:

) (Interface .
.
:Solid-Solid Interface(1
.
:
.a ):(Electronic Industry
.
.b ):(Catalytic Processes

. Rh
ZnO :

 Rh ZnO
:

:Solid-Liquid Interface(2 :

H+ OH-
H+ .

:
H2 O2 ) (H

20% G
) ( G0= nFE0 90% .

.b / )(Electrolyte/Semiconductors
1 3
)(Hole
. .
.

.c/ )(Solid/Nonelectrolyte
.
Reactive
. ) (Wetting ) (Spreading
.
(3/ )(Solid/Gas Interface

Metal Oxidation.a
Tarnishing .b

.c ) (Vapor Deposition ) (PVD

) (CVD .
Desulphurization
H2 . :
Ni/Al2O3

Ni/Al2O3
)CO + 3 H2 (g

1000 K

CO + 3 H2 (g) CH4 + H2O

1000 K

CH4 + H2O

H2 CO .
:
Fe2O3/CuO
)(water-gas shift

)CO2(g) + H2 (g

CO(g) + H2O

CO2 H2 CO2
CO2 . CO2
CO2 .
:

Ag Cu .

 (4/)(Liquid/Liquid Interface

Extraction

Spreading

(5/: )(Foaming/anti foaming

(1 : )PT (V ) (Interface
(2 :
(3 :
)(Bulk
IR
Surface to Bulk atomic ratio are very small.(1
107
(107)3=1021 61014 .

S/V=61014/1021=610-7

 IR
107 .
. 10000 :
S/V=6108/1012=610-4
1000 .
.
Surface gets dirty very quickly.(2

P
2mkT

1/ 2

. C 1 P 8kT

=
=

4
4 kT m

ZW

10-10atm 10-2 Pa ) (M=32gr/mol 300K :

S-1.m-2

. Zw=2.710+17 0.1 2.71016

2010-20 m2 2010-202.71016=0.0056
m2 19
.
Surface Structures are unknown.(3
.

How are the surface & bulk properties related?(4
bulk .

What Properties of solid does control the catalytic activity & selectivity?(5
) (Q d
.
.
Nature of adsorption

:
(1 Physisorption
(2 Chemisorption
:

. :
.a )(Permanent Dipole
.b )(Induced Dipole
.c )(Quadrupole

) (Adsorbate ).(Adsorbent
.

.
7

 :
. :
.a )(Electronic Interaction
.b )(Exchange & Sharing of electrons

.
.

. G=H-TS
G <0 . S
) (. H .
.

 :

:H2

H2/D2 .
(
CO


1 M2 S
. x M2
y .
. 2
Q .
Rossington Eley IB
81 kcal/mol )(

13 kcal/mol . 3
. A B
.
8 kcal/mol ) 2Qa-D(H-H Qa
) D(H-H H2 .

Desorption

10

 :3

11

 Ea(ads)~5 kcal/mol :

3
.
x A
B . x min.
y
.
) (Cu :

12



.
5 :

:
(1 M2 (S-M)y
(S-M)x .
(2 M2 (S-M)y

13

(3 M2
.
.
(S-M)y
).
(.

6
:

14


) (. ABXEF.
:1



.

:2 :
.1 -
.2
.3 ) (.
.4

15

 :
:
.1 : .
.2 : .
.3 :
.

:
:



.

. 2
:

Surface Coverage

16

 ) (1- .


) (1-

rads = k ads (1 ) P

kads P ) (1-
.
:

ka kd K
.
:
( :

= KP

( :

=1

17

 : A B PA PB
.
. :
ka(A)PA(1-A-B ) = k d(A).A

)r ads(A)=r des(A

ka(B)PB(1-A-B) = k d(B).B

)r ads(B)=r des(B

- A B :
A=KAPA/1+KAPA+KBPB
B=KBPB/1+KAPA+KBPB
A=KAPA/KBPB~0
)KA=ka(A)/kd(A
)KB=ka(B)/kd(B
KB>>KA PB>>PA :
B A .
n :
A=KAPA/1+KiPi
18

 :
:

:
Surface is homogenous .a
.
:
.
K
K
. :

O
W

O
O

.
.
.

19

No adsorbate adsorbate interaction exists.b

- Hads
.
Only monolayer adsorption .c

.
No surface mobility .d

.
: :
=n/nmonolayer=V/Vmonolayer

20

: .
Vm 1/Vm .
.

21

 :
) ( :

.

.
.

. .

22



.
.
)
( .
H Isosteric heat of adsorption :

23

 :
:

) ( ) ( ~1
.

:
) c0 mg/lit (ppm
) Ce ( .
qe :
qe=(C0-Ce)V/W
:V
:W
)1/qe=1/qm+(1/KLqm)(1/Ce
24

)qm: monolayer adsorption capacity of the adsorbent.(mg/gr

)KL: Langmuir adsorption constant.(lit/mg
Energy of adsorption.

KL: related to the free

) R ( :
RL=1/1+KL.C0
:C0 )(mg/lit
:KL )(lit/mg
RL: .
unfavorable adsorption.
Linear adsorption.
favorable adsorption.
Irreversible adsorption.

RL>1
RL=1
0<RL<1
RL=0

:

.
.
25

N I :

) N(Q :

a Q :

26

 :1
) N(Q Q :

Q=0 H

P .
:2

:
qe =KF.Ce1/n
Lnqe= LnKF + (1/n)LnCe
KF: Constant that related to bonding energy.
1/n: indicating adsorption intensity or the surface heterogeneity.
27

 - -)(B.E.T
Emmette .
I II III .

28

 :
. . BET Langmuir .
. . ) (


.
.
) heat of
(liquidification .
. -
)( .
BET .

29

 a2b1a1 b2 .
a1b2/a2b1 :

H1 HL
) (net heat of adsorption HL
.
Hill J. Chem. Phys. 1948, 14, 263
:

a1b2/a2b1 1
1 .

30

 -
a1b2/a2b1 1
.
BET .

:1
I BET ) (.
II .

:2
C
C~1
.

Slygin-Frumkin :Temkin
) N(Q N(Q)=Q+
:

31

 H .
:

:
BET :
Langmuir : chemisorption & Physisorption
Freundlich : chemisorption & Physisorption
Temkin: chemisorption
BET: multilayer Physisorption

32

 :
Redlich-Peterson isotherm:

Dubinin-Radushkevich isotherm:
) (DR
.
. :

:K
:Qm
:
)=RT(1+1/Ce
Lnqe 2) K (mol-2 kg-2 Qm
) (mg/gr . ) (E

:

33

 -:
UHV
. 10-2 Torr 10-3 3
10-8 .
4 . -
:

(V2)2 13 4 .
2 1 1 2 . 2 1
.
. . P1
V
:

Rotary Pump
Mcleod gauge

34

3
4

 4 . .
Peq .

:neq Peq
: .
.

35

(1 I . II
. I . III

. IV V
. I P0
.
P0 . II III P0

. IV V
.
(2 :
36

Macropores

Mesopores

Micropores

)(>50 nm

)(2-50 nm

)(<2 nm

Type II

Type IV

Type I

) --(

) -(

) -(

Type III

Type V

) (

) (

------

(3 qads
. - . Hads=N.qads
. Hads
) (repulsive lateral interaction Hads
.
(4 .
:
( .
( .
( Anealing 50% 80%
.
. .
.
37

( HeNeArKr .

:
( ) etching ( :
.
( H2 .
( O2 .
( ) PVD.(CVD

38


(1 CO Charcoal 273K .
. Ka .
1 .
700
46.1

600
41.6

500
36.9

400
31.5

300
25.5

200
18.6

100
10.2

)P(torr
)V(cm3

:
=V/Vm=KP/1+KP

P/V=P/Vm+1/KVm

(2 :
700
48

600
45.5

500
40

400
34.1

300
27.3

200
19.3

100
10.3

)P(torr
)V(cm3
K=7.410-3
Vm=150 cm3

39

(3 CO TiO2 . :
250
73.9

240
63.5

230
54

220
45.2

200
30

210
37.1

)T(K
)P(torr
KP=/1-

LnK+LnP=Ln /1-
d LnK/dT+dLnP/dT=0

/RT2

dLnP/dT=-dLnK/dT=-H

(4 H0ads :
250
96

240
80

230
66

220
53

210
41.9

200
32.4

)T(K
)P(torr
H0=-9.0KJ/mol

40

 .5 N2 TiO2 75 .
BET Vmon C .
75 P*=570 Torr 273
1 . N2 0.16 nm2 .
1204.7
1254

164.4
1146

127.7
1046

87.5
935

45.8
822

14
720

1.2
601

)P(torr
)V(cm3

1/CVm=3.410-3
C-1/CVm=1.2310-3
C=363
Vm=810cm3
V=810cm3

(6 :
204.7
950

164.4
860

127.7
790

87.5
719

45.8
649

14
559

1.2
235

)P(torr
)V(cm3
C=290
Vm=620cm3

(7
1
r=0.9979
)Lang .(P/V vs.P
Freund .(LnP vs.LnP) r=0.9969

41


zsigmondly



.

pa pd .
Mc bain .
.

) rb (
:

2v
)
rn RT

Pa = P 0 exp(+

rn<rb rn
.

. rb
.
.

42

2v
)
2nRT

Pd = P 0 exp(

rn rn < rb
Pa > Pb .

)(4

)(2

)(3

)(1

pa
. cohan
pa pd cohan
L r
.

r 2 L

43

2L r

2Lr

( 0 ) n = 2Lr

:
2Lrr
v

= n

A B :
P
2Lrr
RTLn a0 = 2Lr
v
P

)(2

v
rRT

Pa = P 0 exp(

pd
.
2v
)
rRT

Pd = P 0 exp(

:
v
rRT

)(3

Ln Pa0
P

Pd
2v
=
0
rRT
P

ln

Pd
P
P
P
= Ln ( a ) 2 d0 = ( a0 ) 2
0
P
P0
P
P

Ln

pa pd .
. 5
.
. :
44

 . 1 : A




) ( 2
2rc rc
rc
pa pd ) ( 3 .
rb
2 rn
2rn 2
rb < 2rn

rb

2rn
rn
rb )( 3
. (n>1) na , a
L >> a A ) ( 3

. a

na
)(n + 1

)(3

) ( n=1 n>1
:
( Pa ) 2
P
< ( d )2
0
P0
P
45

 n
Mc bain
A .

rb rn :
rn<rb<2rn rb
rb
rn
. rn
) ( 3 .
2rn

46

 .2 :B




B
.

47

 . 3 : C

C
.

1

P2
A 2
.
B . B
2 rn
.

48

 4 : D

C

.

5 : E
C
.

49


A
.
.

2rn
rn .
.
-6
5


.

50










pa pd
.

- -
)(Surface tension & contact angle
.
.

-
.

51



.
.

: .
:
.

52

 :

.
.
) ( .
:
(1 = F/2L N/m
) ( SI ) dyne/cm (cas .
.
(2 .
(3 N/m*m/m=J/m2
.

:
Contact angle
. :

53

 .
:

) ( .
- - .
LG.
- SG - SL
- . .

54

SG=SL+LG* cos
)(Wetting
. 180 .
0<>180
. :
Kw=SG-SL/SL
K>1 K<-1 .

55

 .
.

SG=SL+LG* cos

:

.
.
.

) (.

.

56

 N
. E0 S0 .
Es :
E=NE0+AEs
N E A .
S :
S=NS0+ASs
Ss .
) ( :
As=Es-TSs
Gs :
Gs=Hs-TSs
Hs ) (
. G :
.
:


. dWs ) (A

57

 : N/m2 dyne/cm2
N/m dyne/cm1
.
)
(. .
105 cal/mol :
105cal/mol=6.94*10-19 J/atom
) 1015 atoms/cm2 ( 1019 atoms/m2
6,94 J/m2 .
: ) (Hsub ) (
:

=0.16Hsub.
-
.
.


58

 :
Reconstruction .

dA

dG=-SdT+VdP+ dA

dA
T,P

=dGT,P

)=(G/A

)dG=d(Gs.A

:
:
(1

(2 .
:
.A)/A)T,PdA=(Gs+A(Gs/A))dA

dGT,P= (G

Gs
:

59

dGT,P=G dA= dA

=Gs
.
) (+.
.

.

=Gs

:
(Gs/T)P = (/T)P =-Ss

=0(1-T/Tc)n

:
Tc ) ( 0

T=E
. n n 1

n 1 .
:

60

Hs=Gs+TSS=- T(/T)P


. Hs Es
s

=-T(/T)P

P,V

(/T)P .
) Gs ( .
Gs. .

:1 =(G/A)T,P

:2 T V .
.
Hs Ss ). (.

61

) (+

) .(dA<0
.

>100 mJ/m2

) ( High energy surf.

. .

:
) (
) ( ) ( .
.
. :

w= wd+ whyd.
hg= hgd+ hgmet.

whyd.:

hgd :

62

hgmet.:


- )
( - ) (
. -
- .
- - -
:

ow=0d+(wd+wh)-2(wd*0d)1/2

63


. .
dt . :
dA=(x+dx)(y+dy)-xy=xdy+ydx

dA

)dW=(xdy+ydx

) (dW=PdV ) * = ( :
dV=(xy).dZ
)dW=P(xy.dZ

O1ABO1A/ B /

x/x + dx =R1/R1+dz , x/R1= x+dx/R1+dz

64

O2B/ C/ O2BC

y/y + dy =R2/R2+dz , y/R2 = y+dy/R2+dz

: a-b/c-d=k a/b=c/d=k
a = bk , c = dk
a-c = bk-dk
a-c = k(b-d)
a-c/b-d = k
: :
x/R1=x+dx/R1+dz =dx/dz ,
y/R2=y+dy/R2+dz =dy/dz ,

dz

dz

=(R1/x)dx ,

=(R2/y)dy ,

dy

dx

/x =dz/R1

/y =dz/R2
:

dA=PdV

(xdy+ydx)= P(x*y*dz)
: xy
(dx/x+dy/y)=P.dz
(dz/R1+dz/R2)=P.dz

P=(1/R1+1/R2)

Laplace equation
P=Pin-Pout

:
: .1
R1=R2=R , P=Pin-Pout= z /R
65

.2 :
R1=R2= , P=0 , Pin= Pout
.3 :
P=/R

R1= , R2=R ,

: .

):(Capillary
.

.

. .
90 .

66

67

)=1/2(.g.h.Rc
:
0,871 0,8 25
12 . .

)~1/2(.g.h.Rc
-3

m*(0.4*10

)m
~2*10 N/m
-2

-3

*9.8 m/s *12*10

Kg/m

~1/2*0.871*10

: Rc ) ( < 90 .
h .
:
.
- ) (:

68

 ) (P ) (Pg .
:

Pg1 Pg2 P0 P .
P=2/r . r
r r ) (I
:

:
CCL4 20 0,9 Torr
.
) (N/m .

69

Torr

1.6 gr/cm3 87,05 2.7*10-2 .2


.1 :
=rhg/2Cos . =1/2rhg
.
.
. 0,02 .

.
.

h1 :

70

.2 ):(Wilhelmy
.
.

. x y W :
)Wdet-W=2(x+y)(Cos
Cos=1
Plate
.
.
.3 (Ring Method):

. .

71

 F R B .

. .
.
B
. B Zuidema
Waters :
1 2 . a b :
2

S /m

a=0.7250
2

S /m

c :
C=0.04534-1.679 r/R
r .

72

b=0.09075

.4 ):(Drop-Volume & Drop Weight methods

. mg
2r .

=mg/2r=Vg/2r
m V r

.
:
100
. 2,53 8.78*10-2 .
. 1,6694 .
73

=mg/2r
m=2.53/100=2.53*10-2 gr

)(

.
COOH OH . -
-
.
.
- :

74


.
.

.
.
.
-
.

Troube

CH2 3 .

emulsification .

.
- .

75



.
.
)(
.

.
. ) (detergent ) dispersing
(agent .

76

 .
.
)( .
:

) (SS .
.
)
-(
.

77

 AA BB.
:

AA BB
. i AA Ci BB
Ci .
AA BB .
10 . SS
AA BB

. A .
.
ni i
SS ) ( :
)ni=ni-(ni+ni
) (Surface exess :
i=ni/A

78

 i . )
( ni
SS .
:
U=TS-PV+iini
U=TS-PV+A+ iini
=Tds+SdT-PdV-VdP+dA+Ad+ iidni+inidi

dU

) (2 :
:
dU=TdS-PdV+idni

) ( :
=TdS-PdV+ dA +idni

dU

)(4 ) (3:
SdT- VdP+ Ad+ inidi=0

=(-ni/A)di=-idi

T , P:const

) ( ) (6 :

=-1d1- 2 d2

1=( /1)T,2

1 2

. .
) (
79

=-2,1d2
2,1=-(/LnC2)T
d

.
2= 20 + RTLnC2
:
2,1=-1/RT(/ LnC2 )T
.
Hydon
.
. 1:1 2
.:
2,1=-1/2RT(/ LnC2)T
- )(Micell
.
).
(.

80


.
.
Mc Bain

.
81

(
.
.
( - ) (

.
. .
.

82


c.m.c
.
. c.m.c
83

 c.m.c
:
( .
c.m.c CH2 .
. 16 c18
.
(
. .
(
c.m.c .
( c.m.c .
)
(.
c.m.c. c.m.c
c.m.c .
.
c.m.c c.m.c.
84


c.m.c .

.
c.m.c min.

.

/dc

) ( c.m.c
c.m.c
. min
. c.m.c

/da

) a ( .

c.m.c
. ) (
.

85



.
:

K= cx/m/(c(1-x))m
:c
:X
:m
G0=-RTLnK
))G0=-RT/mLnK =-RT/mLn(cx/m)+RTLn(c(1-x
c.m.c c.m.c x~0 :
)G0~RTLn(c.m.c
)S0=-(G0/T)P=-RT(dLn(c.m.c)/dT)-RLn(c.m.c
86

)H0=G0+TS0=-RT2(dLn(c.m.c)/dT

c.m.c
) ( ) (+
.
)(Krafft

.

.
. c.m.c
.
.
.
)(
)(
.

87

( ) (A .
(
. - - .
( .
) (B

) (A dA
(OA+Ow+WA)dA OA
Ow WA .
.
Initial spreading coefficient
:
88

. S .
)(
. :

WA-(OA+OW)=S

72.8-(30.0+52.1)=-9.3

-n

72.8-(21.8+50.8)=+0.2

-n

72.8-(27.5+85.5)=+36.8

-n

.
) (

OW

S . S WA
OW . -n
.
. :
Sinit.=72.8-(28.9+35.0)=+8.9 mN/m
Wa 62.4 mN/m Ow
28,8 :
89

mN/m

Sfinal=62.4-(28.8+35.0)=-1.4

.

. .

90


)(Comparison of chemisorptive bond with simple ionic band
:
.
. .
)(Free electron theory
.
) . (1

:1

) (1 :
)(1

h 2 d 2
= E
2m dx 2

) 2 (3
n x
)) , n = 1, 2,3,... (2
Na
)(3

( n ( x) = A sin
n2h2
8m( Na) 2

= En

) (Lattice points .
n 2 .

91

 :2 n
E E+dE . )(Density of states
1

. E 2 . 3
.

:3


. ,
) (Fermi level Ef .
4 .

:4

92

 ) Ef ( Ef .
Ef ) (4
Ef

)(4

N ( E )dE

= No. of states

. Ef
. .
) (vacuum ) (work function .
.
: A
) (A+ . ) (I A
. ( I f 0) . A
) . ( p 0 A+
e2
) (image potential ) . ( * p 0
4r

:
Le 2
)) (5
* 4r

Q = ( LI L

: A
) (A- ) ( L f 0
) . ( LA0 p 0
. :
Le2
)) (6
* 4r

Q = ( L LA0

.
) ( L 90 14 . 312
Le2
333 312 . )
* 4r

93

( 50 .

1
Wm + H 2 W H
2

Q0 = +150 kcal.mol 1

. H2 H+ .
+20 .
N H O W .
. K Na Cs .W

.
: K Na Cs W
Le 2
* 4r

Qobs

Qcalc.

118 104 Na/W

)44.5(1.83

32.0

30.5

104

99

)35.5(2.27

44

40.8

104 Cs/W

89

54

48.7

K/W

LI

)31.1(2.62A

.
.
O2 .
O2 .
Cl2 . O2 / Ag Cl2
Cl2 .
(Adsorption and d-bands) d
d . d
. d .
94

 s . .
s s s p
p s . .
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. Si Si .
. ps d
. d .
:
-1 .
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dE

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-3 .
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-3 d .

95

 )(Adsorption and catalysis on semiconductors

.
.
.

:5

:6

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Eg . Eg ) (Eg=1ev
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Eg . Ge 1ev CaO Eg 10ev
. (compound
96

 O2- S2- p .
. O2- S2- .
.
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97

 :8 n

p
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:9 p

98

 ) (Fermi level .

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99

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100

 :13

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101

 :14 p.

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:15 A

102