng lng cua chat ien giai manh vao nong o co dang nh tren H.V.4 va a c Conraus a ra cong thc thc nghiem sau ay:
=o-A.C1/2=o-A1.C1/2-A2.C1/2 (V-12), trong o A, A1 va A2 la cac hang so kinh nghiem.
+ o dan ien khong nhng phu thuoc vao tong so ion co mat trong dung dch ma con phu thuoc vao o nht cua dung dch va nhiet o. - Khi tang nong o th o nht cua dung dch tang; do o, lam giam toc o chuyen ong cua cac ion va v vay, o dan ien giam. - Khi tang nhiet o th o nht cua dung dch giam, do o o dan ien tang (khac vi chat dan ien loai1). + o dan ien khi pha loang vo cung cua chat ien giai bang tong o dan ien khi pha loang vo cung cua cac ion tao nen chat ien giai o, tc la: o=o++o-(V-13).
Thac s Tran Kim Cng
Khoa hoa hoc

IV. Phng phap o o dan ien va ng dung cua no:
- 41 -
1. Phng phap o: a. ieu kien:
e o o dan ien cua dung dch chat ien giai can phai:
+ o c nhiet o chnh xac va gi c nhiet o khong oi trong suot qua trnh o.
+ Loai tr c s phan cc ien cc. + o chnh xac cac ai lng ien. b. Nguyen tac: Dung cau Vettn e o ien tr cua dung dch, t o suy ra o dan ien. c. Cau tao cua cau Vettn: c neu ra tren H.V.5.
E ~ R2 R1
G R3 Rx
H.V.5: S o cau tao cua cau Vettn gom: E la nguon ien xoay chieu, R 1va R2 la cac bien tr, R3 la ien tr so sanh a biet, Rx la ien tr cua dung dch can o, G la dung cu o iem khongcua dong ien (ong nghe, galvanomet, ). d. Cach o: ieu chnh R1 va R2 sao cho dong ien i qua G=0, luc o ong nghe khong keu hay keu nho nhat, ta at c can bang cau. Theo nh luat Kiecsop (Kirchhoff), ta co: Rx/R3=R1 /R2 Rx=R1.R3/R2. Ma Rx = l / S. nen suy ra: =l/S.Rx. Viec xac nh l/S trong thc te la rat kho chnh xac nen ngi ta thng co nh l/S=k goi la hang so bnh va xac nh no nh vao viec o ien tr cua 1 dung dch mau a biet chnh xac o dan ien m. Ta co: Rm=l/S.m=k/m k=Rm.m=Rm.m /Rx (V-14). T gia tr cua , ta co the suy ra .
2. ng dung cua viec o o dan ien: a. Xac nh o phan li cua chat ien giai yeu:=C/0=C/(0++0-).
Nh vao viec o o dan ien, ta xac nh c C, con 0+va 0- co san trong cac bang tra cu cua so tay hoa hoc, ta de dang xac nh c .
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng b. Xac nh o tan cua chat t tan:
- 42 -
Neu goi S la o tan cua chat t tan (ng lng gam/lit) th ta co:
=.1000/C=.1000/S. V chat t tan nen dung dch bao hoa cua no la dung dch rat loang va v vay, o va do o, S=.1000/ o=.1000/(0++0-). c. Chuan o dan ien ke:
+ Nguyen tac cua phng phap chuan o nay la da vao s khac nhau ve o dan ien cua cac ion. Trong qua trnh chuan o, tai iem tng ng, o dan ien se co s thay oi ot ngot. + V du: Khi chuan o dung dch HCl bang dung dch NaOH, dung dch CH3COOH bang dung dch NaOH th o th bieu dien s phu thuoc cua o dan ien () vao the tch dung dch NaOH cho vao nh tren H.V.6, H.V.7 tng ng.
Vt H.V.6
VddNaOH
Vt H.V.7
V ddNaOH
Thac s Tran Kim Cng
Khoa hoa hoc
- 43 -
CHNG VI. NGUYEN TO GANVANIC.

I. Cac khai niem m au:
+ ien cc: la kim loai nam tiep xuc vi dung dch chat ien phan. V du: Zn / Zn2+, Cu / Cu2+, + Nguyen to ganvanic: la he cac ien cc khac nhau b ngan cach bi 1 lp dung dch chat ien phan, co kha nang sinh cong ien, c dung lam nguon ien. V du: nguyen to anien-Jacobi la nguyen to ganvanic c tao thanh t 2 kim loai Zn va Cu nhung trong 2 dung dch muoi cua chung (Cu/Cu2+va Zn/Zn2+) va cac dung dch tiep xuc vi nhau qua mang ngan xop. + Cach viet cau tao cua nguyen to ganvanic: - Ranh gii kim loai-dung dch c k hieu bang 1 net ng, ranh gii dung dchdung dch c k hieu bang 2 net ng. -T trai sang phai lan lt ngi ta at ien cc am, dung dch cua ien cc am, cau noi, dung dch cua ien cc dng va cuoi cung la ien cc dng. V du: nguyen to anien-Jacobi c viet la: (-) Zn/Zn2+//Cu2+/Cu (+). + The ien cc: la the xuat hien tren ranh gii kim loai-dung dch cua ien cc. The ien cc co the xac nh c bang cach o sc ien ong cua nguyen to ganvanic c cau tao gom ien cc o va ien cc so sanh co the a biet (ien cc hydro tieu chuan co the bang khong, ien cc calomen co the bang 0,2412von, ). + Sc ien ong cua nguyen to ganvanic: la hieu cua 2 the ien cc. V du: nguyen to anien-Jacobi co sc ien ong: E= + = Cu 2 + / Cu Zn +2 / Zn .
II. The cua tng ien cc:
The cua tng ien cc rieng biet c o bang cach so sanh no vi 1 ien cc khac tao thanh nguyen to ganvanic. ien cc so sanh la ien cc co the a biet va tng oi on nh (thng la ien cc hydro hoac ien cc calomen). Neu ien cc so sanh la ien cc hydro tieu chuan th dau cua the ien cc la dau dng neu trong nguyen to nay ien cc nghien cu la ien cc dng va ngc lai, la am neu ien cc nghien cu la ien cc am. V sc ien ong luon luon dng (G=-nFE<0, qua trnh t dien bien) nen e tnh sc ien ong cua nguyen to ganvanic da vao the ien cc, ta can phai lay the cua ien cc dng (co the dng hn hoac t am hn) tr i the cua ien cc am (co the t dng hn hoac am hn).
Thac s Tran Kim Cng
Khoa hoa hoc

III. Phng phap o sc ien ong:
- 44 -
1. Nguyen tac:
Cac nguyen tac thng dung e o sc ien ong cua nguyen to ganvanic (E) eu da tren phng phap bo chnh Pogenooc. u iem cua phng phap nay la cho nh phng phap bo chnh Pogenooc, ta co the xac nh c E khi mach h, noi khac i khi dong ien khong chay qua nguyen to ganvanic. Nguyen to ganvanic ch co the coi la thuan nghch khi co 1 dong ien vo cung nho chay qua nguyen to. Do o, nguyen to ganvanic trang thai mach h la ieu kien l tng e o E cua no lam viec thuan nghch.
2. Bnh o E:
H.VI.1 hoac H.VI.2.

E
ddKCl bh
ddMIn+ MI dd KCl bh
ddMIIn+ MII
MI dd MIn+
MII dd MIIn+
H.VI.1
H.VI.2
3. Dung cu dung e o E (ien the ke) va cach o E:
Dung cu dung e o E c ve tren H.VI.3 gom 1 nguon ien C noi xuong cac au cua mot day dan ong nhat AB co ien tr cao. Nguon ien C la accu co sc ien ong on nh va ln hn sc ien ong can o. Nguyen to Ex noi au am vi iem A la iem noi vi au am cua accu. ien cc th 2 (ien cc dng) cua nguyen to ganvanic c noi qua ien ke G ti con chay D. Con chay D se dch chuyen tren day AB en khi dong ien qua G bang khong (kim ien ke G ch so khong). S sut the tren oan AD trong mach accu C se bo chnh mot cach chnh xac sc ien ong cua nguyen to Ex. Ta bat cong tac k1 sang pha nguyen to chuan Et/c co sc ien ong a biet chnh xac. e kim ien ke G ch so khong phai dch chuyen con chay D sang v tr mi tren oan AB la D. S sut the tren oan ADse bo chnh 1 cach chnh xac sc ien ong cua nguyen to Et/c. V day dan AB ong nhat nen ta co: Ex/Eaccu=AD/AB va Et/c/Eaccu =AD/ AB; suy ra: Ex=Et/c.AD/AD.
Thac s Tran Kim Cng
Khoa hoa hoc

C
- 45 -
+
k
A k1
D D'
- Ex+
G
- +
Et/c
H.VI.3
IV. Cac qua trnh xay ra trong nguyen to ganvanic:
1. Cac phan ng ien cc va phan ng chung:
Trong nguyen to ganvanic, ien cc nao co the am hn hoac t dng hn se la ien cc am; ien cc o, se co s chuyen ion kim loai vao dung dch, tc la kim loai b hoa tan hay con goi la b oxihoa; con ien cc co the dng hn hoac t am hn se la ien cc dng va se b kh (tao ra tren ien cc kim loai hoac kh ,). Ket qua cua 2 phan ng ien cc la cho ta 1 dong ien chay qua day dan kim loai. Nh vay, ien cc am, xay ra qua trnh oxihoa va ien cc dng, xay ra qua trnh kh; do vay, phan ng chung trong nguyen to ganvanic la phan ng oxihoa-kh. V du: nguyen to anien-Jacobi ( - Zn/Zn2+//Cu2+/Cu +): (-)Zn=Zn2++2e, qua trnh oxihoa (Zn b tan ra); (+) Cu2++2e=Cu, qua trnh kh (Cu ket tua tren ien cc Cu); va phan ng chung: Zn+Cu2+=Zn2++Cu.
2. Chieu dong ien:
Trong nguyen to ganvanic, do cac phan ng ien cc ma lam cho cac e chuyen qua day dan kim loai t ien cc co the am hn hoac t dng hn (ien cc am) sang ien cc co the t am hn hoac dng hn (ien cc dng); do o, dong dien trong day dan se i t ien cc dng sang ien cc am. V du: nguyen to -Zn /Zn2+/Cu2+/Cu+, co chieu dong ien c ch ra tren H.VI.4.
e I
anod (- ) Zn SO422+ Zn
catod (+) SO42Cu2+ Cu
Thac s Tran Kim Cng
Khoa hoa hoc
- 46 -
H.VI.4: S o ve chieu chuyen ong cua cac cation, anion, ien t va chieu dong ien trong nguyen to anien-Jacobi.
Thac s Tran Kim Cng
Khoa hoa hoc
- 47 -
CHNG VII. NHIET ONG HOC CUA CAC MACH IEN HOA VA
THE IEN CC.

I. Moi lien he gia the ang nhiet ang ap G va sc ien ong cua nguyen to
ganvanic E va phng trnh the ien cc:
+ Nh chung ta a biet trong nhiet ong hoc th Amax = -G=nFE (VII-1). + Xet nguyen to ganvanic: (-)MI /MIn+//MIIn+/MII (+). - anod (-), xay ra qua trnh oxihoa sau: MI = MIn+ +ne. - catod (+), xay ra qua trnh kh sau: MIIn+ +ne = MII. - Phan ng chung: MI+MIIn+=MIn++MII . - Khi phan ng at en trang thai can bang th theo nh luat tac dung khoi lng, aM + n a M + n . a M II I I (VII-3) K = (VII-2) ta co: K = a +n n .a M M II cb aM+ I II cb Theo nhiet ong hoc, ta co: G = RTln (VII-4) E=-G/nF=
o trong o: E =
+n I +n II
a M+ n
I
a M+ n
II
- RTln(
a M+ n
I
a M+ n
II
)cb =-RT(lnK-ln
a M+n
I
a M+n
II
n RT RT a M RT a M + lnKln =Eo ln I (VII-5), nF nF a M nF a M + n II
RT ln K (VII-6). nF
RT a Ox ln (VII-7). nF a Kh
+ Phng trnh the ien cc tong quat (phng trnh Nec) nh sau:
Ox / Kh = o Ox / Kh +
25oC, phng trnh Nec nh sau:

o Ox / Kh = Ox / Kh +
1,987.298,15.2,303 a Ox 0,059 a Ox o lg = Ox lg / Kh + 23062.n a Kh n a Kh
(VII-8).
II. The ien cc:
1. Phan loai ien cc: a. ien cc loai 1: + Cau tao: la he gom kim loai hoac a kim c nhung trong dung dch cha ion kim loai hoac a kim o. + S o ien cc : M/ Mn+ , A/ An-. + The ien cc:
Thac s Tran Kim Cng
Khoa hoa hoc
- 48 -
- oi vi ien cc kim loai: Phng trnh phan ng ien cc: Mn++ne=M.
+ Phng trnh the ien cc: M n + / M = o Mn+ / M

- oi vi ien cc a kim:
RT ln a M n + (VII-9). nF
Phng trnh phan ng ien cc: A + ne = An-.

o Phng trnh the ien cc: A / A n = A / A n +
a RT ln A (VII-10). nF a A n
+ Cac v du: - V du 1: ien cc niken (Ni/Ni2+). Phng trnh phan ng ien cc: Ni2++2e=Ni.
+ Phng trnh the ien cc: Ni 2 + / Ni = o Ni 2 + / Ni

-V du 2: ien cc clo ((Pt)Cl2/Cl-). Phng trnh phan ng ien cc:Cl2+2e=2Cl- . Phng trnh the ien cc: Cl
b. ien cc loai 2:
2
RT ln a Ni 2 + . nF
/ Cl
o = Cl
/ Cl
RT PCl 2 ln 2 . 2F a Cl
+ Cau tao: la he gom 1 kim loai c phu1 hp chat kho tan cua kim loai o (muoi hoac oxit) va c nhung vao dung dch cha anion cua hp chat kho tan o. + S o ien cc : M,MA/An- .
+ The ien cc:
- Phng trnh phan ng ien cc: MA+ne=M+An-.

o - Phng trnh the ien cc: A n / MA ,M = A n / MA ,M +
a MA RT ln . nF a M .a A n
= o A n / MA , M
RT ln a A n (VII-11). nF
ien cc loai 2 co the ien cc rat on nh, de lap lai; do o, chung thng c dung lam ien cc so sanh.
+ Cac ien cc loai 2 ien hnh (quan trong trong thc te): - ien cc calomen: (Pt)Hg, Hg2Cl2/Cl-. Phng trnh phan ng ien cc: Hg2Cl2 + 2e = 2Hg + 2Cl-.
Thac s Tran Kim Cng
Khoa hoa hoc
- 49 -
Phng trnh the ien cc: cal. =ocal. -
RT RT 2 o ln a Cl ln a Cl . = cal. 2F F
oi vi ien cc calomen, vi dung dch KCl bao hoa va nhiet o 250c, the ien cc la 0,2412 von .
- ien cc bac-bacclorua: Ag, AgCl / Cl- . Phng trnh phan ng ien cc: AgCl + 1e = Ag + Cl-.
o Phng trnh the ien cc: Cl / AgCl,Ag = Cl / AgCl , Ag
RT ln a Cl F
o o + Chu y: A n / MA,M = M + n / M +
RT ln TMA (VII-12). nF
c. ien cc loai 3: + Cau tao: la he gom kim loai tiep xuc vi 2 muoi kho tan co chung anion c nhung vao dung dch cha cation cua muoi kho tan th 2.
+ S o ien cc: M,MA,MA/Mn+ (TMA<<TMA). + V du: Pb, PbC2O4, CaC2O4/Ca+2. Pb+CaC2O4=PbC2O4+Ca2++2e.

( Pb
-2 +2 +2 Pb + 2e , Pb + C2O4
PbC2O4,
)
CaC2O4
Ca
+2
+ C 2O4
-2
(VII-13)
T cac phng trnh phan ng ien cc a c mo ta (VII-13), ta suy ra phng trnh the ien cc cua ien cc v du tren nh sau:
Pb + 2 / Pb = o + Pb + 2 / Pb
RT TPbC2O4 RT o ln ln a Pb + 2 = Pb+ 2 / Pb + 2F a C O 2 2F
2 4
= o + Pb + 2 / Pb
o = 1 +
RT TPbC2 O 4 RT RT TCaC2O4 RT ln = o + + ln a Ca + 2 ln ln TPbC2O 4 Pb + 2 / Pb 2F TCaC2 O 4 2F 2F a Ca + 2 2F
RT TPbC 2O 4 RT o o ln ln a Ca + 2 (VII-14), trong o: 1 = Pb + 2 / Pb + (VII-15). 2F TCaC2O 4 2F
d. ien cc oxihoa-kh: + Cau tao: la he gom 1 kim loai tr nhung trong dung dch cha ca dang oxihoa va dang kh.
+ S o ien cc: Pt (Au, )/Ox, Kh. + Phng trnh the ien cc: - Phng trnh phan ng ien cc: Ox+ne=Kh.
Thac s Tran Kim Cng
Khoa hoa hoc
- 50 -
o - Phng trnh the ien cc: Ox / Kh = Ox / Kh +
RT a Ox ln (VII-16). nF a Kh
+ V du:
o - Pt/Fe3+,Fe2+: Fe3++1e=Fe2+, Fe+ 3 / Fe+ 2 = Fe+ 3 / Fe+ 2 +
RT a Fe+3 ln . F a Fe+ 2
- Pt/H+,MnO4-, Mn2+:MnO4-+8H++5e=Mn2++4H2O
MnO ,H + / Mn + 2 =
4
o MnO 4 , H + / Mn + 2
.a 8 RT a MnO H+ 4 + ln . a Mn + 2 5F
e. ien cc hon hong: + Cau tao: la he gom hon hong cua 1 kim loai tiep xuc vi dung dch cha ion kim loai o.
+ S o ien cc: (Hg)M/Mn+ .

+ Phng trnh the ien cc:
- Phng trnh phan ng ien cc:Mn++ne=M(Hg).

o - Phng trnh the ien cc: M + n / M,Hg = M + n / M,Hg +
RT a M + n ln (VII-17). nF a M ( Hg)
+ V du:(Hg)Cd/Cd2+.
o Cd2++2e=Cd (Hg), Cd + 2 / Cd ,Hg = Cd + 2 / Cd ,Hg +
a +2 RT ln Cd 2F a Cd ( Hg )
f. ien cc kh:
+ Cau tao: la he gom 1 kim loai tr (Pt, Au, ) tiep xuc vi kh va dung dch cha ion cua kh o. + V du: ien cc hidro, ien cc clo,
+ Phng trnh the ien cc:
Xet ien cc hidro: Pt, H2/H+. - Phng trnh phan ng ien cc: 2H++2e=H2.
o - Phng trnh the ien cc: H + / H = H + / H + 2 2 2 RT a H + ln (VII-18). 2F PH 2
o 25oc va PH 2 =1 atm, H + / H = H + / H + 0,059 lg a H + = 0,059.pH

2 2
(VII-19), v o H
/ H2
= 0 va pH = lg a H + .
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 2. Mot so ng dung cua viec o sc ien ong: a. o o pH cua dung dch:
- 51 -
+ Nguyen tac cua phep o la lap 1 nguyen to ganvanic gom 1 ien cc so sanh (thng la ien cc calomen) va 1 ien cc co the phu thuoc vao pH cua dung dch c goi la ien cc ch th (thng la ien cc hydro, ien cc thuy tinh, ). + ien cc ch th la ien cc hydro: Cau tao cua nguyen to ganvanic trong trng hp nay nh sau: (-)(Pt), H2 (P=1atm)/H+//KCl/Hg2Cl2,Hg (Pt) (+). E = cal. + 0,059.pH pH =
E cal. (VII-20). 0,059
+ ien cc ch th la ien cc thuy tinh: Cau tao cua nguyen to ganvanic trong trng hp nay la: (-)(Pt)Hg, Hg2Cl2/KCl//H+/ien cc thuy tinh (+).
E = tt cal.
o cal. E = 0,059.pH cal. pH = tt (VII-21). 0,059

o tt
b. Chuan o ien the ke (chuan o o the):
+ Nguyen tac: tai iem tng ng cua cac phan ng khac nhau (trung hoa, tao phc, ket tua, oxihoa-kh,) c xac nh bang bc nhay the ac trng . + V du: chuan o dung dch NaCl bang dung dch AgNO3; muon vay, ta phai lap nguyen to ganvanic sau ay: (-) (Pt) Hg, Hg2Cl2/KCl//NaCl/AgCl,Ag (+). Trong qua trnh chuan o, ta o the cua na nguyen to ben phai hoac o E cua nguyen to tren, roi xay dng o th bieu dien s phu thuoc cua hoac E vao lng dung dch AgNO3 them vao, o th o co dang nh tren H.VII.1.
E()
Vt
VddAgNO3
H.VII.1: ng cong chuan o o the dung dch NaCl bang dung dch AgNO3.
o o E = Cl / AgCl,Ag cal. = Cl 0,059 lg a Cl cal. = E 1 0,059 lg a Cl (VII-22). / AgCl, Ag
Ta co:
Thac s Tran Kim Cng
Khoa hoa hoc
- 52 -
Khi cho dung dch AgNO3 cho vao cang nhieu th nong o Cl cang be; do o, E cua nguyen to ganvanic tren (hoac cua ien cc bac-bac clorua) cang ln.
c. Xac nh tch so tan cua muoi kho tan:
Gia s ta xac nh tch so tan cua AgCl; muon vay, ta lap nguyen ro sau: (-)Ag, AgCl/HCl/Cl2 (P=1atm)(Pt)(+) Phng trnh phan ng chung: 2Ag+Cl2=2AgCl. V AgCl nam can bang vi cac ion Ag+ va Cl- trong dung dch bao hoa nen phan ng tren co the viet di dang:
Ag + 1 Cl2 = AgCl 2 Ag + Cl+
Ta co: E = Cl
2 / Cl
Cl / AgCl ,Ag
= o Cl
/ Cl
0,059 lg a Cl o 0,059 lg TAgCl + 0,059 lg a Cl Ag + / Ag o 0,059 lg TAgCl Ag + / Ag

= k TAgCl = 10 k (VII-23).
= o Cl
lg TAgCl = o Cl
2
/ Cl
/ Cl
o E Ag + / Ag 0,059
d. Xac nh hang so khong ben cua phc:

Gia s ta co ion phc Ag(CN ) 2 phan li theo phng trnh phan ng sau:
Ag(CN)2 Ag + + 2CN
Hang so khong ben cua phc Ag(CN ) 2
a + .a 2 Ag CN ( K) = a c xac nh Ag ( CN )
2
cb
nh viec thiet lap nguyen to sau: ( )Ag / Ag( CN ) 2 , CN / / AgNO 3 / Ag( + ) .
Cac phng trnh phan ng ien cc:
( + ): Ag + + 1e = Ag; ( ): Ag + 2CN
= Ag(CN ) 2 + 1e .
Phng trnh phan ng chung: Ag + + 2CN = Ag(CN ) 2 .
E = Ag + / Ag CN ,Ag (CN ) / Ag = o + 0,059 lg a Ag + o Ag + / Ag Ag + / Ag

2
0,059 lg K 0,059 lg a Ag( CN ) + 2.0,059 lg a CN =

2
= 0,059 lg a Ag + 0,059 lg K 0,059 lg a Ag ( CN ) + 0,118 lg a CN .

2
Thac s Tran Kim Cng
Khoa hoa hoc
- 53 -
lg K =
24).
0,059 lg a Ag + E 0,059 lg a Ag ( CN ) + 0,118 lg a CN

2
0,059
= x K = 10 x (VII-
Thac s Tran Kim Cng
Khoa hoa hoc
- 54 -
* CAC BAI TAP IEN HOA HOC *

cm2.lg-1.Tnh hang so phan li cua acid acetic trong dung dch tren va tnh pH cua dung dch acid acetic tren. Cho =349,8 va o,CH COO =40,9 -1.cm2.lg-1.
o ,H +
3
BAI 1: o dan ien ng lng cua dung dch acid acetic1,59.10-4M la 127,7-1.
GIAI:
o ,CH 3COOH = o ,H + + o ,CH COO =349,8+40,9=390,7

3
=c/o=127,7/390,70,32685. + Phng trnh phan ng phan li:
CH3COOH
CH3COO + H
C . C Ka = (1 )C
2 C = 1 -
= 0,316852.1,59.10-4/(1-0,32685)2,5234.10-5. C H + =C=0,32685.1,59.10-4=0,5197.10-4pH=-lg C H + =-lg5,197+5=4,2842. --------------------------------ng nay trong ieu kien hoan toan thuan nghch ap suat va nhiet o khong oi. Cho o = -0,402v (nhiet o la biet: a Cd +2 = 0,125 , a Zn2 + =0,001, Zn2 + / Zn =-0,763 v va o Cd 2 + / Cd
BAI 2: Tnh hang so can bang cua phan ng:Zn +Cd2+=Zn2++Cd va cong cua phan
25oc).
GIAI:
- o =-0,402-(-0,763)=0,361 (v) Eo = o Cd 2 + / Cd Zn 2 + / Zn Go= -nFEo =-RTlnKlgK=2.0,361/0,059 12,24K=1012,24. Amax=nFE ma E=+--, Cd 2 + / Cd =-0,402+0,0295lg0,125=-0,4286 (v) va Zn 2 + / Zn =-0,763+0,0295lg0,001=-0,8515 (v). E=-0,4286 -(-0,8515)=0,4229(v)Amax=2.23062.0,4229=19505,84 (cal/mol). ----------------------------xay ra cac phan ng sau:
BAI 3: Phai lap cac nguyen to ganvanic va cac ien cc nh the nao e trong o
1. Cd+Cu2+=Cd2++Cu. 2. 2Ag++H2=2Ag + 2H+.3. H2+Cl2=2HCl. 4. Zn+2Fe3+ =Zn2++2Fe2+.
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng GIAI:
- 55 -
1. (-)Cd=Cd2++2e (-) Cd/Cd2+; (+)Cu2++2e=Cu (+)Cu/Cu2+.Ta co: nguyen to ganvanic la ()Cd/Cd2+//Cu2+/Cu (+). 2. Tng t, ta co: (-)(Pt)H2/H+//Ag+/Ag (+). 3. Tng t, ta co: (-) (Pt)H2/H+//Cl-/Cl2 (Pt) (+). 4. Tng t, ta co: (-) Zn/Zn2+//Fe3+, Fe2+/Pt (+). --------------------------------ghep vi ien cc calomen (cal.=0,2412 v, nhiet o la 25oc).Xac nh dau cua ien cc kim loai trong tng trng hp va viet cac phng trnh phan ng ien cc va phan ng chung.
BAI 4: Tnh sc ien ong cua cac nguyen to ganvanic tao bi cac ien cc kim loai
1. Ag/Ag+, co a Ag + =0,5 va o=0,8 v. 2. Co/Co2+, co a Co +2 =0,063 va o=-0,277 v. 3. Pb/Pb2+, co a Pb +2 =1,26 va o=-0,126 v.

GIAI:
0 1. Ag + / Ag = Ag + / Ag + 0,059 lg a Ag + =0,8+0,059lg0,50,782(v)>cal ien cc Ag/Ag+
la ien cc dng E=+--=0,782-0,2412=0,5408 (v). Cac phng trnh phan ng:(-) 2Hg+2Cl-=Hg2Cl2+2e; (+) Ag++e=Ag; 2Hg +2Ag++2Cl-=Hg2Cl2+2Ag. 2. Tng t nh tren, ta suy ra: Co+2 / Co =-0,312v; ien cc Co/Co+2 la ien cc am; E=0,5532v; cac phng trnh phan ng:(-) Co=Co2++2e;(+)Hg2Cl2+2e=2Hg +2Cl-; Co+Hg2Cl2=Co2++2Cl-+2Hg.
3. Tng t nh tren, ta suy ra: Pb +2 / Pb =-0,123v; ien cc Pb/Pb+2 la ien cc am; E=0,3642v; cac phng trnh phan ng :(-)Pb=Pb2++2e;(+)Hg2Cl2+2e =2Hg + 2Cl-; Pb+Hg2Cl2=Pb2++2Cl-+2Hg.
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng Phan III. HOA HOC CHAT KEO.
- 56 -
CHNG VIII. KHAI NIEM VE CHAT KEO VA PHNG PHAP
IEU CHE DUNG DCH KEO.

I. Khai niem ve chat keo:
1. nh ngha he keo:
La he ma o tng phan tan -chat tan-c phan chia nho en trang thai tap hp cac phan t co kch thc c 1-100 m va c phan bo trong mot moi trng goi la moi trng phan tan (dung moi). Toan bo he thong o goi la he keo hay dung keo, o la he a phan tan va la he d the.
2. o phan tan (D):
La ai lng nghch ao cua kch thc hat keo (a), tc la D = 1/a (cm-1).
Da vao kch thc hat cua tng phan tan hoac o phan tan, ta co the phan ra cac loai he sau:
D(cm-1) Dung that a(cm)

a. Tng phan tan:
10+7 dch 10-7 He keo 10-5
10+5 He phan tan vi d the He phan tan tho
3. Tng phan tan va moi trng phan tan:
Co the la chat kh, chat long hoac chat ran. b. Moi trng phan tan: Co the la chat kh, chat long hoac chat ran. c. V du: Hon hp kh (K/K), sng mu hoac may (L/K), khoi hoac bui (R/K), bot (K/L), nhu tng (L/L), huyen phu (R/L), bot ran (K/R), nhu tng ran (L/R), dung dch ran nh hp kim, a qu, (R/R).
4. ac diem cua cac he keo:
+ Co kha nang phan tan ang sang: khi chieu 1 chum anh sang manh vao dung dch keo th thay uc v he keo la he d the. + Khuech tan rat cham do kch thc hat keo ln. + Khong ben vng tap hp, tc la de lien ket lai vi nhau thanh hat ln hn e lam giam nang lng t do be mat, tc la de b keo tu. + Co kha nang tham tch, tc la cac hat keo khong i qua c mang ban tham.
Thac s Tran Kim Cng
Khoa hoa hoc
- 57 -
+ Thng co hien tng ien di (cac hat keo thng chuyen ong trong ien trng) v cac hat keo thng mang ien.
5. oi tng nghien cu cua hoa hoc chat keo:
Nghien cu he keo, he vi d the, he tho va he ban keo.

6. Yngha cua hoa hoc chat keo:
+ Vu tru la he keo khong loo la nhng am bui ln. + Cac hien tng kh tng co lien quan en hoa keo nh may, sng mu, tuyet, s tao thanh cac vung ong bang chau tho, + Co y ngha to ln trong tho nhng hoc, canh tac hoc. at la he keo phc tap; kch thc, hnh dang cung nh ban chat cua cac hat keo at quyet nh kha nang tham t, kha nang hap phu cua at cung nh gi cac ion xac nh trong at, + Trong cong nghiep, hau nh nganh nao cung lien quan en hoa hoc chat keo nh nganh cong nghiep cao su, luyen kim, cong nghiep silicat, thuoc da, cong nghiep hoa hoc, nhuom, dc pham, thc pham, cong nghiep dau mo,
II. ieu che dung dch keo:
1. Nguyen tac ieu che dung dch keo:
+ V he keo co kch thc hat nam trung gian gia kch thc phan t va kch thc cac hat tho hn nen co 2 phng phap ieu che dung dch keo la phng phap phan tan (chia nho cac hat tho hn) va phng phap ngng tu (tap hp cac phan t, ion hoac cac hat be hn thanh cac hat ln hn). + ieu kien e ieu che dung dch keo la tng phan tan phai t tan hoac khong tan trong moi trng phan tan va trong he phai co chat on nh nham khong cho cac hat lien ket lai voi nhau thanh hat ln hn, tc la e tranh s keo tu.
2. Cac phng phap ieu che dung dch keo: a. Phng phap phan tan: + Dung nang lng (c nang, ien nang, sieu am, ) e chia nho cac hat tho hn roi phan bo chung vao moi trng phan tan. + Cac hien tng phan tan thng gap trong t nhien va i song:
- Qua trnh tao thanh bui do phong hoa. - Qua trnh tao thanh nc phu sa do phong hoa va ra troi. - S xay bot, xay ca phe, s tao thanh sa voi, sa uong,... + Cac phng phap phan tan: co nhieu phng phap phan tan nh phan tan bang c hoc (xay, nghien, khuay, lac,...), phan tan bang sieu am, phan tan bang ho quang ien va phan tan nh s keo tano la qua trnh lam tan chat ket tua do s keo tu gay ra (co 4 loai keo tan la keo tan bang cach ra ket tua, keo tan bang cach cho them chat ien li, keo tan bang cach cho them chat hoat ong be mat va
Thac s Tran Kim Cng
Khoa hoa hoc
- 58 -
keo tan bang phng phap hoa hoc; hien tng keo tan khong co li trong hoa hoc phan tch). b. Phng phap ngng tu: + o la qua trnh tap hp cac phan t, ion hoac hat nho hn thanh hat co kch thc ln hn. + Cac phng phap ngng tu:
- Ngng tu trc tiep: cho hi mot chat vao dung moi, o a co chat on nh, ta thu c dung dch keo. - Ngng tu bang phng phap thay the dung moi: cho dung dch that cua mot chat tan trong dung moi s cap vao dung moi th cap (chat tan phai tan tot trong dung moi s cap nhng t tan hoac khong tan trong dung moi th cap va hai dung moi phai tan tot vao nhau), ta thu c dung dch keo. - Ngng tu bang phng phap hoa hoc:
* Bang phan ng trao oi,v du: cho dung dch AgNO3 vao dung dch KI co nong o eu rat nho va rat khac nhau th ta thu c dung dch keo AgI (Neu tha AgNO3 th ta thu c keo dng va neu tha KI th ta thu c keo am). * Bang phan ng thuy phan, v du: tong hp keo Fe(OH)3 co mau o, trong suot rat ep bang phan ng thuy phan FeCl3. * Bang phan ng oxi hoa, v du: oxihoa H2S bang O2 , ta thu c keo S (cung vi qua trnh tren con co phan ng tao ra H2S5O6 lam chat on nh).
* Nh phan ng kh, v du: tong hp keo Au bang cach kh kaliaurat bang formaldehit trong moi trng kalicarbonat.
Thac s Tran Kim Cng
Khoa hoa hoc
- 59 -
Chng IX. TNH CHAT ONG HOC PHAN T VA S PHAN TAN
ANH SANG CUA CAC HE PHAN TAN

I. Tnh chat ong hoc phan t cua cac he phan tan:
1. Khai niem ve s khuech tan:
La qua trnh lam ong eu nong o phan t, ion hay cac hat keo trong he. o la qua trnh t y xay ra trong he do anh hng cua chuyen ong nhiet. Qua trnh khuech tan la qua trnh bat thuan nghch, no co c khi va ch khi co gradient nong o dC ( 0). dx
2. o ben vng sa lang:
+ Tuy thuoc vao kch thc cua hat tng phan tan ma anh hng cua trong trng va s khuech tan manh hn hay yeu hn. - Nhng he co kch thc hat be th chu anh hng cua trong trng be nhng lai chu anh hng cua s khuech tan manh, nhng he o cac hat phan bo eu va khong b sa lang- o la nhng he ben vng sa lang. - Nhng he phan tan tho co kch thc hat ln th chu anh hng cua trong trng ln nhng lai chu anh hng cua s khuech tan be va do o, se b sa lang- o la nhng he khong ben vng sa lang. - Dung dch keo chiem v tr trung gian gia hai loai he noi tren. + Co hai trng hp sa lang la: - Trng hp 1: cac hat sa lang oc lap, khong lien ket lai vi nhau; s sa lang xay ra cham. Nhng he o la nhng he ben vng lien ket (t gap trong thc te ). - Trng hp 2: cac hat lien ket lai vi nhau thanh hat ln hn tng cum 1 (o la s keo tu). Nhng he o la nhng he khong ben vng lien ket (pho bien trong thc te ).
II. S phan tan anh sang:
a. Hien tng:
Khi chieu 1 chum anh sang manh qua dung dch keo th thay co 1 dai sang hnh non m uc - o la hien tng phan tan anh sang cua dung dch keo, hien tng o con goi la hien tng Tanhan (Tyndahl). b. Nguyen nhan:
Tia sang tren ng i cua no gap nhng hat cua tng phan tan va tuy thuoc vao he thc gia o dai cua song anh sang va kch thc hat tng phan tan ma hien tng co s khac nhau.
Thac s Tran Kim Cng
Khoa hoa hoc
- 60 -
+ Neu kch thc hat ln hn bc song anh sang th anh sang se phan xa tren be mat hat di nhng goc xac nh. Hien tng nay quan sat c nhng he tho he keo nh huyen phu, bui, sng mu, ... + Neu kch thc hat be hn th se xay ra s nhieu xa anh sang. Do ket qua cua s nhieu xa, tia sang phan tan co ac iem khac vi tia sang phan xa la no toa i theo moi hng. - Neu kch thc hat nho hn nhieu th anh sang phan tan theo cac 0o va 180o so vi tia ti la manh hn ca. - Neu kch thc hat xap x bang th anh sang phan tan theo goc 0o la manh nhat. c. Phng trnh Raylay (Rayleigh):
n2 n2 .v2 2 . I0 + Phng trnh: Ipt = 24 21 4 n1 + 2 n 2 2

3
(IX-1), trong o: n1 va n2 la chiet
suat cua tng phan tan va moi trng phan tan tng ng, la nong o hat, v la the tch moi hat, la o dai song cua anh sang ti va Io va Ipt la cng o cua anh sang ti va anh sang phan tan tng ng.
Phng trnh Raylay ch ap dung c cho he keo kha loang, hat hnh cau, khong dan ien va kch thc hat nho hn 0,1 . oi vi cac he keo co kch thc hat ln hn th Ipt ty le nghch vi co luy tha nho hn 4.
+ T phng trnh Raylay ta rut ra mot vai nhan xet sau ay: - Khi cac hat co kch thc nhat nh th Ipt ty le thuan vi nhng khi rat ln th anh sang b phan tan nhieu lan (co s phan tan th cap) va v vay, phng trnh Raylay phai c bo chnh. - Ipt ty le thuan vi v2 va vi hat hnh cau th Ipt ty le thuan vi r6. Khi nong o trong lng khong oi, o phan tan cua dung dch keo cang cao (tc la kch thc hat cang nho) th anh sang phan tan cang yeu . - V Ipt ty le nghch vi 4 nen khi tia sang co cang nho th cang b phan tan manh va ngc lai, khi cang ln th cang t b phan tan (chu yeu truyen thang). ieu nay giai thch mau nc bien buoi tra thng co mau xanh, con bnh minh va hoang hon thng co mau o. - Trong cac dung dch keo kim loai, anh sang phan tan manh hn trong cac dung dch polimer v ty trong cua kim loai ln hn nhieu so vi moi trng phan tan va do vay, chiet suat ln hn nhieu moi trng phan tan, trong khi o ty trong cua cac polimer khac t moi trng phan tan. - Anh sang phan tan oi vi dung dch that la rat yeu v phan t co kch thc nho be (v rat be) nen tch so .v2 trong phng trnh Raylay khong ang ke. Tuy nhien, s phan tan anh sang van co the manh khi chieu vao dung dch that 1 chum anh sang co rat be, nh tia Rnghen chang han.
Thac s Tran Kim Cng
Khoa hoa hoc
- 61 -
CHNG X. S HAP PHU, TNH CHAT IEN CUA CAC HE KEO VA
S KEO TU
I. S hap phu:
1. Khai niem ve s hap phu: + nh ngha s hap phu: la s chat cha cac phan t kh, long hay ran hoa tan len be mat phan cach tng. Be mat phan cach tng co the la kh- ran, kh - long, longlong va long- ran.
+ Trong s hap phu, ngi ta phan biet hai loai chat la: - Chat b hap phu: chat chat cha. - Vat hap phu : chat b chat cha. V du : * Qua trnh hap phu cua NO2 tren be mat than hoat tnh. * Qua trnh hap phu cua xa phong tren be mat vai si - dung dch. dch. * Qua trnh hap phu cua acid acetic tren be mat than hoat tnh - dung
Trong cac v du tren, NO2, xa phong va acid acetic la chat b hap phu va than hoat tnh, vai si va than hoat tnh la vat hap phu. + Ngi ta chia s hap phu thanh 2 loai sau: - Hap phu vat ly hay hap phu Vandervan: lc hap phu la lc phan t va bao gi cung thuan nghch. - Hap phu hoa hoc: lc hap phu co ban chat hoa hoc va luon luon bat thuan nghch.
2. Phng trnh hap phu cua Frendlich (Freundlich):
+ Phng trnh hap phu cua Frendlich: = .P (X-1); =.C (X-2), trong o: la ai lng hap phu, va la cac hang so, C la nong o chat b hap phu va P la ap suat cua chat b hap phu. + Ngi ta co the tm cac hang so trong phng trnh Frendlich bang thc nghiem nh sau: - T (X-2), ta suy ra: lg = lgC + lg (X-3). - Bang thc nghiem, ta tm c cac gia tr 1, 2,...ng vi C1, C2,...t o, ta suy ra c lg1, lg2,...ng vi lgC1, lgC2,... - Ve o th bieu dien s phu thuoc cua lg vao lgC co dang nh tren H.X.1.
Thac s Tran Kim Cng
Khoa hoa hoc
- 62 -
- T o th H.X.1, ta suy ra c cac hang so nh sau: = tg va OB = lg = 10 OB .

3. S phu thuoc cua vao T:
Khi tang nhiet o th s hap phu giam, tc la giam, v s hap phu luon luon toa nhiet, va ngc lai (xem H.X.2).
4. Phng trnh hap phu cua Langmuya (Langmuir):
+ Phng trnh hap phu cua Langmuya:=max. trong o A vamax la cac hang so. + T phng trnh Langmuir, ta suy ra:
P C (X-4); =max. (X-5), P+A C+A
C 1 A .C + = (X-6). max max C C co dang nh tren H.X.3.
+ Bang thc nghiem, ta xay dng c o th
+ T o th, ta suy ra : tg = 1/ max max = cotg va OB= A/ max A = OB. cotg

5. S hap phu tren ranh gii dung dch - chat kh: a. Sc cang be mat ( ):
+ Lc tac dung len mot n v chieu dai be mat e tach chat ra khoi be mat goi la sc cang be mat, tc la nang lng t do cua 1 n v be mat (yn/cm, erg/cm2).
Thac s Tran Kim Cng
Khoa hoa hoc
- 63 -
+ Chat long cang phan cc th noi ap cang ln va do o, sc cang be mat cang ln va ngc lai. V du: H 2 O > C 2 H 5OH > C 6 H 6 .
b. Chat hoat ong be mat (chat hbm) : Khi hoa tan 1 chat nao o vao chat long th tuy thuoc vao sc cang be mat cua dung dch (dd) va cua dung moi (dm) ma ngi ta chia chat o ra cac loai chat sau ay: i. Chat hbm: la chat co kha nang chat cha len lp be mat, ngha la > 0, tc la co s hap phu dng.
Chat hbm phai la chat: + Co be hn dm, v the s chat cha no len lp be mat mi t y nhiet ong hoc va ket qua la dd be hn dm. + Co o tan tng oi be, v neu khong the th no co xu hng ri khoi be mat e tan sau vao chat long.
ac iem chat hbm la cau tao phan t gom 2 phan: phan phan cc la nhng nhom chc va phan khong phan cc la nhng goc hyrocarbon. V du: cac acid beo va muoi cua chung, acid ankylsunfonic, ankylarylsunfonic va muoi cua chung,...
khoi be mat e tan sau vao chat long, ta co < 0, tc la co s hap phu am. Nhng chat khbm co tnh chat sau:
ii. Chat khong hoat ong be mat (chat khbm): la chat co xu hng ri
+ Co ln hn dm, v the qua trnh ri khoi be mat mi t y nhiet ong hoc, ket qua la dd ln hn dm. + Co o tan cao, v the chat tan mi t y ri khoi be mat e tan sau vao chat long.
V du: cac chat ien ly nh acid, baz va muoi vo c.
khong lam thay oi ang ke sc cang be mat cua dung moi. V du: ng saccaroz.
iii.Chat t hoat ong be mat: s co mat cua loai chat nay trong chat long
phan loai chat hbm, chat khbm va chat t hbm(xem H.X.4). c. Phng trnh hap phu cua Gipx (Gibbs): + Phng trnh hap phu cua Gipx: =
iv.Tom lai: Ta co the da vao s phu thuoc cua dd vao nong o dung dch e
C d . (X-7), trong o: C la nong o RT dC dung dch, R la hang so kh, T la nhiet o tuyet oi va la sc cang be mat cua dung dch.
+ T phng trnh Gipx, ta nhan thay rang:
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- Neu C tang ma tang, tc la d/dC>0, th <0, ta noi rang nong o chat tan tren lp be mat be hn trong dung dch, ta co s hap phu am. - Neu C tang ma giam, tc la d/dC < 0, th >0, ta noi rang nong o chat tan tren lp be mat ln hn trong dung dch, ta co s hap phu dng. - Neu khong oi theo C th chat tan phan bo eu va khong co s hap phu. - ai lng -d/dC=G goi la o hbm hay tnh hbm. Ta co: = G.
d. Phng trnh hap phu cua Sitkovxki:
C (X-8). RT
+ Khi nong o cua chat hbm be th o -== k.C (X-9).
C + 1) (X-10), trong A o: B la hang so, t phu thuoc vao ban chat cua chat hbm va bang 0,2 20oC, A la hang so ac trng cho moi chat hbm, k la hang so, o va la sc cang be mat cua dung moi va dung dch tng ng.
+ Khi nong o cua chat hbm khong be th =o-=o.B.ln ( + Phng trnh Sitkovxki ap dung tot cho cac acid beo co so nguyen t carbon khong qua ln ( 8 ). + Ta co the dung phng trnh Sitkovxki e chuyen phng trnh Gipx thanh phng trnh Langmuya. Ta se chng minh ieu o nh sau: T phng trnh: o -=o.Bln ( -
C dC + 1) -d = o.Bdln (C + A) =o.B ( ) A A+C
B B B C d d = o . Thay = o vao phng trnh Gipx, ta c: = o . . dC C + A dC C + A RT A + C B C at o = max , ta co: = max. , ay la phng trnh Langmuya. A+C RT
+ Nhan xet: - A trong phng trnh Sitkovxki cung chnh la A trong phng trnh Langmuya. - max phu thuoc vao nhiet o, khi nhiet o tang th max giam va do o, giam va ngc lai. e. Qui tac uclo-Traobe ( Duclaux-Traube): + Qui tac nay neu len anh hng cua cau tao va kch thc cua phan t chat hbm en s hap phu. + Nh a noi tren, chat hbm phan t gom 2 phan: - Phan phan cc co momen lng cc ln, la nhng nhom chc nh -COOH, COO-, -OH, -NH2, -SO4H, -SO4-,..., c k hieu la o.
Thac s Tran Kim Cng
Khoa hoa hoc
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- Phan khong phan cc la goc hydrocarbon no hoac khong no hoac thm nh C17H35-, C17H33-, C12H25C6H4-,...., c k hieu la hoac . + Chieu dai cua goc hydrocarbon co anh hng ln en o hbm cua chat hbm. + uclo-Traobe thay rang: o hbm cua acid hu c no trong nc trong mot day ong ang tang len theo so nguyen t carbon cua goc hydrocarbon, trung bnh mot nhom CH2 tang 3,2 lan. Co the phat bieu qui tac nay mot cach khac la khi chieu dai cua acid beo tang theo cap so cong th o hbm (-d/dC) tang theo cap so nhan. + Nguyen nhan cua s phu thuoc o la: Khi chieu dai mach tang th o tan giam va do o, xu hng chuyen len be mat tang. + Qui tac uclo-Traobe con ap dung tot cho cac day ong ang khac cua cac chat hbm nh ru, amin, + Qui tac uclo-Traobe khong ung cac nhiet o ln hn nhiet o phong va khong ap dung cho dung moi khac nc.
6. S hap phu tren ranh gii dung dch-vat ran: ay la s hap phu quan trong nhat oi vi hoa hoc chat keo v no gan lien vi nhieu hien tng va qua trnh xay ra trong cac he keo: s tao thanh, tnh ben vng va s pha huy cac lioson. Trong s hap phu, ngi ta phan biet s hap phu phan t va s hap phu chat ien li. a. S hap phu phan t:
+ Lng chat b hap phu tren 1 gam vat hap phu (mmol/gam) tren be mat vat ran C C C C . V.1000 = 0 . v (X-11), dung dch c tnh theo cong thc sau: = 0 m m trong o: Co va C la nong o ban au va sau khi co can bang hap phu cua dung dch chat b hap phu, m la khoi lng vat hap phu (g), V la the tch dung dch chat b hap phu (lt) va v la the tch dung dch chat b hap phu (ml). + S hap phu tren be mat vat ran -dung dch cung tuan theo cac phng trnh hap phu, thng dung nhat la phng trnh Langmuya va co khi dung phng trnh Frendlich nong o nho. Nhac lai cac phng trnh hap phu: phng trnh Frendlich: = .C ; phng C C d ; phng trnh Gipx: = ; phng trnh trnh Langmuya: =max A+C RT dC Sitkovxki: khi nong o nho:o-=kC va khi nong o khong nho:o-=o C .B.ln( + 1) . A + Cac yeu to anh hng en s hap phu: - Anh hng cua moi trng: Moi trng va chat tan canh tranh nhau trong s hap phu nhng cau t nao co sc cang be mat be hn se b hap phu manh hn.
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- Anh hng cua tnh chat vat hap phu: Ban chat va o xop cua vat hap phu co anh hng ln en s hap phu. * Vat hap phu khong phan cc hap phu chat khong phan cc manh hn va ngc lai. * Vat hap phu co o xop cang ln (lo xop cang be) se hap phu manh hn va ngc lai. - Anh hng cua chat b hap phu: * Qui tac Rebinia noi rang chat C se b hap phu len be mat phan cach tng A-B neu chat C thoa man ieu kien sau: A < C < B hoac B < C < A ( la hang so ien moi). * Rebinia con a ra mo hnh cua s hap phu nh H.X.5.
* S hap phu tang khi khoi lng phan t cua chat b hap phu cang ln va ngi ta thay rang chat thm hap phu tot hn chat khong thm. V du: C17H35COOH >C15H31COOH; C12H25C6H4SO3H >C17H35COOH; C12H25C6H4SO3H >C18H37SO3H. * S hap phu tren ranh gii vat ran -dung dch cung thoa man ve mat nh tnh qui tac uclo-Traobe. V du: C3H7COOH > C2H5COOH > CH3COOH. - Anh hng cua nhiet o va thi gian: * S hap phu trong dung dch cham hn trong tng kh v s khuech tan cua chat trong tng kh nhanh hn trong tng long do o nht cua chat kh be hn nhieu o nht cua chat long. * S hap phu cac phan t ln cong kenh len vat hap phu co lo xop be rat cham. Khoi lng chat b hap phu cang ln th thi gian e at c en trang thai can bang hap phu cang ln. * Khi tang nhiet o th s hap phu trong dung dch giam do s hap phu toa nhiet. + Y ngha cua s hap phu trong t nhien va ky thuat: - Co y ngha ln trong c the sinh vat, ac biet la van e xuc tac men. - Co y ngha ln trong ky thuat nh tay trang ng bang than, tay trang dau bang at set, tach cac nguyen to hiem bang hap phu, ...
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng b. S hap phu chat ien li:
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+ Nh ta a biet, chat ien li tren be mat thoang cua dung dch chung b hap phu am, chat ien li la chat khong hbm. + Khi co mat trong dung dch mot vat hap phu ran th tren be mat phan cach vat ran-dung dch thng co s hap phu dng nhng chat ien li. + Ban chat cua vat hap phu co y ngha quyet nh trong s hap phu cac ion. - Cac ion co kha nang phan cc thng ch b hap phu tren cac be mat co cac phan t phan cc hoac ion. - Cac ion ngc dau vi ion cua vat hap phu se b hap phu. + Ban chat cua chat ien li cung co anh hng ln en s hap phu. - Cac ion co cunh hoa tr, ion nao co ban knh ln hn se b hap phu manh hn. V du: Na+ < K+ < Rb+; Cl- < Br- < NO3- < I- < CNS-. - Ion co hoa tr cang cao th cang b hap phu manh. V du: K+ < Ca2+ < Al3+ < Th4+ ; Cl- < SO4- < PO43-. + S hap phu chat ien li la s hap phu chon loc. V du: Tinh the AgI neu trong dung dch co KI va KCl th ion I- se b hap phu len be mat AgI tao nen ion quyet nh the hieu cua hat keo AgI (keo am).
+ S hap phu ion co s hap phu trao oi io. o la trao oi gia ion cua lp ien kep vi ion cua moi trng; ngoai ra con co the xay ra s hap phu ca vi cac ion tao nen vat hap phu o khi chung ien li ra. ieu nay thng xay ra oi vi cac nha trao oi ion (trong sac ky trao oi ion vi cac cot trao oi ion cationit va anionit). + ac iem cua s hap phu trao oi ion:
- o la s hap phu ac biet, ngha la s hap phu ch xay ra oi vi nhng ion xac nh. Noi cach khac la ban chat cua tng ran va lp ien kep tren be mat tng ran cung nh ban chat cua ion b hap phu co anh hng ln en s hap phu trao oi. Trong s hap phu trao oi, ngi ta chia ra vat hap phu acid, baz va lng tnh. * Vat hap phu acid x s nh mot acid va co kha nang trao oi vi cation cua dung dch, v du nh SiO2 (mSiO2.nSiO32-.2(n-x)H+.2xH+). * Vat hap phu baz x s nh mot baz va co kha nang trao oi vi anion cua dung dch, v du nh Fe(OH)3. * Vat hap phu lng tnh x s nh mot chat lng tnh va co kha nang trao oi vi anion hoac cation la tuy thuoc vao ieu kien moi trng, v du nh Al(OH)2 SiO3H. - Khong phai luon luon thuan nghch.
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- Xay ra cham hn nhieu so vi s hap phu phan t. - Co the lam thay oi pH cua moi trng khi trao oi H+ hoac OH- . V du:
[VHP ]H + Na + Cl [VHP ]Na + H + Cl [VHP ]OH + Na + Cl [VHP ]Cl + Na + OH

+ + + + + + + +
+ Y ngha cua s hap phu trao oi: co y ngha ln trong ky thuat, nong nghiep, hoa hoc,... - Trong nong nghiep: kha nang hap phu cua at va gi nhng ion xac nh trong at. - Trong ky thuat: ky thuat nhuom, cong nghiep lam mem nc, ... - Trong hoa hoc: e tach cac chat qu t dung dch rat loang, trong hoa hoc phan tch, ...
II. Tnh chat ien cua cac he keo va s keo tu:
1. Cau tao cua hat keo:
+ Hat keo gom1 nhan, thng co cau tao tinh the, va lp ien kep bao quanh. Toan bo he thong o goi la mixen hay hat keo. + V du: - V du 1: Keo dng AgI co cau tao nh sau:
- V du 2: Keo am AgI co cau tao nh sau:
Thac s Tran Kim Cng
Khoa hoa hoc
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-V du 3: Keo Fe(OH)3 dng co cau tao nh sau:
2. S lc cac thuyet ve cau tao lp ien kep: a. Thuyet Hemhon (Helmholtz):
+ Thuyet nay coi lp kep la 1 tu ien phang, the giam theo 1 ng thang. + Mo hnh lp kep theo kieu Hemhon c ch ra tren H.X.6.
b. Thuyet Guy-Sepmen(Gouy-Chapman):
+ Quan iem cua thuyet nay la cac ion nghch co cau tao khuech tan va the giam dan theo 1 ng cong . + Mo hnh lp kep cua Guy-Sepmen c ch ra tren H.X.7. c. Thuyet Stec (Stern): + Lp kep gom 2 phan: phan the giam theo 1 ng thang (lp hap phu) va phan the giam theo 1 ng cong (lp khuech tan). + Mo hnh lp kep cua Stec c ch ra tren H.X.8.
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 3. S keo tu: a. Khai niem ve s keo tu:
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+ o ben vng cua 1 he keo tc la kha nang cua no duy tr c trang thai phan tan khong oi theo thi gian. + Cac he keo khac vi cac dung dch that cung nh cac dung dch polimer la co be mat rieng ln nen chung la nhng he khong ben vng nhiet ong hoc va do o, khong ben vng tap hp. + Chnh v vay ma van e lam cho he keo ben vng la van e quan trong cua hoa hoc chat keo va s keo tu la hien tng cung het sc quan trong va ac trng cho cac he keo. + Tnh khong ben vng cua he keo the hien theo hai cach la: - So hat giam i do ket qua cua s tai ket tinh, tc la qua trnh ket tinh cac hat ln thanh hat ln hn va cac hat nho th b tan dan ra. Nhng trng nay t gap va khong pho bien oi vi cac he keo. - Cac hat lien ket lai vi nhau thanh nhng tap hp (thanh hat ln hn-o la s keo tu). ay la trng pho bien va co y ngha quan trong trong thc te.
S lien ket cac hat keo lai vi nhau la do ket qua cua s va cham gia cac hat nhng khong phai va cham nao cung dan ti hieu qua ma ch co 1 so va cham co hieu qua, phu thuoc vao tnh chat be mat cua cac hat keo. Khi a vao he keo1 lng nho chat co kha nang hap phu th nhng tnh chat be mat cua hat keo b thay oi manh va do o, ket qua cua s va cham cung se thay oi. Khi hau het cac va cham eu dan en hieu qua, ta co s keo tu nhanh va khi khong phai nh vay, ta co s keo tu cham hoac he keo ben vng.
+ Co hai lc xuat hien gia cac hat keo la: - Lc hut phan t Vandecvan. - Lc ay tnh ien do cac hat keo mang ien cung dau. Tuy thuoc vao tng quan gia 2 lc noi tren ma he keo ben vng hay b keo tu. Khi lc hut thang lc ay th he keo b keo tu va ngc lai, khi lc hut thua lc ay th he keo ben vng. b. S keo tu bang chat ien li: + Hau het cac chat ien li eu co kha nang gay keo tu he keo. + Kha nang gay keo tu cua chat ien li c ac trng bang nong o toi thieu cua no can e gay keo tu mot he keo nhat nh vi mot toc o nhat nh -o la ngng keo tu va c bieu th bang n v mmol/lt hoac mlg/lt, k hieu ngng keo tu la .
Thac s Tran Kim Cng
Khoa hoa hoc
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+ Gia tr phu thuoc vao nong o cua dung dch keo; do o, gia tr cua cac tac gia khac nhau la khac nhau. + Quy tac Sunde-Hacdi (Schoulze-Hardi): - Ch co ion ngc dau vi hat keo mi co kha nang gay keo tu he keo. - Cac ion co hoa tr cang cang cao th kha nang gay keo tu cang ln, cang nho. + Kha nang gay keo tu cua cac ion cung hoa tr tang khi ban knh ion tang oi vi cation va giam oi vi anion. V du: oi vi keo am th Li+ < Na+ < K+ va oi vi keo dng th Cl- > Br- > I-. + Cac ion hu c co kha nang gay keo tu manh hn nhieu cac ion vo c cung hoa tr v cac ion hu c co kha nang hap phu manh hn nhieu. Cac ion hu c cung hoa tr, ion nao co kha nang hap phu manh hn se co kha nang gay keo tu manh hn . V du: C17H35COO- >C15H31COO-; C12H25C6H4SO3- >C12H25SO4-; C17H35COO- > Cl-; C16H33NH3+ >Na+. + Ngi ta thay rang s keo tu bat au xay ra the de ta ti han la khoang 30 mv (khong xet dau). + S phu thuoc cua toc to keo tu (v) vao nong o chat ien li cho vao (C) c bieu bien bang o th H.X.9.
Tren o th H.X.9, vung 1 la vung dung dch keo ben vng, vung 2 la vung dung dch keo co s keo tu cham va vung 3 la vung dung dch keo co s keo tu nhanh.
Thac s Tran Kim Cng
Khoa hoa hoc
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CHNG XI. CAC HE VI MOI TRNG PHAN TAN KH, LONG
VA RAN VA XA PHONG.
I. Cac he vi moi trng phan tan kh, long va ran:
1. Cac he vi moi trng phan tan kh: Cac he vi moi trng phan tan kh goi la cac son kh hay aeroson. o ben vng cua cac he nay thng thap hn cua cac he keo. Kch thc va hnh dang hat cua he phu thuoc vao phng phap ieu che va trang thai tap hp cua tng phan tan. a. Phan loai son kh:
+ Sng mu: tng phan tan long, cac hat co kch thc c 10-5 10-3cm (0,1 10 ). + Khoi: tng phan tan ran, c chia ra lam hai loai sau: - Bui: co kch thc hat c ln hn10-3 cm. - Khoi thc: co kch thc hat c 10-7 10-3 cm.
Cac hat tng phan tan cua khoi noi chung co kha nang hap thu 1 lng rat ln nc cua kh quyen, luc o he va la khoi va la sng mu. b. ac trng tong quat cua son kh:
+ Co o phan tan thap hn he keo. + Khac vi son long (lioson) la he rat loang va co o nht thap hn. + Chuyen ong Brao xay ra cc manh va s sa lang xay ra nhanh hn lioson. + Cac son kh thng khong mang ien. c. Cac tnh chat cua son kh: + S phan tan anh sang cua son kh ln hn cua son long rat nhieu v chiet suat cua tng phan tan va moi trng phan tan cua son kh khac nhau rat nhieu. ieu nay c ng dung rong rai trong viec tao ra man khoi e nguy trang cac muc tieu kinh te va quoc phong trong chien tranh. + Khoi va sng mu noi chung eu co mau trang v cac hat kha ln nen chung phan tan eu cac tia sang co o dai song khac nhau. + S sa lang: v o nht cua moi trng phan tan thap va v chuyen ong nhiet ln ma cac hat son kh khong ben vng tap hp, de b keo tu va sa lang rat nhanh . + Cac son kh co hien tng nhiet di, ket tua nhiet va quang di va ch ac trng cho son kh. - Nhiet di la hien tng cac hat son kh t y ri khoi vat nong, tc la chuyen ong t ni nong en ni lanh. - Ket tua nhiet la hien tng cac hat son kh bam vao vung lanh cua vat c lam nong khong ong eu.
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- Quang di la hien tng di chuyen cua cac hat son kh khi chung c chieu sang t mot pha. Hien tng quang di dng oi vi hat khong trong suot, chuyen ong theo chieu cua tia ti. Hien tng quang di am oi vi hat trong suot, chuyen ong ngc lai vi chieu cua tia ti v mat sau cua hat b tia khuc xa lam nong nhieu hn. Hien tng quang di la trng hp ac biet cua hien tng nhiet di.
Hien tng quang di, nhiet di va ket tua nhiet co y ngha to ln oi vi s chuyen ong cua cac son kh trong kh quyen; no lien quan en may mu va ma. + o ben vng tap hp cua cac son kh:
- Cac son kh co o phan tan cao nen co tnh ben vng sa lang nhng khong ben vng tap hp v nhng hat ln co toc o sa lang cao con nhng hat nho th do chuyen ong Brao manh ma so va cham gia cac hat ln, do o de lien ket lai vi nhau, tc la de b keo tu. - S keo tu cua cac son kh la qua trnh keo tu nhanh va nhanh hn lioson. ieu nay giai thch tai sao sng mu buoi sang nhanh tan va khi ta quet nha co bui nhng cung rat nhanh het bui. - Toc o keo tu cang ln khi nong o hat cang cao. ieu nay giai thch tai sao trong thien nhien cac son kh rat loang. - Ngoai nong o ra con nhieu yeu to co the gay keo tu he son kh nh o a phan tan hnh dang hat, ien tch khac nhau gia cac hat, s khuay lac, song sieu am dong oi lu,...
- Tnh chat ien cua son kh: Trong moi trng phan tan kh, xung quanh cac hat khong the xuat hien lp ien kep nh trong son long. Nhng trong nhng ieu kien nhat nh, cac hat son kh co the mang ien va ien tch cua chung thng khong ln lam. d. Y ngha thc te cua son kh:
+ Son kh rat pho bien trong t nhien va ky thuat. Aeroson (may va sng mu) quyet nh ma nang va kh hau cua cac vung, co anh hng ln en nong nghiep. + Phan hoa, bao t cua cac vi khuan va cua moc, cac hat nhe chuyen t cho no en cho kia eu dang son kh. + Trong luyen kim va trong cong nghiep hoa hoc, son kh sinh ra dang khoi, cha nhieu chat qu va gay o nhiem moi trng. + Ngay nay, ngi ta dung nhieu chat dang son kh nh a chat ot dang son kh vao lo; khi quet voi, sn, nhuom mau th ngi ta dung may phun cac chat thanh hat nho; thuoc tr sau, tr nam, diet co eu c phun di dang son kh; trong y hoc, nhieu loai thuoc c a vao c the di dang son kh; trong quoc phong, ngi ta dung son kh e nguy trang va e lam nhieu viec khac;...
+ Ngoai ra, son kh con co nhieu tac hai nen can phai pha huy chung. Khoi cua nhng nha may cong nghiep thng lam ban moi trng, lam hai sc khoe cua con Thac s Tran Kim Cng Khoa hoa hoc
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ngi va ong vat. Neu khong kh co o am cao th khoi co the tao thanh sng mu day ac nh Luan on (nc Anh). Trong cong nghiep, co nhieu loai may gay ra nhieu bui nh may tan, may nghien, may xay, may sang,... Bui nay lam ban cong xng, san pham, may moc va khong kh. 2. Cac he vi moi trng phan tan long: Thuoc loai he nay co huyen phu, nhu tng va bot. ay la cac he vi d the. a. Huyen phu:
+ Huyen phu la he co tng phan tan ran va cac hat huyen phu co kch thc ln hn hat keo. Huyen phu co y ngha thc te trong thien nhien va trong k thuat ln hn nhieu so vi cac he keo ien hnh. + at am, at set ngao dung trong nganh san xuat gom, voi va va xi mang dung trong nganh xay dng, sn mau,... eu la huyen phu. + Huyen phu cung hap thu va phan tan anh sang. Cac hat cua huyen phu co the nhn thay c trong knh hien vi. + Huyen phu khong ben vng sa lang, cac hat huyen phu khong co chuyen ong Brao, khong co kha nang khuech tan va khong co ap suat tham thau v cac hat huyen phu rat ln. + Cac hat huyen phu cung co lp vo son vat hoa va lp ien kep tren be mat hat. Khi cho chat ien li vao he th huyen phu b keo tu, cac hat lien ket lai thanh hat ln hn roi sa lang. +Trong huyen phu, co mot so qua trnh ac trng nh sa lang, tuyen noi, loc,... Cac qua trnh nay khong ac trng lam cho he keo. b. Nhu tng: + ieu kien e tao ra nhu tng la: - Tng phan tan (long) va moi trng phan tan (long) khong tan hoac t tan vao nhau. - Trong he phai co chat on nh goi la chat nhu hoa. + ac trng cua nhu tng la hat bao gi cung co hnh cau v tng phan tan la long. + Phan loai nhu tng:
Co nhieu cach phan loai nhu tng nhng sau ay ta ch xet mot cach phan loai nhu tng la phan loai theo ban chat cua tng phan tan va moi trng phan tan:
- Neu tng phan tan la chat long khong phan cc (dau), con moi trng phan tan la chat long phan cc (nc) th ngi ta goi o la nhu tng thuan hoac nhu tng loai 1 va k hieu la D/N (dau trong nc).
Thac s Tran Kim Cng
Khoa hoa hoc
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- Neu tng phan tan la chat long phan cc (nc), con moi trng phan tan la chat long khong phan cc (dau) th ngi ta goi o la nhu tng nghch hoac nhu tng loai 2 va k hieu la N/D (nc trong dau).
Ta co the xac nh loai nhu tng D/N hay N/D qua cac tnh chat sau ay: * Xac nh kha nang cua nhu tng ang khao sat co tham t 1 be mat a nc hoac ghet nc hay khong. * Xac nh kha nang tron lan vi nc va dau. * Xac nh mau cua nhu tng khi cho 1 pham mau ch tan c trong mot tng cua nhu tng, v du nh dung suan III la chat ch th ch tan trong dau. * o o dan ien cua nhu tng. Neu nhu tng tham t be mat a nc, tron lan vi nc, khong mau khi dung suan III va co o dan ien cao th o la nhu tng D/N. Ngc lai, neu nhu tng tham t be mat ghet nc, tron lan vi dau, co mau o khi dung suanIII va co o dan ien thap th o la nhu tng N/D. + o ben vng tap hp cua nhu tng va ban chat cua chat nhu hoa:
- Nhu tng la he khong ben vng tap hp v co nang lng t do be mat ln, cac hat nhu tng t y lien ket lai vi nhau thanh nhng tap hp va cuoi cung, he tach thanh 2 lp. - e anh gia o ben vng cua nhu tng, ngi ta dung toc o phan lp nhu tng, thi gian ton tai cua nhu tng va thi gian song cua tng hat. - Nhu tng ben vng la nh trong he co chat nhu hoa hap phu len be mat hat lam giam sc cang be mat va gay ra lc ay gia cac hat. o ben vng cua nhu tng phu thuoc vao ban chat va nong o cua chat nhu hoa. Ban chat cua chat nhu hoa con quyet nh loai nhu tng. Qui tac Bancrop (Bancroft): * Neu chat nhu hoa tan trong nc tot hn trong dau (a nc) th se tao thanh nhu tng D/N. * Neu chat nhu hoa tan trong dau tot hn trong nc (a dau) th se tao thanh nhu tng N /D.
Giai thch: v chat nhu hoa co vai tro can tr khong cho cac hat dnh ket lai vi nhau khi cac phan t chat nhu hoa nam tren be mat hat, ngha la chat nhu hoa phai tan tot trong moi trng phan tan va t tan trong tng phan tan.
- Chat nhu hoa thng dung la chat hbm, xa phong, polimer,... - Noi chung, tac dung nhu hoa cua chat hbm phu thuoc vao s tng quan gia phan phan cc va phan khong phan cc cua phan t ve mat tng tac vi hai tng. Neu tng tac gia nhom phan cc vi nc va tng tac gia goc hydrocarbon khong phan cc vi dau la tng ng nhau th phan t chat hbm se hoa tan eu trong hai tng va se nam tren be mat phan cach tng ch khong b hut manh vao trong the tch mot tng nao ca. S khong tng
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xng gia 2 tng tac tren se quyet nh loai nhu tng. Neu chat nhu hoa co nhom phan cc tac dung manh hn nhom khong phan cc th no se hoa tan trong nc tot hn trong dau va se on nh cho nhu tng dau trong nc. Ngc lai, neu nhom khong phan cc tac dung manh hn nhom phan cc th chat hbm se hoa tan trong dau tot hn trong nc va se on nh cho nhu tng nc trong dau. +S ao tng:
- S ao tng la mot hien tng ac trng cho nhu tng. Neu them vao nhu tng mot lng ln chat hbm co tac dung on nh cho nhu tng loai ngc vi no th se xay ra s ao tng, khi o tng phan tan cua nhu tng ban au chuyen thanh moi trng phan tan cua nhu tng mi va moi trng phan tan cua nhu tng ban au chuyen thanh tng phan tan cua nhu tng mi.
- V du: Gia s ta co nhu tng D/N c on nh bang xa phong C17H35COONa, neu ta them (C17H35COO)2Ca vi mot lng kha kha, hoac them CaCl2 vao nhu tng tren th ta se thu c nhu tng N/D c on nh bang (C17H35COO)2Ca. c. Bot: + Bot la he phan tan kh trong moi trng phan tan long. o phan tan cua bot rat tho (be), cac hat bot co kch thc c mm hoac cm. Cac hat bot chu s nen cua cac hat ben canh nen b mat dang hnh cau, tr thanh nhng hnh a dien phan cach nhau bi mot mang rat mong cua moi trng phan tan. Mang trong bot thng co mau sac, o la do hien tng giao thoa anh sang gay ra, ieu o chng to chieu day cua mang tng ng vi bc song sang sang. + Bot ch tao thanh khi trong he co chat tao bot. Cac chat hbm co kha nang tao bot nh cac ru mach dai, acid beo, xa phong va cac chat tay ra, protit, saponin, .... o cung chnh la cac chat nhu hoa cho nhu tng dau trong nc. + e anh gia o ben vng cua bot, ngi ta dung thi gian song cua tng bot hoac thi gian song cua cot bot. + o ben vng cua bot phu thuoc vao ban chat va nong o cua chat tao bot va cac yeu to ben ngoai. + Bot co the ieu che bang cach suc kh vao dung dch chat tao bot hoac khuay, lac dung dch chat tao bot. + Bot co y ngha thc te ln. Bot c dung trong qua trnh tuyen noi e lam giau quang. Bot la yeu to quan trong trong tay ra. Bot dung trong cu hoa cha kh CO2 can tr khong cho khong kh tiep xuc vi vat chay,
3. Cac he vi moi trng phan tan ran: Cac he vi moi trng phan tan ran thng goi la son ran. Chung co the c chia ra thanh 3 loai sau:
+ Cac he vi tng phan tan kh (K/R): o la bot ran, loai he nay co hat rat tho.
Thac s Tran Kim Cng
Khoa hoa hoc
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Trong thien nhien ta thng gap a bot, loai a nay rat xop va nhe, dung e lam bot mai va lam be tong bot trong xay dng. Trong cong nghiep, co nhieu loai bot ran nhan tao nh thuy tinh bot, be tong bot, vat lieu cach ien, cach nhiet, cao su xop, nha xop, ... + Cac he vi tng phan tan long (L/R): o la nhu tng ran, rat t gap trong thc the va i song (v du: Hg/P). + Cac he vi tng phan tan ran (R/R): la he co y ngha quan trong hn ca, v du: thuy tinh mau, cac a qu, men, hp kim, ... - Thuy tinh mau cha nhng hat kim loai hoac oxt kim loai phan tan di dang keo lam cho thuy tinh co mau sac, ham lng cua chung ch t 0,01 0,1%. - Nhng a qu cha nhieu oxt kim loai phan bo di dang keo va co mau sac tuy theo tng loai oxt. - Men la he phan tan cha nhng hat keo cua chat sac to trong thuy tinh silicat lam cho no mat o trong suot va tr nen co mau sac. Chat sac to co the la TiO2 , Ca3 (PO4)2, - Muoi mo cung la mot he keo cha 1 lng natri kim loai vo cung nho (0,0001%) tromg natriclorua. - Cac hp kim nh gang, thep,... cha cac hp chat kim loai di dang keo.
ac tnh chung cua cac he vi moi trng phan tan ran la khong co s keo tu v o nht cua moi trng phan tan qua ln, can tr s chuyen ong cua cac hat. Cac he vi moi trng phan tan ran c ieu che bang cach phan tan kh, long, ran trong moi trng phan tan long (nong chay). Khi moi trng phan tan cha ong ac th he con mang tnh chat cua son long, c goi la son nong; con khi moi trng phan tan a ong ac th he la son ran.
II. Xa phong:
1. nh ngha, cau tao va phan loai xa phong: a. nh ngha:
+ Xa phong theo ngha hep: la muoi cua monoacid beo, co phan t tng oi ln, co tnh hbm va do o, co nhieu tnh chat quan trong trong i song va trong k thuat, trc het la kha nang tay ra. V du: C15H31COONa, C17H33COONa, C17H35COONa,... + Xa phong theo ngha rong: la tat ca cac chat co kha nang tay ra v cac chat co khanang tay ra co cau tao phan t gan vi xa phong va cung co cac tnh chat hoa l, tnh chat k thuat quan trong ta xa phong. Con muoi cua mono acid beo neu tren c goi la xa phong thng e phan biet. V du: C12H25SO4Na, C12H25C6H4SO3Na, ...
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng b. Cau tao cua xa phong:
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Xa phong noi chung eu la nhng chat phan cc, phan t cua chung gom 2 phan: phan a lu phan cc va phan ghet lu khong phan cc.
+ Phan a lu phan cc thng la cac nhom nh chc: -COO-, -SO4-, -SO3-, cac nhom cha nit, cac nhom -CH2-O-CH2- kem theo nhom -OH, ... + Phan ghet lu khong phan cc la goc parafin thang hoac phan nhanh, vong bezen hoac naphtalen vi goc ankyl,...
Phan a lu co the nam mot au, 2 au hoac gia phan t. c. Phan loai xa phong: Da vao cau tao, ngi ta chia xa phong thanh bon loai sau ay:
+ Xa phong anion hbm: loai xa phong nay khi hoa tan trong nc th phan li ra anion hu c hbm va cation vo c. V du: C15H31COONa, C17H33COONa, C12H25SO4Na, C12H25C6H4SO3Na, CnH2n+1SO4M (M=Na, K, NH4), CnH2n+1C6H4SO3M (M = Na, K, NH4), ...
+ Xa phong cation hbm: loai xa phong nay khi hoa tan trong nc th phan li ra cation hu c hbm va anion vo c.
V du: C18H37NH3Cl octadecylamoniclorua. + Xa phong lng tnh: loai xa phong nay khi tan trong nc th phan li ra anion hu c hbm va cation hu c hbm la tuy thuoc vao pH cua moi trng (trong moi trng acid, chung phan li ra cation hu c hbm; con trong moi trng baz, chung phan li ra anion hu c hbm). V du: H2N-C17H34-COONa aminostearatnatri. + Xa phong khong phan li: loai xa phong nay khi tan trong nc th khong co kha nang phan li thanh ion. V du: CnH2n+1(-O-CH2-CH2-)m-OH.
2. Cac tnh chat hoa ly cua xa phong: a. Tnh tan trong nc:
+ Tnh chat au tien quyet nh moi tnh chat khac cua xa phong la tnh tan trong nc. + Tnh tan trong nc phu thuoc vao cac yeu to sau: ban chat va v tr cua nhom phan cc, chieu dai cua mach hyrocarbon, nhiet o va ban chat cua ion vo c. + Xa phong thng la muoi cua acid beo, co t 10 20 nguyen t carbon trong phan t, khi hoa tan thng b thuy phan mot phan thanh acid beo. Muoi cua kim loai kiem, v du: C15H31COONa, C17H33COONa, ..., thng tan tot trong nc. Muoi cua kim loai hoa tr cao hn nh canxi, magie, nhom, sat,... khong tan trong nc nhng lai tao thanh chat ban keo trong moi trng dau.
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng b. Tnh hoat ong be mat:
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+ Khi cho xa phong vao nc th sc cang be mat cua nc giam xuong, luc o nong o xa phong tren be mat ln hn nong o xa phong trong dung dch, ta noi rang co s hap phu dng cac phan t xa phong. S phan bo cac phan t xa phong tren be mat nc nh tren H.XI.1.
o o o o o o o o o o
H.XI.1. + V co s hap phu cac phan t xa phong len be mat phan cach tng nc -khong kh ma sc cang be mat cua nc giam (v xp < n). + S hap phu cac phan t xa phong len be mat nc cung tuan theo phng trnh C d (XI-1). Ta thay rang > 0 nen ta suy ra hap phu Gipx (Gibbs): = RT dC d/dC nho hn khong, tc la giam khi C tang. + Tnh hbm cua xa phong phu thuoc vao ban chat va v tr cua nhom phan cc va chieu dai va cau tao cua goc hyrocarbon quyet nh. Khi chieu dai cua goc hidrocarbon tang th tnh hbm tang. + Xa phong con lam giam sc cang be mat gia tng, tc la sc cang be mat gia 2 chat long hoac gia chat long va chat ran (AB=A -B). AB se giam khi cho xa phong vao he cha A va B. Trong qua trnh tay ra, ai lng sc cang be mat gia tng quan trong hn ai lng sc cang be mat cua nc -khong kh nhieu. c. Kha nang tham t: + S tham t rat quan trong cho qua trnh tay ra. - Be mat thuy tinh, silicat, xenluloz, tinh bot, ... tham t nc rat tot. - Cac be mat ghet nc nh parafin, dau mo, lu huynh, ... tham t nc rat khong tot. - Cac loai vai sach tham t nc rat tot, con vai ban co dnh dau m th tham t nc rat khong tot; vai sach cung kho ngam nc vao ben trong v sc cang be mat cua nc rat ln. + V vay, can phai dung chat hbm (xa phong) e lam giam sc cang be mat cua nc va sc cang be mat gia 2 tng be mat vai si va nc. + Trong qua trnh tay ra, xa phong ong vai tro chat hbm. + S tham t vai si va o dung cung tuan theo phng trnh Iung:
R-K = R-L +L-K. cos (XI-2).
Thac s Tran Kim Cng
Khoa hoa hoc
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Khi them xa phong vao nc th R-L va L-K eu giam, do o cos tang len, tc la giam xuong, cung co ngha la s tham t tang len.
+ Kha nang tham t phu thuoc vao nong o xa phong, nhiet o, v tr va ban chat nhom phan cc, chieu dai va cau tao cua goc hydrocarbon. d. Kha nang nhu hoa: + Khi cho xa phong vao nhu tng th nhu tng tng oi ben vng; nh vay, xa phong lam chat nhu hoa cho nhu tng. + Tac dung cua xa phong la lam giam sc cang be mat gia 2 tng dau va nc; do o, tao ieu kien cho s tao thanh nhu tng de dang khi co xa phong. Cac phan t xa phong hap phu len be mat hat nhu tng va lp o bao ve khong cho cac hat nhu tng lien ket lai vi nhau. + Trong qua trnh tay ra, xa phong lam cho s tham t xay ra de dang va chat ban dau, m c tach ra khoi be mat vai si va c gi trong nc giat dang nhu tng bang chat nhu hoa la xa phong. + Kha nang nhu hoa cua xa phong phu thuoc vao v tr va ban chat cua nhom phan cc, cau tao va chieu dai cua goc hydrocarbon va nong o cua xa phong. e. Kha nang tao bot: + S tao bot (K/L) kem theo s tang be mat phan cach tng kh-long rat manh, v the s tao bot ch co the xay ra khi sc cang be mat be. Ta se at c ieu nay khi cho them xa phong vao nc. Nc tinh khiet khong co kha nang tao bot nhng nc co xa phong co kha nang tao bot rat tot. + Kha nang tao bot cua xa phong phu thuoc vao v tr va ban chat cua nhom phan cc, cau tao va chieu dai cua goc hydrocarbon va nong o cua xa phong. + Bot co y ngha ln trong cac nganh san xuat polimer, cu hoa, khoan, tuyen noi,... Trong qua trnh tay ra, bot cung gop1 phan quan trong trong viec tach va gi chat ban trong nc giat. f. Kha nang tao mixen: + Trong dung dch, xa phong co the ton tai dang phan t, ion hoac mixen. Mixen la tap hp cac phan t xa phong phan li hoac khong phan li. + Trong dung dch loang, xa phong ton tai dang phan t va ion. + Khi nong o xa phong at ti nong o ti han tao mixen ( NTM ) th trong he bat au tao ra kha nhieu mixen hnh cau. Trong mixen hnh cau, do lc hut Vanecvan ma cac goc hydrocarbon quay au vao nhau, con phan phan cc phan li th do tnh u nc va do lc ay tnh ien gia cac nhom phan cc cung dau nen quay ra ngoai. Mixen hnh cau co ien tch kha cao va ve mat cau tao giong mixen keo. Trong mixen cung co lp ien kep va moi mixen co khoang 50 phan t xa phong. ng knh cua mixen xap x 2 lan chieu dai phan t xa phong. Khoi lng phan t cua mixen co 12000 22000 vc.
Thac s Tran Kim Cng
Khoa hoa hoc
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+ Khi nong o xa phong cao hn th trong he se tao thanh mixen hnh tam va ien tch cua mixen hnh tam nho hn mixen hnh cau do s ien li giam khi nong o tang. + Ngi ta thay rang tai NTM cac tnh chat cua xa phong nh sc cang be mat, chiet suat, o nht, o dan ien ,... eu thay oi ot ngot do s co mat cua mixen. V vay, ta co the xac nh NTM da vao s thay oi ot ngot o khi khao sat 1 trong nhng tnh chat noi tren. + NTM co y ngha thc te ln v tai nong o o, theo Rebinia, kha nang tay ra cua xa phong la ln nhat. + Cac yeu to anh hng en NTM: - NTM giam khi khoi lng phan t cua xa phong tang v khi khoi lng phan t cua xa phong tang th o tan cua xa phong giam, do o xu hng tao mixen tang. - NTM giam khi giam nhiet o v khi giam nhiet o th chuyen ong Brao giam, do o xu hng tao mixen tang. - NTM giam khi them chat ien li vao he. V du: ngi ta hay them cac chat on nh natriclorua, natricarbonat, natrisilicat, natriphosphat,... vao xa phong e lam tang kha nang tao mixen cua xa phong. Khi them chat ien li vao xa phong th kha nang tao mi xen tang v kha nang hidrat hoa cua chat ien li lam tang nong o cua xa phong len va s co mat cua chat ien li lam giam kha nang ien li cua xa phong. +Trong moi trng dau, xa phong cung co kha nang tao mi xen nhng trong trng hp nay, cac phan t xa phong trong mixen se quay nhom phan cc vao trong va hng goc hydrocarbon khong phan cc ra ngoai. g. Kha nang hoa tan keo: + Nhieu chat hu c khong tan trong nc nh cac hydrocarbon thm, khong thm, cac pham mau kho tan,... nhng chung co kha nang hoa tan keo trong dung dch xa phong kha am ac tao thanh dung dch trong suot, ben vng nhiet ong hoc. + S hoa tan keo la qua trnh hoa tan cac chat hu c vao trong phan goc hydrocarbon cua mixen, luon luon co trong dung dch xa phong kha am ac. Ket qua cua s hoa tan keo la cac phan t chat ban nam trong mixen va kch thc mixen tang len. + Hien tng hoa tan keo co ng dung cc ky quan trong trong qua trnh tong hp cac polimer bang phng phap trung hp cac hydrocarbon khong no trong nhu tng e thu c cao su tong hp, chat deo tong hp, sn tong hp,... + Xa phong trong moi trng dau co kha nang hoa tan nc vao trong dau, o la qua trnh hoa tan keo nghch, co y ngha ln trong cong nghiep thc pham.
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+ Kha nang hoa tan keo phu thuoc vao v tr va ban chat cua nhom phan cc, chieu dai va cau tao cua goc hydrocarbon va nong o xa phong. h. Kha nang tay ra: + No tong hp tat ca cac tnh chat ac trng cua xa phong nh kha nang tham t, kha nang nhu hoa, kha nang hoa tan keo, kha nang tao bot,... + Ai cung biet rang giat quan ao va ra dung cu bang xa phong sach hn bang nc nguyen chat. + Kha nang tay ra cua xa phong lien quan en cac yeu to sau ay: - Xa phong lam giam sc cang be mat cua nc;v vay, dung dch xa phong de tham t vai si va ngam vao ben trong nhng ke h cua vai si (mao quan cua vai si), trong khi o nc nguyen chat kho ngam vao ben trong mao quan cua vai si v sc cang be mat cua nc cao. - Cac phan t xa phong hap phu len be mat vai si va be mat chat ban ran hay long tao thanh mot lp hap phu co kha nang hydrat hoa manh; do vay, tao ra mot ap suat che va lam cho cac hat chat ban de tach ra khoi be mat vai si roi chuyen vao dung dch xa phong dang huyen phu hay nhu tng. - Nhng mang hap phu tren be mat hat ban lam cho cac hat co o ben lien ket rat ln, can tr s lien ket chung lai vi nhau cung nh vi be mat vai si. - Dung dch xa phong de tao bot va v vay mot phan chat ban se tach vao bot, nhat la nhng hat ban co kha nang tham t kem se dnh vao cac hat bot giong nh qua trnh tuyen noi. - Kha nang tay ra cua xa phong ch co nong o ln NTM, chng to kha nang tay ra cua xa phong co lien quan en kha nang hoa tan keo cua chat ban dau m vao mixen. + Kha nang tay ra cua xa phong phu thuoc vao ban chat va v tr cua nhom phan cc, chieu dai va cau tao cua goc hydrocarbon, moi trng va nong o cua xa phong. - Ngi ta thay rang xa phong ma phan t co vong thm co kha nang tay ra ln hn v tnh hbm cao hn, co kha nang hoa tan keo ln hn, co kha nan g tao bot ln hn,... Trong xa phong va bot giat, ngi ta thng co them mot lng ang ke dodecylbenzensunfonatnatri e lam tang kha nang tay ra cua xa phong va bot giat. - Trong xa phong va bot giat, ngi ta cung co them mot chat natriclorua natricarbonat, natrisilicat, natriphotphat,.....e lam tang kha nang tao mixen, tnh hbm, kha nang tay ra, ...
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng Phan IV. HOA HOC POLIMER. CHNG XII. M AU.
I. nh ngha va mot so tnh chat c ly ac trng cua cac polimer:
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1. nh ngha: Polimer hay hp chat cao phan t la nhng hp chat co kch thc va khoi lng phan t cao, c cau tao t nhng mat xch ong eu, co tnh chat c ly ac trng khac vi nhng chat thap phan t .
2. Mot so tnh chat c ly ac trng: a. Cac tnh chat u viet: + Co kha nang bien dang an hoi thuan nghch; thng c dung lam nem, xam lop xe ap, xe may, o to, ...
+ Co o ben c hoc cao, lai t b mai mon, ben vi moi trng nen co the thay the kim loai va hp kim trong cac vat dung va trong cac chi tiet may. + Co tnh cach ien va cach nhiet tot nen co the dung lam vat lieu cach nhiet, cach ien. + Co tnh bam dnh cao nen co the dung lam keo dan go, thuy tinh, kim loai, ... + Co kha nang keo si, tao mang, khong tham nc nen co the dung lam t si e det vai, an li, ao i ma, ..., e lam sn, ... + Co ty trong nho hn nhieu kim loai va hp kim nen tien li cho viec s dung va chuyen ch. b. Nhc iem:
+ Kha nang chu nhiet khong cao nen ch s dung c trong mot khoang nhiet o nhat nh.
+ Mot so polimer co o ben c hoc khong cao. + Thng de b lao hoa do tac dung cua mot so yeu to ben ngoai nh oxi khong kh, anh sang, ... lam cho chung tr nen don, de ran nt kem pham chat.
Thac s Tran Kim Cng
Khoa hoa hoc
- 84 -
3. Nhng iem giong nhau va khac nhau gia polimer va chat thap phan t:
ai lng + Khoi lng phan t
Chat thap phan t Khoi lng phan t la 1 hang so, ac trng tng chat, v du: MgCl2 co khoi lng phan t la 95 vc.
Polimer Khoi lng phan t khong phai la hang so, ch la mot ai lng thong ke, co tnh chat trung bnh, v du cao su thien nhien co khoi lng phan t trung bnh la 100000 500000 vc. La ai lng thay oi, dung lam khai niem, co tnh chat thong ke, v du: Tnc (PE) la 120 121oC. Co the ton tai 2 trang thai ran long nhng khong ton tai trang thai hi v nhiet o phan huy nho hn nhiet o soi nen cha kp chuyen sang trang thai hi a b phan huy. Hoa tan rat cham, phai qua giai oan trng phong roi mi en giai oan hoa tan. Khong bao gi co hien tng ca phan t tham gia phan ng ma tng oan mach phan t phan ng oc lap.
+ Tnc,T
La mot ai lng co nh, v du: Tnc,T cua nc la 0oC. Co the ton tai ca 3 trang thai: kh, long, ran.
+ Trang thai tap hp
+ S hoa tan trong dung moi thch hp + Kha nang phan ng
Hoa tan nhanh.
Thng tng phan t phan ng.
II. Phan loai polimer:
1. Phan loai theo nguon goc:
+ Polimer thien nhien: la polimer co san trong thien nhien nh cao su thien nhien, xenluloz, tinh bot, ... + Polimer nhan tao: la polimer c bien tnh t polimer thien nhien nh axetatxenlu-loz, nitroxenluloz, si len, si visco, ... + Polimer tong hp: la polimer c tao ra nh tong hp t nhng hp chat thap phan t bang phan ng trung hp va phan ng trung ngng nh PVC, PP, PE , t nilon, ...
2. Phan loai theo thanh phan hoa hoc:
+ Mach carbon.
Thac s Tran Kim Cng
Khoa hoa hoc
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+ D mach. + C kim.
3. Phan loai theo hnh dang mach:
+ Mach thang. + Mach phan nhanh. + Mach khong gian (mang li khong gian).
4. Phan loai theo tnh chat nhiet:
+ Polimer nhiet deo nh PE, PP, PVC, ... co the gia cong c bang nhiet (u viet cua loai nay). + Polimer nhiet ran nh PF (nha phenolformaldehit), UF ( nha ureaformaldehit), ... co cau tao mang li khong gian.
Nha nhiet ran khac vi nha nhiet deo la nha nhiet ran khi nhiet o tang th co phan ng va khong b mem nen khong gia cong c bang nhiet.
III. Mot so polimer tieu bieu:
Hien nay, ngi ta a khai thac va tong hp ra hang trieu polimer khac nhau nhng tren thc te ngi ta mi s dung rong rai ch mot so khong ln cac polimer.
1. Cac chat deo trung hp: a. Polietylen (PE):
+ Phng trnh phan ng trung hp: nCH2=CH2 ( -CH2-CH2-)n + PE c tong hp bang hai phng phap sau: - Trung hp goc (xuc tac la chat tao ra goc t do) nhiet o c 100 130oC, polimer thu c co khoi lng phan t trung bnh t 1000 2000 vc, thuoc loai polimer tinh the, co nhiet o nong chay thap. - Trung hp ion vi he xuc tac la TiCl4+Al(CH3)3 thu c polimer co tnh nang c ly tot hn. + Tnh tan: nhiet o phong no khong tan trong bat ky dung moi nao nhng nhiet o tren 70oC no tan c trong tetracloruacarbon, toluen, xylen, ... + No tr vi moi trng hoa hoc, co kha nang chong am cao, cach ien tot. + ng dung: lam vat lieu cach ien, chat bao quan chong an mon hoa hoc, bao goi, lam si, ... + Nhc iem: nhiet o nong chay thap nen khong chu nhiet, kha nang chong bc xa nhat la bc xa t ngoai rat kem nen rat de b lao hoa theo thi gian (mach de b t ra di tac dung cua anh sang).
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng b. Polivinylclorua (PVC):
- 86 -
+ Phng trnh phan ng trung hp:

n CH2=CH Cl CH 2 CH Cl n
+ PVC c tong hp bang phng phap trung hp goc, no thuoc loai polimer vo nh hnh, co Tg = 80oC (Tg la nhiet o ma tai o he chuyen t trang thai ran sang trang thai co gian) . + Tnh tan: PVC la polimer phan cc nen no tan tot trong mot so dung moi phan cc nh cloroform, ... nhng toc o tan cham. + Tnh nang: o ben c hoc thap hn PE nhng an hoi hn. + ng dung: lam mang cng, keo si, vai i ma, ong dan nc, ban chai, ... c. Polipropylen (PP): + Phng trnh phan ng trung hp:
n CH 2=CH CH3 CH 2 CH CH3 n
+ PP c tong hp bang phng phap trung hp ion vi he xuc tac TiCl3+(C2H5)3Al ap suat 1 3atm; PP nhan c la polimer tinh the, co cau tao lap the ieu hoa, co nhiet o nong chay trung bnh la 180 182oC, co kha nang chong am cao, co tnh nh hng nen co kha nang tao mang dung lam sn cach ien, keo si, lam ong dan, bnh ac qui, ... Co nhieu u iem hn PE nhng gia thanh cao hn PE nen t c s dung hn PE (ch s dung khi can thiet). d. Polistyren: + Phng trnh phan ng trung hp:
n CH 2=CH CH 2 CH n
+ Polistryren c tong hp bang phng phap trung hp goc; no thuoc loai polimer vo nh hnh, co Tg la 80oC. + Tan c trong dung moi hu c khong phan cc, nhat la dung moi co vong thm nh benzen, xylen, ... ngay nhiet o thng. + Mach cng, gion, co tnh cach ien, cach nhiet tot, o ben nhiet va c yeu. + Cong dung: dung lam bao b cho cac may moc, linh kien ien t, lam cac thiet b chu lanh, lam vat cach am, ...
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng e. Polimetylmetacrylat(con goi la thuy tinh hu c):
- 87 -
+ Phng trnh phan ng trung hp:

CH3 n CH2=C COOCH3 CH3 CH2 C n COOCH3
+ Polimetylmetacrylat c tong hp bang phng phap trung hp goc; no thuoc loai polimer vo nh hnh, co Tg la 98oC. + No tan c trong dung moi hu c phan cc. + No trong nh thuy tinh, o ben c hoc tng t nh kim loai, ben vi moi trng kh quyen c dung lam knh oto, may bay, c dung lam sn nc, ... f. Polivinylacetat (PVA): + Phng trnh phan ng trung hp:
n CH2=CH OOCCH3 CH2 CH n OOCCH3
+ PVA c tong hp bang phng phap trung hp goc. + No tan c trong dung moi hu c phan cc, co the tao mang nen co the dung lam sn va keo dan, co the keo si, ... Loai nguyen thuy t c dung, thng dung dang bien tnh la:
CH 2 CH CH2 CH OOCCH3
+ n NaOH n - nCH COONa 3 OOCCH3
CH2
CH CH2 CH OOCCH3 OH
Polivinylacetat a c bien tnh co tnh bam dnh cao nen c dung lam keo dan. ay la mot loai keo dan rat ac trng e dan da, dan kimloai, ... g. Poliacrilnitril: + Phng trnh phan ng trung hp:
n CH 2=CH CN CH2 CH CN n
+ No c tong hp bang phng phap trung hp goc; no thuoc loai polimer tinh the, co nhiet o nong chay trung bnh la 200oC; no tan c trong dung moi hu c phan cc nhiet o cao. + ng dung: keo si va ong trung hp vi 1,3-butadien e lam cao su tong hp. h. Teflon: + Phng trnh phan ng trung hp: nCF2=CF2 (-CF2-CF2-)n
Thac s Tran Kim Cng
Khoa hoa hoc
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+ No c tong hp bang phng phap trung hp goc; no thuoc loai polimer tinh the, co nhiet o nong chay trung bnh la 340oC; no khong tan trong bat ky dung moi nao; no chu lanh, chu nhiet tot ( -80oC 300oC), co o ben c hoc cao, chu c nhng va cham manh, rat cng, cng hn ca kim loai. + o ben hoa hoc: no rat tr, vi moi trng co tnh oxi hoa manh no van tr, ben hn ca vang va thuy tinh. Vi nhng u iem neu tren, teflon c goi la niem t hao cua polimer. + Nhc iem duy nhat cua teflon la co o ben phong xa yeu, nhat la cac tia , , . Khi b tac ong cua tia phong xa th mach cua teflon b t ra, de b lao hoa. + ng dung: dung e lam vat lieu qu, dung e che tao cac chi tiet ac biet trong may moc , nhat la trong ky nghe hang khong.
2. Cac nha trung ngng: a. Nha phenolformaldehit:
+ Phng trnh phan ng trung ngng tao thanh nha phenolformaldehit mach thang (nha novolac):
OH
OH
+ n CH2O
-n H2O
CH2
+ Neu lay ty le 1:2 ve so mol cua phenol va formaldehit va xuc tac acid th ta se thu c polimer mach thang (nha novolac) co ac iem de nong chay, de hoa tan, nhat la trong formaldehit. + Neu lay ty le ve so mol cua phenol va formaldehit la nho hn 1:2 va vi xuc tac la kiem th se thu c nha co cau truc mang li khong gian (nha rezolic) nh sau:
OH CH 2 CH2 OH
CH 2 OH CH2 CH2 OH CH2 CH2
Thng nha novolac khong ben de chuyen sang nha rezolic. + Tnh chat: ben vi moi trng vi sinh; khi b phan huy co tnh bam dnh cao vi kim loai, go, da, thuy tinh. Nhc iem: don nen han che trong viec s dung.
Thac s Tran Kim Cng
Khoa hoa hoc
- 89 -
+ ng dung: - Dung lam keo dan. - Da vao tnh oc e chong mot so moi mot. - Dung e san xuat cac loai chat deo lp, v du: cho giay, vai tam nha bakelit (ten chung cua hai loai nha tren) roi ep thanh tam. Nhng tam nay co o ben c hoc cao, co kha nang cach nhiet tot. - Dung lam cot ep. - Dung lam nguyen lieu cho mc but bi. b. Nha ureaformaldehit: + Phng trnh phan ng tao ra monome t urea va formaldehit:
+ Ngng tu trc tiep gia urea va formaldehit vi xuc tac acid, ta thu c nha ureaformaldehit . Phan ng tao ra nha mach thang nh sau:
n H 2N C O NH 2
+
nCH 2O
H NH C O
NH CH 2
OH
(n-1) H 2O
Neu d CH2O th cho ra polimer mach khong gian nh sau:
+ Nha ureaformaldehit co cau truc mang li khong gian co nhiet o nong chay rat cao, nhng kha nang hoa tan kem, khong mau. No de dang cho viec nhuom mau nen c dung lam cac o vat can trang tr. Nha ureaformaldehit co tnh bam dnh cao nen c dung lam keo dan go, san xuat lp chat deo, lam cot ep.
3. T si hoa hoc: Ngi ta ieu che t si hoa hoc (t si nhan tao va t si tong hp) nh sau:
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng a. T si tong hp:
- 90 -
Thng c ieu che nh phng phap trung hp hoac trung ngng cac monomer. Polimer dung lam t si loai nay thng la poliamid, poliester va poliacrilnitril. Sau ay ta se xet hai loai t si tong hp la poliamid va poliester: + Poliamid: ngi ta thng tong hp poliamid bang phan ng trung ngng gia acid dicarboxylic va hp chat diamin.
T nilon-6,6 ( iem nong chay la 255oC )

+ Poliester: ngi ta thng tong hp poliester bang phan ng gia ankandiol va acid dicarboxylic.
Poliester (iem nong chay la 220oC 222oC)
+ Hai loai polimer tren thuoc loai polimer tinh the, hau nh khong tan trong dung moi hu c. + So sanh hai loai polimer tren th poliester co nhieu u iem hn nen chung c dung lam len tong hp. b. T si nhan tao:
Bien tnh mot so polimer thien nhien ta co the thu c t si nhan tao, v du: t visco t xenluloz, ... 4. Cao su tong hp: a. Cao su butadien:
+ No c tong hp bang phng phap trung hp khoi butadien vi viec dung xuc tac natri (phng phap Lebeep c cao su buna). Hien nay, ngi ta ieu che cao su butadien bang phng phap trung hp goc nhu tng vi viec dung chat khi mao peoxit, diazo hay trung hp nhiet o thap vi s co mat cua BF3. Phan ng trung hp co the trung hp 1,4 va 1,2. Tuy theo ieu kien phan ng ma polimer thu c loai nao chiem u the hn. + Cao su butadien c dung lam sam lop oto, xe may, ..., giay va cac mat hang cao su khac, ngoai ra con c dung e san xuat nha ebonit. + Copolimer cua butadien vi styren va acrilnitril la nhng loai cao su tong hp thong dung nhat.
- 91 -
- Khi a them styren vao phan t polibutadien th lam cho tnh chat cua cao su tong hp phan nao giong vi cao su thien nhien nhng o trng trong cac dau khoang va o tham nc thap hn nhieu so vi cao su thien nhien. No b lao hoa rat cham va tnh an hoi con gi c nhiet o thap. Nhc iem cua no la kho uon gap va khong dan c. - Khi a them acrilnitril vao phan t polibutadien th kha nang trng cua cao su trong dau m va cac san pham dau mo giam i mot cach ang ke. Cao su butadien -acrilnitril c s dung e san xuat ra cac san pham chu xang dau va dung lam bao phu chong an mon trong cong nghiep hoa hoc. b. Cao su isopren: + No c tong hp bang cach trung hp nhu tng isopren khi co mat cua chat khi mao la cac peoxyt hoac hp chat diazo. + Ve tnh chat cao su isopren tong hp nh tren khac han vi cao su thien nhien. No khong ket tinh c du la lam lanh hay keo cang va ch so c ly thap. ieu nay c giai thch bang cau truc khong ieu hoa cua mach phan t polimer. Qua nghien cu, ngi ta thay rang cac mat xch c s trong cao su isopren tong hp ket hp vi nhau theo kieu trans -1,4, cis-1,2 va cis 1,4 nh H.XII.1. + Gan ay, ngi ta a tong hp c cao su cis -1,4-poliisopren ieu hoa lap the co khoi lng phan t len en 2 trieu vc, ve cau truc va tnh chat rat giong cao su thien nhien. + Copolimer cua isopren va isobutylen c goi la cao su butyl, co mot tam quan trong to ln trong ky thuat. No tan c trong hydrocarbon mach thang. o tham kh cua cao su butyl nho hn cao su thien nhien t 1020 lan; v vay, cao su butyl c dung san xuat cac loai thanh pham khong tham kh.
H.XII.1
5. Cac polimer thien nhien: a. Xenluloz:
+ Cong thc phan t cua xenluloz la (C6H10O5)n. Trong mot mat xch cua no co 3
Thac s Tran Kim Cng
Khoa hoa hoc
- 92 -
+ Muon chuyen xenluloz thanh si nhan tao th phai hoa tan xenluloz vao kiem vi s co mat cua CS2, phan ng xay ra nh sau:
Giai oan nay nham muc ch dung NaOH e cat ngan mach lai e cho mach mem mai hn va de tham t hn. Sau o, ngi ta ket tua dung dch thu c bang H2SO4 theo s o sau:
+ e tang tnh nang s dung, ngi ta con bien tnh xenluloz bang cach cho xenluloz tac dung vi acid acetic hoac acid nitric e tao ra cac acetatxenluloz va nitratxenluloz. V du:[C6H7O2(OH)3]n + nCH3COOH [C6H7O2(OH)2OOCCH3]n + nH2O. (monoacetatxenluloz) Co the the 1, 2 hoac ca 3 nhom -OH trong 1 mat xch bang 1, 2 hoac 3 goc acetat hoac goc nitrat e tao ra cac san pham mono, i hoac tri acetat hoac nitratxenluloz. Acetatxenluloz la mot loai si co o ben c ly cao, trong suot, c dung lam chat deo. Nitrat xenluloz la mot chat no co sc cong pha ln nen c dung lam chat no; no con c dung lam phim, sn bong co o ben anh sang tot. b. Cao su thien nhien: + o la cao su isopren, co cau tao nh sau:
CH3 C C CH2 CH2 CH2 H CH3 C C CH2 H
, co cau tao lap the ieu hoa dang cis -1,4.
+ Khoi lng phan t trung bnh cua cao su thien nhien t 100.000 500.000 vc. Gia tr cua khoi lng phan t trung bnh phu thuoc vao cay trong.
- 93 -
+ Tnh chat c ly: hien nay, cha co 1 loai cao su tong hp nao co the so sanh c vi cao su thien nhien v no chu c o mai mon tot, co tnh an hoi cao, co kha nang bam dnh cao. Qua trnh lu hoa cao su xay ra de dang, ty trong thap, tng oi ben vi moi trng va gia thanh khong cao lam. + Ngoai cao su nguyen chat, con co cac loai cao su bien tnh sau: - Cao su clorohoa: ( -C10H11Cl7-)n, c ieu che t cao su thien nhien. ng dung: trong cac loai cao su bien tnh, cao su cloro hoa chiem mot v tr quan trong. Cong dung ln nhat cua no la e san xuat ra mot loai sn chu c nc bien, khong thay the c. Ngoai ra, no con c dung lam o gia da, mc in, vat lieu cach ien, chu c mt hoa chat. - Cao su hydroclorohoa: (-C5H9Cl-)n, c tong hp t cao su thien nhien bang cach cho cao su thien nhien tac dung vi HCl khan trong he dung moi gom C6H6 va CHCl3 10oC. Tnh nang: la loai cao su chu c moi trng acid cao, co kha nang an hoi tng oi tot trong khoang nhiet o t 80 en 100oC, cao su hidroclorohoa tr nen mem co kha nang tao mang mong, co the thay the PE. Ngoai ra, no con c s dung lam vat lieu cach ien. - Cao su ong vong: la san pham cua s vong hoa cao su thien nhien, c hai mat xch isopren tao thanh mot vong (xem H.XII.2).
Tnh nang: no ben vi moi trng hoa chat, co kha nang tao mang mong rat tot, co tnh an hoi cao, thng c dung e bao boc cac vat lieu sac canh va s dung rong rai lam keo dan kim loai do co o bam dnh rat cao. - Cao su epoxi: no c tong hp bang cach oxi hoa noi oi cua cao su thien nhien bang oxi khong kh, phan ng o nh sau:
Tnh nang: co kha nang bam dnh cao nen c dung lam keo dan, nha dan va chat deo hoa.
Thac s Tran Kim Cng
Khoa hoa hoc
- 94 -
- Cao su bien tnh bang cach ong trung hp vi cac loai khac, v du CH2 = CH CN, CH2 = C(CH3)COOCH3, CH2= CH - C6H5, ... e lam thay oi nhng tnh chat cua cao su.
Thac s Tran Kim Cng
Khoa hoa hoc
- 95 -
CHNG XIII. TONG HP POLIMER BANG PHAN NG TRUNG
HP.
I. Mot so khai niem:
1. nh ngha phan ng trung hp:
La qua trnh nhieu phan t nho ket hp vi nhau e tao thanh nhng phan t ln hn va khong co s tach cac san pham phu.
2. Phan loai phan ng trung hp: Tuy thuoc vao cau tao cua monomer va tac nhan khi mao cho phan ng trung hp ma ta co the co cac loai phan ng trung hp khac nhau sau ay:
+ Neu co phan t A-B co kha nang phan li ong li nh sau: A-B A +B , moi phan t cha 1e t do, th ta co phan ng trung hp goc. + Neu co phan t A-B phan li d li nh sau: A-BA++ B- th ta co phan ng trung hp ion. - Neu A+ hoat ong hn B- th ta co phan ng trung hp cation. - Ngc lai, neu B- hoat ong hn A+ th ta co phan ng trung hp anion.
3. ac iem chung cua cac monomer tham gia phan ng trung hp la:
Trong phan t cua chung phai co lien ket boi hoac lien ket mach vong khong ben.
II. Tong hp polimer bang phng phap trung hp goc:
1. Goc t do:
Muon co phan ng trung hp goc phai co goc t do. a. nh ngha goc t do: La nguyen t hay nhom nguyen t cha 1e khong co cap (e oc than) qu ao ngoai cung cua mnh. b. Cac phng phap tao ra goc t do: + Goc t do c tao thanh do s phan li ong li cua cac hp chat cha cac lien ket khong ben nh -O-O-, -O-S,
Thac s Tran Kim Cng
Khoa hoa hoc
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+ Goc t do c hnh thanh la do tac dung cua anh sang (khi mao quang hoa).
hv V du: C6H5-CH=CH2 C6H5 +CH2=CH
+ Dung tia co tan so cao (, , , (tia phong xa)).

tpx V du: CCl 4 CCl 3 + Cl .
+ Dung cac chat oxihoa-kh . V du: Fe 2+ + H 2 O2 HO + HO + Fe 3+ .

c. Tnh chat cua goc t do:
V du: C2H 5 + Co kha nang ket hp: 2C2H 5 C4H10. + Co kha nang phan li: 2C2H 5 C2H6 + C2H4.
+ Co kha nang chuyen mach: C2H 5 + S C2H5S , trong o S la phan t khac.
2. Nhiet ong hoc cua phan ng trung hp goc:
Nh ta a biet trong nhiet ong hoa hoc, muon 1 phan ng hoa hoc xay ra th
G = H -TS < 0.
+ Neu H >0, S < 0 th G >0, tc la phan ng khong xay ra bat k nhiet o nao (Gp > GM, xem H.XIII.1). + Neu H< 0, S >0 th G< 0, tc la phan ng xay ra moi nhiet o (xem H.XIII.2). + Neu H >0 (phan ng thu nhiet), S >0 th muon G< 0 th TS >H => T > S , co ngha la phan ng phai c tien hanh nhiet o cao (T >Tth) va nhiet
o cang cao th cang thuan li v phan ng thu nhiet (xem H.XIII.3).
+ Neu H< 0 (phan ng toa nhiet), S< 0 th muon phan ng xay ra th H<TS => T< S , tc la phan ng xay ra nhiet o thap (T<Tth, xem H.XIII.4).
Thac s Tran Kim Cng
Khoa hoa hoc
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3. C che va ong hoc cua phan ng trung hp goc: Phan ng trung hp noi chung va phan ng trung goc noi rieng la phan ng day chuyen xay ra theo 3 giai oan: giai oan khi mao, giai oan phat trien mach va giai oan ngat mach. Sau ay la c che va ong hoc cua cac giai oan o cua phan ng trung hp goc: a. Giai oan khi mao:
km R-R(xuc tac) 2 R (cham, quyet nh)
R + M 2 R1 (nhanh)
vk = kk . f.C (XIII-1), trong o: f bang ty so gia nong o goc t do tham gia phan ng vi M va tong nong o goc t do sinh ra va f co gia tr t 0,3 en 1, c xac nh bang thc nghiem khi phan tch so manh cua goc t do trong polimer, C la nong o cua xuc tac (chat khi mao). V du: xet phan ng trung hp styren, khi mao bang peoxitbenzoyl, ta co: C6H5COO-OOCC6H5
,k k t 2C 6 H 5 COO
o
C 6 H 5 COO + CH2=CH
k1
C6H5COO-CH2-CH C6H5
C6H5 b. Giai oan phat trien mach:
Bao gom hang loat cac bc cong monomer vao trung tam phan ng nh sau:
k2 R2 R1 + M k3 R3 R2 + M
------------------------kn Rn Rn 1 + M
Sau moi bc eu tao ra 1 goc t do mi co kha nang phan ng nh goc cu nhng ln hn goc cu 1 nhom monomer.
Thac s Tran Kim Cng
Khoa hoa hoc
- 98 -
-------------------------------------------------------------
Neu gia thiet rang sau mot thi gian phan ng vp khong oi, tc la khong phu = R3 =...= Rn = R va ta thuoc vao o dai cua goc t do tao thanh, th khi o R1 = R2 co: vp=kp. R .M (XIII-2). c. Giai oan ngat mach: Co the xay ra theo 2 c che sau ay:
ng + Rm R n + Rm + Ngat mach bat can oi: Rn
E = 2 5 kcal/mol .
ng + Ngat mach tai ket hp: Rn + Rm Rn-Rm
E = 0 4 kcal/mol . Ca hai trng hp eu co: vng = kng. R 2 (XIII-3).

Nh vay, 2 phan ng tren eu la phan ng bac 2, co s tham gia cua 2 goc; E cua 2 kieu ngat mach tren khac nhau rat t nen trong thc te xay ra ong thi theo ca 2 kieu. Nhiem vu cua ta bay gi la xac nh toc o phan ng (vp). Muon vay, ta phai xet phan ng trang thai dng ng vi nong o cua chat trung gian khong oi , tc la co bao nhieu goc t do c hnh thanh nh phan ng khi mao th cung co bay nhieu goc t do b mat i do phan ng ngat mach, tc la vk = vng va khi o vpu = vp =kp.M. R (XIII-4). Ngi ta tm R qua bieu thc sau:
vng = vk hay kk.f.C = kng R
k k . f.C => R = k ng
1/ 2
Thac s Tran Kim Cng
Khoa hoa hoc

f. k k => vp = kp k ng
1/ 2
- 99 -
.M.C1/2 = K.M.C1/2 (XIII-5).
Bieu thc (XIII-5) thng ch ap dung cho trng hp o chuyen hoa thap. Nhan xet: Toc o phan ng phu thuoc bac nhat vao nong o monomer, bac 1/2 nong o chat khi mao va phu thuoc vao nhiet o qua K, trong a so cac trng hp nhiet o tang th toc o phan ng tang. 4. o trung hp ( P ):
+ nh ngha: la so nhom monomer trung bnh co trong mot mach polimer. + Bieu thc tnh P : P =
vp v ng
1/ 2
(XIII-6), trang thai dng th vng=vk nen P =
vp vk
Ta co: P =
kp (k k . k ng . f )
M M = K '. 1/ 2 (XIII-7). 1/ 2 C C
+ Nhan xet: o trung hp ty le thuan vi nong o monomer, tc la khi nong o monomer tang th khoi lng phan t cua polimer tang, o trung hp ty le nghch vi C1/2, tc la o trung hp giam khi tang nong o chat khi mao, trong khi o toc o phan ng lai tang. Do vay, muon cho phan ng xay ra vi toc o ln va co o trung hp ln th phai chon ieu kien toi u ve nong o chat khi mao. Trong a so cac trng hp ngi ta chon C/M <1/1000, co vay mi am bao yeu cau tren.
+ o th bieu dien s phu thuoc cua toc o phan ng va o trung hp vao nong o monomer va nong o xuc tac c ch ra tren H.XIII.5 va H.XIII.6.
+ Anh hng cua nhiet o: tr phng phap khi mao quang hoa va tia phong xa, con lai cac phng phap khi mao khac khi nhiet o tang th o trung hp giam, lam cho khoi lng phan t cua polimer b giam mac du toc o phan ng tang. Do vay, ta can phai chon ieu kien toi u cho phan ng ve nhiet o.
5. Chat lam chuyen mach, chat lam cham va chat c che:
Trong nhieu trng hp, ngoai 3 giai oan chnh tren cua phan ng trung hp la giai oan khi mao, phat trien mach va ngat mach, con co giai oan chuyen mach. Noi chung, qua trnh chuyen mach ch co anh hng en khoi lng phan t cua polimer.
Thac s Tran Kim Cng
Khoa hoa hoc
- 100 -
Xet phan ng trung hp, trong o trung tam phan ng la Rn va co chat AX (co the la dung moi hoac monomer hoac polimer, ...), neu Rn co u kha nang lam t lien ket A-X th chung ta nhan c mot goc mi theo phan ng nh sau: Rn + A-X Rn-X + A (phan ng chuyen mach).
Tuy theo tnh chat cua goc A mi sinh ra ma ngi ta chia chat A-X thanh mot trong nhng loai chat sau: + Chat chuyen mach thong thng (con goi la chat ieu chnh) nh CCl4, C2H4Cl2, ..., cac mercaptan nh amylmercaptan, tert-butylmercaptan, ...
+ Chat lam chat cham: lam cho phan ng b cham lai-o la trng hp goc A kem . hoat ong hn Rn + Chat c che: lam cho phan ng b ngng hoan toan-o la trng hp goc A khong hoat ong.
Chat c che ong mot vai tro rat quan trong trong thc te, thng dung e bao quan monomer, chong lao hoa polimer, ...
V du: do anh hng cua anh sang, oxi khong kh co kha nang khuech tan vao mach polimer tao ra cac peoxit lam sinh ra goc t do va v vay, lam cat mach polimer. o la nguyen nhan lam cho dep nha, vai i ma, ... cng va gion sau mot thi gian s dung (s lao hoa). Do vay, cong nghiep chong lao hoa ang phat trien rat manh.
6. ong trung hp goc:
+ La phan ng trung hp goc gia cac monomer khac nhau, san pham cua qua trnh trung hp la copolimer hay polimer ong trung hp. +V du: cao su tong hp co tnh chu xang dau rat kem, con polivinylcianua (poliacrylnitril) rat tr vi moi trng xang dau; v vay, neu ta tien hanh ong trung hp butadien vi acrylnitril th ta se nhan c nhng copolimer co kha nang chu xang dau rat tot. + Khi ta tien hanh ong trung hp 2 monomer M1va M2 th ta thu c copolimer cua M1 va M2. Neu thay oi thanh phan cua M1 va M2 trong hon hp phan ng th ta se nhan c hang loat copolimer co nhng tnh chat rat khac nhau. + Hien nay, copolimer c s dung rong rai trong cong nghiep. Bang phng phap ong trung hp, ngi ta a che tao ra nhng vat lieu polimer co tnh nang s dung tuy theo y muon cua con ngi.
III. Tong hp polimer bang phng phap trung hp cation:
1. Chat xuc tac:
Co the dung mot so chat xuc tac chu yeu sau ay:
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng a. Xuc tac acid Areniuyt (cha proton):
- 101 -
V du nh H2SO4, HClO4, chung de khi mao cho phan ng trung hp cation.
Vi ieu kien la cac anion cua acid phai kem hoat ong, tc la o ai nhan khong cao; do vay, cac acid halogenhidric t khi c dung lam xuc tac cho phan ng trung hp cation.
Tren thc te, acid Areniuyt khong c dung nhieu v polimer thu c co khoi lng phan t khong cao (ch c vai nghn vc). b. Xuc tac acid Liuyt:
La nhng chat co kha nang nhan cap e nh cac muoi halogenua cua bo, nhom, thiec, titan, ... Qua thc te, ngi ta thay rang muon cho phan ng trung hp cation xay ra th ngoai xuc tac acid Liuyt con phai dung them chat ong xuc tac baz Liuyt, v du nh amoniac, nc, ru, ... e khi tham gia phan ng khi mao th chat ong xuc tac tng tac vi chat xuc tac. V du: AlCl3 + C2H5OH H+[AlCl3C2H5O]cap ion H+ + [AlCl3C2H5O]ion acid Liuyt baz Liuyt
Tuy theo moi trng phan ng ma cac phc tren co the ton tai dang cap ion hay ion. Moi trng cang phan cc th can bang chuyen dch sang dang ion cang ln. c. Mot so chat xuc tac khac: + Khi cho acid Liuyt tng tac vi cac ankylhalogenua th cac san pham thu c cung co kha nang khi mao cho phan ng trung hp cation. V du: R-Cl + TiCl3 + (C6H5)3C-Cl + 2I2
I+ + I 3
R+[TiCl4]-
(C6H5)3C+ + Cl-
2. C che va ong hoc cua phan ng trung hp cation:
Phan ng trung hp cation noi rieng va ion noi chung co nhieu yeu to anh hng en toc o phan ng. Do vay, chung ta kho co the a ra 1 s o phan ng ve c che cung nh ong hoc that chnh xac. Moi khi viet phan ng phai neu ro cac ieu kien xay ra, bi v nhng ieu kien khac nhau th c che va ong hoc cua phan ng cung khac nhau. Trong trng hp n gian nhat, phan ng trung hp cation bao gom 3 giai oan nh nhng phan ng trung hp khac- o la giai oan khi mao, phat trien mach va ngat mach. V du: xet phan ng trung hp day vinyl co cong thc chung la CH2=CH-X ( X la nhom ay e ) vi xuc tac la SnCl4/H2O, ta co:
- 102 -
SnCl4 + H2O
H+[SnCl4OH]+ cap ion
H+ + [SnCl4OH]- ( cham ) ion
Xuc tac co the ton tai dang cap ion hay ion; do vay, chung ta phai xet ca hai trng hp sau: + Trng hp 1: phan ng xay ra tren cap ion. + Trng hp 2: phan ng xay ra tren ion. a. Xet trng hp 1: Phan ng xay ra tren cap ion.
i. Giai oan khi mao: xuc tac tan cong vao monomer tao nen trung tam
phan ng la cation hu c (ion carboni hay carbocation) nh sau:
ii. Giai oan phat trien mach: cap ion mi sinh ra phan ng vi monomer
tao nen mot chuoi phan ng phat trien mach.
iii. Giai oan ngat mach: co nhieu kieu ngat mach khac nhau nh sau:
+ Kieu ngat mach t ong: do mot tng tac nao o lam cho cac ion dng va am tach ra khoi nhau thanh phan t trung hoa va chat xuc tac c tach ra.
+ Kieu tach proton:
+ Kieu chuyen mach:
Thac s Tran Kim Cng
Khoa hoa hoc
- 103 -
Neu ngat mach theo kieu th 1 va th 2 (thng xay ra hn) th vng=kng.R (XIII10); con neu ngat mach theo kieu th 3 th vng=kng.R.M (XIII-11). Ta xac nh toc o phan ng vi gia thiet la phan ng trang thai dng, tc la vk = vng hay kk.f.Cxt =kng. R va khi o vp = vp = kp.M. R , ta suy ra: vp =
k k .k p.f k ng . M. C xt = K. M. C xt (XIII-12). ay la phng trnh ong hoc cua
phan ng trung hp cation theo c che cap ion trong trng hp n gian nhat. Nh vay, toc o phan ng phu thuoc vao nong o monomer, nong o chat xuc tac va nhiet o. o trung hp P =
vp v ng = kp k ng M (XIII-13). Nh vay, o trung hp phu thuoc vao
nong o monomer va nhiet o nhng khong phu thuoc vao nong o chat xuc tac. b. Xet trng hp 2: Phan ng xay ra tren ion.
i. Giai oan khi mao:
ii. Giai oan phat trien mach:
--------------------------------------------------------
vp = kp.M.R (XIII-15).
iii. Giai oan ngat mach:
Thac s Tran Kim Cng
Khoa hoa hoc
- 104 -
trang thai dng, vp =vp=
k p.kk .f k ng
. M = K. M (XIII-17) va P =
kp k ng
M (XIII-18). C xt
Nh vay, toc o phan ng phu thuoc vao nong o monomer, nhiet o nhng khong phu thuoc vao nong o chat xuc tac; con o trung hp ty le thuan vi nong o monomer, ty le nghch vi nong o chat xuc tac va phu thuoc vao nhiet o.
IV. Tong hp polimer bang phng phap trung hp anion:
Trung tam phan ng cua phan ng trung hp anion la nhng anion hu c (carbanion). Nhng monomer co kha nang tham gia phan ng trung hp anion la cac monomer thuoc day vinyl CH2=CH-Y vi Y la nhom hut e, thng xuat hien cac hp chat co lien ket nh sau: -NN, C=O, nhng hp chat d vong, 1. Chat xuc tac:
+ Cac amid cua kimloai kiem (MNH2). V du: KNH2 /NH3 long, KNH2
K++ NH 2 NH 2 se khi mao cho phan ng trung hp anion. Xuc tac loai amid cua kimloai kiem thng dung cho phan ng trung hp anion theo c che ion.
+ Cac hp chat c kim cua cac kim loai kiem, v du: metylkali, butylkali, etylnatri, ... V du: C2H5Na Na+ C2H5cap ion Cap ion nay se khi mao cho phan ng trung hp aniontheo c che cap ion. + Xuc tac Xigle-Natta: la phc he cua cac hp chat c kim nhom I, III vi nhng clorua kimloai thuoc nhom IV, VIII, trong o he xuc tac c kim cua nhom va clorua Titan c s dung nhieu nhat. V du:
Cl Cl Ti Cl C2H5
TiCl 3
(C2H5) 3Al
Al
C2H5 C2H5
Phc nay se khi mao cho phan ng trung hp anion.
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 2. C che va ong hoc cua phan ng trung hp anion:
- 105 -
Tuy theo chat xuc tac s dung ma ta co cac loai phan ng trung hp anion theo c che ion, cap ion hay phoi tr. a. Phan ng trung hp anion theo c che ion: Xet phan ng trung hp day vinyl (CH2=CH-Y, trong o Y la nhom hut e) vi xuc tac NaNH2 va dung moi la NH3.

NaNH2 (trong NH3) Na++ NH 2 ( nhanh)
Dung moi NH3 co kha nang sonvat hoa rat manh , lam cho NaNH2 phan li ra ion va ton tai dang ion . Kha nang phan li cua NaNH2 c ac trng bang hang so can bang K va K=
[ Na + ][ NH 2 ] , trong o NH 2 se khi mao cho phan ng trung hp anion. [ NaNH 2 ]
vk = kk [ NH 2 ]. M = k k .
K.[ NaNH 2 ] . M (XIII-19) [ Na + ]
--------------------------------------------------------------------------------
ai phan t ang phat trien. ac iem cua chung la co tnh hoat ong rat cao nhng lai tng oi on nh. Do o, trong nhieu trng hp phan ng co the xay ra en cung khi khong con monomer na neu nh trong he khong co tap chat co kha nang lam ngat mach. Ket qua la ta nhan c polimer con cha cac trung tam hoat ong, tc la van con co kha nang khi mao cho phan ng trung hp khac. Cac polimer o goi la cac polimer "song". Do o, giai oan ngat mach, a so cac trng hp khong xay ra va khi o vng = 0 va vp = vp =kp.M.R- (XIII-21).
iii. Giai oan ngat mach: c thc hien nh s tham gia cua cac carbanion
- 106 -
Co the cho rang nong o cua cac trung tam phan ng bang nong o chat xuc tac, tc la R- = Cxt va ta co: vp=vp= kp.M.Cxt (XIII-22).
Nhan xet: Toc o phan ng phu thuoc vao nong o xuc tac, nong o monomer va vp nhiet o, con P = = (XIII-23), tc la phan ng xay ra en cung khi khong v ng con monomer na. b. Phan ng trung hp anion theo c che cap ion:
Xet phan ng trung hp day vinyl vi xuc tac la hp chat c kim C4H9Li. Phan ng xay ra theo 3 giai oan sau:
iii. Giai oan ngat mach: Neu phan ng xay ra trong moi trng khan, khong co dung moi th ta se nhan c polimersong.
vp = vp = kp.M.R (XIII-26) va P =
vp v ng = (XIII-27).
Thac s Tran Kim Cng
Khoa hoa hoc
- 107 -
CHNG XIV. TONG HP POLIMER BANG PHNG PHAP TRUNG
NGNG.
I. Mot so khai niem:
1. nh ngha phan ng trung ngng:
Phan ng trung ngng la qua trnh lien ket cac monomer lai vi nhau e tao thanh polimer, co kem theo s tach cac san pham phu thap phan t nh nc, amoniac, kh carbonic, ...
2. ieu kien e monomer tham gia phan ng trung ngng:
La cac monomer phai cha t nhat 2 nhom chc trong phan t, cac nhom chc thng gap la: COOH, -NH2, -OH, -COCl, ...
3. ac iem cua phan ng trung ngng:
+ Phan ng trung ngng khac vi phan ng trung hp la san pham cua phan ng trung ngng co thanh phan nguyen to khac vi thanh phan cua monomer ban au.
Qua trnh trung ngng tren la gia cac monomer khac loai c goi la phan ng ong trung ngng hay trung ngng khac loai, con qua trnh trung ngng ch co 1 loai monomer tham gia phan ng goi la phan ng trung ngng cung loai.
+ Neu monomer co 3 nhom chc tr len th khi trung ngng se nhan c polimer co cau truc mang li khong gian. V du: Khi cho acid terephtalic tac dung vi glicerin th ta nhan c nc va nha glyptal co cau truc mang li khong gian nh sau:
II. Can bang trung ngng va khoi lng phan t cua polimer:
Xet phan ng tong quat:
Thac s Tran Kim Cng
Khoa hoa hoc
- 108 -
Phan ng nay xay ra la do tng tac cua nhom cacboxyl (-COOH) va nhom hidroxyl (-OH). Hang so can bang K ch phu thuoc vao ban chat cua cac nhom chc, khong phu thuoc vao R va R'; v vay, chung ta xem phan ng ester hoa tren la phan ng cua -COOH va -OH nh sau:
ac iem cua phan ng trung ngng la phan ng thuan nghch, tc la phan ng xay ra theo ca 2 chieu, va K co gia tr tng oi thap. V du: Phan ng trung ngng tao thanh polietylenterephtalat co K la 4,9 280oC va phan ng trung ngng tao thanh poliamid co K la 305 260oC. Do K nho nen khoi lng phan t cua polimer thu c thap, thng co gia tr t 1.000 en 15.000 vc, trong khi o khoi lng phan t cua polimer thu c t phan ng trung hp thng t 100.000 en 1.000.000 vc.
Cac yeu to anh hng en can bang trung ngng:

1. Anh hng cua nhiet o: Nhiet o rat t anh hng en o trung hp, tc la rat t anh hng en khoi lng phan t cua polimer. Tuy nhien, phan ng trung ngng luon luon thu nhiet (H= 8 10kcal/mol); do vay, ngi ta phai thng xuyen cung cap nhiet cho he phan ng. Neu ngng cung cap nhiet th phan ng se ngng ngay tc khac.
Khi tang nhiet o th toc o phan ng tang nen phan ng nhanh at en trang thai can bang nhng khong the tang nhiet o len mai v oi hoi trang thiet b ky thuat hien ai. Khi tang nhiet o th lam cho can bang trung ngng chuyen dch ve pha thuan tao ra polimer co khoi lng phan t ln hn do co s tach cac chat thap phan t ra khoi he phan ng nh nc, kh cacbonic, ... Mat khac, khi tang nhiet o th cung lam tang kha nang cua phan ng ong vong. Do vay, ngi ta ch tang nhiet o en 1 nhiet o toi u nao o, thng nhiet o toi u la 100 en 200oC.
2. Anh hng cua xuc tac:
Phan ng trung ngng mang tnh chat ion, rat nhay vi chat xuc tac. Xuc tac co tac dung lam tang toc o phan ng va tang o trung hp. V du: xuc tac cho phan ng tao thanh poliester la acid vo c, cac muoi acid, oxit kimloai, ..., cua phan ng formaldehit vi phenol va vi urea la kiem va acid.
3. Anh hng cua hp chat n chc:
Neu trong he phan ng co cha hp chat n chc, co kha nang phan ng vi 1 trong cac nhom chc cua monomer th chung se lam phong toa cac nhom chc o gay nen s ngat mach, lam cho phan ng trung ngng co the b ngng lai khi mot loai nhom chc a phan ng het.
Thac s Tran Kim Cng
Khoa hoa hoc
Giao trnh Hoa ly dung cho SV nganh Moi trng 4. Anh hng cua monomer:
- 109 -
Hang so can bang khong phu thuoc vao nong o monomer nhng toc o phan ng se tang khi nong o monomer tang, lam cho can bang trung ngng nhanh at c va do vay, polimer thu c co khoi lng phan t ln hn. Mat khac, e cho khoi lng phan t cua polimer ln hn, ta phai tach cac san pham phu ra khoi he phan ng. Neu muon polimer thu c co khoi lng phan t ln th ta phai lay 2 monomer co ty le ve so mol la 1:1 (neu so nhom chc trong 2 monomer nh nhau).
III. ong hoc cua phan ng trung ngng:
+ ac iem chung cua phan ng trung ngng la xay ra tng oi cham, tng bc mot, trong khi o cac monomer lai b bien oi tng oi nhanh. Phan ng phat trien mach xay ra la do tng tac gia cac phan t co khoi lng phan t khac nhau. Do o, ong hoc cua phan ng trung ngng phai la tong cua cac phan ng khac nhau va v vay, rat kho khan trong viec nghien cu. e n gian, Flory a neu ra 3 gia thiet sau ay: - Hang so can bang cua phan ng gia cac nhom chc khong phu thuoc vao o dai cua mach phan t, tc la kha nang phan ng cua cac nhom chc khong phu thuoc vao khoi lng phan t cua cac mach polimer va monomer. - Kha nang phan ng cua ca hai nhom chc trong cac monomer eu nh nhau. - Kha nang phan ng cua moi nhom chc khong phu thuoc nhom chc th 2 a phan ng hay cha. + Bay gi, ta se xet ong hoc cua phan ng tong hp poliester.
v= -
dC acid dC = r = k. C COOH . C OH (phan ng bac 2). dt dt
+ Ngi ta thay rang oi vi phan ng trung ngng th ty le ve thanh phan cua cac monomer se quyet nh en khoi lng phan t cua polimer tao thanh. Neu 2 monomer eu co 2 nhom chc trong phan t va neu lay so mol cua 2 monomer o nh nhau th ta se thu c polimer co khoi lng phan t ln nhat. Ta chng minh ieu o nh sau: Gia s co 2 monomer th 1 va th 2 la X-R-X va Y-R-Y ( X, Y la cac nhom chc ) va so mol cua chung tng ng la xo va yo (ban au); goi xt va yt la so mol monomer th 1 va th 2 thi iem t trong hon hp phan ng. Neu at xo > yo th
Thac s Tran Kim Cng
Khoa hoa hoc
- 110 -
xo + yo ; theo gia thiet khi t th y t 0 va P t = xt + yt xo +1 xo + yo yo = = khi t th xt = xo y o nen ta suy ra: P t = xo yo xo 1 yo

ta co: Pt =
xo + yo ; ma x t
m +1 (XIVm 1
2), trong o: m=xo/yo. m

Pt
2 3
1,1 21
1,01 201
1,001 2001
1,0001 20001
Qua ket qua tren, ta de dang thay rang khi xo = yo th P t co gia tr cao nhat. + Ta cung can biet rang o trung hp phu thuoc vao thi gian; thi gian cang ln th o trung hp cang ln. Do vay, neu phan ng trung ngng nao o c tien hanh vi thi gian be th se thu c polimer co khoi lng phan t be (chat lng san pham khong tot).
Thac s Tran Kim Cng
Khoa hoa hoc
- 111 -
CHNG XV. TNH CHAT C L CUA POLIMER.

I. Tnh mem deo cua polimer:
1. Nguyen nhan xuat hien tnh mem deo: a. at van e:
Polimer la nhng hp chat co khoi lng phan t ln, co kch thc chieu dai (l) ln hn nhieu so vi chieu ngang (a). Ma oi vi 1 vat the bat k du thap phan t hay cao phan t khi ma chieu dai ln hn nhieu chieu ngang eu co tnh mem deo. Ngoai s khac nhau nhieu ve l va a, oi vi polimer, tnh mem deo con do1 nguyen nhan khac. b. Xet phan t polietylen:
+ e n gian, trc tien, ta xet phan t etan.
Mot trong nhng loai ong phan ien hnh cua etan va day ong ang cua no la s hnh thanh cac ong phan cau dang. ong phan cau dang la s phan bo trong khong gian cua cac nguyen t hay nhom nguyen t khi quay quanh truc lien ket hoa tr. Trong phan t etan co 7 lien ket nh sau:
Luc au,Vanhop cho rang cac nguyen t co the quay hoan toan t do va nh the co vo so ong phan cau dang khac nhau. Tren thc te, e am bao cac goc lien ket luon luon bang 109o28v carbon trong etan co lai hoa sp3 va do xuat hien cac tng tac ay cua cac nguyen t hydro khi gan nhau nen cac nhom CH3 se quay khong hoan toan t do, se b han che bi cac yeu to noi tren. V vay, hien tng quay tren c goi la hien tng noi quay b ham. Neu chung ta at mat nhn t pha nhom CH3 th 1 th nhom CH3 th 1 nhn thay c k hieu la va nhom CH3 th 2 b che khuat c k hieu la . Khi khao sat cac cau dang cua no bang cach co nh C1, quay C2 cac goc t 0o
Thac s Tran Kim Cng
Khoa hoa hoc
- 112 -
en 360o th chung ta se nhan c cac cau dang H.XV.1.

Nh vay, khi quay nhom CH3 xung quanh truc lien ket chnh C C mot vong 360o th he xuat hien 3 cau dang che khuat va 3 cau dang xen ke. cau dang xen ke, cac nguyen t H cua C1 vao v tr xen ke vi cac nguyen t H cua C2 nen chung xa nhau nhat; do vay, chung t tng tac vi nhau nhat va do o, he co nang lng cc tieu. dang che khuat, cac nguyen t H cua C1 vao v tr che khuat vi cac nguyen t H cua C2 nen chung tng tac vi nhau nhieu nhat va v vay, he kem ben, ng vi nang lng cc ai. Hieu cua 2 mc nang lng cua 2 cau dang che khuat va xen ke la U=Umax -Umin=2,8 kcal/mol.
Khi bieu dien s phu thuoc cua noi nang U vao goc quay th ta se nhan c ng cong co dang hnh sin ng vi cc ai la cau dang che khuat va cc tieu la
cau dang xen ke ( xem H.XV.2 ) . + Xet phan t polietylen: Ta k hieu phan t polietylen la R-CH2-CH2-R ( 2 au mach la R va R). Trong trng hp ac biet, khi R trung vi R th ta co: R-CH2-CH2-R. Ta k hieu nhom RCH2- th 1 nhn thay la va nhom RCH2- th 2 b che khuat la . Gi nguyen C1, quay C2 t 0o en 360o, ta se nhan c cac cau dang H.XV.3.
Nh vay, sau khi quay 1 vong 360o xung quanh truc lien ket C-C th ta se nhan c 6 ong phan cau dang ng vi 4 loai cau dang khac nhau (co 1 ong phan cau dang xen ke nhau ng vi U1=U7=Umin, ben nhat; 1 ong phan cau dang che khuat ng vi U4=Umax, kem ben vng nhat; 2 ong phan cau dang ng vi U2=U6; 2 ong phan cau dang ng vi U3=U5).
Thac s Tran Kim Cng
Khoa hoa hoc
- 113 -
Khi bieu dien s phu thuoc cua noi nang U vao goc quay th ta se nhan c ng cong co dang nh tren H.XV.4.
Nh vay, khi ch xet 1 lien ket C-C th a co 4 loai ong phan cau dang khac nhau. Neu xet hien tng noi quay xung quanh cac lien ket cua phan t PE th he se trai qua rat nhieu ong phan cau dang khac nhau.Phan t cang dai th cac ong phan cau dang co the co cang nhieu. o la nguyen nhan sinh ra tnh mem deo cua polimer.
+ Ket luan: Nguyen nhan gay ra tnh mem deo cua polimer la kha nang noi quay cua cac nhom nguyen t va nguyen t xung quanh truc lien ket hoa tr cua mach chnh cho ra nhieu ong phan cau dang khac nhau.
2. Cac yeu to anh hng en tnh mem deo cua polimer: a. Yeu to nhiet ong:
Gia s trang thai au, polimer trang thai ng vi mc nang lng U1; do chuyen ong nhiet hoac do tac dung cua ngoai lc, cac phan t polimer chuyen sang trang thai 2 ng vi mc nang lng U2. Neu bieu dien s phu thuoc cua U vao ng i th ta se co o th co dang nh tren H.XV.5. T o th, ta co: U=U2U1. Neu U cang nho th mach polimer cang de dang chuyen t trang thai 1 (ban au) sang trang thai 2 (cuoi). Do vay, U co anh hng en tnh mem deo cua polimer va c goi la o mem deo nhiet ong hoc. b. Yeu to ong hoc: Muon chuyen t trang thai 1 sang trang thai 2, he phai vt qua 1 hang rao nang lng E (nang lng hoat hoa). E la yeu to quyet nh en toc o cua qua trnh va E c goi la o mem deo ong hoc.
Thac s Tran Kim Cng
Khoa hoa hoc
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Neu U cang nho va E cang nho th mach polimer cang mem deo.
c. Anh hng cua cac nhom the:
Xet day polivinyl, khi the 1 nguyen t H cua PE bang 1 nhom the khac nh sau:
CH2 CH , n H CH2 CH , n Cl CH2 CH , n CH3 CH2 CH n C6H5
Neu nhom the cang phan cc va cang cong kenh th kha nang tng tac cua cac nhom o cang ln va v vay, cang lam can tr s quay cua mach polimer; do o, tnh mem deo cua polimer cang giam. Trong day tren, PVC va polistyren kem mem deo hn so vi PP va PE. Cung v l do tren ma a so cac polimer trung ngng co o mem deo thap hn so vi polimer trung hp. d. Anh hng cua khoi lng phan t cua polimer: Khoi lng phan t cua polimer anh hng khong ang ke en o mem deo cua polimer. Tuy nhien, polimer co mach cang dai, tc la khoi lng phan t cang ln, th lam cho toc o cua qua trnh chuyen t trang thai nay sang trang thai kia cang cham. e. Anh hng cua mat o mang li khong gian: Cac polimer co mang li khong gian tha th t anh hng en o mem deo, con cac polimer co mang li khong gian day th co anh hng. V du: cao su thien nhien khi a lu huynh vao lu hoa t 1 en 2% th co kha nang an hoi t 10 en 20 lan nhng khi ham lng lu huynh khong di 5% th chung rat cng va khi o, chung la nha ebonit, do cac cau noi lu huynh lam can tr s quay cua phan t. f. Anh hng cua nhiet o: Khi tang nhiet o th linh o chuyen ong nhiet cua phan t tang len nen tnh mem deo tang len.
Thac s Tran Kim Cng
Khoa hoa hoc

II. Cac trang thai vat l c ban cua polimer:
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1. Trang thai tap hp cua polimer: a. oi vi hp chat thap phan t:
Cac hp chat thap phan t co the ton tai 3 trang thai tap hp la kh (K), long (L) va ran (R). b. oi vi polimer: Polimer ch ton tai 2 trang thai la ran va long, khong ton tai trang thai kh . Do khoi lng phan t cua polimer rat ln nen nang lng tng tac gia cac phan t rat ln; do o, nhiet hoa hi cua polimer ln hn nhiet phan huy va v vay, polimer b phan huy trc khi hoa hi.
2. Trang thai tng cua polimer: a. oi vi hp chat thap phan t:
Theo quan iem nhiet ong hoc, da vao s bien oi nhiet o va cac thong so nhiet ong khac, vat the co the ton tai 3 trang thai tng la R, L va K. nh ngha tng: la 1 phan cua he, ngan cach vi nhng phan khac bi be mat phan cach. Trong 1 tng phai co thanh phan va cac tnh chat nhiet ong ong nhat hoac bien oi lien tuc theo toa o khong gian. Neu chung ta so sanh trang thai tap hp va trang thai tng th chung ta co: Trang thai tap hp: Trang thai tng: tng tinh the b. oi vi polimer:
R L K t ng vh t ng long tng kh
Da vao cach sap xep cac phan t trong khong gian, ngi ta chia polimer thanh 2 tng la tng tinh the va tng vo nh hnh. + Tng vo nh hnh cua polimer: trong o cac phan t c sap xep theo 1 trat t trat t gan. t. Trat t gan: trong o kch thc vung co trat t nho hn nhieu kch thc phan
+ Tng tinh the cua polimer: trong o cac phan t c sap xep theo 1 trat t xa. Trat t xa: trong o kch thc vung co trat t ln hn nhieu kch thc phan t.
3. S chuyen trang thai vat l cua cac vat the:
Ta se xet 3 loai mau vat la vat the tinh the thap phan t, thuy tinh thap phan t va polimer vo nh hnh.
Thac s Tran Kim Cng
Khoa hoa hoc
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Khi tac dung 1 lc F khong oi vao 3 loai mau vat tren, vi toc o lc khong oi, tang dan nhiet o len th khi khao sat s bien dang cua mau vat () vao nhiet o (T) th ta se nhan c cac dang o th tren H.XV.6.
+ oi vi vat the tinh the thap phan t, qua trnh chuyen he t trang thai ran sang trang thai long la qua trnh chuyen tng, xay ra 1 nhiet o nhat nh, goi la nhiet o nong chay. Tai nhiet o nong chay, cac thong so nhiet ong nh noi nang U, entanpi H, entropi S, o bien dang , eu bien thien nhay vot. ay, bien thien nhay vot la do s bien dang t thuan nghch sang bat thuan nghch -o la s bien dang chay. + oi vi thuy tinh thap phan t, qua trnh chuyen t trang thai thuy tinh sang trang thai chay khong phai la qua trnh chuyen tng. ay ch la qua trnh chuyen t trang thai vat l ran sang trang thai vat l long c xac nh bang nhiet o hoa thuy tinh (Tg). Tg khong phai la 1 ai lng xac nh ma Tg co the giao ong trong mot khoang 10 20o la tuy thuoc vao ban chat cua cau t va ieu kien ben ngoai nh toc o un nong hay lam lanh, lc tac dung c hoc, + oi vi polimer vo nh hnh, o th cua no c chia thanh 3 vung ng vi 3 trang thai vat l khac nhau la: - T T en Tg, he ton tai trang thai thuy tinh, thng co gia tr nho; tai vung nay, polimer nam trang thai ran. - T Tg en Tc, he ton tai trang thai co gian co o mem deo cao.Trang thai vat l nay ch thay cac polimer, con cac chat thap phan t khong co. - T Tc en T, polimer trang thai chay. V du: poliisobutylen nhiet o thng ton tai trang thai co gian, co tnh an hoi cao, khi un nong th co the chuyen sang trang thai chay nht, con khi lam lanh th co the chuyen sang trang thai thuy tinh (gion).
Thac s Tran Kim Cng
Khoa hoa hoc

III. ng cong c nhiet cua polimer vo nh hnh: xem H.XV.7.
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1. Trang thai co gian:
+ Ch xuat hien polimer . + Ban chat co gian cua polimer khac han ban chat an hoi cua chat ran nhng lai tng t nh ban chat an hoi cua chat kh. Chang han, neu ta co mot mau cao su va ta tac dung vao o lc F th mach phan t ang trang thai cuon cong (tng t nh cai lo xo) lap tc b duoi ra. Khi khong co lc tac dung na th do chuyen ong nhiet, mach phan t lai co lai. + Bay gi, ta se xet xem luc duoi ra hay co vao o th yeu to nao thay oi va yeu to nao quyet nh en toc o bien dang cua polimer. Theo nguyen ly I cua nhiet ong hoc, khi cung cap cho he 1 lng nhiet e vat lieu polimer b bien dang la Q = dU + A (XV-1). Mat khac, theo nguyen ly II cua nhiet ong hoc, oi vi qua trnh thuan nghch th Q = TdS (XV-2). T (XV-1,2), ta suy ra: TdS = dU + A (XV-3). Khi keo mau ra th cong keo mau la A=-Fdl (XV-4), trong o: F la lc tac dung, dau tr la do lc t ben ngoai, dl la o bien dang.
S U T (XV-3,4), ta suy ra: Fdl=dU TdS F = T (XV-5). l T l T

Bieu thc nay cho biet rang khi tac dung 1 lc t ben ngoai vao he th gay ra 2 s bien oi la U va S. - oi vi cac chat trang thai tinh the, khi co ngoai lc tac dung len he th cac vat ran se giao ong xung quanh v tr can bang va do o, S cua he thay oi khong U S ang ke, tc la: 0 , nen F = (XV-6 ). l T l T - oi vi polimer co o co gian cao, khi keo th cong cua ngoai lc hoan toan bien thanh nhiet, ch can 1 nang lng nho th S cua he se thay oi rat manh va
Thac s Tran Kim Cng
Khoa hoa hoc
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giam i rat nhanh do phan t b duoi ra tng t nh s giam the tch trong qua S F = T (XV-7). trnh nen kh tc la l T
Vay, ban chat cua s bien dang co gian la chuyen ong nhiet cua cac oan mach quyet nh, hoan toan phu thuoc vao yeu to entropi. 2. Trang thai thuy tinh:
+ Cac hp chat thap phan t va polimer eu co ton tai trang thai thuy tinh. trang thai nay, cac chat trang thai ran vo nh hnh. Cau tao cua polimer trang thai thuy tinh la cac phan t nhng hnh dang ngau nhien, khong tuan theo 1 trat t nao ca. Do kch thc ln, cong kenh nen trang thai thuy tinh hoa, cac polimer khong the sap xep chat che c va gia cac mach polimer vi nhau thng xuat hien nhng khoang trong; v vay, chung thng co cau truc xop. Chnh v vay ma linh o chuyen ong nhiet cua cac nhom trong polimer tng oi cao, lam cho polimer van co kha nang b bien dang, nhng s bien dang khong cao nh trang thai co gian; trong khi o, o ben c hoc lai cao hn va kha nang chu nhiet cung tot hn. + Cac yeu to anh hng en Tg: - o phan cc cua mach: Polimer co o phan cc cang ln th Tg cang cao v nang lng tng tac gia cac phan t co cc ln hn khong co cc. - Mat o va kch thc cua nhom the: Neu nhom the cang ln va cang cong kenh th Tg cang cao bi v cac nhom the co anh hng en linh o chuyen ong nhiet cua mach phan t . Mat khac, trong phan t co nhom the, cac nhom the se c phan bo eu an hn va do o, Tg cao. V du: Copolimer butaienstyren goi la CKC: neu CKC10 (tc 10% styren) th Tg =-80oC; neu CKC50 th Tg=-46oC; neu CKC90 th Tg=+34oC. - Khoi lng phan t cua polimer: Ban au, khi khoi lng phan t cua polimer tang th Tg tang nhng sau o, khi khoi lng phan t cua polimer tang en 1 gia tr nao o (gia tr gii han), khi trong he a xuat hien trang thai co gian, th Tg khong phu thuoc vao khoi lng phan t cua polimer na.
3. Trang thai chay:
+ Trang thai chay la polimer trang thai long co o nht rat cao. + C che cua s chay la: theo l thuyet ve cau truc chat long, trang thai long, cac phan t co cau truc giong nh mang li xop, cha nhieu lo trong. Bnh thng, cac phan t luon luon chuyen ong giao ong xung quanh v tr can bang va luon
Thac s Tran Kim Cng
Khoa hoa hoc
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luon thay oi v tr bang cach nhay vao cac lo trong va e lai cac lo trong khac sau no. Nhng lo trong nay chuyen ong hon loan trong the tch chat long. + Khi 1 phan t nay muon tach ra khoi cac phan t xung quanh e nhay vao cac lo trong th can phai co 1 nang lng u ln e vt qua hang rao the nang (nang lng ln hn hoac bang nang lng hoat hoa cua s chay). Bieu thc bieu dien s phu thuoc cua o nht vao nang lng hoat hoa va nhiet o nh sau: =A.e-E/RT (XV-8). S phu thuoc cua nang lng hoat hoa E vao Mp nh tren H.XV.8. T s phu thuoc o, ta thay rang: ban au, khi Mp tang th E tang nhng sau o, khi Mp a tang en Mp,gh th E khong tang na va khong phu thuoc vao Mp na. Ket hp cac d kien tren ta co the a ra ket luan sau: c che cua s chay cua polimer la do chuyen ong nhiet. n v cua chuyen ong nhiet la nhng oan mach oc lap. Do o, di tac dung cua ngoai lc, cac oan mach di chuyen theo chieu tac dung cua lc, tng t nh s di chuyen cua con sau o, lam cho trung tam phan t di chuyen theo. + ac iem quan trong cua s chay cua polimer la trong qua trnh chay, o nht cua he khong ngng tang len do phan t polimer b duoi ra lam cho nang lng tng tac gia cac phan t tang len, bi v nang lng tng tac gia cac phan t duoi thang ln hn nang lng tng tac gia cac phan t khi cuon cong. + Hieu ng tang o nht trong qua trnh chay cua polimer c ng dung rong rai trong k thuat keo si va tao mang mong (trong k nghe sn). + Trong thc te, ngi ta thay co 2 phng phap lam t si sau ay: - Chuyen polimer sang trang thai chay nht, roi nen qua mot khuon giong nh khuon lam bun, roi dung khong kh nong say kho. - Hoa tan polimer vao dung moi thch hp, roi nen qua 1 lo thanh dong vao chat co kha nang gay keo tu, ta thu c polimer dang si.
IV. Trang thai tinh the cua polimer:
+ So sanh hp chat thap phan t va polimer: xem B.XV.1. Hp chat thap phan t -Tinh the la 1 he ong nhat, gia cac tinh the co be mat phan chia ro ret. -Khi ket tinh th toan bo he eu trang thai tinh the. Polimer - Tinh the khong ong nhat, gia cac tinh the khong co be mat phan chia. - Khi ket tinh th he va ton tai trang thai tinh the , va ton tai trang thai vo nh hnh nhng vung co trat t ln hn vung khong co trat t, o ket tinh bao gi cung nho hn 100%. - Nhiet o nong chay, nhiet o ket tinh
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-Nhiet o nong chay, nhiet o ket tinh la hang so, la 1 ai lng vat ly co the dung e xac nh chat o. B.XV.1
ch la 1 ai lng co tnh chat thong ke, trung bnh.
+ ac iem cua polimer khi ket tinh la bao gi cung co hien tng nh hng, lam cho mach polimer b duoi ra, do o o nht tang len; v vay, kha nang tao mang, keo si cua polimer tinh the cung de dang hn. + Kha nang bien dang an hoi cua polimer tinh the be hn polimer vo nh hnh. + Tnh bat ang hng va o ben c hoc: Trong polimer tinh the, cac phan t c sap xep theo 1 chieu nhat nh. Neu tac dung 1 lc theo phng nh hng th polimer co o ben c hoc rat cao. Ngc lai, neu lc tac dung theo phng vuong goc vi phng thang ng th o ben c hoc thap bi v o ben c hoc theo phng nh hng c quyet nh bi cac lien ket hoa hoc mach chnh, con theo phng nam ngang c quyet nh bi cac lien ket vat l yeu hn. + ieu kien e ket tinh 1 polimer la: - Mach polimer phai co 1 o mem deo nhat nh. Neu mach cng qua th kha nang linh ong kem nen kho co ieu kien e sap xep theo 1 trat t on nh. Neu mach mem qua th cung khong ket tinh c v no se linh ong qua nen co tac dung pha v nhng trnh t sap xep khac nhau. - oi hoi polimer phai co 1 o phan cc nhat nh. Neu lng cc ln th mach se cng nen kho ket tinh. Ngc lai, neu khong lng cc th mach se mem lam han che qua trnh ket tinh. - Nhom the khong qua cong kenh. - Che o nhiet o: toc o lam lanh cho qua trnh ket tinh phai thch hp. Neu lam lanh ot ngot (nhanh qua) th polimer khong ket tinh c.
Thac s Tran Kim Cng
Khoa hoa hoc
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CHNG XVI. DUNG DCH POLIMER. Dung dch polimer la dung dch that. No khac vi dung dch keo cho dung dch that qua trnh hoa tan la qua trnh t dien bien, tc la Ght<0.
I. Qua trnh hoa tan polimer:
+ Khi cho polimer vao 1 dung moi thch hp th khac vi cac chat thap phan t (do khoi lng phan t thap nen qua trnh hoa tan la qua trnh khuech tan tng ho cua ca chat tan lan dung moi), cac polimer qua trnh hoa tan bao gi cung xay ra qua 2 giai oan sau: giai oan trng va giai oan hoa tan. + Do kch thc phan t cua polimer rat ln so vi kch thc phan t cua chat thap phan t nen au tien, dung moi se khuech tan vao polimer, lam cho polimer b trng phong len; khi o, kch thc cua polimer tang len nhng hnh dang polimer khong thay oi. Giai oan nay can phai co thi gian tng oi ln (hang ngay). Sau khi ket thuc giai oan trng th linh o chuyen ong nhiet cua mach polimer tang dan len va s hoa tan chuyen sang giai oan mio la giai oan khuech tan tng ho cua ca 2 chat vao nhau. + Giai oan hoa tan: - Neu polimer mach thang hoac mach phan nhanh, khong co mang li khong gian, th qua trnh hoa tan c tiep dien cho en khi tao thanh dung dch that. - Neu polimer co cau tao mang li khong gian th qua trnh hoa tan ch xay ra cho en khi ket thuc giai oan trng; sau o, kch thc mau polimer se khong oi v qua trnh hoa tan khong the lam pha v cac lien ket cau noi cau tao nen mang li trong polimer. + Trong thc te, ngi ta dung ca dung dch am ac va dung dch loang. Dung dch loang la dung dch co nong o c t 0,5% tr xuong. + Neu goi o trng la th =
m1 m o v vo 100% (XVI-1) hoac = 1 100% mo vo
(XVI-2), trong o: m1 va mo la khoi lng polimer sau khi trng len va khoi lng polimer ban au, v1 va vo la the tch polimer sau khi trng len va the tch polimer ban au.
II. ac tnh cua dung dch polimer am ac:
+ Do ban than polimer co o nht rat cao nen ngay ca cac dung dch polimer loang cung co o nht rat ln, con cac dung dch cha 20 en 30% dung moi th ve tnh nang c hoc van giong polimer ban au. ieu khac nhau c ban ve tnh chat cua cac dung dch o vi polimer la nhiet o hoa thuy tinh va nhiet o chay long giam khi tang ham lng dung moi. Tuy nhien, luc o, cac tnh chat khac cung b bien oi t nhieu.
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+ Cac dung moi nh the mem hn va deo hn so vi polimer ban au. T o, ngi ta goi cac chat thap phan t a vao trong polimer la chat lam mem hay chat hoa deo. Sau ay la mot so chat hoa deo thng dung: - Nguon goc thien nhien: * Dau thc vat: dau beo, * Dau thong va cac san pham t dau thong. * San pham chng than a, dau mo, - Nguon goc tong hp: chu yeu la ester nh DBP (dibutylphtalat), DOP (dioctylphtalat), DOA (dioctyladipat), Nhng ester nay thng dung chat deo hoa cho sn, nha, + Khi a 1 lng ln chat hoa deo vao polimer th o ben cua he b giam i nhieu. ieu o gii han lieu dung chat hoa deo trong thc te. + Khi a 1 lng ln dung moi vao th lam cho dung dch polimer co o chay ln trong mot khoang nhiet o tng oi rong. Cac loai sn va cac loai keo khac nhau la nhng dung dch nh the. Tuy nhien, cac he nay rat linh ong so vi polimer tinh khiet va van gi c toan bo cac tnh chat an hoi cao phc hp va cac tnh chat khac, co chang ch khac la toc o cua cac qua trnh nay tng oi cao. + Tnh chat cua cac dung dch polimer am ac rat ang c quan tam v khong nhng e hieu biet qua trnh ieu che va x l cac dung dch polimer ma con e s dung cac polimer a c hoa deo trong cac san pham khac nhau sao cho hp l nhat.
cua polimer:
III. Dung dch loang cua polimer va phng phap xac nh khoi lng phan t
1. Dung dch loang cua polimer:
+ Khai niem dung dch loang: la dung dch polimer trong o thc te khong xay ra s va cham gia cac ai phan t. + Gii han gia dung dch loang va dung dch khong loang cua polimer phu thuoc vao khoi lng phan t cua polimer. Polimer co khoi lng phan t cang ln th nong o gii han cua dung dch loang cang nho, co ngha la polimer co o trung hp cang cao th nong o gii han cua dung dch loang cang nho, va ngc lai. + Cac dung dch loang cung tuan theo cac nh luat ve dung dch nh nh luat Raun, Vanhop,
2. Cac phng phap xac nh khoi lng phan t cua polimer:
Polimer la he a phan tan nen gia tr khoi lng phan t cua no xac nh c du bang phng phap nay hay phng phap khac eu la gia tr khoi lng phan t
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trung bnh. Thong thng, co 3 phng phap chnh e xac nh khoi lng phan t cua polimer la phng phap trung bnh so, phng phap trung bnh trong lng va phng phap o o nht, tuy nhien sau ay chung ta ch xet 1 phng phap e xac nh khoi lng phan t cua polimer la phng phap o o nht:
ay la 1 trong nhng phng phap thong dung nhat (de lam, tng oi chnh xac). C s cua phng phap nay la da vao s phu thuoc cua o nht vao khoi lng phan t chat tan.
Trong khai niem o nht, ngi ta phan biet o nht tuyet oi, o nht tng oi, o nht rieng, o nht rut gon vao nht ac trng. + o nht tuyet oi: theo Poaday, khi 1 chat long chay qua 1 mao quan co ban knh r di tac dung cua ap suat P, sau thi gian chay t chat long chay c the tch v th o nht tuyet oi la: =k.d.t (XVI-3), trong o: k la he so nht ke, d la ty trong cua chat long va t la thi gian chay. + o nht tng oi: td =
dd t = (XVI-4), trong o t va to la thi gian chay dm t o
cua dung dch va dung moi tng ng. + o nht rieng: r =
t to = td 1 (XVI-5). to
+ o nht rut gon: rg =
r (XVI-6), trong o C la nong o dung dch (so gam C chat tan/100ml dung moi).
+ o nht ac trng: [] = lim
r (XVI-7). C 0 C
Gia o nht ac trng va khoi lng phan t cua polimer lien he vi nhau bang he thc sau:
(XVI-8), trong o: K la hang so phu thuoc vao ban chat cua dung moi va nhiet o va co gia tr t 0,5 en 0,8. Bieu thc (XVI-8) la bieu thc do MakEuvin neu ra.
[] = K.M
[] c xac nh bang thc nghiem nh sau:

Pha cac dung dch polimer co nong o la C1, C2, , Cmax=1 g/100 ml, roi o o nht (qua thi gian chay) va t o, suy ra: r1 , r 2 ,..., r max . Sau o, ta tnh ra c o nht rut gon ng vi cac nong o khac nhau la: r r1 r2 , ,..., max . Ve o th bieu dien s phu thuoc cua r vao C (xem H.XVI.1) C1 C 2 C max C va t o th, ta suy ra c o nht ac trng [] = OA .
Thac s Tran Kim Cng
Khoa hoa hoc
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Biet o nht ac trng, ta suy ra c M theo bieu thc nh sau:
M = 10
lg [ ] lg K
(XVI-9).
Thac s Tran Kim Cng
Khoa hoa hoc
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Muc Luc
Phan I. ONG HOA HOC. ......................................................................................... 2 Chng I. MOT SO KHAI NIEM C BAN................................................................. 2 I. Toc o cua phan ng hoa hoc: ............................................................................. 2 II. S phan loai ong hoc cac phan ng hoa hoc:................................................... 3 III. Phng trnh ong hoc va hang so toc o cua phan ng hoa hoc: ................... 6 Chng II. ONG HOC CUA MOT SO PHAN NG HOA HOC. ............................ 8 I. Phan ng mot chieu bac mot: ............................................................................... 8 II. Phan ng mot chieu bac hai: ............................................................................... 8 III. Phan ng mot chieu bac ba:............................................................................... 9 IV. Phan ng mot chieu bac khong: ...................................................................... 10 V. Phan ng mot chieu bac n:................................................................................ 11 VI. Cac phng phap xac nh bac phan ng: ...................................................... 11 VII. Phan ng thuan nghch: .................................................................................. 14 VIII. Phan ng song song: ...................................................................................... 16 IX. Phan ng noi tiep: ............................................................................................ 18 Chng III. LY THUYET VE CAC QUA TRNH S CAP. ...................................... 21 I. Anh hng cua nhiet o en toc o phan ng:.................................................. 21 II. Thuyet va cham hoat ong va thuyet phc chat hoat ong:............................ 23 Chng IV. PHAN NG QUANG HOA, PHAN NG DAY CHUYEN VA KHAI NIEM VE XUC TAC. ................................................................................................ 25 I. Phan ng quang hoa:........................................................................................... 25 II. Phan ng day chuyen: ....................................................................................... 27 III. Nguyen ly nong o on nh va viec ap dung nguyen ly nay trong viec xac nh phng trnh ong hoc cua phan ng phc tap: ............................................ 32 IV. Khai niem ve xuc tac:...................................................................................... 33 Phan II. IEN HOA HOC......................................................................................... 38 Chng V. DUNG DCH CAC CHAT IEN GIAI. .................................................. 38 I. Tnh chat chung cua dung dch: .......................................................................... 38 II. Dung dch cac chat ien giai:............................................................................ 38 III. o dan ien cua dung dch chat ien giai:...................................................... 39 IV. Phng phap o o dan ien va ng dung cua no:......................................... 41 Chng VI. NGUYEN TO GANVANIC..................................................................... 43 I. Cac khai niem m au:....................................................................................... 43 II. The cua tng ien cc: ...................................................................................... 43 III. Phng phap o sc ien ong: ....................................................................... 44 IV. Cac qua trnh xay ra trong nguyen to ganvanic:............................................. 45
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Chng VII. NHIET ONG HOC CUA CAC MACH IEN HOA VA THE IEN CC.......................................................................................................................... 47 I. Moi lien he gia the ang nhiet ang ap G va sc ien ong cua nguyen to ganvanic E va phng trnh the ien cc: ............................................................. 47 II. The ien cc: ..................................................................................................... 47 Phan III. HOA HOC CHAT KEO. ........................................................................... 56 Chng VIII. KHAI NIEM VE CHAT KEO VA PHNG PHAP IEU CHE DUNG DCH KEO................................................................................................................ 56 I. Khai niem ve chat keo:....................................................................................... 56 II. ieu che dung dch keo:.................................................................................... 57 Chng IX. TNH CHAT ONG HOC PHAN T VA S PHAN TAN ANH SANG CUA CAC HE PHAN TAN ....................................................................................... 59 I. Tnh chat ong hoc phan t cua cac he phan tan: ............................................. 59 II. S phan tan anh sang: ....................................................................................... 59 Chng X. S hap phu, tnh chat ien cua cac he keo va s keo tu ......................... 61 I. S hap phu: .......................................................................................................... 61 II. Tnh chat ien cua cac he keo va s keo tu: .................................................... 68 Chng XI. Cac he vi moi trng phan tan kh, long va ran va xa phonG. .......... 72 I. Cac he vi moi trng phan tan kh, long va ran:............................................. 72 II. Xa phong:........................................................................................................... 77 Phan IV. HOA HOC POLIMER. .............................................................................. 83 Chng XII. M AU. ............................................................................................. 83 I. nh ngha va mot so tnh chat c ly ac trng cua cac polimer:..................... 83 II. Phan loai polimer:.............................................................................................. 84 III. Mot so polimer tieu bieu:................................................................................. 85 Chng XIII. TONG HP POLIMER BANG PHAN NG TRUNG HP. .............. 95 I. Mot so khai niem: ............................................................................................... 95 II. Tong hp polimer bang phng phap trung hp goc: ...................................... 95 III. Tong hp polimer bang phng phap trung hp cation: ............................... 100 IV. Tong hp polimer bang phng phap trung hp anion:................................ 104 Chng XIV. tong hp polimer bang phng phap trung ngng............................ 107 I. Mot so khai niem: ............................................................................................. 107 II. Can bang trung ngng va khoi lng phan t cua polimer:........................... 107 III. ong hoc cua phan ng trung ngng:............................................................ 109 Chng XV. TNH CHAT C L CUA POLIMER.................................................. 111 I. Tnh mem deo cua polimer: ............................................................................. 111 II. Cac trang thai vat l c ban cua polimer:........................................................ 115 III. ng cong c nhiet cua polimer vo nh hnh: xem H.XV.7...................... 117 IV. Trang thai tinh the cua polimer: .................................................................... 119
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Chng XVI. DUNG DCH POLIMER................................................................... 121 I. Qua trnh hoa tan polimer:................................................................................ 121 II. ac tnh cua dung dch polimer am ac: ...................................................... 121 III. Dung dch loang cua polimer va phng phap xac nh khoi lng phan t cua polimer: .......................................................................................................... 122
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TRNG AI HOC A LAT

TRAN KIM CNG - 2002

Khi t 0 th toc o trung bnh ( v ) se tien en toc o thc (v), tc la

thi iem t1, thi iem t2, Ta co: v =

Tng t nh tren, ta suy ra: v =

Thac s Tran Kim Cng

Khoa hoa hoc

/ 1 dC A 2 1 dC A1 1 dC A 2 1 dC A1/ = =L= / = / = L (I-11). 1 dt 2 dt 1 dt 2 dt

II. S phan loai ong hoc cac phan ng hoa hoc:

Thac s Tran Kim Cng

Khoa hoa hoc

Giao trnh Hoa ly dung cho SV nganh Moi trng

v = k. C 2 A (I-21), trong o CA, CB la nong o cua chat tham gia phan ng A, B.

Thac s Tran Kim Cng

Khoa hoa hoc

ong hoc cua phan ng nh sau: v = . C Aii = . C A11 . C A22 .L (I-29). i =1

Thac s Tran Kim Cng

Khoa hoa hoc

Thac s Tran Kim Cng

Khoa hoa hoc

Giao trnh Hoa ly dung cho SV nganh Moi trng

CHNG II. ONG HOC CUA MOT SO PHAN NG HOA HOC.

d(a x ) dx = = k (a x ) (II-1). Lay tch phan phng trnh (II-1), ta c: dt dt

CH 3 COOC 2 H 5 + NaOH CH 3 COONa + C 2 H 5 OH;2HI H 2 + I 2 A + B sp;2A sp

Thac s Tran Kim Cng

Khoa hoa hoc

d ( a x) d ( b x) dx = = = k.(a x)( b x) (II-6). dt dt dt

Phan li bien so va lay tch phan phng trnh (II-6) nay, ta c:

ieu kien: a = b. V vay, a-x = b-x nen ta co: v =

III. Phan ng mot chieu bac ba:

Thac s Tran Kim Cng

Khoa hoa hoc

a b a-x b-x c-x

ieu kien: a=b=c; do o, ta co: a-x = b-x = c-x; va v vay, ta co:

1 vao t la mot ng thang i ( a x) 2

b. Ca ba chat tham gia phan ng co nong o ban au khac nhau:

a-x b-x c-x

a-x b-x ...

1 a Vi n =1, ta co: k = ln (II-21). t ax

1 1 1 n 1 (II-22). ay la phng trnh n 1 t ( n 1) (a x) a

1 1 1 1 1 k= ( ) = kt + . Nh vay, ng bieu dien s phu thuoc cua t ax a ax a

1 vao t la mot ng thang, co dang nh tren H.II.2. ax

dC = kC n = tg (II-25). T phng trnh (II-25), ta co: dt n n tg 1 = kC 1 va tg 2 = kC 2

lg C1 ,lg C 2 ,lg tg 1 ,lg tg 2 va thay vao phng trnh (II-26), ta suy ra c n.

Thac s Tran Kim Cng

Khoa hoa hoc

Giao trnh Hoa ly dung cho SV nganh Moi trng

t1/ 2 ,1 a 2 = T o, ta suy ra: t1 / 2 , 2 a 1

lg t1/ 2 ,1 lg t1/ 2 , 2 (II-29). lg a 2 lg a1

tng ng thi iem t.

Thac s Tran Kim Cng

Khoa hoa hoc

Giao trnh Hoa ly dung cho SV nganh Moi trng

b. ong hoc cua phan ng thuan nghch bac 1-1:

Thac s Tran Kim Cng

Giao trnh Hoa ly dung cho SV nganh Moi trng

+ Phng trnh phan ng song song dang tong quat:

B1 + ... B2 + ... Bn + ...

dx dx1 = k 1 ( a x ) ( II-39 ); v A C = 2 = k 2 ( a x ) (II-40). dt dt

Thac s Tran Kim Cng

Khoa hoa hoc

Giao trnh Hoa ly dung cho SV nganh Moi trng

Tng t, t cac phng trnh (II-40,43), ta cung tm c:

(II-46). trnh (II-45,46), ta suy ra: x1: x 2 = k 1: k 2 (II-47)