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18A/88 INH VN T - TP. HI DNG

S DNG PHNG PHP TH XC NH BC PHN NG

V TNH HNG S CN BNG
Mai Chu Phng
THPT Chuyn Lam sn-Thanh Ha
I.1. C s l thuyt.
I.1.1. Phn ng bc mt.
A sn phm
Phng trnh ng hc dng tch phn:
C = Co.e-kt (1)

kt=ln

Co
(2)
C

Trong : k: hng s tc phn ng

Co: nng ban u ca cht tham gia phn ng A.
C : nng cht A ti thi im t.
t : thi gian phn ng.
T phng trnh (1) v (2) nhn thy nu ta kho st s ph thuc nng cht phn ng theo thi gian
nh phng trnh (1) th vic xc nh hng s tc phn ng k l kh khn v y l hm m, cn nu
kho st phng trnh (2) th thy phng trnh (2) chnh l phng trnh tuyn tnh bc nht dng y=ax,

Co
Co
trong y=ln
, a=k, x=t. Do , da vo s liu thc nghim ta kho st hm ln
=f(t) ph thuc
C
C
tuyn tnh theo thi gian vi dc ca th xc nh c hng s tc phn ng k=tg
C0
ln C

Hnh 1: th biu din s ph thuc logarit nng cht tham gia phn ng theo thi gian.
I.1.2. Phn ng bc hai.
I.1.2.1. Trng hp 1: Nng ban u ca hai cht tham gia phn ng khc nhau.
A + B sn phm
t=0
C10
C02
0
t
C1
C2
x
Phng trnh tc phn ng dng tch phn:

kt=

1
C10 .C2
ln
C02 -C10 C02 .C1

(3)

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C2
C0
(4)
=(C02 -C10 )kt+ln 02
C1
C1
C
T phng trnh (4) c ln 2 ph thuc tuyn tnh vo thi gian v ng biu din s ph thuc ny c
C1
Suy ra:

ln

C02
dng y=ax + b vi dc ca th bng tg =(C -C )k v ct trc tung ti ln 0 .
C1
tg
Suy ra:
k= 0 0
C2 -C1
0
2

0
1

C2
ln C1

C 20
0
ln C1

Hnh 2: th biu din s ph thuc logarit nng hai cht tham gia phn ng theo thi gian.
I.1.2.2. Trng hp hai: Nng ban u ca hai cht tham gia phn ng bng nhau a=b hay C02 =C10 .
Phng trnh tc phn ng dng tch phn:

1 1
= +kt (5)
C C0

Phng trnh (5) biu din nghch o ca nng cht tham gia phn ng ti thi im t ph thuc tuyn
tnh theo thi gian. ng biu din

1
1
=f(t) c dng y=ax+b, c dc bng k=tg , ct trc tung ti 0
C
C

1
C

1
C0

Hnh 3: th biu din s ph thuc nghch o nng cht tham gia phn ng theo thi gian.
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18A/88 INH VN T - TP. HI DNG

Nh vy, trong phng php th ngi ta th cc s liu thc nghim vo dng tch phn ca
phng trnh ng hc tm s ph hp. Trc ht gi nh phn ng c bc n. Sau t dng tch phn
ca phng trnh ng hc tm mt hm ca nng cht tham gia phn ng ph thuc tuyn tnh theo thi
gian. V ng biu din ca hm ny da vo cc kt qu thc nghim. S thng hng ca cc im biu
din chng t tnh ng n ca bc phn ng gi nh, t cng xc nh c hng s tc phn ng da
vo dc ca th
I.1.3. Cch dng th biu din s ph thuc tuyn tnh.
C th xy dng th dng y=ax, y=ax+b da trn phn mm Microsoft Office Excel, hoc dng
th trn giy li.
I.1.3.2. Dng th trn phn mm Microsoft Office Excel.
Bc 1: M mn hnh Microsoft Office Excel.
Bc 2: Nhp s liu theo ct cc gi tr x, y tng ng ca phng trnh dng y=ax hay y=ax+b.
Bc 3: Bi en hai ct s liu, sau ln lt vo Insert/Chart/XY(Scatter)/Chart subtype/Next/Next/Finish.
Bc 4: Tch phi chut vo vng khng gian trng trong th, vo Chart Options, nhp cch biu din
trc honh Value (X) axis, cch biu din trc tung Value (Y) axis.
Bc 5: Tch phi chut vo mt im thc nghim, vo
Add Trendline/Linear/Display equation on chart/Ok c ng thng biu din hm ph thuc v phng
trnh hi quy. T thu c h s gc ca th, do tnh c hng s tc phn ng.
Vic dng th trn phn mm Microsoft Office Excel, sau my tnh hi quy li thu c ng
chun trn c s phng php bnh phng ti thiu.
I.1.3.1. Dng th trn giy.
Bc 1: Gi thit phn ng tun theo ng hc bc no .
Bc 2: Chuyn sang phng trnh ng hc dng tch phn.
Bc 3: K bng tnh s liu biu din s ph thuc thch hp ca nng theo thi gian.
Bc 4: Dng th biu din s ph thuc dng thch hp ca nng theo thi gian bng cch v cc
im thc nghim. Sau k ng chun.
Ch : i vi dng th trn giy li cn ch chn t l xch trn giy sao cho ph hp, gc to
khng nht thit phi l im khng. Sau khi dng c cc im thc nghim th dng ng chun
khng phi l ng i qua nhiu im thc nghim, m ng chun l ng ti u khi tng bnh
phng khong cch t cc im thc nghim n ng chun l nh nht, nn k ng chun da vo
khong cch ti cc im thc nghim.
Bc 5: Dng mt tam gic vung bt k c cnh huyn nm trn ng chun (u mt ca cnh huyn
tam gic ny khng nn trng vi bt c im thc nghim no cho kt qu thu c khch quan).
Bc 6: Tnh h s gc tg da trn vic o di hai cnh gc vung.
Ch : di hai cnh gc vung ny phi tng ng vi t l xch c chia trn trc honh v trc
tung, khng phi l di o c trn thc hay trn giy li.
Ngoi cch dng th c th kim tra li tnh ng n ca phng php bng cch so snh vi
cch tnh theo phng php bnh phng ti thiu hay phng php trung bnh.
Phng php ny c th p dng v m rng cho vic xc nh cc thng s khc nh nng lng
hot ho, cc gi tr nhit ng, h s hp th trong o trc quang.
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II.2. Bi tp vn dng.
Bi 1: (Trch thi Olympic ho hc quc t ln th 41-Anh 2009)[8] Bin tnh protein.
i vi cc phn t protein nh, phn ng khng bin tnh c th biu din theo cn bng sau:
Protein bin tnh
Protein khng bin tnh
Ta c th gi s rng cc phn ng bin tnh protein ch xy ra qua mt giai on. Phn ng bin tnh
protein l phn ng bc nht, hng s tc ca phn ng ny c th xc nh bng cch theo di cng
hunh quang khi lm bin tnh mt mu protein khng bin tnh ban u (thng thng bng cch thay i
pH ca dung dch). Bt u t dung dch protein khng bin tnh c nng 1,0 M, ngi ta lm bin tnh
protein v o c nng ca cc protein khng bin tnh 25 oC theo thi gian:
Thi gian (ms)
0
10
20
30
40
Nng ( M)
1
0,64
0,36
0,23
0,14
V mt th thch hp, t tnh hng s tc ca phn ng bin tnh protein k 250C
Bi gii:
Do phn ng bin tnh ca protein l phn ng bc nht nn c phng trnh ng hc dng tch phn l:

kt=ln

Co
C

Trong : k l hng s tc phn ng bin tnh protein.

C0: nng protein khng bin tnh ban u.

T s liu thc nghim ta c bng s liu sau:
Thi gian
0
10
20
30
40
(ms)
Nng
1,00 0,64 0,36 0,23 0,14
( M )

ln

Co

C: nng protein khng bin tnh ti thi im t.

Dng cc im thc nghim c to (t, ln

Co
),
C

sau k ng chun.

0,446 1,022 1,470 1,966

Dng tam gic vung bt k ABC. Da vo t l xch chia trn trc honh
CB 0, 975
=
0, 0505
v trc tung tnh c tg=
AB 19,3
Kim tra li kt qu dng th trn giy vi kt qu dng th trn phn mm Microsoft Office Excel
2.5

ln(C/C)

y = 0.0501x - 0.026
R2 = 0.9975

1.5
1
0.5
0
0

10

20

30

40

50

t(ms)

T th ta thy h s gc k=0,0501 ms-1 hay k=50s-1. Nh vy kt qu thu c bng cch dng th trn
giy hon ton ph hp.
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ln(Co/C)

2,0
C
1,5

1,0
B
A
0,5

10

20

30

40

t(ms)

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Bi 2: (Trch trong bi tp chun b Olympic ho hc quc t ln th 40 Hungari 2008)[7]

Phn ng ca axeton vi brom sinh ra bromaxeton.
a) Vit phng trnh ha hc ca phn ng nu nh axeton d.
Khi nghin cu c ch phn ng th ngi ta thc hin mt s th nghim ng hc sau 25 C trong dung
dch nc bng cch o nng ca Br2 bng phng php trc quang. ng cong ng hc tng ng
c ghi li khi nng u ca cc cht l [Br2]0 = 0.520 mmol/dm3, [C3H6O]0 = 0.300 mol/dm3, v
[HClO4]0 = 0.050 mol/dm3.
t (min)
0
2
4
6
8
10 12 14
3
[Br2] (mol/dm ) 520 471 415 377 322 269 223 173
t (min)
16 18 20 22 24 26 28 30
3
[Br2] (mol/dm ) 124 69 20
0
0
0
0
0
b) Tc nhn phn ng ht trong th nghim ny l?
c) Bc ca phn ng i vi tc nhn ny l?
Thi im m xy ra bc gy v tnh cht (characteristic break point) trn ng cong ng hc c
gi l thi gian phn ng v n c o trong dung dch nc 25 C. Bng sau cho ta mt vi gi tr thi
gian phn ng trong mt vi th nghim khc nhau ( ch pht, ch giy)
thi gian phn ng
[C3 H6 O]0
[Br2 ]0
[HClO4 ]0

mmol/dm3 mmol/dm3 mmol/dm3

0.151
300
50
556
0.138
300
100
244
0.395
300
100
732
0.520
100
100
3037
0.520
200
100
1513
0.520
500
100
609
0.520
300
200
455
0.520
300
400
228
d) Xc nh bc phn ng ng vi ba cht tham gia.
e) Vit biu thc tc tng qut.
Mt phng php in ha khc cho php ta s dng nng Br2 b hn. mt ng cong ng hc vi
nng cc cht u [Br2]0 = 1.80 mol/dm3, [C3H6O]0 = 1.30 mmol/dm3, v [HClO4]0 = 0.100 mol/dm3
c cho bng sau:
t (s)
0
10
20
30
40
50
60
70
3
[Br2] (mol/dm ) 1.80 1.57 1.39 1.27 1.06 0.97 0.82 0.73
t (s)
80
90
100 110 120 130 140 150
3
[Br2] (mol/dm ) 0.66 0.58 0.49 0.45 0.39 0.34 0.30 0.26
f) Tc nhn phn ng ht trong th nghim ny l?
g) Bc ca phn ng i vi tc nhn ny l?
Bi gii:
a) Phn ng

b) Br2 l tc nhn gii hn (cht phn ng ht)

c) th ng hc ca phn ng (ng cong ng hc)

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ng cong ng hc lc ny l mt ng thng nn qu trnh ny l qu trnh bc 0 ca brom

d) Do qu trnh l bc 0 i vi Br2 v tt c cc cht tc nhn khc u lng d nn gi tr tc l mt
hng s trong mi th nghim. N c th c tnh mt cch n gin: v = [Br2]o / tphn nn
Vi tphn ng l thi gian phn ng. S ph thuc gia tc phn ng vo tc nhn phn ng ht c th c
kho st trc tip t cng thc. V th vn tc nh l mt hm ca nng axeton trong mi trng axit
(nng khng i 0,100 mol/dm3) cho:

th l mt ng thng, phn ng c bc 1 ng vi axeton.

V th nh l mt hm ca nng axit vi nng axeton gi khng i (0,300 mol/dm3) cho:

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th l mt ng thng, phn ng c bc 1 i vi [H+]

e) v= ka[C3H6O][H+]
f) Br2 l tc nhn gii hn (cht phn ng ht)
g) ng cong ng hc:

ng ny khng hn l ng thng nn qu trnh ny khng phi bc 0. Kim tra vi phn ng bc 1 th

thy c kh nng bng cch xy dng mt s ph thuc vo logarit. th c dng iu nh sau:

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Cc im c th thng hng vi nhau. Nh vy qu trnh ny l bc 1 vi brom

Mt phng php khc l xc nh thi gian bn hu t nhng cp gi tr nng cho. T rt ra c
s phn hu Br2 tun theo quy lut phn ng bc 1.
Bi 3: nghin cu ng hc ca cc phn ng gia ion Br- v ClO-:
Br- + ClO- BrO- + Clngi ta trn ln 100 ml dung dch NaClO 0,1M vi 48 ml dung dch NaOH 0,5M v 21 ml nc ct. Hn
hp ny c t vo my iu nhit 298K. Sau cho 81ml dung dch KBr 1% (cng 298K) vo hn
hp trn. Sau mi khong thi gian xc nh (t) ngi ta ly mu v xc nh lng BrO- trong mu. Kt
qu thu c nh sau:
t(pht)
0
3,65
7,65
15,05
26,00
47,60
90,60
2
0,0560
0,0953
0,1420
0,1800
0,2117
0,2367
C - .10 (M) 0
BrO

Nng ca NaClO v KBr trong hn hp phn ng t=0 ln lt bng 0,003230M v 0,002508M. pH cu

dung dch l 11,28. Xc nh bc v hng s tc phn ng.
Bi gii:
Gi s phn ng c ng hc bc hai. Phng trnh ng hc ca phn ng l:
v=k.C Br- .CClOt=0

Br- + ClO-
C10
C02

C1

Br

CClO =C0ClO -CBrO

-

Ta c bng s liu sau:

t(pht)
0
3
2,508
C - .10

C2

CBr =C0Br -CBrO

-

BrO- + Cl0
0

3,65
1,948

7,65
1,555

15,05
1,088

26,00
0,708

47,60
0,391

90,60
0,141

CClO .103

3,230

2,670

2,227

1,810

1,430

1,113

0,863

CClO
CBr

0,253

0,315

0,381

0,509

0,703

1,046

1,812

ln

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Dng th c to cc im l (t, ln

CClO
)
CBr
-

ln

CClOCBr-

2,0

1,6
C
1,2

0,8

B
A

0,4

t(pht)
0

40

20

60

80

100

Dng tam gic vung bt k ABC. Da vo t l xch chia trn trc honh
v trc tung tnh c

k=

tg=

CB 0,66
=
0, 0174
AB 38

tg
0, 0174

24,100( M 1. ph1 )
0
3
C -C Br - (3, 230 2,508).10
0
ClO-

C th kim tra li kt qu da vo dng th trn Microsoft Office Excel hoc

gii theo phng php trung bnh thy kt qu hon thon ph hp.

Bi tp vn dng.
1. thu c oxi ngi ta phn hu 15cm3 dung dch H2O2 vi s c mt ca cht xc tc. Th tch oxi thu
c theo thi gian nh sau:
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t(pht)
V(ml)O2

2
1,3

4
2,36

6
3,36

18A/88 INH VN T - TP. HI DNG

8
3,98

6,18
p s: Bc nht, k=0,124 ph-1

2. ng hc ca phn ng gia natri thiosunfat vi propylbromua:

S O2- +RBr RS O- +Br- , c nghin cu 37,30C. Nng ca S2 O32- sau mi khong thi gian t
2 3
2 3
c xc nh bng phng php chun th tch. Th tch dung dch I2 nng 0,02572N dng chun
hn hp phn ng (10,02ml) cc thi im khc nhau c cho di y:
t(s)
0
1110
2010
3192
5052
7380
11232

37,63
35,20
31,90
29,86
28,04
26,01
22,24
v I 2 (ml) 0
Nng ca S2 O32- ban u l 0,100M. Xc nh hng s tc phn ng.
p s: k=0,001636M-1.s-1
3. Etylen oxit b nhit phn theo phng trnh:
O (k)

CH4(k) + CO(k)
687,7K p sut chung ca hn hp trong phn ngbin i theo thi gian nh sau:
t(pht)
0
5
7
9
12
18
5
-2
P.10 (N.m )
0,155
0,163
0,168
0,172
0,178
0,188
P(mmHg)
116,51
120,56
125,72
128,74
133,23
141,37
Hy chngt rng phn ng phn hu etylen oxit l bc nht v tnh hng s tc ca phn ng.
4. Dng phng php th hy xc nh bc ca phn ng:
(CH3)3CBr(aq) + H2O(l) (CH3)3COH(aq) + H+ + Brt cc d kin thc nghim sau y 298K
t(s)
0
15000
35000
55000
95000
145000
[(CH3)3CBr]
0,0380
0,0308
0,0233
0,0176
0,0100
0,00502
-1
(mol.l )
p s: bc nht.
5. i vi phn ng x phng ho etyl axetat
CH3COOC2H5 + OH CH3COO- + C2H5OH
thi im ban u t=0 hn hp phn ng cha este v xt vi nng bng nhau 0,05M. Phn ng c
theo di bng cch mi thi im t ngi ta ly 10ml hn hp phn ng ri chun lng xt cn li
bng dung dch HCl 0,01M. Kt qu thu c nh sau:
t(pht)
4
9
15
24
37
53
VHCl(ml)
44,1
38,6
33,7
27,9
22,9
18,5
Xc nh bc phn ng, hng s tc phn ng v thi gian na phn ng.
p s: Bc hai, k=0,647M-1.pht-1
6. Styren phn ng vi axit hipoclor cho ta clohirin C6H5 -CHOH-CH2Cl. Cht ny chuyn thnh epoxit
trong mi trng kim:
C6H 5
O + Cl- + H2O
C6H5-CHOH-CH2Cl + OH-
l mt phn ng bc hai. Hy gii thch ti sao trong mi trng m phn ng l bc mt.
180C v trong mi trng m ngi ta o nng Cl-(k hiu l x) theo thi gian v thu c kt qu
sau:
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TI LIU LUYN THI & BI DNG KIN THC NM 2011

t(pht)
180
360
480
1140
1260
3
10 x(mol/l)
1,15
2,10
2,70
4,88
5,21
-3
Nng ban u ca clohirin l 6,86.10 mol/l. Sau khi kim tra li bc phn ng hy tnh hng s tc
ca phn ng ny.
p s: k=1,05.10-3 pht-1
7. Trong dung dch axit yu, H2O2 tc dng vi ion thiosunfat theo s sau:

H 2 O 2 + 2S2 O 32- + 2H+ 2H2O + S4 O 62Tc phn ng khng ph thuc vo nng ion H+ trong khong pH t 4-6. Vi nng ban u
[H2O2]=0,03680M; [ S2 O32- ]=0,02040M. 25oC v pH=5 ta thu c nhng s liu sau:
t(pht)
16
3 10,30
2[ S2 O3 ].10

36
5,18

43
4,16

52
3,13

Xc nh bc phn ng v tnh hng s tc ca phn ng.

p s: Bc hai, k=3,17.10-2lit.mol-1.giy-1

OH 2CH3COCH3 c km theo mt s tng th tch kh

8. Cho phn ng sau: CH3COCH2C(CH3)2OH
ln. Lng CH3COCH2C(CH3)2OH t l thun vi vic tng th tch. T cc s liu sau:
t(pht)
0
10
20
30
40
50
60

S gin n
0
60,8
97,7
119,9
133,4
141,4
146,1
153,8
th tch
p s: Bc nht.

TI LIU THAM KHO

1. Trn Th , ng Trn Phch, C s l thuyt cc phn ng ho hc, Nh xut bn gio dc.
2. Nguyn Vn Du, Trn Hip Hi, Lm Ngc Thim, Nguyn Th Thu, Bi tp ho l, Nh xut bn gio
dc.
3. Trn Vn Nhn, Ho l tp 3, Nh xut bn gio dc.
4. V ng , C s l thuyt cc qu trnh ho hc, Nh xut bn gio dc.
5. Ren. DIDIER, Ho hc i cng tp 2, Nh xut bn gio dc.
6. Ren. DIDIER, Bi tp ho hc i cng tp 2, Nh xut bn gio dc.
7. Bi tp chun b Olympic ha hc quc t ln th 40-Hungari 2008.
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