Chng 3

CN BNG HA HC
3.1. Hng s cn bng
3.1.1. Cc loi hng s cn bng

Phn ng: aA(k) + bB(k)

K P

cC(k) + dD(k)

Hng s cn bng tnh theo p sut :

PCc .PDd

PAa .PBb cb
Hng s cn bng tnh theo nng mol/l:
C c .C d
K C Ca Db
C A .C B cb
Hng s cn bng tnh theo phn mol:
x cC .x dD
K x a b
x A .x B cb
Hng s cn bng tnh theo s mol:
n cC .n dD
K n a b
n A .n B cb
Mi quan h ca cc hng s cn bng:
K P K C . RT

K x .P n K n .
n i

cb

n l bin thin s mol kh ca h.

n = (c + d) (a + b)
Nu n = 0 ta c Kp = KC = Kx = Kn
3.1.2. Phng trnh ng nhit Vant Hoff

Xt phn ng: aA(k) + bB(k)

cC(k) + dD(k)
0
Ti nhit khng i, ta c: G T G T RTln P
Vi

G 0T RTlnK P

PCc .PDd
PAa .PBb

Trong : PA, PB, PC, PD l p sut ring phn ti thi im bt k

G T RTln

P
KP

Nu P > KP: phn ng xy ra theo chiu nghch

Nu P < KP: phn ng xy ra theo chiu thun
Nu P = KP: phn ng t cn bng
1

Ch :

P
n
i

P C (RT) n x .P n n

3.2. Cn bng trong h d th

3.2.1. Biu din hng s cn bng
Nu cc phn ng xy ra trong cc h d th m cc cht trong pha rn hoc pha lng
khng to thnh dung dch th biu thc nh ngha hng s cn bng khng c mt cc cht
rn v cht lng.
V d: Fe2O3(r) + 3CO(k) = 2Fe(r) + 3CO2(k)
Hng s cn bng: K P

3
PCO
2
3
PCO

3.2.2. p sut phn ly

p sut hi do s phn ly ca mt cht to thnh l c trng cho cht mi nhit
c gi l p sut phn ly.
V d: CaCO3(r) = CaO(r) + CO2(k)
p sut phn ly: PCO2 K P
3.2.3. phn ly
phn ly l lng cht phn ly so vi lng cht ban u:

n
no

n: lng cht phn ly

no: lng cht ban u
3.3. Cc yu t nh hng n hng s cn bng
3.3.1. nh hng ca nhit n hng s cn bng
T phng trnh ng p Vant Hoff
dlnK P
H

dT
RT 2

Trong khong nhit nh t T1 n T2, xem H khng i. Ly tch phn 2 v, ta c:

K p T2
H 1 1

ln

K p T1
R T2 T1
Nu phn ng thu nhit, H > 0

dlnK P
0 : nh vy khi nhit tng, gi tr Kp cng
dT

tng, phn ng dch chuyn theo chiu thun.

Nu phn ng ta nhit, H < 0,

dlnK P
0 : nh vy khi nhit tng, gi tr K p s
dT

gim, phn ng dch chuyn theo chiu nghch.

2

3.3.2. nh hng ca p sut

n
Ti nhit khng i ta c: K p K x .P const

Nu n > 0: Khi tng p sut P, gi tr Pn cng tng, do Kx gim, cn bng s dch

chuyn theo chiu nghch.
Nu n < 0: Khi tng p sut P, gi tr P n gim, do Kx tng, cn bng dch chuyn
theo chiu thun.
Nu n = 0: th Kp = Kx = const. Khi p sut chung P khng nh hng g n cn
bng phn ng.
3.4. Bi tp mu
V d 1. Hng s cn bng ca phn ng:
CO(k) + H2O(h)

CO2(k) + H2(k) 800K l 4,12.

un hn hp cha 20% CO v 80% H2O (% khi lng) n 800K. Xc nh lng hydro

sinh ra nu dng 1 kg nc.
Gii
Gi x l s mol ca H2O tham gia phn ng.
CO

H2O

250
28

1000
18

x
(

250
x
28

CO2

x
(

1000
x)
18

H2

)
V n = 0, ta c hng s cn bng:
KP Kn

n CO 2 .n H 2
n CO .n H 2O

x2
4,12
250
1000

x .
x
28
18

Gii phng trnh ta c: x = 8,55 (mol)

Vy khi lng H2 sinh ra: m = 17,1 (g)
V d 2. 2000C hng s cn bng Kp ca phn ng dehydro ha ru Isopropylic trong pha
kh:
CH3CHOHCH3(k)

H3CCOCH3(k) + H2

bng 6,92.104 Pa. Tnh phn ly ca ru 2000C v di p sut 9,7.104Pa. (Khi tnh chp
nhn hn hp kh tun theo nh lut kh l tng).
Gii
3

Gi a l s mol ban u ca CH3CHOHCH3.

x l s mol CH3CHOHCH3 phn ly, ta c:
CH3CHOHCH3(k)

H3CCOCH3(k) + H2

(a x)

Tng s mol cc cht lc cn bng: n i a x

KP

K n .
n i

cb

x.x P
.

a x a x

vi n = 1

2
0,97.x
0,692
2
2

a x

x = 0,764a

Vy phn ly:

x
0,764
a

V d 3. un nng ti 4450C mt bnh kn cha 8 mol I2 v 5,3 mol H2 th to ra 9,5 mol HI lc

cn bng. Xc nh lng HI thu c khi xut pht t 8 mol I2 v 3 mol H2.
Gii
Gi x l s mol H2 tham gia phn ng:
H2

I2

2HI

5,3

Phn ng

2x

Cn bng

(5,3 x)

(8 x)

2x

Ban u

Theo bi: 2x = 9,5 x = 4,75 (mol)

Hng s cn bng:
n 2HI
4x 2
Kn

50,49
n H 2 .n I2 5,3 x 8 x

Hn hp 8 mol I2 v 3 mol H2.

H2

I2

2HI

Ban u

Phn ng

2y

Cn bng

(3 y)

(8 y)

2y

V nhit khng i nn hng s cn bng cng khng i:

4

4y 2
50,49
3 y 8 y

Kn

y = 2,87

S mol HI to thnh: nHI = 5,74 (mol)

V d 4. Hng s cn bng ca phn ng:
PCl3(k) + Cl2(k)

PCl5(k)

-1

500K l KP = 3 atm .
a.

Tnh phn ly ca PCl5 1atm v 8 atm.

b.

p sut no, phn ly l 10%.

c.

Phi thm bao nhiu mol Cl2 vo 1mol PCl5 phn ly ca PCl5 8 atm l 10%.
Gii

a.

Tnh phn ly ca PCl5

Gi a l s mol PCl5 ban u
l phn ly ca PCl5, ta c:
PCl5(k)
Ban u

a
a

0
a

0
a

a(1-)

Phn ng
Cn bng
Ta c

P
ni

KP Kn

PCl3(k) + Cl2(k)

a
P

a1 a1

Vi n = 1, ni = a(1+)

P. 2
1

3P2 = 1 - 2

1
1 3P
0,5
0,2

p sut no phn ly l 10%

Ta c

c.

1
3

Vi P = 1 atm
Vi P = 8 atm
b.

P. 2
1

2
3
1

0,12.P
1

2
3
1 0,1

P = 33 atm

Lng Cl2 cn thm vo

Gi b l s mol Cl2 cn thm vo:
5

PCl5(k)
Ban u

Ta c:

PCl3(k) + Cl2(k)

Phn ng

0,1

0,1

0,1

Cn bng

0,9

0,1

(b + 0,1)

K P K n

ni
0,1. b 0,1
8
1

0,9
b

1,1
3

b = 0,5 (mol)

V d 5. C th iu ch Cl2 bng phn ng

4HCl(k) + O2 = 2H2O(h) + 2Cl2
Xc nh HSCB KP ca phn ng 3860C, bit rng nhit v p sut 1 atm, khi cho
mt mol HCl tc dng vi 0,48 mol O2 th khi cn bng s c 0,402 mol Cl2.
Gii
Gi x l s mol O2 tham gia phn ng.
Tng s mol lc cn bng:

n i 1,48 x ; n = -1

Theo bi ta c: 2x = 0,402 x = 0,201 (mol)

4HCl(k) +

O2

2H2O(k)

+ 2Cl2(k)

0,48

4x

2x

2x

(1 - 4x)

(0,48 - x)

2x

2x

Hng s cn bng:

K P K n .

P
ni

cb
n

P
2x . 2x

4
0,48 x .1 4x n i cb
1
4

0,402
1

81,2 (atm-1)

0,279 . 0,196 4 1,279

KP

KP

V d 6. Cho Fe d tc dng vi hi nc theo phn ng:

3Fe + 4H2O(h) = Fe3O4(r) + 4H2
2000C nu p sut ban u ca hi nc l 1,315 atm, th khi cn bng p sut ring
phn ca hydro l 1,255 atm. Xc nh lng hydro to thnh khi cho hi nc 3atm vo
bnh 2 lit cha st d nhit .
Gii
6

Gi x l s mol H2O tham gia phn ng:

3Fe +

4H2O(h)

Fe3O4(r)

+ 4H2

1,315

(1,315 - x)

Theo bi ta c: x = 1,255 (atm)

Hng s cn bng:
PH4
1,255

KP 4

PH O 1,315 1,255
2

1,91.10 5

Gi x l p sut ring phn ca H2 lc cn bng:

3Fe +

4H2O(h)

Fe3O4(r)

+ 4H2

(3 x)

V nhit khng i nn hng s cn bng cng khng i:

PH4 2 x 4
5

KP 4
1,91.10
PH 2O 3 x

x = 2,863 (atm)

S mol kh H2 sinh ra:

PV nRT n

P.V
2,863 2

0,148
RT
0,082 473

(mol)

Khi lng kh H2 sinh ra: m H 2 2 0,148 0,296 (g)

V d 7. p sut tng cng do phn ng nhit phn
2FeSO4(r) = Fe2O3(r) + SO2(k) + SO3(k)
nhit 929K l 0,9 atm.
a.

Tnh hng s cn bng KP 929K ca phn ng.

b.

Tnh p sut tng cng khi cn bng nu cho d FeSO4 vo bnh c SO2 vi p sut u
l 0,6 atm 929K.
Gii

a.

Hng s cn bng:
K p PSO 2 .PSO 3 0,45 0,45 0,2025 (atm2)

b.

p sut tng cng:

Gi x l s mol ca SO3 sinh ra:
7

2FeSO4

Fe2O3(r) + SO2

SO3

0,6

(0,6 + x)

V nhit khng i nn hng s cn bng cng khng i:

K p PSO2 .PSO3 x. 0,6 x 0,2025

x2 + 0,6x - 0,2025 = 0

x = 0,24 (atm)

p sut ca hn hp:
P PSO2 PSO3 0,24 084 1,08 (atm)

V d 8. Tnh HSCB KP 250C ca phn ng

CO + 2H2 = CH3OH(k)
bit rng nng lng t do chun Go i vi phn ng
CO + 2H2 = CH3OH(l)
bng -29,1 KJ/mol v p sut hi ca metanol 250C bng 16200 Pa.
Gii

Ta c:

CO + 2H2 = CH3OH(k)

(1)

CO + 2H2 = CH3OH(l)

(2)

K P(2)

K P(1)

PCO .PH22

PCH3OH
PCO .PH22

PCH3OH .K P(2)

0
RTlnK P(2)
Mt khc: G(2)

G (2)

K P(2) exp

RT

29,1.10 3
126168
exp

8,314 298

Suy ra: K P(1)

(atm-3)

16200
126168 20177 (atm-2)
1,013.10 5

V d 9. Hng s cn bng 1000K ca phn ng:

2H2O(h) = 2H2 + O2 l KP = 7,76.10-21 atm.
p sut phn ly ca FeO nhit l 3,1.10-18 atm. Hy xc nh HSCB KP 1000K ca phn
ng
8

FeO(r) + H2 = Fe(r) + H2O(h)

Gii
2H2O(h) = 2H2 + O2
2FeO(r) = 2Fe(r)

(1)
O2

(2)

FeO(r) + H2 = Fe(r) + H2O(h)

(3)

Ta c: 2p. (3) = p. (2) - p. (1)

G0(3) = G0(2) - G0(1)

2RTlnK P(3) RTlnK P(2) RTlnK P(1)

2lnK P(3) lnK P(2) lnK P(1)

K P(2)

K 2P(3)

K P(1)

M: Kp(1) = 7,76.10-21 (atm)

Kp(2) = 3,1.10-18 (atm)
Suy ra: K P(3)

K P(2)
K P(1)

3,1.10 18
19,99
7,76.10 21

V d 10. Cho phn ng:

CuSO4.3H2O(r) = CuSO4(r) + 3H2O(h)
bit hng s cn bng KP 250C l 10-6atm3. Tnh lng hi nc ti thiu phi thm vo bnh
2 lt 25oC chuyn hon ton 0,01 mol CuSO4 thnh CuSO4.3H2O.
Gii
Gi x l mol H2O thm vo:
CuSO4.3H2O(r)

CuSO4(r)

+ 3H2O(h)

Ban u

0,01

Phn ng

0,01

0,03

Cn bng

0,00

(x - 0,03)

Tng s mol ti thi im cn bng:

x 0,03

(mol)

Hng s cn bng:
P
n
i

Kp Kn

x 0,03

RT

2
1

0,082 298 x 0,03 10 2

x 3,08.10 2

1
10 6

(mol)

V d 11. Cho kh COF2 qua xc tc 1000oC s xy ra phn ng

9

2COF2(k)

CO2 + CF4(k)

Lm lnh nhanh hn hp cn bng ri cho qua dung dch Ba(OH)2 hp thu COF2 v CO2 th
c 500 ml hn hp cn bng s cn li 200ml khng b hp thu.
a.
b.

Tnh HSCB KP ca phn ng.

Bit KP tng 1% khi tng 1oC ln cn 1000oC, tnh Ho, So v Go ca phn ng
1000oC.
Gii

a.

Tnh HSCB KP ca phn ng

Gi x l s mol COF2 tham gia phn ng:
2COF2(k)

CO2

CF4(k)

a
x
2
x
2

x
(a x)
Tng s mol lc cn bng:
Ta c:

n CF4

VCF4

ni Vi

x
2
x
2

ni a

x
2 200

a 500

4a
5

V n = 0, hng s cn bng:
KP Kn

b.

n CO2 .n CF4
2
n COF
2

x

2

a x 2

4a 2
252 4
a
25

Kp tng 10% khi tng 1oC ln cn 1000oC.

Hng s cn bng KP 1001oC:
Kp = 4 + 0,04 = 4,04

Ta c:

ln

K p(T2 )
K p(T1 )

0
1
H1000
1

R
T2 T1

K p(T2 )

4,04
K p(T1 ) 1,987ln 4

32065 (cal)
1
1
1
1

T2 T1
1274 1273
Rln

0
H1000

0
G 1000
RTlnK p(1000) 1,987 1273 ln4 3507 (cal)

Ta li c: G01000 = H01000 - TS01000

H1000 G 1000 32065 3507
0
S1000

27,94 (cal/K)
0

1273

V d 12. 1000K hng s cn bng ca phn ng:

10

C(gr)

CO2(k)

2CO(k)

l Kp =1,85 atm v hiu ng trung bnh l 41130 cal. Xc nh thnh phn pha kh cn bng
ti 1000K v 1200K bit p sut tng cng l 1atm.
Gii
1000K: gi xCO v x CO 2 l phn mol ca cc kh cn bng:
Ta c, hng s cn bng: K K x . n vi n = 2 1 =1
Suy ra: K

2
x CO
x CO 2

M: x CO x CO2 1 x CO2 1 x CO
2
x CO
K
1 x CO

2
K .x CO K 0
Vy x CO
2
1,85.x CO 1,85 0
Vi Kp = 1,85 atm x CO

(1)

Gii phng trnh ta c: xCO= 0,72 v x CO 2 = 0,28.

ln
ln

K ,2
K ,1

K ,1200
1,85

1
1

R 2 1

41130 1
1

1,987 1200 1000

Ta tnh c:
KP,1200 = 58,28 atm
Thay vo phng trnh (1) c:
2
x CO
58,28.x CO 58,28 0

Gii phng trnh ta c: xCO = 0,98 x CO 2 = 0,02

V d 13. Cho cc d kin sau:
H0298,tt
(KJ/mol)
G0298
(KJ/mol)
Cp,298
(J/mol.K)

CO

CO2

Pb

PbO

-110,43

-393,13

-219,03

-137,14

-394,00

-189,14

29,05

36,61

26,50

46,27

Chp nhn nhit dung khng thay i trong khong nhit 25 -1270C.
a. Tnh G0, H0, Kp 250C ca phn ng:
b.

PbO(r) + CO(k) = Pb(r) +

Biu th 0 = f(T) di dng mt hm ca nhit .

CO2(k)

11

c.

Tnh Kp 1270C.
Gii

a.

Tnh G0, H0, Kp 250C ca phn ng:

H0298 = -393,13 + 0 + 110,43 + 219,03 = -63,67 (KJ)
G0298 = -394 + 0 + 137,14 + 198,14 = -67,72 (KJ)

Hng s cn bng:
lnK P

G 0298
67,72.10 3

27,33
RT
8,314 298

b.

Kp = 7,4.1011 (atm)
Biu th 0 di dng mt hm ca T.
Cp,298 = 36,61 + 26,50 29,05 46,27
= - 12,21 (J/K)
0 0298

(12,21)d

298

298

63670

(12,21)d 63670 12,21( 298)

60031,42 12,21

c.

(J)

Tnh Kp 1270C
ln
ln

P, T2
P, T1
K p,T2
K p,T1

1
1

R 2 1
63670 1
1

6,55
8,314 400 298

,400 e 6,55 7,4.1011 1,055.10 9

(atm)

V d 14. Cho phn ng v cc s liu tng ng sau:

Ckc(r)
H0298
(Kcal/mol)
S0298
(cal/mol.K)
Cp
(cal/mol. K)

2H2(k)

CH4(k)

0,453

-7,093

0,568

31,21

44,50

2,18

6,52

4,170

a.

Hy xc nh G0298 v Kp298 ca phn ng trn.

b.

250C khi trn 0,55 mol kh CH4 vi 0,1 mol kh H2 trong bnh cha Ckc rn (d), th phn
ng xy ra theo chiu no nu p sut tng cng gi khng i 1 atm? Gii thch.

c.

Kh H2 c nn vo bnh c cha Ckc rn d iu kin p sut 1 atm v nhit 298K.

d.

Hy xc nh p sut ring phn ca CH4 khi cn bng nhit p sut trn.

Thit lp phng trnh H0 = f(T) (phng trnh ch c s v T) v tnh H0 10000K.
12

Gii
a.

H0298(p) = -7,093 0,453 = -7,546 (Kcal)

S0298(p) = 44,50 0,568 2x31,21 = -18,488 (cal)
G0298 = -7546 + 298x18,488 = -2036,576 (cal)
KP298 = 31,169 (atm-1)

b.

c.

P
p n
n
i

0,55

2
0,1 0,1 0,55

35,75(atm 1 )

p > Kp suy ra phn ng xy ra theo chiu nghch.

PCH
K p 2 31,169 PCH 31,169PH2
PH
4

2
Ta c PCH PH 1 31,169PH PH 1 0
4

Ta c PH2 0,164(atm) , PCH4 0,836(atm)

d.

H 0T H0298

C p dT 7546 11,05(T 298)

298

Vy H0T 11,05T 4253,1 (cal)

0
H1000
11,05 1000 4253,1 15303,1 (cal)

= - 15,3031 (Kcal)
3.5. Bi tp t gii
1.

Ti 500C v p sut 0,344 atm, phn ly ca N2O4 thnh NO2 l 63%. Xc nh KP v KC.
S: Kp = 0,867 (atm); KC= 0,034 (mol/l)

2.

630C hng s cn bng KP ca phn ng:

N2O4

2NO2 l 1,27. Xc nh thnh phn hn hp cn bng khi:

a.

p sut chung bng 1atm.

b.

p sut chung bng 10 atm.

S: a. 65,8% NO2; 34,2% N2O4
b. 29,8% NO2; 70,2% N2O4

3.

un 746g I2 vi 16,2g H2 trong mt bnh kn c th tch 1000 lit n 420 0C th cn bng

thu c 721g HI. Nu thm vo hn hp u 1000g I 2 v 5g H2 th lng HI to thnh l
bao nhiu?
S: 1582 g

4.

Xc nh hng s cn bng Kp ca phn ng sau 700K

SO2 + 1/2O2 = SO3

Bit rng 500K hng s cn bng Kp = 2,138.105 atm

trong khong nhit 500 700K l -23400 cal.

-1/2

v hiu ng nhit trung bnh

13

S: 2,6.10+2 atm-1/2
5.

1000K hng s cn bng ca phn ng:

2SO3(k) + O2(k)

2SO3(k)

C hng s cn bng KP = 3,5 atm-1. Tnh p sut ring phn lc cn bng ca SO2 v
SO3 nu p sut chung ca h bng 1 atm v p sut cn bng ca O2 l 0,1 atm.
S: PSO 0,75 atm ,
2

PSO3 0,15 atm

6.

Tnh G0 v hng s cn bng Kp 250C ca phn ng sau:

NO + O3

NO2 + O2 .

Cho bit cc s liu sau:

7.

0
298, tt

0
298

(KJ/mol)

(J/mol.K)

NO2

O2

NO

O3

33,81

90,25

142,12

240,35

240,82

210,25

237,42

S: Kp= 5.1034
298K phn ng: NO + 1/2O 2 = NO2, c G0 = -34,82 (KJ) v H0 = -56,34 (KJ). Xc
nh hng s cn bng ca phn ng 298K v 598K.
S: Kp= 1,3.106 2980K v Kp= 12 5980K

8.

nhit T v p sut P xc nh, mt hn hp kh cn bng gm 3 mol N 2, 1 mol H2 v

1 mol NH3.
a.

Xc nh hng s cn bng Kx ca phn ng.

3H2(k) + N2(k)

b.

2NH3(k)

Cn bng s dch chuyn theo chiu no, khi thm 0,1 mol N 2 vo hn hp cn bng
T v P khng i.
S: a. Kx= 8,33; b. Kx = 8,39

9.

Hng s cn bng ca phn ng:

PCl3(k) + Cl2(k)

PCl5 (k) 500K l KP = 3 atm-1.

a.

Tnh phn ly ca PCl5 2 atm v 20 atm.

b.

p sut no, phn ly l 15%.

S: a. 44,7%; 13%; b. 14,48 atm

10.

Cho phn ng thy phn este axetat etyl.

CH3COOC2H5 + H2O

CH3COOH + C2H5OH
14

Nu ban u s mol ca este bng s mol nc th khi cn bng c 1/3 lng este b thy
phn.
a.

Xc nh hng s cn bng ca phn ng thy phn.

b.

Tnh s mol este b thy phn khi s mol nc ln gp 10 ln s mol este.

c.

Tnh t l mol gia nc v este khi cn bng 99% este b thy phn.
S: a. Kn = 0,15; b. 75,9%; c. 393 ln

11.

Cho phn ng:

C2H4(k) + H2(k)

C2H6(k)

Lp cng thc tnh s mol ca C2H6 trong hn hp cn bng theo s mol ban u ca
C2H4 l a, ca H2 l b, hng s cn bng Kp v p sut cn bng ca h l P.
S.

12.

Cho phn ng: CO

Cl2

ab

a b 2
4

abPK P
P.K P 1

COCl2

C phng trnh m t s ph thuc ca Kp vo nhit T l:

a.

lgKp(atm) = 5020/T 1,75lgT 1,158.

Tm phng trnh m t s ph thuc nhit : G0T = f(T) v H0T = g(T).

b.

Tnh G0, H0, S0 v hng s cn bng KP, KC 700K.

c.

Hn hp phn ng sau s xy ra theo chiu no 1atm v 700K:

2 mol CO; 5 mol Cl2 v mol 3 COCl2.
0,4 mol CO; 1,6 mol Cl2 v 8 mol COCl2.

13.

C th iu ch Cl2 bng phn ng:

4HCl(k) + O2

2H2O(h)

2Cl2

Xc nh HSCB KP ca phn ng 386 C, bit rng nhit v p sut 1 atm, khi

cho 1 mol HCl tc dng vi 0,5 mol O2 th khi cn bng s c 0,4 mol Cl2.
S: Kp = 69,3 atm-1
14.

400C, hng s cn bng ca phn ng:

LiCl.3NH3(r)

LiCl.NH3(r)

2NH3(k)

l Kp = 9 atm , nhit ny phi thm bao nhiu mol NH 3 vo mt bnh c th tch 5 lit cha
0,1mol LiCl.NH3(r) tt c LiCl.NH3(r) chuyn thnh LiCl.3NH3(r).

15