1

)(

5
5
5
5
5
6
8
8
9
12
12
14
15
16
17
18
21
24
25
25
27
27
29
30
31
32
37
38
39
39
39
40
40
41
42
44
44
45
46






CP CV

G





S,G,H,U

KP )(
-

- -

48
48
49
50
51
52
58
60
60
61
62
62
63
63
64
66
67
68
71
72
72
73
74
78
80
81
82
84
85
86
87
99
103
105
105
107
110
113
118

 G

) (

A B

119
122
128
150
162
190
191
195
195
196
202
203
205
208
214
220
220
224
226

228
233
246
372

 (
:
: .
:
-1 ) (
-2 )(
.a
.b
.c
-3 )(
:
.
)( :
:
-1
-2
:

 -1
-2
-3
:
-1 : V1 .
1m3 = 103 lit = 106 Cm3 = 109 mm3
-2 P :
1 Pa = 1 Nm-2 = 1 Kg m-1 S-2
:
1 atm = 101.325 KPa
1 bar = 105 Pa = 100 KPa
1 atm = 760 mmHg = 760 Torr
-3 : T
)(
. .

 )( .
T
. :
) + 273.15 ( ) = ( T
-4 : m
. Kg .
.


.
. ) (mole mol
.
) (
12 12 .
1 mol = 6.023 1023
.

 )(
n .
NA .
) ( .
NA = 6.023 1023 mol -1
n N

M
12.01 gr. mol-1 18.02 gr. mol-1
. .

:


:

) T n(

1
p

.
.
: ) (Limiting Law .
.

Jacques Charles
) (Gay Lussac .
) p,n( VT

 PV .

: .
:
) -273oc ( .
V = at + b

10

V1 V2 V3
= = ....
=
K = f ( p, n) T1 T2 T3
PV = P V = ....
1 1
2 2
:
.
-1
) . (
-2 ) (
.

1 V
1
) (
=>=

Vo T P
273

11

Vo
V
: V-T
273
T

: .
:
.
)(STP
PV PoVo
=
= cte
T
To

1atm ) (STP
22.414 liters .

PoVo
1atm 22.414 liters
=
= 0.082057 liter .atm / deg ree.mol
To
273.16 deg ree.mole

12

 :
P,V,T,n

T
P

P T , n

= V

V = ( KT ) p , n

PV = KT

:
: n

)V=f(P,T

V
V
V
V
dp +
= dV
) dT = dp + dT => (1
P
T
T P
p T

K
PV
V
=
=
=
P
P2
P2
T

V
V

=
T P T
) (1 .

dV dp dT
+
=
=> ln V + ln P = ln T + ln C
V
P
T

PV = CT

13

22.4
= 0.082
273

= 1 22.4 = C 273 => C

C R

lit.atm
Cal
J
= 1.986
= 8.314
mol. deg
mol. deg
mol. deg

R = 0.082

: R .

PV ghV mgh
J
=
=
=
nT
nT
nT
mol. deg

= PV = nRT => R

: .
PV = nRT

m
MP
= RT =>
M
RT

: 6 20 740ToR
:
740
6
PV
760
=
= 0.243mol = 4.38 grHco
=n
RT 0.083 293

>=PV=nRT

760 TOR = 1 atm

:
: (Partial Pressure) :
= Pi
.

pt = Pi

14

 :
)(Partial Volume

.
Vt = Vi
) (

mole fraction

ni
) (nt = ni
nt

= Xi

Xi =1
:
.
: :

RT

P1 = n1

V
P1V = n1 RT

P V = n RT
RT
2
2
P2 = n2
V
.

.
.
>=
>= >=

.

.

15

P1 + P2 + .... = (n 1 + n2 + ...)

RT
V

P1 + P2 + .... = pt
n1 + n 2 + .... = nt
=> pt = nt

RT
V

:

RT
P
RT
=> >=
V2 = n2
P
RT
V1+V2+=(n1+n2+)
P
V1 = n1

V1+V2+=Vt
n1+n2+=nt
=> Vt=nt

RT
P

ni = Xi nt

, Vi = Xi Vt ,

Pi = Xi Pt

>= Pt Vt = nt RT
i >= Pi Vt = ni RT

Pi ni
= = X i => Pi = X i Pt
Pt nt

16

 : .
: 1mol 2mol 3mol .
22.4lit 273K
.
:
PtVt=ntRT
6 0.082 273
=> Pt = 6 atm
22.4

1
Po 2 = X o 2 Pt = 6 = 1atm
6
1
PN 2 = X N 2 Pt = 6 = 2 atm
3
1
PH 2 = X H 2 Pt = 6 = 3 atm
2
1
= Vo 2 = X o 2Vt = 22.4
6
1
= V H 2 = X N 2Vt = 22.4
3
1
= 22.4
2

XO2 = 1

>=

= Pt

Pi = XiPt

1
3
1
= XH
2

= XO2
2

= V H 2 = X H 2Vt

:
.

.

17

PA
PK
RA = A
MA
MA

RA

) K= f (T,
:
.
-1 .
-2 .
-3 .
-4 )( .
-5 .
: .
-6 .
-7 .

3
RT
2

:
: EK
: R
: T

18

= EK

 :
.
:
:
.
uX ) u
( A .

.
du x
dt

19

=m

dmu x
dt

= fX

 : x
+2mux
-1

mux

-2

-mux

A x 2mux

FX = f x
) FX = 2mux ( A

ux
2L

20

: A

mu x 2
u
= FX = 2mu x X
2L
L

U X Ux
:

F mu x2 mu x2
= P= = 3
A
V
L

m(u X ) i2 m
)= u x2 (1

V
v
i =1
N

=p

:
n
.
2 . 1
.

u x2

=
)=> u 2 = Nu 2 => (2
x

m
Nu x2
v

u x2

= (1), (2) => p

u . uX

21

 .
)u2 = u2X + u2y + u2Z => (3
:

X Z

)u x2 = u y2 = u z2 => (4

(3), (4) => u 2 = u x2 + u y2 + u z2 = 3u x2

mN 2
u
3V

= p

.
.

1
2N
mN 2eK
= eK = mu 2 => p

= => p
eK
2
3V
m
3V
2
) PV = NeK => (5
3
3
)eK = KT => (6
2
2 3

(6), (5) => PV = N KT => PV = NKT

3 2

22

R
T => PV = nRT
Na

PV = N

...

.

.
:
Urms
U rms = U 2

3
1
3RT
3RT
= RT = Mu 2 => u 2
= => U rms = u 2
M
M
2
2

= EK

:
( ) K (
25 .
( ) (Urms 25 .
(

R
Na

23

=K

>=

R = Na K

 : R
: Na

3
KT
2
3
EK = RT
2

= eK

3RT
M

= Urms

:
.
-1 :

N2o4 N2 . 2
2 .
-2 :
.
:

Vid = V

24

nRT
:
P

= Vid

nRT

p

:
) Z (
.

V
V

=Z

Z .
: P0 Z1

RT
PV
= Z
P
RT

= Vid

V
V

=Z

:
.
Z
. Z P :

25

PV
) = 1 + bP => PV = RT (1 + bP
RT

=Z

Z Z
.
. ooc


.
Z .
Z .

) ( .

26

 :
.

PV
= 1 + B p P + C p P 2 + D p P 2 + ....
RT

=Z

. ) ( .
.
.
.

B
C
D
PV
= 1 + V + V2 + V3 + ...
RT
V V
V

=Z

: :
Bv = RTBp

:
:

.
.

27

 .
: Tc

) (.

: Tc ) (L , g-L , g Tc
.

28

 :
.
: A PA=7 B PB=8
.
) (PA=8,PA=7

)
B,A PcB=8,PcA=7 (
: Reduced Parameters


.
:

T
P
V
= , PR
= , VR
TC
PC
VC

= TR

( B,A
)A : (P=2 ,V=4 ,n=1
)B : (P=2 ,V=4 ,n=1

29


.
A ,B :
)A : (PR = 2 , VR = 4 , n=1
)B : (PR = 2 , VR = 4 , n=1
B,A TR ) .
T (
:
PV=nRT .
RT

P

= Vid

. :

RT

P

= Vid :

n :
nRT
+ nVb P(V nVb ) = nRT
P

= Vreal

30

 Vb b
.

P(V nb ) = nRT

:

. .

' :P
'P
n
V

n2
V2

an 2
P' = 2
V

31

 P(V-nb)=nRT .

an 2
( P + P)(V nb) = nRT => ( P + 2 )(V nb) = nRT
V
.
b
.
:
Co2 320 .
.
P

26.2

26.2

26.3

10

2.52

2.53

2.63

40

0.54

0.55

0.66

100

0.098

0.1

0.26

PV

RT

P .

32

 Z=1 .
.

Z
=0

T
=
T
:
B
P0

PV
= 1 + BP P + C P P 2 + ....
RT
Z
) = BP + 2C P P + .... => (1
P T
=Z

P0 BP ) (1 .

Z
: > 0
P T
Z
< 0
P T
: .

33

T5

T3

T4

T2

T1

-0.3 +0.1

-2.3 -1.4 -1

BP

CP

DP

: T5,T4 BP .
:
) (

TC

) (

VC

: PC
: a

nRT
an 2
an 2
= p + 2 (V nb) = nRT => p
2

V
nb

V
V

34

 Min,Max
.

2a
RTc
p
+
=0
==0

2
3
V

(
)
Vc
b
V

Pc,Vc,Tc

2 p
2 RTc
6a

>= = 0

=0
3
4
V 2
Vc
b
V
(

Pc,Vc,Tc
c

nRTc
an 2
2
Vc nb Vc

)(n=1

= => Pc

a
8a
=
,
T
C
27bR
27b 2

= Vc = 3b, Pc

1
b = VC , a = 3PCVC2
3

35

 :
Z .
3ba
PcVc 27b 2 3
=Z
=
=
8aR
RTc
8
27bR

.
P,V,T
.
:

a
)(V b) = RT => (1
V2
P
a
= PR
=> P = PR PC = PR
)=> (2
Pc
27b 2
V
)=> V = VRVC = VR 3b => (3
= VR
VC
T
8a
= TR
=> T = TRTC = TR
)=> (4
TC
27bR
: p +

2 3 4 1 R,b,a
:

3
1
8
PR + 2 VR = TR

3 3
VR

) (

36

 :

.
a
RT
a

>= 2
= : P + 2 (V b) = RT => P
V b V
V

a
PV
V
a
1
=> P = RT

>=
=

>=

RT V b RTV
V b RTV 2
1

a
b
a

= 1
b RTV V
RTV
1
V
1

PV
>=
=
RT

:
(1-x)-1 = 1+x+x2+x3+

PV
a
b b
= 1 + + + ....
RT
RTV
V V
2

PV
a 1 b

= 1+ b
+ + ...
RT
RT

V V

(
)
B
b
V
RT

C = b 2
V

37

 :
: mater
.
: system
. .
.
:
. .
: .
: :
(1 A B B C A C
.
(2 A B B A
.

38

 :

.

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

39

 -5 : .
: .
: Universe
+ =

.
: .
: .
:
2 :
-1
-2
.
.
:
.
P,V,m(n),T,P,H,G,S,

40

 .
.
:
. ... v m
.
: .
2 :
-1
-2

.
:
-1 ) ( .
-2 ) ( .
-3 ) ( .
-4 ) ( .
-5 ) (

41

 -6 ) (

:
.
(
0/000001
-0/000001 ) (
15
.
(
.
:
.
:
A
A .

w = Fdx

42

dw=Fdx

 : ...

P-V :

dw = Fex dx
F
) Pex = ex => dw = Pex Adx => ( Adx = dV
A
=> dw = Pex dV

:
: 1

Pex=0

w = Pex dx = 0

: 2

Pex=k

) w = Kdv = K (V2 V1

: 3

)Pex=f(P

)(Pex~P

Pex=P-

nRT
V

= Pex P

V
nRT
V
P
dv = 2 nRTd ln v = RT ln 2 = RT ln 1
V1
V
V1
P2

: P-V .

43

V2

=w

V1

 :

) (.
:
-1 ) (

intensive

.
...
extensive

-2 ) (

. ...
:
.

44

 : )
(.
:

.

Euniv = 0
:

. :

Euniv = Esys + Ether + EMech=0

Esys = Eb Ea = -Ether - EMech
: :
EK

45

 EP
U )
(
: .

Esys = U
:
.
. .

:
: w

)W = E => (1

: E

)Esys = U => (2
)q = -Ether=> (3

)U = q w => (4
: .
) (4 .
)dU = q - w => (5

46

 : .
) (U
-1
-2 )

( .
-3 ) .
2 2 (.
-4 .
-5 .
-6 ) (5 .
w,q -7 .
( 100 1atm
.
:
T1 = T2 = 373 k
w

>= du = q 2 q w 2 w => U 2 U1 = q w
1
1

47

u2

u1

)U2 U1 = Lv P(v2 v1
: lv

:
1 2 :
)2(P,V2 , T2 , U2 , H2

)1(P,V1 , T1 , U1 , H1

u = q w
>= )U2 U1 = q P (V2 V1) => q=(u2 + PV2) (u1+PV1

=> q( p ) = H q( p ) = dH

U 2 + PV2 = H 2

U1 + PV1 = H1

u
H .
.

48

 :
) (
H<0 H>0
.
: dq(p)=dH
)H = U+PV => dH = du + d(PV) = du+Pdv + Vdp => (1
) du = dq dw = dq Pexdv => (2
=> dH = dq PdV + Pdv + Vdp = dq+Vdp )(2) , (1
dP = 0 => dH = dq
:

U = q(V) => du = dq
( 10cal 1atm 100cm3
H,u :
(
P1 = 1atm

n1 = 1

P2 = 1atm

n2 = 1

) H = q => H = q = 10 cal (

49

 w = Pdv = P(V2-V1) = 1 0.1 >= u = q w

1.986
= 2.42 cal
0.082

= 0.1 lit atm = 0.1

u = 10 2.42 = 7.58 cal

:
H,U H,U
.
U
=0
V

U
=0
p

H
=0
V

H
=0
P

H,U :
)U = f(T,V
U
U
= dU
dV +
dT
V
T

V
:
U
= dU
dT
T V

50

 :
:
-1
-2
:
.

q
q
=
T T

-1

C = lim
T 0

U
= CV
V
T

U
=
V T

q
q
CV = lim V = V
T T
T 0

.
-2

qP qP
H
=
= => C P

T T
T P

C P = lim
T 0

: :
-1
-2

du = CVdT
H
dH = CPdT + dp => dH = CPdT
P T

51

3
5
R, C P = R
2
2

= CV

CV,CP w .
:
:

3
3
3
RT = R => CV = R
2
2
2

= q = EK

RT
RT
q = E K + w = 1.5R + P(V2 V1 ) = P 2 1 + 1.5R = 2.5R
P
P
5
CP = R
2

CP CV :
CP CV
CP CV .

dV
T

U
dV => CV dT +
T
V

U
dT +
V
V

U
= u = f (V , T ) => dU
T

>= H = U + PV => dH = dU + PdV + VdP

H
U
dH = CV dT +
= CV +
>= dV + PdV + VdP
T P
V T
V
U V

+ p
T P
V T T P

52

U
p +
P
V

V
= = c p => c p cV
P
T

R
= p = R
P

RT
p
V
c p cv = p
= p
T
T P

:
W= Pex dv
)w = p(V2 V1

)1

) w=Pex(V2-V1
V
P
W = RT ln 2 = RT ln 1
V1
P2

)2

du=q-w )3) (q=0

: du=-w
: CVdT = -Pexdv
: CVdT = -Pdv

T2
V
)= R ln 2 => (
T1
V1

RT
dT
dV
dv => CV
= -R
V
T
V

CVdT =

CV ln 1 2 .

:
R + CV

V
P V
= 1 => 2 = 1
V2
P1 V2

CV

V
PV
= 1 => (2) => 2 2
V2
P1V1

53

CV

() T2
T
1

CP
CV
R C P CV
=
=1
CV
CV

>=

CV

T V
=> 2 = 1 )(2
T1 V2

V
= 2
V1

T V
2 = 1
T1 V2

P2 V1
= => P1V1 = P2V2
P1 V2

:
Pex=P2 .
: :

=> PV =cte >= q=0

)1

=> PV = cte >= T=cte

)2

P
=cte
T
V
=cte
>= >= P=cte )4
T
>= >= V=cte

( :

54

)3

 300k 10atm 1atm

. .
-1

P2 = 1

B
V2 = 24.6
T = 300
2

P1 = 10

AV1 = 2.46
T = 300
1

P1V1 = nRT1
10 V1 = 1 0.082 300 => V1 = 2.46
P1V1 = P2V2 => V2 = 24.6

du = dq dw
=> U=0

55

du = CVdT =0

=> H=0

V2
=w
V1

pdV = RT ln

dH=CPdT=0

dq = dw => Pex dV

10
= 1378 cal = q
1

=> w = 300 1.986 ln

:
.

-2

P1V1 = P2V2
1

1
5

CP
5

= >= ) = 2.46(10
== 2
3
CV
3

P
P
= 1 => V2 = V1 1
P2

P2

V2

V1

P2 = 1
B2 = V2 = 9.84
T = 120k
2

= w

q =0

du=dq-dw u

9.84 1
= 120k
=P2V2=RT2=>T2
0.082

u=CVdT=1.5R (T2-T1) = 1.5R (120-300)= -536 cal =>w=536cal

: ) (1378cal
) (1378cal . .
) . (

56

 )(536cal
) (-536cal.
-3
Pext = P2

P2 = 1

B1 V2 = 10V1 = 24.6
T = 300k
2
u = q w
= )u = 0 => q=w = Pexdv - P2dv=> q=w = P2 (V2 V1

RT RT
TP
P
= ) P2 2 1 => q = w = R (T2 1 2 ) = RT (1 2
P2
P1
P1
P2
1
1.986 300 (1 ) = 536.2 cal
10
536.2 cal
536.2
-4

Pex = P2 = 1
du = dq dw => dq=0 => du = -dw => CVdT = -Pextdv

57

1.5RdT = dv
1

>= 1.5R dT = -dv

= )1.5R (T2 T1) = -P2 (V2-V1) => 1.5R (T2 T1

RT
RT
P
P2 2 1 = R(T2 T1 2 ) => T2 = 192k
P1
P1
P2
u = CV (T2-T1) = 1.5R (192-300) =-321

RT2 192 0.083

=
P2
1

= V2

0
321cal
-321cal

:
:
) ( .

58

)A(P,T2

)A(P,T1

 )
C p (
qP = H
dH=CPdT
T2

T1 CP ( A)dT

= )H=HA(P,T2) HA (P,T1

( 25 ) (Pb 700k

) PbL(600,P) PbL(700,P )PbS (298,P) PbS (600,P
qP = H
700

600

600

298

H = 25C P ( Pb) S dT + 25L f + 25C P ( Pb) L dT

: 2 .

-1 )( H>0
-2 )( H<0

59

 )Hf (Heat of formation

. Co2 f
:
C+O2 CO2

) H = Hf (CO2

)Hf (CO2

:

) (
) (
.
: ) (o
) . ) Hof (CO2 : (CO2
.
:
Hom , Hof .
Ho+ )(

60

 :
) (H
.
aA+bB cC + dD
]) H = [cHf(C) + dHf(D)] [aHf(A) + bHf(B

[aHf(A) + bHf(B)]:

[cHf(C) + dHf(D)]:

( 1atm 298k

Fe2O3 + 2A1 = A12O3 + 2Fe
) Hof = Hof (Al2O3) + 2Hof(Fe) - 2Hof(A1) - Hof(fe2O3

Kcal
Kcal
+ o o + 196.5
mol
mol
Kcal

Ho = -202.6
mol
= 392.1

61

 :
.
H,U

.

:

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

62

 :
:
-1 .
-2 .
) ( .
.
.
) ( .

)(S

Entropy

.
-1 :

.
-2 :

.

63

q
T

) (
.

= ds

:
-1 .

Suniv=0
=0 + Ssur Suniv=Ssys
-2 .

Suniv = Ssys + Ssur >0

.
( Fe
.
Fe Tm l

64

Fe Tm S

+ H m0
= = 0 S+ S S
Tm

( Fe 500k S

.

H m0
=
Tm

S
S Fe

L
S Fe

0
q
H m
=
T Tm + 500

= S
= S
q,T :

0
0
H m
H m

Tm
Tm + 500

: q .

65

= Suniv

 :
A B .

P2
V
2
T2
A
U 2
H 2

S 2

P1
V
1
T1
A
U1
H1

S1

A B .
:
.
: .

66

 :
: .
(
(
.
U = qrev - wrev
U = qirev - wirev
U :
U = U
qrev wrev = qirev - wirev

qrev
)(
T

qrev qirev = wrev - wirev

= S = - S

qirev
)(
T

= S

qrev
) ( )(
T

= S

S .

qrev qirev

T
T

= + SSunivers = Sirev = S

qrev qirev wrev wirev

=
T
T

67

 Sunivers : Wrev>Wirev , qrev>qirev

wrev .
:
.
:
AB

Wrev = pdv
Wirev = Pextdv

:
2 .
.
.
degradation of Energy
.

.

68

 wrev-wirev .
.
) ( .
: wirev .
(
2 .
) . (300k

V
RT
dV = RT ln 2
V
V1

= wrev = pdV

Wrev = 1.986 300 ln2 = 415 cal

69

 >= u=0 => q = w

qrev wrev
V
R
=
= dV = R ln 2 = R ln 2 = 1.38
Srev=
V1
T
T
V
415
Srev = Srev = S =- 1.38

300

Wirev = Pext dv

u = 0 => qirev = wirev = Pext dv = P2 dv = P2 (V2 V1 )

RT RT
P
= RT 1 2

qirev = wirev = P2
P1
P2
P1
1 1
qirev = 300 1.986 1 = 300 1.986 = 297 cal
2 2
= wrev wirev = 415 297 = 118 cal
Sirev = 1.38
Sirev =

qirev (q =) 297
300
T

= -0.99

Sunivers = 1.38 0.99 = 0.39

. Sunivers

Sunivers =

Wrev Wirev
T

415 297
=0.39
300

70

 :
.
.

w = q2 q 1
.

71

q2 = w + q1

 :
:
:
: .
:
.
w q2 q1
q
=
= 1 1
q2
q2
q2

q1 q2
.
:
.

.
.

72

 :
W=WAB + WBC + WCD + WDA

VB
VA
V
= RT1 ln D
VC

)WBC = CV(T1-T2

W AB = RT2 ln

)WDA = CV (T2-T1

WCD

VB
VA

q2 = W AB = RT2 ln

T
W q 2 q1 T2 T1
=
=
= 1 1
q2
q2
T2
T2

.
.
.

73

 :
:
-1


.
-2

.

( 1 2 T2,T1 .T2>T1
1 2

q

T

= S .

74

 ( A B S .
du = q - w => q = du + w => qrev = du + pdv

RT
dT R
q
dV => rev = CV
+ dV
V
T
T V

qrev = CV dT +

= ds = CV dln T+ RdlnV => ds = S2 S1

T2
V
+ R ln 2
T1
V1

Ssys = CVln

:
.
: S .

T2
P
+ R ln 1
T1
P2

75

S SYS = C P ln

0
=0
T

= S

) (

=0)=> Suniv=Ssys => (S +SSuniv = S

T2
V2
1
+
R
=
R
+ R ln 2 < 0
ln
1
.
5
ln
Ssys = CV ln
T1
V1
5
.
: .
Suniv .
Suniv .

T2
+R ln2 = 0
T1

Suniv = Ssys = 1.5 R ln

T2 = 0.62 T1
: w

76

 -1 S ) .
10
(

H t0
= S t
Tt

)(t: transformation
-2 S

AT1 AT2
dT
:

dT
, dH = C P dT
T

Cp

T2

T1

= S = ST2 ST1

ds = C P

( 5 298 700
.
600
600
700
( Pb) 298
S ( Pb) S ( Pb) L ( Pb) L

o
298
S o = S o ( Pb) 700
L S ( Pb) S

dT H o m
dT
S o
600
700
= 298 C P ( Pb) S
+
+ 600 C P ( Pb) L
5
T
600
T

-3 S
2AL + Fe2O3 = Al2O3 + 2Fe
o
o
o
S Al
+ 2 S ofe 2 S AL
S Fe
2 O3
2 O3

77

= So

 S op S Ro

= So

298 .
: .
(5 T2 T1 .

? = ST2
( R P ) T2

dT
T2
T
ST
T
dT
( R 1 P )T1
S 2 = 2 C P
T1
T
T2 C P
ST2 = S1 + ST1 + S2 => ST2 = ST1 +
dT
T1
T
T

S1 = 1 C P

: .
Ssys : S
.
S S
.

:
.

78

 2
.
-1 ) G (
-2 ) A (
G<0 , A<0 .
G=0 , A=0 .
G>0 , A>0 .
: A,G
A = U TS

G = H TS

: A,G
.
: )dG = dH Tds => (1

dH = dqP

q
+ dsirev
T

= ds

=>q=dH=Tds-TdSirev =>(1) dG=Tds-TdSirev Tds=-TdSirev

dsirev>0 . dG<0

79

 G :
aA+bBcC+dD

G=cGC + dGD aGA bGB

)G=c (HC-TSC) + d(HD-TSD)-a(HA-TSA)-b(HB-TSB
)G(T) = H(T) - TS(T
)G(T)o=Ho(T)-TSo(T
( 1atm 25oc
.
4Na+O22Na2O
: Go298 = Ho298 298 So298

Go298 = 2 (-100.7)-298(-0.069)=-182.3 Kcal

Go298<0 ) (
: H KJ Kcal S J
cal .
4
2
Al + O2 Al 2 O3
3
3

80

Go298 = Ho298 298 So298 = -396 Kcal

:
du=q-w
du = Tds PdV

(I)

H = U + PV
dH=du+Pdv+vdP = TdS PdV + PdV + VdP = Tds + VdP

dH = Tds + VdP (II)

A = U ST
dA=du-sdT-Tds=Tds-PdV-Tds-SdT

dA = sdT Pdv (III)

G = H TS
dG = dH Tds-SdT = -SdT+VdP => G = VdP SdT (IV)
.
G = f(T,P)

G
G
dG =
dT +
dP => (1)
T P
P

81

 ) (IV ) (1 :

G
G

) = S => (2
) = V => (3
T P
T T
:
: Z :
)Z = f(x,y

2Z
2z
=
x y y x
G .

2G
2G
)=> (4
>= )G = f (T , P
=
TP PT

V
S

=
P

P
T

=> ) (4 ) (3 )(2

P
T

=
S V
V S
V
T

=
P S S P
P
S

=
V T T V

:
.
S .

82

 ( H,U T,V,P
.
du=Tds-PdV

?=
V T

U
dS
P
nR

= T
P = T
P = T
P =0
V T
dV T
T V
V

=0
T

?=
T

dV
dV
dS

= T
P
= T
dT
dP T
dP T
T

du=Tds-Pdv

dV

P
dP T
T

=0
T

nRT
U
>= = 0
= V + P
2
V
P

:
T

(CV=2+10-3T) Cv T1,V1,P1 T2,V2,P2

.

83

 :
G .
G=H-TS

dG=-SdT+VdP

G
G

= S => G = H + T
G = H
T P
T

) (G T

= H
2
T

P T

>=

H
T2

G
T
G
T P
T2

: .
: .

T
= H => d G = H dT

T
T
T2
T2

P
A .

84

 A

T = U
T
T2

:
.
S0 >= T 0 >=

= S
T P

:
.
) S (
) (

.

.

) ( :
.

85

 :
.
-1 :

-2
-3
:
.
(A)T=0 (A)T=T

CP
dT
T

= S = ST S o

:

Tm-Hom
H m
=9J
deg
Tm

= S m.

86

 Tm Hm
.

%80
Sm 8 16 .
HV TV
SV HV TV

.

HV
= 88 J
deg
TV
S,G,H,U :

87

= SV

 )
1atm ( .
.
H (1 :
H :
)H=f(P,T

H
H
= dH
dP +
dT
P T
T P
dH=Tds+vdp

+V
P

V
= T
T
T

: .

1 V

V T P

) = VT + V = V (1 T
P T
dH=V(1-T)dp+Cp dT
T

V (1 T )dp + 2 CpdT
T1

88

P2

P1

=)H=H(P2,T2)-H(P1,T1

P2

P1 V (1 T )dp

T T1 CP

P2 CP P1
T2 .
( Fe Cm3

7.1

=3*10-5deg-1 Fe 1 10at
298k .

V (1 T )dp

100

=dH=V(1-T)dp=>H

200atm
:
V(1-T) (100-1) = 7.1 10-3 (1- 3 10-5 298) =71J
: 3 100at .
(2 : S
)S=f(P,T

S
S
ds = dp + dT
P T
T P

CP
dT
T

89

= => dS

 s
dp

p
T

= => dS

U
S
= V
=
T P
P T

dT

CP
T

: dS=-VdP => ds=-Vdp +

:
P
T
Cp
V
dp + 2 Cpd ln T
dT => S = 2
P1
T1 T
P1
T1
T
V R
P
T
= => S = R ln 2 + Cp ln 2
T P
P1
T1
T2

S = 2 Vdp +

(3 : G
G
)
(
o
T2 H
H o
G o
T

=
>=
=
T
T1 T 2 dt
T
T2

G P,T .
)G = f(T,P
dG=VdP >= dG=VdP-SdT
:
-1

RT
P

90

= V

nRT
P

=V

RT
) : ( dp dG = RTd ln P
P

= dG

P2
RT
dp = RTd ln P
P1
p

P2
P1

P2

= dG

P1

P2

P1

G(P2,T) G(P1,T) =RTln

P1 = Po = 1
G-Go = RT lnP
G = Go + RT lnP
(2
.

:
:
) f= f(p

dG=RT dlnF

f2
f1

G = RTd ln F = RF ln

f2,f1 P2,P1 ) f=f(p .

91

 ) f=f(p .
p
f
RT
= (V
)dp
p 0
p

RT ln

RT
Z 1
V
= RT

p Z 1
f
=
dp
p 0 p

ln

GT0 = H T0 TST0
Cp
dT
298 T
T

0
0
H T0 = H 298
+ C P dT , S T0 = S 298
+
298

Cp=a+bT+CT-2

GT0 = A + BT log T + CT + DT 2 + ET 1
.

GT0 = A + BT log T + C T
( Al2o3 900k 1000k
.
:
2 Al + 3 2 O2 = Al 2 O3
0
0
G o = H 900
900S900

92

 : :
C , B, A :
A = 400810.B = 398.C = 87.64

GoT = 400810 + 3.98 T log T 87.64T

T<932

932k H .
T=900k Go900 .
: Al2O3 Al2O3

) ( Al2 O3 = 2 Al + 3 2 O2

GoT .
1000k GoT :

Go = 40576 + 3.75 T log T 92.22T

T=1000
.
(
1200K ) ( :
H2Og

Cus

H2g

Cu2Os

J/deg

33.5

24.2

29

70

Cp

J/deg

188

33

131

94

So298

93

J/deg

-294

Ho298

-164

(Cu2O+H2=H2O+2Cu)1200

Go1200 = Ho1200 1200 So1200 = -128200 j

0
CpdT + H 298

dT
0
+ S 298
T

1200

0
H 1200
=

298

Cp

1200

0
S1200
=

298

Go
Cu2O+H2= H2O+2Cu Go .

1
O2
2
1
Cu2O2Cu+ O2
2

H2OH2 +

Go
Go .
: CP
0
0
ST0 = S 298
+ 298 Cp dT , T0 = H 298
+ 298 Cp dT
T
T

SoT,HoT GoT :
0
0
GT0 = H 298
+ TS 298

94

 ( Me Tm Me Me
T2,T1 Go T T1 T2
.
)Me (s) Me (L

GoSL=G(T)=>GoT=HoT-TSoT

CPS = CPL

) SoT,HoT (

Go>0 ) .
( } Go>0,T<Tm { SL

95

 Go<0 )
( } Go<0,T>Tm { SL
G .
.

)aA(PA)+bB(PB) = cC(PC)+dD(PD
)(1

)(2
Go

)aA(P=1) + bB(P=1) = cC(P=1)+dD(P=1

G=G1 + Go + G2
G2,G1 .

f2
f1

G = GP2 GP1 = RT ln
dG = vdP

dG = RT dln P

dG = RT dlnf

1
1
+ bRT ln
PA
PB

G1 = aRT ln

PC
P
+ dRT ln D
1
1

G2 = cRT ln

G o = RT ln Kp

eq

96

P CP d
G = G o + RT ln C D
P aP b
A B

 :
Go KP
.
(
1000
.

CO,H2O,H2,CO2 4 3 2 1
1000 .
:
CO2 + H2 = CO + H2O
Go1000 = + 3950 J

Go = -RT ln Kp

3950 = -8.314 1000 ln Kp KP,1000 = 0.62

Go>0

:
2 1
3 4

=> G1000 = +3950 + 1000 8.314 ln

PH Co PCO
PH 2 PCO2

G1000 = G o + RT ln

G* = - 10946 J

97

 .
.
aA + bB = cC + dD

CCc C Dd
KC = a b
C AC B

d
X Cc X D

X Aa X Bb

= Kx

Go = -RT ln Kp

:
Kx,KP

n A PA
=
nt
Pt
d

= XA

PC PD

P
P
K X = t a t b K X = K P ( Pt ) ( c d + a +b ) , (c d + a + b) = n
PA PB

Pt Pt

)=> KP = KX (Pt) (c+d-a-b

)KP = KX Pt n => (1
: KP=Kx .
Pt=1

n=0

ni
RT
V

98

= PV = nRT PiV = niRT => Pi

ni
C : i
V
Pi = CiRT =>(1) KP = KC (RT)n
( a H2 b Cl2 c
HCl T
x H2 . .
Cl2 + H2 = 2HC1
:
(b-x)H2
) nt=(a-x)+(b-x)+(c+2x >=
nt=a+b+c

(a-x)Cl2
(c+2x)Hcl

ax
bx
c + 2x
= ,KH2
= , Hcl
a+b+c
a+b+c
a+b+c

ncl 2
nt

= Xcl2

= KP = KX (Pt)n => n

c + 2x

2
X Hcl
) (c + 2 x
a+b+c

= KX
= KX
=
X cl2 X H 2
) a x b x (a x)(b x

a + b + c a + b + c

2-1-1=0 => KP = KX
:

99

(
2CO + CO2 C
:
:
C + CO2 + Q 2CO
.
.
:

1 2 .
.
: .
:
.

100

 :
( 100 SO3 0/2 0/2
.

PSO2 PO2 2
PSO3

=K

[SO2 ][O2 ]2
=K
] [SO3

( SO2 O2 1000k
.
:

10 4 0/4
.

nt = (1 ) + 1 + = 2
2
2

1
2 ,X
= X SO 2
= , X O2
= SO3

2
2
2
2
2
2

101

1
1

n = 1 1 =

2
2 KP = K X
pt = 1

) K P = K X ( Pt

X SO3

1
X O2 X SO2
2

= KX

= Go=-94600 + 89.37T Go1000 = -1000 Rln KP ,

-5230(j) = -1000 8.314 ln KP => KP = 1.876

2
1

1 1
2

2 2

2
2

= K P = K X = 1.876

:
-1 .
-2 .
.
: Go Go = HoT-TSoT.
(Go=-94600+89.37)Go
:

So=89.37

Ho=-94600

.
: H,S T CP
.

102

 KP )( :

G o

H o
T

=

T2

Go = -RT ln Kp

( R ln Kp ) H o
ln Kp + H o
H
=

=
= d ln Kp
dT
T
T
T2
RT 2
RT 2

d ln Kp H o
H o 1
d
=
= d ln Kp
1
R
R
T
d
T

( CP LnKp

1
T

.
H 1
H o 1
d ln Kp =
d
R
T
R
T

103

= d ln Kp

1

T

K , ) K (

: (Kp=10) 690k
600 CP,-10200 cal 0/4 CO 0/2 H2O
800k 5
.
: CP H
H o 1
10200 1
= , + C 10
+ C C = 5.14
.
R
T
1.986 690
10200 1
5.14 Kp = 3.6
.
1.986 800

= ln Kp

= ln Kp

n = 1 => Kp = Kx

104

X
0.6

= X H2

x
0 .6

= X CO2

0 .2 x
0.6

= X H 2O

0 .4 x
0.6

X2
= 3.6 x = 0.167
)(0.4 x)(0.2 x

= X CO

= K X = Kp

P
0.4 0.167
= X CO = CO PCO = X CO Pt
7.872 = 3.05
0.6
Pt

:

.

:
.
.
:
dU = Q W

105

 : .
.

) ( :
.
.
.
.
.
)
( .

(
A B C
A+ B C

:
.
: 3
.

106

 :
:

) ( .
:

) (:
: PV=nRT ) (
.
.
) ( Macroscopic state
) (Microscopic state .

) ( :
-1 ) (.....
700 k .
.
. G
.

107

H 2 + 1 O 2 H 2 O
2

 .
.

:
) (1 ) (dU = Q W .
.
) ( .

) Q (2 .
: )
(
.

: ) (
Q = CdT

(U = )QV = CV dT CV CP
C P CV = nR

(H = )QP = C P dT
U

P + V

V
T

= C P CV

) W (3 .
. . . . .
= e +

108

 : :

PdV .

= Pex dV

= 0

: .

(
1 2 .

: 1

= Pex dV = 0 Pex=0

: 2 .

=Pex = K

= Pex dV = KdV
V2
) KdV = K (V 2 V 1
V1

: 3
.
P Pex
nRT
V
dV = nRT ln 2
V
V1

V2

V1

= PdV

V2

V1

109

= = Pex dV = PdV

) du (4 .
.
. .
.

U : . .
) U =f ( T , n , P , V

U : T , n , V , P .

T , V , P .
U .
)U=F(T,P

)U=f(T,V

)U=f(T,V

: .

:
du= Q

:
du= QP - Pdv
P

(V V ) (U + PV ) (U + PV ) = Q
1

110

U = U2 U1 = Q P P

 : Q = H

-1 :
(
2

T
H = 2 C P dT
T1

CP = a +bT +CT

Tt

T
T
H = tC P dT + Lt + 2 C P dT
T1
Tt

aA + bB =C

-2
298 k

(
Hess

) H298 = H 298 (C) a H 298 ( A ) b H 298 (B

( ) ( T

: Q1 298 T
: Q2 298 T

= Q Q
1

298

Q H o H o
T

C P dT

dT + b

298

111

CP

298

= Q + H o

= a

298

dT

H o

Q = CP
298

 -3 : .

:


.
) (S .
:
.
.
.
.
. .
Q
T

= dS

:
-1

112

dU = Q

du

dU = Qr r

)dU = Qr PdV (1

) : du = nCV dT (2
nRdV
V

Q
T

nRT
dT
=
dV nCV
V
T

(1), (2) nCV dT = Q

r

dT
dV
+ nR
S = nC v ln T 2 + nR ln V 2
T
V
V1
T1

= dS dS = nCV

Q
T

-2 ) ( :
T Cp
S = 2
dT
T1 T

( .
(

Lt
T Cp
T Cp
dT
S = t dT +
+ 2
T1 T
T
Tt T

aA + bB =C

-3 :
(
o

)= S 298 (C ) aS 298 ( A) bS 298 ( B

o
298

:

.
: :

113

 -1 .

-3

-2 .

Cp
dT
T

298

= S0
298

S 0o
( ) ( T
2

= Q Q
1

S S

298

: Q1 298 T
C

dT

Q = CTP
T

298

: Q2 298 T
B

dT

298

dT + b

CP

298

= a

-4 : .

: ) ( disorder
) (Mixedupness

.
.
S > S
:

114

 ( ) ( : .
( ) ( : .

.
: V=5 lit P=1 atm n=2
mol .
.
) (
( :

C , B , A .

3u , 2u

, u , 0 .

3u

3u

3u

0
u
u

u
0
2u

2u
2u
0

5
6
7

2u

2u
2u

0
u

u
1150

9
10

1
10
3
10

4
10

 10 110 .
.
.
.

4 : .
-1 )(S

-3 ) (

-2

-4

.
S = F ( ) :

.

S = K ln

: .
+ SC

th

S =S

116

Thermal Entropy

: S th

Configurational Entropy

: SC

= K ln Th

Th

= K ln C

.
.

( : Configurational

4A

4B

16

3B,1A

3A,1B

36

2B,2A

2A,2B

16

1B,3A

V 1A,3B

4A

V 4B

(NA + NB )! = (4 + 4 )! = 70
!4!4

117

!NA! NB

 II .
: S C
C

N A A N B B

!) (NA + NB
!NA! NB

= K ln C = K ln
2

2
C
1
C

S = S S = K ln

]!= K [ln( NA + NB )! ln NA! ln NB

lnN! NlnN-N

ln N A + N A N B ln N B + N B

R = K Na

[(N + N )ln(N + N ) (N + N ) N

= nB . N a

: K

= nA. N a ,

=K

: R

] S C = KN a [n A ln X A + n B ln X B ] = R[n A ln X A + n B ln X B

n ln x

118

S C = R
i =1

 ( 10 20 .
)(R=2

Ag

+ n Ag ln X

0.051
= 0.22
0 / 051 + 0 / 185

0 / 185
= 0.78
0 / 051 + 0 / 185

10
= 0.051mol
197

20
= 0.185mol
107 / 88

Au

Ag

Au

= R n Au ln X

S = 0.25

Au

n
Ag

:
: ) ( :

.
:

A=U-TS

G=H-TS

P , T G

v , T

G<0

A A <0

. G
. A
: G
-1 ) T (

dG = VdP SdT

119

P
G (P 2 ) G (P1) = 2 VdP
P1
RT
P

( 1

dG = VdP

=V
G (P 2 ) G (P1) = RT ln P 2

1 .
o

G (P1) = G

= 1atm

P
1

G ( P ) G (1) = RT ln

G = G 0 + RT ln P

: = + RT ln P
o

= + RT ln f ) f
o

(
:

V-P

.
( .

--------

--------

--------

--------

10

) P(atm

V Cm 3

P
G (P 2 ) G (P1) = 2 VdP
P1

120

 -2 ) : (
H
G
= 2
T T P
T

Ho
= 2
P
T

Go

T T

G o H o

=
2
T T
T

C P = a + bT + CT 2

H = C P dT

G o = A + BT ln T + CT

) G o = F (T

-3
G P T G
.

121

 :
.
( : .
:

2CO + O 2 = 2CO 2

( : .
) : (

) = Al 2 O3 ( ) + 3 2 o2 ( Al

:
(

: Al .
:
D , C , B , A .
) aA( g , Pa ) + bB( g , PB ) = cC ( g , PC ) + dD( g , PD

G :

D
b

C
a

G = G + RT ln P P
P P
o

122

 G .
: G < 0 - .
D , C .

B , A

: G = 0 .

.
-

: G > 0

D , C B , A .
: ) (
) B , A ( D , C
G = 0
.
c d
G = RT ln PCa PbD

P A PB

G = 0

G = 0 (

123

D
b

C
a

P P
P P

G 0 = F (T ) , G 0 = RT ln K

G 0 = A + BT ln T + CT K . :

a=1

: ) (
:

. i
.
i
o
i

a=P
P
i

i
:

o
i

o
i

P
o
i

i i

124

P cu
cu

cu

cu

-1 :
.
-2 : Cu
Ag , Cu .
<1

cu
o
cu

:
d

D
b

C
a

+ RT ln a a
aa

P
P

cu

G .

G = G

: ) ( . a=1

:
-1

2 Al + 3 O2 = Al 2 O3
2

-2

CuCO3 = CaO + CO2

-3

Feo + CO = Fe + CO2

-4

Fe + S 2 ( g ) = FeS 2

.
:

125

 M e :

a
a .p

MeO2
O2

=1

MeO2

=1 ,

Me

Me + O 2 = MeO 2

G o = RT ln K = RT ln G = 0

Me

:
= RT ln PO 2

O2

G = RT ln

: .
.

O2

P . 3
.
-1

> PO 2

-2

= PO 2

-3 < PO 2

O2

O2

O2

( ) (SiO
2

3
mmHg

10

oc

1000

.
.
T = 1000 o c = 1273 K

126

Si + O2 = SiO2

G = 153000Cal

T = 1273 K

) G 0 = f (T

at
o

G = + RT ln Po2 153000 = +2 1273 ln Po2

= 5.37 10 27 atm
= 0.21 atm

Po

>

Po
2

Po

10 3 0.21
7
Po2 = 760 = 2.7610 atm

.
:

Po

Po2

Po > Po

3
mmHg

10

3
mmHg

10

) .

(.
:

G .

G T

G = A + BT ln T + CT
.

) ( :

127

G = A + BT
o

 :
o

-1

G T .

-2 .
2Cu + 1 O2 = Cu 2 O 4Cu + O2 = 2 Cu 2 O
2

tg = S
:
-1

G ) .

oc

T = 700 (

-2

G = H o T S

T=0K

G = H o H o ) .
(

128

 -3
o

G = H o T S

S .
o

S .

: .
.
o

= S > o

S < o

: 2 .
-1

C + O 2 = CO 2

-2

2C + O 2 = 2CO

.
.
o

= S < o

S > o

-4 )
(
(

)(1
)(2

G = H T S

Me( S ) + O2 = MeO2

G = H T S

Me( L) + O2 = MeO2

129

S m > o T S m < o

S = S Sm

G = H T S

H = H Hm ,

S . 2

1 .
:

S .

(
) Me + O2 = Me O2 ( S
)Me + O2 = Me O2 ( L

: .
: . .
: .
.
.

130

 -5
M Me .

T<Tp

G = G = A B > o

131

 G MO
M T

MeO

MeO

2 MO + Me = 2M + MeO2

G = G < 0 , T > T P
o

MeO

) .

:
.
) ( 1
) (2) (.

132

 : .
) . M
2

MeO

-6

= RT ln P
O2

R ln P
O2

RT ln PO 2 (

RT ln PO 2 T

=0

(T = 0K

133

R ln P --
O2

PO
1

10 1

---

10 2

---

134

PO

.

3

PO

PO

Me

10

Me 800 .

T .

10

PO

= RT ln P
O2

PO

T G P
O2
o

PO = 10

oC

T = 750

atm

Ti

. .
:

PO

PO

2 .

-1
) = F (T

Ti + O2 = TiO 2

-2 T
-3
-4

Ti

PO

PO

= RT ln P
O2

) (10
4

PO

135

 :
.
. .
= 94200 0.2T

Cal

= 94200 Cal = 94200 4.18= 400000 J

T =0

= 53400 41.9T

C + O2 = CO2

2C + O2 = 2CO

2CO + O2 = 2CO2

T =0
)( 4

H 400 KJ

)(1

)(2

H = 250 Kj

C + CO2 = 2CO

)( 3

1 2 4 )
(
:

+ C = 2CO

CO

G = 0

136

Boudourd

2
PCO
40800 41.7 T = RT ln
PCO a

2
2

=1

+ Pco2 = 1 ,

PCO

CO

2
PCO

P (1 P ).1

2
PCO
G = RT ln P
a CO
o

40800 41.7 T = RT ln

CO

CO .
Pco

Pco + P
CO 2

= %CO

%CO

:
-1 CO .
oc

T < 400

oc

CO

T > 1000 CO .

137

----

----

----

----

----

----

----

----

 -2 I CO
.

2CO CO2 + C

I CO
.
) (
.

C + CO2 2CO

CO

-3 < 1

C + CO 2 = 2CO

1 . CO
.
: ) (.

138

 :
.
CO .

PO

CO / CO 2

CO / CO2

PO

2CO + O2 = 2CO 2

CO / CO2 .
2CO + O2 = 2CO2

139

PO

.
PCO

:
2

PO

PCO

PCO2

PCO

PO 2

.
:

PO

CO / CO2

CO / CO2

)(PO 2
) 2Co + O = 2CO (PO
2

Me + O2 = MeO2

Me / MeO2

CO 2

PO

MeO

Me

CO

PO

PCO2

) (T

) (P

O 2 Me1MeO2

<

CO 2

PCO

)(PO 2

CO

CO / CO2

) (P

Me / MeO 2

O2

MeO2 + 2CO = Me + 2CO

>

CO2

)(PO 2

CO

CO / CO2

.
Me + 2CO 2 = MeO2 + 2CO

PCO
PCO

140

2CO + O2 = 2CO2

= 135000 + 41.5T

2CO + O2 = 2CO2

G :
=1

PCO
PCO

) 2CO (1atm ) + O2 (1atm ) = 2CO2 (1atm

.
)2CO(1atm ) + O2 (1atm ) = 2CO 2 (P atm ) (1

P
=P
1

PCO
PCO

) (1 .
G = 135000 + 41.5T

) 2CO(1atm ) + O2 (1atm ) = 2CO 2 (1atm

141

)( 2

G = 2 RT ln P

) 2CO(1atm ) = 2CO2 (Patm

)(3

G ) (1 G 2 3 .
G =- 135000 + 41/5T + 2RTlnP =- 135000 + ( 41.5 + 2 RlnP ) T

142

 : CO / CO2

Me

MeO

.
Me + O2 MeO2
2CO + O2 2CO2

+ 2CO = Me + 2CO2

H H
2

CO

MeO

CO

.
2CO + O2 = 2CO2

2H + O = 2H
2

143

oC

( FeO
.

600

CO

CO FeO .

G = 0 T = 600 oC 2 FeO = 2 Fe + O2

144

=873
: G = RT ln Po2 T
Po2 = 2.9 10

25

25

< 2.9 10

Po

-
FeO + CO = Fe + CO2 G = 0

P
= RT ln CO 2
PCO

o
2

1
2 O2

G = G + G

FeO = Fe +

1
=
2 O2 CO2

1
100 = 44.2%
1 + 1.26

< 1.26

CO +
1

CO
2
1+
PCO

PCO
PCO

PCO
+ PCO

.
:

145

PCO

= %CO

44.2%Co

 : .
Me + S 2 = MeS 2

( :
G = 0

G = RT ln Ps 2

Ps

= RT ln

T
2

Ps

: .
:

H H
2

.
S

2H + S = 2H
2

146

Me + Cl 2 = MeCl 2

.
.

( K
1500 .

(
2Cr + 3H 2 O = Cr 2 O3 + 3H 2

147

) (1

P
H2
= 3RT ln
PH O
2

PH

H 2O

G = RT ln
o

G = 0

.
o
1

= Cr 2 O3
= 3H 2 O

----------------------------) ( 2

G = G G

2 O2

2 O2

2Cr + 3

+3

3H

-----------------------2Cr + 3H 2 O = Cr 2 O3 + 3H 2

) (2 ) (1

PH
PH 2O

.

= 0.998

PH 2 + PH 2O = 1

PH

0/2
.

148

= 0.002

PH 2O

149

 :
phase Equilibria in one component system :
.
:
p =1atm
P= 1atm

P=1atm

20

oc

P = 1atm

298

=T

=T

) (

oc

T= 0

oc

T>100

:

-1 ) (
-2 ) (
-3 ) (

150

C, B , A

G =G

G =G

G =G

) A( ) A( G

G = G A G A

G <G

. G > 0

oc

1atm .

)O( S ) = H 2 O( L

) G H 2 O ( s ) = G H 2 O (l

oc

T > 0

)O( S ) H 2 ( L

atm

) G H 2 O (l ) < G H 2 O ( s

oc

T < 0

atm

.
) < G H 2O (l

151

) G H 2O(s

 : .
dG=Vdp-SdT

:
= S
P

) = S H 2O (l
P

) = S H 2O ( s
P

) G H 2O(l

) G H 2O(s

. .
) S H 2 O (l ) > S H 2 O ( s

P = 1atm

oc

p > 1atm

oc

P < 1atm

oc

T = 0 .

T = 0 .

)O( S ) H 2 O( L

T = 0 .

) O( L) H 2 O( S

H
2

dG= Vdp SdT

G
>V = V V
P

152

 G
.
T , P .
( P , T
: T P , :
T dT P dP .

) (T + dT ), (P + dP

, .

dG = dG

dP S dT = V dP S dT

: ,
S
H
= , S
V
T

dG , dG

S S
V V

dG=VdP-SdT

S ,S

) (S S )dT = (V V

dP
=
dP
dT

153

H
dP
=
dT T .V

:
: 1 ) ( :
3

mole

cm

Cal
mole K

V 1 10

S 2 6

: V = 4, S 4

dP
cal
= 1
3
dT
cm K

.
dP H
H dT
T H dT
=
P 2 P1 2
.
= dP
dT TV
V T
T 1 V T

T ,T
2

H
V

H T2 dT H T2 H T2 T1 + T1
=
=
ln
ln

V T1 T V T1 V
T1

= P2 P1

H
T
H
ln 1 +
= ln 1 + T2 T1 P2 P1
V
V
T1
T1

P P

H T
.

V T

oc

=
1

= ln(1 + x) x P2 P1 = P

(
cm 3

T .

) (327
oc

10.94 10.65

gr . .

20

cal

154

1150

oC

T = 347

oC

atm

? = P = 1 , T = 327 , P

P
H
P P
H
=
=

T T T .V
T T .V

)Pb( S ) = Pb( L
dP
H
=
dT T .V

oC

T = 327 = 600

P = 3073atm

.atm
H = 1150 = 1150 41 Cm
mole.K
cal

207
207
=

10.65 10.94

) Po ( S

) Po ( L

V = V

( 2 . :
.

L = V
: T
.
V = V V V L V V >> V L V = V V

RT
dP
dP
H
H

=
dT
2
P
dT
P
RT
R
T
T

155

H
H
H
d ln P
=
= d ln P
= dT ln P
dT + C
2
2
2
dT
RT
RT
RT

:
H : T.
H
+C
RT

: H = C P dT + C1 C
C P C P ln P =
V

A
+B
T

= : ln P

C P : .

C P = K

H = KdT + C1 = KT + C1
KT + C1
d ln P
H
K
=
=
ln P = ln T C1 + C
2
2
dT
R
RT
RT
RT
A
+ B ln T + C
T
L

C P : T.
2

= : ln P
V

C P = C P C P

(a +bT +CT ) (a+bT +C T ) = a + bT + CT

2

b 2 C

+
2T
T C1

H = C P dT + C1 H = aT +

d ln P
H
=

2
dT
RT

.
A
+ B ln T + CT + D
T

= : ln P

( 1181 .
27560 )(Cp

156

 .
K

1000

d ln P
H
=
2
dT
RT

dP H
=
dT TV

H
27560
+ C ln 1 =
+C
RT
2 1181

CP =0

ln P =

13780
+ 11.66
T

C = 11.66 ln P =

P = 0.12atm

:
.

157

T = 1000

aT

 : oA

)O ( S ) = H 2 O ( L

dP H
=
dT TV

H
TV

P T .
H
V

H > 0

V < 0 V > 0

H
<0
V

V > 0

H
>0
V

158

 T P T
.
: oB .

) O( L) = H 2 O(V

: H

dP H
=
dT TV

A +B

A + B ln T + C
= ln P
T

A
+ B ln T + CT + D
T

: oC
) S ( S ) = H 2 O(V

: H

: V

V V
V

dP H
=
dT TV
A +B

ln P = A + B ln T + C
T

A T + B ln T + CT + D

: O
(

Triple Point
NaF .
34450
2.01ln T + 33.74
T

ln P(atm) =

31090
2.52 ln T + 34.66
T

159

ln P(atm) =

 : A NaF
: B
: C NaF
: E NaF

: A .
? = P = 1atm T

31090
2.52 ln T + 34.66 T = 2006K
T

0=

) f(T T . T
) F(T . .

: B .
, P = 2.310 atm
4

T = 1239

160

H
d ln P
d ln P 31090 2.32 31090 2.52T
H
=

=
=
2
2
2
2
dT
dT
T
RT
T
T
RT

:C

H = R(31090 2.52T ) = 258500 20.95T

H = 216500 j

( 0 )

H
RT

d 34450

2.01ln T + 33.74 =

dT
T

H
RT

S
2

S
2

= 33150 j

161

:D

:
H S = 286400 16.71 T

H m = H S H V H m = 27900 + 4.24T
T = 1239 K

= H m + H V

d ln P
=
dT

aT

L
S
dH
C P = C C = 4.24 J
P
P
K
dT

:E

= C P

Solution Thermo.

.
: . . . .
:

Sio

Al o

Cao,

.
: 2
.
.
) (P,T .
.
-1 ni :
-2

ni
+ ...

-3

n +n

= Xi

100

mi

m1 + m2 + ...

= wt %i

3 ) ( .

162

 ( A-10%B 10 B . = 0.9
= 0.1

.
-1

-2

-1 .
o

P =P X
i

:
: Pi i

: Poi i

: X i
i

: .

163

:
:

P ,P
B

P ,P
B

-1 B
-2

B B
o

P .X
B

B A .
=

. .

164

P +P
A

+ PB X B

=P
o

P X
A

P (1 X ) + P X
o

)X

PA

(P

=P

-2 :
.
.

0 -1

. B . .

) (P = K X
B

. B B
.

165

 1 -2

P X
B

(P

-3 :
B

:
B
o

P
P

:
B

: B

: P B B

: B

.
o

P X

,a = X

= PB
B

:
-1

<1

-2

>1

0
B

aB =

K X
P
B

166

B
o
B

P
P

=P X
P
B

=1

B
0
B

P
= a
P
B

Partial Molar Quantities

(
0

: V B B

:V B B

: H 0B B

: S B B

: S B B

: B

167

= F T , P, n1 , n2 , n3 ,...

( G Q:
+

dn
n1,n3,..

P ,T ,

dn2 +

= F T , P, n1 , n2 , n3 ,...

Q
dn1 +
n 2

Q
+
dn1
n2

n1

n 2,..

P ,T ,

T ,P,

n1

dP +
n1,n 2,n3,..

T,

Q
= dQ
n1

dT +
n1,n 2,...

P,

Q
T

T , P

n j i

T ,P,

Q
Q
ni
=

) Q ( i

) i ( :

n j i

168

= dQ

T , P,

G
G
ni
=

dQ

:
CC

CC

+ ....

=V

= V Fe

Fe

V
CC

dQ = Q dn + Q dn

n Fe

=V

T , P ,...
CC

Fe .

:
)+ .... (1

Q ,Q

. . .

dQ = Q dn + Q dn

) : Q = n1 Q + n2 Q + .... (2
1

+ ...

dn + n dQ + Q dn
2

(1) dQ = n1 d Q + Q
1

n1 d Q + n2 d Q + .... = 0 ni d Q = 0 ) (1 )(2
i

i =1

Gibbs-Duhem Equation

( A-B B
A .

---

-----

--0.4

--0.3

--0.2

0.1

169

SB

XB

 :
=0

A- 30 %B

n dS +n dS
B

X
X dS
B

n +n

=0

dS

: Q

X dS
B

X .d S
A

.
i

?=
V A
? = V B

Q ) ( A- B
.
B

X d Q + Q dX
B

170

= dQ

X Q +X Q
B

X Q +X Q
B

: X A d Q + X B d Q = 0
A

n +n

X d Q + Q dX

Q = n Q + n Q

=
B

Q
n +n
A

Q
==QQ

n A + nB

+ Q . dX B
B

dQ = Q A . dX A Q B . dX A

dX

dQ = Q

X A+ X B =1

dX A + dX B = 0 dX A = dX B
dQ

= Q Q
A

dX

X Q +X Q
B

= Q

:
dQ
B

dX

) X
B

= Q + (1

dQ
X ) dA
A

= Q + (1

:
Q A- B
:

----

0.2

0.1

----

----

----

Q ----

A-30 %B .

:
Q -1

-2

. .

171

 -3

HB

MA

) (

XB

dQ
XB

dX

) X
B

][Q

XB

= HB = HN + NB , NB = EF

dQ
HN
= =

EN
dX B
HN = (1

dQ
XB

dX

HN = EN .

EN = FB = 1 AF = 1

HB = HN + NB

XB

: HB = Q

dQ
XB

dX

) X
B

HB = Q + (1

Q Q .

) (G :
: G
B :

172

Q +X Q
B

(Q = X

G (P2 ) G (P1) = RT ln P2

G B G B = RT ln P0B
0

G =n G +n G
A

G G = n (G G
2

= n A (RT

)+ n (G
B

G =n G +n G

G B = n A G + nB G

ln a ) + n (RT ln a )
A

G = RT (n A ln a A + nB ln a B )
M

n A + nB
M

G = RT

(X A ln a

173

+ X B ln a B

) ( G = Integral Force Energy Of Mixing

i

, G = RT

X ln a
i

G = G G o = RT ln a B
B
B
B

i =1

:
0

-1 .
-2
-3

-4

P =P X
i

i = 1, ai = X i
M

G = G Gi = RT ln

X ln X

G = RT
M

i =1

) dG = VdP SdT (
=V

:
.
:
i

G i

=V

T ,i

G oi
= V

P
T

= V V i V = V i
i

174

) (G i G oi

T ,C

 .
=0

M
i

= 0 , V

G
H
= 2

T T
T

-5

= H2i

P ,C

Gi

T T

o
o
Gi
H
= 2i
T T
T

) (H H
0

(R ln xi ) =
T

) ( H
= H

) (G G

=0

P ,C

0
i

= 0, H

M
i

H = Hi , H
i

.
G = H TS 6

= 0 T S S = R ln xi
i

x ln x

G = H T S

RT ln x

S = R .
M

i =1

175

 (
.

V = n AV A + nBV B
B

0
B

X V
B

0
A

X V

X V
A

= =V i V

V = (1 X B )V B + X BV B
0

X V

)X

V
= =V
n A + nB

V
0

V = V A + V B V A

+ X B =1
X A

( Au -45% Cu
.

oC

25

1400

) (

176

 .
.

177

mol

dT

) Cu ( L

CP

1400

dT + L f +
Cu

) Cu ( S

1356

CP

1
= H

64

1356

298

M 1
H 2 = H = 0 H = H 1 + H 2
Cu 64

dT

) Cu ( L

CP

Lf

1400

1356

1356

= 0.45 S = S 1 + S 2

) Cu ( S

dT +

x ) X
i

CP
T

1 1356
= S1
64 298

M
1
1
S 2 = S = ( R ln
Cu
64
64

:
.

< 1

> 1

178

a = X
i

 .
(
-

A %30 B

A 30% B

= 0 .3

= 0 .8

) ( )
(

:
.
:
G
H
= 2

T T
T

Hi
2

P ,C

M
H
G i
G

= 2 T
T
T

G .

M
i
2

+ RT ln
H

RT

X ) = RT ln
i

G = RT ln ai = RT ln
i

ln i

P ,C

H i < 0.

179

)(ln i

P ,C

R
T

ln

T .

X i .
.
1 ln T
i

H i > 0.

1 ln T

:
:

ln

T .

.
:
=V

dG = VdP SdT

180

G iM

= V
P

= V

T ,C
M
i

V
RT

ln i
RT
RT
RT
=
=
+

ln

ln
ln
a
x
G

T ,C

V i < 0 V i > 0 .

:

0
1

=1

0
1

= 1

=
i

181

:
: A B .
X i d Q = 0 G = Q A B

GB = 0

) + X d (G
B

0
A

X d (G G
A

+ XB dG = 0
B

X d (RT ln a ) + X d (RT ln a ) = 0
B

)= 0 (1

X d ln a
B

X d ln a

X dG
A

: X A + X B = 1 dX A + dX B = 0

)= 0 ( 2

X d ln X
B

X d ln X
A

=0

182

dX
X

dx
X

=0

X d ln 5 + X d ln 5
B

)(1) , (2

:
: B .

: B .
B

ln x

=0

d ln a B = 0 + d

X d ln x

)= dx B (2
A

X d ln a
A

X dx
X X

= d ln x A

ln a B = ln k B + ln

dx
x

)(1

X
d ln X
X
B

K X

d ln a

= (2) , (3) d ln a A

ln a A = ln x A + ln C a A = CX A
A

= 1 C = 1

= 1

: .

183

X
d ln a
X
B

X B =0
X A =1

ln a A

X d ln a
X
A

= 0 d ln a A =

ln a A

X d ln a
B

X d ln a
X
B

X
= B=1
XA
XB
X B =0

ln a A

X A, X B
=

X A =1
A
X B =0

X d ln a
X
B

X d ln a

ln a

X B, X A
X A =1 d
,

X B =0

ln a B

B
A

X
X

= 0

= 0

.
.
---- 1

----

0.2

0.1

---- 1

----

----

----

184

X
a

ln a

=0

X d ln
X
B

X d ln
B

X
= B
=0
X
B
XB

a , d ln
X
X
B

ln

X d ln
X
B

ln

.
o
B

0
B
B

185

ln

i =
A B :

(1 X i )

ln = ln
(1 X A) X
A

2
B

=
B

ln = ln
(1 X B) X
B

2
A

X d ln
A

X d ln
B

(1) (2)

d ln

= A X B d
2

d ln

X B =1

ln

XB

X d ln

d ln

ln

= 0 ln = B X A
2

X d ln
B

X d ln
X
A

=0

(1)

X d + 2 X dX
2

XB

X B =1

X A X B d A

(2)

XB

2 X dX

X B =1

(3)

: d (x. y ) = xdy + ydx xdy = d (x. y ) ydx

X A X B d A = d ( X A X B A ) A d ( X A X B ) (4)
(4), (3) ln = 2 X A A dX B d ( X A X B A ) + A d ( X A X B )
B

ln

= 2 X A A dX B

X X + X dX
A

+ A X A dX B (5)

= 1 dX A = dX B (6)

(5), (6) ln = X A X B A (2A X A + A X B A X A ) dX B

B

186

X ) dX
A

X =X
= A X A X B B B A dX B
X B =1

= X A X B A (2 X A +

ln

ln

oC

320

Hg Bi

.
0.063

0.33

---

0.092

0.65

---

0.893 0.851 --0.908 ---

0.95

X Hg

0.961 0.93

a Hg

Hg 20 % Bi :

X d ln
X
Hg

Hg

Bi

Bi

= 0 ln

Bi

X d ln
Bi

Hg

X d ln
Hg

Hg
o
Hg

187

P
P

Hg

Hg

d log

Hg
Bi

X
X

X =0.2
= Bi
X Bi =0

X Bi =0.2

Bi

---

---

0.95

---

---

0.961
0.95

log

Hg

Hg
Hg

a
X

Hg

---

---

---

---

---

---

Hg
Bi

X
X

log Hg

Bi

80
= 4 = 1.36 a Bi = 1.36 0.2 = 0.272
Bi
20

188

Hg
Bi

X
X

oC

435

( Cd Zn

.
2

= 0.38 X Cd 0.13 X Cd

Zn

log

- .
Cd -50 %Zn .
X
= X A X B B A B dX A
X A=1

A : Cd , B : Zn

X
= X Cd X Zn Zn Cd Zn dX Cd
X Cd =1

ln
)(1 X Zn
Zn

= Zn

Cd

ln

Zn

2.303 log
2
Cd

) = 2.303(0.38 0.13 X Cd

Zn

0.13 X Cd
2

Cd

2
Cd

(0.38 X

ln

= Zn

Zn = 2.303

X
= X Cd X Zn 2.303(0.38 0.13 X Cd ) 2.303 Cd (0.38 0.13 X Cd )dX Cd
X Cd =1
=

= 0.5

Cd

= 0.5

Cd

) :

Zn

189

ln

ln
) (1 X i
i

Cd

Cd

ln

Cd

= ( i

X
X
)= X A X B B A B dX A = X A X B B B A dX A = X A X B B B ( X A 1
1
=
XA
X A=1

+ 1) = B X B X B = B X B
2

X ) = X ( X
B

= X A X B B B (

) ln = A X B (1
2

ln
X

)= B X B (2
2

ln
X

ln
X

ln

: A = B ) (1 )(2

:
- .
- .
B

ln
X

2
B

: Excess Functions

ln
X

XS

.
id

= Q Q

XS

:
Q : Q
id

Q : Q .

190

ln

id

=H H

XS

.

:

XS

id

:G

= G G

XS

G : G
id

G : .

0
B

X G
B

0
A

(X

0
0
G
+ X B G B G id X A G 0 + X B G 0
X
AGA
A
B

=


M ,id
M
G
G

) X ln X
B

X ln a ) RT ( X ln X
A

= RT ln A

XS

= RT ( X A ln a A +

)= G

X ln
B

M ,id

id

) (

ln

= G G = G G

Solution

(X

XS

:
-1 . .
: A B

-2 .

191

= G G

RT

Regular

M ,id

XS

XS

= S (id ) ,

= S

M ,id

XS

=0

.
:
(1)

XS

id

= G G G

G
RT

= G G
M

XS

RT X X
A

(2)

id

[X ln X
A

G
=

XS

= RT

(X

ln
X
A

ln
X

XS

= RT

(X

ln

X ln a )]
B

X ln
B

ln = X B , ln = X B
2

X X

G
B

= RT ( X A ln a A +

RT X X
A

M ,id

X ln X ] G

XS

= G G = G G

: =

M ,id

M
M ,id
M ,id

M
M
T

S
T

XS =
= H

XS

XS

XS

= H

) = RT X

X (X
B

X )

RT X X
A

.( 3)

ln
ln

192

i
i

(T ) T
=
(T ) T
2

 G
= S
T P

: dG = VdP SdT

XS
i

= S
P ,C

=0

P ,C
XS

G iXS

= 0

XS

= 0,

XS
i

) (T ) = RT ln (T
i

G iXS

746

RT 1 ln

G (T ) = G (T ) G = RT ln
ln (T ) = T

ln (T ) T
XS

XS

XS

)(1 Pb

= 0.737

ln

Pb

- .

oC

25

746

Pb- 50%Sn

-1 .
-2 :
- Pb 50 %Sn

1000

= = Sn

193

Pb

Pb

ln
(1 X Pb)
Pb

= 0.737

Sn

ln

= 0.737

Sn

L
H =

600

298

CP

= G

Pb

Pb
f

Pb ( S )

S = 298

CP

Pb ( S )

ln
(1 X Sn)
Sn

XS

Pb

L
dT +

= 0.737

(1 X Sn)

Pb

= 1150cal , Tm = 600 K
dT + L f +
Pb

746

600

RT ln

= 3952

600

Pb

CP

Pb ( L )

+ H

-
M
Pb

= RT [ 0.737(1 0.5)]

Cal

Pb
f

600

194

746

600

CP

Pb ( L )

dT + S

M
Pb

- (2)

(id ) = R ln X Pb
Cal
K

Cal
H
3952
=
= 5.3
T
K
746

= 0.87 0.5 = 0.435

Pb

Pb

= +9.52

= S

746
(1000) = 0.87
Pb
1000

(S

Pb

Pb

)(1000
)(746

Pb

Pb

ln
ln

:
-1
-2 X

-3
-4
-5

-1 :
.
.

=T

T
=

195

 -2

1mole
X mole A + X mole B

) X ln a
B

A B :

= RT ( X A ln a A +

) X ln x

= RT ( X A ln x A +

:
= H T S = H T S

M ,id

) (X ln X + X ln X
B

= RT XA XB + RT

196

 :
) < 0 ( . .
) > 0 ( .
) (
.
) ( :
.
:
:

) X ln x
B

=0

= RT ( X A ln x A +

M ,id

= TS

= H TS
M

M ,id

) X ln x
B

+ RT ( X A ln

RT X X
A

197

 - A , B ) .
A , B ( .

A 30 %B

-1 E . = 0

-2 : A,B
-3 : A, B

= EF

= EK

G
M

G .

198

 - .
:
-1 :

=0

-2 : A , B

= EF

-3 : A , B

= EK

, ) ( .
: , .
, .

199

G =G
G =G

) () = G A (
M

M
A

G G = G G
M

, ,

.
i

aA = aA

RT ln a

RT ln a

M
i

RT ln a

a =a

200

.
) (1 (> 0) : .

) (2 (>>> 0) .

201

 -3 :
.
: .
0

: i

: i .

G G = RT ln a
i

: i .
)( L
) (S

RT ln a

= )( L

RT ln a

= ) (S

G G

G G

:
) (S

)(1

)G B ( L) G B (S ) = G F ( B
0

B
)( L
B

a
G ( L) G (S ) = RT ln
a

)( B) = H F ( B) TS F ( B
0

) (3

) 1 T ( 2
LF
B
Tm
B

1 T
RT T B
m

B
F

=L

S
B
L
B

0B
F

0
F

ln a ) (1 )(2
a

202

T C
LF + B C P dT T LFB + B P dT )(3
Tm
T m T m T

: Gibbs Phase

. C

) ( A , B , C , . . . P ) (, ,.....

.

.
) ( C 1 ) 1 + ( ) 1 + ( =

= 1+1+C1=C+1

:
C
) ( C 1 .
) ( C + 1 P :
) P ( C+1

.
P . P 1 .

T =T =T
= ...

P =P =P

203

P1

P 1

= ...

= =

= ...
= ...

= =

= =

P 1

P 1

P 1

C ) C(P-1
) : P-1 + P-1 + C( P-1 ) = ( P-1 ) ( C+2

) : F = P (C+1 ) ( P-1 ) ( C+2

F=CP+2

.
(

C=1
F = 3-P

P=1

F=2

P=2

F=1

P=3

F =0

204

F = 1-P +2

 :
F=CP+2
F=2P+2=4P

F=3P

C=2

: F = 0 .
:
.
: F = 3 P
.
:

L +

:

.
:
.

205

<T <T A

206

. B , A

A( S ) +

mole

(1)

(2) X mole
A

A( L) +

mole B( L) 1mole G = ?

A( S ) =

mole

A( L)

mole

mole B( L) 1mole liquied

solution

T A G
G = X G
G = RT ( X ln X + X ln X )
(I )
G = G + G = RT ( X ln X + X ln X ) + X G
A

G
G

= X B G F
0

T B G

= RT ( X A ln x A +

= RT ( X A ln x A +

X ln x )
B

X ln x ) X G
B

0
F

. II I 2
( I) :

= 0 G L = G F
M

207

= 1 G L = 0
M

= 0 G S = 0
M

II

= 1 G S = G F
M

<E
<F

>F

.
L , .

<E

L .

F , E .

:
< F

< E E

L F .
L

= L G = G

G G = RT ln a

L
B

ln X

) 0( L

= G B + RT

ln X

208

) 0( S

G B + RT

1 T

TB

B
F

= G F

) 0( B

) 0( L

) 0( S

= GB GB

B
L
B

RT ln X
X

1 T

TB

: T .

B
F

B
L
B

RT ln X
X

B , A
) (
.

) X ln x
B

+ RT ( X A ln x A +

RT X X
A

:
( G .

209

 < E

A .

) = L ( A
A

ln a

G = G A + RT
A

ln a = G + RT ln a
A

L
A

G =G
A

G A + RT
) L(S

A .

ln a

) 0( S

= G A + RT

) 0( S
)( A

) L( S

: a A A A
=1
)L( L
A

LF

TA
A

ln a

) 0( L

= G A + RT

) 0( S

= G A G A = G F
0S

)0 ( A

0L

) L(S

aA

)L( L
A

ln a
A

)L( L
A

: A ) (

A
A

a = X
A

210

RT

1 T
RT T A
F

=L

)L( L
A

ln a

 .
:

RT ln a

RT ln

ln
)(1 X A
A

M
A

XS
A

. B

. A :

211

=1

T
T A

T
T A

ln(1 + x) = x
X 0

L 1
ln x = RT

ln (1 X ) = L 1
RT
A

T T
L
T RTX
) X B = RT F 1 , A B = A (T A T = T
TA
LF T A
L

B
A

=
T = RX T
T
L
T

L
B

=
, RX
T L
T

L
B

RTX
L
A

: ) T
T A ( .....
( .

212

<F

< < E , +L : E

>F

L:

L, : EF

= L
L

G + RT ln a = G + RT ln a

G =G
A

A :

= aA

A :
)L( L
A

)1 T (1
F

T A
A

ln a

) 0(l

= G A + RT

= G F

)0 ( A

) 0( S

) ( S

ln a

) 0( L

= GA GA

+ RT

)L( L
A

) 0( S

ln a

RT

) ( S

RT ln a

B . B
A .
) (3

) (2), ln(1 X ) X

1
LF

TF
A

A ) (a
L

L
A

)L( L
A

ln a

= 1

) ( S

(1), (2), (3) RTX B RT

a = .X

: T

ln
)(1 X A
A

ln
)(1 X A
A

F
.

213

F
K

ln (T ) = T
ln (F ) T
F

RT ln

H
B

ln

)(1 X B

(T ) T
=
(T ) T

RT X X
A

ln
)(1 X A
A

A
A

ln
ln
M

ln
)(1 X A

H
M

= H

XS

:
.
.
B , A .
:
-1
-2
-3

214

AB

A+

X
< 0.25 ,

<0

B ) B

AB
3

G
RT

G = + RT ln a B a B = e
0

A3 B
B

= RT ln

a3 .a

A B + AB

< 0.5 ,

G = 0 ,

= 3A + B

= 1, a A = 1

A3 B

(a

< 0.25

A B + 2B = 3 AB
3

ln a

= 1, a B = 1 = 2RT
A3
a AB

AB
2

a A3B , a B
G 2

G = 0 G 2 = RT ln
0

T .
0.5 < X B < 0.75
G 3

2 RT

aB = e

AB + 2B = AB3

2 RT

G3 = 2 RT ln a B a B = e
0

> 0.75

=1

215

a
G = RT ln AB
a a
AB

 :
M

X G

RT ln a

: X B

M
A

X )G

M
B

= (1

M
B

X G

RT ln a

M
B

= G
A

X G

)X

a ,a

216

M
A

= G
M

M
B

(G

X Q +X Q
B

= G +
A

M
A

=Q

 :
M

AB

-1 : A , B

AB
3

. .
0.75 mole A + 0/25 mole B 1 mole

) + 0.25 ln a B

X ln a ) = RT (0.75 ln a
B

= RT ( X A ln a A +

+ ln a B = 0.25 RT ln a B . a B

(ln a

-2 A ,B

AB
3

= RT ln a A . a B

(a ) = 1
A3 B
3

1: 2

a .a

3A + B

= RT ln

G A B = 4 G A B
0

217

A B
m

= 0.25RT

1
0

G
m+n

( ) U-C (

UC ,U C ,UC
3

G . .
0

= - 105000 + 6.28 T

= - 115900 + 10.9 T

2U + 3C = U 2 C 3

U + 2C = UC 2

)3

= - 236800 + 25.1 T
3

U + C = UC

)1

0
2

1750

X C .
- 0/5 < X C < 0/6
.
1
0

G
UC
2

UC

1
( - 105000 + 6.28 1750 ) = - 47000 J
2

1
1
0
= ( - 236800 + 25.1 1750 ) = - 38580 J

G
U
C
2
3
5
5
1
0
= 32280

G
3

GUC
M

=
2

218

G U C
M

=
3

(
0.5 < X B < 0.6

EF

= 0.5
F

= 47000

X
G

= 0.6

= 38580

= 84200 X C 89100

= 0 G = G = 89100 = RT ln aU aU = 2.2 10
M

= 1 G = G = 4900 = RT ln aC aC = 0.714
M

219

 :
-

:
.
-1 :
(
-1 B B A 30% B
-2 B
-3 .


:

220

a = X
B

1 a B 1, RB = 1
FH
AH

B
B

a
X

) B ( F , E EF 0 . 1

.
) . ( S .
SB=1
B

= 0 aB

f X
B

H
B

FH FH
=
AH MH

f =a
X

B
B

M , F FM 0 1

= 1

H
B

221

 a
a .
:
0

B
B

a
a

B
H
B

a = X
B

f X
B

H
B

:
.
(

) .
( .
1t % = t % B
aB

, t % B 0
1t %

f B = 1

.t % B

222

1t %

1t %

t % B

t % B

a = X
B

B
1t %
B

B
1 t%

.t % B

100 M B

100

t % B

t % B
B

M
100 M
A

t % B

.t % B

1t %

1t %

100 t % B
A

B
B

m
M

m
M
+

A
A

m
M

B
2 t%
B

( B A 70% B 0.35 .
B B 0.25
. .
-1

A 70 % B

-2 B A 70% B
-3 B A B B
-4 B
:
(1 1.4

H
B

= 0.25

0.35
H
B

223

a =
a
B
H
B

(2

=2

(3

=1

(0.35 0.7) = 0.25

B

=
0

0R

= G B + RT ln a B
G
B
ln a B
0H
H

= G B + RT ln a B
G
B

(4

G = G + RT
B

: G B G B = RT ln aHB = RT ln = RT ln 0.25
0

0R

0H

- :

a
a P

SiO 2
O2

Si

G = 0 G = RT ln K G = RT ln

a SiO 2

a Si PO 2

.
1
K

SiO2 , Si ( 1 a = 1

O2

1
O2

=K

SiO2 ( 2 Si
SiO 2

a SiO 2 < 1

O2

<

O2

a
1 P

SiO 2

=K

O2

O2

PO 2 = PO 2 . a SiO 2 K ) (1 ) (2

224

 Si ( 3 SiO 2

O2

>

O2

P
a

O2
Si

=
Si

Ka

(4 Si

O2

a p

O2

=K

Si

a
a P
Sio 2

SiO2

O2

=K

Si

K : .
:
:
: Me + O2 = MeO2 .

a
a P

MeO 2
O2

G = 0 G = RT ln
0

Me

.
(

Si + O2 = SiO2

a
a P

SiO2
O2

) G Me GO = F (T
2

Si

MeO2

(G

= RT ln

Me .

225

0H

G Me GO

SiO2

= RT ln

PO2
Si
Si

Si

MeO2

Si
H
Si

RT ln Sio

a
a P

SiO2
O2

Si

G = G
0

a
G = RT ln
a P

SiO2

O2

Si

a
a

0
G = RT ln

:
F=CP+2
N R
F = ( N R) P +2 .
] = P [ ( N 1 ) + 2

( M O 2 MO 2 :
F = ( N R) P + 2

M + O 2 = MO 2

{ N = 3 ( M , O 2 , MO 2

226

)
)

{ R = 1 ( M + O 2 = MO 2

- - ( { P = 3

F = (3 1) 3 + 2 F = 1

:
+
+

( 2

Me CO CO2 MeO

MeO + CO+Me + CO2

CO

{ N = 4 ( MeO , CO , Me

) { R = 1 ( M + O2 = Mo2
) - -

( {P= 3

: C= 3 .
C = N-R =4 -1 = 3

C = Me , C , O= 3

:
-1 .
-2 .
( M | MO | CO | CO2 | MC | C

227

M + C = MC

)(b
) (d

1
= MO (a) ,
2 O2

M+

1
= CO
2 O2

C+

(C ) , C + O2 = CO2
1
= MO M
2 O2

) (a :

) (d) , (C :
)(f

(e) , C + 2 MO = CO2 + 2 M

MO + C = CO + M

) (F) , (e) , (b
.
F =CP+2
) C = ( N R ) = 6 3 = 3 (M , O , C
P = 5 F = C P + 2 = 35+ 2 F = 0

Stability diagrams

:
-1 :
.

228

 -2

.
(

VOS

) (V O | V O | VOSO | SO | SO
3

229

oC

T = 700

oC

T = 700

SO , SO
3

V2O5

.
4

V O ,VOSO
2

:

.
( V-OS .
4

V 2O V O VOSO

SO , SO
3

:
)(1

V O + SO = V O + SO
5

230

)a

PSO

1
a

PSO

) = f (T

2
3

PSO
PSO

T K a

=
a

PSO , PSO

(2

2VOSO = V O + SO + SO

K
PSO
b

PSO

PSO . PSO

PSO

)(b

231

PSO

)K C = PSO 3 PSO 3 = K C (3

PSO

2VOSO 4 = V 2 O 4 + 2SO 3

PO

) (C

3 1 2 3 :

232

: Cu O S
) . (
CuS Cu , Cu 2 O, Cu 2 S , Cu,....

) (

.
-1

233

 -2
:

G = H TS dG = dH Tds SdT
H =U + PV

dG = du + pdv + vdp Tds

(Q )+ PdV TdS dG = + Pdv

r

= dG

=
+ Pdv

r r

dG = (Pdv + r ) + Pdv dG = r

G = r

: r

) ( G = -

n :
= nFE G = nFE

:
: n
: F ) 96500

cal1
volt

( 23060

: E
) (EMF .
:
0

= nFE

G < 0 -1 E > 0
G > 0 -2 E < 0

.
.

234

M (a ) = M (a ) + ne
n+

) M (a ) + ne = M (a

n+

) M (a ) + M (a ) = M (a ) + M (a
n+

n+

.
0
0
G = G + RT ln a 2 a 1 G = nFE , G = nFE o
a1. a2

RT a2 a1
ln
nF a1 . a2

=E

.
:
0

E =E E

:
0

E =E +E

235

E = Ec + Ea

E = EC Ea

: H , S

G = nFE dG = VdP SdT

)= S (1
P

G
E
) (2

= nF
T

S = nF

)(2

)(1

G = H TS H = G + TS

E
= nF E T

T
P

E
H = nFE + TnF

) ( E
P

E

T

H , S , G .

:
H = U + PV dH = du + PdV + VdP

dH = Q r + PdV + VdP dH = Q (PdV + r ) + PdV + VdP

r

= Q r + VdP dH = Q r + VdP
r

236

dH = Q

)= dG (2) , dG = dH TdS (3
Q = TS

)dH = Q r (1

(1), (2), (3) Q = TdS

r

Zn + CuSO4 = Cu + ZnSO4

= 49900 3/32 T Cal :

K

298

) Cal ( 2

= - 49900

S = 3.32

Cal

Q = TS = 298 3/32 = 990

237

G = H TS
0

 o = 49900

S o = 3.32
Q = = 49900

:
-

.

M (a ) M (a ) M
n+

n+

) Cu (

CuSo

) ( : Cu CuSo4

(a ) = M (a ) + M
n+

M +M

) M (a ) = M (a
n+

n+

238

= CuSo4

) (

) (

CuSo

a
a

1
2

RT
ln
nF

=E

EMF .
2
1

a
a

ln

RT

E=

nF

=0

) M (a 2

n+

M (a1) M
) M (a1) = M (a 2

:
RT a 2
ln
nF a1

= 0, E =

RT a 2
ln
,
nF a1

=E

.
( Hg %1/36 Sn
( Hg - %1/36 Sn ) .
oC

30

at

2+

Sn

) ( Sn

E = 1.7 mV

.

.

239

0.38210

M
Sn

, H

.
oC

Sn

Cal

= 1690 ,T m = 232

Sn
F

- ) . ( ) = Sn Sn ( S
RT a sn
2 303
ln
1.710 3 =
ln a Sn
nF
2 23060
a1

E=

a Sn = 0.88

a
1 T a L = 0.286
RT ln Sn L Sn
F
Sn

L
Tm
a Sn
o

H Sn

-
Cal
mol

Sn

M
Sn

H = H Sn = 3690

E
H = nF E T

E
Cal
M
S Sn = S = nF = 17.6 K
T P

Formation Cell

.
.

) Pb Pbo( ) o , (Pt
2

)( L

240

M
Sn


.
.
1

) Pb (L ) + 2 O 2 ( g ) = PbO (L

.
. .
. .
+ 2e

++

Pb

= Pb

.
1
2
+ 2e = o
o
2
2

241

 PbO

.
o

= nFE

:
PbO
1
2
O2

RT
ln
nF

a P
.
Pb

=E

:

.
.
:
-1

+ 2e = Cu

2+

Cu

-2

-3

O + 4e = 4O H

2+

-4

= + 2e

Fe

=+e

:
2+

-1
-2

Cu = Cu + 2e
+4e

O+

2H

242

= 4O H

2H
2

3+

O + 2H

Fe

 -3
-4

= 2H + 2e
+e

3+

Fe

2+

Fe

:
:

E + I + E + E
R

=V

:
= E r

] [E E
a

= I R )
(
: E R

-1 .
-2

: .

243

2+

Cu

2+

Cu

:
.
( )
( 99/3 % Cu

Cu So
2

50 A 0/005
. .
:

V = E r + I R + E R + E
= 50 0.005 = 0.25V

=0 ,

= EC Ea

244

E = 0

 ) : (
+ 2e = Cu

2+

Cu

= )a (= 1
E E
)a (= 1
Cu
2+

Cu

+ 2e = Cu

E =E
a

2+

a
[Cu

Cu
2+

0 V = 0.25V

245

RT
ln
2F

E =E
C

Cu
RT
ln
2F

E =E
a

(
: PV = cte .
- :

V = KT

= 0 .5

2 vt

= Cp Cv

1 v
= v
v t p

1 v

v p T

:
.
STP P = 1atm T = 0 oc v = 22.4lit

SATP P = 1atm T = 25 oc v = 22.8lit

)( : .

PV = nRT
P = atm
V = Lit
n= mol
=R
=T

246

cal
lit atm
cm 3 atm
= 0.0821
= 82
mok
mol k
mol k

= 1.987

molk

R = 8.314 j

P = cRT

: c

: M PM = RT
:
: :

1
T

= v

1
p

ni
ni

=
= Xi

:
M = Mi Xi

Pi=PtXi

Vi=Vt.Xi

M B TA
.
M A TB

R A PA
=
RB PB
= R

: PV=RT+BP+CP2+ .
.
.

247

an 2
( P + 2 )(v nb) = nRT
V
a,b .
:
nRTc
an 2

Vc nb Vc 2

= 0

2P
2

= Pc

= 0
V

VC = 3b

8a
27bR

v 1 = 8 T
r 3 3 r

= Tc

a
27b 2

= Pc

P
= Pr
Pc

V
P + 3
V
=

r
r v 2
Vc
:
r

T
= Tr

Tc

) (

248

 -1
a

PV = RT + P b

RT

a
RT

BV = b

B
Bp = V
RT

a
RT
a
RT
a
RT

=b

<b

nRT
V nb

-2 :

> b

=P

-3 :
RT Va ab

=0
V 3 V 2b +
+
P p
p

249

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

T A = TB
TB = TC
T A = TC
) ( :
v

W = 2 Pext .dv
v1

U= Q W

w>0

W<0

w = 0 Pext = 0

250

 Pext=k

)w=k(v2-v1

) (

V
p
W = nRT ln 2 = nRT ln 1
V1
P2

nRT
V

= Pext = P

: max
.
: .
: P=atm 1atm.
: .
.
: .

: .

)U=f(T,P,v,n
)U=f(T,P

>=

n=cte

)U=f(T,v
)U=f(P,v
V,T,P . .
: .

251

 : .

dU = Q w
= dU

= Q
= w
:
(1 .
(2 .
(3 .
.
.
Qv=mCvT
Qp=mCpT
(4 .
Q Q.
:

3
RT
2

= U .

:
V = cte w = 0 U = Qv = n.cv T

P=cte U=Qp-W => w=P(v2-v1)=> qp=H=nCP.T

252

3
5
R, C P = R, C P CV = R
2
2

= CV

= 0.5

P
+

V
T

2 VT

= C P CV

6.5

= C P CV

: :

U = 0

H = U + PV
]( P2V2 P1V1 ) = 0[nRT nRT = 0
U =0

H = 0

Q=0

Cp 2.5
=
: = 1.66
Cv 1.5

=r

) : (
R

253

V
= 1
V2

Cv

T2

T1

PV = cte
TV 1 = cte
K = PV

dv

w = V 2

) : (.

R

Pext
Cv +
Pin
T2 = T1
Cp

= T2
= T1

U = w
P
3
) R (T2 T1 ) = R (T2 2 T1
P1
2
) (
V
U = 0 Q = W = nRT ln 2
V1

P1
P2

= nRT ln

: .
: .

P,V
. P,V

254

 : H < 0

H > 0

: 1 .
. :
.
:
.

aA+bB = cC+dD

[]

) H = cH o 298 (C ) + dH o 298 (D ) aH o 298 ( A) + bH o 298 (B

T1 T2 :
T

H = n T 2 Cp.dT
1

T1 T2 ) . (Tm

SL

H = n T m Cp ( S ) dT + nl f + n T 2 Cp ( L ) dT
1
m

255

 aA+bBP 298k
T.
T

0
H T0 H 298
= 298 Cp p dT a 298 Cp A dT + b 298 Cp dT = 298 Cp.dT

CP CP =Cp
:

+Lv

LV

-Lv

VL

+Lf
-Lf

SL

LS

LV

SL

SV

: .

Qr
T

= ds

Q
T

256

= ds

Q
T

ds

 :
)( .

w Q2 Q1
Q
= 1 1
=
Q2
Q2
Q2
T1
T2

= =

=1

= W

= Q1

= Q2

= T1

= T2

:
.

257

 : CD,AB
: AD,BC

T1
Q
= 1 1 :
T2
Q2

= 1

:
.

:
.

258

 :
.

T2
V2
S = ncv ln + nR ln
T1
V1
.

T2
P
+ nR ln 1
T1
P2

S = nc p ln

:
dT

Cp

S = n T 2

SL
L
nl f
T2 Cp
Cp S
+
dT
dT +
T
Tm Tm T

Tm

S = n

T1

:
600oc . 590oc
.

259

)Pb( L,590
) Pb( S ,590
S3

S1
S

)2 Pb( S ,600
)Pb( L,600

S = S1 + S 2 + S3
) (S
863Cp
Lf
dT
+
dT
873 873 T

)( L

873Cp

= S

863

: T

aA + bB P
B
)( P
T Cp A

T Cp
T Cp
Cp
dT
=
dT + b
dT a
= dT
298 T
298 T
298 T
298 T

0
S 298

ST0

: )H
( :

H
T
) S S (.
:
:

S = Kln W

+ = W

260

= S

R
8.314
=
Na 6.02 10 23

= K

!) ( NA + NB
!NA! NB

NA A NB B

=W

) S c = R (n A ln X A + nB ln X B n A + n B
) S c = R ( X A ln X A + X B ln X B
:
:

A=U-TS

G = H TS

A0 - G0

: A

A=-wr
G

G = -wr
dG = dH Tds SdT
= dU + Pdv + vdP TdS sdT = dQ dw (-pdv- dwr ) + pdv + vdP TdS
sdT dG = -dwr

261

: :
U
dU = TdS PdV i = i
ni

S
S ,V

=T
V

= P
S

H
dH = TdS + VdP i = i
ni

S
S,P

=T
P

=V
S

G
dG = VdP SdT i = i
ni

= S
T P
P ,T

=V
P T

A
dA = PdV SdT i = i
ni

= _S
T V
V ,T

A
= P

V T

= S
T

G = 20300 + 2.1T ln T 29.5T

,
= S
T

P
T

=
S V
V S

S
V

=
P T
T S

V
T

P S S P

P
S

V T T V

. :
U
=0

V T

262

 : .
a 2
U
= n2

V T V

: .

=0
T

2VT

= Cp Cv

:i
i I.
G

j i

i = i
ni T , P, n

: .
:
N

dG = Vdp SdT + i dni

) (i

: T P
:

=
G A = G A

A = A

GB = GB

B = B

: T
T .
: 590 .

263

)xPb( S ,600

)Pb( L,590
H=0

S2

S1

)Pb(L,600

dT xl f = 0

)( L

873

863 Cp

H = H1 + H2 = 0

= x
H=0 S .

S = S1 + S2
xl f
873

dT

) (S

873 Cp

S = 863

:
.

G
= S

G S .

264

 : .
.
:
.
w=1

S=k lnw=0
:




P

H = 2 V (1 T )dP
P1

H
=0
P

1
H = 0
T

:
P

S = 2 VdP
P1

P
S = nR ln 1
P2

1
=

T
P

G = P2 V .dP
1

265

P2
P1

G = nRT ln

1 P1 = 1atm
Gi Gio = nRT lnPi
Gi = Gio + nRT lnPi
i = io + RT lnPi

f2
f1

: f

G = nRT ln

: .
f
p Z 1
dP
= 0
p
p

ln

f
1 f P
P

P0

p
f
RT
= V
dP
p 0
P

RT ln

T = V
T
T2

T = H
T
T2

:
G = H - TS

G
= S
T

G = 20300 21.2T
20300 S 21/2 .

266

 Go : .

Go = A + BT lnT + CT + DT2+
G ... Go Go
.
G :

aA + bB = cC + dD

PDd PCc
PAa PBb

G = G + RT ln
G = 0

PDd P c
C
G = RT ln
P a JP b
A B
= RT ln K P
o

: KP

)n = (c+d) (a+b
: KC

KP = KC (RT)n

: KX

KP = KX (Pt)n

KP = KC = KX

n = 0

KP = KX

Pt = 1

:
.

). (

267

 KP : Go Go .
:

H o
= ln K P
RT
d ln KP H o
=
dT
RT 2

) K P (T2 ) H o (T2 T1
=
) K P (T1
2.303RT1T2

log

G :

aA + bB = cC + dD

a Dd .aCc
G = G + RT ln a b
a AaB
o

Go = RT ln KP

:
:

a Dd acc
G = RT ln a b
a AaB e
o

ai = 1

268

Pio

Pi
Pio

= ai

G = 0

1 atm = 14.7 PSi

1 atm = 760 mmHg
1 mmHg = 1 Torr
1 atm = 105 Pa
: .
: .

( p(v-b)=RT b v
. ) W=RTln(Vf-b/Vi-b
Vi . Vf .
(1
(2
(3
(4
:)(4
( 100 300k 5 gr/cm3 1000k
4 gr/cm3 . 10 300 k 1000k
atm-cm3

700 (1

500 (2

5 (4

50 (3

:)(3
V

W = V 2 Pext dv
1

)w=P(V2-V1

269

Pext = Pair=1

m
m 100 100
3
w = 1 2 1 = 1

= 5atm cm

5
2 1 4

10 mole w=5 10=50 atm-cm3

( .

300 . Cv 1.5R Cp 2.5R

cal

R=2 cal/molok
1800 (2

180 (1

300 (3

1500 (4

:)(1

V = cte
U = Q-W = nCvT

300
= 120
2.5

= H = nCp T => 300=n(2.5 RT) => nRT

Q = nRT (1.5) = 120 1.5 = 180

( 100cm3 .
105 90 cm3 .
105 atm-cm3

)(atm-cm3
106 (1

105 (2

104 3

:)(4

)H = U + (Pv

270

107 (4

)H = U + (P2V2-P1V1) = 105 + (105 90 1 100

H = 107 atm Cm

(
1085cal
)(

165.5 (1

122.4 (2

220.4 (3

178.5 (4

:)(1

V2
V1

Q = nRT ln
V1 = 22.4 Lit

72
22 / 4

1085 = 1 6.986 ln
V2 = 165.5 Lit

( 6 .
300

R=2 cal/mol k
(1 134 oc

Cv=3 cal/mol k

(2 100 oc 134oc
(4 100 oc 300 oc

(3 - 99 oc 300 oc

271

 :) (2 .

w=0
Q=0

U = -w
nCv dT = -Pext dv

. .

nCv T = 0 T = 0 T2=T1
:

TV 1 = cte
T1V1 1 = T2V2 1

573(V1)0.66 = T2(6V1)0.66
573 = T2 (6)0.66
T2 = 173 K=-99oc

( 20 . A
5 B 3 atm 298 k

B )A(g) + 4B(g) = D(g

1.45 (1

3.55 (2

2.56 (4

0.45 (3

:)(1

nt = 1-+5-4+=6-4

)A(g) + 4B(g) =D(g

0

PD
PA .PB4

G o = RT ln

272

5-4

1-


64
ln
1 5 4
64 64
3

Pv=nRT
320 = n 0.0821 298

n = 2.45 = 6 4
5-4(0.88) = 1.45 B

=0.88

( T
100cm3 . 20.08oc 20.70 .
4.184J/g.k
0.37J/g.k ):(k

701.1 (1

990.2 (2

299.2 (4

994.9 (3

:)(3
T

m T e Cp H 2O dT + mT e Cp Bross dT = 0

= 0 + HH
20.7

.7 0.37 dT = 0 => T = 721o C = 994 K

10020.08184dT + 1T20
1

273

( 700Kpa 0.015m3 140Kpa

. ):(m3,KJ

= 1.39
23.1 (1 0.048

4.62 (2 0.048

9.69 (3 0.048

33.6 (4 0.075

:)(3
PV = K

P1V1 = P2V 2
700(0.015)1.39 = 140(V2)1.39
1.39
)0.048 700(0.015
dv = 9.69
1.39

dv = 0.015

w = V 2

V2 = 0.048 m3

( . A

20 (1

-20 (2

40 (3

(4

274

 :) (1
.
: .

:
:
Go T .

Go = A+BT

(1 1.
(2 Ho .

(3 -S .
(4 .
(5 .
(6 .

275

)Hom = Ho(L) - Ho(S

)Som = So(L) - So(S
(7
.

T<T : M + MeO2 = Me + MO2

T> T : Me + MO2 = MeO2 + M
:

C+CO2 = 2CO
Pco+Pco2 = 1 atm

P 2 co
G = RT ln
Pco2 .a c
o

Pco
Pco + Pco2

276

=%Co

%CO

PCO2

PCO

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

*****

PCO2

2
PCO

T
*****

: I Co Co2

: II Co
) ( Co
.
ac .
CO .
: 1 .
:

Me +O2 = MeO2 Go (Po2)e

277

2CO +O2 = 2CO2 Go (Po2)e

co

co2

(Po2)e > (Po2)e

co

co2

(Po2)e < (Po2)e

Me + 2CO2 = MeO2 + 2CO

= Go = Go1 - Go2
Go < 0
Go>0
:

278

dP S
H
=
=
dT V TV
: S
: H

: V ...

-1 . .

P2 P1 H
=
T2 T1 T1V
T2 = P2
T1 = P1
-2
d log P
H
=
dT
2.303RT 2

d ln P H
=
dT
RT 2

H R

279

d ln kp H o
=
dT
RT 2

 H +C
RT

= Cp=0 => H=K => lnP

Cp=K => H=KT+C1=> lnp= K lnT- C1 +C

RT

Cp=f(T)=>H= f (T )dT = ...

lnp = . Lnp = A +BlnT+CT+D

T

) (C .

P=1 atm

H
+ c = 0 => C
RTb

ln 1 = 0 =

= Tb
:
:
.
: .
: Pi i
: Pio i

Pi=Poi.xi
.

.
:1
:2
:3

280

 : : A-B

0.3

0 .2

XB

186

81

64

: P = PAo XA + PBo XB

P = P A + PB

PBo=186

PAo=64

XA=1 XB=0 PAo

XA=0 XB=1 PBo
P=64 0.8 + 186 0.2 = 88 > 81
.
.
.

XB<E

=<

XB0

B .
B .

XB0

281

X=0.8

 : PB=oB.XB
: oB

XB>D

XB 1

B .

B XB1.
: PB=PBo.XB
:

Pi = Pio Xi
=> ai = Xi

ai = i Xi

= i ) i (

i=1
i>1 +
i<1 -
* Q :

282

Pi
Pio

= ai

 Q = X AQ A + X B QB 1-

Q Q A = A
Q QB = B
: S = X A S A + X B S B

S = X A S A + X B S B
:

X i dQi = 0

2-

X A dQA + X B dQB = 0
:

.

dQ
dX A
dQ
dX B

) 3- Q A = Q + (1 X A

) QB = Q + (1 X B

: Q QB , Q A
.
.
Q .

283

Gi M = Gi Gio = RT ln ai
G M = RT Xi ln ai
M

: Gi i

: Gi
o

: Gi i

: G

)Ca(a=0.9)=Ca(a=0.5

Go Go=0 .
Go=0

K=1
:

Sio 2 = Si + O2

) >(Po2 )(Po2
) <(Po2 )(Po2

284

0.5
0.9

G = G o + RT ln

Cp.dT

0
H T0 H 298
=

298

0
Cp = 0 => H T0 = H 298
0
ST0 = S 298
0
GT0 G298

) G(0S ) = G(0L

Go(S) = ..

Ni(S)+O 2 = NiO2

= )Go(L

Ni(L)+O2 = NiO2

= H

T2

G o

= ) G(0S

Ho(S) = A
Go(L) Ho(L) = B
Lf = B-A

G o
o

T = S

Go(S) So(S) = A
Go(L) Go(L) = B

Som = B-A

( ( (
:
(1
(2
(3

285

 (4
: (3

( 10 5 .
50 .
10 :

0 (1

100 J/K (2

50 J/K (3

500 J/K (4

: (1

Q
=0
T

= Q = 0 S

( T1 T2 .
) : Cp (

s+2Cp(T2-T1)/(T1+T2) (1
s=Cpln 2(T2-T1)/(T1+T2) (2
s=Cpln (T1+T2)/2T1+Cpln (T1+T2)/2T2 (3
s=Cp ln (T1+T2)/T1.T2 (4
:(3
T
T + T2
S (T1) = nCp ln e = Cp ln 1
T1
2T1

T +T
Te = 1 e
2

286

T
T + T2
S (T2 ) = nCp ln e = Cp ln 1
T2
2T2
) S = S (T1) + S (T2

( 1 2 .
180cal 0.3cal/ok .
30

600 (1

500 (2

700 (3

1000 (4

U=Qr-wr

: (3 )(

180=Qr-30
Qr
210
= => 0.3
T = 700 K
T
T

= S

Qr = 210

( 1083oc 3100 cal/mol .

847oc .

cal/mol ok

Cp(s)=7

-3218cal/mol (1

-3336 cal/mol (2

-2864 cal/mol (3

-2982 cal/mol (4

Cp(l)=7.5

:(4

Cp = Cp S Cp L

LS

1120

1356 Cp.dT
1120

(Cp S Cp L )dT

287

0
H T0 H 1356
=

0
0
H1120
H1356
=

1356

Cal
mol

0
H1120
= 2982

1120

0
H1120
(3100) = 1356 (7 7.5)dT

(
. 44.8
100 .

1/37 (2

-1/37 (1

5/72 (4

(3

:(2
T
v
cal
44.8
S = ncv ln 2 + nR ln 2 = 1 1.986 ln
= 1.37
T1
v1
mol
22.4

]H2O(1)[-10oc,1 atm] H2O(s)[-10 oc,1 atm

Cp H2O(1)=75.3 J/mol k

Cp H2O(s)=37.7 J/mol k
6008J/mol.
-22 J/mol k (1

4/1 J/mol k (2

-20/6 J/mol k (3

-22/85 J/mol k (4

:(3
S

S=S1+S2+S3

) H 2 O(10 / L) H 2 O (10 / S
S1

S 3

)H 2 O(0 / L
) H 2 O (0 / S
S2

6008 263 37.7

273 75.3
S = 263
+ 273
dT
T
273
T
T
= 20 / 6

288

( :
(1
(2
(3
(4
:(4
V
S = nR ln 2
V1

U = 0

(
298 k 10 .
7.31 5.75 118.7 ):(J
-44 (1

-4400 (2

-4.4 (3

-440 (4

:(3

H=U+(PV) => H-U=(PV)=P2V2 P1V1

m
m
atm
118.7 118.7
= 10
= P (V2 V1 ) = P

= 44 3
7.31 5.75
an
2 1

8.314
= 4.4 J
82

289

44

( -15 oc .
6kJ/mol 37.3J/mol.
-19.9 J/mol.k (1

21.1 J/mol.k (2

19.9 J/mol.k (3

-21.1 J/mol.k (4

:(2
CpdT
37.3dT
H 015 5440.5
=
= 21.1 j
K
T
258

15

H 015 H 00 = 0

15

H 015 (6000) = 0

S o

H 015 = 5440.5

( .
3 A 1 B .
:

0 (1

Rln8 (2

Rln16 (3

Rln4 (4

:(3

S = S A + S B
v2
v
cv
cv
+ B ln 2 = 3R ln + 1R ln = 4 R ln 2 = R ln 16
v1
v1
v
v

290

= A R ln

( A+2B=3C 1000 10-5.

A,B 0/5 C 0/3

-1982 (1

1982 (2

-9930 (3

9930 (4

: (2
ac3
a A .a B 2
= 19831

(0.3) 3
0.5 (0.5) 2

G = RT ln K + RT ln

= 1.987 1000 ln 10 5 + 1.987 1000 ln

( 1500K 0/002 .
:

)H2O(g)=H2+1.2O2(g

64/3 (1

49 (2

37 (3

29/6 (4

: (2
1 2 10 5
1.00001

1
O2
2

= X H2 O

2 10 5
1.00001

= X H2

1 10 5
1.00001

H 2O = H 2 +

0
0.001
100

= X o2

1
0.002
100

0.002
100

nt = 1+10-5 = 1.00001

291

X H 2 . X o2
X H2 o

G = RT ln
G o = 49 Kcal

( 298ok cal/mol k

Go=-40500-3.92TlogT+29.5T cal
-29.5 (1

29.5 (2

(3

2Cu+1.2O2=Cu2O
-18.10 (4

:(4

G o
= S o
T

( A B C T .
:

G=3RTln 1/3 (1

G=-RTln 1/3 (2

G=RTln 1/3 (3

G=-3RTln 1/3 (4

: (1
G = RT X i ln X i , G = RT ni ln X i
1
1
1
1

= RT 1ln + 1 ln + 1ln = 3RT ln

3
30
3
3

( CO+2H2=CH3OH :

lnKp=-17660/T -8.82ln T+T+28.8

292

 Ho T

Ho=-17660R+8.82RT+RT2 (1
Ho=17660R+8.82RT-RT2 (2
Ho=17660R+8.82RT+RT2 (3
Ho=17660R-8.82RT+RT2 (4
:(4

d ln KP H o
=
dT
RT 2

( 2000 k .
. ):(mmHg

Go(cal)=259940+4.33TlogT -59.12T
2.451019 (1

3.17510-21 (2

1.8610-16 (3

7.210-22 (4

ZrO2=Zr+O2

: (3

Go = -RTlnPO2
170.28 103 = -1.987 2000 ln PO2
760 atm

( T .

)Go=-40500-1.702TlnT+29.5T (cal
Ho

293

-40500+3.92 T (1

-40500-1.702T (2

-40500+1.702lnT (3

-40500+1.702T (4

:(4

G o H o

T = T2

( 600 oc 20 CO 20
FeO Fe

)Go=147900-150.15T (J
1.8 (1

3.6 (3

20 (2

FeO+CO=Fe+CO2

18.2 (4

:(1
Pco2
Pco

16.81 10 3 = 8.314 873 ln

Pco2
Pco

G o = RT ln

Pco2
Pco = 0.91
= 0.098

Pco
Pco2 = 0.09
Pco + Pco2 = 1atm
Pco2 0.09
=
= 0.09
Pt
1

= X CO 2

=n fe nCo2=XCo2.nt = 0.09 20 = 1.8

( Fe2O3 CuO 900 SO3.

SO3 CuO CuSO4 Fe2O3 .

)Go=-11269 (cal

CuO+SO3=CuSO4

)Go=-3970 (cal

Fe2O3+3SO3=Fe2(SO4)3

294

PSO3>0.48 (2

0.02<PSO3<0.84 (1

1.810-3<PSO3<0.48 (4

PSO3<1.810-3 (3
: (4

1
Pso3
Pso3 = 1.8 10-3

1
Pso3

11269 = 1.987 900 ln

1
Pso3

1.8 10-3 < Pso3 < 0.48

Pso3 = 0.48

G o = RT ln

1
Pso3

G o = RT ln

3970 = 1.987 900 ln

( ) C6H5CH3(g)+3H2C6H11CH3(g 555k
10.646 . 23 H2 %70 C6H5CH3 C6H11CH3 %7
)( :
(1

(3

(2

(4

: (4
Pc4 H11CH 3
Pc4 H 5CH 3 P 3 H 2

>0

0.07
0.23(0.7) 3

295

G o = RT ln K + RT ln

= 1.987 555 ln 0.646 + 1.987 555 ln

( CH4 212,8kCal/mol
CO2,H2O -68.22 -94.05
CH4 kcal/mol

18.9 (2

-17.9 (1

-35.8 (4

-136.6 (3

:(1

CH4 + 2O2 = CO2 + 2H2O

o
o
o
H o = H Co
+ 2H H
H CH
2
2O
4
4

o
212.8 = 94.05 + 2(68.22) H CH

mol

= 17.9 Kcal

o
H CH
4

( M 900 oc
. M M .

Wpb=207

Go1173k=-301248 J

3Pb+3.2O2=3PbO

Wm=122

Go1173k=-334720 J

2M+3.2O2=M2O3

%18 (1

%0.18 (2

%11.4 (3

%1.8 (4

: (3
a2
G o = RT ln M
a P 3b

a = x

G1o

3
3Pb + O2 = 3PbO
2

G2o

2M + 3 2 O2 = M 2 O3

-------------------------------------------------------------

3Pb + M2O3 = 2M + 3PbO

G- = Go1 - Go2 = 33472J

296

XM 2

XM + XPb = 1

X pb 3

XM2
X Pb 3

33472 = -8.314 1173ln

33472 = -8.314 1173ln 100

XM = 0.143 XPb= 0.857
MM = 0.143 122 = 17.44
MPb = 0.857 207 = 177.4

17.44
100 = 8.9%
17.44 + 177.4

= M

( 1000 k

1986 (2

2000 (1

2182 (4

(3
:(4

i = io + RT ln Pi
i = io RT ln 3Pi
3Pi
= 1.987 1000 ln 3
Pi

i i = RT ln
= 2197

( XH2O=0.96,XO2=0.03,XH2=0.01 15
: 700oC

Go=-393 KJ

297

2H2+O2=2H2O

 .
(1
(2
(3
(4

(0.96)2
0.15 0.012
0.96
0.15 0.01

: (1

PH2 2 o
PH2 2 Po2
<0

(0.95 5) 2
)(0.01 5) 2 (0.03 5

G = G + RT ln

Pi = X i Pt G = 393000 + 8.314 973 ln

(
1155k

1940k 9.02J/mol k .

3,43J/mol k .

1723.7 k (1

1405.5 k (2

1980.8 k (3

1895.6 k (4

: (1

298

S=S1 + S2 = 3.43 + 9.02 = 12.45

S1 =
S2 =

L f1
T1
L f2
T2

=> 3.431155=3961.6=Lf1
=> 9.021940=17498.8=Lf2

Lf = Lf1 + Lf2

S =
12.45 =

Lf
T
3961.6 + 17498.8
T

T = 1723.7 K

299

2)ai = Xi

1) Pi = Pio x i

= RT ln X i

4) Gi

3) i = 1

= H iM = 0

6) H

= RT X i ln X i

5) G

.
V M = Vi M = 0

)7

.
GiM = H iM (= 0 ) TS iM = RT ln Xi

S iM = R ln Xi

= R Xi ln Xi

)8

9) S

: :
-1 .
-2 .
:

a-X

300

 :
.
H iM

:
p, c
RT 2

ln i

:
.

Vi M < 0

H iM < 0

Vi M > 0

H iM > 0

Vi M

=
RT
T , C

ln i

:
.

XAd lna A + XB dlnaB = 0

XAd lnA + XB dln B = 0

301

XAd lnXA + XBd lnXB = 0

`
XB
d ln a B
XA

ln a A a A = a B

B =0

A =1

.
:
ln i
(1 X i ) 2

= i

.
X = ...

ln A = X A X B B X A=1 B dX A
A

:
.
: .
ln A ln B
=
2
X B2
XA

302

A = B

 29500
(1 X sn ) 2
RT

= ln sn

ln sn
29500
=
2
RT
) (1 X sn

?=cu

Xcu = 0.03

= sn

T = 900

sn = cu
:

QXS = Q - Qid

Q QXS :
Q Qid :

= RT lni
= RT Xi lni

XS

XS

Gi i

G XS = G M G M ,id
RT Xi ln ai RT Xi ln Xi

)( :

(1 A = B

= R Xi ln Xi

M
M

2) S

3) S i = R ln Xi

303

= Si XS = 0

XS

4) S

= H XS = H M = RT X A X B

XS

5) G

XS
XS
M
6) Gi = H i = H i = RT lni

lni (T2 ) T1
=
lni (T1 ) T2

)7

)8) GM = RTXAXB+RT(XAlnXA+XB ln XB

Gi XS , G XS

)9

= S XS = 0

G XS

:
(1

a BR = B X B
X B 1
B 1
(2 :
.

a BH = f B .xB
xB 0
: f B

304

aBR
0
=

B
aBH
0

: B B B .
-3 :

) a1Bwt % = f B1wt % ( wt % B
:
a BR
MA
= 0B
1wt %
100M B
aB

: M A A
: M B B
-4 :

a BS
T
B
RT ln L = L f 1 B = G
T
aB
f

:
Go : ) . Go (G
aSiO2
aSiR .PO2

= osi

a siR
a siH

G o = RT ln

a
G = RT ln H sio 2
a Si .PO2
o

305

R
Si + O2 = SiO2
H

G o = RT ln

asio 2
asiR
osi

G o = RT ln

. po 2

a sio2
R
si

a . po

RT lnosi
2

G o = G o RT lnosi
G(oH ) G(oR ) = RT ln osi

G(oH ) G(R ) = RT lnosi 2

o
o
G(o1wt
%) GR = RT lnB .

MA
100M B
: :

M(S)= M(1wt%)
. 1 M
M ( S ) M ( L) M (1% wt )
1424
3 1424
3

T
L f 1 B
T
f

+ RT lnom M N

100M M

: GM
GM = RT(XAlnXA+XB lnXB)<0
GM= RT(XAlnXA+XB lnXB) + RTXAXB
< 0
> 0

=0

306

 : GM
.
B,A .
B,A .

GM-Xi ai-Xi

307

308

P+F=C+2
: .
: .

P=3 f=0
P=2 f=1
C = N-R
= N
= R
: P+F=C+1

P+F = C

3 :
3 :
4 :
: .

MS-MOS COg CO2g

= MS
= MoS

309

 = Cog- CO2g
C = M C o = 3
:
. GM X B
.

310

=L

G A = G AL

) a (A,
T
= RT ln ( L , L ) = LAf 1 A
T
aA
f

)( o
A

)o( L
A

) : A(, A
) : A(L,L A

:
.
.

311


) X A (,
T
A
RT ln ( L, L ) = l f 1 A
T
XA
f

:
.
)*( :

=
a A = a A
a B = a B

) G AL = G Ao (S

312

) G Ao ( S ) + RT ln a A( L, S ) = G Ao ( S
) o( L
)( L, L
) = G Ao ( S
G A + RT ln a A

a ( L,S ) = 1

RT ln a ( L , L ) = LA L T
A
f

T fA

) :a A(L,S A
) : aA(L,L A
:
.

GM = RT(XAlnaA(L,S) + XBlnaB(L,S))=0

a lA,s = 0, a Bl ,s = 0
:
Lf A

1 T
= exp
RT T fA

1 T
TB
f

LBf
= exp
RT

) ( L,L

= XB

XA

)aA(L,L)=XA(L,L

1 X A

)aB(L,L)=XB(L,L

) ( L,L

) ( L,L

: B B
A .

313

LAF T
2

: :

314

) (

R T fA

)( L,L

XB

315

 T
T fA

LAf 1

) a A (,
)a A( L, L

RT ln

( CO+2H2 CH3OH
:

Ln Kp=-17660/T-8.82 lnT+0.00685 T+28.8

Ho

Ho=17660R-8.82RT+0.00685RT2 (1
Ho=-17660R-8.82RT+0.00685RT2 (2
Ho=17660R+8.82RT-0.00685RT2 (3
Ho=-17660R+8.82RTlnT+0.00685RT2 (4
: (1
d ln K P H o
=
dT
RT 2

( 1 gr/cc 0/917 gr/cc .

10 . -0/08 .
J/mol k

2/1 (1

18/58 (2

8/8 (3

: (2

316

88 (4

P2 P1 S
H
=
=
T2 T1 V T1V
S = 183.37 atm Cm 3
= 18.58 J

1
1
18

1 0.917

10 1
=
0.08

(
1 2
(1
(2
(3
(4
: (1

Qr
T

= S

( 800 3/6 700

9 .

1900 (1

10190 (2

11900 (3

19110 (4

: (2
) Kp (T2 ) H o (T2 T1
=
) Kp (T1
2.303RT1T2

317

log

)H o (700 800
9
=
3.6 2.3 1.987 700 800
H o = 10250cal

log

(
(1
(2
(3
(4
: (2

( A 1000 A 800
. A 200
.

4/28 (2

2/48 (1

4/82 (3

8/42 (4

: (1
1000 + 800
= 900
2
900 200
900 200
= S
dT +
dT = 2.48 J
800 T
1000 T

= Te

( SiO2=Si+O2 T P

GSiO2 = GSi + GO2 (1

-oSiO2+ osi+ oO2 (2

318

G=Go=0 (3

(4

: (1

( 298 .

)2HCl(aq)+Zn(s)=ZnCl2(aq)+H2(g
0 (1

500 (2

600 (3

2500 (4

: (1
: =
:

( Cu2O H2 1000
) CuO,H2O -59000 -42000
1000 . Cp 7
(.
7500 (1

7500 (2

8500 (3

8500 (4

: (4

Cu2O + H2 = 2Cu+H2O
o

) H = H ( H 2 o ) H ( cu 2 o

319

= -59000 + 42000 = -17000

17000
= 8500
2

= H

( CO2+H2=CO+H2O 690 0/1.

XH2=0.6

XH2O=0.05
-5300 (1
1000 (3

XCO2=0.1

XCO=0.25

-3150 (2
5300 (4

: (3

X H 2 o . X co
X H 2 . X co2

G = RT ln K + RT ln
CO2 + H2 = CO + H2O

n = 0

KP = KX
0.05 0.25
0.6 0.1

G = 1.987 690 ln 0.1 + 1.987 690 ln

cal

G = 1012.8

( A A-B
A-oA=RTlnXA-KXB2 k . B-oB

RTlnXB+KXA2 (1

RTlnXB+KXB2 (2

2RTlnXB+KXB (3

-RT ln XB 2KXB + KXB2 (4

: (4

320

 A Ao = RT ln X A KX B 2
B Bo = ?

X i di = 0

X A d A + X B d B = 0

1
2 KX A + 2 K = X B d B
X A RT
XA

RT 2 K (1 X B ) 2 2 K (1 X B )
d B =
+

XB
XB
XB
B=-RTln XB 2KlnXB + 2KB + 2K lnXB + KXB2 4KXB
B - Bo = -RT ln XB 2KXB + KXB2

. M3O4 MO (

. M

M+1/2 O2=MO

Go=-62050+14.95T cal

3M+2O2=M3O4

Go=-260700+74.75T cal
836K-M3O4 (2

836K-MO (1

972K-MO (4

972K-M3O4 (3
(2 :

4 M + 1 O2 = MO G10 =

2
3M + 2O = M O G 0 =
2
3 4
2

M + M3O4 = 4MO

Go = 0

Go = 4Go1 - Go2

321

T = 836 K

= 12500 14.95 T
M3O4

Go298 >0

:
.
G = wr
G = nfE

: n ) (
: f
: E

Go = -nFEo
= Eo

E>0 G<0

E<0 G>0

)F = 96500 G (J
)F = 23060 G(cal
:

M1(a1) M1n+ (a1) + ne (ox) Eo

322

M2n+ (a2) +ne M2 (a2) (Re) EoC

) : M1 (a1) + M2n+(a2) M1n+ (a1) + M2 (a2

RT a2 .a1
ln
nF a1.a2

E = Eo

Eo = EoC - Eoa

Eo = EoC + Eoa.

: :
Eo . .

E
S = nF
T P
E

T

E
H = nF E .T
T P

Q = T.S
: Q
dH = Q wr

323

M M n + (a1 ) M n + (a2 ) M
a1 a2
RT a1
ln
nF
a2

) (a2 ) = M n + (a1

n+

=E

Eo :

: .

G<0 E>0 a1<a2

:
.

) M (a1 ) M n + M n + M (a2
) : M(a1) = M(a2
Eo : .
a2
a1

E = RT ln
nF

a2<a1

E>0

G<0

V = -Er+IR+ER+En
= Er
= IR

324

 = ER
= En
:

1
2 H + + O 2 + 2e = H 2 O
2

2 H 2 + O2 + 4e = 4OH

2 H + + 2e H 2

2 H 2 O + 2e = H 2 + 2OH
) Pt ( PO2 = 10 5 ) H + H + pt ( PO2 = 10 7
)Hcl ( w = 1) Hcl ( w = 1

Eo1

Fe2+ + 2e Fe

Eo2

Fe3+ + 3e Fe

EoEo2 Eo1

Fe3+ + e Fe2+

Go3 = Go2 - Go1

. CO/CO2

325

Fe3O4

M:

W : FeO
I : Fe
Fe2 O3

: %Co .
: %Co .

326

H:

( 1 100
. 40/63 Kg/mol .

VH2O(1)=0.0188 L/mol

VH2O(g)=30.6 L/mol
10.05 KJ (1

33.68 KJ (2

37.53 KJ (3

43.73 KJ (4

: (3

U = Q W
V2

w = Pex dV = P(V2 V1 ) = 1(30.6 0.0188) = 30.58 lit atm

V1

= 3.096 KJ

U = 40.63 3.096 = 37.53 KJ

( .

Go=40800-41.7T cal

C+CO2=2CO

..... .......
(1

(2

(3

(4

: (3

( 100

327

)COCl2(g)=CO(g)+Cl2(g
8 10 . SoR373=30 cal/k HoR373

-9

:
-25 (1

-2/4 (2

25 (4

2/4 (3

: (4

Go = -RTlnK
)Go = -1.987 373 ln (810-9
Go = 13817.9

Go = Ho - TSo
13817.9 = Ho 373 30

Ho = 25103 cal

( N2+O2=2NO 2200 k 1/1 10 .

-3

2200 k NO

VNO=0%Vt (1

VNO=1.3%Vt (2

VNO=0.65%Vt (3

VNO=100%Vt (4

: 2
2

PNO
=
0.79 0.21

Pt=1VNO=0.013

PNO = 0.013
VNo = Vt.VNo
VNo = 1.3%Vt

328

1.1 10

P
K = NO
PN 2 .PO2

( Go=-7000+15.25T cal/mol
.

459 (1

416 (2

732 (4

186 (3

: (2
1
2 Ag + O2 = Ag 2 O
2

Go = -70 + 15.25T cal

= 0.21

(P

O2

1
Po2

G o = RT ln

( 929 0/9
.

)2FeSO4(s)=Fe2O3(s)+SO2(g)+SO3(g
Go .

2947/96 (1

-2947/96 (2

388/97 (3

-388/97 (4

: (1
G = RT ln PSo2 .PSo2
PSo2 + PSO2 = 0.9atm
PSo2 + PSo3 = 0.45

Go = -1.987 929 ln 0.452 = 2947.9

329

( 1000oc

CO2+C=2CO (1

FeO+C=CO (2

FeO+CO=CO2+Fe (3

2FeO+C=CO2+2Fe (4

: (3

( H2O %40 H2%60 850 C Fe-

Ni .

Go=-3150+1.85T cal
85 (1

87/6 (2

88/2 (3

Fe+H2O=FeO+H2
92/8 (4

: (4

Fe+H2O = FeO + H2
PH 2
PH 2O .a fe

G o = RT ln

-3150 + 1.85 1123 = -1.987 1123

X fe = 0.928

0 .6
0.4 x fe

ln

( 250 1 15
. 5 j/degree

330

R=0.082 lit.atm/degree.mol=8.31 j/degree.mol

8/22 (2

6/58 (1

24 (4

22 (3

: (1

1dm3 = 1 lit

PV = nRT

V2
V1

1 15 = n 0.0821 25

S = nR ln

n = 0.73
, V2 = 6.58

V2
15

5 = 0.73 8.314 ln

( B,A 350 ml 25oC 1

. 0/6 A
) MB=50 MA=30 (.

XA=0.54 (1

XA=0.48 (2

XA=0.4 (3

XA=0.048 (4

: (3
m
RT
M

= PV

M=41.94

350 0.9
=
0.0821 298
1000 M

M = XiMi
)41.94=30XA + 50(1-XA
XA=0.4

331

( 1 520
.

Hm,Sn=7070 j/mol, Tm.Sn=505 K

-899/5 (1

-7519/75 (2

j/degree.mol

Cp(1)=34.7-9.210-3T

j/degree.mol

Cp(s)=18.5+2010-3T
-15039/5 (4

-7969/5 (3

: (3

)2Sn(L,520) 2Sn(L,505) 1Sn(S,505

505

H = 2 (34.7 9.2 10 3 T )dT 7070 = 7969.5

520

( 200 200 90oC .

1 .

5/2 (1

Cp(1)=75.5 j/degree.mol

Hm.H20=6.01 Kj/mol

MH20=18 g/mol

Cp(s)=38 j/mol.degree

8/4 (2

10/4 (3

16/8 (4

: (1

) = 0() + H(H
T 90
T 0 0
200
200 T
200 T
6010 +
75.5dT = 0
75.5dT +

18 363
18
18 273

332

T = 502oC

( A 1 268
.
j/degree .

Hm,A=9956 J/mol

Tm.A=278.5 K

Cp(s)=123.6 j/degree.mol

Cp(1)=127.3 j/degree.mol

-33/89 (1

33/89 (3

35/61 (2

-35/61 (4

: (4

)A(L,268) A (S,268
)A(L,278.5) A(S,278.5
268 123.6
127.3
9956
dT
+
dT = 35.6
T
278.5 278.5 T

278.5

= S

268

( 297/5 SO2
394 CO2 CS2

CS2+3O2=CO2+2SO2
1109/9 CS2
-120/9 (1

120/9 (2

-460 (3

333

460 (4

 : (2

CS2 + 2O2 = CO2 + 2SO2

= Hoco2 + 2Ho so2 - Hocs2Ho

)-1109.9 = -394 + 2 (-297.5) - Ho(CS2

Ho (CS2) = 120.9 KJ

( 30 A,B
.

V=109.4-16.8 XA-2.64 X2A

A
V A = 16.8 5.28 X A (1
V A = 92.6 5.28 X A + 2.64 X 2 A (2
V A = 92.6 + 5.28 X A 2.64 X A2 (3
V A = 92.6 5.28 X A (4

:(2
dV
dX A

) V A = V + (1 X A

dV
= 16.8 5.28 X A
dX A

334

V A = 92.6 5.28 X A + 2.64 X A2

( 435
. 30 .

0/3 (1

1/363 (2

0/47 (4

0/409 (3

: (3
lnzn
= 0.87 0.3 X cd
2
X cd

= zn

0.3

lncd = X zn . X cd . zn zn .d Xcd
1

0.3

lncd = 0.3 0.7(0.87 0.3 0.3) (0.87 0.3 X cs )dX cd

1

cd = 1.36

acd = 1.36 0.3 = 0.409

( Pb-Sn .
20

log Pb =-0.32(1-Xpb)2
0/12 (1

0/81 (2

0/19 (4

0/16 (3

: (1
= 2.3 (0.32) = 0.736
sn = 0.62

lnsn lnsn
=
2
X pb
0.8 2

= pb = sn => 0.736
a sn = 0.62 0.2 = 0.12

335

2.3 logp
X 2 sn

lnpb
X 2 sn

= pb

( A A-B
. A A-B :

LogyoA=-985.4T-0.36
(1

(2

(3

(4

: (2
H AM < 0

985.4 H AM
=
T2
2.3RT 2

d logoA
H AM
=
dT
2.3RT 2

( .

Go=-62200+5.53T cal/mol Fe3C

Fe3C=3Fe+C

(1
(2 1121/15
(3 1121/15
(4
: (4

= Go = 0 T
> T
< T

336

(
6850
-0.755LogT+11.24
T

=Log(Pzn)s/g

6620
-1.255LogT+12.34
T

=Log(Pzn)1/g

(1 673
(2 680
(3 1181
(4
: (3
6850
0.755 log T + 11.24 T = 1131
T

= log 760

6620
1.255 log T + 12.34 T = 1181
T

= log 760

( 693 1181 .
1765
27560 .

1000
0/24 (2

0/024 (1

337

 0/12 (4

0/012 (3
: (4

H = 27560

Cp = 0

27560
+C
RT

= ln p

27560
+ C => C = 11.6
1.986 1181

= ln p

Hb = 27560

22560
+ 11.6 P = 0.12atm
1.987 1000

= ln p

( .
.
2
sn

Ln Pb =-0.75 X

700 Pb-Sn %60

800
:

R=2cal/mol.k
(1

1000

(2

(3

568

(4

1432

: (3

338

Cp(pb,1)=10 cal/mol.k

H
)pb(700

) , 800 ( pb

H 2
800

800

700

700

)pb (800

H 1

H = 10dT + RT lnpb 10dT + 1.987 800(0.75 0.6 2 ) = 568cal

1750 (1

Go(J)=-489100+197T

)2Ni(s)+O2=2NiO(s

Go(J)=-524300+217.4T

)2Ni(1)+O2=2NiO(s

1725 (2

1800 (3

1825 (4

:(2

T = 1725 K

GoL = GoS

( c+co2=2co .

)Go=40800-41.7T (cal
co :
(1
(2
(3
(4
:(3

339

( .

Go(cal)=54551-60.77T

CH4+H2O=CO+3H2

Go(cal)=-7765+7.2T

CO+H2O=CO2+H2

(1
(2
(3
(4
:(4

CH4 + CO2 = 2CO + 2H2

Go = Go1 - Go2 = 623.6 57.9T

p

( A-B . B 0.5 .
m

S =Rln2 (2

s =-RTln2 (1

H =-2RTln2 (4

H =-RTln2 (3

: (2

SM = -R (XA lnXA + XBlnXB ) =- R(0.5 ln0.5+0.5 ln0.5) =R ln2

340

( Hm=200Xcu.Xcd
.

100 cal/mol (1

50 cal/mol (2

200 cal/mol (3

25 cal/mol (4

: (2

HM = 200 xcd xcu

2
H M cd = RT lnCd = RT X Cu

RT = 200
H M Cd = 200(0.5) 2 = 50

( %70 234k 1.5 .

)(cal/mol
-518 (1

-281 (2

-2167 (3

+2167 (4

: (2

GM = RT XHgXSn
)+ RT(XHglnXHg+Xsn lnXsn

ln1.5
= 0.827
0.7 2

lnHg
2
Sn

GM = 1.98723400.70.3+1.987234(0.7ln0.7+0.3ln0.3) = -203

341

( 900oc . 961oc
2690 .

CpAg(s)=5,CpAg(1)=7.3 cal/mol ok
3,6 kcal/mol (1

2,55 kcal/mol (2

4,3 kcal/mol (3

2 kcal/mol (4

: (2
900

0
Cp.dT => H 900
2690 = (7.3 5)dT

900

961

K cal

0
0
H 900
H 961
=

961

Ho900 = 2.55

( 1000 CO2,CO 80
CO . 0.225 . Go
CO2,CO -50 -95

R=2 cal/mol K
0.45 (1

1.7 (2

0.25 (3

1.17 (4

:(4

CO2 + C = 2Co

Go = 25 Go(CO) - Go(CO2)=2(-50)+95=-5K cal

2

Pco
0.8 2
=> 5000 = 1.987 1000 ln
Pco2 aC
0.2 ae

c = 0.258

342

G o = RT ln

Pt = 1 => P = X

0.258
= 1.14
0.225

= c

(
o

G =-1698769+321.79T

2Al+3.2O2=Al2O3

G =-731154+205.39T

Mg+1/2O2=MgO

(1
(2 1745
(3 1500
(4
: (2
2 Al + 3MgO = Al2 O3 + 3Mg

Go = Go1 - 3Go2
Go = 494693 294.39T
Go = 0 => T = 1680

T > 1680
T < 1680

( 1000
2 :
o

G =-95.3 kcal

2C+O2=2CO

G =-94 kcal

C+O2=CO2

(1 1.57

1 (2

0.636 (3

343

0.1 (4

(1 :

1-2

C + CO2 = 2CO

Go = Go1 - Go2
= -1.3 Kcal
P 2 co
Pco2

G o = RT

1300 = 1.987 1000 ln

2
pCO
pco2

pco
Pco = 1.22
= 1.92

pco2
P = 0.78
Pco + Pco2 = 2 co2

1300oc MgO (
:
o

Mg(g)+1.2O2(g)=MgO(s)

G (1573)=-416666 J

1.8610-10 atm (3

1.8610-8atm (1

3.7210-10atm (4

1.8610-9 atm (2
(2 :

G o = RT ln

1
1
2
o2

= 416666 J = 8.314 1573 ln

PMg P

Po2 = 3.7510-10 atm

Pair = 5Po2 = 1.8710-9atm

344

2 Po2 Po2 2

( 10.94 10.65 .
20oc .
327oc 207 . 1150 .

72,5 atm (1

2995 atm (2

1550 atm (3

1237 atm (4

: (2

P2 P1 H
=
T2 T1 T1V
82
P 2 1
1.987
=
= 3073atm
20
207 207
500

1065 1094
1150

( mmHg 1600 oc .
53.7 Kcal/mol 2095oc .

R=1.987 cal mol K

0.49 (1

49 (2

86.25 (4

37.23 (3

:(3
53700
+c
1.987T

ln p =

H
+C
RT

= ln p

H = 53700

53700
+C
)1.987 (2095 + 273

C = 11.4

345

ln1 =

P = 37.230 mHg

( A,B .

V=100 XA + 80 XB + 2.5 XA XB
V XA,XB A,B . A
XA=0.2 cm3/mol

101.6 (1

121.6 (3

61.6 (2

81.6 (4

:
dV
dX A

) V A = V + (1 X A
V A ( X A = 0.2) = 101.6

dV
= 100 80 + 2.5 5 X A
dX A

( .

lnP(1,atm)=-33000/T+20

LnP(s,atm)=-34000/T+28

Lt=33000cal,Tb=1560 k (1

Lt=34000cal, Tb=1214 k (2

Lt=2000cal,Tb=1650 k (3

Lt=66000cal,Tb=1650 k (4

: (3
Lg
Lg
d ln p H 33000
=
=
dT
RT 2
T2

H L g = 33000 R
d ln p s g H S g 34000
=
=
dT
RT 2
T2

346

Lg
33000
+ 20
T

= ln 1

= 1650 K T
H L g = H S g H l g

H S g = 34000 R

= 1000R = 2000 cal

( RTln Al =1750(1-XAL)2 .
50 550 oC ) R (cal/mol

0.48 (1

0.65 (2

0.0622 (4

0.37 (3

: (2
1750
RT
zn = 1.3

lnA1
2

) (1 X AL

= AL

lnzn
lnzn
1750
=
=
1.987 823 (1 zn ) 2
0.52

azn = 1.3 0.5 = 0.65

( 1000 k
. 20 .
m

) H =200Xcu.Xcd (cal

4.95 (1

1.004 (2

3.1 (4

2.75 (3

: (2

HM = 200 Xcu.Xcd

RT = 200
200
RT

200
1.987 1000
Cu = 1.004

347

lnCu
2

) (1 X Cu

lnCu
0.2 2

( 1300 k .
80 .
.

0.6

0.7

0.8

0.9

Xcu

0.728

0.837

0.922

0.981

cu

-3510 cal/mol (1

-4200 cal/mol (2

-840 cal/mol (3

-1050 cal/mol (4

:(3 -
= 2.03

ln 0.922
0 .2 2

lnCu
2
X zn

GXS = RT XAXB

GXS = 1.987 1300 -2.03 0.2 0.8 = -840 cal

( 1000 oc A,B 0.25 0.75

) ( m -2000 .
A
B .

-5332J (1

-2666J (2

-8244J (3

-16488J (4

: (2

HM = -2000J = RTXAXB

348

-200 = RT 0.25 0.75

RT= -1066.6

)HM = -1066.6 (0.5)(0.5

= -2666.6

( :
o

G =21270-6.4T cal

1 Mo2S3+H2= 2 MO+H2S
3
3

G =-15445.72-0.396T cal

CaO+H2S=CaS+H2

:
(1
(2
(3
(4
: (1

+21
1 MO2 S 3 + CaO + H 2 = 2 MO + CaS + H 2 o
3
3

Go = Go1 + Go2 = +5824.28 6.79T

T

( Go .
o

G =-92000+18T cal

349

Mn+ 1 2 O2=MnO

C+ 1 2 O2=CO

G =-27000-22T cal

co .

1825 k (1

1300 k (2

1625 k (3

1500 k (4

: 3
Mn+CO=MnO+C Go=Go1+Go2=-65000+90T

Go=0 T=1625 K

( .
o

G =-99650+22.82T cal

)Mg(s)+ 1 2 S2(g)=MgS(s

G =-101800+25.15T cal

)Mg(1)+ 1 2 S2(g)=MgS(g

923 oc (1

915 oc (2

650 oc (3

642 oc (4

:3

Go(S) = Go(L) => T=923 K = 650oC

( %70 CO2 %15 CO %15 .

.
o

G =-394100-0.8T J

350

C+O2=CO2

2C+O2=2CO

G =-223400-175.3T J

897,13 oc (1

624,2 oc (2

978,2 oc (3

705,2 oc (4

:2
2-1 : C+CO2=2CO Go = Go2 - Go1

0.152
=-8.314Tln
0.15

P2
=-RTln CO
PCO2

G =170700-174.5T=>G

=> T = 897 K = 624 oc

( 357oc 59120J/mol .

27,66J/mol k 20,79
:

lnP(atm)=-7114/T +11.3 (1
lnP(atm)=-7635/T -0.83lnT+17.46 (2
lnP(atm)=-6593.5/T +0.83lnT+5.14 (3
lnP=7114/T -11.3 (4
: 3

C=Cpv-Cp1 = -6.87 => H=-6.87T+C1

59120=-6.87630+C1 => C1 = 63448
d ln p H 6.87T + 63448
0.82 7631
=
=
=
+
+C
T
T
dT
RT
8.314T 2

7631
+C => C=17.4
630
351

ln 1 = -0.82ln630 -

0.82 7631
+
+ 17.4
T
T

= lnp

( A-B 400 k
.
m

) H =-14500 XA XB (1- 350/T

(1 .
(2 .
(3 .
(4.

:1

350

RTXAXB
400

HM= -14500 XAXB 1

HM<0 .

( .
m

) H =-29700 XZn (1-Xzn) (J

Xzn=0.8 :

-4752 J/mol (1

-29700 J/mol (2

-19008 J/mol (3

-1188 J/mol (4

:3

352

RT=-29700 => = RTln cu =RTX2zn

-29700 0.82 = -19008

M
=
Cu

( A-B T A XA=0.4
0.35 . B

0.593 (1

0.565 (2

0.942 (3

0.515 (4

: 2

lnA lnB
=
2
XB
X A2
A = B

0.35
ln

0.4 = lnB => = 0.94

B
0.6 2
0.4 2
aB = 0.94 0.6 = 0.565

( Au-Cu .
900 k . %50

CXS(cal)=-6800XAu Xcu
0.39 (1

0.194 (2

0.5 (3

: 2

353

0.05 (4

RT = -6800

lncu
6800
6800
>=
=

2
RT
RT
X Au

lncu
6800
=
=> cu = 0.38 => acu = 0.38 0.5 = 0.194
900 1.987
0.52

(
.

)[Zn]pb-zn+(PbCl2) = [Pb]pb-zn+(ZnCl2
Go 390oC -15090 ZnCl2
0.983 .
a Zn = 29 X Zn .

ZnCl2-PbCl2 .

2,1 10-5 (1

3,2 10-4 (2

4,3 10-3 (3

3035 10-2 (4

: 1
) 0.983 (1 X Zn
(1 0.983) 29 X Zn

=> 15090 = 1.987 0.663 ln

X ZnCl 2 a Pb
X PbCl 2 a Zn

G o = RT ln

=> X zn = 2.1 10 5

354

( Zn-Cd 800k Zn,Cd

Cd 1.352 . ):(J
-2000 (1

2000 (2

-2600 (3

-2400 (4

: 3

)GM=RTXzn.Xcd+RT(XznlnXzn+Xcdln Xcd

ln 1.352
) 0.50.5+8.314800(0.5ln0.5+0.5ln0.5
0
.
52

GM = 8.314800
GM=-2604j

( ) (3330 k
3,7210-3atm/ k . ):(kJ

343 (1

334 (2

433 (3

82 (4

:1

d ln P H
=
>=
2
dT
RT
H = 343kj

8.314 3330 2

= 3.72 10 3

(
CH4+2H2O=CO2+4H2 700 1500
:

355

 (1

:1

(2

(3

(4

( 1000 k Pco/Pco2 0.6

0.0082 (1

)Go=-564800+173T (J

2CO+O2=2CO2

)Go=-489100+197T (J

2Ni+O2=2NiO

0.0041 (2

0.0042 (4

0.0024 (3

:( 2
1-2
2Co+2NiO=2Ni+2CO2

Go=Go1 - Go2 = -75700-24T

PCO 2

PCO .0.6 2

=> 99700 = 8.314 1000 ln

PCO
2

PCO .a NiO

G = RT ln

PCO
= 0.0041
PCO2

( 1200 oC .

)RTlnZn = -20920Xcu2 (J

356

 0.003 .
1200c %60 )(mmHg

0.003 (1

0.0018 (2

0.0014 (4

0.0012 (3

: 4
20920
RT

lnzn

= zn

2
X co

zn=cu
lncu
20920 lncu
20920
=
>=
=
2
RT
8.314 1473 0.4 2
X Zn

cu = 0.76

cu=0.760.6=0.45
P
acu = cu
=> Pcu = 0.0014
o
Pcu
0.003

( A A-B .

LnA=651.6 (1-XA)2/T
B XB=0.6 )(T=1200 oC
1.07 (1

1.09 (2

(4

1.17 (3

:1
65.16
T

lnA

X B2

=A

A=B
651.6 lnB
=
=> B = 1.07
T
0 .4 2

357

( SnS .

Log Psns(atm)=-8687/T + 5.65

SnS

40 kj (1

166 kcal (2

(3

166 kj (4

: 4
8087
H
H
d log p
=
>=
=
=> H = 166kj
2
2
dT
T
2.3RT
8.314T 2

( A-B .

cm3/mol

V=100XA+80XB+2.5XAXB

A XB=0.8 )(cm3

180 (1

102 (2

80 (3

22.5 (4

:) 2 " (

( Cu-Ag 1423k .
%60 560cal/mol .

0.85 (1

0.73 (2

0.4 (3

0.24 (4

:2
XS
GCu
= 560
XS
GCu
= RT lncu 560 = 1.987 1423 lncu cu = 1.22

358

cu = 1.220.6=0.73

( A-B .
.

Hm=-12500XA.XB

J/mol
B A :
(1

e-1623.7/T (3

e-6797/T (2

e13500/T (4

: 3
RT=-12500

12500
RT

lnB 12500
1503 2
ln
=

=
XA
B
8.314T
T
X A2
AXA=1 B .

1503
B = exp

( )( Gi=RTln ai .
i

Si=-Rlnai (1

Si=Rln ai (2

Si=-Rlni-RlnXi (3

Si=-Rlni-RT(dlni/dT)-RlnXi (4

:4

359

Gi = RTlnai
Gi

= Si
T

) Gi=RT ln (i . X i
= RT lni + RT lnXi

Gi
d lni
= R lni + RT
+RlnXi = -Si
T
dT
lni
Si = R lni RT
R ln X i

( A-B T Hm XA,XB
. Hm XB
(1

H Am H Bm

(2

H Am + H Bm

(3

H m H Am

(4

H Bm H Am

: 4

) (1 X B
H M = X A H AM + X B H BM
dH M
= H AM + H BM
dx B

( A-B 0/25 .
AO2,BO2 10-20 600
B

Go=-75800+21.2Tcal LfB=15Kcal Tm=1000K

360

)B(s)+O2(g) = BO2(S

0/001 (1

0/004 (2

(3

- 2.7 10 5 (4

6.84 10 6

:4

1
Po2 .a BR , S
1
20

.a BR, S

10

G o = RT ln

63080 = 1.987 600 ln

1.0510-3

= a BR , S

a BR , S
= oB
L, S
aB
= 0.25 => aBh, s = 0.004

0.004
600

h, l
5
=

15000
1

a B = 2.6 10
h, L
aB
1000

1.05 103

aBh, s

a h, s
T
RT ln Bh,l = LF 1
aB
TF

1.987 600 ln

( Au-Cu 45
1050 .

) 3100
(

0 (1

46.98J (2

48.44 J (3

:1

361

3100 J (4

( ln P=A/T+BlnT+C .
:

0 (1

(2 a+bT

(3 a+bT+cT-2

(4 T

: 4
d ln p + H
A B H
=

= +
2
dT
RT
T 2 T RT 2
dH
= + BR
dT

= H = AR + BRT Cp

( 1000 Cu-Cd .

Hm=200 XCu (1-XCu) cal

Cu-50% Cd

1/025 (1

0/1 (2

0/25 (3

0/513 (4

: 4
RT=200
lncd 200
200

=
2
RT
RT
X cu

lncd
200
=
cd = 1.02
0.52 1.987 1000
acd=1.02 0.5=0.513

( AB XB1 .......

362

 A,B (1
A,B (2
A (3 B
B (4 A

: 4
XB1

( ln P=-16000/T + 20 .
2000 Cp

R=2 cal/mol k
32 (1

30 (2

20 (3

16 (4

:2
sv s v
16000 H
H
=
d ln p
2
=
T
RT 2
dV
RT 2
sv
H = 32000cal
l v
H = 32000 2000 = 30 Kcal

( CO2 CaO,CaCo3 1030 921

0/01 0/1 . CaCO3

363

 CO2 1 )
(.

Ho=166 , T=1168 (1

Ho=166 , T=1090 (2

Ho=72.3 , T=1168 (3

Ho=72.3 , T=1090 (4

: 2
CaCa3 = CaO + CO2

) (

Pco2 Kp

G o = RT ln

) K P (T2 ) H o (T2 T1
0.01
)H o (1030 921
=
log
=
2.3RT1T2
0.1 2.3 8.314 921 1030
) K P (T1

log

H o = 166kj

= 830k

) 166000(T2 921
1
=
T2
0.1 2.3 8.314 T2 921

log

( .

Ln P (atm)= -40350/T - 1.12 lnT + 23.79

12970
1500oC

334/47 (1

318/96 (3

331/93 (2

305/99 (4

: 2

40350 1.12 H L v
d ln p1 v 1 v
=

=
=
dT
T
RT 2
T2
RT 2
H L v = 318960 j

364

H s v = 318960 + 12970 = 331.9kj

( A-B B
.

(1 XB=0.5 .
(2 0<XB<1 .
(3 0<XB<1 .
(4 0<XB<1
.

:3

( Cu(S),Cu2S(S),Cu2O(S),O2(g),S2(g) :

(1 2
(2 0
(3 3

365

 (4 1

: 4
P+F=C+24+F=3+2F=1
P=4
C=3
( ) H2O(g),H2(g),Fe3O4(s),Fe(s
. :

0 (1

1 (3

2 (2

3 (4

: 3
C=3 , P=3
P+F = C+1
3+F=3+1 F=1

( Cu-Sn 1000 %2.71

%10.42 . 12970
1000 )
1083 (.

0.025 (1

0.896 (3

0.104 (2

0.973 (4

: 4
" "
.

366

1273
L
= 129701
acu = 0.9
1356

a
T
1
=
RT ln cu
L
F
L
acu
TF

1 0.0271
L
acu

8.314 1273 ln

( ) M(s)/MO(s)/CO(g)/CO2(g)/C(s

1 (1

2 (2

0 (4

3 (3

:2
P=3

c=3

P+F=C+2=>3+F=3+2=>F=2

( 610 K 1220cal/mol .
Cp G
600K

50cal (1

-180cal (2

-20cal (4

78cal (3

: 4
sL

= G

T
G = LF 1
TF

600
12201
= 20cal
610

LS.

367

( A,B 1073 K 1273 K .

Cp .
.
2146 2546

XA=0.43,TE=690 K (1

XA=0.2,TE=1000 K (2

XA=0.5,TE=960 K (3

XA=0.3,TE=450 K (4

:1

T
= LF 1
TF

L, L

: RT ln x A

1.987 T ln x AL, L = 25461

1273
.

XA = 0.43

=> T=690

( A-20%B . T

5 B B . A
600 K A 1200 . Cp A

312 K (1

615 K (2

436.5 K (3

512 K (4

368

 :4

aS
T
RT ln A = LF 1
L
aA
TF

0.95
T

= 12001
T = 512 k
0 .8
600

1.987T ln

( 960.5 oC 18 kj/mol
%99.5 %0.5
.

2.5 oC (1

-4.5 oC (3

-7 oC (2

-3.5 oC (4

: 4
.
LAg .T
0 .5
18000T
X Ba = F

=
T = 3.5
2
100 8.314 1233.5 2
RT Ag

( 610 1220cal/mol
. .
600 :
20 (1

(2

20 (3

2420 (4

:3

"

369

( 1 600 X2=0.2
0.8 . 1
:

0.8 (1

(2

1 (3

(4 0.8

: 1
a1=0.8=X1

1 = 1

P o = cte a p

p
po

=a

( A-B XB=0.8 B,A .

A-B .
A-B 80 B .
G B,A

370

GA=1000-T cal

GB=17000-3T cal
RlnXA=1-1000/T (1

RlnXB=1700-3T (2

RTlnXA=700-2T (3

RTlnXB=1700-3T (4

: 1

) = G A (G A = 1000 T

T
RT ln a AL, L = LF 1
T
F

a lA, l = X A

=> 1000 T = -RT ln XA

=> R ln XA= 1000 + 1
T

( 1 1356
3100cal/mol .

G 1350
)( :
-155/13 (1

-1550/113 (2

0 (3

3100/1356 (4

:2

= G

T
LF 1
TF

1350 1550
31001

=
1356
113

1550
113

G =

>=

371

 :
-1
-2 :..

-3
-4

-5 ) (
-6

372