Bi ging mn C s l thuyt Ha hc

CHNG III: CN BNG HO HC

I.PHN NG THUN NGHCH V PHN NG 1 CHIU
1.Phn ng thun nghch
L phn ng xy ra theo hai chiu tri ngc nhau trong cng mt iu kin (c
im ca phn ng thun nghch: khng tin hnh n cng m dn n cn bng)
V d: N
2
O
4
(k) <=> 2NO
2
(k)
Khi ly kh NO
2
(hoc N
2
O
4
) nghin cu --> lun thu c ng thi c kh N
2
O
4

(hoc NO
2
) trong bnh ngay nhit thng do tn ti s chuyn ho gia hai kh trn -
-> gi phn ng trn l phn ng thun nghch.
2.Phn ng 1 chiu: L phn ng ch xy ra theo mt chiu xc nh
V d: Phn ng phn hu KClO
3
(xc tc MnO
2
) : KClO
3
--> KCl + 3/2O
2

c im: tin hnh ti cng
3.Trng thi cn bng ho hc
Mt phn ng khi t trng thi cn bng th:
-
Xt v mt ng hc: vt=vn

-
Xt v mt nhit ng: 0 =
p
G

* Vy trng thi cn bng ho hc: l trng thi ca phn ng thun nghch khi tc
phn ng thun bng tc phn ng nghch (hoc khi bin thin th ng p bng
khng).
* c im ca trng thi cn bng ho hc:
- L cn bng ng (phn ng vn xy ra theo 2 chiu ngc nhau nhng vt=vn).
-Ti trng thi cn bng thnh phn ca cc cht khng thay i: cht tham gia
phn ng mt i bao nhiu theo phn ng thun th li c sinh ra by nhiu theo phn
ng nghch).
- Trng thi cn bng ch tn ti khi cc iu kin thc hin phn ng (C, t
0
,p)
khng i.
II.PHNG TRNH NG NHIT VANT HOFF. HNG S CN BNG K
1.Thit lp phng trnh ng nhit Vant Hoff
Xt phn ng: aA + bB <=> cC + dD
T=const v A,B,C,D l cc kh l tng
Ta c:

+ + = = ) ( ) ( ) ( ) (
B A D C i i T
b a d c tg sp G
M:
i T i T i
P RT ln
) , ( ) (
+ =
0
(i vi 1 mol)
=>
c
C T C C T C T C
P RT c P cRT c c ln ln
) ( ) ( ) (
+ = + =
0 0
(cho c mol)
Tng t:
b
B T B T B
P RT b b ln
) ( ) (
+ =
0
:
d
D T D T D
P RT d d ln
) ( ) (
+ =
0

Bi ging mn C s l thuyt Ha hc




a
A T A T A
P RT a a ln
) ( ) (
+ =
0

=>
)] ln ( ) ln [( )] ln ( ) ln [(
) ( ) ( ) ( ) (
b
B T B
a
A T A
d
D T D
c
C T C T
P RT b P RT a P RT d P RT c G + + + + + + =
0 0 0 0

bd
b
B
a
A
d
D
c
C
T T T T T
P P
P P
RT B b A a D d C c G

+ + + =
.
.
ln )] ( ) ( ( ) ( ) ( [(
0 0 0 0

bd
b
B
a
A
d
D
c
C
T T
P P
P P
RT G G

+ =
.
.
ln
0

Pi: p sut ring phn ca cc cht kh i= A,B,C,D)
t
P
bd
b
B
a
A
d
D
c
C
P P
P P
=

.
.

=>
P T T
RT G G ln + =
0
(*)
- Ti trng thi cn bng==> 0 =
T
G =>
cb
b
B
a
A
d
D
c
C
T
P P
P P
RT G

=
.
.
ln
0

t: const K
P P
P P
p
cb
b
B
a
A
d
D
c
C
= =

.
.
T=const (v trng thi cn bng, thnh phn cc
cht khng bin i na)
==>
P T
K RT G ln =
0
(**)
v
P
P
T
K
RT G

ln = (***)
Trong :
0
T T
G G ,
,
(J)
R=8,314J.K
-1
mol
-1

P (atm)
Cc phng trnh (*) (**) v (***) c gi l cc dng khc nhau ca phng trnh
ng nhit Vant Hoff
2.Phng trnh hng s cn bng K:
a.Hng s cn bng Kp
cb
b
B
a
A
d
D
c
C
p
P P
P P
K

=
.
.
Pi: p sut cc kh trng thi CB
- KP khng c n v.
- Kp ch ph thuc vo bn cht phn ng v nhit .
- i vi 1 phn ng xc nh, T=const --> Kp=const --> gi l hng s cn
bng ca phn ng.
b.Cc hng s cn bng khc
Bi ging mn C s l thuyt Ha hc



*
cb
b
B
a
A
d
D
c
C
C
C C
C C
K

=
.
.
Ci: nng mol/lit cc cht trng thi cn bng
- KC ph thuc vo bn cht phn ng v nhit .
- i vi 1 phn ng xc nh --> KC =f(T): KC ch ph thuc vo nhit
*
cb
b
B
a
A
d
D
c
C
n
n n
n n
K

=
.
.
ni; s mol kh i trng thi cn bng
Kn

ph thuc vo bn cht cc cht , T v P chung ca h khi cn bng v tng s mol
kh ca h khi cn bng
*
cb
b
B
a
A
d
D
c
C
N
N N
N N
K

=
.
.
Ni: nng phn mol ca kh i:

=
i
i
i
n
n
N
KN

ph thuc vo bn cht cc cht , T v P chung ca h khi cn bng
c.Mi quan h gia cc hng s cn bng
- Ta c P
i
V=n
i
RT (V th tch hn hp kh (lt))
=> RT C
V
RT n
P
i
i
i
= = thay vo phng trnh Kp ta c
( ) ( )
( ) ( )
( ) ( ) [ ] n
c
a b d c
a
A
b
B
d
D
c
C
a
A
b
B
d
D
c
C
P
RT K RT
C C
C C
RT C RT C
RT C RT C
K
+ +
= = = ) .(
.
.

n = s mol kh sn phm- s mol kh tham gia (da vo phng trnh phn ng)
Vy
n
c P
RT K K

= ) .( (vi R= 0,082 atm.l.mol
-1
K
-1
)
-Mt khc ta c:
P
n
n
P N P
i
i
i i
. .

= = --> thay vo Kp ta c:

n
cb N P
P K K

= . v
n
cb
i
n P
n
P
K K

.

(
i
n )
cb
tng s mol kh c mt trong h phn ng khi cn bng.
Vy c:
n
cb
i
n
n
cb N
n
C P
n
P
K P K RT K K

= = =

. . ) (
*Nhn xt:
- Khi 0 = n (tng s mol kh 2 v phn ng bng nhau) --> K
p
=K
C
=K
n
=K
N
=K=f(T)
- i vi 1 phn ng cho th:
+ K
p
,K
C
ch ph thuc vo nhit
+ K
N
ph thuc vo nhit , P chung ca h khi cn bng
Bi ging mn C s l thuyt Ha hc



+K
n
ph thuc vo T,P chung ca h khi cn bng, tng s mol kh ca h khi cn
bng.
* Ch :
- Gi tr hng s cn bng K ca phn ng u phi gn vi 1 phn ng c th no .
V d: SO
2
(k) + 1/2O
2
(k) <=> SO
3
(k)
2
1
2 2
3
O SO
SO
P
P P
P
K
.
=
2SO
2
(k) + O
2
(k) <=> 2SO
3
(k)
2
2
2
2 2
3
P
O SO
SO
P
K
P P
P
K = =
.
'
SO
3
(k) <=> SO
2
(k) + 1/2O
2
(k)
1
2
1
3
2 2
= =
P
SO
O SO
P
K
P
P P
K
.
' '

- Nu K c gi tr kh ln --> coi phn ng xy ra hon ton, K nh -> phn ng thun
nghch.
- Nu phn ng c cht rn hoc cht lng tham gia (v khng tan ln vo cc cht khc)
th chng khng c mt trong phng trnh hng s cn bng ( v
0
) ( ) ( T i T i
= trong
sut qu trnh phn ng--> khng cn RTlnPi)
V d: Fe
2
O
3
(r) + 3 CO(k) <=> 2Fe(r) + 3 CO
2
(k) Kp=
3
3
2
CO
CO
P
P

Hg(l) + 1/2 O
2
(k) <=> HgO(r)
2
1
2
1
O
P
P
K =
3. Cc phng php xc nh hng s cn bng
a.Xc nh theo thnh phn cc cht ti thi im cn bng
V d: CaCO
3
(r) <=> CaO(r) + CO
2
(k)
Nung CaCO
3
nhit T , khi cn bng: mmHg P
CO
740
2
= .Tnh Kp
Gii:
760
740
2
= =
CO P
P K
b.Xc nh thng qua 1 s i lng nhit ng

P T
K RT G ln =
0

==>

=
RT
G
K
T
P
0
exp
V d: Tnh Kp ca phn ng sau 25
0
C:
2NH
3
(k) <=> N
2
(k) + 3H
2
(k) bit
1
3
0
298
65 16

= mol kJ NH G
s
. , ) (
,

Gii:
Bi ging mn C s l thuyt Ha hc



1
3
0
298
0
298
3 33 65 16 2 2

+ = = = mol kJ NH G G
s
. , ) , )( ( ) (
,

6
3 0
298
10 45 1
298 314 8
10 3 33
298

=

= . ,
. ,
. ,
exp
.
exp
R
G
K
P

c. Xc nh theo phng php gin tip: Phn tch qu trnh theo 1 chu trnh kn
V d:
C
gr
O
2
(k) CO
2
(k)
CO(k) O
2
(k) 1/2
K
P
=?
K
1
K
2

0
2
0
1
0
G G G + =
) ln ( ) ln ( ln
2 1
K RT K RT K RT
P
+ =
lnKP=lnK
1
+lnK
2
==> K=K
1
.K
2

III.S CHUYN DCH CN BNG. NGUYN L LE CHATIELIER
1.S chuyn dch cn bng
- Xt v mt nhit ng, khi phn ng t trng thi cn bng--> 0 = G --> 1 =
P
P
K

khi
h ang trng thi cn bng nu ta thay i mt trong cc thng s trng thi (P,T,C)
ca h --> 0 G => cn bng b ph v, qu trnh s tin hnh theo chiu 0 < G t
ti trng thi cn bng mi ng vi cc thng s mi (P,T,C).
- Xt v mt ng hc, khi phn ng t trng thi cn bng --> vt=vn => v=0. Khi h
t trng thi cn bng, ta thay i 1 trong cc thng s trng thi (P,C,T) => vt vn ==>
qu trnh tin hnh theo chiu v > 0 t trng thi cn bng mi ng vi cc thng
s mi.
==> gi l s chuyn dch cn bng.
nh ngha: S chuyn dch cn bng l s chuyn t trng thi cn bng ny sang trng
thi cn bng khc di nh hng ca cc tc ng bn ngoi (P,T,C) ln h.
2.nh hng ca nhit ti s chuyn dch cn bng. Phng trnh ng p Vant
Hoff
Xt phn ng: aA + bB <=> cC + dD P=const
Ta c:
RT
G
K
T
P
0

= ln
Mt khc:
2
0 0
T
H
T
G
T
T
P
T

=

do : =>
2
0
RT
H
T
K
T
P
P

=

ln
=> phng trnh ng p Vant Hoff
Bi ging mn C s l thuyt Ha hc



- Nu 0
0
>
T
H (phn ng thu nhit) --> hm ng bin
+ Khi nhit tng --> K
p
tng --> cn bng chuyn dch theo chiu thun ( chiu
thu nhit)
+ Nu T gim --> K
p
gim ==> cn bng chuyn dch theo chiu nghch ( chiu
to nhit)
- Nu 0
0
<
T
H (phn ng to nhit) --> hm nghch bin:
+Khi nhit tng --> K
p
gim --> cn bng chuyn dch theo chiu nghch (
chiu thu nhit)
+Nu T gim --> K
p
gim ==> cn bng chuyn dch theo chiu thun ( chiu to
nhit)
* Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi:
+ Khi nhit tng th cn bng chuyn dch theo chiu lm gim nhit ca h
l chiu thu nhit c 0 >
T
H
+ Khi nhit gim th cn bng chuyn dch theo chiu lm tng nhit ca h
l chiu to nhit c 0 <
T
H
* T phng trnh Vant Hoff suy ra:
T
RT
H
K
T
P

= . ln
2
0

Nu trong khong nhit T
1
-->T
2
hp -->c th coi const H
T
=
0
th:

=
2
1
2
1
2
0
T
T
T
T
P
T
dT
R
H
K d ln
=>

=
2 1
0
1 1
ln
1
2
T T R
H
K
K
T
T
P
P

vi
0
H (J) v R=8,314 J.K
-1
mol
-1

3. nh hng ca p sut n s chuyn dch cn bng
Ta c:
n
cb N P
P K K

= .
V Kp khng ph thuc vo P--> thay i P th K
p
=const nn:
- Nu 0 > n : khi tng P--> K
N
gim ( gi K
p
=const) => chuyn dch cn bng theo
chiu nghch ( lm gim s mol kh) v ngc li
- Nu 0 < n : khi tng P--> K
N
tng ( gi K
p
=const) => chuyn dch cn bng theo
chiu thun ( lm gim s mol kh) v ngc li khi P gim --> K
N
gim --> cn bng
dch chuyn theo chiu nghch ( lm tng s mol kh)
- Nu 0 = n => P khng nh hng ti s chuyn dch cn bng
* Nhn xt: Kt qu ca s chuyn dch cn bng l chng li s thay i bn ngoi:
Bi ging mn C s l thuyt Ha hc



- Nu P tng => cn bng chuyn dch theo chiu P gim (gim s mol kh
0 < n )
- Nu P gim => cn bng chuyn dch theo chiu tng P (tng s mol kh
0 > n )
4. nh hng ca nng
Xt phn ng: aA + bB <=> cC + dD c const
C C
C C
K
cb
b
B
a
A
d
D
c
C
C
=

=
.
.
T=const
- Nu tng C
A
, C
B
=> cn bng chuyn dch theo chiu tng C
C
,C
D
( gi K
C
=const) =>
cn bng chuyn dch theo chiu thun lm gim C
A
,C
B
- Nu gim C
A
, C
B
=> cn bng chuyn dch theo chiu gim C
C
,C
D
( gi K
C
=const)
=> cn bng chuyn dch theo chiu nghch lm tng C
A
,C
B

* Nhn xt: Kt qu ca s chuyn dch cn bng l chng li thay i bn ngoi.Nu
tng C
i
th cn bng chuyn dch theo chiu lm gim C
i
v ngc li.
5. Nguyn l chuyn dch cn bng Le Chatelier
Khi mt h ang trng thi cn bng, nu ta thay i 1 trong cc thng s trng
thi ca h ( T, P hoc C) th cn bng s chuyn dch theo chiu chng li s thay i
.
















Ti liu tham kho:

1. Nguyn nh Chi, C S L Thuyt Ha Hc, NXB GD, 2004.
2. Nguyn Hnh, , C S L Thuyt Ha Hc, Tp 2, NXB GD 1997.
3. L Mu Quyn, C S L Thuyt Ha Hc - Phn Bi Tp, NXB KHKT, 2000.