BI 3: XC TC NG TH - PHN NG PHN HY H2O2

I Mc ch th nghim:
Xc nh hng s tc , chu k bn hy v nng lng hot ha ca phn ng phn
hy H2O2 vi Cu2+ l cht xc tc.
II C s l thuyt:
H2O2 t phn hy theo phng trnh sau:
H2 O2

H2 O + O 2

Tc phn ng tng nhanh khi c cc cht xc tc Pt, mui ca cc kim loi chuyn tip,
Phn ng tin hnh theo 2 giai on:
1.

HOOH

2.

HOOH + 2H+

O2

2H+

2 H2O

2 H2O2

( chm )
( nhanh )

2H2O + O2

Tc tng qut ca phn ng c xc nh bi giai on 1 v do phn ng

xy ra theo bc 1.
III Dng c v ha cht:
1. Dng c:
Bnh tam gic 100ml:

Pipet:

B iu nhit:

2. Ha cht:
Dung dch H2O2 30%
Dung dch CuSO4 10%
Dung dch H2SO4 10%
Dung dch KMnO4 0,1N
IV Tin trnh thc hnh:
1. Thc hin phn ng 300C

Ly 1ml dung dch H2O2 v 19ml nc ct cho vo mt bnh nn; ly 10ml dung
dch CuSO4 10% cho vo mt bnh nn khc.

c c hai bnh ny vo b iu nhit 300C trong 25 pht.

Trn chung hai bnh li vi nhau, lc vi ln trn u hn hp, vn hn hp
trong bnh iu nhit. Sau ly 2ml hn hp phn ng cho vo mt bnh nn c cha
sn 3ml H2SO4 10% ri chun vi KMnO4 0,1N. Khi bt u nh git KMnO4 u
tin th ghi thi gian, l thi im t = 0. Ghi s ml KMnO4 dng.
Sau 5, 10, 15, 20, v 30 pht k t thi im t = 0 li ly 2ml em chun .
2. Thc hin tng t 400C

V Kt qu thc nghim:
t (pht)
V (KMnO4) (ml)
C (H2O2) (N)
V (KMnO4) (ml)
C (H2O2) (N)

300C
400C

0
1.8
0.09
2.4
0.12

5
0.9
0.045
1.4
0.07

10
0.8
0.04
1.3
0.065

15
0.6
0.03
1.2
0.06

20
0.5
0.025
1
0.05

30
0.4
0.02
0.8
0.04

Cch tnh C(H2O2) nh sau:

Theo nh lut ng lng: CH
CH 2 O2 =

2 O2

.VH 2 O2 = C KMnO 4 .VKMnO 4

CKMnO 4 .VKMnO 4
VH 2 O2

1. Tnh hng s tc :
Th nghim xy ra cc phng trnh phn ng sau:
2 H2O2

CuSO4

O2

2KMnO4 + 5 H2O2 + 6H+

2H2O

(1)

K+ + Mn2+ + 5O2 + 8H2O2 ( 2 )

Ta thy phng trnh (1) l phn ng phn hy H2O2 l phng trnh bc nht nn
hng s tc c tnh theo cng thc sau:
1 C( H 2O2 ) 1 C0( H 2O2 )
K = ln
= . ln
t C0 ( H 2O2 ) t
C( H 2O2 )
0

30 C
400C

K5
0.1386
0.1078

K10
0.0811
0.0613

K15
0.0732
0.0462

K20
0.064
0.0438

K30
0.0501
0.0366

Hng s tc trung bnh: K =

K 5 + K10 + K15 + K 20 + K 30
5

300C: Ktb = 0.0814 ph-1

400C: Ktb = 0.0591 ph-1
2. Tnh nng lng hot ha ca phn ng:
E = R ln

K T2 1
1
0.0591 1
1
4
= 8.314 ln

= 2.81 10
0.0814 313 303
K T1 T2 T1

3. Tnh chu k bn hy:

300C: t1 / 2 =

ln 2
= 8.52 ( s )
K

400C: t1 / 2 =

ln 2
= 11 .7( s )
K

BI 4: XC NH BC PHN NG
I. MC CH
Trong bi ny chng ta xc nh bc ring v bc chung ca phn ng:
Fe3+

I-

Fe2+

1/2 I2

II. C S L THUYT
xc nh bc ring theo

, chng ta s dng phng php vi phn

ca Vant-hoff.
Gi s vn tc u ca phn ng c xc nh bng phng trnh:
(1)
Trong ,
(
(

l nng u ca
l nng u ca
l bc ring phn ca

Ly logarit ca phng trnh (1) ta c:

lg

= lgk + lg

+ lg

(2)

Nu tin hnh mt chui cc th nghim vi nhng nng u ca

nhau trong khi nng ca
mt chui nng ca

c gi khng i, ta c th xc nh c
khng i, chng ta s xc nh c

c bc tng qut ca phn ng n =

khc
. V

. T tnh

Chui th nghim th nht cho ta dng nh sau ca phng trnh (2)

lg

=A+

lg(

Xy dng th lg
vi tg=

= - lg(

ta c ng thng vi gc nghing

. Tng t c th xc nh

xc nh vn tc thi im u

thng s dng phng trnh

kinh nghim sau:

l nng mol ca

sinh ra mi thi im t

t l thi gian phn ng

, l nhng hng s nghim
Ly o hm
=

ti t=o, ta c:
(3)

Nh vy xy dng th

ta xc nh c hng s thc nghim t

y c th tnh c vn tc u ca phn ng (3).

l nng mol ca
sinh ra. Lng

ti thi im t, c th xc nh thng qua nng

c th c kim sot bng cch cho vo hn hp phn ng

dung dch Na2S2O3 vi nhng lng bit trc chnh xc km theo h tinh bt.
Khi ton b lng Na2S2O3 tc dunhj ht vi

c sinh ra trong qu trnh phn

ng th lng

mi sinh ra trong hn hp phn ng cng vi h tinh bt s cho

mu xanh.
Nng

ti mi thi im t c xc nh theo biu thc:

=

: nng ng lng ca
: ton b th tch dung dch

c cho vo hn hp phn ng

cho n thi im t.
: nng ca Fe2+ c cho vo hn hp phn ng cho n thi im t.
: th tch ca hn hp phn ng ( qui v th tch u khng i).
III. TH NGHIM
1. Xc nh bc ring theo Fe3+:

Dng ng ht cho vo 4 bnh tam gic cc ha cht vi lng chnh xc theo

thnh phn bng sau:
Dung dch
Fe(NO3)3M/60,ml
HNO3 0,1M,ml
KNO3 1M,ml
H2O,ml

Bnh 1
10
10
40
20

Bnh 2
20
10
30
20

Bnh 3
30
10
20
20

Bnh 4
40
10
10
20

Tin hnh th nghim ln lt vi tng bnh.

Cho vo bnh 1 vi git h tinh bt v ng 20ml dung dch KI M/40. Ghi
nhn thi im bt u phn ng v khng tt ng h trong sut th nghim ca
tng bnh. Dng buret cho mt lng nht nh

0,01N (V1).

Khi dung dch c mu xanh tr li, ghi nhn thi im t1- l lc I2 sinh ra
tc dng vi

- V2 v ghi nhn thi im t2 xut hin li mu xanh (V2 l

tng lng

hin din trong hn hp phn ng cho thi im t2 , V2 c

trc tip trn buret ).

Tip tc theo di tin trnh phn ng nh vy cho n khi khong 8 im V1- t1.
Lng

nh vo va sao cho khong cch gia hai ti lin tip

khong 1 pht ri. Ton b th nghim vi 1 bnh khng qu 10-15 pht m phi
t nht 8 im. Lm nh vy vi cc bnh cn li.
2. Xc nh bc ring theo

Dng ng ht cho vo 4 bnh tam gic cc ha cht vi lng chnh xc theo

thnh phn bng sau:
Dung dch
KI M/40, ml
HNO3 0,1M, ml
H2O, ml
KNO3, ml

Bnh 1
10
10
27,5
32,5

Bnh 2
20
10
20
30

Bnh 3
30
10
12,5
27,5

Bnh 4
40
10
5
25

Cho vo bnh 1 vi git tinh bt v 20ml dd Fe(NO3)3M/60, lc mnh, ghi thi

im bt u phn ng. Cc bc tip theo c tin hnh tng t nh phn xc
nh bc ting theo Fe3+ .
IV. KT QU
Chui th nghim 1:

Bnh 1:(C0)I =1,667x10-3

t,giy
115
100
100
110
110
118
100
100

(104)

ml
2.6
3.0
3.4
3.9
4.4
4.9
5.3
5.8

2.6x10-4
3 x10-4
3.4 x10-4
3.9 x10-4
4.4 x10-4
4.9 x10-4
5.3 x10-4
5.8 x10-4

0.38
0.33
0.29
0.26
0.23
0.20
0.19
0.17

8.7x10-3
0.01
0.01
9.1 x10-3
9.1 x10-3
8.5 x10-3
0.01
0.01

Chui th nghim 1 bnh 1

T biu trn ta c c gi tr = 19.297

Bnh 2: (C0)I =3,33 x10-3

50
50
60
55
59
61
62
60

(104)

ml

t,giy
2.3
3.0
3.8
4.5
5.3
6.0
6.8
7.5

2.3 x10-4
3.0 x10-4
3.8 x10-4
4.5 x10-4
5.3 x10-4
6.0 x10-4
6.8 x10-4
7.5 x10-4

0.44
0.33
0.26
0.22
0.19
0.17
0.15
0.13

0.02
0.02
0.017
0.018
0.017
0.016
0.016
0.017

Chui th nghim 1 bnh 2

T biu trn ta c c gi tr = 57.552

Bnh 3: (C0)I =5x10-3

t,giy
32
30
32
30
35
30
35
35

(104)

ml
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0

3.5 x10-4
4.0 x10-4
4.5 x10-4
5.0 x10-4
5.5 x10-4
6.0 x10-4
6.5 x10-4
7.0 x10-4

0.29
0.25
0.22
0.20
0.18
0.17
0.15
0.14

0.031
0.033
0.031
0.033
0.028
0.033
0.028
0.028

Chui th nghim 1 bnh 3

T biu trn ta c c gi tr = 11.353

Bnh 4: (C0)I = 6,67 x10-3

50
40
40
40
45
50
49
40

(104)

ml

t,giy
5.9
6.6
7.3
8.0
8.8
9.6
10.5
11.4

5.9 x10-4
6.6 x10-4
7.3 x10-4
8.0 x10-4
8.8 x10-4
9.6 x10-4
10.5 x10-4
11.4 x10-4

0.17
0.15
0.14
0.13
0.11
0.10
0.95
0.88

0.02
0.025
0.025
0.025
0.022
0.02
0.02
0.025

Chui th nghim 1 bnh 4

T biu trn ta c c gi tr = 11.782

th xc nh bc ring phn ca I-

bc ring phn ca I- l 0.29

Chui th nghim 2:
Bnh 1: (C0)Fe3+ = 2.5 x10-3

t,giy

ml

(104)

60
65
60
60
64
65
60
65

2.6 x10-4
3.2 x10-4
3.8 x10-4
4.4 x10-4
5.0 x10-4
5.6 x10-4
6.2 x10-4
6.8 x10-4

2.6
3.2
3.8
4.4
5.0
5.6
6.2
6.8

0.38
0.31
0.26
0.23
0.20
0.18
0.16
0.15

0.017
0.015
0.017
0.017
0.016
0.015
0.017
0.015

Chui th nghim 2 bnh 1

T biu trn ta c c gi tr = 22.727
Bnh 2: (C0)Fe3+ =5 x10-3

t,giy
120
120
120
110
110
100
100
110

(104)

ml
2.8
3.3
3.8
4.3
4.8
5.3
5.8
6.4

2.8 x10-4
3.3 x10-4
3.8 x10-4
4.3 x10-4
4.8 x10-4
5.3 x10-4
5.8 x10-4
6.4 x10-4

0.36
0.30
0.26
0.23
0.20
0.19
0.17
0.16

8.3 x10-3
8.3 x10-3
8.3 x10-3
9.1 x10-3
9.1 x10-3
0.01
0.01
9.1 x10-3

Chui th nghim 2 bnh 2

T biu trn ta c c gi tr = 76.433
Bnh 3: (C0)Fe3+ = 7,5 x10-3

t,giy
60
60
55
55
59
58
55
55

(104)

ml
4.4
5.4
6.2
6.0
6.8
7.6
8.2
9.0

4.4 x10-4
5.4 x10-4
6.2 x10-4
6.0 x10-4
6.8 x10-4
7.6 x10-4
8.2 x10-4
9.0 x10-4

0.23
0.19
0.16
0.17
0.15
0.13
0.12
0.11

0.017
0.017
0.018
0.018
0.017
0.017
0.018
0.018

Chui th nghim 2 bnh 3

T biu trn ta c c gi tr = 35
Bnh 4: (C0)Fe3+ = 0,01

t,giy
30
30
25
30
30
28
29
29

(104)

ml
2.7
3.7
4.7
5.8
6.8
7.6
8.6
9.7

2.7 x10-4
3.7 x10-4
4.7 x10-4
5.8 x10-4
6.8 x10-4
7.6 x10-4
8.6 x10-4
9.7 x10-4

0.37
0.27
0.21
0.17
0.15
0.13
0.12
0.10

0.03
0.03
0.04
0.03
0.03
0.04
0.03
0.03

Chui th nghim 2 bnh 4

T biu trn ta c c gi tr = 2.6667

Biu xc nh bc ring phn ca Fe3+

bc ring phn ca Fe3+ l 0.97

bc chung ca phn ng l n=0.97+0.29=1.26

BI 5: KHO XC TC THY PHN ESTER

XC NH NNG LNG HOT HA CA PHN NG
I- MC CH
Kho st tc phn ng thy phn ester nhiu nhit t xc nh
nng lng hot ha ca phn ng.
I- C S L THUYT

Nng lng ha ha Ea da vo phng trnh Arrhenius:

lg k =

Ea
+ lg k
2,303 RT

o k nhiu nhit T khc nhau, v ng biu din lgk theo

l

1
, h s gc
T

Ea
v tung l lgk*
2.303 R

Khi bit Ea ta phng tnh k2 T2 nu bit c k1 T1. T (1) suy ra:

lg

Ea 1
k2
1

=
k1
2,303 R T1 T2

Acetate etyl: CH3COOC2H5 hay RCOOR

RCOOR + H2O

RCOOH + ROH

Nu c xc tc ion H+ th phn ng xy ra nhanh hn

RCOOR + H2O

RCOOH + ROH

Do nng ca acid CH3COOH v ru C2H5OH hin din rt t nn phn ng

thun nghch coi nh khng ng k. Phng trnh ng hc:

d [ RCOOR ']
= k 1[RCOOR' ]
dt

y l hm bt mt nn: lg ( a x ) =

k1 t
+ lg a
2,303

vi: a l nng u ca acid acetat etyl

(a - x) l nng thi im t
- Gi V l th tch dung dch NaOH cn chun 10ml mu lc phn ng xy
ra hon ton.
- Gi V0 l th tch dung dch NaOH cn chun 10ml mu lc mi bt u
phn ng.
- Gi Vt l th tch dung dch NaOH cn chun 10ml mu thi im t.
V th tch t l vi nng nn:
lg (V Vt ) =

k1t
+ lg (V V0 )
2,303

V ng biu din lg(V-Vt) theo t, suy ra k t h s gc ca ng biu

din.
II- TIN TRNH TH NGHIM
1. Thc hin phn ng 30oC

Cho 5ml ester acetat etyl vo bnh nh mc 100ml, 100ml dung dch HCl
0.2N vo cc 100ml ri c hai vo b iu nhit. Khong 10 pht, ly cc HCl
cho vo bnh nh mc ti ng vch. Ghi nhn thi im t0. Lc u hn hp vi
ln ri vo my iu nhit, sau ht nhanh 10ml cho vo bnh nn 250ml c
cha sn 50ml nc ct c ngm lnh trc ngng phn ng. Ghi nhn
thi im t1.

nh phn acid bng dung dch NaOH 0.1N vi ch th phenolphtalein n khi

xut hin mu hng nht. Ghi nhn th tch t1 thi im t1.
Sau 10 pht lp li s nh phn nh trn 6 ln na, t2 l thi gian tnh t t0,
tng t i vi cc im cn li.
Kt qu:
t ( pht)

Vt (ml)

V - Vt

5
15
25

16
17
18

67.2

51.2
50.2
49.2

lg(V Vt )

V ng biu din lg(V - Vt) theo t

V ng biu din lg(V-Vt)

Ta c: VT1 = 16 (ml)

1.709
1.700
1.692

VT2 = (5000*d)/M = (5000*0.901)/88 = 51.2

Vy V = VT1 + VT2 = 51.2 + 16 = 67.2 (ml)
T phng trnh (*) v th suy ra k1/2.303 = -0.0011 v lgk* = 1.713
k1 = 2.5333 x 10-3 v k* = 51
2. Thc hin phn ng 40oC

Lm tng t nh trn nhng 40oC.

Kt qu:
t ( pht)

Vt (ml)

V - Vt

lg(V Vt )

5
15
25

19.6
21.4
22.6

V ng biu din lg(V - Vt) theo t

Ta c: VT1 = 19.6 (ml)

70.8

51.2
49.4
48.2

1.709
1.694
1.683

VT2 = (5000*d)/M = (5000*0.901)/88 = 51.2

Vy V = VT1 + VT2 = 51.2 + 19.6 = 70.8 (ml)
T phng trnh (*) v th suy ra k2/2.303 = -0.001 v lgk* = 1.714
K2 = 2.303 x 10-3 v k* = 51
Tnh Ea: t phng trnh lg

Ea 1
k2
1

=
k1
2,303 R T1 T2

vi T1 = 303, T2 = 313, R = 8.314

Ea = 1982958.214