. .

...
...

2008

1.1.
1.2.
1.3.
1.3.1.
1.3.2.
1.3.3.
1.4.
1.4.1.
1.5.

1
1
3
3
3
4
6
7
8

RUTHERFORD
OHR

SENBERG

10

2.1.
2.2.
2.3.
2.4.
2.5.
2.6.
2.7.
2.8.
2.8.1.
2.8.2.
2.9.
2.10.
2.10.1.
2.10.2.
2.11.
2.12.
2.13.
2.13.1.
2.13.2.
2.13.3.
2.14.

10
11
12
12
13
13
14
16
16
16
17
17
18
19
21
22
24
25
26
27
30

BORN HABER



()






-
-

sp3
sp2
sp

3 -

31

3.1.
3.2.
3.3.
3.3.1.
3.3.2.
3.4.
3.5.
3.6.

31
31
33
33
33
34
34

LAVOISER LAPLACE

HESS


I

3.7.
3.8.
3.9.
3.10.
3.11.

2
3

35
36
37
37
37
38

39

4.1.
4.2.
4.3.
4.4.
4.5.

39
39
40
40

4.5.1.
4.5.1.1.
4.5.1.2.
4.5.1.3.
4.5.1.4.
4.5.1.5.
4.5.2.
4.5.3.
4.5.4.
4.5.5.
4.6.
4.7.
4.8.
4.9.

VANT HOFF

1
2

41
41
41
42
42
43
43
44
44
44
45
45
46
46
47

48

5.1.
5.2.
5.3.
5.3.1.
5.3.2.
5.3.3.
5.4.
5.5.

48
48
48
48
49
50
51
53

LE CHATELIER VANT HOFF




(GULDBERG WAAGE)

59

6.1.
6.2.
6.3.

59
59
60

II

6.4.
6.5.
6.6.
6.7.
6.8.
6.9.
6.10.
6.11.
6.12.
6.13.
6.14.
6.15.
6.16.

&

BRNSTED LOWRY
LEWIS

OSTWALD

pH
HENDERSON HASSELBACH

61
62
63
63
64
64
65
66
67
68
69
73
74

77

7.1.
7.2.
7.3.
7.4.
7.5.
7.6.

77
77
79
84
86
87

NERNST

89

8.1.
8.2.
8.2.1.
8.2.2.
8.2.3.

89
91
91
91

8.3.
8.3.1.
8.3.2.
8.3.3.
8.3.4.
8.3.5.
8.3.6.
8.3.7.
8.4.
8.4.1.

(
)

WAGNER

III

91
92
92
92
92
93
93
93
93
93
95

8.4.2.
8.4.3.
8.5.
8.6.
8.6.1.
8.6.2.
8.6.3.
8.6.4.
8.6.5.
8.6.6.
8.6.7.
8.6.8.

95

95

95

97

97
p
97

98

99

99

100

101

102
105
105
107

IV

. . . , 1

1.1. RUTHERFORD (1911)

,

e- , .
,
: 10-13 cm, 10-8 cm.
Rutherford:
, (
RaC) 20000.

1.2. OHR (1914)

Rutherford. Niels Bohr

2 ( ).
Bohr
=hv .
Bohr:
1. e- :

FCoulomb

me ue2
k e2
1
e2
2
= 2 = F =
= me ue =
r
r
2
2r

(1.1.)

e:
eme : e

ue :
r:
k:

e
.

2. e- ,
mue r = n
h:

r:

h
2

h
:
2

(1.2.)

Plank h=6,62510-23 ergs = 6,62610-34 Js

. . . , 1

r=

h2
n2
2
2
4 me

(1.3.)

n=1 r1=0,529 .
3. e-

= +

e2 e2 e2

=
+ =
2r r 2r

2 2 me 4 1
2
h2
n

(1.4.)

n (
) .
:

2 2 me 4
=
= 2,18 1018 Js
2
h

4.
:

= 2 1 = h =
c:

hc

2 2 me 4
c h3

1
1
2 2
n1 n2

2 .

1.1: .

(1.5.)

. . . , 1
2
L K:
1

2 2 me 4 1 1
= 1,21 105 cm
c h3 12 22

Bohr:
( 1 e-
)
.
, ,
Sommerfield, , ,
.

1.3.

, , ,
Schrdinger, Heisenberg, Sommerfield Dirac
.

. :
h
(Plank De Broglie): =
m

1.3.1. SENBERG (1927)

Heisenberg
.
h
: ( ) ( )
(1.6.)
4

1.3.2.

e-
().
:
= (x, y, z, t) = (x, y, z)sin(2t)

, .

. . . , 1

1.2: .

1.3.3.

Laplace (1.7.):

1 2
= 2 2
t
2

(1.7.)

2 2 2
2 +
+ 2
2
x
y

1
sin (2t ) = 2 4 2 2 sin (2t )

2
2

+
4

= 0
+ 4 = 0

2

2
me2 u e2 2me
2me

=
=

E
=
( V )

2
2
2

h
h
h

(1.8.)

(1.9.)

(1.7.) (1.8.) Schrdinger

2:

+
2

8 2 me
h

(E V ) = 0

(1.10.)

. . . , 1
:

me e- V = f (r)

Schrdinger
e- V = f (r).
H 2
e- ( ).
Schrdinger
(1.10.)
.

,
.
:
(r, , ) = R (r) () ()
3
Schrdinger:
R

n: 1, 2, 3, . ,

: 0, 1, 2, ., n-1

m: -l, ., 0, ., l

(2+1 )

3
Schrdinger :
i) n:

.
ii) :

.
iii) m:

. . . , 1
iv) spin ms ():

e-.
(n, , m, ms)
Schrdinger.

1.3: () 2
() Li.

1.4.

(atomic orbital)
e- .
1.1: .
n
1

2
3

0
0
1
0
1
2
0
1
2
3

1s
2s
2p
3s
3p
3d
4s
4p
4d
4f

m
0
0
-1, 0, 1
0
-1, 0, 1
-2, -1, 0, 1, 2
0
-1, 0, 1
-2, -1, 0, 1, 2
-3, -2, -1, 0, 1, 2, 3

ms

2
K (2)
2
L (8)
6
2
M (18)
6
10
2
6
N (32)
10
14

. . . , 1
1.4.1.

s, p d
1.5. .
n
( ).
L
K

1.4: e- Rb.

1.5: () s, () p () d .

. . . , 1
1.5.

e- 3 :
1.
,

.
, (
) (..
1s, 2s 2p,
3s, 3p 4s ( 3d
):
n=7

7s

7p

7d

7f

7g

n =6

6s

6p

6d

6f

6g

n =5

5s

5p

5d

5f

5g

n =4

4s

4p

4d

4f

n =3

3s

3p

3d

n =2

2s

2p

n =1

1s

2. A Pauli
2 e- (n, , m, ms)
.
A Pauli:
-

e-
n
max e- = 2n2

(1.11.)

8 e-.

3. spin ( Hund)
e- ,
spin.

. . . , 1
2p 2 :

spin : S = + + = 3/2
2 spin
S = - + = 1/2

: e- .
:
19

1s2 2s2 2p6

K

18Ar

: 1s2 2s2 2p6

K

10Ne

4s1

3s2 3p6

: [Ar] 4s1

: [Ne] 3s2 3p6

: 1s2 2s2 2p6

K

29Cu

3s2 3p6

: 1s2 2s2 2p6

K

3s2 3p6
M

4s1 3d10 : [Ar] 4s1 3d10 ( )

N

. . . , 2

2
,
.

2.1.

e- .
:
-
- (

)
- .
2
, .. 2 1 e-
, 1 e- 2 e-
+ + :

1 .

e
+
A

e
B +
B

e-.
2.

+
+

+ -.
3.

+
+

e
2
:

e-
() .
4.

+
+

e
2
:

10

. . . , 2

,
()
.
Linus Pauling

. Pauling
2 1,7,
.
(.
Sanderson, Allred Rochow, Allen, Mulliken Jaff ..).

2.2. (KOSSEL)
.
Na+ Cl-
11Na
17Cl

1e
: [Ne] 3s1

1e
: [Ne] 3s2 3p5 +

11Na
17Cl

: [Ne]

: [Ne] 3s2 3p6

2.

,
.
Ionic Potential ():
( 1 ) (
2, 3, .. ) .
(+) eV/ kJ/mol.
Electron affinity ():
.
( = f (Z)).
,
.
:
(+) :
(-) : .

11

. . . , 2
2.3.


:

(+g ) + X (g ) (s)
:
-

Coulomb ( )
(
)
van der Waals
( ,
0 ).

2.4. BORN HABER (1919)

Hess
.
.
NaCl(s)
:
Na(s) + Cl2(g) NaCl(s)

f = -411 kJ/mol

:
1. :

Na(s) Na(g)

= +108 kJ/mol

2. :

Cl2(g) Cl(g)

= +242/2 kJ/mol

3. :

Na(g) Na+(g) + e-

= +496 kJ/mol

4. :

Cl(g) + e- Cl-(g)

. . = -349 kJ/mol

5. :

Na+(g) + Cl-(g) NaCl(s)

U=?

Hess:
f = + + + . . + U U = -787 kJ/mol.
Born Haber
.

12

. . . , 2
f, , ,
. ..
f
Na(s) + Cl2(g)
NaCl(s)

Na(g)

Cl(g) . . Cl-(g) + Na+(g)

2.1: Born Haber

NaCl.

2.5.
,
( ).
(.. [Fe(H2O)6]3+), (..
[Ni(NH3)4]2+), .

2.6. (VAN DER WAALS)

, :
-
-
- ( London).

2.2: () - ()
.

13

. . . , 2
2.7.

.
:
(
) :
-
- .

2.3: ()
, () , () (.. ) ()
.
(H2O),

(1 atm, 25C) ,
(H2S) (
).

14

. . . , 2

(
) DNA

( 2.5).

2.4: --.

()

()

2.5: () DNA () .

15

. . . , 2
2.8. ()
e- ( )
e- ( ).
.
e- e- e spin , .

.

2.8.1.
e-
e-,
e-.
NH4+:

+ + [

]+

[ ]+

2.8.2.

e-.
( )
7 e- 2
1 e-:





3 e-, ..
He2+ NO
N O
4 e-,
.. LiCH3, BeC2H6
BF3:

16

. . . , 2
H

Li C H

H
H

H C Be C H

H
H

Li
e-

Be 2 e-

F B F

F

B 3
e-

2.9.
:

. e-
. e-
e- .
,
2 ( 2.6),
Li2.

()

()

2.6: ()
2 () Li2.

2.10.
e-

.
17

. . . , 2
.
.

2.10.1.

.
*.

()

()

2.7:
2 () () .
,
, .
( 2.8). e .
.

2.8:
2.

18

. . . , 2

, ( ).
( ).
e- 2
r 2 ( 2.9).
, ro,
.

2.9: 2
.

2.10.2.
2 e- spin
.
.
2 ( 2.10) 2
s (s-s ).

2.10: - s-s 2.

19

. . . , 2
HF ( 2.11)
1s 2pz F (s-p ).

2.11: - s-p
F.
H2O ( 2.12) s
2py, 2pz (8:
[e] 2s2 2px2 2py1 2pz1) 2 s-p (
90).

2.12: - s-p
H2O.

( 2.13).

20

. . . , 2

2.13: H2O.

F2 ( 2.14) 2p
e- - p-p.

2.14: - p-p F2.

2.11. -
-
( s p)
( 2.15 2.16) ( s-s, s-p, p-p).
.

21

. . . , 2

2.15: - : ()
s-s, () s-p () p-p.

2.16: - . ()
s-s, () s-p () p-p.

2.12. -
,
. -
- () .
- ( 2.17 2.18).

22

. . . , 2

2.17: - .

2.18: () - ()
.

- 2 (
2.19) 7: [e] 2s2 2px1 2py1 2pz1
2px, 2py 2pz . 2px .
2py 2pz ( ).
-
.
2.20
-, - - .

23

. . . , 2

2.19: 2 - 2 - .

2.20: -, - - .

2.13.
C. e-
.
C 6C: 1s2 2s2 2px1 2py1 2pz0
e- 2s 2pz,

24

. . . , 2
( 2.21) 6C: 1s2 2s1
2px1 2py1 2pz1 4 sp3
.

2.21: sp3 C.

2.13.1. sp3
( sp3)
.
CH4 ( 2.22) 4 s-sp3
1s sp3
C.

2.22: CH4.
CCl4 - psp3.
- -

.
2.13.2. sp2
25

. . . , 2

5: 1s2 2s2 2px1 2py0 2pz0.
3 e-
2s 2p ( 2.23).
5: 1s2 2s1 2px1
2py1 2pz0.
sp2
120 .

3s
2p
2s
1s

2.23: sp2 .
BF3
3 - p-sp2 2p
F sp2 .
CH2=CH2 ( 2.24) C
2s e- 2 3 e- 2p,
e- (.. 2pz). xy 3 sp2 pz z. :
-

- sp2sp2 C
- s-sp2 C

- p-p C
.

26

. . . , 2

2.24: CH2=CH2.

2.13.3. sp

Be 4Be: 1s2 2s2 2px0 2py0 2pz0.
Be sp
e- s 2p ( 2.25 2.26)
180 ( ).

2.25: sp Be.

27

. . . , 2

2.26: sp.
sp BeH2
- s-sp,
BeCl2 -
p-sp.
CHCH ( 2.27) C
sp 2s
2p .
C sp x- p
. :
- - sp-sp C
- - s-sp C

- - p-p C.

2.27: CHCH.

28

. . . , 2
, CO2 ( 2.28) :
- - p-sp C O
- - p-p C O,
.

2.28: CO2.
2.29
sp, sp2 sp3.

2.29: sp, sp2 sp3.

29

. . . , 2
2.14.

-
.
-1,3
CH2=CH-CH=CH2 ( 2.30) C6H6 ( 2.31).

2.30: -1,3 CH2=CH-CH=CH2.

2.31: C6H6.
30

. . . , 3

3.1.
: .
: .
:
.
:

.
:

(.. P, V, T).
Q W.
:
.
():
,
,
. ,
.
. E .

3.2. 1 ( )

Q
W .

= Q + W

(3.1.)

dE = dQ + dW

(3.2.)

31

. . . , 3

Q =

(3.3.)

1
W =

(3.4.)

.
P
V,
V2

W = P dV

(3.5.)

V1

( ) dV=0
1

= QV

(3.6.)

QV (QV < 0),

.

( ),
W = P (V2 V1 ) = P V

(3.7.)

Q P = ( E 2 + P V2 ) ( E1 + P V1 )

(3.8.)

(H):
.
H = E + P V

(3.9.)

:
()
(QP).

= 2 1 = + ( P V ) = QP

(3.10.)

P V 0 .

32

. . . , 3
(
),

( P V ) = n R T

(3.11.)

= + n R T

(3.12.)

n (moles)
.

3.3.

,
.

3.3.1. LAVOISER LAPLACE

H 1 mole
( )
1 mole ( ).

3.3.2.

+ +
moles A moles B moles
moles =1 atm =25C.
,

C + O2 CO2 - 94 kcal (= -94 kcal)

2C + H2 C2H2 + 54 kcal (= +54 kcal).
H T 25C
25C.

33

. . . , 3
3.4. HESS (1840)

H
.
,
34 ,
, Hess
:

34 + 3 34 + 32 (= -34,03 kcal)
:

34 + 24 + 2

= -18,829 kcal

II:

NaH2PO4 + NaOH Na2HPO4 + H2O

=-12,251 kcal

III:

Na2HPO4 + NaOH Na3PO4 + H2O

=-6,950 kcal

= + + = (-18,829 - 12,251 - 6,95) kcal

= -34,03 kcal.

3.5.

.
:

+ + + +
(3.13):

= ( + + ) ( + + )

(3.13.)

, ,
.

Hess:
f .
, f
CH4 :
o
C(s) + 2H2(g) CH4(g) + CH
4

34

. . . , 3
:

C(s) + O2(g) CO2(g)

=-94,05 kcal

II:

2H2(g) + O2(g) 2H2O(l)

=-268,32 kcal=
=-136,64 kcal

III:

2H2O(l) + CO2(g) CH4(g) + 2O2(g)

=+212,8 kcal

o
o
= + + = (-94,05-136,64 +212,8) kcal CH
=-17,89 kcal
CH
4

3.6.

(C): H
1 mole 1 1C.
V :

CV =

dQV dEV
=
dT
dT

(3.14.).

Av P :

CP =

dQP dH P
=
dT
dT

(3.15.).

n moles
T2

QV = n CV dT

(3.16.)

T1

T2

QP = n C P dT

(3.17.).

T1

QV QP:

QV = n CV Q P = n C P .

H = E + P V

d (P V )
dH dE d ( P V )
=
+
C P = CV +
dT dT
dT
dT

1 mole
d (P V ) d (R T )
d (T )
=
= R
=R
dT
dT
dT

35

(3.19.)

(3.18.).

. . . , 3
(3.20.) Cp CV:
C P + CV = R (3.20.).
A ,

T2

H 2 = H1 + CP dT

(3.21.)

T1

+ + + +

CP
CP = (CPA + CPB + ) (CPA + CPB + )

(3.22.).

3.7.

(S)
:
dS =

dQ .

(3.23.)

Q.
.
P
T2

S = n CP
T1

dT
T

(3.24.)

dT
T

(3.25.)

V
T2

S = n CV
T1

Cp Cv
1 2

S = n CP ln

T2
T1

36

(3.26.)

. . . , 3

S = n CV ln

T2
T1

(3.27.)

3.8. 2

,
.

,
.

3.9. 3

(0 -273,15C).

:
+ + + +

i =1

j =1

S = ( S A + S B ) ( S A + S B ) S = S S

(3.28.)

3.10.

():

= S

(3.29.)

Gibbs (G):
G = H S

(3.30.)

H A G Gibbs
.
:
dA = dE T dS S dT = P dV S dT

37

(3.31.)

. . . , 3

dG = dH T dS S dT = V dP S dT

(3.32.)

G Gibbs (
)

.
:

= 0, G = 0

A :

< 0 G < 0

3.11.

Gibbs

( ).
G Gibbs moles i,
P, moles i
.

i =

G
ni P ,T , n =

(3.33.)

P T, ,
.
P T,
,
(
).

38

. . . , 4

4.1.
,

.
:
- :

- : .

4.2.

.

+ +

.
, :
t1 [A1]
t1 + t [1] + []
(4.1.)

([ 1] + [ ]) [ 1]
[ ]
=
(t1 + t ) t1
t

(4.1.)

t 0,
t

d [ A]
dt

(4.2.)

d [ A]
dt
39

(4.3.)

. . . , 4
4.3.

i) :
(.. ,
, ...)
.
.
ii) :


.
.
.

4.4.

4.1.
t1

dC A
dt

= tan

(4.4.)

t = t1

t1 .

4.1:
( ).

40

. . . , 4
(to=0),
,
4.1.
,
.

4.5.

:
1.
2.
3.
4.
5.

4.5.1.

:
+ + + +

d [ A]
= k [ A] p [ B]q
dt

(4.5.)

[], []: , t
k: ,

(k = f (T)).
(4.5.) .

4.5.1.1.

p q (p + q)
( (4.5.)).

41

. . . , 4

( ) .
, .
0,
(.. ).

+ + + +

.

4.5.1.2. VANT HOFF

( + ).
(AsH3) ()
1 2 :
AsH3 As + 3/2H2

= k [ AsH 3 ]

(1 )

2 + 2 2

= k [H 2 ] [I2 ]

(2 )

: (..
AsH3 As + 3/2H2)
: (..
2 + 2 2).

4.5.1.3.

.
( )
.
, , 1, 2 (..
3/2).
,
.
,
,

42

. . . , 4
,
.

22 3
2, 2 :
2 + 22 2 + 22
:

+ 22 + 2

+ 2 + 2

( )

4.5.1.4. 1

+
t=0 CA= mol/l, t x moles ,
t ( - x).

x dx
t
dx
= k ( x) dx = k (a x) dt
= k dt
x
0
dt

x = (1 e k t )

(4.6.)

4.5.1.5. 2

+ +
( mol/l) , x y moles
t ,

dx
= k ( x) ( y )
dt

(4.7.)

= x=y,
k 2 t
dx
2
=
= k ( x) x =
1 + k t
dt
43

(4.8.)

. . . , 4
>> -y ,

dx
= k ( x)
dt

(4.9.)

1 .

4.5.2.

,
( ).
,

. Arrhenius

k = Ae

E
R T

(4.10.)

ln k = ln A

:
:

E
R T

(4.11.)

(4.11.)
,
lnk 1/T (
k ).
10C
2 3 .

4.5.3.

,

. (
) ( ).

4.5.4.

.
44

. . . , 4
,
, .

4.5.5.

,
.
:
(.. Pt
22 + 2 22).
:
(..
22 CHCl3).
:
(.. HCN, As,
H2S, HgCl2 ..).
:
(..
3+, Fe2O3 Fe).
O :
, ..
CO(g) 2(g)

(g)
2CO(g) + O2(g) 2
2CO2(g) .

:
, ..
Pt(s)
Pt

(s)

22.
22 + 2

4.6.

1.
.
2. .
3. ( )
.
45

. . . , 4
4. ,
.
5.

(1 ).
6. .
,
.

4.7.

+ -.

4.8.

I)
,
.

+
() :

+
+ +
.

II)

.
46

. . . , 4
III)

( , ).

.
.

4.9.

.
.
,


(..
CO 2
CH3OH, CH4 ).

47

. . . , 5

5.1.

,
.
,
,
.

. moles/l
, moles/l
, ,

.
,

.

5.2. LE CHATELIER VANT HOFF

Le Chatelier Vant Hoff,
:

, .

5.3.
3 :
-

5.3.1.
Le Chatelier Vant Hoff,

48

. . . , 5
(
Q).

++-Q
,
,

++

,
,

+++Q

(Q0), .
:

.

,
, ( )
(
,
,
).

5.3.2.
:
-
-
.
Le Chatelier Vant Hoff,

.
3
2 2,

49

. . . , 5
2(g) + 32(g) 23(g)

(
= 11kcal )
3

moles

.

,
(
).
, 3
, V.=1+3=4
V.=2. ,
, 3
( ,
,
).

2 + 2 2
.

5.3.3.
Le Chatelier Vant Hoff


,

.

++

+ + ,

+ + .

,
Guldberg Waage.

50

. . . , 5
5.4. (GULDBERG WAAGE)
:

+ +

(5.1.) (5.2.)

= k [ A] [ ] (5.1.)

= k [ A] [ ] (5.2.)
, P
, ,
k/k
,
.

= k [ A] [ ] = k [ A] [ ]

KC =

[ A] [ ]
[ A] [ ]

[ A] [ ] k
= = KC
k
[ A] [ ]
(5.3.)

[], [], [] []: ,

.

2 + 2 2
2 2 moles ,
x moles 2x moles HI,
(-x) moles 2, (-x) moles 2 2x moles HI
V
:
2

2 x

V
=
.
x x

V
V

51

. . . , 5
(g) + (g) (g) + (g)

,
P ( (5.4.))
, , ( Dalton)

P = PA + PB + PA + PB

(5.4.)

Pi i (5.5.)

Pi =

ni R T
=C i R T
V

(5.5.)

ni, Ci moles ( moles/l) i , R

(R=0,082 latm/moleK), V
.
KC

KP =

PA PB
PA PB

(5.6.)

KP
, KC KP

K P = K C (R T )

(5.7.)

=( + ) ( + ).
,
, KP KC.

3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2(g)
KP

P =

PH42
PH42O

CaCO3

52

. . . , 5
CaCO3(s) CaO(s) + CO2(g)

KC

C = [CO2 ] .

5.5.
1

2
2 . mole 2
7/9 C.
:

moles H2 moles 2 () V l.

2 + 2 2

(moles)
2

7
9

7
9

7
9
14
9

V l
:
[ 2 ] =

2 mole
9 V
l

[I 2 ] =

2 mole
9 V
l

[ I ] =

14 mole
9 V
l

53

. . . , 5
C
2

14

2
[ ]
9 V

KC =
K C = 49
KC =
[ 2 ] [ 2 ]
2 2

9 V 9 V
: C
( ) .

PCl5
PCl3 Cl2. 250C
1 atm.
d=2,69 g/l PCl5 KC
250C. PCl5=208,5.
:

moles PCl5
.

PCl5 PCl3 + Cl2

(moles)
PCl5

PCl3

Cl2

moles
n = ( ) + + n = (1 + )

54

. . . , 5
P V =n R T

m
d

V =

m
d

Lavoisier ( )
m
PCl5
PCI 5
m = m
= 208,5 g

208,5
= (1 + ) R T
d

P = 1 atm, d = 2,69 g/l, R = 0,082 latm/molK T = (273 + 250) K

PCl5
= 0,806 = 80,6 %.
V l
:
(1 0,806)
mol/l
V
0,806
mol/l
[ PCl3 ] = [Cl 2 ] =
V
[ PCl5 ] =

V =

m
d

m = 208,5 g

V =

208,5
208,5
(1 0,806)
V =
l V = 77,5 l [ PCl5 ] =
mol/l
d
2,69
77,5

55

. . . , 5
[ PCl5 ] = 2,5 103

[ PCl3 ] = [Cl2 ] =

mole
l

mole
0,806 mole
[ PCl3 ] = [Cl 2 ] = 10 2
.
77,5
l
l

C 250C
[ PCl3 ] [Cl2 ]
102 102
KC =
mol/l
KC =
[ PCl5 ]
2,5 10 3

K C = 4 102 mol/l.

4 moles
SO2, 2 moles NO2, 6 moles SO3, 5
moles NO. 2 moles
SO2, 8 moles NO2, 5 moles
SO3, 4 moles NO .
.
:

C

6
[ SO3 ] [ NO ]
KC =
KC = V
4
[ SO2 ] [ NO2 ]
V

mol 5

l V
mol 2

l V

mol
l K = 3,75
C
mol

K C = 3,75
4 :
SO2: (4 + 2) = 6 moles
NO2: (2 + 8) = 10 moles
SO3: (6 + 5) = 11 moles
NO: (5 + 4) = 9 moles

56

. . . , 5
mole
l
l
mole
[NO2] = 10/V
l
mole
[SO3] = 11/V
l
mole
[NO] = 9/V
.
l
[SO2] = 6/V

Le Chatelier Vant Hoff

,
Guldberg Waage.
,
KC,
, .
11 9

[ SO3 ] [ NO ]
V
V = 1,65
=
=
[ SO2 ] [ NO2 ] 6 10
V V

< KC,
( = KC).

= KC = 3,75,
SO3 N
SO2 NO2 (
).

mole
)
l

SO2 + NO2 SO3 + NO

SO2

NO2

SO3

NO

6
V
x
V

10
V
x
V

11
V

9
V

6 x

V V

10 x
V

x
V
11 + x
V

x
V
9+ x
V

57

. . . , 5
11 + x 9 + x
11 + x 9 + x

[ SO3 ] [ NO ]
V
V
V
V = 3,75
KC =
KC =

6 x 10 x
6 x 10 x
[ SO2 ] [ NO2 ]

V
V
V
V

2,75 x 2 80 x + 126 = 0 x = 1,67

( x
) :
SO2 = 4,33 moles, NO2 = 8,33 moles, SO3 = 12,67 moles NO = 10,67 moles.

58

. . . , 6

6.1.
.
( )
, .
:

(
).

6.2.
(solubility)
, P
T, .

( P
T) 3 :
:

.
:
.
:

.

59

. . . , 6
6.3.
1. :
x=

ni

(6.1.)

n
i =1

ni moles i.
2. Molarity (M):

olarity =

moles
1l

(6.2.)

3. Molality (m):

molality =

moles
1000 g

(6.3.)

4. % / (% w/w):

(% w/w) =

g
100 g

(6.4.)

5. % / (% w/v):

(% w/v) =

g
100ml

(6.5.)

6. / (% v/v):
(% v/v) =

ml
100ml

(6.6.)

7. Normality ():

Normality =

gr eqs
1l

(6.7.)

:
(mole):
(.B.)
,
(, ), Avogadro
=6.0231023, (.. 1 mole 2SO4 = 98 g = 6.0231023 2SO4)

60

. . . , 6
(gr-eq):
mole
..

1gr eq =

1mole
. .

(6.8.)

(.. 1 gr-eq HCl = 1 mole HCl/1 = 36,5 g, 1 gr-eq H2SO4 = 1 mole H2SO4/2 = 49 g).

n
V

(6.9.)

N=

gr eqs
(6.10.)
V

V l, ()
() (6.11.):

(6.11.)

(..) .

6.4.

,
i Vi
n

V, V = Vi , moles
i =1

1 V1 + N 2 V2 + ... + N i Vi = N V

(6.12.)

.
V2 (N2=0), (6.12.)
(6.13)

1 V1 = N (V1 + V2 )

61

(6.13.)

. . . , 6
6.5. &

T
( ).

,
( 6.1).

6.1:
.

.

2 (
9 mg/l 25C)
,
( 6 mg/l 25C)
,
.
,
.

62

. . . , 6
6.6.

, Svante Arrhenius,
.

+ + .
Arrhenious:
+ (
3+).
Arrhenious:
-.

6.7. BRNSTED LOWRY

() () + +
Brnsted Lowry:
.
Brnsted Lowry:
.

:

Cl + H2O H3O+ + Cl

63

. . . , 6
NaOH + H2O [Na(H2O)]+ + OH

:
(.. HCl, H2SO4).
:
(CH3COOH, NH4OH).
:
moles

moles
=

(6.14.)
moles

6.8. LEWIS
Lewis:
e-.
Lewis:
e-.

6.9.

,

+ 2 3+ +
+ 2 + + Guldberg Waage
, a

b

Ka =

[ H 3O + ] [ A ]
[ HA]

64

(6.15.)

. . . , 6

[ BH + ] [OH ]
Kb =
[ B]

(6.16.).

6.10. OSTWALD

C
.
mole
(
)
l

+ 2 3+ +

3+

(1 a)C

2
=
C
1

(6.17.)

mole
(
)
l

+ 2 + +

(1 a)C

2
C
b =
1

65

(6.18.)

. . . , 6
Ostwald:
.
K
< 10 2 K < 103
C
1 a 1 Ostwald

(6.19.)

(6.20.)

[ H 3O + ] = a C
[OH ] = a C

Ka C

(6.21.)

Kb C

(6.22.)

:
:

> 60 %

10 % < < 60 %

< 10%

6.11.

2
2 + 22 23+ + 2-, =

[ 3 + ]2 [ 2 ]
[ 2 ]

,
2 + 2 3+ + - 1 =

66

[ 3 + ] [ ]
[ 2 ]

. . . , 6

[ 3 + ] [ 2 ]
+ 2 3 + , 2 =
[ ]
-

2-

1 2
:
= 1 2

(6.23.).

6.12.

.
,
C1 ,
, C2.
:
(

mole
)
l

+ 2 3+ +
C1
C1
-

HX + H2O H3O+ + -

3+

C1

C1

C1+C2 C1

(1a)C1

HX
C2
C2

H2O

H3O+

C2

C2

C2+C1

C2

a =

[ H 3O + ] [{ A ]
(a C1 + C2 ) a C1
a =

[ HA]
(1 a ) C1
a =

a 2 C1 + a C2
(1 a )

(6.24.)

1 a 1 2 0 ,

(6.25.)

C2
67

. . . , 6


.

.

6.13. pH

, .

H2O + H2O H3O+ + OH (6.26.)

[ 3 + ] [ ]
[ 2 ]2

(6.26.)

[ 3 + ] [ ]
[ 2 ]2 = = [ 3 + ] [ ]
[ 2 ]2

w = [ 3 + ] [ ]

(6.27.)

=25C P=1 atm S.

Srensen Kw=10-14,

[3+] = [-] =

w = 107 gr-ions/l

(6.28.).

3+ (=10-7 gr-ions/l), Srensen

, pH (pontius Hydrogenii)
pOH :
pH = log[ H 3O + ]

(6.29.)

pH = log[OH ] (6.30.)

Kw
pK w = log K w pKw=14 25C.
(6.28.), (6.29.) (6.30.), 25C :

68

. . . , 6
pK w = pH + pOH

(6.31.)

pH,
, :

0

14

:
pH pOH Srensen
, pH pOH
(< 0 > 14).

pH pH
< 0 pH > 14 .
pH
,
( conductivity
.

S (Siemens) 1 S=1 -1).
pH ,
3+ -
(6.32.) (6.33.)
[ H 3O + ] = 10 pH
[OH ] = 10 pOH = 1014 pH

(6.32.)
(6.33.)

6.14. HENDERSON - HASSELBACH

pH

.

:

.. / (CH3COOH / CH3COONa)

.. / (NH3 / NH4Cl)

69

. . . , 6

.. CH3COOH
NaOH,

CH3COOH + NaOH CH3COONa + H2O.

3+
CH3COO-,

H3O+ + CH3COO- CH3COOH

, . pH
.
HA/MA ( ),
:
HA + H2O H3O+ + A-

+ + -

[H 3 O + ] [ ]
[ ]
[]
[H 3 O + ] = =

[ ]
[ ]
[ ]
pH = pK a + log

[ ]
(6.34.).
[]

.
B/BA (
+ ),
:
+ 2 + + -

+ + -

(6.35.) pOH
b
pH = pK b + log

[ ]
[ ]

70

(6.35.)

. . . , 6

(6.34.) (6.35.) Henderson

[ ]
[ ]
Hasselbach .

[]
[ ]
.
1:
pH HCl 1,810-5 ;

( )
1,810-8 HCl 1,810-8 H3O+
Cl + H2O H3O+ + Cl-

pH = log(1,8 105 ) = 4,75

2:
pH / (CH3COOH /
CH3COONa) 0,1 ; = 1,810-5.

( )

CH3COOH + H2O CH3COO- + H3O+

CH3COONa CH3COO- + Na+

Henderson Hasselbach
,
pH = log(1,8 10 5 ) + log

0,1
= 4,75
0,1

3:
HCl 1,810-5 1,810-5
moles a,
. pH ;

71

. . . , 6
HCl + a aCl + H2O

1,810-5 HCI 1,810-5

NaOH. ,
H2O [H3O+] = 10-7 , pH
7 (pH = 7).
4:
0,1M CH3COOH / 0,1M CH3COONa
1,810-5 mol Na,
. pH ;

Na

CH3COOH + Na CH3COOa + H2O

1,810-5 mol CH3COOH

1,810-5 mol OH 1,810-5 mol
CH3COONa.

(

mole
)
l

CH3COOH + H2O CH3COO- + H3O+

CH3COOH
0,1 -1,810-5
x
0,1 -1,810-5-x

CH3COO-

H3O+

x+0,1+1,810-5

CH3COONa CH3COO- + Na+

CH3COO-

Na+

0,1+1,810-5

0,1+1,810-5

x+0,1+1,810-5

0,1+1,810-5

CH3COONa
0,1+1,810-5
0,1+1,810-5
-

x (x + 0,1 + 1,8 10-5 )

x 2 + (0,1 + 1,8 10-5 )
5
1
,
8
10

0,1 x - 1,8 10-5

0,1 x - 1,8 10- 5

x = 1,8 10-5 pH = 4,75

Henderson Hasselbach
pH = pK a + log

0,1 + 1,8 10 5
[CH 3COO ]

pH = log(1,8 10 5 ) + log
5
[CH 3COOH ]
0,1 1,8 10

pH = 4,75 + 1,2 105 pH 4,75

72

. . . , 6

, ( 3) pH
4,75 7 ,
( Na)
pH .

6.15.

.


AgCl(s) Ag+ + Cl-

Ag+ Cl-
AgCl(s) , Ag+ Cl .

[Ag + ] [Cl- ]
[ Ag + ] [Cl ] = K [AgCl(s) ] = K sp =
[AgCl(s) ]

,
sp (solubility product),
.
sp
.
Ag+ Cl-
sp,
:

[ Ag + ] [Cl ] < K sp

[ Ag + ] [Cl ] = K sp

[ Ag + ] [Cl ] > K sp

AgCl [ Ag + ] [Cl ] = K sp .
Ag3PO4

73

. . . , 6
Ag3PO4(s) 3Ag+ + PO43-

sp = [ Ag + ]3 [ PO43 ] .
5:
Ca3(PO4)2 25C
sp=1,310-32;

Ca3(PO4)2

Ca3(PO4)2(s) 3Ca2+ + 2PO43-

x mol/lt Ca3(PO4)2(s)
3x gr-ions Ca2+/l 2x gr-ions PO43-/l.
sp

spCa ( PO ) = [Ca 2+ ]3 [ PO43 ] 2 spCa ( PO ) = (3 x) 3 (2 x) 2

3

4 2

spCa ( PO )
3

x=

108

4 2

x=5

4 2

mol
1,3 10 32
.
x = 1,64 10 7
l
108

6.16. (DEBYE HUCKEL)

.

. ,
.
,

r = 0,281

:
:
J:

2 J

(6.36.)

74

. . . , 6

1 n
J = Ci Z i
2 i =1
Ci:
Zi:

(6.37.)

CuSO4 0,01M
NaCl 0,01M
CuSO4 Cu2+ + SO42-

NaCl Na+ + Cl-

J CuSO4 =

1
(0,01 22 + 0,01 22 ) = 0,04
2

J NaCl =

1
(0,01 12 + 0,01 12 ) = 0,01
2

.
, .
() <1:
C
.
, C

= C

(6.38.)

+ + -

[ + ] [ ]
=
[ ]

+

(6.39.)

.
( )
(6.40.)
3

e2 2 2

Z2 2 J
ln =
3
k
T

10

75

(6.40.)

. . . , 6

e:
:
:
J:
:
k:

NA:

Boltzmann 1,380621016 erg/grad
Avogadro 6,0231023.

25C :
log = 0,5065 Z 2 2 J

(6.41.)

25C
log = 0,5065 Z + Z 2 J

(6.42.)

Z+ - .

,
.

76

. . . , 7

7.1.

.

,
.

,

.

.

7.2.
(CuS4) (Zn)
(Cu)
Zn Zn, o
Zn2+.
:
Zn + CuS4 Cu + ZnS4 Q

Zn + Cu2+ Cu + Zn2+ Q.
7.1
, Daniel.

.
:
nSO4 CuS4.

.

o
U, (..
Cl, 3)
( 7.2).

77

. . . , 7

7.1: Daniel.

7.2: Daniel .
nSO4
Zn
CuS4 Cu. Av
, ,

Zn
Zn Zn2+ + 2e

78

. . . , 7
Cu
Cu2+ + 2e- Cu


Zn + CuS4 Cu + ZnS4 Q
,
7.1
.
Zn Zn2+,
Cu,
Cu2+ ,
Cu.
,
. '
(..
Zn Zn2+)
,
(.. Cu2+ Cu)
.


,
' :
-
-
- .

7.3.
(Oxidation):
,
(. .). ,
().
, (..
C ).
(Reduction):
,
(. .). ,
(+).
, (..
KMnO4, 2Cr2O7).

79

. . . , 7

,

+ ne n
.
, ,

.
, ,
.
, ()
.
,
( ) '
7.1.
, ,
, G
.

G (7.1.)

G = n F

(7.1.)

F Faraday 96487 C (Coulomb) 23,061

kcal/Volt.
()
2
3+ P T.
7.3,
.
' , ,
Pt, HCl
(=1) 25C.
Pt
2, 1 atm, 2
3+ :
2 + 22 2 3+ + 2e
Pt, ,
' .
7.1 (.. Cu),
, Pt,

80

. . . , 7
1 atm, (
) 1
25C.

( =25C, =1
Pi=l atm), ()
o
E25
.
o
C

7.3: 2
.

o
0 ( E25
o ( H 2 ) = 0 ),
C
7.3.
. ,

2,
0.
, ..
Cu, 7.3,
, .. CuSO4 =1
=25C. :
():

( )

2 + 22 2 3+ + 2e-

(+):

( )

Cu2+ + 2e- Cu

2 + Cu2+ + 22 2 3+ + Cu

o
Cu E25
o ( Cu ) = +0 ,34V .
C

81

. . . , 7
,
,

. , .. ,
2, ,
.
, ( .. Cu)
.

.
,
. ,

,
,

.
,

7.1.
7.1: .

(V)

Li+ + e- Li
+ + e-
Ca2+ + 2e- Ca
Na+ + e- Na
Mg2+ + 2e- Mg
Al3+ + 3e- Al
Zn2+ + 2e- Zn
Fe2+ + 2e- Fe
Cr3+ + 3e- Cr
Sn2+ + 2e- Sn
Pb2+ + 2e- Pb
2H+ + 2e- H2
Cu2+ + 2e- Cu
Au3+ + 3e- Au

- 3,05
- 2,92
- 2,76
- 2,71
- 1,87
- 1,69
- 0,76
- 0,41
- 0,50
- 0,14
- 0,13
0,00
+ 0,34
+ 1,36

.. Li ,
(-3,05 V)
.
(

82

. . . , 7
)
( 2 .. Cu, Au,
Pt ..),
() ,
.
(
Daniel),
Zn2+ + 2e- Zn,

=-0,76 V

Cu2+ + 2e- Cu, =+0,34 V

o
o
( Zn) = 0,76V < E25
E25
o
o ( Cu ) = +0 ,34V , Zn
C
C

Cu2+.

Zn2+ + 2e- Zn,

=-0,76 V

2 3+ + 2e- 2 + 22, =0 V
Zn
2:
Zn + 2 3+ Zn2+ + 2 + 22
2.

.
,
,
.
H2 Cu2+ Cu,
, ,
.
, ,
. H2/Cu,

Pt, H3O+ (=1) / 2 (P=1 atm) // Cu2+ (=1) / Cu

83

. . . , 7
7.4. NERNST

,
, (=1, =1
atm, =25C=298 ). Av o ,
()
, .
.. :
Co2+ + 2e- Co,

=-0,277 V

Ni2+ + 2e- Ni,

=-0,250 V

:
Co + Ni2+ Co2+ + Ni,

=+0,03 V

Ni2+ 0,01
Co2+ 1 M,
.


(
) .
:
+ + + +
(7.2.), Nernst:

= (
n:
:
R:

F:

a
R T
ln A
nF
aA

a A
R T
)
ln
nF
aA

(7.2.)

Faraday.

T=25C=298 K Faraday (F)

(R) ,

84

. . . , 7
:
p (Ox) = q (Red)
Ox Red
, Nernst :

= +

ap
0,059
log qOx
n
aRe d

(7.3.)

,

1. ,
Co/Ni 7.3., =0,03 V, n=2,
(Ni2+)=0,01 (Co2+)=1,00 M,
:
Co + Ni2+ Co2+ + Ni
Ni2+ Co2+ :

= 0,03V +

0,059
0,01
log
V = 0,029V
2
1

.
:
Co2+ + Ni Co + Ni2+
=0, Nernst

= 0,059 log(H 3 O + ) E = 0,059 pH

(7.4.)

.. HCl 0.01 ( pH=2), :

= 0,059 2V = 0,118V
, , ..
,
Co2+ Ni2+,
, 0. ,
, :
+ + + +

85

. . . , 7
Gibbs =0 ( 5).
Nernst
, :
R T
=
ln
(7.5.).
nF
(7.1.) (7.5.)

G o = R T ln K

(7.6.)

, .
(7.5.)

=e

n F
R T

K =e

G o
R T

(7.7.)

G,
.

7.5.

()
.
.
7.4. . ,
,
' ,
(.. ),
.
,
ZnCl2, Zn2+
Cl-, :
(+):

2Cl- + 2e- Cl2

():

Zn2+ + 2e- Zn

2Cl- + Zn2+ Cl2 + Zn

86

. . . , 7
(+) ,

() .

7.4: .

,
,
.
'
( ). ,
,

.

7.6.

1832 1833 Faraday ,

:
1. ,
, o
( ) o .

1 Faraday
,
' , (7.8.):

87

. . . , 7
m = k q = k i t
m:
q:
i:
t:

k:

(7.8.)

2. ,
,
,
, :

m=
m:
n:
q:
F:
i:
t:

..:

M . .
M . .
q =
i t
nF
nF

(7.9.)

Faraday


.. .

2 Faraday
Faraday (F)
(1
greq) .
M .B.
M .B.
,

Faraday (F),
n
nF

1 C.

88

. . . , 8

8.1.
,
,

.
.
.

' ,
,
.
,
,
, / .
( )
,
.

, 7


.

,
.
2 . , ,
,
.
7,

, 7.1.

,
(.. Li
(-3,05 V)
).
( 2 ..
Cu, Au, Pt ..),
()
,
.

89

. . . , 8
7.1: .

(V)

Li+ + e- Li
+ + e-
Ca2+ + 2e- Ca
Na+ + e- Na
Mg2+ + 2e- Mg
Al3+ + 3e- Al
Zn2+ + 2e- Zn
Fe2+ + 2e- Fe
Cr3+ + 3e- Cr
Sn2+ + 2e- Sn
Pb2+ + 2e- Pb
2H+ + 2e- H2
Cu2+ + 2e- Cu
Au3+ + 3e- Au

- 3,05
- 2,92
- 2,76
- 2,71
- 1,87
- 1,69
- 0,76
- 0,41
- 0,50
- 0,14
- 0,13
0,00
+ 0,34
+ 1,36

,
.
,

,

.
, ,
.

..:
- (..
)

-
,
(Concentration cells)
- ,
,
.. ,
(Stress cells) .

( ).

90

. . . , 8
8.2.
.
, .
,
,
.
:

8.2.1.

( 2),
( ) .

.
, . '

.
(..
CO2, SO2, H2S, xy ...
)
.
.. :
4Fe + 32 + x2O 2Fe2O3(2O)x

8.2.2.
.
,
,
.

8.2.3.
)

.
' .
.
Zn H2SO4
:

91

. . . , 8
Zn + H2SO4 ZnSO4 + H2

8.3.
:

8.3.1.
,
.
, ,
.
.
Cr ( = -0,74V),
Zn ( = -0,76 V), i ( = -0,89 V) l ( = -1,71 V)
Fe ( =-0,41V). Cr,
Zn, i, l ,
,
,
. Fe
,
.

8.3.2.

.
.


.

8.3.3.
,
.
.

( p )
.

92

. . . , 8
( p) (p=7)
( pH).

8.3.4.

.



.

8.3.5.

.

8.3.6.

,
,
.
, , ,
.

8.3.7.


.
.

8.4.

.
,
:

93

. . . , 8

1. r1 dh

dt ,

r1 =

dh
dt

(8.1.)

2. r2 dm
dt
,

r2 =

dm
dt

(8.2.)

m = pS h
m:
p:
S:

h:

(8.3.)

(8.1.), (8.2.) (8.3.) :

r2 =

dm
dh
r2 = p S
r2 = p S r1
dt
dt

(8.4.)

(8.4.)
:

r=

dy
dt

(8.5.)

r:

dy:

dt: dy.

.

.
r(t)
, (8.5.)

94

. . . , 8
dy = r (t ) dt (8.6.)
, y 0 y t 0 t,
y=y(t).
t. ,
y=y(t), (8.5.)
r (t).
y= y(t)

.
y=y(t),
:

8.4.1. WAGNER

:
y2 = K t

(8.7.)

8.4.2.

y = K t

(8.8.)

8.4.3.

(..
) :
y = e K t

(8.9.).

8.5.

95

. . . , 8
.
:
(i)
(ii)
(iii) (.. )
( )
(iv)

(v) (..
),
,
(vi) : ,
, ,
.

(0,003 % w/v),
.
(vii) :
.
,
, ,
. '
, ,
.
:

,
(),
.
.
(viii) :

. ,
()
.
Mg ,
Mg.
(ix) :
()
(.. , , , ...)
(.. , , ...).

96

. . . , 8
(.. ),
.
Fe, / (Fe/Sn)
.
(..
),
,
/ (Zn/Fe), n
Fe.
(x) : ,
(.. , , ,
...), .

8.6.

8.6.1.

()
(.. , ...)
.
,
.

, (..
)
.

8.6.2. p

Portland
:
8.1: , Portland.

3CaOSiO2

C3S

45-65%

2CaOSiO2

C2S

15-35%

3CaOAl2O3

C3A

4-14%

C4AF

10-18%

4CaOAl2O3Fe2O3

97

(% w/w)

. . . , 8
H ()
,
(
).
, ,
, :
2(2CaOSiO2) + 42O 3CaO2SiO232O + Ca(OH)2
2(3CaOSiO2) + 62O 3CaO2SiO232O + 3Ca(OH)2
3CaOAl2O3 + 62O 3CaOAl2O362O
4CaOAl2O3Fe2O3 + x2O 3CaOAl2O362O + CaOFe2O3x2O

(Ca(OH)2). 25 %
,
.

p, 12,5 13,9.


() .

( ),
Cl- ,
( )
.
.

8.6.3.

, p .
p.
CO2
0.03 % w/w.
CO2
, ,
SO2 (
). CO2
:
Ca(OH)2 + 2O + CO2 CaCO3 + 22O
CaCO3
.

98

. . . , 8
,
, ,
- p 9,5
.
, , ,
, ....

8.6.4.

.

Ca(OH)2.
. (W/C) .
, 40 % .
,
0,5 0,6.

.
,
( 10 15 %) .
. .
.
. .
.
.
(... 1997).

8.6.5.

() . , ,
:

99

. . . , 8

()
.

/
/
(/ ,
...).
4 ,
.

(..
).
.
,
( ) ,
()
.
.

. ,
.

,
.

8.6.6.

.
1. ( ..)
, .
2. ,

3.
4.

5. .
,
( )
0,1 % w/v CH3CH2OH.

pH .

100

. . . , 8

p > 9,0

p 8,4

p < 8,4

8.6.7.

. ,
,
.
:
1.
.
.
2. .
/
.
3. .
% w/w
. (ACI)
:
(
) 0,08 % w/w.
0,10 % w/w
0,20 % w/w.
0,4 % w/w
0,6 % w/w
.

4.
(..
). ,
,
.
5. .
6. .
7. .

101

. . . , 8
8. .
9. (corrosion inhibitors)
.

,

.
.
, ,

.

8.6.8.

(. .). . .
1973
,
,
, .
. .

.
. .
,
,
,
, .
. . :

, ,

.

().
. , , ,
,
(>15 mm)

102

. . . , 8
.
, .

, (-0,85 V
Cu/CuSO4)
:

.
.

,
,

.
,

.
,

, .
,

. ,
1,10 V 0,90 V
. (
) ,
,
.

103

. . . , 8

104

. . . ,

1. D. D. Ebbing, S. D. Gammon, , 6 , .
, 2002
2. J. N. Murell, S. F. A. Kettle, J. N. Tedder,
, 2 , ,
2006
3. . . , 1. , ,
1999
4. . . , 2. , 1 ,
, 1986
5. . . , , 2 ,
, 2006
6. . , . , , 1 ,
, 1995
7. . , , , 1994
8. . , & &
, , 2007
9. . , . , , ,
2003
10. . . , , 2 , ,
2003
11. . , , , 2005
12. . , . , . ,
, . , 2006
13. . . , , 3 , .
, 1999
14. . . , 441 , 2 ,
. , 2004
15. I. S. Butler, J. F. Harrod, , ,
, 1995
16. . , , ,
1995
17. . , , ...,
1990
18. . , , ..., 1990
19. . , . , ,
1983
20. . , , ...., 1972
21. . , , 1980
22. . , ,
, 1976
23. . . , , 3 ,
, 1954
24. . , , ,
1996

105

. . . ,
25. . , , ..., 1990
26. . , , ..., 1997
27. . . , , 5
, . , 1991
28. . . , , 11 ,
. , 1992
29. . . , , 5 , .
, 1992
30. . . ,
, . , 1999
31. . . , , . , 1990
32. R. L. Pecsok, L. D. Shields, T. Cairns, I. G. Mc William,
, 2 , . . , 1980
33. J. Mc Murry, , 6 ,
, 2007
34. J. Mc Murry, , 5 ,
, 2006
35. . . , , 2 , ,
1989
36. . . , , 2 , ,
1989
37. . . , . . , , ,
1996
38. . , , , 1995
39. . , ,
, 1991
40. P. W. Atkins, , 3 ,
, 2005
41. P. W. Atkins, , 3 ,
, 2005
42. . , , . , 1999
43. . . , , , ,
1994
44. . , , 2: , ,
1994
45. . , . , , 2 ,
, 1992
46. . , . , ,
, 1994
47. . . , ,
, 2000
48. . . , , ,
, 1994.

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