()

40123 3 1 2549

(Chemical Equilibrium)

Note

 ()
40123 3 1 2549

1.
()
2.
(1)
(2)
3. 3
(1) (Open system)

(2) (Closed system)

(3) (Isolated system)

4. 3
(1) (solid , liquid , gas)
(2) (solute + solvent = solution)
(3) (reactants
products)
3
5. ()
(1)
(2)

(3)
()
(4)

(5)
=

(6) (Chemical equilibrium)

 ()
40123 3 1 2549

1
[Co (H2O)6] 2+ + 4 Cl()

[CoCl4]2- + 6 H2O
()

[CoCl4]2-
[Co (H2O)6] 2+

(Chemical Equilibrium)

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40123 3 1 2549

1.

(in a state of equilibrium, the concentrations of reactants and products no longer
change with time)
N2O4 (g)

2NO2 (g)

100 c
N2O4
NO2 NO2
N2O4 N2O4
N2O4 NO2
( N2O4 ) ( N2O4 )

Note

 ()
40123 3 1 2549

2 Reaching equilibrium on the macroscopic and molecular levels.

At equilibrium : ratefwd = raterev

1.

2.

 ()
40123 3 1 2549
2.


kfwd [N2O4]

krev [NO2]2

kfwd
krev
[ NO 2 ] 2
=
[ N 2O 4 ]

k fwd
k rev

[ NO 2 ] 2
=
[ N 2O 4 ]

k fwd
k rev

K (Equilibrium Constant)

cC + dD

aA + bB
K

[C ]c [ D ]d
[ A ]a [ B ]b

K is equal to a particular ratio of equilibrium product
and reactant concentration terms at a particular temperature.

 ()
40123 3 1 2549

50% k
1. K
N2 (g) + O2 (g)
2 NO (g)
K = 1x10-30

1000 K
NO (g)
2. K
2 CO2 (g)
K = 2.2 x1022
2 CO (g) + O2 (g)
1000 K
(goes to completion)
3. K (intermediate)
Br2 (g) + Cl2 (g) K = 5
2 BrCl (g)
K

3 K

 ()
40123 3 1 2549
3.
K
r ()

K




C + D
2A+B
K =

k1
[C ][ D ]
=
k 2 [ A] 2 [B ]

2A
A2 + B

A2
C+D

K =

k1
[A ]
= 22
k 2 [ A]

K =

k3
[C ][ D ]
=
k 4 [ A2 ] [B ]

K = k 1k 2 =

K =

[ A2 ] [C ][ D ]
x
[ A] 2 [ A2 ][ B ]
[C ][ D ]
[ A] 2 [B ]

 ()
40123 3 1 2549
2 A + B

K =

[C ][ D ]
[ A] 2 [B ]

C + D

4.
1. (Homogeneous equilibrium)

N2O4
Kc =

[NO 2 ] 2
[N 2O 4 ]

Kc


mol/dm3 P = (n/V) RT
KP =

P 2 NO 2
PN 2O 4

PNO PN O atm NO2 N2O4

Kp
2

2. (Heterogeneous equilibrium)


CaCO3 (s)

CaO (s) + CO2 (g)

 ()
40123 3 1 2549

KC =

[CaO ][CO2 ]
[CaCO3 ]

CaCO3 CaO
()

(
)
( 8.96 g/cm3) 20 C
1 1
8 . 96 g
cm

1mol
= 0 . 141 mol / dm
63 . 55 g

= 141 mol / dm

CaCO3

[CaCO3 ]
K C = [CO2 ]
[CaO ]

[CaCO3] [CaO] KC

K C = [CO 2 ]

Note

10

 ()
40123 3 1 2549
5. KC KP

b B (g)

a A (g)

a b KC
KC =

[B ] b
[ A] a

KP
KP

PbB
= a
P A

PA P B A B

PA V = nA RT
PA =

n A RT
V

V B
PB V = nB RT
PB =

n B RT
V

PA PB KP
B

KP

n B RT

V
=
n A RT

11

=
a

nB

V
nA

(RT ) b a
a

 ()
40123 3 1 2549
nA / V nB / V mol/dm3 [A] [B]

KP =

[B ] b
(RT ) n
[ A] a

= K C (RT) n
n = b - a
= -
KP KC n = 0

2 HI (g)
H2 (g) + I2 (g) [HI] 1.56 x 10-2
mol/dm3 , [H2] 3.56 x 10-3 mol/dm3 [I2] 1.25 x 10-3 mol/dm3 KC KP

KC =

[H 2 ][ I 2 ]
[HI ] 2
( 3 . 56 x 10 3 ) x (1 . 25 x 10 3 )
(1 . 56 x 10 2 ) 2

K C = 1 . 83 x 10 2

K P = K C (RT )

n = 1 + 1 2 = 0
KP = KC = 1.83 x 10-2

12

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40123 3 1 2549
6.

1.
2.
3.
4.
5.

(Le Chateliers Principle)

( )





6.1

A + B
C + D
A
A
( A)
A B
C D

13

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40123 3 1 2549
C
C
( C)
A B
C D

1.
2.

Ba2+(aq) + SO42- (aq)

BaSO4 (s)
Na2SO4

..

Na2SO4
K
.
Ba2+
SO42- BaSO4 Ba2+
[Ba2+] [SO42-] K

14

 ()
40123 3 1 2549
6.2

1 : (
- H)
C + D + energy
A+ B
) ()


(A B ) (C D
)
) ()

A B C D

2 : (
H)
1
C + D
A + B + energy
) ()


(C D ) (A B
)
) ()

A B C D

15

 ()
40123 3 1 2549
6.3

()

PV = n RT
n
P = RT
V

P V
n/V
mol/dm3
3

1 :
2 :
3 :
1
N2 (g) + O2 (g)
2 NO (g)

2
N2 (g) + 3H2 (g)
2NH3 (g)

PV = nRT n P n P

16

 ()
40123 3 1 2549


(mol/dm3)

3
PCl3 (g) + Cl2 (g)
PCl5 (g)
2
6.4
( )



6.5

17

 ()
40123 3 1 2549
7.


(NH3)
H2 N2
N2 (g) + 3 H2 (g)

2 NH3 (g)

NH3
1. ()
2. ()
3.

500 C

350

18

 ()
40123 3 1 2549
8.
1 N2
O2
(1) N2 (g) + O2 (g)
2 NO (g)
K = 4.3 x 10-25
(2) 2NO (g) + O2 (g)
2 NO2 (g)
K = 6.4 x 109
K
(1) + (2)
(1) N2 (g) + O2 (g)
(2)
2NO (g) + O2 (g)
: N2 (g) + 2O2 (g)

2 NO (g)
2 NO2 (g)
2 NO2 (g)

K =

[NO 2 ] 2
[N 2 ][O 2 ] 2

K
(1)

K1 =

[NO ] 2
[N 2 ][O 2 ]

(2)

K2 =

[NO 2 ] 2
[NO ] 2 [O 2 ]

K
K =

K1 x K2

[NO 2 ] 2
[NO ] 2
x
[N 2 ][O 2 ]
[NO ] 2 [O 2 ]

K =

[NO 2 ] 2
[N 2 ][O 2 ] 2

=
=

(4.3 x 10-25) (6.4 x 109)

2.8 x 10-15

19

 ()
40123 3 1 2549
K
1.
2. / (Initial) t = 0
3. /
()
()
4. / (Final) t = te 2 + 3
/
K

1
K

2 NO (g) + O2 (g) NO2 , NO O2

2 NO2 (g)
1 , 0.8 0.2 1
O2 0.3

1
2 NO (g)
+
O2 (g)
2 NO2 (g)
2
1.0
0.8
0.2
mol / dm3
3
- 2a
+ 2a
+a
mol / dm3
4
1 2a
0.8 + 2a
0.2 + a
mol / dm3
O2 0.3
0.2 + a
=
0.3
a
=
0.1

20

 ()
40123 3 1 2549
[NO ] 2 [O 2 ]
K =
[NO 2 ] 2

2
(
1 ) (0 . 3 )
=

(0. 8 )2
= 0.47

2
K

H2 44.8 .. STP I2 44.8 .. STP

250 C 2 K 4 H2 , I2
HI
1
H2 (g)
+
I2 (g)
2 HI (g)
2
44 . 8
=2
22 . 4

44 . 8
=2
22 . 4

3
-a
4
2a

(2-a) / 2

-a

mol

+ 2a

mol

2a
a

mol
mol/dm3

2a
(2-a) / 2
K =

[HI ] 2
[H 2 ][ I 2 ]

4=

a2

2=

2 a

a
2 a

21

2a
2 a

 ()
40123 3 1 2549

2 ( 2-a) =
a
=
[H2] = [I2] =
=
[HI]
=
=

2a
1
(2-a) / 2

a
1

mol
mol / dm3
mol / dm3

9.
(Solubility)

AgCl

AgCl (s)
Ag+ (aq) + Cl- (aq)

(Ag+
and Cl- ion)


K = [ Ag + ][Cl ]

22

 ()
40123 3 1 2549
K Ksp (Solubility product constant)

MgF2
MgF2 (s)
Mg2+ (aq) + 2F-(aq) Ksp = [Mg2+][F-]2
Ag2CO3
Ag2CO3(s)
2Ag+ (aq) + CO32- Ksp = [Ag+]2[CO32-]
Ksp
Ax By (s)

x Aa+ (aq) + y Bb- (aq)

Ksp = [Aa+]x [Bb-]y

Ksp
1.

(25 c)
2.
Ksp Ksp
3.
AgCl Ksp = 1.6 x 10-10 Q
Q = [Ag+] [ Cl-]

Q
<
Ksp Unsaturate solution
Q
=
Ksp Saturated solution
Q
>
Ksp Supersaturated solution ; AgCl will
precipitate out until the product of the ionic concentrations is equal to 1.6 x 10-10

Ksp

23

 ()
40123 3 1 2549

1 Ag2SO4 1.5 x 10-2

25 C Ksp

Ag2SO4 (s)
2 Ag+ (aq) + SO42- (aq)
1 Ag2SO4 Ag+ 2 SO42- 1
Ag2SO4 1.5x10-2 1

2 (1.5 x 10-2 ) =
3.0 x 10-2

[Ag+] =
[SO42-] =
1.5 x 10-2

Ksp
Ksp =
[Ag+]2 [ SO42-]
=
(3.0 x 10-2)2 (1.5 x 10-2)
=
1.4 x 10-5
2 Cu(OH)2 Ksp 2.2 x 10-20 Cu(OH)2

25 C

Cu (OH)2 (s)

Cu2+ (aq)

Ksp
2.20 x 10-20
a3
a3

0
+a
a
=
=
=
=

[Cu2+] [ OH-]2
( a ) ( 2a )2
(2.20 x 10-20) / 4
5.50 x 10-21

24

2 OH- (aq)
0
+a
a

5.50 x 10-21

 ()
40123 3 1 2549
a

1.8 x 10-7

mol / dm3

Cu (OH)2 97.57 g/mol

Cu (OH)2
=

1 . 8 x 10 7 mol Cu (OH ) 2 97 . 57 g Cu (OH ) 2

x
1 L sol n
1mol Cu (OH ) 2

= 1.8 x 10-5 g/L

25

 ()
40123 3 1 2549

1. K Kp KC
KP KC
.
2 NOCl(g)
2 NO (g) + Cl2 (g)
.
COCl2(g)
CO (g) + Cl2 (g)
.
NO(g)
N2 (g) + O2 (g)
ZnO (s) + CO (g)
.
Zn (s) + CO2(g)
.
MgSO4(s)
MgO (s) + SO3 (g)

CaO (s) + CO2 (g) 800 C

2. CaCO3 (s)
CO2 0.236 atm () KP () KC

26

 ()
40123 3 1 2549
3. ( NH4CO2NH2 )
NH4CO2NH2 (s)
2NH3 (g) + CO2 (g)

40 C (NH3 CO2) 0.363 atm
(KP)

4. KC H2 (g) + CO2 (g)

H2O (g) + CO (g)
4.2 1650 C CO2 0.8 5
H2 0.80

27

 ()
40123 3 1 2549
5.

H2 (g) + Cl2 (g)

H2

2 HCl (g) + 68 kJ

[Cl2]

[HCl]

2 NH3 (g)
6. N2 (g) + 3H2 (g)

NH3
6.1
6.2
6.3

..

.

28