3

KW

K .
K .

.
K

K .

KW

KW

- -

adsorptionEF
absorptionKadsorbate adsorbent

W
W J

surfactant

W J

catalysts

K E3-1F KE F

KPhysisorptionChemisorption

- -

KWE3-1F
Physisorption

Chemisorption

J J

J J

J J

J J
J

W
K

WKexothermic
G = H - TS

(3-1)

K T G S H

G E F

K H K

WW
CH3CH2OH CH2=CH2 + H2O
CH3CH2OH CH3CHO + H2

- -

dehydration

Kdehydrogenation

WEFW

N2 + 3H2 } 2NH3

Fe(111) : Fe(100) : Fe(110) = 400 : 25 : 1

Cu, W, Ni, Pt

K KAl

E3-2FK
K

KWE3-2F

SO2

NH3

CO2

N2

H2

Adsorption isotherm

K
K

KESTP = 1 atm , 0 oCF

K JE3-1F
- -

WK

Solid + Gas adsorbed gas + heat

(3-2)

K J WE3-1F

E3-2FK

W
E3-2F

KEa Fmonolayer .

KEb-c Fnon-porous .

KE d-e F porous .

b, e K

a KE F E F

K
KLangmuir isotherm

- -

KWE3-2F

K .

.
KE3-3F

K .
P
Gas

Solid

KWE3-3F

EVbFZEVfFW
Vf = Kf P (1- )
Vb = Kb e-Q/RT

(3-3)
(3-4)

- -

P Kf

T R Q Kb (1- )
WE3-4FE3-3FK
/ (1- ) = K P

(3-5)

E3-5FKK= (Kf/Kb) eQ/RT

= KP/(1+KP)

W
(3-6)

= V / Vm

(3-7)

FVm V

WE3-7FE3-6FK =1E

V/Vm = K P / ( 1 K P )
(3-8)
E3-9FVm K

P/V = 1/KVm + P/Vm

(3-9)
E3-4F

P/V

slope = 1/Vm
Intercept = 1/KVm

P

KWE3-4F

K

- -

KVm
2

23

-20

A(m ) = Vm (cm ) 6.02 10 16.2 ( ) 10 / 22414

(3-10)
23
6.0210 16.2 2

KE1 atm, 273KF22414

K

P Vm/ T = P V/ T
(3-11)
KT = 273 K P =1 atm P T V
o

W(Q)

P1, P2 T1, T2 K
n (P2/P1) = (Q/R) {(T2 - T1) / T2T1}

W
(3-12)

WKK 1/P
n (K1/K2) = (Q/R) {(T2 - T1) / T2T1}
(3-13)

{ W
K{
n (P2/P1) = (Q/R) {(T2 - T1) / T2T1}
n (32/4.8) = (Q/2) {(250-190)/190250}
Q = 3003.7 cal mol-1

{ W
K

A(m2) = Vm (cm3) 6.02 1023 16.2 (2) / 22414

= 2.86 6.02 1023 16.2 (2) 10-20 / 22414
= 124.4 m2
- -

W
Q = Ho ( 1- )

(3-14)

K Ho

WE3-4FK
Vb = Kb exp{- Ho (1- )/RT}

(3-15)

Vf = Vb

Kf P (1- ) = b exp{- Ho (1- )/RT}

(3-16)

D P = { /(1- )} eC
(3-17)
o
(3-18)
D = Kf/Kb exp{H /RT}
o
C = H /RT
(3-19)
E3-19F /(1- ) 1 W

= (1/C) n P + G

(3-20)
PE3-21FKG = (1/C) n DW

K 0.5

:BET
Brunauer-Emmett-TellerW
K
V
Vm

WK

[1 (P / P )]
o

C P / Po

o
1 + P / P

(C 1)

(3-21)

K Po C

V P P
o

1
+
CVm

(C 1)
CVm

- -

P
Po

(3-22)

K1/CVm C-1/CVm P/Po P/V(Po-P)

KE3-5FVm

P/V(Po-P)

slope = c-1/cVm
Intercept = 1/cVm
o

P/P

KEBT WE3-5F

W
10nm micropores W

mesopores 100nm macropores

K10-100 nm

KWE3-6F

desorption KE3-6F
K

KP1>P2P2P1



- -

WEF

KE3-7F porosimeter

KWE3-7F

W
P = 2 cos / r

(3-23)
P

PKr
KE3-23F

K Dr
W

Dr = - (P/r) d(V-Vo)/dP
(3-24)
r DrK Vo P r V

K
WE3-3F

- -

KWE3-3F
EnmF EatmF
8550
147
74
49
37
29
25
21

1.7
98
197
296
395
493
592
691

Wreundlich isotherm
Wa = K C1/n
(3-25)
Wa n K
KEFC










- -

KW .
W .

K K

K K

K K

K K

.
K

K .

.
K

K .

.
K

K .

WECFEF .

K K

K K

K K

K K

{ .

K {

K
K
- -

K .

{
n = 2K{

{ {

.
{ {

KK{{

K {
K{

.
P, mmHg 100
V, cm3
10.2

200 300 400 500 600 700

18.6 25.5 31.4 36.9 41.6 46.1

K K

{ .

K{
K

- -

Physisorption

Chemisorption

J J

J J

J J

J J
J

.
W K
K

W K
K

W K
K

W K
KEF

W .

P/V

slope = 1/Vm
Intercept = 1/KVm

P

Vm

- -

.
A gas (cm2) K

EVm FK
WA (m2) Vm
A = Vm (cm3) 6.021023 Agas10-20/22414

W .

Wa = K C1/n

C Wa K n
K

K JW .

K J

H = Ho(1 ) :

K = 0 Ho
W

= 1/C n PC

KPC G

W .
V
Vm

[1 (P / P )]
o

C P / Po

o
1 + P / P

) (C 1)

W
(C 1) P
1
P
=
+

V Po P

CVm

CVm

Po

K1/CVm C-1/CVm P/Po P/V(Po-P)

KVm

- -

P/V(Po-P)

slope = c-1/cVm
Intercept = 1/cVm
o

P/P

KEBT

K .
W

Dr = - (P/r) d(V-Vo)/dP
r DrK Vo P r V

2 J3 J3 J2 J .
W .

N/Nm = K C / ( 1 + K C )

- -

K Nm N
K C
:

N = (0.1 0.01)/1000 = 0.0099 mol

0.009/Nm = 10000.01/{1+(10000.01)}
Nm = 0.0099 mol

A = Nm 6.0210232310-20
= 0.0099 6.0210232310-20
= 1370.8 m2

Wa = (0.5 0.35) 200/1000 = 0.03 g

1/n

Wa = K C
K = Wa/C1/n = 0.03/(0.35)1/2 = 0.05

W .

n (C2/C1) = (Q/R) {(T2 - T1) / T2T1}

Q = RT2T1/(T2-T1) n (C2/C1)
= 2298313/15 n (0.05/0.2)
= -17.242 kcal mol-1

W .

n (K1/K2) = (Q/R) {(T2 - T1) / T2T1}

40 20 C K2 K1
W

/1 = KC

0.25/1-0.25 = K10.05
K = 0.0167
0.5/1-0.5 = K20.45

K2 = 0.225
Q = RT2T1/(T2-T1) n (K1/K2)
= 2298313n (0.0167/0.225)
- -

= -23.867 kcal mol-1

WA .

A = Vm 6.021023 12.610-20 W/22414

.W Wm
A = 0.21 6.021023 12.610-20 10/22414
= 7.1 m2.

W .

P/V = 1/KVm + P/Vm

K Vm K V P

K1/KVm 1/Vm PP/V

K 0.11Vm 9.13

experimental
best fit

15

P/V, mmHg/cm

14

13

12

11

10

9
0

200

400

600

800

P, mmHg

A = Vm 6.021023 19 10-20 /22414

= 0.11 6.021023 19 10-20 /22414 = 0.56 cm2

- -

W .

n (P2/P1) = (Q/R) {(T2 - T1) / T2T1}

KT2 T1 P2 P1 Q

n(P2/4.6) = (-20000/2) (60/239353)

P2 = 0.013 atm.

- -