PliAN bA HONG HOA HOC

CHUVNG X
HONG HOC HiNH THUG

1. DOng hoc cac phan Ong don gran

Cac_phan (mg dein gian c6 thd dtroc xem la cac phan irng tuan
theo nhang quy luat &Ong hoc don gian nhat va ve hinh thin: c6
the xem chting chi g6m c6 mot giai (loan tac dung.

Khac v6i phan ting don gian, cac phan ling so cap IA nhiing phan
irng ma miic do phan tin khOng the phan tich thanh nhiing phin
itng don gian ho'n nth.

S6 cac phan tin cac chat tham gia vao phan (mg don gian chi g6m
mot giai doan tac dung, la phan tin s6 cua phan (mg. ThOng
thitarng ngtrefi to chi gap cac phandrig don phan, Itta- ng phan. T6c

311
 d0 cita phan ling hod hoc &roc do bang bieit thien ltrong chat tdc
dung (hay san pham) trong don vi th6i gian. Neu luo'ng cdc chat
throe bie'u thi bang nong dO thi t6c dO v cUa phan img :

A --> B
duce bidu dien bang phuong trinh :

d[A] d[B]
v -= ( ) =
dt dt

Theo dinh luat kinh nghiem cua Gunbec - Vago, t6c (10 ti le vdi
Ming dO cdc chat tdc dung, do do doi vdi phan ung Wing quat :

aA + bB + cC + = san pham
to co:

v= [B]R.

k IA hang s6 t6c dO phan tIng, no chi phu thuOc vAo nhiet dO.
'Ring a +13 + y + IA bac cua phan tlng. Cdc bac rieng phan y,
13, a khOng nhat thiet phai bang cdc he s6 hop fink a, b, c cua
phan (mg.

Trong Ong hod hoc ngtr6i to con hay dung khdi niem th6i gian
rata phan fmg ki hieu bang chit T. Do là thoi. gian can thiel de'
mot nira nong dO dau cila chat tdc dung mat di trong qua trinh
phan Cmg. D6i vOi cdc phan itng hat nhan, th6i gian nira phan ting'
dutic goi to chu ki ban hity.

D6i voi cdc phaniting mot chieu, cdc phtrong trinh dOng hoc
ttrong nmg dtroc ghi lai trong bang sau day :

312
 Bac Phuang trinh Phuang trinh Thai gian ThU nguyen
phan dpng hoc dpng hoc nCra phan hang so. t6c
Crng (clang vi phan) (darig tich phan) Ung T dp k
0 dx/dt = k kt = x 1 -1
mol.L .s
1 dx/dt = k(a-x) a 2 0,6932 s- 1
kt= In In =
a-x . k k

2 dx/dt = k(a-x)(b-x) 1 b(a - x) -i -1

L.mol .s
kt= In
. a -b a(b - x)

1 -i -1
2 dx/dt = k(a-x)2
kt- x
L.mol .s
a(a - x) k.a

3 -2 2 1
3 dx/dt = k(a-x)3 kt=1/2(a-x)2-1/2a2 mol .L .S
2
2a .k

n dx/dt = k(a-x)n 2n-1-1

kt= 1 . ( mo1)1-a S_1
n-1 "
_
r 1 1
[(a _ x)n-1 an-1

fle dinh bac cila phan ting hod hoc, ngueii ta có thd dp dung
xac
met trong cdc phtrung phdp thuc nghiem sau day :

1. Phuung phap the-

Dem the nOng do caa .mot chat nao do tim dugc bang thtrc
nghiem of nhang tlioi didm khdc nhau vao phuong trinh deng hoc
dra plias' ring bac 1, bac 2 ... xem phtrung trinh nao cho dugc gid
trj kheng doi ciia hang so t6c dO k.

2. Phuang phap do thi

a) D6i v6i phan img bac 1 ta có :

313
 kt
1g (a - x) = lg a
2, 303

Su phu thuOc cita lg (a - x) vao t la tuy6n tinh. Do d6c cna

dtiOng thing tg a. = - k/2,303. Tir day cc') the xac dinh hang s6
t6c dO k.

Phuong phap dO thi cho k6t qua tot hon-phuong phap th6.

b) D6i v6i phan (mg bac 2, phuang trinh Ong hoc duoc,vi6t du6i
dang :

ig a - x b k - b)
= lg + t
(b-x ) a 2,303

/ a- x
RO rang la su phu thuOc cita lg vao t 1a tuy6n tinh v6i :

k(a -b)
tg a =
2, 303

3. Pluton phap thin gian nira phan ring

D6i v6i phan img mot chi6u bac 1, thOri gian phan img T la
hang dinh voi mot phan Ung da cho va khOng phu thuOc vao
nOng dO ban dau. _

0,6932
z=
k

Trong truing hop chung, d6i vii phan ling bac n # 1 va có nong
do dau cua cac chat phan iing bang nhau thi :

const
t=
a n-1

314
 Sau khi bien d6i, phuong trinh t nay c6 dang

Ig t = (1 - n) Ig a + Ig const

Ro rang is tren do thi str phu thuQc lg t vA6 Ig a IA diremg thang

v6i tg a = 1 - n ; va hang s6 t6c (10 ducic xac dinh bang doan
thang thu dtryc khi &Ong thang bidu dien cat true tung tai g6c
toa

Ngoai ra, khi xac dinh t & hai n6ng dO ban dau a l va a2 thi
phtrong trinh t a tren se trot thAnh
( jn-1
a2
t2 \ al

hoac = (n -1)1g-a-1
T2 al
Tir day to de dang xac dinh dtroc bac n cua phan irn

2. thing hoc cac [Man ting phtic tap

Trong Ong hoa hoc, cac phan 1mg phdc tap bao gom cac phan
ung thuan nghich, song song, n6i

1. Phan frng thOn nghich b4c 1

k,
A B
k,

Goi a la 'tong (10 dau cila A ; x IA do giam 'tong dQ A sau th6i

gian t va xe IA (10 giam nOng do A khi dat tai trang thai can bang.
Khi do, n6ng dO ctia A va B se là nhu• sau :

315
 t=0 Can bang
A a a—x a — xe
0 x xe
2,303 ig xe
=
t xe — x

ki
= K (hang s6 can bang)

Tir hai phuong trinh nay, ta tinh dtroc k 1 va k, mot each rieng re.

D6i v(i phan (.mg thuan nghich bac 2.

ki
A+B C+D
k2

vOi cac dieu kien nOng (10 dau dm A va B bang nhau va bang a ;
con nOng dO dau ciaa C va D bang 0 ; Goi x IA (.10 giam nOng dO
cira A va B sau tiled gian t, ta co :

1 —
k1 —k, = 1 . In m2 (m1
t mi —m, mi(m, —x)

(1± K)
vai =
1—K'

1 k,

Biel hang s6 can bang K, se tinh throe m 1 va m,, tic do tinh &roc
hieu k1 — k, ; k i va k„ se duce x6c inh klii bi6t ti s6 k1/k, va
hieu ki — k,.

316
2. Phan (mg song song mot chieu bac 1

D6i vdri phan (mg song song clang nay, pinrcing trinh Ong hoc se
2,3031g a
la : k i + k2 =
t a -x

VOi a la ming dO chat A or t = 0 ; x la dO giam nong dO chat A O.

tai thOi didm t.

Tuong to nhlr tren, d6i v&i phan (mg song song mot chieu bac hai
dang :

C+D

A+13'

2,303 b(a - x)
to co : k i + = ig
t(a - b) a(b -x)

voq a va b la n6ng d0 chat. A va B tai t = 0

3. Phan (nig n6i tiep

Dang don gian nhat caa loci phan (mg nay ducic bien thi bang
phixo'ng trinh :

kt k2
A B C

317
 t=0 a 0 0
t a-x x -- j
y

x a(1-e-1(11 ) ; [A] = a - x = a.e-k11

j=[C] = [k 2 (1 _ e-kit )- - e-k2t )1

k2 - k t

kia
e - e-k2t
k, - ki
Khao sat su bie'n thien ming (.10 cac chat dau.A, chat trung gian B
va san phdm cu6i ding C, to tinh du6c thM gian t max dd san
phdm trung gian B dat n6ng d6 cure dai [13}-inax :

ln(ki /k2 )
k1 -1(2

k2
l -k2
[B]am =a k, k

Bai tap ca loi giii

Bai 1. Su phan hay N105 :

2 N205 = 2 N204 + 02
tuan theo guy luat &Ong hoc dm phan img bac 1 vai hang s6 t6c
(.16 k = 0,002 phUl l . H6i co bao nhieu phan tram N 205 bi phan
hay sau 2 gRi ?

318
 Giai.

Hang s6 t6c (10 cua phan tIng bac 1 khOng phu thuQc cach bieu
thi n6ng do, do do „dat a = 100 thi :

1 100
k= 1n
t 100—x

Ap dung bang s6, ta co :

2 303 100
0,002 = ' lg
60,2 100—x

do do x = 21,35%.

Bai 2. Su phan hay H2 O, trong dung dich nude la phan (mg bac 1. De
tim gia tri trung binh dm hang s6 t6c (10 phin img, ngtrefi ta dem
chudn (10 cUng mot the rich dung dich 112 0, i cac thi diem
khac nhau bang dung dich KMnO4 thi thu du'orc k'6t qua sau :

t [phut] 0 10 20 30

n - the tich KMnO4 (mL. ) 21,6 12,4 7,2 4,1

Xac dinh hang s6 t6c (10 k caa phan ung phan hay H202.

Giai.

Hang s6 t6c do phan img mot chieu bac 1 dtryc xac dinh bang
phtro'ng trinh :

2 3031 a
k= ' g
t a—x

VI hang s6 t6c dO cita phan Cmg bac 1 khong phu thuQc cach bieu
thi tieing do nen co the thay nong do dau a bang the tich KMnO4

319
 da dung dd chuan dO dung dich H202 ?I thOi didm t = 0 ; con gia
tri a — x duoc thay bang s6 ml KMnO 4 dung de' chuan dO dung
dich H2O, cac thOi didm t da cho.

Vay :

2 303 21 6
ki = ' lg ' = 0,0553
10 12,4

2 303 21 6
k2 = ' = 0,0555
20 7,2

2303 21,6
k = lg = 0,0555
- 30 4.1

1 (k, + +k,) = 0,0554 phut-1

—
k=3

Bai 3. Su thity phan axetat etyl bang xut la phan itng bac 2. Su bidn
thien luong axetat etyl va xiit theo thOi gian ducic cho dudi day :

t (giay) 0 393 669 1010 1265

Lacing kiam (mol) 0,5638 0,4866 0,4467 0,4113 0,3879

Lacing este (mol) 0,3114 0,2342 0,1943 0,1589 0,1354

Tinh gia tri trung binh dm hang s6 t6c dO phan titng.

Giai.
Goi a va 11 la luting xiit va axetat etyl or thOi didm t = 0 va x la
luring ruou hay natri axetat hinh thanh sau thOi gian t, to co
phuong trinh dQng hoc sau :

320
 = 2,303 b(a —x)
k lg
t(a —b), a(b—x)

2,303 0,3114(0,5638 — 0,0772)

1(1 = 1g = 0,138
393.(0,5638— 0,3114) 0,5638(0,3114 — 0,0772)

2,303 0,3114(0,5638 — 0,1171)

k2 = 18
669.(0,5638— 0, 3114) 0,5638(0,3114 — 0,1171) = 0,141.

2,303 0,3114(0,5638— 0,1525)

k3 = lg = 0,140
1010.0,5638-0,3114) 0,5638(0,3114 —0,1525)

2,303 0,3114(0,5638— 0,1760)

k4 = lg = 0,143
1265.(0,5638 — 0,3114) 0,5638(0,3114 — 0,1760)

1 .
k = —(0,138
4 +0,141+ 0,140 + 0,143) = 0,140 mol .gtay

Bai 4. Axit fomic se klar trOpeOlin yai sir có mat cila xtic tac Pt theo
phtrong trinh :

/ OH
HSO — —N=N + 4HCOOH S.P.
\
OH

Duai day la kel qua do diro'c cua skr Wen thien nong dO trOpeOlin
theo thCri gian :

t (phUt) 1 2 3 6 10 14 20 26 33 40

0.103 5 4,82 4,7 4,25 3,76 3,30 2,6 2 0,94 0,15

[mot/1]

21-BTHL-A 321
 Hay chirng to rang phan (mg dien ra theo bac khOng.

Giai.

Ve do till bleu dien skr bi6n thien nong c10 tropeOlin theo tired
gian. DO thi thu dune IA rn6t dung thang (hinh X.1), cluing to
phan kha trOpeOlin bang HCOOH Ia phan irng bac 0. Phan
ung khOng dien ra theo ti le hop thdc.

c.io3

0 10 20 30 t

Hinh X.1

Bai 5. Sur phan hiry axeton dien ra theo phuang trinh :

CH3COCH3 ---> C2H 4 +H, +CO

Theo thii gian phan Ting, ap suat chung caa he do clinic IA

nhu sau :

t [phut] 0 6,5 13 19,9

p [mm Hg] 312 408 488 562

Hay chirng to phan Crng IA bac 1 va tinh hang s6 t6c d6.

Giai.

322 21-BTHL-B
De? chumg minh phan ting phan hity axeton la bac 1 ta sir dung
phtrong phap the cac ki'en vao phtrong trinh &Ong hoc bac 1 xem
cac hang s6 t6c dO thu duck: c6 hang dinh hay khOng. Vi dp suit ti
le v6i ming dO -chat nen trong phuong trinh Ong hoc, nong dO
axeton duot thay bang dp suit rieng phan. Goi 130 la dp suit dau cua
axeton va x la ap suit rieng phan cita C2H4 6 th6i didm t, ta c6.
PH = Pco = x. Ap suit axeton c th6i didm t la po - x.
2

Nhu vay, ap suit chung cua he bang :

p=(po -x)+x+x+x=po + 2x

suy ra : x = P-P°
2

va : 13- Po 3Po
Po -x = Po
2 2

Hang s6 t6c do cila phan ting mot chidu bac 1 la :

2,303
k= 1g p°
t po -x

2,303 2p
k= lg
t 3po - x

Ap dung bang s6 ta c6

2 303 2.312
= ' lg = 0,02568 phu't
6,5 3.312 -408

2,303 2.312
k2 = 1g = 0,02552 phut-1
13 3.312-488

323
 , 2,303 2.312
K3 — 1g = 0,02569phtlt-
19,9 3.312-562

13 (0,02568 +0,02552 +0,02569) = 0,02563 phut'

k =—

Bai 6. O 25°C su thity phan axetat metyl vei su co mat cUa HCI du,
nong dO 0,05M la phan (mg bac 1. The tich NaOH dung de trung
hoa 25cm3 hen hep phan img theo thei gian la nhu sau

t [plait] 0 21 75 119 co
r 31 24,4 25,8 29,3 31,7 47,2
VNaOH
Bang phueng phalli de thi hay giai tich, hay tinh hang s6 t6c dO
va thei gian nira pilau (mg.

1) Phueng phap giai tich tinh hang s6 t6c de k.

2,303 a
k= 1g
t a —x

6 day a la neng de dfiu dia. este ;

a — x la nOng de este Cr thei diem t.

Neu V. 6 thei diem t = 00 là the tich dng vei sir ke't thuc phan
Ling they phan este trong mei trueng axit ;

Vo la the tich Ling vei thei diem t = 0 thi hieu V. — Vo se ti le

vei Ming dO dau dm este. Con hieu — V, se ti le vei neng de

este i7 cac thei diem t (V, la the tich o thei diem t). Do do

324
 2,303 Voo V o = 0,003016
1(1 = u
t •oo - Vt

2,303 47,2 -24 4

k2 = 1g ' = 0,003224
75 47,2 -29,3

2,303 47,2-24,4
k3 = 1g = 0,003244
119 47,2-31,7

= 0,003161 phiit-1

2) Phuung phap do thi :

Ta 'sit& lai bidu auk s6 t& dO :

V - V0
kt = 2,3031g
V., - Vt

Ig(v_ - vt)

1,4

1,3

1,2

1,1
0 40 80 120 t

Hinh X.2

325
 hoac kt = 2,3031g (NT - Vo ) 72,3031g - N/1 )

Tir day ta thay rang•n6u day la phan ling bac 1 thi lg (Vco Vi)
phai phu thuOc bac nhg vao tiled gian t.

Thuc vay, de; thi thu dtrot trong toa d() lg (N/ c, - Vt) - t la dung
thang vOi do d6c - k/2,303 = - 1,46.10 3, titc k = 3,36.10 3 phut 1
(hinh X.2).

0,693 0,693
Th6i gian rata phan frng t = = = 206,3 phut
•k 3,36.10-3

BM 7. De xac dinh bac cUa phan ting :

2C,H5 - OH + 2Br, -+ CH3COOC,H5 +4HBr

ngir6i ta lam hai thi nghiem vcci k6t qua sau :

Thi. nghiem N6ng d0 brom [moil/L) Th6i gian [giM

4,24.107-3 0
I
1,12.10-3 1 Y,1

8,14.10-3 0
II
4,07.10-3 12,5 i

Xac dinh bac ciia phan ting tren khi co du riscru etylic.

Giai.

Theo diOu ki'en cua dau bai, ta thAy cr CA hai thOi

gian dOu Crng vCri nira nOng (.16 dau da mat di trong qua trIrth phan
ung, do do bac n dia phan Ling se la :

326
 n=

Thay bang s6 ta dttqc :

11,1
lg--
12,5 +1=0,821
n=
8,14
lg
4,24

Vay phan Ong brom-hoa rugu etylic du la phis' Ong bac 1.

Bai 8. Dgi vai phan Ong don gian A -÷ B, khi nong dg dau cila A
bidn thien tir 0,51 mol/L den 1,03 mol/L thi thin gian nira phan
Ong giarn tir 150 den 75 giay i 25°C. Xac Binh bac dot phan Ong
va hang s6 Vic d6 i 25°C.

til
lg
n= 12 + 1
Ap dung bidu thdc :
a2
lg—
al

150
lg
ta dogc : n= 75 +1
1,03
4 0,51

suy ra : n 2.

Doi v6i phan ting b4c 2, ta c6 thgi gian aim pilaff Ong :

327
 1
k.a

1
suy ra hang so t6c dO k = 1 = =1,31.10-2 MOi-1.1.giay-1
t.a 150.0,51

Bai 9. Deli vai phan tIng : A B,

k2

cac hang s6 t6c do k1 = 300 giay71 ; k, = 100 giay-I. 6 thM

• diem t = 0 chi co chat A va khang có chat B. HOi trong bao lau
thi mat nth krong ban dau chat A bie'n thanh chat B ?
Giai.
kl
A B
k2
t= 0 a 0

a a
t
2

Ap dung cang thirc da cho :

ki + k2 = 1 ln X e
t Xe --X

6 day nong dO ltic can bang xe dircic xac dinh thong qua hang s6
can bang K :
[B]
K = = Xe
[A] a - xe
Sau khi bien doi to dime :

328
 aK
xe
1+K

aK - x(1+ K) '
va Xe — X =
1+K

2,303 aK
Cu6i cling k1 + k, = 1g
t aK - x -Kx

a
vi x= I.

2 303 aK
nen k i + k2 = ' 1g
a Ka
aK

2,303 2K
1g
T 2K -1-K

= 2,303 1g 2K
T K -1

VI K = kl
k2

2,303 2ki
nen T = 1g
ki k2 k1 -1(2

2,303 2.300 -3 pay

lg = 2,7.10
300+100 300 -100

Bai 10. O 453°C su (long phan hod cis - trans dm dimetyl

xiclopropan la pilau Cmg thudn nghich bdc 1. Thanh phan phan
tram dm Mn hop phan Crng. then thoi gian ducfc cho dt.r6i day :

329
 t [giay] 0 45 90 225 270 360 495 675 00

% dang trans 0 10,8 18,9 37,7 41,8 49,3 56,5 62,7 70

Tinh hang so can bang va hang s6 t6c (10 phan tIng dung phan
hoa va hang s6 t6c dO phan ring nghich.

Giii.
Su dung phan hoa,cis - trans &roc bi6u din bang phirung trinh :

ki
bong phan cis [Yong phan trans
k,

Goi a IA phan tram hic dau cita dang cis ; con x là phan tram
dang trans 6 th6i di6m t ; nhu th6, phan tram dang cis 6 th6i
di6m t là (a — x).

T6c (10 phan irrig hinh thanh clang trans là :

dx
k i (a —x)—k,x
dt

O trang thai can bang, t6c dO phan dug bang kh6ng, do do :

k1 (a — xe) = k2xe

v6i xe IA phan tram (long phan trans 6 trang thai can bang. Hang
so can bang K &roc xac dinh bang :

K_ ki = x e
k, a — xe

Theo di6u ki6n dau bAi thi xe = 70% a, con (a — xe) = 30% a.

70
Vay.: K= = 2,33
30

330
Hang so to:5'c dO phan irng da cho bang

2,303 xe
ki + k2 = k = lg
t xe -X

k1 +k2
hay ig xe - lg (xe - x) =
2,303

Tir day thSy rang do tilt cua lg (xe - x) phtt thuOc t phai la dtrilng
/0 (lc1 +k 2 \
thang viii dO chic tga = (Hinh X.3).
2,303 i)

Ig(xe -

1,80

1,40 DO d6c = -1,46.10-3 giay

1,00

200 400 600

HinleX.3

t [gray] 0 45 90 225 270 360 495 675

x 0 10,8 18,9 37,7 41,8 49,3 56,5 62,7

xe - x 70 59,2 51,1 32,3 28,2 20,7 13,5 7,3

Ig (xe - x) 1,845 1,772 1,708 1,509 1,450 1,316 1,130 0,863

331
 Ttr do thi ta tinh dtmc dO deic tga = - = - 1,46.10-3.
2,303

Vay k = ki + k2 = 2,303 . 1,46. 103

= 3,36. 103 giay I

Ta lai co k1/k2 = 2,33, do do k1 = 2,33 k2.

Thay vao phtrang trinh k ta c6 :

?,33 k, + k2 = 3,36. 10-3

3 36A 0-3
k2 = ' = 1,01.10-3 giay-1
3,33

k1= 2,33 k, = 2,33. 1,01.10 3 = 2,35. 103 giay 1

Bai 11. Phan tlng song song ti-en hanh theo sir do :
B
k/
A
\C

Xac Binh cac hang so t6c dO k1 va k2, bi6t rang trong hon hop
cac san phdm phan (mg co 35% chat B, con nOng do chat A giam
di mat nira sau 410 giay.
Giai.
D6i vdi phan (mg song song mot chieu bac 1, ta c6 :
2,303 a
ki + k, = 1g
t a-x

332
 ,
n6u x = a/2 thl k1 + k2 = 0,6930693= 1,68.10-3
T 410

San phdm phan (mg gom c6 B va C, trong do B chi6m 35%, vay

C chi6m 65%.

k35
Taco: = = 0,537 (2)
k2 65

Giai he phtrong trinh (1) va (2) to &roc :

k1 = 0,59. 10 3 giay 1

= 1,09. 10 3 giay I

Bai 12. D6i vOi phan ting n6i ti6p

k, k2
A --> B --> C

nong dO chat B dat gia tri ckrc dai sau 103 giay ; con Wong dO
chat A giam di 2 lan sau 160 giay. ?Lac dinh k 1 va k,.

Giai.

Hang s6 k1 dtroc xac dinh the() th6i gian nira phan img cfra A
hien thanh B.

0 693
k= ' = 4,31.10 3 giay
" 160

2,3031g k2
ki
Ap dung cOng thirc t max =
k2 —k1

333
 k
2,3031g
4,31.10--
103 =
k, —4,31.10-3

Giai phaung trinh to dtrqc : k, = 4,13. 10-3 gia.y I .

Bai tap tit giii

X.1. d 913K, hang s6 t6c d6 phan irng dehidro hod metylamin :

H3CNIT2 --> HCN + 2H2

bang 5.10 3 giay-I . Tinh thii gian de n6ng d6 metylamin giam

di 2 lan.

Dap so : 138 giay

X.2. Hang s6 t6c dO phan irng to oxi hod to khir cita ion hidro bromu
trong mOi trubng kiern :

3 BrO BrO3 + 2Br

bang 9,3.10 4 (mol/L).giay . Nong dO dau cua ion BrO bang

0,1 mol/L. Tinh thUi gian de 30c,4 lacing BrO mat di trong
phan (mg.

Dcip so : 4,61.103 giay.

X.3. O 17°C phan (mg hreang phan tir :

A + B --> S.P

334
 xay ra vai nong dO dau ciia chat B bang 2,5 mol/L. Su theo dOi
qua trinh bie'n dOi chat A theo th6i gian thu dtroc ket qua sau :

CA [mol/L] 104 10 7,91 6,31 5,01 3,98

t [phut] 0 10 20 30 40

Hay chang to rang phan (mg tren la bac 2 va tinh hang s6 t6c dO.

-4
Dap so': 1,54.10 mol-1 .L.ph

X.4. O 50°C phan ring phan huy clo benzendiazoni :

C6H5N-)C1 —> C6H50 + N2

xay ra v6i nong dO dau bang 10 g/L.

Kel qua theo doi Wong N2 thoat ra theo th6i gian thu &roc nhtr
sau :

t [phut] 6 9 12 14 18 22 24 26 30 co

VN2 [cm3 ] 19,3 26 32,6 36 41,3 45 46,5 48,4 50,4 58,3

Xac dinh bac cita phan ting, hang s6 t6c (10 va thed gian nira
phan

DOp so : b4c 1 ; 1,2.10 3phtit I ; 630 giay.

X.5. Dtrai day Ia lc& qua thu duvc d6i v6i sir phan huy glucozo trong
dung dich nuerc :

C [mol/L] 56 55,3 54,2 52,5 49

t [phtit] 0 45 120 240 480

335
 Hay chcrng to rang phan ang phan hay glucozo la bac I. Tinh
hang s6 toc d6 va th6i gian nua phan ang.

Dap sa 2,72.10 4phia I ; 6.103 phut.

X.6. Slater da nghien ccru d6ng hoc caa phan Ling giCra Na,S2 03 va
CH3I 6 20°C va thu cluoc ke't qua sau :

t [phtit] 0 4,75 10 20 35 55 co

[Na2S2O3] 35,35 30,5 27 23,2 20,3 18,6 17,1

[CH3I] 18,25 13,4 9,9 6,1 3,2 1,5 0

Bang do thi va bang phtrong phap giai tich hay chung to rang
phan Ung da cho là bac 2.

X.7. Phan ang trung hoa nitro etan trong dung dich na6c cluqc m6 to
bang phaong trinh d0ng hoc :

d[OH-] d[C,H5NO2]
k [C,H5NO2] [OH ]
dt dt

O 0°C va n6ng d0 dau caa hai chat la 0,01 mol/L, th6i gian nira
phan ling bang 150 giay. Tinh hang s6 t6c

Dap so : 0,667 mol .L:giay 1

X.8. Phan ang giCra metyliodua va trietylamin trong CC14 xay ra theo
phuong trInh :

H3CI ± (C2I-1,-)1N —> [(C415)3 - N+ - CH3I--]

D theo dOi str bien d6i amin theo th6i gian, ngtecti to ti"e'n hanh
hai dot ail nghi'em sau :

336
 flat I vgi nong do dau cua CH3I va (C2HS)3N bang 4,6.10 2 va
0,403 mol/L.

t [phut) 0 13 26 43 65 90 170

Camin [mol/L] 0,103 0,397 0,392 0,386 0,380 0,375 0,365

Dot II vgi nong dg dau cua hai chat nhu nhau 0,224 mol/L.

t [phut] 0 2 10 20 40 90 150 200

Camin [mol/L] 0,224 0,221 0,212 0,201 0,183 0,149 0,122 0,106

Hay chi:mg to rang trong ca hai dot thi nghiOn, bac cda phan tIng
bang 2 va xac Binh hang s6 t6c dg.

Dap se; : 2,5.10 2mol 1 .L.ph

X.9. d 3 10°C su phan hity AsH3 (khi) :

2 AsH3 --> 2 As + 3 H2

dugc theo dal bang su bie'n thien dp suat theo thgi gian :

t [gig] 0 5,5 6,5 8

p [mmHg] 7 3 3,32 805,78 • 8 1 8,1 1 8 3 5,34

Hay chtIng to phan Crng phan tidy khi asin 1a bac 1. Tinh hang s6
tgc dg.

Dcip .56 : 0,0404 gig 1

X.10. Smith va Lorensen da khao sat su thuy phan axetat etyl trong
mgi trugng kiem g 30°C :

CH3C00C2H5 + NaOH —> CH3COONa + C,H5OH

22-BTHL-A 337
 Nong dO dau cita hai chat bang 0,05 mol/L.

Theo doi str giarn nong do este x theo thei gian, hai Ong thu &roc
lc& qua nhu sau

t [phut] 4 9 15 24 37 53 83

- 3
x .10 [mol/ L]5,91 11,42 16,30 22,07 27,17 31,47 36;44

Bang do thi hay chting to bac cda phan ang bang 2. Xac Binh
hang so t6c dO theo phtrong phap do thi va bang anh town.

Dap so : 0,640 mol '.L.ph1

X.11. Khi thily phan alkyl bromua trong dung dich rtrou - ntroc

RBr + OH ROH + Br

ngu0i to thay rang vari ming do dau cua hai chat bang 0,04 mol/L
thi de thu cltroc 0,005 mol/L Br, can 47.103 giay. Song O. nOng
dO dam hai chat la 0,1 mol/L, de dat &roc mut do chuy6n hoa
rihtr track thi th0i gian phai la 4,7.103 giay. Tinh hang s6 t6c dO
thily phan.

flap so : Phan irng bac 2 ; 2,13.10 3 mol 1 .L.giay 1

X.12. Su phan hit)/ etan :

C2H6 C,114 + H2

0 856K dtroc theo dOi dua vao sty bin thien ap suat chung p cita
he theo thOi gian o the' tich c6

p [mmHg] 384 390 394 396 400 405 408

t [giay] 0 29 50 64 84 114 134

338 22-BTHL-B
 Xac dinh hang s6 t6c de cita phan king bac 1 & tren bang 2
phuong phrip giai tich va do thi.

Dap so : 4,83.10 4giay 1

X.13. D6i su phan hay trong pha khi cira etilen oxit or 687K :

C2H40 —> CH4 + CO

ngutri to thu &roc kel qua sau :

Phe. [mmHg] 116,5 122,6 125,7 128,7 133,2 141,4

t [phut] 0 5 7 9 12 18

Hay chting to rang su phan hay C2H40 la phan ling bac 1 (bang
do thi) va al-1h hang s6 t6c de phan Ling.

Dap so : 1,43.10-2phat-1

X.14. Da kien duati day, thu cluo'c trong su phan hay NH3 tren be mat
vonfram :

Ap suat clau [mmHg] 65 105 150 185

T [giay] 290 460 670 820

Xac dinh bac caa phan (mg.

Dap so- :b4c 0

X.15. Axetat etyl bi thay phan vai six có mat dm NaOH. Nong de dm
hai chit thai diem t = 0 bang 5.10 2 mol/L. ThOi gian nira phan
Ling bang 1800 giay, con thi gian de 75% phan Ling duoc tien

339
 hanh la 5400 giay. Xac dinh bac cita phan tIng va hang s6 toc do
phan

Dap sa": bac 2 ; k = 1,11.10-2mol 1 .L giay

X.16. D6i vgi qua trinh nhiet phan trong pha khi :

A (K) ---> B (K)

ngubi ta thu dugc ket qua sau :

t [phut] 0 5 10 15 30 00

Ptoan phan [mmHg] 200 267 300 320 350 400

Xac dinh bac dm Oki ling bang c16 thi.

Dap sa- : bac 2.

X.17. Ngtroi ta phan huy 15cm3 dung dich H2O, co xtic tac de thu
dugc oxi va nuoc. Neu su phan hity xay ra hoan toan thi-thu dugc
6,18 cm3 oxi dieu kien tieu chuan. O cac thgi diem trung gian,
the tich oxi thu dugc la nhu sau :

t [phdt] 2 4 6 8 14

Vo,(cm3 ) 1,24 2,36 3,36 3,98 5,23

Xac dinh bac cita phan 1mg va hang s6 t6c de phan 1mg.

Dap so.: Bac 1 ; 0,134 phut

X.18. Bang phuang phap dp ke. ngtrgi ta theo dOi t6c dg phan huy
N70 tren be mat day yang d6t nong 6 990°C va thu dugc du
kien sau :

340
 t [plult] - 0 30 . 52 .100

p [mmHg] 200 232 250 272

a) Gia thi6t rang san phdm phan fmg IA N:2 va 0,, hay tinh dp
suit cu6i cling va th61 gian nira phan img.

b) Cling tai• nhiet dO teen, song ap sugt dau IA 400 mmHg, con
th6i gian nira phan (mg IA 52 phtit, thi phan se dien ra
theo bac may ?

Dap se : a) 300 mmHg ; i = 3120 giay,

b) bac 1

X.19. 6 700°C phan img :

2 NO + 2 H2 N, + 2 H,0

diem ra v(i cac dieu kien nhu sau :

Ap sugt dau rieng phan PNO = f(t)

pNo [atm] pH, [atm] t [giay] pNo [atm]

0,5 0,2 30 0,00245
0,5 0,1 30 0,0012 -
0,25 0,2 30 0,00061
a) Co the rut rakel luan gi ye quy luat dOng hoc dm phan (mg
dua vac) du kien tren ?

b) Tinh hang s6 t6c

Dap so" : a) Bac 3 ; b) 4,9.10 2.atm-2.giay-1

X.20. 6 600°C PH3 (K) phan tich thanh P4 (K) va H,. Ap sugt toan
plian ciia he then thOri gian throe ghi lai dtrai day :

341
 t [giay] 0 60 120 co

p [mmHg] 262,40 272,90 275,53 276,40

a) Cho bia bac cna phan ring. Tinh hang s6 t6c do.

b) Phan tIng nghich tuan theo quy luat Ong hoc dudi clang

h
/dt =k,pp .p H2
n

Xac dinh a va b.

c) Gia thiet rang dp suat dau cita PH3 IA 18 mmHg, t = 20 giay

va phan (mg la bac 1 d6i vdi PH3. Hay tinh hang s6 t6c d6 k1
cfra tatting hop nay.

Neu su phan tich PH3 la phan (mg bac 2 thi hang s6 t6c dO
k1 se la bao nhieu ?

Dap so : a) bac 1 ; 0,023 giay I ;

b) a = 1/4 ; b = 3/2.; c) 0,035 giay' ; 2,7.103mmHg ' .giay I

ki
• X.21. Phan (mg A B (bloc (lac trang bang cac du ki6n sau : ruing

dr) dau Oa A bang 0,05 mol/ L, cua B bang 0 ; nang d6 cUa A Cr

trang thai can bang la 0,01 mol/ L. Xac dinh ti s6

Dap sO.: 4

ki
X.22. D6i vdi phan ring : A B, nguOi to thi6t lap &roc rang
k2

k1 = 0,2 giay I va k, = 0,4 giay'. Nong d6 dau cUa A va B bang

342
 0,8 va 0,3 mol/ L. Xac dinh n6ng do lac can bang xe va hang s6
toc dO k (k = k1 + k7).

Dap se; : 0,06 ; 2/3

X.23. Hang s6 can bang caa phan (-mg thuan nghich bac I bang 10.
Hang s6 t6c do phan Ling thuan bang 0,2. Hay xac dinh th6i gian
de nong d6 chat dau va san pham dat tOi trang thai can bang ne-u
tai t = 0 trong he chi c6 chat &in.

Dap sa- : 21

X.24. Phan ting este hod etanol bang axit fomic trong mai tru6ng axit
clohidric a 25°C dien ra theo phuung trinh :

k1
C2H5OH + HCOOH ---1 HCO0C11-15 + H2O
k2

Trong tru6ng hop phan Ung tien hanh v6i lirong du etanol thi
hang s6 t6c dQ phan tzng este hoa bang 1,85.10 3 phut-I , mat

khac hang s6 t6c d0 phan ting nghich bang 1,76.10-3

Bia Ong d0 dau cua axit fomic bang 0,07 mol/ L. Xac dinh :

a) I\16ng do can bang dm fomiat etyl.

b) Th6i gian de si este hod tie'n hanh clugc 80%.

Dap so' : a) 0,0359
b) t08 = 2,67.104 giay

X.25. Su dong phan hod cis - trans dia. stilben 6 280°C dien ra theo
phuong trinh :

343
 Ph Ph
\ /
C =C
/ \
H H
Qua trinh ctiuydn hod thuan nghich cila 2 clang cis - trans theo
, thYi gian dtryc cho dtroi day :

t [giay] 0 1830 3816 7260 12006 00

% thing phan cis 100 88,1 76,3 62 48,5 17

Tinh tong hang s6 t6c do k1, k,.

Dap so : 8,10.10 5 giay 1

X.26. O 20°C ngtrYi to theo dOi bieit d6i a glucozo thanh

SIT
glucozo va ngtryc lai dua vao g6c quay quang hoc theo thYi gian
va thu dtroc kei qua sau :

Goc quay a [0] 20,26 18,92 16,82 15,22 14,06 13,18 10,60
t [phut] 10 20 40 60 80 100 can bang

a —glucozo 13 — glucozo
k2

Chirng minh rang day la phan (mg thuan nghiCh bac 1 va tinh
k1 + k2.

DO so : 1,46.10 2
k1
X.27. Phan img song song : A —› B
k
2

344
 dircfc dac tiling bang cac dit ki6n sau : hi6u suat ciia sir hinh
.thanh san pham B la 63% ; th6i gian nira phan ling cila sir bi6n
cl6i A la 19 phut. Tim k1 \fa k2.

flap so' : 2,30.10 2 ,

1,35.10 2 pluit 1

X.28. Sr phan huy rugu izopropylic v6i. V203 lam xtic tac din ra
theo phirang trinh

C3H60

C3H7OH k2 > C3H6

C3H8

Gia thi6t rang phan irng theo moi hiking la mot chieu bac 1, hay
thi6t lap bidu thdc hang so tOc d() phan ling k (k = k1 + k2 + k3) voi
a la Ming d6 dam cua C3H7OH, x la dO giam n6ng dO C3H7OH sau
thai gian t. Xac Binh ming dO dau cua C3H7OH n6u sau 4,3 giay 6
588K, n6ng d6 cac chat trong hon hop phan ling la nhu sau :

Cc3H7ox = 27,4 ; Cc3H6 0 = 7,5 ; CC3H6 = 8,1 ; CC3H8 = 1,7 ;

Dap so : 44,7 mol/L

X.29. Doi voi phan ling song song mot chi6u bac 1 :

A
C

345
 Su phu thuQc nong (10 cac chat A va B vao thiri gian t dtroc bidu
thi bang cac phuong trinh sau :

CA = a.e-11'08`
a.(1 _ e-0,06t
CB )

Hay cho bidt trong ba phuo'ng trinh duOi day, phoning trinh nao
bidu thi dung su phu thuQc nong (10 chat C vao thin gian :
-0,081 -0,06t
Cc = a(e —e )
= _ e-o,o2t)
Cc all
-0,041)
Cc = a(1 — e

a la nong d() dau cita A.

X.30. ChUng minh rang d6i viii phan (mg n6i_tidp dang :

k1 k2
>C
A >B

thi, dieu kien k t >> k2 va ki<k,, co thd sir dung phtro'ng trinh
dung hoc cUa pilau img mot chieu bac .1 thOng thuOng de dac
trtrng cho qua trinh Wen dOi tren.

k1
X.31. Cho phan Crng not tie-p : A---> B k2 > C

Khi nong (10 chat B dat gia tri corn dai thi ti s6 nong dO cac chat
A va B (CA/CB) bang 4:5 ; con thei gian dd 25% chat A chuydn
hod la 85 giay. Xac dinh k1 va k,.

Dap so : 3,38.10 3 ; 15,3.10 3 giay-1

346
X.32. Su phan hay phong x4 dOng vi 21°Bi di6n ra theo so do :

210
Br• (5 ngay dem) 210 Po (138 ngay dem)
208Pb

Xac dinh their gian (ngay) de luting (king vi 210Po dal gia tri
cuc dai.

Dap so.: 24,87 ngay dem

X.33.Su phan hay phOng xa caa (king vi 30Zn dien ra theo so dO :

3 0 Z a —> 3 G a —> 3 2 Ge

Ham luting cue dai caa (long vi phong xa gali se dal duorc sau
30,3 gra' theo do thi ti s6 gifla s6 nguyen to caa (long yr kern va
s6 nguyen tit caa dOng vi gali la 3,48. Xac dinh chu ki ban hay
caa (long vi kern va gali.

Dcip so- : 41,5 ; 11,9 gra.

347
 CHOONG XI
DING HOC CAC QUA TRiNH SO CAP

Anh tufting cua nhiOt di) den 16c dt) pilau Ling
Theo quy tat: kinh nghiem am Van H6p thi m6i khi nhiet de
tang them 10 de thi hang s6 t6c de tang va do do t6c de phan
Ung tang len tit 2 den 4 Ian :

y = kt+to 4
kt

Met each dinh luong, Areniut citng da thiet lap &roc su phu
thuee cad hang s6 t6c de k vao nhiet de dtrOi clang vi plan :

clink E
dT RT2

6 day E Ia nang Wong hoat hod.

Phuo'ng trinh Areniut con dtroc via dtrOi clang khdc :

348
 E
k e RT

v6i A la thira s6 Areniut va co ding thin nguyen v6i hang s6 t6c

dO. Thira s6 A con bieu thi tan s6 va cham gift cdc phdn tir cita
cac chaftac dung.

fle xdc dinh nang luting hoat hod E, ta có the sir dung mot trong
cdc phtrung phdp sau :

a) Phuorng phdp dO thi :

Logarit 2 ve"phiro'ng trinh Areniut :

E
lgk = IgA
2,303 RT

Tirday ta thgy do thi cua sir •phu thtiOc lgk vao. nghich dao cua
nhiet dO tuyet d6i phai Ia mot &rang thang v6i he s6 goc
tga = — E/2,303R.

b) PI-arcing phdp xac dinh hang s6 Vic deo fr 2 nhiet dO :

1g
k 'T
2 = E 1 1
kTI 2,303R Tt T2

2. Li thuy6t t6c ao !iatt ung

1. Thuy& va cham va va cham boat diing

Li thuyet dau ti'en ye t6c dO phan ung khang dinh rang, de hai
phan tir A Va B có the phan (mg v6i nhau thi trade het phai CO six
va chant gifra hai phan tir va t6c dO phan ting se phu thuOc vao s6
va cham nay. D6i vOi phan (mg gifta hai phan tir khi ding Ioai

349
 kidu 2A C + D, thuy6t dOng hoc chSt khi cho phep to thie't lap
duoc bidu thirc ve tan s6 va cham, tilc la s6 va cham trong don vi
thOi gian va guy vd dorn vi thd tich :

)1/2
2 2 RT
ZAA .=.11 G

o day n la s6 phan tir chfit A trong don vi thd tich ; a la ban kinh
va cham ; M - kh6i luting phan tit.

Neu va cham xay ra giita hai phan tit khac loai clang :
A+B-->C+D

thi s6 va cham se bang :

( 87cRT 1/2
2
ZAB = nA•n-. aAB
\ )

day nA va nB la s6 phan tit A va B trong don vi thd tich ; cYAB la

ban kinh va chain trung binh va duoc xac dinh bang :

aA +C713
C7 AB

IA la kh6i Wong rut gon tdc la :

M A .MB
=
MA + '13

Neu chi c6 va cham Oita cac phan tir thi cling chua dua den phan
ling, ma phan irng chi c6 thd xay ra n6u it luc va cham, cac phan
tit phai c6 mOt nang Wong du nao do. Areniut goi cac phan tit

350
nay IA phan tir hoat Ong. Khi do t6c dO phan trng gift hai phan
tir ding loci se 14 :

v = 2 ZAA.e -E/RT

Mat khac Ong hod hoc cho to :

k [A]2 = k . n2

Tit day bidu fink hang s6 t6c dO phan dng Wong phan tir cimg
loai se duoc xac dinh bang :

1 z .„-E/RT 2 nRT )IE/RT

/2
k =n2 AA = 4(1 e-
2
Ill
n

D6i vOi hai phan tit khac loci A va B thi t6c dr) phan trng :

v = ZAB.e-EiRT

vi v = nen hang s6 t6c dO k se bang :

nA.nB
)1/2
8irla .e-E/RT
k = crAB

So sanh bidu thdc hang s6 t6c dO ding nhu t6c dO phan dng tinh
wan theo thuy6t va cham hoat Ong vOi cac gia tri thuc nghiem
tuong (mg cho thay khOng có su phit hop (cac gia tri ii thuy6t
thuOng lon ho'n gia tri thuc nghiem) do do cac phtro'ng trinh v6
t6c dO va hang s6 t6c dO phai &roc hieu chinh bang each dua
them mot dai luting P — goi la thira s6 khOng gian, khi ay :

v = P.ZAB.e -E/RT
-E/RT
k = P-ZAB.e (kh i nA = nB = 1)

351
2. Thuyit phic chit hoat tiiing
Thuy& nay van gift nguyen nhirng luan didm co ban cita thuy&
va cham hoat Ong song cc') phat tridn them j kieit cho rang trong
qua trinh phan (mg xugt hien mot san phdm trung gian tam thQi
goi la pink chat hoat Ong. Gifra phirc chat hoat Ong va cac chat
tham gia phan tIng va cac san phgm c6 can bang va can bang nay
c6 thd ducic nghien am bang con &King nhiet dOng thong
thuQng. Thuc vay nal A va B la cac chat dau, C va D la cac san
phdm, X# la phirc chat hoat Ong (san phdm trung gian true c khi
phan huy thanh san phdm) thi can bang sau duck; thi6t lap :

A + B X#- C + D

T6c (IQ hinh thanh san phgm duct )(Ile dinh bang t6c dO cita su
chuydn pink chat hoat Ong sang trang thai chuydn tiep. Neu
Ae la bien thienthe"diing ap drig v6i hai trang thai ddu va phdc_
hoat Ong thi hang s6 t6c do duct xac dinh bang bidu thtic :

AG*
Ink = + const
RT

hoac sau khi bi6n dfii to c6 :

kT -
Ink PIT = _me RT

day k là hang s6 Bonxman ; h la hang s6 Plang.

AG

vi e RT

352
 kT
nen kPSI= —

v6i K là hang s6 can bang gift hai trdng thai deu va phtic hoat
Ong.

VI OG = OHS — TAS

k _ kT R .e RT
nen
P" h

6' day AS va OH# la entropi hoat hod va entanpi hoat hod.

Gina All va E co mot lien he : Alf = E — n.R.T

n bang 1 deli v6i phan dng don phan tir trong pha khi hoac deli'
v6i mot phan irng trong pha lOng. n se bang 2 deli v6i phan Ung
luting phan tir trong pha khi. Thay Ale bang gid tri da cho
phuo'ng trinh tren vao bieu fink kP to dtroc :

E
kT 1+— RT
k u = — e E .e —
P h

deli v6i phan irng don phan tir trong pha khi va. phan (mg trong
pha long. COn deli v6i phan ting Wong phan to trong pha
hang s6 t6c (.16 duoc xdc Binh bang :

E
kT 2+
k = —e E .e RT .
P" h

So sa.nh bidu thitc nay vii phuong trinh Areniut ta thgy deli v6i
phan irng ItrOng phan tir :

23-BTHL-A 353
 AS
kT 2 +-7'
A= e
h

AS
kT n+
MOt cach tong (vat : A = —e .E

vori n IA phan tir s6 cua phan

BM tap ce lei giai

Bai 1. He s6 nhiet (10 cUa phan (mg bang 3,5. ei 15°C hang s6 t6c d0
cua phan ill-1g nay hang 0,2 giay-1. Tim hang s6 t6c (10 Cr 40°C.

Giai.

Ap dung cOng thirc : 1(15+25 25/10 = (35)2,5

k15 7

kao = k15(3, 5)2.5 = 0,2.(3,5)2'5 = 4,6 giay-1

BM 2. Phan ling trong pha khi gitia amoniac va NO2 i7 giai down dau la
phan ting bac 2. Tinh nang luting hoat hoa va tri s6 A cita phuung
trinh Areniut, bie't rang et hai nhiet dO 600 va 716 K, hang s6 t6c dO
cua gia tri limn (mg hang 0,385 va 16 Imol/Ll I .giay I .

Giii.
Ap dung Ong thirc da bie't :

(
I
to co : Ig-
k r 2,303R T2

354 23-BTHL-B
 16 E (716-600
1g
0,385 2,303.8,314 716.600

E = 114,8 ki/mol

Thira s6 A duot xac dinh bang phuong trinh :

1g k = lg A
2,303 RT

114800
1g16= lgA
2,303.8,314.716

A = 3,8 . 109 [mol//] 1 giay 1

BM 3. Dueri day la du kien v6 str phu thuOc cila hang s6 t6c (10 Olin
phan hity axit axeto dicacboxylic trong nude (phan (mg bac
nhk) vao nhiet do :

t 0 10 20 30 40 50 60

k.105 giay 1 2,46 10,8 47,5 163 576 1850 5480

Xdc dinh nang Wong hoat hod.

Giii.

Tir phtrong trinh Areniut k = A.e E/RT

E
ta rut ra : lg k lg A
2,303RT

do thi cua lgk phu thuOc 1/T se la chkrng thang v6i he s6 goc
bang (hinh XI.1).
2,303R

355
 lgk 5,391 4,033 4,677 3,212 3,760 2,267 2,739

103/T 3,603 3,534 3,413 3,300 3,195 3,696 3,003

lgk
1

tga= -5,08.103

3,2 3,4 3,6 10'/T

Hinh XI.1

Tir do thi to thy E = 5, 08.103

2,303R

E = 2,303 . 8,314.5,08.103 = 97,3 kJ/mol

Bai 4. Trong mot phan (mg bac nhdt ti6n hanh Cr 27°C, n6ng (10 chdt
&du giarn di mot nira sau 5000 gidy. O 37°C, n6ng dO Odin di 2
tan sau 1000 giay. Xac Binh :

a) Hang s6 t6c (16 r'r 27°C.

b) Thad gian de Ong (16 dau giam Vri 1/4 el 37°C.

c) Nang luring boat hod.

Giai.

356
 kt = 0,693

0,693 —4 ys1
= = 1 39.10 pay
pa
27
274c 5000

0,693 -4 1
b) k = = 6,93.10 giay
37°C 1000

Th6i gian can thief de tieing dO &Ili a giant t(1i 1/4 tri s6 datt
37°C dtrqc xdc dinh bang cOng thin; :

1 a
t1/4 = .2,3031g
6,93.10-4 1/4a

= 2000 giay (bang 2.t)

6,93.10-4
6, 93.10-4 E ( 310-300
c) 18 _4
1,39.10 2,303.8,314 k 310.300

E = 124 kJ/mol
k1
Bai 5. Cho phan img : A(k) B(k)+C(k)
k,

25°C: = 0,2 giay

k,. = 4.10 4 glay-1.atm-1

Cdc gid tri k1 va k, se tang gap dOi khi nang nhiet dO len 35°C.
Xdc dinh :

a) Hang s6 can bang ct 25°C.

b) Nang hryng hoat hod d6i v6i phan frng thuan va nghich.

357
Giai.

02 4
a) - Hang so can bang K = kI = ' .10 = 500 atm
k2 4

E T2 -T1
- Theo Areniut 1g - =
kTi 2,303R T21).

E (308-298
lg 2=
2,303.8,314 k 308.298

= 52,52 kJ/mot
Bai 6. Tinh hang s6 toc c16 va toc (.10 caa phan tIng phan hay HI or
700K (Judi ap sugt 1 atm, biE1 rang ban nth va chant bang
350.10-12 m va E = 184 kJ/mol.

Giai.

S6 phan to trong don vi t116 tick (1m3) dtro'c tinh theo cling fink :

n = P .NA
RT
1,01325.105 N.m-2.1.6,073.1023
8,314.700
= 1,05.1025
/2
(7ERT
S6 va cham ZAA = 2n 2o2
M)

( 3,14.8,314.700 \t/2
=2.(1,05.1025)2.(3,5.10 K:52
178.10-3
= 1,02.1034 al -3.giay-1

358
 T6c (10 phan phan hily HI Cr 700 K là :
-
V = 2 ZAA.e E/RT

184000
8,314 700
= 2.1,02.1034e

= 3,75.1020/m3 .giay

= 6,23.10-4 mol/n13.giay

Hang s6 toc (10 k bang :

(TrIn, \ .1 /2 _ E
k = 462 e RT
\ M I

/2 184000
(3,14.8,31.700
= 4.(3,5.1010)2 e 8.314.700
p8.10-3

= 3,40.103{) m3.giay-1

Bai 7. TInh hang s6 t6c dC? phan img :

H2 = 2 HI

6
. 556K va ap sudt 1 atm n6u ban kinh va cham cua hidro Id

200.10 12 m,-dia iot la 500.10-12 m va nang luyng hoat hod bang

170 kJ/mol.

Giai.
Ap dung bidu thirc tinh hang s6 t6c do cud phan ling gifra H2 va
I2, ta co :

359
 E
2 87ERT .e - RT
k (Yu y \I

2
6„, 6H2 6I2 (200+ 5000).10-12 = 3,5.10-10 m
"") -12 2 2

MH2 -MI 2 = 2.254

= _2
MH2 +M12 2+254

170000
k (3,5.1010 )2 8.3,1416.8,314.556 xe
8314'556 .6,02.1023
2.10 3
-6
= 8,4.10 mol-1
.m3.giay
,, -1

Bai 8. D6i vori su phan fthy este etylvinyl, thira s6 truck lay thira bang
2,7.101I giay-1. Tinh bi6n thien entropi hoat hod. & 530°C. Giai
thich y nghia cua gid. tri tim dude.

Giii.

Thd nguyen cua thira s6 A cho thay phan Ling phan !My da cho la
bac 1; do do thira s6 A dtrgc bidu thi bang :

OSA
A = —e

Logarit
Logarit hai ve" cho to :

kT
lnA = ln— + 1+ OS

360
 = R 2,3031g A - 2,3031g
h

(
= 8,314 2,3031g2,7.10" -2,3031g 1,38.10-23.803 1
6 625.10-34

- 42,7 J/K.mol

Gia tri am cua bie'n thien entropi hoat hod. chung to mire dO trat
at caa he phan img ; not each khdc, str hinh thanh phirc hoat
Ong kern theo sir Oita bac ttr do.

Bai 9. D6i vdi sU phan hay dun phan tit caa diaxetyl 6 285°C, thira s6
A bang 8,7.1015 giay 1. 'nth LN,S.

Giii.

Hang s6 t6c (10 kpu caa phan ung phan hay diaxetyl lien he v6i
hang hryng hoat hod va bien thien entropi hoat hod bang
plarong trinh :

ASS E
AS
k kT 1+ R .e RT
PIT
11

Matkhdc, thira s6 A &rye xdc Binh bang he'thirc :

k =Ae E/RT (2)

So sdnh (1) va (2) to th4 :

AS
kT 1+ p
A = —.e —
h

361
 Logarit hai ye" to duck: :

kT AS
In A = ln— +1+
h R

kT
AS = R 2,3031g A -1- 2,3031g
h

1,38.10-23.558
= 8,314 2,3031g8,7.1015 -1-2 3031g
_
6 625.10-34

AS = 8,314 1(2,303.15,940) - I (2,303.13,065)1 =

46,6 J/K.mo 1

Bai tap to giii

XI.1. T6c de phan ang se tang •len bao nhieu lan n6u tang nhiet de
cua phan dug tit 20°C len 100°C ; bie't he s6 nhiet de dm phan
(mg bang 2.
. Dap so : 512 Fan
XI.2. Phai tien hanh phan (mg & nhiet de nao n6u t6c de plian tIng
xay ra & 50°C giam di 10 lan. He s6 nhiet ,de cita t6c de phan
(mg bang 2,5.

Dap so : 25°C
XI.3. Hang s6 t6c do phan irng nghich ciao throng bieen thien theo
nhiet de nhu sau :

362
 t °C 20 30 50

k.104 [phut -1] 2,758 10,98 137,4

Tinh he s6 nhiet dO cua t6c d6 phan (mg d6i v(ri m6i khoing
nhiet (10 va gia tri trung Binh cua he s6 nhiet 06 trong khoang tit
20 den 50°C.

Dap 3,98 ; 3,53 ; 3,68

XI.4. 6 10°C phan ting gifia 1 L dung dich axetat etyl 0,05N voi 1L
dung dich NaOH 0,05N ti6n hanh chive 50% trong theri gian
16,8 phut. Hi s6 nhiet d6 cua t6c (16 phan img hang 2..Xdc dinh
theri gian de xa phong hod &rot mot nira Itryng este or 35°C.

Dap so.: 2,97 phtit

XI.5. CS 25°C m6t phan (mg da cho se ke-t thtic sau 2,5 gig. Chgp nhan
he s6 nhiet (16 cua t6c dO phan,ting bang 3, hay tinh nhiet (10 ma
tai do phan ting se k6t thitc trong 20 phut.

Dap so- : 46,2°C

XI.6. Hang s6 Vie d6 phan timg phan hit), HI & 280°C bang
7,96.10 7 phdt 1, CI 300°C bang 3,26.10-6 phut 1. Mc dinh nang
Wong hoat hod, hang s6 t6c dO phan (mg & 290°C va he s6 nhiet
do cua the d6 phan (mg.

Dap so.: 185,6 kJ ;

1,63.10 6phtit-1 ; 2,02

XI.7. Str phu thuOc cua hang s6 toc do phan hay photphin :

363
 4 PH3 —> P4 + 6H,

vao nhiet d6 duoc bidu thi bang phuong trinh :

Ig k = 1896 3 + 2 lg T + 12,130.

Xdc trinh nang lac-mg hoat hod cUa. phan Crng er 800K.

Dap so": 276 k.f.mol 1

XIX Su nhidt phan etan tuan theo phuccng trinh d6ng hoc dm phan
(mg bac 1. Su phu thu0c dia hang s6 t6c (16 vao nhidt do throe
cho duOi day :

k.10 5 [giay 1 ] 2,5 4,7 8,2 12,3 23,1 35,3 57,6 92,4

T [K] 823 833 843 853 863 873 883 893

Xac dinh nang luting hoat hod va thin. s6 Areniut A.

Dap so : 304 k.l.mol 1

XI.9. D6i vdi mOt phan 1mg da cho, hang s6 t6c (10 O 35°C Ion gap
dOi hang s6 t6c (10 el 25°C. 'firth nang luting hoat hod.

Dap so : 53 k.I.mol I

XI.10. D6i vOi su phan huy dibutyl thay ngan va dietyl thily ngan,
phtaing trinh Areniut ttrang (mg dude bidu thi nhu sau :

193kJ
k = 1015'2. RT
e

1800
k = 1014'1. e RT

364
 Xac dinh nhiet de ma tai do hang s6 Vic de bang nhau.

Dap so : 617K.

XI.11. Doi voi phan (mg :

1-170, + 2HI = 2112 0 +

hang s6 tee de phu thuec vao nhiet de nhu sau :

t °C 20 30

k [mol. L 1 .phtit 1 ] 4,32 8,38

Tinh nang luong hoat hod va hang s6 toe de & 25°C.

Dap se; : 48,78 kJ/mol ; 6J04.mol I . L.phtit I

XI.12. Su thity phan trong mOi trueng kiem ctia iodua etyl theo nhiet
de dirge ghi lai dtrei day :

t °C 15 30 60 90

k.103 [moll I .giay I ] 0,0507 0,335 8,13 119

Xdc dinh nang luong hoat hod va tiara s6 Areniut A.

Drip so' : 90 kJ/mol ; 1,1.1012.

XI.13. Bizt rang thei gian de 50% N2 0 phan bUy 6 nhiet de khOng
• dei ti le nghich v6i di) suat dau ;-xac'clinh bac ena phan t-mg nay.

cac nhiet do khac nhau, dei voi phan Ling tren, thu throe dft
kien awe nghiem sau :

365
 t °C 694 757

Ap suat dau [mmHg] 294 360

T [giay] 1520 212

Xac dinh

a) Hang s6 t6c do 6 694 va 757°C.

b) Nang luting hoat hod.

c) Thira s6 Areniut A

Dap so- : bac 2 ; 0,135 mmHg 1 .giay 1 NIA 0,842 mmHg .giay 1
241 kJ/mol ; A = 1,4.1012

XI.14. Hai phan ting bac nhat A va B c6 ding mot thira s6 Areniut.
Nang luting hoat hod EA cfia phan ring A16n bon EB cna phan

ting B 10,46 k.I.mo1-1. 6 100°C phan ling A tie'n hanh dugc 30%.
trong 60 phdt ; n6ng do dau cna chat phan ung trong A là 0,1
mol/ L. Hoi cling o nhiet de) tren, dd phan ung B tie'n hanh dugc
70% thi then gian can thie't is bao nhieu ; nong d6 dau cna chat
phan ting trong B IA 0,05 mol/ L.

Dap so: 417 giay.

XI.15. Sir phan tiny mgt hgp chat A trong dung dich IA phan Ong bac
1 v6i Rang luting boat hod IA 52,3 kJ.mo1 1 . 6 10°C dung dich
10% chat A phan tiny dirg.c 10% trong 10 phut. 116i mac dO phan
hny sau 20 phut cna dung dich 20% chat A 6 20°C IA bao nhieu ?

Dap sr; : 36,2%.

366
XI.16. O 404K hang s6 t6c (10 cua phan tIng don phan tar hang
4,14.10-4 giay-1. Biet rang nang luting hoat hod E bang
108 k.T.mol-1, tinh AS nhiet do tren.

Dcip so : - 187 J/K.mol

XI.17. 'Firth AS# cua phan (mg :

1m
NO + H2 = +112,,

6 827°C nal hang s6 t6c de bang 145,6 moli1, 2.giay 1 va nang

luting hoat hod E bang 184 kJ.mol 1.

Dap so : - 72 J/K.mol
XI.18. Met phan (mg da chi) c6 the to dien ra hoac xay ra do xilc tac.
Bi6n thien entropi hoat hod cua truYng hop thir nhal 16n ho'n
trirong hyp thd hai 10 J/K.mol. Mat khac, nang luting hoat hod
lai co gia tri 16n ho'n truing hop sau 10 kJ.mo1 1. Hay xac dinh
ti s6 cdc hang s6 t6c de 6' 25°C.

Dap so- : 5,89.10 2

XI.19. Dina vao six xac dinh th6i gian rata Olin (mg, hay chting to
rang phan ang bac nhdt co nang luting hoat hod E bang 107
kJ.mol l se khOng xay ra voi t6c do c6 the do du6c rihiet do
phong ne"u phan ling nay cc') thira s6 A binh thirong,

XI.20. D6i vOi phan (mg phan huy ete vinyl etylic, thira s6 A bang
2,7.1011giay 1. Tinh AS 6 530°C. Gill thich IC& qui OM du6c.

367
 flap s6 : — 42,7 J/K.mol

XI.21. Doi vOi mit phan irng bac hai i 300K, thira so' A bang
3,64.10" mo1.1_ i giay i 'filth •AS nhie:t d0 nay d6i voi n6ng
d0 chtfan 1 mol/L,

Dap sr> : — 40,3 J/K.mol.

XI.22. Chap nhan kinh va cham trung binh cua phan tir H, va
I, bang 2.10 8cm, tinh hang s6 t6c (10 dia :

H, + 12 = 2 HI

700K n6u nang Wong hoat hoa bang 166,2 k.T.mol 1 va thira s6
khOrig gian P bang 0,47.

Dap so: 38 cm3/mol.giay.

368
 CHU'gNG XII
PHAN LONG QUANG HOA
VA PHAN O'NG DAY CHUYEN

1. Phan ling quang hoa

Phan (mg quang hod hoc la phan img xay ra (lath tdc dung cita tia
birc xa thuOc vung nhin thy va \lung to ngoai. Theo dinh luat
duong luting quang hod hoc, n6u anh sang gay ra bi6n dOi hod
hoc thl luting tir (photon) duoc hdp thu gay ra su Nen d6i
cUa mot phan tir chdt phan Ling.

Nang Wong cita 1 photon bang : E= h.v = h.0 (1)

X

trong do: h la hang s6 Plank

v la tan s6 buc xa

C la Vic di bac xa anh sang trong chan khOng

X la btrOc song cUa Mc xa

24-BTHL-A 369
 D6i vOi 1 mol photon (lAnhstanh photon) c6 nang lining bang:

h.0
E = Avo•
N•E=N•hv=N
Avo* • Avo (2)

O day NAvo la s6 Avogadro.

Giai doan so cap cila phan (mg hod hoc trong vimg bac x4 tren
luOn tuan theo dinh luat nay.

Hien suat ltrong tit duoc dinh nghia nhu sau:

S6 phan tir chat phan img chuydn hod

(3)
So photon he hap thy

T6c dO phan quang hod hoc :

do
v= = q).— (4)
dt hv

trong do n la s6 phan tit chat da phan fmg tai thori diem t

(13 la hieu suat luting tit

AI la nang Luang he hap thy.

2. Phan ling day chuydn

1. Dinh nghia : Phan irrig day chuyen la loci phan img ph& tap,
trong do co su hinh thanh cac tidu phan hoat Ong (nhfing g6c •
hay nguyen tit to do). Nhang tidu phan hoat Ong nay tham gia
vao phan (mg va ,14i tao ra nhirng tidu phan hoat dOng mOi.
NhUng tidu phan mdi nay lai lap Lai qua trinh tren lam cho phan
ling ph& trien xa hen.

370 24-BTHL-B
2. BOng hoc cila phin (mg day chuy6i

M6t each nghiem ngat thi khong the mieu to phan (mg day
chuyen bang nMt phuong trinh ti Wong. Chat dau bi tieu thu va
san-phdm duoc hinh thanh trong giai doan phat tridn mach. VI
vay, t6c do phan.Ung duoc tinh theo mot au tir nao do hang t6c
do giai doan phat tridn mach trong d6 eau tir nghien cdu bi tieu
thu hoac duoc hinh thanh. N6u mot mat mach gom hai phan ting
so cap, trong moi phan ting de'u c6 sir tieu thu chat dau va tao
thanh san phdm, nghia là:

R 7 +A t D
k-- > L,1 R ;

k2
R ; + A, > B, + R

trong do R 1 va R ; la cac tieu phan hoat &Ong ;

- At, A, la cac chat dau ; B1 , B, la cac san phdm.

Khi do, t6c do phan tIng day chuyen throe vier:

`
dAd
Bil d[
= - =ki[R:1[Ad (1)
dt dt

d[A21 d[B2 ]
hoac = k2[R; ][A,]• (2)
dt dt

Mu6n vie't phuong trinh vi phan elm ail1

- g d0 g6c to do phai ke
den toe d0 sinh mach va ngat mach. Phan (mg sinh mach tao ra
snot trong cac goc to do, chang han R:. Khi d6 t6c d0 hinh

thank gCic R i va R ; arcing ang se la :

371
 d[R i l
= vo — kaR; liA114- k2[R2][A2]-vmi
dt

d[R21 — ki[R; ][AJ- k2[R:][A2] - vm,

dt

trong do : vc, la t6c d6 sinh mach;

vmi ,vm, la t6c d6 mat g6c ttr do•R; va R 2 arcing irng.

Vi cac g6c tir do la cac lieu phan trung gian rat hoat Ong, nen
trong toan 17.6 qua trinh nong (10 cua Chung tlurc to coi nhukhOng
d6i (Ming d6 citing), khi do: v0 = vm1+ ''m,.

Ta'''ng hop lig& mach bac 1:

v rn 1 = [R;] va vm2= km2 ER21.

Trgemg hop rig& mach bac 2:

Vm I = 2km1. [R [ 2 Va 'm2 = 2km2 1R 2

trong do k1111 va km, la hang so t6c d6 ngdt mach.

Bai tap co lei giii

BM 1. Hoi axeton dm:Ye chiCiu sang hang anh sang co btffic song
X = 313 nm 56,7°C, phan huy then pinrong trinh phan tirng :

CH3COCH3 C1H6 + CO

372
 The tich binh phan ling la 59 ml. Hai axeton hap thu 91,5% nang
luting ainh sang tgi. Ap sual (Mu cila he IA 766,2 mmHg, sau 7
gig dtrgc chi& sang, lip suatcaa he tang len den 783,2 mmHg.
Nang ltro'ng tai he la 48100 ec/giay. Tinh hieu swat 1*c:frig tir caa.
phan (mg.

Giai.

S6 phan tir axeton da chuyen hod:

AP.V 17.59.10-3.6,013.1023
n ax = •NAvo = = 0,294.102°
RT 0,082.760.329,7

S6 quang rir he hap thu: -

91,5.48100.10-7.3600.7.313.10-9
11 h,, = 1,746.1020
100.6,625.10-34.3.108

nAx 0,294.1020
= = = 0,17
nh v 1,746.1020

Bai 2. Mgt dung dich gom axit oxalic va uranyl dugc chi& sang
bang bac xa c6 X = 300 nm. Thuc nghiem cho thay, trung binh 1
photon bi hap thu lam chuyen hod 0,57 phan tir oxalic. Tinh
nang luting bac xa can thiet de phan hay 1 mol axit oxalic.

Giai.

Nang luting cila 1 photon bac xa bang :

h.0 6,625.10-34.3.108 -19 J

E= h.v = = = 6,625.10
X 3.10-7

Nang luting can thiet de phan hay 1 viol axit oxalic là :

373
 E_
N .6 - 1023.6 6'7 5.10-19 = 7.105 J
6 073
0,57 0,57

Bai 3. Phan :

HN3 + 1120 —> N, + NH,OH

co hi'eu suat 'Yong ti:r cp = 1,02 khi dtroc chi& atilt sang co kr& song
X = 214 nm va ctrOng dO chi& sang 10 = 1,0.10 7 mol.dm 3.giay 1.
ThOi gian chit;:u sang la 39,38 phtit. TInh lacing san phdm
thu dtroc.

Giai.

S6 mol HN3 da phan irng la:

nc.d= (17- I„.t = 1,02.1,0.10-7.39,38.60 = 2,41.104 mol.dm 3.giay

S6 mol san phfim thu cluvc:

nsp = nN2-1-1
n N 20H
,2,41.10-4MOWM-3.gifiy

BM 4. Phan ling glint H, va Br, xay ra theo co the sau:

H2 (kill) + Br, (Ulf) 2HBr (khi)

(1). Sinh mach :

kl
Br, -f 2Br•

(2). Phat tridn mach :

‘k2
Br* + H, HBr +

374
 k3
1-1•+ Br, ---> HBr + Br•

(3). Lam cham phan Ung :

k4
H• + HBr —> H, + Br•

(4). Ngat mach :

k5
Br* + Br• + M --> Br2 + M

Tim t6c dQ hinh thanh HBr theo co the day chuyen tren.

Giai.

Tir co the tretrco the Niel:

Phuo'ng trinh tCic do hinh thanh san pham HBr nhu sau:

d [HBr]
= k2[Br][H2]+ k3[1-1][Br2]— k4[H][HBr] (1)
dt

Phuong trinh .t6c dO hinh thanh cac tidu phan hoat dOng (H• va
Be) va dp dung phuong pilaf) nOng dO dirng :

dIFI] = k
2[Br][H21— k3[H][Br2] — k4[H][HBr] = 0 (2)
dt

d I-Br]
= 2k [Br2] — k, [Br][H2] +
dt
+ k3[11][Brd + kall]filBr] — 2k5[Br]2 = 0 (3)

Tir (2) va. (3) tim duqc nOng do ding ciia H va Br:

375
 11/2
[Brd
[Br] = (4)
k5

1/2
/k5)112 [H2][Br2]
[H] = k2(ki (5)
k3 [Br2 ]+ k4 [HBr]

Thay [Br] va [H] tit (4) va (5) vao (1) va bien ddi to dttoc:

d [HBr] 2k2(ki / k5 )1/2 [H2 ][ Br2 ]3/2

(6)
dt [Br2 ]+(k4 /k3)[HBr]

Plutong trinh (6) phi' hop v(ii plutong trInh thuc

Bai 5. Phan itng clo hoa axit fomic trong pha khi xay ra theo co ch6
day chuy6n sau :
k0
— Sinh mach : Cl, --> 2C1*

k1
— Mat trien mach : C1• + HCOOH --> HC1 + •COOH
k2
Cl2 + •COOH -> HC1 + CO, + C1•

k3
— NgAt mach : CI* + thanh binh Cl (thanh binh)
Hay cluing to phtto'ng trinh dOng hoc cila phan (mg có dang:

d[C11]
= k[C1,][HCOOH]
dt
Giai.

376
Tir co the phan Cmg cho thay plurong trinh t6c (10 tieu thu C12 co
thd duoc via.:

d[C12
] = k2[C12][COOH] (1)
dt

T6c dO hinh thanh cac tidu phan hoat dOng, dp dung (king thoi
phuong phap nOng dO dirng d6i vdi cac tidu phan do, ta co:

d[Cl]
= 2k0 [C12] - k [CI] [HCOOH] +
dt
+ k2[C1,][COOH] - k3[Cl] = 0 (2)

d[COOH] = k [C1] [HCOOH] - k2[C1, ] [COOH] = 0 (3)

dt

Ka hop (2) va (3) tim duoc Ming (10 cna Cl :

2ko [C12 ]
[CI] = (4)
k3

Thay (4) vao phirong trinh (3) tim &roc Ming dO cUa COOH :

2k.k1
[COOH] = [HCOOH] (5)
k2k3

Thay (5) vao (1) va Nal doi ta duoc•:

d[C12 ] 2kok1
k3 [C12][HCOOH] (6)
dt

(6) là phuong trinh phai tim vdi k = 2koki

k3

377
Bai tap giai
Trong co the Olin Ling quang phan metanthiol (CH3SH) CO hai
giai clop hap thu bitc x4 :

(1) CH3SH + hv --> CH3S + H

(2) CH3SH + hv —> CH3 + SH

116i phan (rug (1) va (2) có xay ra duce khOng neU chieU btrc
x4 co buo'c song 254 nm va 214 um vao he phan img. Bi6t
nang luoug can thiel de pha vo' lien ket S-H trong phan Ung (1)
khoang 368 kJ/mol va lien ket C-S trong phan iing (2) khoang
289 k.1/mol.

Dap so" : E1(214 nrn) = 559 kJ/mol

E2(254 nm) =471 kJ/mol
CO the gay ra ca. phan Ung (1) va (2).
XII.2. Axeton bi phan hay duai tac dung dia anh sang co btrac song
300 nm. Nang luong caa lien ket C-H IA 414 kJ/mol, caa lien ket
C-C is 331 kJ/mol va caa lien 1(6 C=0 la 728 kJ/mol. Hoi phan
(mg co xay ra duck; khOng? VA cho bie't san pham caa phan Ung
so cap.

Dap so": E = 399kJ/mol; lien lc& C-C bi pha v(

cho 2 g6c là CH; va *CH 3C=0.

XII.3. Phan drig Brom hod axit xinamic xay ra dudi tac dung caa bac
x4 co buck song bang 435,8 nm va nhiet di) 30°C. Phucfng trinh .
phan img nhu sau:

C6H5-CH=CH-COOH + C6H5-CHBr-CHBr-COOH

378
 Khi chien bCrc xa tren vOi cueing (10 1,4.103J/giay trong then gian
1105 giay thi luring brom giam 0,075 mmol. Tinh hieu suat luvng
bier dung dich tap thu 80% nang Wong dm bac xa di qua.

Dcip sa. : cp = 16,5

XIL4. Mot nam thu hooch trung binh 5 tan sari pham hau co' kik)
tren 1 ha vOi thieu nhiet cua chat hity co la 16,72.103kJ/kg.
Mat trOi chi6u sang trung binh 8 giO moi ngay vOi caong dO
41,8kJ/m2 .phat. 'Firth hieu suat chuyen quang nang thanh
hod ming.

Dap so : 6,11%

XII.5. a) Nang lacing lien ke't H-H trong phan tit 112 1a 414kJ/mol.
Hoi can phai chi6u bac x4 có btrOc song bao nhieu de pha vO lien
ket tren.

b) Phan tir H, khOng hap thu bac x4 trong vung co birac song do,
vi vay can chat cam quang tap thu nang lao'ng, sau d6 truyilin
sang cho phan to H,. Hni Hg (hat) hay Na (TEA) d6ng vai tro chat
cam quang reit ho'n trong phan crng nay, tau hoi Hg hap thy bac
xa có btrOc song 253,6519 nm, con hoi Na hap thu bac xa co
buck song 330,2988 nm.

Dap so.: a) 289 nm; b) Hg

XII.6. Phan ang phan hny nhiet etan thanh etilen \fa hidro xay ra theo
co the sau:

(a) Sinh mach : CH3CH3 > H3C• + •CH3

(b) Phat trien mach :

379
 k2
CH3CH3 + •CH3 > CH4 + CH3CH,•

k,
CH3CH,• > CH,= CH, + I-P

CH3CH3 + k4 > CH3CH,• + H.,

(c) Ngat mach: CH3CH,• H• 1(5 > CH3CH3

Hay chting t6 phuong trinh t6c dO phan hity elan c6 dang:

d[C,116 ]
= k[CH3CH3]
dt

XII.7. Phan ung : Cl, + CO —> COCI, xay ra theo co ch6 gia thiCA sau:

kl
Cl, --=`
\- 2CI•
k2

C1* + CO COCl•
k4

k5
COO' + Cl, ---> COO, + CI°

Ap dung phuong phap n6.ng dO dIrni doi v6i Cl va COC1, tim

phuong trinh t6c dO hinh thanh COC1,.

, d[C0C11] = k3k5(k1
Dap s6 : 1 k2)1 12 [CO][C12 ]1/2
dt k4 +k5

XII.8. Co ch6 nhiet phan andehit axetic ?i520°C va 0,2 bar nhtt sau:

380
 CH3CHO k1 > CH3* + CHO*

k2 > CH
CH3* + CH3CHO 4 + CH3C0*

k3
CH3C0* > CO + CH3*

CH3* + CH3* C,H6

Tim phrrong trinh t6c dO phan huy CH3CHO, cho rang g6c CHO*
kern boat thing c6 the 136 qua.

d[CH3CHO]
Dap : = k,(k1/2k4)1/2[CH3CH0]312
dt

XII.9. Phan (mg girra 11, va 0, xay ra theo co the sau :

(a) 112 + 02 k > 2 OH*

(b) H, + OH• k2 > H,0 + H*

k3
(c) 0, + > OH* + *0*

(d) *0* + II, . ka > OH* +

Ii• k5 > P (hap phu tren thanh binh)

(e)
Tim Ming dO cUa F1*. Trong diet' kien nao phan chuye'n sang
vUng ne; ?

2k1 {H21[02
Dap : [H] =
L.5

381
 CHUIING XIII
XCIC TAC

Tem tat li thuOt

Xiic tat.: la ItiO tuong thay dOi t6c (.10 hoac kich thich phan irng
gay ra do tdc dung cita mot s6 chat goi la chat xtic tdc. Chat xtic
tdc sau khi tham gia vao qua trinh, khOng bi thay dOi ve plitrung
diem hod hoc cling nhu Nie Itrong cita chting.

Vai tre cua xtic tdc trong cdc [than ling hod hoc là dua phan (mg
di theo con dtrOng thuan loi hcin v6 mat nang luting bang each
tao san pinim trung gian vdi it nhat mOt trong cdc chat phan

Xuc tdc IA (long thd khi chat mit; talc nava cling pha vdi cac chat
tham gia phan irng. Mott s6 chat xuc tdc doing the thuOng dung IA
cdc dung dich axit, bazo, muCii cna cdc kim - loai chuydn tiep.

Xtic tdc la di thd khi chat xtic tdc nam khOng cling pha vdi cdc—
chat tham gia phan ling. Chat xitc tdc di tile, thuOng la chat ran ;

382
phan Ting hod hoc xay ra tren be mat chat )(Ix tdc. Cdc chat
xtic tdc di the thOng gap la cdc kim loaf chuyen ti6p, cdc oxit
kim loai,

Moi phan frng gala cdc chat klif .xay ra tren be mat chat xtic tdc
ran deu có the chia ra lam 5 giai doan n6i ti6p nhau:
1. Chat phan ring chuyen tOi be Mat chat xtic tdc ;

2. ‘Hdp phu cdc-chat phan Ong len be mat chat )(tic tdc ;

3. Phan Ong tren be mat ;

4. Khir hap phu san pham phan ting khOi be mat ;

5. San pham phan chuyen khOi be mat vat) the itch pha khi
T6c dO chung cua qua trinh dtroc quyet Binh giai doan chain
nhat. Trong xtic tdc di•the qud trinh chuyen chat tit the Itch dell
be mat chat xtic tdc (su khu6ch tan) rat quan trong. T6c dQ qua
trinh nay tuan theo phtrong trInh sau:

dC D.S
s —Cx ) (1)
dt = 6.V (C
trong do, C - nOng dO chat Ulf ;
t - thei gian khue-ch tan ;
D - he s6 khuech tdn ;
S-be mat;
V - the Lich cUa he ;
Cs va Cx - n6ng dO chat kW, tren be mat va or khoang-
cdch 6 tinh tir be mat .vao the tich.
'F 6c dO khue-ch tan phu thuOc nhiet dO theo phtrong trinh
Areniut :

383
 D = Do. e-Ekt/RT (2)

T6c dO phan img hod hoc be mat phu thuOc vao luting chat phan
irng du9c hap phu tren be mat chat mic tac.

- Khi c6 1 chat duqc hap phu, phuong trinh toc dO phan rng be
mat c6

dP
v= - =k.8 (3)
dt

K.P
v6i 0 =
1+K.P

K - hang s6 can bang hap phu ;

P - dp suat hcci cita chat phan

- Khi c6 (king thoi 2 chat duoc hap phu tren We mat chat xlic tac,
phuong trinh t6c (10 phan rng 136 mat c6 dang:

dP
v.= -- = k.0A0B (4)
dt

KA PA KB PB
v6i A =- 1+K P +K P
A A B B ; °B ± KA PA +KBPB

Bai tap ca 101 giii

XtIc tac d6ng th4 -

Bai 1. Mot phan i ng xuc tac (long the xay ra theo the sau:

k1 Ric
R1 + C (a)

384
 k2
R1C —> R1 + C (b)
k
RiC + R, P+C (c)
Ap dung nguyen II n6ng (16' dimg d6i vdi R 1C, tim phuong trinh
t6c dO hinh thanh san pham P. 6 day C la chat xac tac.
Giai.

Tir co the phan ting c6 thd viet duoc phuong trinh t6c dO hinh
thanh R1 C, thing thin lip dung nguyen li ruing dO &mg d6i v6i
R1C, ta

d[R1C] ki[R i ][C] —k2[R IC] —k3[R1 C][R2[ = 0

dt

Tit (1) tim duoc: [R1C] = k1 {R1][C]

k2+k3[R, ]

Tir co ch6 to co the via phuong trinh t6c d6 hinh thanh san pham P :
dP
= k3[R1C][R2] (3)
dt

Thay [R1 C] tir (2) vao (3) va bieit ddi ta duoc:

dP ki k3[R1][R2 ][C]
(4)
dt k2 +k3[R2 ]

Bai 2. Qua trinh phan hay 03 trong tang binh luu khi duoc kich thich
bai nguyen tir Cl (dttqc sinh ra tir cac chat CFC du6i tac dung
cita bdc x4 mat trim) xay ra nhu sau :

Cl. + 03 k1 02 + CIO. (a)

25-BTHL-A
385
 k~
CIO + 0 02 + (b)

Tim phuo'ng trinh t6c dO phan tirng phan hay 03.

Giai.

Ur co che- c6 the vi6t phuong trinh t6c dO giai doan (a) :

d[ 3 ]
.0 = ki[Cl][03] (1)
dt

d [CIO]
• = [C11103] — kACIONO I = 0 (2)
dt

T6c do caa giai doan 1 bang t6c de? phan (mg phan hay 03, nghia

IA: d [03] = ki ECI1103], day ding chinh IA phuong trinh phai tim.
dt

Xac lac di thg

Bai 3. Phan (mg oxi hoa CO hang 02 tren xdc tac Pd[111] xay ra theo
co the ducx de nghi nhu sau:

02 + 2S k1 > 20hp (a)

CO + S COhp (b)

COhp + 0hp CO2 (c)

6 day S la tam xtic tac. Thuc nghiem tim tidy phuong trinh t6c
dO phan (mg c6 dang :

386 25-BTHL-B
 k.P02
V= (1)
Pco

Dtra vao CO cite phan (mg, hay giai thich ket qua tren.

Giai.

Tit co the phan (mg cho day ca 02 .1-an CO ding bi. hap phu len.
be mat Pd. Neu ca hai chat hap phu ngang nhau thi phuo'ng trinh
t6c dO co clang :

= ks 002 • °co (2)

Ko,P02
V6i 002 = ;C
c= K coPco
O
1+0
1( 2 1132 + KcoPco 1 + K02 P0,, + KcoPco

Thay 002 va Oco vao (2) to dtryc :

ks K02 Po2 KcoPco

v= (3)
(1+1<021)02 +KcoPco)2 .

trong do ks la hang s6 t6c dO Than Cmg tren be mat xac tac.

De co clang (1) thi KcoPco >> K02 P02 \fa rat lOn hon 1. Dieu do

c6 nghia la CO bi hgp phu rat mph (8co »002 ). Khi .d6 (3)
tth thanh :

ksKo, = k PO, ksK02

v= "z 4 k=
KcoPco Pco Kco

387
Bai tap tg giai
XIII.1. MQt phan Cmg xtic tac di the xay ra theo co ch6 :
k1
HA + R RH+ + A- (a)
k2

k3
RH+ + A- --> HA + I (b)
k4
I ---> P + H,0 (c)
trong do : HA - axit khOng phan li ;
R- chat phan Cmg ;
I - san phdm trung gian ;
P - san phdm phan (mg.
Tim phuong trinh t6c dO hinh thanh san phdm P. Cho biel giai
doan (b) dien ra cham nhat.

Dap so : d[P] = k1k3 [IlAi[R]

dt

XIII.2. Ion Br trong mOi truOng axit xtic tac cho phan (mg phan hay
H2O, thanh H,0 va 02 . Phan Cmg xay ra theo cac giai doan:

H202 + Br-+ H+ k1 > HBrO + H,0 (a)

HBrO + H2O, k2 > H2O + Br + H++ 0, (b)

Ap dung phuong phap nong tic) dUng d6i vdi HBrO. Tim phuong
trinh t6c dO phan hity H„0, va cho bi6t anh hu6ng cita chat xuc
tac d6n t6c dO phan Cmg nghien

388
 d[,02
11 ]
Dap so : = 2k1 [H2021[H+ ][Br-- j
dt

XIII.3. Phan ang oxi hod H, thanh hoi nt.t6c &roc xtic tac 1361 khl NO
xay ra theo co the day chuyen sau:

2NO + 0, k1 > 2NO2 .(a)

NO, + H,
k2 HNO2+ H.
> (b)

1-1° + NO, k3 > NO + OH. (c)

OH.+ H,
k4 > H20 + H' (d)
• k
OH + NO2 5 > HNO3 (c)

OH.+ NO k6 > HNO, (g)

Hay chi ra :

1. Giai doan sinh mach (khoi mao), phat tridn mach va ngat mach.

2. Chu trinh hoat Ong cua chgt xtic tac.

XIIL4. Khi nghien ecru anh hteing cita chgt xtic tac Ne, SF6 va CC14
den toc do phan ung tai ka he cac nguyen ttr Brom, Degraff va
Lang da thu &roc ket qua sau:
too 94 76 46 24 96 63 39 26 96 75 54 26

k.109
22,13
m2s-1 1,07 1,13 1,36 1,48 4,39 6,19 6,87 8,56 9,95 12,01 14,92

Khi 14e SF6 CCI4

Hay cho bier chat kill nao xitc tac tot nhgt cho pha'n (mg tren.

389
 Dap so : Ea dm phan (mg vOi cac Ulf Ne, SF6 va CCI4
ttrong (mg — 4,4 ; — 8,2 va —10,5 kJ/mol ;

XIII.5. Phan (mg phanNH3 tren xtic tac Pt & 1000°C co phtrong
trinh t6c dO thtrcrighiem:

d[NH3 kPH3
dt

Hay dua ra co the phan Ling xtic tac phi' hop vii phuong trinh _
thuc nghiem tren.

XIII.6. Cac mau oxit : MgO, A1,03, SiO, tilt& khi chup ph6 IR duoc
dtra ra ngoai khOng khi. Phan tich ph6 IR ciia cac mau cho thay:
Ph6 IR cila mau MgO xuat hien cac van ph6 ciia hop chat
cacbonat; cita A1,03 cling xuat hien dam ph6 do nhung vOi
cuing de rat nh6, con SiO, thi hoan town khOng co darn pli6 dO.
Hay giai thich ket qua tren.

XIII.7. Than (IA hoac dau me) dtroc dung de san xuat khi t6ng hop
(CO + H,) va cung cap 11, cho t6ng hop NH3.•Cac khi nay till&
khi sir dung can phai loai het Itru huSmh, vi sao ? Phuong Oaf)
loai hru huStnh ?

XIII.8. Nang luting hoat hod cua phan ling tang hop NH3 ar H2 va N,
or 600K khi khong co chat xtic tac bang 326 kJ/mol. Khi dung
chat xiic tac vonfram nang luting hoat hod bang163 kJ/mol, can
xtic tac la sat thi nang luting hoat hod bang 175 kl/mol. Hoi toe _
dO phan (mg tang bao nhieu Ian khi dung chat )(tic tac d6i \Ai
m6i twang hop.

Dap so : vii xtic tac W: 1,5.1014; vdi xuc tac Fe: 1,3.1013

390