Sxoliko Vivlio PDF

1
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.
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. ,
.

, -
, .
H
, - ,
, .

,
.
,
.
:
.
.
-
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.
...,
. .
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.
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,
.
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, , -
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, , .
H
22-0188-02.indd 5
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.. , , . , 1992.
.. , H , . , 1994.
.. , , . , , 1995.
.. N.E. , , 4 , , 1970.
. , , . , 1980.
. , . , K. , . , . , B , , , 1996.
. , . , K. , . , . , , ,
, , 1997.
. , K. , N. , N. , . , B , , ,
1998.
. , K. , N. , N. , . , , , ,
1998.
. , . , K. , -, . , 1995.
. , . , , . , 1997.
. , . , K. , , . , 1995.
. , . , K. , A , . , 1996.
. , . , B , , 1998.
B. , A. , . , - , , 1992.
B. , A. , . , - , , 1992.
. , . , , , 1983.
, A
, , , 1997.
, A (
, , , 1997.
.. , , . . - . , , 1998.
.. , A.M. , , , , . , 1994.
. , , . , 1982.
. , , . , 1999.
Z. , , . , 1997.
. , , . , 2 , 1994.
K. , K. , , , 1993.
. , . , A , , 1998.
A. , . , B , , 1986.
A. , . , B - , , 1986.
J. Mc Murry, , , , 1998.
Morrison Boyd, , , 1991.
.K. , , . , 1996.
.K. , , . , 1996.
. , B. , . , K. , , ,
1998.
.. , , , 1981.
. , , . . , 1988.
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7
.. , , & , . , 1996.
K.A. , , , . , 1997.
P.W. Atkins, H , . , 1993.
P.W. Atkins, , . , 1995.
R.P. Feynman, , . , 1998.
Morisson and Boyd, , 4 , . . , 1988.
Nuffield Advanced Science, - 1 11, . .. , 1998.
D. Abbot, Advanced Level Chemistry Basic Exercises, J.M. Dent and Sons Ltd., London, 1967.
P.W. Atkins, J.A. Beran, General Chemistry, 2nd Ed., Freeman and Company, 1990.
P.W. Atkins, L. Jones, Chemistry, 3rd Ed., Freeman and Company, 1997.
P.W. Atkins, Molecules, W.H. Freeman and Company, New York, 1987.
Becker-Wentworth, General Chemistry, Houghton Mifflin Co, Boston, 1980.
J.E. Brady, General Chemistry, John Wiley and Sons, 5th Ed., 1990.
T. Brown, H. Le May, B. Bursten, Chemistry - The Central Science, 7th Ed., Prentice - Hall, 1997.
Chadwick, Chemistry, George Allen & Unwin Ltd., London, 1977.
R. Chang, Chemistry, 6th Ed., McGraw-Hill, 1998.
G.W. Daub, W. Seese, Basic Chemistry, Prentice - Hall, 1996.
D.D. Ebbing, General Chemistry, 5th Ed., Houghton Miffin Co, 1996.
W. Eisner, et al. Elemente Chemie I, Ernst Klett Verlag, Stuttgart, 1986.
M. Freemantle, Chemistry in Action, Mac Milan Education, London, 1987.
R.G. Gillespie, D. Humphreys, N.C. Baird, E.A. Robinsen, Chemistry, 2nd Ed., Allyn and Bacon, Massachusetts, 1989.
G. Hill, Chemistry Counts, Hodder and Stoughton, London, 1986.
G. Hill and J. Holman, Chemistry in Context, 4th Ed., Nelson, 1995.
J.W. Hill and D.K. Kolb, Chemistry for Changing Times, Prentice - Hall, 1998.
J.W. Hill and R.H. Petrucci, General Chemistry, Prentice - Hall, 1996.
N.R. Kneen, M.J. Rogers, P. Simpson, Chemistry, Addison-Wesley Ltd., 1972.
J.C. Kotz and P. Treichel, Chemistry and Chemical Reactivity, 3rd Ed., Saunders College Publishing, USA, 1996.
P. Lebrun, A. Cunnighton, R. Vogel, Chimie 1er D.E., Hatier, 1979.
T. Lister and J. Renshaw, Understanding Chemistry, 2nd Ed., Stanley Thornes Ltd., 1991.
H. Meislich, H. Nechamkin, J. Sharefkin, Organic Chemistry, McGraw-Hill, 1977.
F.J. Moore, A History of Chemistry, McGraw-Hill, 1939.
Murray S. Peter, Principles of Organic Chemistry, 2nd Ed., Heinemann Educational, 1977.
E.N. Rausden, A-Level Chemistry, Stanley Thornes Ltd., 1985.
J.L. Rosenberg, College Chemistry, 5th Ed., McGraw-Hill Book Company, 1972.
Richards, Cram, Hammond, Elements of Organic Chemistry, McGraw-Hill, 1967.
K.K. Sharma, D.S. Sharma, Problems in Organic Chemistry, Vikas Publishing House Ltd., 1994.
P. Yurkanis Bruice, Organic Chemistry, Prentice - Hall, 1992.
S. Zumdahl, Chemical Principles, Houghton Mifflin, 3rd Ed., 1998.
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1.1 - .................................................................................................... 13
1.2 . ............................................................................ 22
1.3 ( s, p, d, f) - ............................................ 26
1.4 ............................................................................ 32
1.5 - ..................................................................................... 36
: (STM)......................................................... 45
: ......................................................................... 47
- ............................................................................................... 48
- - ......................................................................................... 50
2.1 ................................................................................................ 63
2.2 , ..................................... 69
2.3 ................................................................................................................... 75
2.4
........................................................................................... 83
: .................................................................... 86
- ............................................................................................... 87
- - ......................................................................................... 88
3 -
3.1 - ............................................................................................................................. 97
3.2 - ....................................................................................................... 102
3.3 - - pH................................................................................ 105
3.4 ........................................................................................................... 115
3.5 ............................................................................................................. 119
3.6 - ............................................................................................................. 124
3.7 ............................................................................................................ 132
: ............................................................. 139
- ............................................................................................ 141
- - ...................................................................................... 143
4.1 .................................................................................................................. 163

4.2 .......................................................................................... 169
4.3 ............................................................................................................................... 174
: ............................................................................... 178
- ............................................................................................. 180
- - ....................................................................................... 181
5.1 - - .................... 189

5.2 ( ) ....................................................... 201
5.3 .......... 215
5.4 - ........................................................................................... 237
: D L ......................................................... 254
- ............................................................................................. 255
- - ....................................................................................... 258
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10
22-0188-02.indd 10
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:
Bohr,
Planck.
,
de Broglie,
Heisenberg
Schrdinger.
.
, .
.
(
Pauli, , Hund). ,
.

. ,
, s, p, d, f.
o Na Ar (3
) .

.
: ,

.
Lewis ( ).
VSEPR
.
22-0188-02.indd 11
1.1 -
1.2
1.3

( s, p, d, f)
1.4

1.5

- ( VSEPR)
-

,
...

-

-
,
, ,
,

C.A. Coulson
5/11/2013 11:34:46
,
, .
, , .
, ,
, ,
.

.
, , .
22-0188-02.indd 12
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13
1

. ,
Bohr , .
, .
( Pauli,
Hund)
.
.
( .. ) .
.
,
. Lewis
.
.
. ,

. VSEPR
.
1.1
- K

Bohr. Bohr (1913)
Rutherford,
Bohr
. Bohr
:
1 ( )

. ,
.
Niels Bohr (1885-1962).

. Rutherford ( Manchester)
Thomson (
Cambridge).

.

Nobel,
Heisenberg Pauli.
Bohr

(
),

.

,
Bohr
,

(
).
Nobel
1922,

107
Ns (nielsbohrium).
22-0188-02.indd 13
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14

:
2 ,18 10 18
J
n2
n = 1, 2, 3, ... ,
.

n, .
, ,
.
( = 0),
. ,
.
,
. ,
, .. .
En =

Bohr. To e

. e-
,

.
2 ( )

,
.
,
,
.
Planck (1900),
(
), :

().
.
Planck , , , . :

(10-10-10-8 s).

.
.
E=hv
h: Planck, 6,63 . 10-34 J s.
Planck, Bohr
:
= E f Ei = h v
, , (i), (Ef),
, . Bohr
.
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15

( 1.1).
().
().
1.1
.

(
),
.
.
,

,

( ).

.

. ,

, ,
, ,

.
Bohr, ,
,
( , .. He, Li ..)
.
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16

De Broglie (1924):
, ,
, .. , ,
() ( ).
( ) , ,
,
.

,
.
, , , m, , u,
:
h
=
mu

. .. , 65 km h-1
< 10-33 m,
. ,
( 10-10 m).

()
Heisenberg (1927):
Max Planck (1858-1947).

.
,

: , ,
.
, Planck
.

.
Planck
.

1918.

(p = m u) , .. .
,
(.. ), ,

, . , ..
, . ,

, . , , , .. ,
, , .

,
Bohr.
, ,
.
22-0188-02.indd 16

(),

(),

.
5/11/2013 11:34:51
17
Schrdinger ,

. ,
.
.
,
.
Schrdinger , n ,
, Bohr ( ).
,
Bohr (
). , Schrdinger
, (n) .
Bohr.

.. (x, y, z), x, y, z .
. ,
, ,
( = 0 0
). , 2 ,
2
.
:
: = 0,1 2 = 0,01
: = -0,3 2 = 0,09
,
.
:
L. de Broglie (1892-1977).
, (
).

1929

.

.
W. Heisenberg (1901-1976).
Bohr,
32 ,

.
2 ( -e2, -e )

.
Schrdinger

.
,
, , . , ,

.
. Schrdinger (1887-1961).
.
,

.

1933.

Planck
.
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18
, ,
( 2) ,
.
1.2
: )
) ) ().

().
( .) ,
,
.
. ,
. ,
.
,
(2),
, .. 90-99% .
, (2)
(), ( ).
22-0188-02.indd 18
...
. (
)

... .
...

Schrdinger
,
Schrdinger ...
... Bohr
,

...
( -
)

V,
,

V.
V
,

.

V..
(. 1.
)
...

, 2
( )

,
...
(J. McMurry
1)
5/11/2013 11:34:54
19

Bohr (n)
, .
( ). Schrdinger
(n), (l)
(ml). (n, l, ml) Schrdinger,
.

(.. He+, Li2+).
, ,
spin (ms),

.
(n) 1, 2, 3 ...
Bohr
. :

( ).
n , , .

( Bohr).
(n)
.
, :
, n
....
....
(l) n, 0, 1, 2, ... (n - 1).

l ().
n l .
.
,
:

, n.

- .

.
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20
, l
....
....
(ml)
l -l, (-l + 1), ..., 0,...l, (l - 1), +l
ml
a x, y, z.

n l.

s: sharp ()
p: principal ()
d: diffuse ()
f: fundamental ().
,
,
.

.
l
(2l + 1) . :
l = 0 ( s), (2 0 + 1) = 1 s
l = 1 ( p), (2 1 + 1) = 3 p
p :
, ml
+ 1
-1
px
pz
py

, n, l, ml.
spin (ms) +1/2 -1/2,

.
spin
(spin).
, ms = +1/2, spin spin
( ), ms = -1/2,
spin spin ( ).
.
, (spin).
spin
, .
,
. :
(n, l, ml, ms) , :
()
()

spin

22-0188-02.indd 20
ms = 1/2
ms = + 1/2

(spin ),

, .
ms = -1/2
ms = +1/2.
5/11/2013 11:34:54
21

,

. ( 2)
.
90-99% .
s (l = 0) ,

. s ,
. n,
s, .

.

.

.
,

,

.
(Morrison Boyd
1)
1.3 1s, 2s 3s ( 2s ).
.
, p ,
1.4.
, ..
.
p , , s,
.
, n 2,
p , . , px, py pz,
, x, y z,
1.4. , s, p . ,
n
p, .
, d (l = 2) (ml: -2, -1, 0, +1, +2) -
s ( s2 )

1s, 2s, 3s .
22-0188-02.indd 21
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22
,
. f (l = 3)
7 (ml: -3, -2, -1, 0, +1, +2, +3).

.

,

.

,

,

(90-95%).
(J. McMurry
1)
1.4 . p , px, py pz
( 2s ) . 2pz 3pz. p
.
1.2
, 1s.
.
. .
, ,
() . , ,

.
22-0188-02.indd 22

p
( p2).
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23
Pauli
Pauli

(n, l, ml , ms). ,
.

, :
1.1 , ,
n
ml
ms
+1/2, -1/2
+1/2, -1/2
-1
0
+1
+1/2, -1/2
+1/2, -1/2
+1/2, -1/2
+1/2, -1/2
-1
0
+1
+1/2, -1/2
+1/2, -1/2
+1/2, -1/2
-2
-1
0
+1
+2
+1/2, -1/2
+1/2, -1/2
+1/2, -1/2
+1/2, -1/2
+1/2, -1/2
(n = 1) s (l = 0),
s,

: (1, 0, 0,
+1/2) (1, 0, 0, -1/2)
L (n = 2) (l = 0, 1), s p .
s
,
p 3 2 = 6
.
W. Pauli (1900-1958).
.

Einstein.

.
(n = 3) (l = 0, 1, 2), s, p d
. s
,
p 3 2 = 6
( ) d
5 2 = 10 ( ).
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24
(n = 4) 4
(l = 0, 1, 2, 3), s, p, d, f , (f)
7 (ml = -3, -2, -1, 0, +1, +2, +3)
2 7 = 14.
1.2
. 5g 6f .. .
1.2

1 s2
2 s2 p 6
3 s2 p6 d10
4 s2 p6 d10 f 14
5 s2 p6 d10 f 14
6 s2 p6 d10
7 s2

Schrdinger
( .. He+,
Li2+ ..).

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

, .
, o
,
,
.
:

.

,
, .

, , . ,
- , ,
. .
22-0188-02.indd 24
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25
1.3

:
1. ,

(n + l).
2.
(n + l)
,

n.
, , 26
, .
1s, 1s2,
2s (1s2 2s2),
2p (1s2 2s2 2p6), 3s
(1s2 2s2 2p6 3s2), 3p (1s2 2s2 2p6 3s2 3p6)
4s (1s2 2s2 2p6 3s2 3p6 4s2).
3d, . , :
26

3d
4s.
4d
5s.
Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2

3d 4s, 4s
, . 3d
4s. 4d 5s.
Fe Fe2+ 4s
3d . , Fe2+ :
Fe2+: 1s2 2s2 2p6 3s2 3p6 3d6

:
Fe: K2 L8 M14 N2 Fe2+: K2 L8 M14
,
, .
.. 24Cr (2-8-13-1) (2-8-12-2).
.
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26
Hund
,
.
Fe, 6 3d
. 3d 10 , d .
Hund
:
(aufbau) :
1. ,
2.
Pauli
3. Hund.
(
) spin.
7 :
: 1s2 2s2 2p3
, :

7
1s
2s
2px
2py
2p
,
:
O : 1s2 2s2 2p4
8
:

1s
2s
8
2px
2py
2p
6C, 9F, 10Ne, 15.
1.3
( s, p, d, f )

Moseley
.
.

7: 1s2 2s2 2p3.
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27
2 ( ) . VA
5 .
:

.
(
) .
,

. , ,

(
)
.
, A
( ) .

(
, )
s, p, d, f,
1.5.
, 1s2 2s2 2p3,
p, (
) p.
, 26Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2 d,
( aufbau)
d. :

( ,
aufbau)
.. s, p, d f.

.
s: s ( ) . , (Na, ..)
(Ca, Mg ..).
. s ,
s . :
:
s1 s2
:
IIA
:
1 2
p: p ,
p .

22-0188-02.indd 27
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28
, , , ,
:
p2
p3
p4
p5
p6
:
p1
: IVA VA
VIA VIIA VIIIA 0
:
13 14
15
16
17
18
, 7N: 1s2 2s2 2p3 p
p3, V 15.
d: d
, ,
d. .
d 10 , d 10
( ). :
:
d1 d2 d3 ... d10
:

IVB
VB
...
: 3
4
5
...
12
, d,
(1s2 2s2 2p6 3s2 3p6 3d6 4s2)
d.
d6
(VIIIB) 8.
f: f ,
f. f 14 , f 14 .
, 6
58-71, ,
7 90-103.
s p
, d
f
.
1.5 .
22-0188-02.indd 28
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29
1.6
. s s, p
p ...

,
. ,
,
.
,
2 3 (
).
1.4
2 (Li-Ne) 3 (Na-Ar).

2
Li
Be
B
c
N

LiCl
BeCl2
BCl3
ccl4
NCl3

(20 C)
/C
1350
487
12
77
71

Cl2O

F
FCl

Ne
-
-101
Na
Mg
Al
Si
P
S
Cl
Ar
3

NaCl
MgCl2
l 2C l 6
SiCl4
PCl3, PCl5
SCl2, S2Cl2
Cl2

,
, (20 C)
/C 1465
1418
423
57
74, 164
59, 138
-35

22-0188-02.indd 29
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30
1.5
2 (Li-Ne) 3 (Na-Ar)
2
Li
Be

C

Li2O
BeO
B 2O 3
CO2, co N2O, NO...

.

(20 C )
3
Na

O 2

-
F
OF2
Ne
-
Mg
Si
Cl
Ar
Cl2

Na2O
MgO
A l 2O 3
SiO2
410, 4O6 so 2, so3

(20 C)

()

2 3 .
s p . 4, ,
s p d .
d, . ,
,
, 3d,
4 2 .
. ,

d
f.

d. T f

(57La)
f 7

(89Ac).

d .
, ,
, ,
.
1 : 4
2 : 5
3 : 6
1 (4 ) 3d ( 4s
). , 2 4d ,
5s . 3 5d , 6s .
22-0188-02.indd 30
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31
1.7
s p,

.
, ,
, :

.

() .
-
-
-
-
-
-
1
.
1.6
1 .
Sc
1s22s22p63s23p6
3d1
4s 2
[Ar]
3d2
4s 2
[Ar]
3d3
4s 2
Cr
[Ar]
3d5
4s 1
[Ar]
3d5
4s 2
Fe
[Ar]
3d6
4s 2
C0
[Ar]
3d7
4s 2
Ni
[Ar]
3d8
4s 2
Cu
[Ar]
3d10
4s 1
Zn
[Ar]
3d10
4s 2
21
22
23
24
25
26
27
28
29
30
Cr Cu
.
,
4s

.
3d
( 5
)
( 10 ),

.
22-0188-02.indd 31
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32
1.7
1 .
Sc
Ti
Cr
Mn
Fe
Co
Ni
Cu
Zn
+1
+3
+2
+2
+2
+2
+2
+2
+3
+3
+3
+3
+3
+3
+3
+4
+4
+2
+2
Sc
n
,

.
+4
+5
+6
+6
+7
1.4

. (
) .
,
,
.
.
- -

1.8 54
.
. :

,
.

.

,
(
). ,
, .
22-0188-02.indd 32

. ,

.
5/11/2013 11:35:05
33

.
( ), - ,
-
. ,
.
,
, d,
.
1.8
,

.

, ,
i 1.
(g) +(g) + e-, i 1 = > 0

I.

IUPAC i.
kJ mol-1.

,
. ,
, i 2, :
+(g) 2+(g) + e-, i 2 = > 0

22-0188-02.indd 33
9/4/2014 11:33:20
34
,
, . , :
i 2 > i 1. : i 3 > i 2 ...

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

. ,

.
1.9 ,
.
22-0188-02.indd 34
5/11/2013 11:35:08
35

.
.
.

1.9.
, ,

.
(ea)

.
: (g) + e- (g)-, < 0
kJ mol-1.
.
,
.
,
. , :
(g)- + e- (g)2-, > 0
,
, ,
.
( ) , .
.
.

, :

.
IUPAC
Eea.

. ,

,
.

.
.
,
, . ,
(.. Cs, Rb). ,
,
, , (.. F, ). ,

.

.
22-0188-02.indd 35
5/11/2013 11:35:08
36
.
1/4 ,
, 3/4 . ,
, ,
.
1.10 .
: , Be, i At.
1.5
Lewis (1875-1946).
.
1912

.

.

Lewis.

D2O 22O.
Lewis

. ,

.
(Kossel,
Lewis). :
.
Lewis, Lewis
( Lewis), ( ) (
1.8).
:
,
( ) ( ),
,
. , .
Lewis ,
.
22-0188-02.indd 36

-

. 1908
Ramsay Kossel
Lewis. Lewis (1916)

,

.
Lewis

,
. ,

.

,
5
.
5/11/2013 11:35:09
37
1.8 Lewis

NaCI :
11
Na (2 L8 1)
17
Cl (K2 L8 M7)
+

Na , Cl

Na + Cl

l23 :
13
Al (K2 L8 3)
2 l + 3
O ( L )
2
3+
2 l , 3
2-
HCl : H Cl
2 : H O H
[[ [
Lewis
,
.. .
Lewis
(NH4Cl) 3 HCl:
H
+
H
H Cl + N H
H
Cl
H
H
.
, .
, , ,
.
. ,
4 .

,

(
).
,

.
Lewis
Lewis
:

22-0188-02.indd 37
9/4/2014 11:33:38
38

. , ,
, , .
.. SO2 : 6 + 2 6 = 18
, SO42-: 6 + 4 6 + 2 = 32
4+: 5 + 4 1 - 1 = 8
.
1 .
1, .
. .. 3 .

( ).
,
.
(
) ,
8 (
). ,
.
8 ,

.
,
.
Br
Cl
S
,
. :
1.1
Lewis HCN.
22-0188-02.indd 38
5/11/2013 11:35:10
39
. : 1 + 4 + 5 = 10.
. C,
.
. ( ):
H C N
, 4 1 0 - 4 = 6,
3 .
. 3 ,
. . , C
.
N
H C
.
C .
N
H C

.
2
H C N
,
.
1.2
Lewis HClO.
. Cl.
. : 1 + 7 + 6 = 14.
. : Cl.
. 14 - 4 = 10 ( 5 ).
. 3 ,
2 . , :
1.3
Lewis BF3.
H
. .
. : 3 + 3 7 = 24.
. :

22-0188-02.indd 39
5/11/2013 11:35:10
40
F
F
. 18 .
, :
BF3

(

).
1.4
Lewis PCl5 .
. .
. : 5 + 5 7 = 40.
. :
Cl
Cl
Cl
Cl
Cl
. 30 .
. :
Cl
Cl
Cl
Cl
Cl
PCl5
10 .
1.5
Lewis SO2.
. S.
. : 6 + 2 6 = 18.
. : S .
. 14 .
6 , .
(S). ,
, . ,
Lewis SO2 :
22-0188-02.indd 40

Os=o
5/11/2013 11:35:10
41
Lewis : HBrO, SF6,

SO3, 3.
- VSEPR ()
Lewis 2 :
H O H
, Lewis
,
. ,
,

VSEPR (Valence, Shell, Electron, Pair, Repulsion). H

,
.
,
. VSEPR,
:
,
,
.
BeCl2. Be
180.
, BeCl2 .

CIBeCl
BeCl2
Lewis
CIBeCI
180
,
, .
.. BF3 3 ,
120.
FBF
BF3
Lewis
22-0188-02.indd 41
120
F
120
F
120
5/11/2013 11:35:11
42
,
,
.
.. C CH4
.
109,5.

CH4
Lewis
HCH
H
H

, ,
.
,
, . ,
.
2 3 CH4,
.
()

,
BF3 .

.

.
1.11 ,
.
,
, ,
, .
.
1.12 ,
.
22-0188-02.indd 42
5/11/2013 11:35:13
43
,
VSEPR :
1. Lewis.
2.
.
3. VSEPR,
.
4. ,
,
, .
Lewis VSEPR.
:
.

( ),

.
Lewis
:
. Br3
. CCl4
. CS2
. 3.
. Be2
22-0188-02.indd 43
5/11/2013 11:35:13
44
1.9 VSEPR
22-0188-02.indd 44
5/11/2013 11:35:15
45
...

(STM)

.
(STM)

De Broglie, Heisenberg Schrdinger
1924 - 1927.

, ,
.
.
,
.
.
, ,
,
...

,
.
. ,
. ,
, ,
.

,
.
22-0188-02.indd 45

.
,
.

- ,
,
, .
,
. ,
,
.
1998

, .
1981
Binnig Rohrer IBM
( 1986)
(STM-Scanning
Tunneling Microscope). ,
5/11/2013 11:35:16
.
. STM
.
- .
.
( )
, ,
. ,

.
(STM), ,
(probe)
.
, 1 - 2 ,
(10-8 cm).
, , .

- .
,
- , - ,
.
.
,

,
, .
. Crommie IBM STM
: ...

, , .
22-0188-02.indd 46
.
(STM).
.
.
. (STM)
.

. .
,
(
), , ,
.
,
14 nm
,
. !
.
5/11/2013 1:11:08
47
...

.
,

Heisnenberg.

. ,
,

. , , De
Broglie,

.

. 1944

M.Born. , ,

,
, .
,
.
Heisenberg
22-0188-02.indd 47

,

.
,
( )
.

,
,

. ,

, , . ,
.

. , ,
.
,

.

....
;
,

Steven Hawking
9/4/2014 12:50:57
48
1. ,
.
,
.
2.
Schrdinger ,

. T 2
.
2 .

(90-99%).
3. 4
.
, n = 1, 2, 3...,
()
- .
.
, l = 0, 1, 2, ...(n - 1),
()
. n
l .
, ml = -l, ..., 0, ..., +l,

x, y, z.
.
spin ms = +1/2, -1/2,
.
spin
.

.
4. s
p
, . ,
px, py pz, x,
y z. , 5 d 7 f
.
5. Pauli:
.

: s2 p6 d10 f 14.
6. ,
,

. .
7. Hund:
22-0188-02.indd 48
5/11/2013 11:35:18
49
( )
spin.
spin.
8. (aufbau)
,
, Pauli
Hund.
9.
( )
, .. s, p, d, f. s .
p . d
10 (). f
.
10.
( ),

.
.
11.
( ),
.

.
12. Lewis
.
Lewis ,
( )
.
.

,
. ,
.
13. ,
, VSEPR.
(
)
, .
Bohr
Heisenberg
De Broglie
Schrdinger

Pauli
Hund
Lewis

VSEPR
22-0188-02.indd 49
5/11/2013 11:35:18
50
- -

1. ;
2. Bohr;
3.
Bohr
;
4. ;
5. de Broglie
Heisenberg ;
6.
Schrdinger ;
7. ;
8. ) (n), )
(l), ) (ml) )
spin (ms); ;
9. s, p, d f ;
10. s p ;
11. (aufbau) ( Pauli,
, Hund).
12. )
) ;
13.
;
14. ;
15.
;
16. ;
17.
;
18. ;
19. ,

;
20. Lewis;
21. ;
22. VSEPR;
23. : BeH2, BF3, CH4, N3, H2.
-
. -
24.
n = 4 n = 2
. Planck, h = 6,63 10-34 J s
22-0188-02.indd 50
= 486,6 nm
5/11/2013 11:35:19
51
25. ,
n = 1 n = 4.
;
. n = 4
.
.

.
.
.
.
n = 4 n = 1
n = 4
n = 2.
.
n = 4 n =1
n = 4 n = 2.
* 26. .
, ,
, .
AgCl
:
AgCl(s) Ag(s) + Cl
O Ag(s) .
.
310 kJ mol -1.

, .
Planck, h = 6,63 10-34 J s = 6,02 1023 mol-1.
27. , 6 106
m s-1; 9 10-28 g Planck,
h = 6,63 10-34 J s.
28.
;
;
7,77 . 1014 s-1

1,23 . 10-10 m
22-0188-02.indd 51
5/11/2013 11:35:20
52
29. ( )
,
.
Bohr
de Broglie
Heisenberg
Schrdinger
30. :
......,
.......... ................... .
.....,
.......... .................. .
......,
.................... ....................... .
spin ......,
.......... ......................... .
31.
:
. 4
.
.
.
.
,
.
. 1s
(1, 1, 1, +1/2).
32.
.
1s
2s
2p
3d
4f
3p
22-0188-02.indd 52
(2,0)
(3,2)
(1,0)
(4,3)
(2,1)
(3,1)
5/11/2013 11:35:21
53
33. 1s, 2s, 2pz, 3px 3s
.
.
.
34. 3px
.
. (3, 0, 0, +1/2) . (3, 2, -1, -1/2) . (3, 3, -1, +1/2) . (3, 1, 1, +1/2)
35.
;
. (1, 0, 0, +1/2)
. (1, 1, 1, -1/2)
. (2, 0, 0, +1/2,)
. (2, 1, -1, +1/2)
. (2, 0, 1, +1/2)
. (3, 2, -2, -1/2)
36.

:
. n = 2, l = 1, ml = -1
. n = 3, l = 0, ml = 0
. n = 4, l = 1, ml = 1
37. :
. 4s . 4p . 6d . 5f
38.
3p .
.
39.
26Fe
. 2 L8 8 8
. 2 L8 9 5
. 2 L8 14 2
. 2 L8 16

40.
,
(aufbau): 4d, 4f, 5s, 5d, 6s.

41.
25n
;
. 1s2 2s2 2p6 3s2 3p6 3d7
. 1s2 2s2 2p6 3s2 3p6 4s2 4p5
. 1s2 2s2 2p6 3s2 3p5 4s2 4p6
. 1s2 2s2 2p6 3s2 3p6 3d5 4s2
22-0188-02.indd 53
5/11/2013 11:35:22
54
42.
;
7
.
.
.
.

43.

: 5, 11Na, 18Ar, 16S.

: 20Ca2+, 19K+, 35Br-.
44.
;

45.
.
.
. 1s1 2s1
. 1s2 2s2 2p2 3d1
. 1s2 2s2 2p6 4s1
. [Ar] 4s1 3d10 4p4
. [Ne] 3s2 3p4 3d1
46. 6C

.
47.
Pauli Hund;
.
48. (1 ) (2 ) .
IA
IIIB
VB
VIIIA
22-0188-02.indd 54
3
5
18
1
5/11/2013 11:35:22
55
49. (1 )
.
I
I
VII
VIII
50. :
.
.
.
.
.
.
51.
17Cl, 22i (), 36Kr
() 58Ce ().
52.
23V, 27Co, 31Ga, 35Br, 40Zr
.

* 53.
17, 24, 35, 56
16, 36, 41, 53 ;
* 54. :

..
, ,
Fe

F2
Na
55.
.

Na
11
CI
17

19
Rb
37
/
2,27
1,54
2,48
0,99
22-0188-02.indd 55
5/11/2013 11:35:22
56
56. .
. ................

........................... ........................... .
. ............................
....................
..................... .......................... .
. .....................

................................
. ...................
.
, ..............
57.
.
.
.

58.

:
. 9F
3Li.
. 11Na
3Li.
. 19
3Li.
. 9F
Li.
3
59. Rb (=37) Na (=11)

(). ,

;
60. Li (=3)
Be (Z=4);

61.
F , Ne .
22-0188-02.indd 56
5/11/2013 11:35:22
57
. Lewis -
62.
Lewis : , Cl, Al,
Na, Ca, , Ne.
63. Lewis
: Na2O, MgCl2, CaO, l K2S.
64. Lewis
: 3, CO2, AlCl3, CH3-CH3, SBr6.
65. Lewis
: O2, H2SO4, HClO4, NH4ClO4, 43.
** 66. Lewis :
1. Mg + N
2. Al + Br
3. Na + S
4. I +Cl
67. Lewis
BeH2 .
68.
Lewis
HC CH .
69. Lewis CF4
.
70. ;
. CH4 . BeCl2 . 3 . BCI3
71. ;
. CH4 . 2O . 3 . BCl3
72. ;
. CH CH . CH2=CH2 . CBr4 . HCl
22-0188-02.indd 57
9/4/2014 11:22:16
58

* 73. ,
.
.

.
,
.
Fe14+ .

Fe13+ Fe14+ 3,5 104 kJ mol-1 1
mol 3/2 RT R = 8,314 J -1 mol-1.
.
74. 4 :
a. n = 4, l = 0, ml = 0, ms = +1/2
. n = 3, l = 2, ml = 1, ms = +1/2
. n = 3, l = 2, ml = -2, ms = -1/2
. n = 3, l = 1, ml = 1, ms = -1/2
.
75. :
Ei 1 = 738 kJ mol-1, Ei 2 = 1450 kJ mol-1, Ei 3= 7,7 103 kJ mol-1 Ei 4= 1,1
104 kJ mol-1.
.
* 76. :
. [He] 2s1 2p5
. [r] 4s2 3d10 4p5
. [Ne] 3s2 3p2 4s1
. [Kr] 5s2 4d10 5p1

.
77.
;
*
3. 7 9F. Mg2+ Ca2+
. Fe2+ Fe3+
78. 8A 6 :
.
;
. 2, Lewis
;
. 2;
22-0188-02.indd 58
2,8.106
9/4/2014 11:26:47
59

** 79.
,
.

A
B

.
. .
. .
. .
. .
. .
.
3.
. .
80. 4 , :
: 1, 2, 3
: 1,2
:
F
: .

BF3 : B F

F
1. To BF3 .
2. F 120.
/

F

3. To BF3 .
4. BF3 .
* 81. 11 16.
. ,
X .
. X ;
. X
3.
. X HCl;
. 3 ( 24)
NaOH;
.
;
22-0188-02.indd 59
5/11/2013 11:35:23
60
.
,
.

.

.

25. , , , ,
31. . . . .
33. . 1s (1, 0, 0)
. 3px (3, 1, 1)
. 2pz (2, 1, 0)
. 2s (2, 0, 0)
. 3s (3, 0, 0)
34.
35. , , ,
36. 2py, 3s, 4px
37. 1, 3, 5, 7
38. (3, 1, -1, 1/2)
(3, 1, 0, 1/2)
(3, 1, 1, 1/2)
39.
40. 5s , 4d, 6s, 4f,
5d
41.
42.
45. . 1s2
. 1s2 2s2 2p3
. 1s2 2s2 2p6 3s1
. [Ar] 3d10 4s2 4p3
. [Ne] 3s2 3p5
46. 1s2 2s2 2p2
(1, 0, 0, +1/2)
22-0188-02.indd 60
(1, 0, 0, -1/2)
(2, 0, 0, +1/2)
(2, 0, 0, -1/2)
(2, 1, 1, -1/2)
(2, 1, 0, -1/2)
47.
,

Pauli , ,
Hund.
51. 17
Cl (3 ,
p)
i (4 ., . d)
22
Kr(4 ., . p)
36
Ce (6 ., . f )
58
52. V, Co, Zr
53. 24, 41
58. . . . .
59. Na, Rb, Rb
60.
1s e- ,
2s e-.
61.
1 e-
F

.
1 e-
Ne

.
70.
71.
72.
74. 3p < 3d < 4s
75.
76. ,
Br
,
,
In
.
77. . 73- . Ca2+
. Fe2+
78.
79. . , . , . ,
. , . , . , .
80.
5/11/2013 11:35:24
XHMIKH

:

.

(U) ().
(S) .

.
(S)
.
(S),
.
(G).
(G), ()
(S).
(G) , (G)
.
G ,
S
. G,
.
G
,
.

.. , ,
, ..
22-0188-02.indd 61
2.1.
2.2. ,

2.3 ,

2.4

-

,
,

R. Emden
5/11/2013 11:35:24
, ,
(H < 0) o (S > 0) H - TS < 0.
, ,
.
. < 0 ( ), S > 0 (
,
).
22-0188-02.indd 62
5/11/2013 11:35:26
63
2

. . ,
, .

, :
1. ;
2. ,
;
3. ;
,
.
. ,
, .
2.1
,
:
: .
: , ..
3 mol CO2 ,
3 mol CO2.
3 :
:
.
:
.
:
.
.

,
..

, ..
. ,

.
2.1 :
, , .
22-0188-02.indd 63
5/11/2013 11:35:28
64

(U). ,
, (,
, , ). ,
( 2 - , ),
( ). ,

.
, U
. ,
U,
.
2.2 H2O(l) 50 g 25 C

( ).

.
,
.
,
.

.
, ,
. :
1
( )
U = U = 0
,
:
. ,
. .
,
.
.
22-0188-02.indd 64
5/11/2013 11:35:29
65
, .. .
,
,
.
, :
2.3 (),
(), .
, , ..
n HCl.
, (
).
2.4 ()
, .

, :
1
( )
U = q + w
:
U = U - U , .
q:
.

,
.

,
. ,
.
22-0188-02.indd 65
5/11/2013 11:35:35
66
w:
.
q w,
:
W (.. )
q>0
W (.. )
w>0
W (.. )
q<0
W (.. )
w<0

2.5 ,
(-) (+).
2.1
, , .
w = +20 kJ
q = +50 kJ.
.
.
,

.

,

.

,
;

1:1015.
;
, 100
, 30 .
.

.
U = q + w = +50 kJ + 20 kJ = +70 kJ
70 kJ.
w = -20 kJ, q = +50 kj.

;
U = q + w = -20 kJ + 50 kJ = +30 kJ.

30 kJ.
w = -40 kJ,
q = +30 kJ.
;
22-0188-02.indd 66
U = -10 kJ
5/11/2013 11:35:36
67
U

, w = 0
:
qv = U
, ,
. ,
,
V = . qv
,
( ).
U
- - U
, .. ,

,
(w) .
-
:
w = -PV
,
. , ,
(V < 0 w > 0)
(V > 0 w < 0). ,
:
qP = U + PV

,

, .
, , ()

- . :
= U + PV
:
H = U + PV
:
qP =
,
- ( ),
.
22-0188-02.indd 67
5/11/2013 11:35:36
68
2.6 -
, .

:
=
<0, , >0
.
,
(25 C, 1 atm, c =1 ) :
= nHof mf
n, m
, . f
, , ,
1 mol ,
( 2, ). , f
,
.
Hf ,
, .
2.3
: 2CO(g) + 2(g) 2CO2(g).
Hf , ,
CO(g): -110,5 kJ mol-1, CO2(g): -393,5 kJ mol-1.
= 2 CO - 2 CO - O
H = 2 mol (-393,5 kJ mol-1) - 2 mol (-110,5 kJ mol-1) - 0
H = -787 kJ + 221 kJ = -566 kJ.
2
:
CH4(g) + 2O(g) CO(g) + 32(g)
f , ,
CH4(g): -75 kJ mol-1, H2O(g): -242 kJ mol-1, CO(g): -110 kJ mol-1.
22-0188-02.indd 68
= +207 kJ
5/11/2013 11:35:38
69

2.2 ,

,
,
:
2.7

(
),

.

. (H < 0).
.
, :
4Fe(s) + 3O2(g) 2Fe2O3(s)
= -1650 kJ
Fe2O3
.
, Fe2O3(s) Fe(s).

(Fe2O3). , ,
, ,
.

Clausius,
- ()
- ( ,
)

.

.

.
2.8 ,
. .
,
,
. ,
.
, .
( > 0)
. :

22-0188-02.indd 69
5/11/2013 11:35:40
70
1. 43 2
43(s) N4 +(aq) + 3-(aq)
= +27,4 kJ
2. :
2(l) 2O(g)
= +44,0 kJ
, (H)
.

.
,

.
,
:
2.9 ,
. ()
.

, .

.

.
,
.

.

.
22-0188-02.indd 70
5/11/2013 11:35:42
71
2.10 .

(, , )
.
, .. , , ,
.
2.11 ,
sol , .
.
, ,
.
,
( .. ,
, )
.
2.12
, > 0
( ),

.
22-0188-02.indd 71
5/11/2013 11:35:44
72
, , S.
,
.
, . , 2 mol C2
3 mol 2 = 2 atm = 25 C , .

. -5 C.

;
.
:
,
, . ,
.
2

:
S + S > 0
2
.

(
-
).

.
, ..

.
:
,
.
,
,

0 C.
,

. ,

.
,

,
.

,
,
,

.
2.13 0 C
S > 0.
22-0188-02.indd 72
5/11/2013 11:35:45
73
So

. ,
:
1.
. ,
S >> S > S
2. .
3. .
4. .
S (25 C, 1 atm,
c = 1 ) :
o
S = nS
o
mS
o
n, m
o
, . S
, (
o
S ,
o
). , S ,
.
2.14 .
22-0188-02.indd 73
5/11/2013 11:35:46
74
2.4
, So,
:
. 2Cu(s) + O2(g) 2CuO(s)
. 22(g) + 2(g) 22O(l)
. N24(g) 2N2(g)
. 2 mol CuO
o
o
1 mol O2 2 mol Cu. S < S
o
o
o
S = S - S < 0
. , 3 mol
o
2 mol . S < 0.
. 1 mol 2 mol , . ,
S > 0.
, S,
:
. NH3(g) + HBr(g) NH4Br(s)
. 2H2(g) + O2(g) 22O(g)
. N2(g) + 32(g) NH3(g)
. Ag2C3(s) Ag2O(s) + CO2(g)
. ZnO(s) + CO2(g) ZnCO3(s)
2.5
S , S,
, :
. 2Cu(s) + 2(g) 2CuO(s)
. CaCO3(s) CaO(s) + CO2(g)
. S = 2S CuO - [2S Cu + S ]
2
o
S = 2 mol(43,5 J K-1mol-1) - [2 mol(33,3 J K-1mol-1) + 204,9 J K-1mol-1]
o
S = 87 J K-1 - 66,6 J K-1 - 204,9 J K-1 = -184,5 J K-1
. S = SCaO + SCO2 - SCaCO3
o
S = 1 mol (3801 J K-1mol-1) + 1 mol (213,7 J K-1mol-1) - 1 mol
(92,9 J K-1mol-1) = 158,9 J K-1
o
S , S,
, :
. 4Fe(s) + 3O2(g) 2Fe2O3(s)
. Fe2O3(s) + 3CO(g) 2Fe(s)+ 3CO2(g)
. N2(g) + 3H2(g) 2NH3(g)
o
22-0188-02.indd 74

Atkins ( )
() .
,

.
,
, , , .

, .
,

,
,
( ).

.

.

.

.
(
)

( ). To
,

.
5/11/2013 11:35:47
75
2.3

,
, .. , . ,
()
(S)
(So). ( )
S ( )
.
. , ,
,
(), .. > 0 S > 0.
,
. ,
.
. ,

,
(
). ..
(S < 0),
S > 0.

,
.
Gibbs
( Gibbs)
G .
, G, :
G = H - TS
,
(U, , S).

:
G = - TS

, ,
. :
G < 0
G > 0
G = 0
G, S

( ).
G
Josiah Willard Gibbs (1839

- 1903). .

.

,

Yale,
.
.
,

.

. ,

,
,
.

.
,
,

.

.
22-0188-02.indd 75
9/4/2014 11:34:13
76
S. :
1. < 0 S > 0 G < 0
, , G
< 0, (.. ) .
2. > 0 S < 0 G > 0
, ,
G > 0, (.. ) .
3. S ,
G.
, S
G ,
G. :
> 0 S > 0 G < 0 ( )

G > 0 ( )
< 0 S < 0 G > 0 ( )

G < 0 ( )
,
:

G < 0 ,
,
.

G < 0,

,

.
G
G (25 C, 1 atm, c = 1 )
:
G = nG f - mGf
n, m
, . Gf
1 mol
(
Gf , ).
G :
G = H -TS
G
S , S S. ,
:
G = - TS = - S.
22-0188-02.indd 76
,
100 C,

1%
S 2%-3%.
5/11/2013 11:35:47
77
2.6

) 25 C ) -10 C. :
2(l) H2O(s) = -6,01 kJ S = -22 J -1
G : G = - TS
) 25 C G = -6010 J - 298 (-22 J -1) = +546 J > 0. ,
25 C ,
.
) -10 C G = -6010 J - 263 (-22 J -1) = -224 J < 0. ,
-10 C .
: C3C2(g) CH3CHO(g) + H2(g)

= +68,95 kJ S = +114,2 J -1.
: . 25 C . 527 C
. G > 0
. G < 0
2.7
(CaO) (CaCO3)
: CaCO3(s) CaO(s) + CO2(g)
= +178,3 kJ S = +160,6 J -1
. G .
.
CaCO3.
. G = - TS
G = 178300 J - 298 (160,6 J -1) = 130,4 kJ > 0.
CaC3 298 .
. :
G = H - TS < 0
H < TS
> H/S
>178300 /160,6
>1110
Tmin CaC3 1110 .
G :
CH3CH2OH(g) CH2=CH2(g) + 2O(g)
: = +45,8 kJ
S = +125,6 J K-1
G = +8,6 kJ
2.8
G : 2(g) + 2(g) 2(g) G

HI kJ mol-1, :
f / kJ mol-1
26,48
S / J mol-1 K-1
130,7
116,1
206,6
22-0188-02.indd 77
5/11/2013 11:35:47
78
:
= 2 - - 2
2
= 2 mol (26,48 kJ mol-1) - 0 - 0 = 52,96 kJ
S :
S = 2S - S - S2
2
S = 2 mol (206,6 J mol-1 K-1) - 1 mol (130,7 J mol-1 K-1) - 1 mol (116,1 J mol-1
K-1) S = + 166,4 J K-1 = + 0,1664 kJ K-1. , G
: G = - TS = 52,96 kJ - 298 K (0,1664 kJ K-1) = +3,4 kJ.
H G +3,4 kJ. , G HI
+1,7 kJ mol-1.
G : C + O2(g) CO2(g),
:
o2
co2
Hf / kJ mol-1
-393,7
S / J mol-1 K-1
5,694
205,03
197,9
G = -299,92 kJ
2.9
: Cl2(l) Cl2(g)
= 20,4 kJ S = 85,4 J -1.
Cl2.
Cl2(l)
Cl2(g). ( ),
: G = 0
, S
, :
G = H - TS = 0
G = H - TS = 0
T = H/S = 239 K
Cl2 239 -34 C.
: C6H6(l) C6H6(g)
= +7,413 kcal S = +21 cal K-1.
S 1 atm.
353
2.10
G Gf
.
:
CH3OH(l)
O2(g)
CO2(g)
H2O(l)
Gf / kJ mol-1
-116,4
-394,4
-237,2
G :
CH3OH(l) + 3/2O2(g) CO2(g) + 2H2O(l)
22-0188-02.indd 78
5/11/2013 11:35:47
79
:
G = nG - mG,
G = G CO2 + 2G H2O - G CH3OH - 3/2GO2
G = 1 mol(-394,4 kJ mol-1) + 2 mol(-237,2 kJ mol-1) - 1 mol(-116,4 kJ
mol-1) - 0 = -752,4 kJ
: CH3OH,
O2 25 C, CH3OH.
,

. G
,
.
G : 2MgO(s) 2Mg(s) + O2(g),

Gf :
Mg(s)
2(g)
MgO(s)
G f / kJ mol-1
-569,6
Go = +1139,2 kJ

C6H6
+124
25 C
6C(s) + 32(g) C6H6(l) Gf = +124 kJ ( )
. ,
C(s) H2(g),
= 1 atm = 25 C.
,
, ,
, ,
. ,
, = 1 atm = 25 C,
:
C6H6(l) 6C(s) + 32(l) G = -124 kJ ( ).
, , 25 C = 1 atm,
,
.
,
.
()
, .
:

.
Gf > 0 (G< 0),
( ). , Gf < 0 (G > 0),
( ).
NO2
+51
HI
+2
-16
NH3
-110
AgCI
-237
2

.
G
.
22-0188-02.indd 79
5/11/2013 11:35:48
80
,

.
2.11
(NaCl)
; ,
,
.
Gf, NaCl = -384,05 kJ mol-1.

.
(C2H2)
; ,
,
.

,
.
.. ,
,

.
( )
, 4.

.
.
To G
,
v ()
(TS). ,
G
, ,
(
).
:
G = wmax
,
. , 40%
, .
60% .
22-0188-02.indd 80
5/11/2013 11:35:48
81

To G
(.. c = 1 )

.
,
. ,
G ( ). G
( )

.
:
G = G + RT lnQ
:
Q: , .. atm (QP)
, mol L-1 (QC ).
G:
.. c = 1 .
, G = nG - mG.
G:

( ).

.

.
.
.
:

,

.
2.15

. .
1.
. .
. .
. .
. .
22-0188-02.indd 81
5/11/2013 11:35:49
82
G = 0 Q = ,
G = G + RT InQ :
G = -RT ln
,
, G
.
G < 0 >1 , G
.
, G > 0 < 1 ,
G, .
,
, Gf

.
2.12

N2(g) + 32(g) 23(g) G = -32,9 kJ
,
100 atm.
Qp:
Qp = PNH 2/(PN PH 3) = 1002/(100 . 1003) = 10-4
3
2
2
, G = G + RTInQ = -55,7 kJ

G = -2,60 kJ
2(g) + I2(g) 2HI(g)
G = 4,26
2
atm, P = 0,024 atm P = 0,23 atm
G = 0,97 kJ
2.13
p 25 C:
N2O4(g) 2NO2(g)

G = +97,89 kJ mol-1 G = +51,31 kJ mol-1
2 4

G = 2G - G = 2 mol(+51,31 kJ mol-1) - 1 mol(+97,89 kJ mol-1)
2
2 4
G = +4,73 kJ
, InKp = -G / RT = -4,73 kJ mol-1 / 2,479 kJ mol-1 = -1,91
Kp = 0,15
22-0188-02.indd 82
9/4/2014 11:35:13
83
p 25 C
2(g) + 32(g) 2NH3(g)
G NH3 = -16,4 kJ mol-1
2.4
p = 5,68 105

,
(.. ).
.
. ,
, Go = -2880 kJ mol-1, .
,
ADP ( ).
, , .. . .
, ADP,
.
M :

,

.
2.16
,

:
Cu2S(s) 2Cu(s) + S(s)
G = +86,2 kJ mol-1,
,
Go.
,
. :
S(s) + 2(g) SO2(g) G = -300,4 kJ mol-1
:
Cu2S(s) + O2(g) 2Cu(s) + SO2(g)

22-0188-02.indd 83
5/11/2013 11:35:50
84
G = (+86,2 kJ mol-1) + (-300,4 kJ mol-1) = -214,2 kJ mol-1.
.

1797,
(
),
:
C() C() G = +2,9 kJ mol-1
,
, G
. ,
(.. 2100 C
100000 atm) Go ,
. ,
( ),
1 .

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

.
( )
, . , .
, NH4NO3,

.
,
, . 43 :
NH4NO3(s) NH+4 (aq) + NO3-(aq)
= +26 kJ

, ,
.
,

. ,
, .
,
22-0188-02.indd 84
5/11/2013 11:35:51
85
.
CaCl2 MgSO4,
:
CaCl2(s) Ca2+(aq) + 2Cl-(aq)
H = -81 kJ
2+
2H = -91 kJ.
MgSO4(s) Mg (aq) + SO4 (aq)
,
(
). ,
.

,
,
. , , ,
. ,
.
22-0188-02.indd 85
5/11/2013 11:35:51
86
...

. .. ,

( ).

.

.

.
, , (

).
( )
( ,
).
:
( )
22-0188-02.indd 86

.
,
,
,
.
.

, , ,

, , .
.

,
, .

,

.

,
.

, .
,

.

.
.
,
.

.
,
,
.
5/11/2013 11:35:51
87
1. : U = q + w.

.
,
.
2. : = U + PV
3. ,
(25 C, 1 atm, c = 1 )
:
= n f - mf
4. S.
, .
, S >> S > S.
5. S
:
S = nS - mS
6. .
,
, . ,
. :
S + S > 0
7.
G, : G = H - TS

: G = H - TS.
8.
, G,

. , G < 0.
9. G (25 C, 1 atm, c = 1 )
:
G = nG f - mGf
10. G : G = -RT lnK
- -
22-0188-02.indd 87
5/11/2013 11:35:51
88
- -

1. ; ;
2. ;
3. ;
4.
;
5. ;
6.
;
7. (G) ;
8. G
S ;
9.
;
10.
;
11. G p
;
-
.
12. .
. .........................
. ,
.
..................
........
13.
.
. .
. .
.
( > 0).
14. ,
:
. , w, ; w;
.
, q,
;
q;
22-0188-02.indd 88
9/4/2014 11:39:53
89
15. :
. -
. - .
16. : Mg + 2HCl MgCl2 + 2

12 kJ
30 kJ.
;
17. A(g) (g) . 50 kJ,
: A(g) + B(g) 2(g) + (g) .
30 kJ. ;
* 18. :
2H2S(g) + SO2(g) 3S(s) + 2H2O(l)
,
, H2S(g): -20,6 kJ mol-1, SO2(g):
-296,9 kJ mol-1, 2O(l): -285,9 kJ mol-1.
* 19. . :
2Al(s) + Fe2O3(s) 2Fe(s) + Al2O3(s)
:
Fe2O3(s): -822,2 kJ mol-1 Al2O3(s): 1675,7 kJ mol-1
. l Fe2O3
, .
,
1 kg l 1,6 kg Fe2O3.
-42 kJ
+20 kJ
-233,7 kJ
. -853,5 kJ
. 8535 kJ
.
20. :
.
.......................
. ................................. .............................
................................
21.
.
. .
. .
.
.
. 25 C : G = S

22-0188-02.indd 89
5/11/2013 11:35:52
90
* 22.
.
2 mol Cl2(g)
5,7 J -1
1 mol 2(l)
223 J -1
1 mol C(s)
446 J -1
1 mol Cl2(g)
70 J -1
. -131,9 J . -1
. +140,9 J . -1
23. S :
. CO(g) + Cl2(g) COCl2(g)
. 22O2(l) 22O(l) + 2(g)
24.
S :
. 2KCl3(s) 2KCl(s) + 3O2(g)
. 2C(s) + 2(g) 2CO(g)
. 494,1 J . -1
. 179,5 J . -1
* 25. S 23, :
. CO(g) + Cl2(g) COCl2(g)
. 22O2(l) 22O(l) + 2(g)
S

23.
CO(g)
S/ J.-1.mol-1 197,9
Cl 2(g)
223
COCl2(g) H2O2(l) H2O(l)

289
102
70
O 2(g)
204,9
* 26. S 24, :
. 2KCl3(s) 2KCl(s) + 3O2(g)
. 2C(s) + 2(g) 2CO(g)
S
24.
S/ J.-1.mol-1
KCl3(s)
KCl(s)
O2(g)
C(s)
CO(g)
143
82,7
204,9
5,7
197,9
27.
.
. .
. .
. .
.
.
.
.
22-0188-02.indd 90
5/11/2013 11:35:52
91
* 28. :
. = -12,6 kJ S = 42 J . -1
. = +12,6 kJ S = 42 J . -1
. ,
. 300 .
* 29. .
;
.

.
* 30. : 2(g) + O2(g) 2NO2(g) :
= -171,6 kJ S = 322 J . -1
G = -75,6 kJ
* 31. . 25 C =
1 atm, : NH3(g) + HCl(g) NH4Cl(s)
: = -177,2 kJ S = -285 J-1
. 25 C p = 1 atm;
. G = -92,27 kJ, .

** 32. H MgO o MgCO3 :
MgCO3(s) MgO(s) + CO2(g)
. G :
MgCO3(s)
MgO(s)
CO2(g)
/ kJ.mol-1
-1112,9
-601,7
-393,7
/ J.mol-1.K-1
65,7
26,8
197,9
. G = 70,02 kJ, . 739K
.
MgCO3.
** 33. . G
:
CaO(s) + 2(l) Ca(OH)2(s)
:
CaO(s)
Ca(OH)2(s)
2(l)
/ kJ.mol-1
-636,5
-986,6
-285,9
39,7
76,1
70
S/ J.mol-1.K-1
. 25 C p = 1 atm;
** 34. . G :

C() C()
. 25 C;
. , ()
25 C;
:
S = 5,69 J . mol-1 . -1
() = 0
= 1,9 kJ/mol
S
= 2,4 J . mol-1 . -1
()
. -7512 kJ, .
22-0188-02.indd 91
9/4/2014 1:25:11
92
* 35. 10,9 kJ/mol
1 atm 5,5 C.
.
** 36. . G :
CH4(g) + 22(g) CO2(g) + 22(l)
:
G/kJ.mol-1
CH4(g)
2(g)
CO2(g)
2(l)
-50,8
-394,4
-237,2
. CH4 25 C p = 1
atm;
. CH4
, ;
** 37. p :
PCl5(g) PCl3(g) + Cl2(g)
G: PCl5(g): -325 kJmol-1, PCl3: -286 kJmol-1 Cl2: 0.
** 38. . G . p 25 C.
22(g) 22(g) + 2(g)
G: 2(g) = -228,6 kJ/mol
-2,87 kJ
.: :
C6H6(s) C6H6 (l)
39,1 J .K-1. mol-1
. -810 kJ,
. ,
.
.:
: G= -2,3RTlogKp
.:
: G= -2,3RTlogKp
. 457,2 kJ, . 4,510-81

-
3. . , . , .
21. . , . , . , .
23. -, +
24. +, +
27. . , . , . , . , .
22-0188-02.indd 92
5/11/2013 11:35:52
93
- -
,
, .
-

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

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

.
1 L STP.
;
2.
1 m , :
4_____________________________
3_____________________________
2_____________________________
1_____________________________
0_____________________________
,
3 kgm.

1 kg .
1,5 kg ;
0,5 m ;

22-0188-02.indd 93
5/11/2013 11:35:53
94
22-0188-02.indd 94
5/11/2013 11:35:53
-

O
3.1
Brnsted - Lowry
3.2 -
3.3 ,
- pH
3.4
3.5
3.6 -
(-)
3.7
-

:

Arrhenius Brnsted - Lowry
.

- .

.
.
( ) .

(Ka, Kb).
: ,
, , ,
.
, w.
pH ,
pH. pH
,
.

.

, .
.
,
.
(Ks),

s.
22-0188-02.indd 95
5/11/2013 11:35:53
. , , , ,
.. . pH .
pH. ,
, .
.
, , pH ( pH ),
.
22-0188-02.indd 96
5/11/2013 11:35:55
97
3
. ,
. .
,

. ,

. Brnsted - Lowry,

().
,
( ) ,
.
pH. Le
Chatelier . ,
,
.

- , .
-
. ,
,
.
3.1 -

. ,
,
.
, (2).

, (
3.1) .
3.1

.
22-0188-02.indd 97
5/11/2013 11:35:56
98
.
, .
. ,
,
. ,
,
, .
, , ()
(), 3.2. ,
. ,
.
,

(). :

.
3.2
, .. NaCl, .
, .. NaCl, :
NaCl(s) Na+(H2) + Cl-(H2)y
2
NaCl(s)
Na+(aq) + Cl-(aq)
,
.
(..
).
,
, .. , .
, ,
,
, ( ).
.
22-0188-02.indd 98
:
, , .
5/11/2013 11:35:56
99
, ,
HCl 3. , ,
HCl H2O, 3+ ()
Cl-. . , ,
3
2, 4+ -.
. :

(.. ) .
3.3 .
HCI . 3 .
- Brnsted - Lowry
Arrhenius,
, . :
Arrhenius

+.

-.
Svante Arrhenius (1859 - 1927).

.

1903
.

:
...
Cleve, (
)

.
'' !!!''
.
,
, ....
Arrhenius

,

.
22-0188-02.indd 99
5/11/2013 11:36:00
100
, ,
, Arrhenius,
. :
. Brnsted - Lowry
. Lewis

Brnsted - Lowry. Brnsted -Lowry,
:

.

.
Brnsted Lowry
3.4 -
Brnsted - Lowry.
HF: HF + 2 3O+ + F HF , , 2O , .
, 3+
F-.
3 :
3 + 2 4+ +
Brnsted - Lowry
, :

, ,
.
,
(), ,

(). HCl
. HCl ,
22-0188-02.indd 100
Johanes Brnsted (1879 1947).

.
.

.
1947,

,
.
Thomas Lowry (1874-1936).

,
. Brnsted
Lowry, ,

.
(
)

Manchester Lapworth (18721941),
Lowry.
9/4/2014 12:53:14
101
( ).
,
, .
,
. ,
.
(
), (
). ,
,
. , :
+

+
-
-. - .
, :
Lewis (1875-1946).

Lewis:
, ..
AICI3 , , .. 3.
+ + +
+
+. + .
, ,
( ).
.
3.1 -
HCl
Cl-
HF
F-
H 2S
HS-
HS-
S2-
2O
H 3O +
2O
4+
NH3
NH3
NH2-
H
+,

,
. ,

,

, .. 3+.
2 HF + 2O 3+ + F-
, 3 + 2O 4+ + - .
, ,
, ,
.
-
22-0188-02.indd 101
9/4/2014 12:54:09
102
,
, 3.1.
Brnsted - Lowry
Arrhenius , .
3.2 -

.
( ) , 100%. , , () , .. .
,
3. , ,
.
- ,
Brnsted - Lowry. ,
, , .
. , ,
().
()
mol mol

().
,
, ,
,
.
( )

.
.
, .. HCl, :
HCl + 2O 3O+ + Cl a = 1.
: HCI, HBr, HI, O 3, HCIO 4 H 2SO4 (
).
.
, .. HF, :
HF + 2 H3O+ + F : HCN, HCIO, HCOOH, CH3COOH.
22-0188-02.indd 102
()
:
1. .
( ).
2. .
CH3COOH
,

.
3. .
,
.
,

.
4. .
,
.
5. .

.

,
,
,
.

100%,
.
5/11/2013 11:36:02
103

Arrhenius
: HCI, HBr, HI, 3 , HCIO4
H2SO4 (
).
:

,
.
:
.
3.5
.
H3O+
, ,
.. 52+ 94+, .
, ..
H2S :
H2S + H2 H3+ + HS- HS- + 2 H3+ + S2 , 34 ,
.
2 .
3.
3 + 2 NH4+ + , , .. F-,
: F- + 2 HF + -
-

,
. :
() ,
,
X .
:
H-CH3 < -2 < - < H-F
, X,
-,
+. :
,
,
X .
:
HF < HCl < HBr < HI
,
X, - ,
+.

X

.

,

.
22-0188-02.indd 103
5/11/2013 11:36:03
104

.
() ,
.
( ) , ..
, -I .
-I :
C6H5- < -2 < -OH < -I < -Br < -Cl < -F < -CN < -2
To -I -,
+,
.
3.6 , ,
- , . , ,
- . , -
HClO +
. HCIO HI.
.
,

.
,
: 3 > 3 > AsH3 > SbH3 > BiH3,
X .
, .. ,
+ . +
:
- < CH3- < C2H5- < -(CH3)2CH- < (CH3)3C- < COO- < , .. C3- , + ,
+, .
CH3NH2 3.
22-0188-02.indd 104
5/11/2013 11:36:04
105
3.1
,
H2S3 H2S4 ;
H2SO4 ,
-I , H2SO4 2SO3.
3.2

CCl3COOH > CHCl2COOH > CH2ClCOOH > CH3COOH;
-I ,
Cl, 3.6.
3.3 , - pH
- pH
.

3O+ () - ().
, :
3.7 .
:
2 + 2 3+ + -
,
, Kw
:
w = [3+] [-]
,

.
:
1000
mol
1000 g
18
= 55, 5 M,
[H 2 O] =
L
L
3+
- .
,
,
.
22-0188-02.indd 105
5/11/2013 11:36:05
106
1 L 1000 g ,

= 1 g mL-1 (25 C).
Kw ,
, . ,
. 25 C :
Kw = 10-14 (25 C)
Kw (mol2/L2) ,
.

,
: [3+] [-] = 10-14 ( 25 C).
: [ 3 +] = [OH -] = x , x 2 = 10 -14
x = 10-7 . :
25 C : [3+] = [-] =10-7
25 C :
[3+] >10-7 [-] < 10 -7

. ,
,
.
,
25 C :
[3+] = [-] = 10-7
.. [3+] = 10-5 M, [3+] [-] = 10-14

[-] = 10-9 . , ,
- .
:
25 C :
[-] > 10-7 [3+] < 10-7

:
/ 25 C:
[3+] [-] = Kw = 10-14
/ 25 C
[3+] = 10-7 = [-]
/ 25 C
[3+] > 10-7 M > [OH-]
() / 25 C
[3+] < 10-7 M < [OH-]
,
3+ .
3+ Srensen 1909
pH:
To pH (-)
H3O+
.
pH = -log[3+]
, [3+]= 10-3 , pH = -log10-3 = 3.
p (-):
S.P.L. Srensen (1868

-1939). .

Carlsberg. 1909
pH (-)

.

,

.

pH :
pKw = -logKw
pa = -logKa
pKb = -logKb
p = -log[OH-]
22-0188-02.indd 106
5/11/2013 11:36:06
107
p = -logX.
:
/ 25 C:
pH + pOH = 14
/ 25 C
pH = 7 = pOH
/ 25 C
pH < 7 < pOH
() / 25 C
pH > 7 > pOH
, 3+ -.
: [3+], [-], pH
p, , ,
. ..,
[OH-] = 10-3 , [3O+] = 10-11
pH = 11 p = 3.
3.8 pH .
pH ,
, , ..
, , ..,
pH
pH. -
pH
pH.
pH ,
,
.
.
-
22-0188-02.indd 107
5/11/2013 11:36:07
108
3.9 pH : . Mg(OH)2 . - CH3COOH.
-
, ,
. ,
:
HCI, HBr, HI, 3 , HCIO4 H2S4 ( ).
100%,
,
.
:
HBr + 2 3+ + r :
HBr + + Br Brnsted - Lowry .. 2-, 2-,
CH 3O -,
.
- (
Arrhenius), .. NaOH Ca(OH)2 ..
..:
NaOH Na+ + OHCa(OH)2 Ca2+ + 2OH-

(3+).

().
3.3
pH 10 L 0,1 mol HCl.
mol/L
n 0, 1 mol
c= =
= 0, 001
V
10 L
To HCl , :
/ mol L-1
-
22-0188-02.indd 108
HCl + H2O H3O+ + Cl0,01

0,01
0,01
0,01
5/11/2013 11:36:08
109
HCl ( ) , 2O. 2O x 3O+
x H2O + H2O H3O+ + OH x
, : [3O+] = (10-2 + x) [-] = x .
[-] = x < 10-7 .
:
[3O+] = 10-2 + x 10-2
pH = -log[3O+] = 2.
:
3O+ HCl
2. 3O+ 2O
HCl, 3O+
HCl.
pH HBr 8,1 g/L;

(pH = 1)
3.4
3O+ HCl 10-7 ;
HCl 2O.
HCl + H2O 3O+ + Cl 10-7
10-7
10-7
H2O + H2O 3O+ +
xM
xM
: [3O+] = 10-7 + x [-] = x .

x < 10-7 .
10-7 + x 10-7 , x 10-7.
x Kw:
Kw = [3O+] [OH-] = 10-14 x (10-7 + x) = 10-14 x = 0,6210-7
[3O+] = 10-7 + 0,62 10-7 = 1,62 10-7 .
- : . 10-3 .
10-7 ;
(. 10-3 . 0,62.10-7 )

, [3O+]
10-6 .
,
[-] 10-6 .
3.5
2 L O3 pH = 1 198 L 2.
pH ;
-
22-0188-02.indd 109
9/4/2014 11:43:13
110
200 L 3,
2 L .
:
pH = 1, [3O+] = 10-1 3 ,
0,1 .
, 2 L 0,2 mol O3
200 L .
: cA =
n 0, 2 mol
=
= 10 3 M, pH = 3.
200 L
V

10 L NaOH pH = 13 90 L 2.
pH ;
(pH = 12)
, 2O,
pH .
3.6
1 L 3 pH = 2 0,09 mol 3.
pH ;
pH
10-2 mol/L. 1 L 0,01
mol 3. :
(0,01 + 0,09) mol = 0,1 mol 3
cA=
n 0, 1 mol
=
= 0, 1 M, pH = 1.
V
1L
4 L pH = 12 0,36 mol
4 L . pH ;
(p = 13)
,
,
3O+ , pH .
-

. ,
.
.
,
:
+ 2O 3O+ + -
22-0188-02.indd 110

,
.

Ka

acid .
5/11/2013 11:36:10
111

:
[H O+ ][A]
Ka = 3
[HA]
2,
,
55,5 .
(Ka )
.
, Ka .
a ,
, .
, :
B + H2O HB+ + OH
:
Kb =
[HB+ ][OH ]
[B]

H+
.

Kb
base
.
Kb
. , Kb
.
,
(.. 102 - 109). ,

(.. 10-4 - 10-15).
a 25 C Kb
.
Ka b
(mol/L),
. ,

mol/L.
3.7
0,01
= 0,01. a pH .
:
=
mol g
mol g
c , ac . , :
22-0188-02.indd 111
5/11/2013 11:36:10
112
+ 2O
0,01
- /
0,01 . 0,01
10-4 10-4
0,01(1 - 0,01)
10-4 10-4
-4
10 10
3 + + -
-4
0,99 1, a = 10-6. , [3O+] = 10-4

. , pH = 4.
3, 0,1 Kb = 10-5. 3
pH .
( = 10-2, pH = 11)
3.8
c
. Ka c .
+ 2 3+ + -
/
- /
c
ac
c(1 - )
ac
ac
ac
ac
[H 3 O + ][ A ] c c 2 c
=
=
[ ]
c ( 1 ) 1
1,
1 - a 1 :
a
K a = 2c =
(1)
c
Ka =
c ..
Kb .
Ostwald

Ka = 2c/(1 - )
Kb = 2c/(1 - )
Ostwald.
,

.
Kb = 2c
Ka = 2c
( )
.
22-0188-02.indd 112
W. Ostwald (1853-1932).
. Arrhenius vant
Hoff . 1902

HNO3 ,

.

o
1909.
Ostwald

.

.
5/11/2013 1:12:18
113

:
0,1, 1 - 1 c - x c
( x ).
Ka c ,
:
a /c 0,01, 1 - 1 c - x c
a Kb
:
+ 2 3O+ + A-
(1)
, , .
-
- + 2O + -
(2)
(1) a .
(2) Kb A-.
:

,

.
H3O + A
[ HA ]
K a HA Kb A = H 3 O+ = Kw
HA
=
[ ]
K a HA =
K b A
Ka HA Kb
=K
:
3.2 / Brnsted - Lowry
a /b 25 C.
a
Kb
109
HI
10-23
108
HBr
Br-
10-22
1,3 106
HCI
CI-
10
7,7 10- 2 1
h2 so4
HSO
3 101
NO3-
3 1 0 -1 6
1,1 10-2
HS4-
so42-
9,1 10-13
7,2 10-4
NO2-
1,4 10-11
6,6 10
1,5 10-11
1,8 10-5
CH3 COOH
ch3 coo-
5,6 10-10
4,4 10
H2 CO3
HCO
2,3 10-8
5,6 10-10
4+
NH3
1,8 10-5
4,7 10
HCO
CO
2,1 10-4
CH3 O-
3 ,1 1 0 1
-4
-7
-11
3,2 10-16
CH3 OH
23
1 10
-17
22-0188-02.indd 113
5/11/2013 11:36:11
114
,
- ,
- Brnsted - Lowry.
, , :
+ +

.
, - .
, (o
) .
3.9
3.2
.
CH3COOH + C32- CH3COO- + HCO3-
,
( HCO3-
CH3COOH) ( CH3COO CO32-).
3.2
: 3 + F- 3- + HF.
CH3OH ( ),
a 10-14 2.
I-, Cl- O3-, b 10-14
2.
3.10
pH NaCl 0,2 .
2O NaCl ,
, :
NaCl Na+ + Cl0,2
0,2 0,2
+
To Na ,
Na+ (H2O)x , NaOH
2O. Cl- ,
HCl, , 2.
Na+ Cl- 2O,
. , NaCl
2O : [+] = [OH-] = 10-7 pH = 7.
22-0188-02.indd 114
5/11/2013 11:36:11
115
pH r 0,2 .
(p = 7)
3.11
pH NH4Cl 0,1 Kb NH = 10-5 Kw = 10-14.
3
To NH4Cl
4+ + ClNH4Cl
0,1 0,1
0,1
, Cl -,
, 2O. , 4+,
3 2.
a 4+ :
KW
NH
= 10 9
KNH3
:

4+ + 2
/
- /

/
0,1
x
(0,1 - x)
KNH + = K w = 109

4
K NH3
109 =
3 + 3+
xx
0,1 x
0,1 - x 0,1 x = 10-5 = [3O+] pH = 5.
NH4F c NH4+ c
F- c .
.
pH
. ,

,
,
Ka Kb. ,
NH4F ,
Ka NH > Kb F( 3.2).
+
4
pH KF 1 a HF = 10-4 w = 10-14.
(pH = 9)
3.4
( )
.
,
, Le
Chatelier.
:
+ 2 3+ + ,
3+ ( ) - (
-). HF
, .. HCl ( 3O+),
-
22-0188-02.indd 115
5/11/2013 11:36:11
116
, .. NaF ( F-), NaCl
HF.
:

, .. -, -,
, .
- ,
- , .
3.11
HF:
) HF 1 ;
) HF 1 NaF 1 ;
) pH .
: a F = 10-4.
) :
1 = 10-2 [3+] = 10-2
) , NaF :
NaF Na+ + F1 1 1
HF F-.
HF + 2 3+
F-
- /
1 - x
1+x
H 3O F x(1 + x)
4
KaHF =
=
= 10
(1 x)
[ HF ]
x 1
= 10 4 x = 10-4,
1 - x 1 1 + x 1
1
x
2 =
= 10 4 [ 3+] = 10-4 .

1
F-
,
.
HF 10-2 10-4,
F-.
. To pH 2 4.
- 3 0,1 NH4Cl 0,02 ,

Kb nh = 2 1 0 -5;
(pH =10)
22-0188-02.indd 116
5/11/2013 11:36:12
117
3.12

co - c
3+ :
H 3O + = Ka
: 0,1 1 - 1
c- x c
Ka /c 0,01 1 - 1
c - x c
[3+] << co [3+] << c.
+ 2
- /
c - x
c+ x
Ka =
3 + + c
[H3O + ][A ] x(c + x)

=
[HA]
c x
c x c c + x c :
H 3O + = Ka

c + c , -
: OH = K b
c
c
[-] << c [OH-] << c.
3.13
4 L NaOH 0,2 1 L HCl 0,3
5 L . pH ;
:
HCl + NaOH NaCl + 2O
. 4 L
NaOH 0,2 0,8 mol NaOH. To 1 L HCl 0,3
0,3 mol HCl. , :
NaOH
HCI NaCl + H2O
/ mol
- / mol
0,8
0,3
0,3
0,3
0,3
/ mol
0,5
0,3
22-0188-02.indd 117
5/11/2013 11:36:12
118
To NaCl ,
, [3O+].
:
c NaOH =
n
V
0,5 mol
= 0,1 M
5L
To NaOH :
NaOH Na+ + OH0,1 0,1
0,1
, [ ] = 0,1 [3O+] = 10-13 p = 13.
1 L O3 0,1 ( ) 0,5 L
NaOH 0,1 ( ) 1,5 L . :
. To pH .
. To pH .
. 3O+ .
Kw = 10-14.
(. p H = 1
22-0188-02.indd 118
. p=13
. [3O+] = 0,033 )

,

:

:
.
(!
).

:
.
Arrhenius, ..
HCI + NaOH NaCl + H2O
.
:
+ , ..
NaF + HCI NaCl + HF
.

:
+ , ..
NH4CI + NaOH NaCl + NH3
+ 2O
.

.
.

.
. B
(Molarity)

.
5/11/2013 11:36:12
119
3.5
- pH
pH
, a .
, pH .
( / -)
( / +).
:
c
[OH-] = Kb
c
pOH = pKb + log
c
c
: HF NaF
(HF / F-) NH4Cl 3 (3 / 4+).

- , , :

c
[H3O+ ] = Ka
c
c
: pH = pK a + log
c
Henderson Hasselbalch,
pH .
, ..
/ - :
.
, c = []
.
, c
= [-]
3.14
pH HCOOH 0,2
HCOONa 0,4 , a HCOOH = 2 10-4.
HCOOH 0,2 / HCOO0,4

pH = pKa + log
c
c
= log (2 10 4 ) + log

, pH = 4.
0, 4
=4
0, 2
pH CH3COOH 0,5 CH3COONa 0,9 ,

Ka CH COOH = 1,8 10-5.
(p = 5)

/ -,
.. HF / NaF, :
1.
.. HF NaF.
-
22-0188-02.indd 119
5/11/2013 11:36:13
120
2.
.. x mol NaOH y mol HF, x < y.
x mol NaOH x mol HF
x mol NaF. (y-x) mol HF
x mol NaF.
,
/ +, .. 3 / NH4Cl, :
1.
.. 3 NH4Cl.
2.
.. x mol 3 y mol HCl, y < x.

,
. pH
, .
3.15
NaOH 0,4 2 L
HF 0,2 pH = 4;
.
Ka HF = 10-4.
, , NaF
HF . NaOH . x L
NaOH 0,4 , :
0,4x mol NaOH 2 0,2 mol = 0,4 mol HF.
HF
NaOH
/ mol
0,4
0,4x
0,4x
0,4x
NaF + H2O
0,4x
/ mol
(0,4 - 0,4x)
0,4x
To (2 + x) L, :
0, 4x
0, 4x
cF =
M
M
2+ x
2 +x
0, 4 0, 4x
c
2+x
[H 3 O + ] = K a c 10 4 = 10 4
0, 4x
2+x
x = 5, 0,5 L NaOH 0,4 .
cHF =
0, 4 0, 4x
M
2+ x
cNaF =
HCl 0,2 500 mL

3 0,6 p=9;
Kb NH = 10-5 Kw = 10-14.
(1 L)
22-0188-02.indd 120
5/11/2013 11:36:13
121

, :
1. pH
.
2. pH ,
. pH
.
,
pH, 1 CH3COOH /
1 CH3COONa .
14
13
12
11
0,01 mol OH
10
9
8
pH
1 L
1L
5
4
0,01 mol H 3O +
3
2
1
0
3.9 pH 0,01 mol 3O+ 0,01 mol . 1 L . 1 L
1 M CH3COOH / 1 CH3COONa
22-0188-02.indd 121
5/11/2013 11:36:13
122

-.

, .

:
1) CH3COOH CH3COONa
CH3COOH
CH3COO-, CH3COONa.
. , .. HCl,
3O+ HCl
CH3COO-, :
CH3COO- + 3O+ CH3COOH + H2O. 3O+
,
p .
. , .. NaOH, -
NaOH
CH3COOH, :
CH3COOH + - 2 + CH3COO-.
p .
, HCl NaOH
CH3COONa CH3COOH,

.
2) 3 NH4Cl
. , .. HCl, 3O+
HCl
3: 3O+ + 3 4+ + 2O.
. , , .. NaOH, -
NaOH
4+: 4+ + - 3 + 2O.

p
:

-
HX
2 +
HX
+ +
HX
3.10
/ X-.
22-0188-02.indd 122
5/11/2013 11:36:13
123

: c1 NaA c2 , [3+]
= a c1 / c2.
10 ,
: 0,1c1 NaA 0,1c2M,
[3O+] = a (0,1c1)/( 0,1c2) = a c1 / c2.
pH
.
:
[3+] = a c / c.
, ,
,
.
3.16
1. 100 ml 2O 0,001 mol HCl.
3O+ 2 .
2. 100 ml HF 1 NaF 0,5
0,001 mol HCl .
3O+ . Ka HF = 10-4.
1. 2 25 C [3+] = 10-7 .
HCl
To HCl , [3O+] = 10-2 . ,
[3O+] HCl 2O 100.000 .
2. . :
HCI :
HCl
/
mol
. .
/
mol
NaF
NaCl
HF
0,001
0,05
0,1
0,001
0,001
0,001
0,001
0,049
0,001
0,101
NaCl, pH ,
HF 0,101 mol NaF 0,049 mol. :
HF
0, 101
0,1
NaF
0, 049
M = 0, 49 M
0,1
, :
[H3O+ ] = K a
c
c
= 10 4
1, 01
= 2, 06 10 4
0, 49
22-0188-02.indd 123
9/4/2014 12:01:13
124
HCl 100 ml 2O
[3O+] 100.000 , 100 ml
[3+] 3%.
1 L 3 0,2 N4Cl 0,4

1 L HCl 0,05 2 L
. [3O+] .
: Kb NH = 210-5 Kw = 10-14.
3
[3O+] = 10-9 , [3O+] = 1,5 10-9

, :
1. ,
..
2. .
pH ( ,
, , ..).
.
3. , , . ,
.
, ( ...
).
3.6 -
-
pH
.

.
:
+ 2
1
()
(-)

,
.
+ 3 +
( )
- ( ).
( ),
10
-. , 10 -. ,
, 1
. ,
- .
22-0188-02.indd 124
5/11/2013 11:36:14
125
pH a .
.
:
pH < pKa - 1,
pH > pKa + 1, pKa = -logKa
(phenol red),
:
+ 2 + 3+
pH 6,6-8,2. pH < 6,6

, , pH > 8,2 -, .
, ,
[] > 10 [-] .
[-] > 10 []
. pH ,
. :
:
a = [+][-] / []

()
[] > 10 [-],
[+] / > 10,
pH < pa - 1

(-)
[-] > 10 [],

[+] / < 0,1,
pH > pa + 1
3.11
. (pH < 6,6),
(6,6 < p < 8,2),
(pH > 8,2).
. ,
pH 8,2-10. , pH < 8,2
( ), pH > 8,2 -,
.
-
22-0188-02.indd 125
5/11/2013 11:36:16
126

:
1. pH
( ).
,
.
2. ,
, .

pH .

pH.

pH
( ).
3.17
: ) ) .
pH = 7, 3 .4
)
) .
NaOH 0,01
) ) .
22-0188-02.indd 126
(. . )
5/11/2013 11:36:18
127
( - )

( )
.
,
( )
, :
3.12 : )
()
) -
)
.
, ()
.

,
.
.

.
.

. -
. :
3+ + - 22
-
22-0188-02.indd 127
5/11/2013 11:36:18
128
(
) pH
.
pH , ,
,
.

. , ,
pH
(
,
).
.
3.13 pH
, .

.
1.
.. HCI NaOH.

. ,
p = 7 ( NaCl
). ..
p
,
3.14, .
22-0188-02.indd 128
5/11/2013 11:36:19
129
14
12
10
pH
2
0
10
15
20
25
30
35
40
45
50
aOH / mL
3.14 ,
.. HCI NaOH.
aOH / mL
0
5
10
15
20
21
22
23
24
25
26
27
28
29
30
35
40
45
50
pH
1.00
1.18
1.37
1.60
1.95
2.06
2.20
2.38
2.69
7.00
11.29
11.59
11.75
11.87
11.96
12.22
12.36
12.46
12.52
2.
.. CH3COOH NaOH.

. ,
p > 7 ( CH3COONa ,
CH3COO-). .. , p
( 3.15). ,
, p

( 3.15).
14
12
10
pH
4
2
10
15
20
25
30
35
40
45
aOH / mL
3.15 ,
.. CH3COOH NaOH.
50
aOH / mL
0
1
2
3
4
5
10
15
20
21
22
23
24
25
26
27
28
29
30
35
40
45
50
pH
2.92
3.47
3.79
3.98
4.13
4.25
4.67
5.03
5.45
5.57
5.72
5.91
6.23
8.78
11.29
11.59
11.75
11.87
11.96
12.22
12.36
12.46
12.52
22-0188-02.indd 129
5/11/2013 11:36:20
130
3.16 () NaOH

( ).
3.
.. 3 HCI.

. ,
p < 7 ( NH4C , 4+).
..
( p
). (
p
).
14
12
10
pH
4
2
0
10
15
20
25
30
35
40
45
CI / mL
3.17 ,
.. 3 HCI.
22-0188-02.indd 130
50
HCI / mL
0
1
2
3
4
5
10
15
20
21
22
23
24
25
26
27
28
29
30
35
40
45
50
pH
11.13
10.64
10.32
10.13
9.98
9.86
9.44
9.08
8.66
8.54
8.39
8.20
2.69
5.28
2.70
2.40
2.22
2.10
2.00
1.70
1.52
1.40
1.30
5/11/2013 11:36:21
131
3.18

NH3

HCI

(
).
3.18
500 mL NaOH 0,2 .
pH :
NaOH / mL
pH
2,0
4,0
6,0
8,0
9,0
9,9
10
10,1
11
12
2,50 2,62 2,81 3,10 3,41 4,41 7,00 9,60 10,6 10,9
. .
. ;
. , ,
;
: (pH: 3 - 4,5), (pH: 6 - 7,5),
(pH: 8 - 10).
. :
pH12
10
7
4
2
0
8 10 12 14 16
aOH / mL
. , NaA (
)
pH = 7. , ,
10 mL NaOH 0,2
-
22-0188-02.indd 131
5/11/2013 11:36:22
132
0,002 mol NaOH. Molarity
c , :
+ NaOH NaA + 2
1 mol
mol
1 mol
0, 002 mol
c = 0,004 M
Molarity 0,004 .
. pH
pH , 7.
.
3.7

,
.
, .. NaCl,
, .. 33.
(
).
.
, 1 mol AgCl 106 L 2 (
1), AgCl , 2
. :
AgCl(s) Ag+(aq) + Cl-(aq)
10-6
10-6
10-6
- / mol L-1:
+
-6
-6
-12
2
[Ag ][Cl ] = 10 10 = 10
, 2 mol AgCl 106 L 2O (
2), AgCl :
-1
210-6
210-6
210-6
- / mol L :
[Ag+][Cl-] = 210-6 210-6 = 410-12 2

12 mol AgCl 106 L 2O ( 3),
10 mol AgCl, 2
mol AgCl . 24
mol AgCl 106 L 2 ( 4). , 10 mol AgCl ,
14 mol AgCl . :
AgCl(s)
/
/
10-5
Ag+(aq) + Cl-(aq)
10-5
10-5
10-5
10-5
[Ag+][Cl-] = 10-10
22-0188-02.indd 132
5/11/2013 11:36:22
133

:
, Ag + Cl AgCl ,
Ag+ Cl-
.

Ks. Ks , ,
.
AgCl
: Ks = [Ag+] [ C l - ].
AgCl
Ks ,
.
[Ag+][Cl-] Ks = 10-10
( 3 4). ,
[Ag+][Cl-] Ks,
1 2, [Ag+][Cl-] 10-12 4 10-12,
.

Ksp.

IUPAC s.
CaF2:
CaF2(s) Ca2+(aq) + 2F-(aq)
Ks = [Ca2+] [F-]2
:
(s) M+(aq) + -(aq)
Ks = [+] [-]

(Ks) (
)
.
Ks
, .
, s
.
AgCl 10-5 mol/L.

AgCl . ,

.
.
22-0188-02.indd 133
5/11/2013 11:36:22
134
:
1. % ., g 100 mL
2. % .., g 100 g
3. mol / L, mol 1 L .

.
50
40
KNO
60
70
g / 100g H 2O
:
1. .
,
()
( ) .
NaCl .
2. .

, s.
3. .
,
, Le Chatelier.
,
. .. AgNO3
NaCl AgCl,
, AgCl(s) Ag+(aq) + Cl-(aq)
, (Ag+ Cl-).
KC
NaCl
30
20
10
CaCrO
0
0 10 20 30 40 50 60 70 80 90
/ C
XHMA 3.19
.
(s)
(s)
s xy, :
MxAy(s)
xy+(aq) +
yAx-(aq)
- /
xs
ys
xs
ys
, s = [My+]x [Ax-]y = (xs)x (ys)y = xxyy sx+y

,
s =x x y y s x+y

Ks, s .
3.19
Ag2CrO4 s = 4 10-12.
. Ag2CrO4 2;
. Ag2CrO4 AgNO3 0,1 ;
. Ag2CrO4 K2CrO4 0,1 ;
. .
22-0188-02.indd 134
9/4/2014 12:02:12
135
. (s) Ag2CrO4 2O.

Ag2CrO4(s) 2Ag+ + CrO42s
- /
2s
Ks = [Ag+]2[CrO42-]= (2s)2 s = 4 10-12 s = 10-4 mol L-1

Ag2CrO4 10-4 mol L-1.
. s1 Ag2CrO4 0,1 AgNO3.
:
AgNO3
/
Ag+(aq)
0,1
0,1
Ag2CrO4(s)
0,1
2Ag+(aq)
s1
+ NO3- (aq)
+ CrO42-(aq)
2s1
s1
0,1 + 2s1
s1
, [Ag+]2[CrO42-] = Ks (0,1 + 2 s1)2 s1 = 4 10-12.

0,1 + 2x 0,1, : (0,1)2 s1= 4 10-12 s1 = 410-10 .
, Ag2CrO4 0,1 AgNO 3
410-10 .
. s2 mol /L Ag2CrO4 K2CrO4 0,1 .
:
K2CrO4
/ M
+ CrO42-(aq)
0,1
0,2
Ag2CrO4(s)
2+(aq)
s2
2Ag+ (aq)
0,1
+
CrO42-(aq)
2s2
s2
2s2
(0,1 + s2)
Ag2CrO4, :
[Ag+]2[CrO42-] = Ks (2s2)2 (0,1 + s2) = 410-12
0,1 + s2 0,1 :
(2s2) 2 0,1 = 410-12 s2 = 10-5,5
. Ag+ CrO42-
Ag 2CrO 4 . Ag+
CrO42-,
[Ag+]
[CrO42-] Ks. ,

.
-
22-0188-02.indd 135
5/11/2013 11:36:22
136

,

.

, Ks.
Qs.
: Qs = [+][-].
Qs,
, Ks . :
Qs < Ks: .
Qs = Ks: , .
Os > Ks: Qs Qs = Ks.
3.20 Qs
Ks, ( )
( ),
.
3.21 .
AgCl . AgCl
AgNO3 NaCl.
22-0188-02.indd 136
5/11/2013 11:36:27
137
3.22
Pbl2
Pb(N3)2 .
3.20
MgCl2 0,01 NaOH.
Ks Mg(OH) = 9 10-12 :
2
. [-] Mg(OH)2,
. [-] Mg(OH)2.
NaOH
. MgCl2
0,01 , NaOH x .
MgCl2 NaOH :
[Mg2+] = 0,01 [OH-] = x .
. Mg(OH)2 :
Qs = [Mg2+] [OH-]2 Ks 0,01 x2 9 10-12 x 3 10-5
: [OH-]max = 3 10-5
. Mg(OH)2 :
Qs = [Mg2+] [OH-]2 > Ks 0,01 x2 > 9 10-12 x > 3 10-5
-
3 10-5 .
Ca(NO3)2 0,01 1 L, NaF.

:
. NaF CaF2,
. NaF CaF2.
Ks CaF = 410-12.
2 10-5 mol NaF
3.21
2 L AgNO3 10-4 2 L NaCl

4 10-5 . AgCl ,
mol AgCl ; Ks AgCl = 10-10.

:
AgNO3 : 5 10-5 NaCl : 2 10-5 .
-
22-0188-02.indd 137
5/11/2013 11:36:28
138
:
[Ag+] = 5 10-5 [Cl-] = 2 10-5 . :
Qs = [Ag+][Cl-] = 5 10-5 2 10-5 = 10-9 > Ks
, AgCl
Qs Qs = Ks.
Ag+
cl-
AgCl(s)
5 10-5
2 10-5
(5 10-5 - x)
(2 10-5 - x)
:
[Ag+][Cl-] = Ks (5 10-5 - x) (2 10-5 - x) = 10-10 x1 = 1,7 10-5 x2 = 5,3 10-5,
: 0 < x < 2 10-5 x1 = 1,7 10-5
4 L AgCl
4 1,7 10-5 mol = 6,8 10-5 mol.
2 L BaCl2 0,01 8 L Na2SO4

10-5 M. mol ;
Ks BaSO = 10-10.
7,95 10-7 mol BaSO4
22-0188-02.indd 138
5/11/2013 11:36:28
139
...

,
,
.

,
p.
p
7,35 - 7,45.
p

.
p
, .. 7,2.
,

..
.
p,
[3+] 4 10-8 ,
.
p
7,6 .
, ..
22-0188-02.indd 139
(8848 m),

p ,
.. 7,7 - 7,8,

.

p
, , .
H2CO3
/ HCO3- ,
:
H2CO3 + 2O HCO3- + 3O+
To CO2 , H2CO3,
( CO2 O2 ).
H2CO3
CO2 ,
. HCO3- / H2CO3 20/1.
HCO3-
H2CO3 p
(). H2CO3
HCO3-, p
().
,
0,01 mol HCl 1 L . , p 7,4 7,2.
, 0,01 mol HCl 1 L
( ),
p 7,0 2,0.
, , .
: HHb + 2 + + HbO2-.
p.

, -
9/4/2014 12:59:42
2,

,
2 .

p 1
,
,
.
22-0188-02.indd 140
,
.. n.
,
,
.

(antacids), ,
- NaHCO3, - Mg(OH)2
..,
.
5/11/2013 11:36:29
141
1.
. H2O .. NaCl(s) Na+(aq) + Cl-(aq).

. H2O (
Brnsted - Lowry). HCl HCI + 2O
3+ + Cl-. 2O .
3 , 3 + 2 NH4+ + -.
2. ( = 1) 2O ,
( < 1) .
.

3.
H+ + A-. -
/ - .
4. 25 C : [3O+][O-] = Kw = 10 -14.
5. pH = -log[H3O+] p = -log[O-].
6. : pH < 7 < p.
: pH > 7 > p.
: pH = 7 = p.
H 3 O + A
7. : K a =
.
HA
8. : K b =
9. Ostwald : Ka =
HB +
OH
.
B
2c
. 0,1 Ka = 2c.
1
10. Kb
- : . - = w.
11.
, .. -, .
12. c
, .. NaA c , , :
co
.
[H3O+ ] = a
c
c

, .. BCI:[OH ] = b
c
22-0188-02.indd 141
5/11/2013 11:36:30
142
13. pH
,
. pH
.
Henderson Hasselbalch: pH = pK a + log
c
c
14. - ( )
p .
15.
,
.
16. (Ks)
, .. Ca3(PO4)2,
[Ca2+]3[PO43-]2 .
17. mol/L
.
18. :
Qs < Ks .
Qs = Ks , .

Qs > Ks Qs
Qs = Ks.

Ostwald
Brnsted - Lowry
22-0188-02.indd 142
5/11/2013 11:36:30
143
- -

1. , .. NaCl, ;
2. Brnsted Lowry;
3. HF ;
4. H3 .
5.
; .
6.
;
7. pH p;
8. pH p 25 C:
i. , ii. , iii. ;
9. ;
10. ;
11. Ostwald;
12. a Kb
(A-);
13. ;
14. ;
15. ;
16. (Ks)
, .., Ca3(PO4)2;
-
.
17. .
. ...........
-
22-0188-02.indd 143
9/4/2014 12:03:30
144

...............................
.
. ...........................
. ...........................
.
. - .......................... .
+ ........................ .
- ......................... .
HF . ................ .
18.
.
. 3 4+.
. 2O 3O+.
.
[3O+][O-] = 10-14.
. : [3+] > [-]
. : [3+| < [-]
* 19.
,
.
. 2H2SO4 + O3 3O+ + O2+ + 2HSO4 . H2O + CO3= OH- + HCO3 . [Fe(H2O)6]3+ + 2O [Fe(H2O)5OH]2+ + 3O+
. 4+ + 2O 3+ 3O+
20. p :
. HCl 0,01
. 10 L 0,1 mol O3
. 10 L O3 0,1
. 100 mL 0,001 mol NaOH
. 100 mL NaOH 10-3 .
. 2, . 2, . 1, . 12, . 11
21. HCl p = 2
, p:
. 1,5
. 12
. 2,5
. 7
22. NaOH p = 13 , p:
. 1
. 12,2
. 7
. 13,5
23. O3 0,001 O3
, p:
. 3,5
. 7
. 6
. 2,3
24. Molarity NaOH pH = 12;
* 25. 3+ HCl 10-7 ;
22-0188-02.indd 144
0,01
1,6 . 10-7
5/11/2013 11:36:30
145
26. (I)
pH (II).
I
II
HCl 10-2
13
r 10-4
NaOH 0,1
11
10-3 M
* 27. To pH NaOH 10-8 :

. p = 6
. p = 8
. p = 7,02
. p = 14
.
28. 200 mL 2O 0,08 g NaOH 200 mL
. pH ;
p = 12
29. 2 L O3, pH = 1, 198 L 2O

200 L . pH ;
pH = 3
30. HA 1 ;
. [-] > [3O+]
. pH 0
. [3O+] = 1
. [3O+] + [A-] = 1
31. [3O+] = 100[OH-].
pH .
* 32. . HCl 1
HCl 3 , HCl 2 ;
. HCl
pH = 1 HCl pH = 3, pH = 2;
33. [OH-] = 510-5 . To pH :
. 9,7
. 8,5
. 5,5
. 4,3

34. mL 50 mL 3
0,63% w/v pH
;
35. x L HCl ( STP)
500 mL. 10 mL
100 mL. pH = 1.
x;
pH = 6
. 1:1, . 1:10
4950 mL
11,2 L
22-0188-02.indd 145
5/11/2013 11:36:30
146
36. 0,12 g Ca 600 mL H2O. pH
;
600 mL. (: Ca + 22O Ca(OH)2 + 2).
pH = 12
. -
37. (I) pH
(II).
I
II
HCl 10-2
0,1 ( = 0,01)
NaOH 10-2
11
3 0,1 ( = 0,01)
12
38. pH 10-2 ;
. 1
. 2
. 4
. 8
39. 0,1 .

( ).
. .
. To pH .
. [-] [3O+].
. a .

40. 1 a = 10-6.
. pH ;
. 10 mL 990 mL 2O
1000 ml . pH ;
. 1:2
;
41. To pH NH3 11. w/v
3 NH3;
3: Kb = 10-5 w = 10-14.
. 3, . 4, . 1:10
0,17% w/v, = 10-2
42. .
.
.............,
............ .............
.
................
pH ............................
22-0188-02.indd 146
5/11/2013 11:36:30
147
43.
1 25 C 1%. a
25 C;
Ka = 10-4
44.
0,1 ;
. To p 1.
. [H3O+] >> [-]
. [3O+] = [-]
. To pH 1.
. To pH 1.
45. 3 L
0,1 p
1 ; a = 10-7.
46. 25 mL 1 Kb = 10-6
75 mL H2O 100 mL .
1: 2 ;
47. mL CH3COOH 0,1
H3O+ 10 mL HCl 0,05 ;
: a CH COOH = 10-5.
297 L
1 /2 = 1/2
500 mL
48.
.
. 10-2
1 = 10-2 1
2 = 510-3, 1 > 2.
. a a
= 25 C, .
. , .. HCI 1
(a = 1), .
. , .. HF 1
, .
* 49. HCOOH p
2. HCOOH
200 mL
HCOOH ;
a = 10-4.
* 50.
.
. p ,
;
. , ;
9,2 g
22-0188-02.indd 147
9/4/2014 12:04:25
148
51. 2%,
4%. ,
;
* 52. CH3COOH 0,1
1 %. [3+] HCOOH
1 10-2 . ;
To HCOOH
53. 5 L NaCl 0,1 . pH ;
pH = 7
54. pH NH4Cl 0,1 ;

Kb 3 = 10-5 Kw = 10-14.
pH = 5
55. 200 mL 2O 1,36 g HCOONa. pH

; a HCOOH = 10-4 Kw = 10-14.
pH = 8,5
* 56. 10 L CH3COONa 1 p = 10 90 L 2O.

pH ;
pH = 9,5
57. 0,1 (I) pH

(II). .
I
II
HCl
13
NaA
NaOH
. a = 105
. a , Kw = 10-14.
.
58. .
. NaF HF 0,1 , :
,
HF ...............,
HF ................. ............ a HF.....
................
. , .. HCl, ,
.. NaCl, HCl .............. ..............
59. CH3COOH
.
. CH3COOH 0,1
. CH3COOH 0,1 CH3COONa 0,1
Ka ch cooh = 10-5.
. 1%, . 0,01%
22-0188-02.indd 148
5/11/2013 11:36:30
149
60.

.
I
II
HCl 0,1
10-2
0,1
HCl 0,1 NaCl 0,1
0,1 NaA 0,1
10-4
61. 3 p
3 0,1 NH4CI 0,1 ;
b NH = 10-5 Kw = 10-14.
= 10-4 p = 9
62. 400 mL CH3COOH 6% w/v 0,82 g CH3COONa

400 mL ().
CH3COOH ; Ka ch cooh = 10-5.
= 4 10-4
* 63. 4 L 3 0,1 3 1%
6 L NH4Cl 0,05 10 L
(). Kb 3 [-] ();
Kw= 10-14.
* 64. . , ,
a = 3 10-4.
0,3 .
. pH = 1,
0,3 . .
[-] = 1,33 10-5
. 3,16 10-2, . 3 10-3
65. To HCl (a = 1), H2SO4

.
(1 = 1) Ka 2 = 1,3 10-2.
p HCl 0,1 H2SO4 0,1 .
66. 200 mL HCl 0,1 300 mL
0,28% w/v. p ;
67. HCI 2 L NaOH
pH = 13 pH ; (
2 L).
p = 2
6,57 g
22-0188-02.indd 149
5/11/2013 11:36:30
150
68. mL 3 0,63% w/v 2 L
NaOH pH = 12
pH = 3;
* 69. HCl
p = 2 pH = 13, p = 11;
70. 100 mL HCl 0,1 () 200 mL 3 0,1 () 300 mL ().
pH A, , ; b NH = 10-5 Kw = 10-14.
222,22 mL
9:1
1, 11, 9
71. CH3COOH 0,5 () 0,1 CH3COOH 100 mL.

. mL ;
. 100 mL () 50 mL CH3COONa 0,2
(). pH (B);
. mL NaOH 0,1 100 mL
() () pH = 5;
: a = 10-5.
** 72. NH3 0,1 ().
. pH (A);
. 110 mL () mol HCl
pH ;
: b NH = 10-5 Kw = 10-14.
. 20 mL, . p = 5, . 50 mL
. 11, . 0,001 mol
73. H2SO4; (1 = 1, a = 1,3 10-2)

2
. HSO4. SO42. 3O+
. H2SO4
** 74. [3+]
0,05 a HA = 410-5 0,1 a HB = 10-5.
** 75. 0,1 0,1
. To pH 1.
. Ka HB, a HA = 0,2 Kw = 10-14;
. ;
1,7310-3
. a =0,05, .
.
76.
.
. 0,1
0,2 .
. NaF KF .
22-0188-02.indd 150
9/4/2014 12:05:08
151

. N3 0,1 NH4Cl 0,2

.
. N4Cl 0,1 NaCl 0,2
.
77. ;
. HCN 0,1 - NaCN 0,2
. 3 0,1 - NH4Cl 0,3
. NH4Cl 0,1 - HCl 0,2
. H2S 0,1 M - NaHS 0,1
. CH3COONa 0,2 - NaOH 0,1
78. a HF = 10-4, b NH = 10-5 Kw= 10-14.
3
(I) p ,
(II).
I
II
3 0,1 4Cl 0,1
HF 1 NaF 0,1
HCl 0,1 NaCl 0,1
10
3 1 NH4Cl 0,1
79. 0,2 L CH3COOH 0,1 3,28 g CH3COONa

. p
; (a = 210-5)
80. 2 L 3 0,5 8 L NH4Cl
0,125 10 L . p
; (b = 10-5 Kw = 10-14)
* 81. CH3COOH 0,1 CH3COONa
0,1 , p = 5.
. a CH3COOH;
. 2 L 18 L 2O .
p ;
. 2 L 0,003 mol NaOH
. p ;
. 2 L 8 L HCl 0,001
10 L . p ;
p = 5
p = 9
Ka = 10-5, pH = 5, p = 5,013,
p = 4,97
* 82. mol NaOH 2 L NH4Cl

0,1 p = 5,
p = 9;
0,1 mol
* 83. HCIO2
0,9 NaClO2 0,3 p = 7;
a = 10-6 Kw = 10-14.
1:30
22-0188-02.indd 151
5/11/2013 11:36:31
152
* 84.
NaA :
. To pH
-.
. To pH pH
.
. To pH pH
.
. To pH
H+
CH3COOH
* 85.
0,1 NaOH 0,2
p = 5; : a CH COOH = 10-5.
3
* 86. 400 mL 3 0,1 NH4Cl 0,1

pH = 9, 400 mL NaOH 0,1 .
pH ; pH;
Kw = 10-14.
4:1
p = 11
. -
* 87. a = 2,510-6.
[] / [-]
10, , [] / [-]
0,1, .
. pH ;
. 3 0,1
. ; b = 10-5.
. p < 4,6, .
88.
,
pH 10 , ,
p 8.
:
. HCl 0,01 ,
. NaOH 0,01 ,
. CH3COOH 0,01 ,
. CH3COONa 0,01
, . ;
* 89. 50 mL CH3COOH 0,1
25 mL NaOH.
,
.
. Molarity NaOH;
. p ;
.
22-0188-02.indd 152
. 0,2 , . p = 8,91,
.
5/11/2013 11:36:31
153
: p: 3 - 4,4
p: 8,3 - 10,1;
: a ch cooh = 10-5.
3
* 90.
CH3COOH (a = 1,810-5) 3 (b = 1,810-5);
p
.
. (p: 3 - 5)
. (p: 4,5 - 6,5)
. (p: 6 - 7,6)
. (p: 7,2 - 8,8)
.
91.
.
.
.
. Ks AgCl > Ks Ag CO , AgCl
2 3
Ag2CO3.
.
.
. Ks .
92.
(I) Ks
(II).
I
II
AgCl: 10-5 M
4 . 10-12
Mg(OH)2: 10-4 M
10-10
Fe(OH)2: 10-5 M
2,7 . 10-31
Al(OH)3: 10-8 M
4 . 10-15
93. 1 L BaSO4 0,00256 g

BaSO4. BaSO4.
r BaSO = 233.
Ks = 1,21.10-10
94. CaF2 100 L 2O;

CaF2: Ks CaF = 410-12 r CaF = 78.
2
0,78 g
* 95. +- Na+A- 0,1

10-8 . Ks .
Ks = 10-9
22-0188-02.indd 153
5/11/2013 11:36:31
154
96. : AgCl
s AgCl = 10-10 Ag2CrO4 s Ag CrO = 4 10-12;
Ag2CrO4
97. To pH n()2 10.

Ks n()2. Kw= 10-14.
5 10-13
98. 0,39 g CaF2,

;
: s CaF = 4 10-12 Mr CaF = 78.
2
50 L
99. 60 C
2 ) 15 C.

60 C 15 C;
* 100. MgCl2 0,1
AgCl 1 L ;
Ks AgCl = 10-10.
* 101. MgCl2 0,01 NaOH. Ks MgCl2
= 9 10-12 :

. [-], Mg(OH)2.

. [-],
Mg(OH)2.
* 102. 1 L NaF 1 1 L MgCl2 c .
c,
Mg(OH)2; : a HF = 10-4, Kw = 10-14 s g(OH) = 9 10-12.
Ks = 27sp
20000 L
3 10-5 M
0,36 M
-3
* 103. 200 mL Ca(N3)2 10 300 mL -
NaF x .
x, CaF2; Ks CaF = 10-12.
2,63 10-4
*104. 400 mL BaCl2 10-5
100 mL K2SO4 10-4

BaSO4. Ks BaSO4;
1,6 10-10
* 105. 200 mL Ba(NO2)2 210-2 200 mL
K2SO4 210-6 . mol BaSO4 ; : Ks BaSO = 10-9.
3,6 10-7
** 106. 20 mL MCl 0,1 ( +
) 10 mL NaOH 0,1 ,
, p = 8.
Ks .
22-0188-02.indd 154
3,3 10-8
9/4/2014 12:06:45
155
** 107. . 3 L Pb(NO3)2 0,04 3 L
NaCl 0,06 , 50% Pb2+ PbCl2.

s PbCl2;
. 3 L Pb(NO3)2 0,04 3 L
NaCl 10-3 . PbCl2;
. 10- 6, .
.
6
+
* 108. [ ] = 10 [3O ].
.

. .

. NaOH 10-4 .

. NH4Cl.

.
NaA.
* 109. 0,1 .
(I)
(II) p . b NH = 10-5 Kw = 10-14.
3
. p
.

. a .
II
HCl
NaA
NaCl
11
NH3
NH4Cl
10
. 1 L NaA 0,1 1 L MgCl2

10-2 2 L ().
Mg(OH)2. Ks Mg(OH) = 10-11.
2
* 110. 1 = 1.

. a ;

. p ;

. 4 L 0,4 mol NaA. p

;

. 2 L 1 2 L
NaOH 0,5 . p
;
. a = 10-7, .
. Ka = 10-6, . p = 3,
. p = 5, = 10-5
. p = 6
* 111. ,
1 .
-
22-0188-02.indd 155
9/4/2014 12:09:40
156

. HCOOH
. HCl
. NaOH
. HCOONa
. NaCl
,
:
pH
14

1 2
p = 4;
1-, 2-, 3-, 4-, 5-

1:2
* 112. 3 0,1 . b NH3= 10-5 Kw

= 10-14.
.
. HCl pH = 12.
. p = 10.
. NH4Cl
NH3
3 .
. 1 = 1 %. 3 .
* 113. 0,01 25 C.

.
. p 12.
. p
13.
. BCl p
p .
. HCl,
p = 7.
** 114. mol NaOH 2 L 1 NaA 1 , 2 L
, p
; Kw = 10-14.

(: )
1,04
* 115. CH3COOH 1 CH3COONa

1 a CH COOH = 10-5.
3

.
22-0188-02.indd 156
5/11/2013 11:36:31
157
. pH = 5.
. NaOH pH
5.
. HCl pH
5,5.
. 4 L
40 L pH 6.
* 116. ,
0,1 .
: KNO3
:
: 3
: 3
: NH4Cl
.
:
pH
13
11
. 100 mL 4
100 mL 5.
pH ;

* 117. 4,2 g NaF 100 mL ().
: Ka HF = 10-4, Kw = 10-14.
. pH (A);
. 20 mL () 10 mL HCl 1 ()
30 mL (). pH
pH ;
. 50 mL () 50 mL
MCI2 0,1 100 mL
() ()2
()2. Ks ()2;
. 1-, 2-, 3-, 4-, 5-

. p = 9
. pH = 9, pH = 0, pH = 4
. 0,25 . 10-11
* 118. To pH RCOONa 0,1

pH RCOONa 0,1 .
;
. pH < 7.
. To pH .
. Kb RCOO- Kb RCOO-.
. RCOOH RCOOH.

* 119.
0,1 : (A) NaCl, () NaOH, () HCOOH, () HCOONa, () HCl.
-
22-0188-02.indd 157
5/11/2013 11:36:31
158
. 100 mL
pH = 4, . mL
;
. ;
.
.
Ka hcooh= 10-4.
** 120. 500 mL NH3 0,08 NH4Cl
0,1 0,05 mol MgCl2 500 mL.
Mg(OH)2;
mol 3 500 mL , Mg(OH)2;
: Ks Mg(OH) = 10-11, b NH = 10-5 Kw = 10-14.
2
. 50 mL (), 50 mL ()
.
. , . 0,01 mol
** 121. mL NaOH .
5 mL NaOH p = 5.
7 mL NaOH
( ,
). a ;
( ).
Ka = 5/710-5
** 122. 1, 2 3
, .
. p ,
NaOH,
10 mL .
.
, ,
.
1
VNaOH
1 mL
16 mL
1 mL

. ,
. p
.
.
.
, NaOH
( ).
. a .
22-0188-02.indd 158
. , . = 1, . 10-3 ,
10-2 , 1,6 10-2 , 10-3
. = 10-4/9.
5/11/2013 11:36:31
159
** 123. 0,3 g 500 mL
0,05 pH = 3. (
).
. STP.
. 100 mL (
) 2
250 mL. pH .
. mol MgCl2 250 mL (), . s Mg(OH) = 10-11.
. 0,28 L, . pH = 8,5,
. 3 10-2 mol
** 124. 1 L AgCl Ag2Cr4 : [Ag+] = 10-4 , [Cl-] = 10-6 , [Cr42-] = 8 10-4 .

. a AgCl Ag2CrO4.
. - Ag+, , 8 10-7 mol
AgCl. mol Ag2CrO4 ;
. 10-10 8 10-12
. 7,68 10-4 mol
** 125. [Cl-] = 10-2 [Br-] = 10-3 .

- AgNO3,
.
. , s AgCl = 10-10
s AgBr = 10-13;
. [Br-] AgCl;
. mol Br-
AgCl;
. AgBr
. 10-5
. 99 10-5

-
90.
91. . , . , . ,
.
18. . , . , . ,
. , .
21.
22.
23.
27.
44. . , . , . ,
. , .
48. . , . , . ,
.
51.
108. . , . ,
. , .
112. . , . ,
30. . , . , . ,
.
33.
38.
39. . , . , . ,
.
73.
76. , . , .
.
77. , ,
84.
88.
. , .
113. . , . ,
. , .
115. . , . ,
. , .
118.
22-0188-02.indd 159
5/11/2013 11:36:32
22-0188-02.indd 160
5/11/2013 11:36:32
4.1
4.2

4.3
-

:
.

( ).

.
().

.. Cu / Cu2+
.

.
()
.

.
,
.
22-0188-02.indd 161
9/4/2014 12:10:41
(Fe23.xH2) ,

4000 .
:
Fe Fe2+ + 2e- 2 + 4+ + 4e- 22
Fe 2+ Fe 3+ ( Fe 23.xH2).
+, , .
pH 9,
.
22-0188-02.indd 162
5/11/2013 11:36:32
163
4
. , , .
- a Kb,

, . ,
,
- .
. ,

. ,
,
.
(
) .

. ,
,
;.
- .
,

.
4.1

.

(
).

( ).

- -
. , n ()
Cu2+, .. CuSO4 . 5H2O (),
Cu2+ n
, :
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
, .
, .
22-0188-02.indd 163
5/11/2013 11:36:32
164
4.1 Zn

Cu2+. Cu2+

Zn

.

.
:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s),
,
:

Zn(s) Zn2+(aq) + 2e2+

Cu (aq) + 2e Cu(s)
,
4.2.,
Zn
Cu,
Cu2+. .
4.2 Daniell John Daniell,
1836.
Daniell
4.3.
, Zn2+,
Zn ( Zn / Zn2+) Cu2+
Cu ( Cu / Cu 2+).

3 KCl NH4Cl 4O3.

.
,
(fritte) .
22-0188-02.indd 164
5/11/2013 11:36:32
165
4.2 Daniell
n Cu
Cu2+, .. CuSO4,
n2+, .. ZnSO4, .

,

.
,
, :
n Cu
Cu. n2+
n2+ Cu2+ Cu2+.
:
(-): Zn, Zn(s) Zn2+(aq) + 2e (+): Cu, Cu2+(aq) + 2e- Cu(s)
n
Cu.
.

.

.

.
() .

(salt bridge).
4.3 Daniell
.
.
22-0188-02.indd 165
5/11/2013 11:36:33
166
( )

, .
Daniell
:
n2+
SO42 - n2+.
n2+, Zn,
. , Cu
Cu2+ .
Cu2+ .

. ,
.
, 4.3,
.

.
,

. , ,
,
.
,
,
.

.
4.4 Daniell .
22-0188-02.indd 166
5/11/2013 11:36:34
167

Daniell
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s),
:
-
Zn(s) Zn2+(aq) + 2e2+
-
Cu (aq) + 2e Cu(s)
:
Zn(s)|Zn2+(aq)|| Cu2+(aq)|Cu(s)
,
() () .
, , ,
.

.

.
, .

:
MnO4- Mn2+
MnO4-+ 8H+ Mn2+ + 4H2O
MnO4- + 8H+ + 5e-
Mn2+ + 4H2O
Cr2O72- Cr3+
Cr2O72- + 14H+ Cr3+ + 7H2O
Cr2O72- + 14H+ + 6e- Cr3+ + 7H2O
4.1
:
2KMnO4 + 5SnCl2 + 16HCl 5SnCl4 +2MnCl2 + 2KCl + 82O
, :
2 . (Mn4- + 5e- + 8+ Mn2+ + 42)
Sn4+ + 2e-)
5 . (Sn2+

4.1 .
2MnO4- + 5Sn2+ + 16+ 5Sn4+ + 2Mn2+ + 82O
Fe2+ Fe3+ Cr2O72-

( H+).
-

,
.
.
, , .
( )
25 C 1 atm
c = 1 .
22-0188-02.indd 167
5/11/2013 11:36:34
168

. , :
> 0,
( ).
< 0, ( ).
= 0, (
).
,

.
.

.
, ,
: = +

Zn, Cu.

914 mV.
4.2

:
Mg(s) + 2Ag+(aq) Mg2+(aq) + 2Ag(s)
:
= -2,37 V
Mg2+(aq) + 2e- Mg(s)
+
= +0,80 V
Ag (aq) + e Ag(s)
:
. = -(-2,37 V)
Mg(s) Mg2+ (aq) + 2e-
+
. = 0,80 V
2Ag (aq) + 2e 2Ag(s)
= . + . = 2,37 V + 0,80 V = 3,17 V
:
Co(s)+ i2+(aq) Co2+(aq) + Ni(s)
:
= -0,28 V
Co2+(aq) + 2e- Co(s)
E = -0,25 V
i2+(aq) + 2e- Ni(s)
(E = +0,03 V)
22-0188-02.indd 168
5/11/2013 11:36:35
169
4.2

-

.

.
, .
,
, :

h = 0 m

h = 30 m,
h = 2917 m

. h = -2 m

.
2H+(aq) + 2e- H2(g) E = 0

:
Zn2+(aq) + 2e- Zn(s) E.
.
:
Zn(s) Zn2+(aq) + 2e- .
.
: . = -.
:

.

, ,
( ):
Zn(s) Zn2+(aq) + 2e- ,
( 4.5)

:
Zn(s) + 2 +(aq) Zn2+(aq) + 2(g)
0,76 V
, :
= +0,76 V
:
:
Zn(s) Zn2+(aq) + 2e- .
:
2+(aq) + 2e- 2 (g) . = 0
= . +
. = - . = 0,76 V - 0 = +0,76 V.

( 4.1).
:

.
:
Fe2+ Fe3+ + e2Fe2+ 2Fe3+ + 2e :
. = -0,77 V
()
, ( = 1 atm, = 25 C, c = 1 M).
22-0188-02.indd 169
9/4/2014 12:12:08
170
()
, ( = 1 atm, = 25 C, c = 1 )

, :
= +

:
Zn(s) + 2+(aq) Zn2+(aq) + 2(g)
4.5.
4.5 Zn / Zn2+.

Cu(s) + 2+(aq) Cu2+(aq) + 2(g),
4.6.
4.6 E Cu / Cu2+.
22-0188-02.indd 170
5/11/2013 11:36:37
171
4.4 4.5
.
HCI 1 .
1 atm ,
.

, .. Ag AgCl.
4.1
(E) .

. = - . , :
Zn (aq) + 2e Zn(s) E. = -0,76 V,
2+
,
: 2+(aq) 2(g)
Zn(s) Zn2+(aq) + 2e- . = 0,76 V.

.
. , ,
H+(aq).
. ,
.
() , F2 Cl2 :
. = +2,85 V
F2 + 2e- 2F . = +1,36 V +2,85 > +1,36
Cl2 + 2e- 2Cl() nO4-
Cr2O72- :
E = 1,5 V
nO4- + 5e- + 8+ Mn2+ + 42O
+
3+
2 = 1,33 V 1,5 > 1,33
Cr2O7 + 6e + 14 2Cr + 72O

. ()
1 .
, nO4 0,1
K2Cr2O7 0,5 ,

. .
.
Nernst. Nernst
.
22-0188-02.indd 171
5/11/2013 11:36:37
172
4.1
( )
22-0188-02.indd 172
5/11/2013 11:36:39
173
.
() .
2(g).
() . ,
.
To Ba Mg :
E = +2,9 V
Ba(s) Ba2+(aq) + 2e-
E = +2,37 V < 2,9 V
Mg(s) Mg2+(aq) + 2e-
2+
O Sn Fe2+ :
E = -0,15V
Sn2+ (aq) Sn4+(aq) + 2e-
2+
3+
-
E = -0,771 V < -0,15 V
Fe (aq) Fe (aq) + e
,
,
.
: F2, CI2, Br2, 2, S.
: , Ba, Ca, Na, Mg, Al, Zn, Fe, H2, Cu,
Hg, Ag, Pt, Au.
4.3
, Au3+ Cr2O72-
/
, ,
1 25 C. ,

, 4.1.
Au 3+ + 3e- Au 1,. = + 1,50 V
Cr2O72- + 6e- + 14H+ 2Cr3+ + 7H2O 2,. = +1,33 V
1 > 2, o Au3+ Cr2O72-.
4.4
, Ca(s) Zn(s);

4.1
Ca(s) Ca2+(aq) + 2e-, 1,. = 2,87 V
Zn(s) Zn2+(aq) + 2e-, 2,. = 0,76 V
1,. > 2,. Ca n.
: Cl-, Br -, F-, I-
(
).
a.
CuSO4
Cu,
:
Fe(s)+Cu2+(aq)Fe2+(aq)+Cu(s)
. Cu
gNO3
Ag, ,
Cu:
Cu(s)+2Ag+(aq)Cu2+(aq)+2Ag(s)
. Zn PbNO3
Pb,
:
n(s)+ Pb2+(aq)n2+(aq)+Pb(aq)
: Ba2+, Au3+, Zn2+, 1+,

Ag+1 (
).
22-0188-02.indd 173
9/4/2014 12:14:20
174
.
> 0,
,
.
,
= 0,
.
Kc .
4.5
Sn2+, Sn4+, Fe2+ Fe3+
1 ( ) ;
Sn2+ + 2Fe3+ Sn4+ + 2Fe2+
, ,

Sn2+ Sn4+ + 2e- . = -0,15 V
2Fe3+ + 2e- 2Fe2+ . = +0,771 V
Sn2+ + 2Fe3+ Sn4+ + 2Fe2+ :
= . + . = -0,15 V + 0,771 V = +0,621 V > 0
> 0 .

= 0 .

;
10Cl- + 2n4- + 16+ 5Cl2 + 2n2+ + 82O
10Br - + 2n4- + 16+ 5Br2 + 2Mn2+ + 82O
10F- + 2n4- + 16+ 5F2 + 2Mn2+ + 8H2O
( .)
4.3

. , , , ,
..

(
).
.

,
.
:
22-0188-02.indd 174
5/11/2013 11:36:39
175
1. (primary)
,
.
, .
, .
:
() Daniell
:
() ,
Daniell ( ),
.
Leclanch, , ,
.. Zn,
( )
nO2 ( ).
ZnCl2 NH4Cl ,
, ().
,
:
( -): Zn(s) Zn2+(aq) + 2e ( -):
2n2 + 2NH4+ (aq) + 2e- n23(s) + 23(g) + 2(l)
4.7 Leclanch .
4.8 .
22-0188-02.indd 175
5/11/2013 11:36:41
176
Leclanch
NH4Cl
.
. :
(-) : Zn(s) + 2OH-(aq) Zn(OH)2(s) + 2e (+) :
2MnO2(s) + 2O(l) + 2e- Mn2O3(s) + 2OH-(aq)
2. (secondary cell)
,
.
,
().
... ,
, .
,
Pb PbO2
H2SO4 20%.

(
alternator).
, , :
2+
(-) : PbSO4(s) + 2e- Pb0(s) + SO42-(aq)

2+
(+) : PbSO4(s) + 22O Pb2(s) + 4+ + SO42-(aq) + 2e-
-

. electrophorus
electicus
. ,
, ,
, ,
,
.
:

.
Pb PbO2

. .
2+
(-) : Pb(s) + SO42-(aq) PbSO4(s) + 2e (+) :

4+
2+
PbO2(s) + 4 +(aq) + SO42- (aq) + 2e- PbSO4(s) + 22O(l)

:
Pb(s) + PbO2(s) + 4+(aq) + 2SO42- (aq) 2PbSO4(s) + 22O(l)
3. (fuel cells)
, , .. CH4 2.
, 4.10.
2
: 2H2(g) + O2(g) 22O(l)

(-) : 220(g) + 4O-(aq) 4H2O(l) + 4e2-
(+) : O20(g)+ 22O + 4e- 4O-
22-0188-02.indd 176
5/11/2013 11:36:41
177

.
.

(Ni-Cd),
Nicad.
Cd
i(),
.
, ,
, ,
:
Cd + 2O- Cd(OH)2 + 2eNiO(OH) + 2O + e-
Ni(OH)2 + OH-
4.9 .
4.10 .
22-0188-02.indd 177
5/11/2013 11:36:44
178
...
: 90 km h-1
: 0-50 km h-1 9 s
: 8 h

70

(superbatteries),

.

. ,

. H
- ,

, , ,

.

.
22-0188-02.indd 178
500
, ,
80.
, General
Motors,

1980.
,

.

1980.

.

5/11/2013 11:36:44
179
.

.
-
30
(30 watt hr Kg-1)
700
.
1700 Kg
-
500 Kg
30 Km 11 Km .

.

50%.

- .
1979 GM
60
watt hr Kg-1.
Na ,

22-0188-02.indd 179
,
Na+,
.
- 600
120 watt hr Kg-1.

. -
.

. Cl2

- - .
.
.

.
, ,
.
5/11/2013 11:36:44
180
1.

.
2.
.
3.
, .
4.

.
5.
> 0.
6.
( )
25 C 1 atm
c = 1 .
7.

2 .
8.
,
0 ( = 0), 2+(aq) + 2e- 2(g).
9. +x + xe-
. . > 0, +x
+.
10. +y + ye-
. . > 0,
2.
11. ,
,
.
12. ,
. ..

= . + ..
13. , > 0,
.
14.
.
22-0188-02.indd 180
5/11/2013 11:36:44
181
15. :
. : .
(i) Daniell (ii) .
. :
() , ,
.
. :
, .. 2,
, .
- -

1. ;
2. :
3.
: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s);
4. ;
5. :
Zn(s) Zn2+(aq) + 2e-;
6. = 0;
7.

;
8. = . + . > 0,
;
22-0188-02.indd 181
5/11/2013 11:36:45
182
9. ;
10. ;
11.

;
12. ;
-
13.
:
.
..............................
........................ .........................
.
. ...............................
..................................... .
. ..............................
..................... .
. ...............
................... .
. ............................
..................................... .
14.

15.

.
. .
. .
.
.
.
.
.

.
* 16.

.
22-0188-02.indd 182
5/11/2013 11:36:45
183
e-
nO4- n2+
Fe3+ Fe2+
Cr2O7 2Cr
2-
BrO
3+
6
5
17. :
. Fe2+ Fe3+ nO4- .
. 22- O2 Cr2O72- .
. S2- S0 Cl2.
18. :
. Sn2+ Sn4+ Cr2O72- .
. Hg Hg2+ nO4- .
. I-1 20 F2.
19. Mg
Mg(NO3)2 1 Ag
AgNO3 1 .
. .
.
.
. .
:
Mg2+(aq) + 2e- Mg(s) = -2,37 V
E = +0,80 V
Ag+(aq) + e- Ag(s)
20. :
Zn2+(aq) + 2e- Zn(s)
E = -0,76 V
2+
E = -0,28 V
Co (aq) + 2e Co(s)
E = -0,25 V
Ni2+(aq) + 2e- Ni(s)
E = +0,34 V
Cu2+(aq) + 2e- Cu(s)
E = +0,80 V
Ag+(aq) + e- Ag(s)

:
Co(s) + Ni2+(aq) Co2+(aq) + Ni(s)
Cu(s) + 2Ag+(aq) Cu2+(aq) + 2Ag(s)
Zn(s) + 2Ag+(aq) Zn2+(aq) + 2Ag(s)
+3,17 V
+1,1 V, +0,03 V, +0,46 V,

+1,56 V
* 21. To E A(s) + B2+(aq) A2+(aq) + B(s)
E = +1,5 V. 2+(aq) A(s) + 2e- . = 1,2 V,

:
2+(aq) + 2e- B(s)
+2,7 V
22-0188-02.indd 183
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184
22. , : Co, Fe,
2, Zn, Al.
23.
:
Fe3+(aq) + e- Fe2+(aq)
2Hg2+(aq) + 2e- Hg22+(aq)
24. :
, Mg, 2, Cu,

.
K(s) +(aq) + e-
+2,37 V
Mg(s) g2+(aq) + 2e-
-0,34 V
H2(g) 2H+(aq) + 2e-
+2,93 V
Cu(s) Cu2+(aq) + 2e-
25.
F2, Cl2, r2, I2

.
F2(g) + 2e- 2F-(aq)
+1,07 V
Cl2(g) + 2e- 2Cl-(aq)
+2,87 V
r2(g) + 2e- 2Br -(aq)
+1,36 V
I2(s) + 2e- 2I-(aq)
+0,35 V
26. Ag(s) Ag+(aq)

;
.
l2.
27.
:
2Fe3+(aq) + 2I-(aq) 2Fe2+(aq) + l2
:
Fe3+(aq) + e- Fe2+(aq) = +0,77 V
= +0,53 V
I2 + 2e- 2I-(aq)
28. o Sn(s) Zn2+(aq)
;
.
22-0188-02.indd 184
5/11/2013 11:36:45
185

* 29. ) 23 V.
V ;
) :
V5+(aq) + e- V4+(aq)
V4+(aq) + e- V3+(aq)
V3+(aq) + e- V2+(aq)
V2+(aq) + 2e- V(s)
= +1,0 V
= +0,36 V
= -0,25 V
= -1,2 V

Zn :
= -0,76 V
n2+(aq) + 2e- Zn(s)
30.
, r2(l)
NaCl NaI 25 C.
.
* 31. 4 :
Sn2+(aq) +2e- Sn(s)

Fe3+(aq) + e- Fe2+(aq)
2Hg2+(aq) + 2e- Hg22+(aq)
Br2(l) + e- Br-(aq)
= -0,14 V
= +0,77 V
E = +0,92 V
E = +1,07 V

.
1. Sn + 2Hg2+(aq) Sn2+(aq) + Hg22+(aq)
2. 2Fe2+(aq)+ 2Hg2+(aq) 2Fe3+(aq) + Hg22+(aq)
3. 2Br-(aq) + Sn2+(aq) Br2(l) + Sn(s)
4. 2Fe2+(aq) + Br2(l) 2Fe3+(aq) +2Br- (aq)

-
15. . , . , . , . , .
23. Hg2+
27.
28.
29. , , ,
30. I-1 2
31. , , ,
22-0188-02.indd 185
5/11/2013 11:36:45
186
22-0188-02.indd 186
5/11/2013 11:36:45

:

.
.
,

.
C-C,
C=C C C.

,
.

( ).
, .
,
.
R, S,

.
, .

.
.
,

.

, ,
, , ..
, ..
.
, ,
.
.
22-0188-02.indd 187
5.1
-
5.2 ( )
5.3
5.4 .

-

.

,

.
Friedrich Whler, 1935
5/11/2013 11:36:45
. (pilot
plant), . ,
().
22-0188-02.indd 188
5/11/2013 11:36:50
189
5
5.1 -
(Valence bond theory)

. ,
, Lewis
VSEPR -
,
.

,
.
,
.
.
,
. ,
,
.
.
:
1. ,

.
2.
,
spin .

.
3.
,
( ) .

:
1. .

.
2.

.
, ,

,

.
,
,
,

.
3.
,
.
4. ,
( )
( ).
() ()

-
, .
2,
.
,
.

22-0188-02.indd 189
5/11/2013 11:36:50
190
/ kJ mol -1
( 5.1).
,
. .
- 0,74 (74 pm). 5.1

- 436 kJ/mol.
-436
0,74

5.1 -
.
,
, ,
.

. ,
s-s () .
() (overlap) s + s . ()
s-p p-p, 5.2. ,
:
() s-s, s-p p-p

.
.
22-0188-02.indd 190

.
(

)
.
5/11/2013 11:36:50
191
5.2 s p p
p ,
, .
,

.
() .
() , ,

( ),
. :
1. T s ,
.
2.
.
3. ,
.
:
p
p ,

.
() p-p
( )
.

.
. F: :

H

1

F
9
1s

2py
1s
2s
2px

2pz
1s 2pz F
, 5.3, .
(HCl, HBr, HI).

22-0188-02.indd 191
9/4/2014 12:16:56
192
5.3 HF.
. 2: 2
:

N

7

N
7
1s
1s

2s
2s

2px
2py
2pz

2px

2py
2pz
p .

, ,
p , p-p
, 5.4.
5.4 2
.
22-0188-02.indd 192
5/11/2013 11:36:52
193
,
, ,
.. .

.
sp
(BeF2)

:

Be

4

F
9
1s
2s
1s 2s

2px

2py
2pz
Be ,
.
BeF2 2s
2p. , :

Be
4
1s

2s

2px

2py

2pz
,
Be BeF2 , s + p
p + p.
BeF2 .

, Pauling
1931.
Linus Pauling (1901-1994).

,

20 .
,
,
.

.

.

, .

1954
, 1962

.
22-0188-02.indd 193
5/11/2013 11:36:53
194
( )
a
( ).

, ,
.
( 5.5). ,

,
, .. .
, Be BeF2 s p
Be
. sp
50% s
50% p. 5.5
.
.

,

.
.
5.5 s p
sp .
sp Be p F ,
:
5.6 sp
Be p F BeF2.
sp2
, BF3
:
22-0188-02.indd 194
9/4/2014 12:17:40
195

B

5

B
5
1s
2s
1s
2s

2s

1s

2px
2py
2pz
2px

2py
2pz
2px
2py
2pz
sp2
sp2
, ,
(sp2), s p .
sp2 ,
:
5.7 s p
sp2 .
sp2 p
F ,
:
5.8 sp2
2p F.
22-0188-02.indd 195
5/11/2013 11:36:58
196
sp3
CH4 . ,
C:

C

6

C
6
1s
2s
1s

1s

2px
2py
2pz
2s

2px

2py
2pz
2s

2px

2py
2pz
s p .
, s, p d , ..
dsp2.
sp3
sp3
(sp3)
s p :
5.9 s p
sp3 .
CH4.

sp3 C s
, 5.10.
22-0188-02.indd 196
5/11/2013 11:37:00
197
5.10 CH4.
C-C

s-sp3
sp3-sp3 .
5.11 C2H6 .
C=C
,
> C = C < .. CH2 = CH2.
:

C
6

C
6
1s
2s
1s
2s

2px

2py
2pz
2s

2px
2py
2pz
1s

2px
2py
2pz
sp2
sp2
sp2
p,
.

22-0188-02.indd 197
5/11/2013 11:37:01
198
sp2-s. C
sp2-sp2 pz-pz.
, > C = C <
. .

, .. .
5.12 (CH2=CH2).
, .

HC CH.

C

6

1s
2s
1s
2s

2px
2py
2pz
2px

2py
2pz
, s p,
sp p
(py, pz), .

C

6
1s sp 2py
2pz
22-0188-02.indd 198
5/11/2013 11:37:01
199
HC CH, C
( sp-s), C
( sp-sp)
( p-p), 5.13.
5.13 (C2H2).
.

. ,
, ,
,
.
.
,
.
() , .
1- C-Cl
Cl, C,
. :

I I I I
CCCCCl
I I I I

. C-Cl C-C, ,
:
H H H H H

C CC C CCI

H H H H H
+
22-0188-02.indd 199
5/11/2013 11:37:02
200
, Cl
( +).
( +)
(
+).
.
( ) ,
.. , -I .
-I :
C6H5- < -2 < -OH < -I < -Br < -Cl < -F < -CN < -NO2.
, .. , +I . +I
:
- < CH3- < C2H5- < -(CH3)2CH - < (CH3)3C- < COO- < O-.

, .

(..
,
3).
22-0188-02.indd 200
5/11/2013 11:37:02
201
5.2
( )

( ).
, ()
.
,
. (cis-trans
), , .
:
( )
( )
Cis -trans
-
,

.
,
, .

. , , ,
.
,
. ,
,
.
22-0188-02.indd 201
5/11/2013 11:37:02
202
(
) .
5.14 ,
.
, .. ,
..
. , ..
, .. ( 5.15).
5.15
( ) ( ).
, .
.

,
(.. ).

(.. ),
).
( )
o.
, .
.
22-0188-02.indd 202
5/11/2013 11:37:06
203
. ,

.

.

.

C*.
E ()

()
,

.

, .
5.16 ( )
.
5.1
( ) ;
, .
) 1-
) 2-
)
) 2-
)
)

CH3CH2CH2OH

*
CH3CH2CHCH3

OH
) CH3CH2CH2COOH
*
) CH3CH2CHCOOH

CH3

C*

-, -, -CH3, -CH2CH3
O C*
-, -CH3,
-COOH, -CH2CH3-
22-0188-02.indd 203
5/11/2013 11:37:09
204
;
, .
) 1-o
) 2-
) 2-
) 1-
R S
,
(C*) . 2- ( ). ,
, ().
,
5.17.
5.17 .
, - ,
.
, , ()
, . 50, Cahn, Ingold Prelog
.
22-0188-02.indd 204
5/11/2013 11:37:11
205
, (
)
.
.

(CHFClBr). ,
: , Br, F Cl.
:
1

C*
C*

(1), (2)
, (3)
,
(4).
, , Br ( 35)
, Cl ( 17)
F ( 9) ( 1).
, : Br > Cl > F > . ,
1, 2,
3, 4. ,
r (1)
(4) H
CI (2)
F (3)
: 1--1-
(CH3CHFCl) :

, .

. , ,
,
.
: Cl > F > C ( -CH3) > . ,
H (4)
(2) F
CH3 (3)
Cl (1)
22-0188-02.indd 205
5/11/2013 11:37:11
206
, , 2-
.
, , ;
H
C
CH3
CH 2CH3
1
OH
, ( )
,
,
.
2-, CH3-
(, , ), -1 CH3CH2-
(C, , ).
,
, CH3CH2- CH3-. :
( -OH) > C ( -CH2CH3) > C ( -CH3) >
H (4)
(3) CH3
CH 2CH3 (2)
OH (1)
, :
2

C*

1,

.
,

.
R S

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

(1 2 3),
22-0188-02.indd 206
5/11/2013 11:37:11
207
R ( Rectus, ).

(1 2 3),

S ( Sinister, ).
.
5.18
.
5.19
.
22-0188-02.indd 207
5/11/2013 11:37:15
208
- -
(.. ,
, ).
. ;

.

.
.

Polaroid Nicol.
5.20 . .
. .

.

.
, ,
, .

(+)
(-).
(+) (-)
. R (+),
S (-), R (-),
S (+).
.

22-0188-02.indd 208

,

(
).
5/11/2013 11:37:18
209
-

. ,
Polaroid
,
.
5.21 .
.
, ,
.

.
[]. .

[],
.
:
[ ] = l c
: .
l: dm
( dm).
c: g/mL (
g/mL).
5.3
10 mL 2 g
100 cm.
+13,4.
;
+13, 4
cm 10 dm [ ] =
=
=
= +6, 7
l = 100
c
10
0
,
2
2g
c=
10 mL
= +13, 4
22-0188-02.indd 209
5/11/2013 11:37:20
210
() 50 mL 5 g
. 40 cm
-8,2.
;
(-32,8)
2 C* -
C*,
,
.
R S.
, , 2
C , ;
:
C*,

2.
, 3 (C*),
23 = 8 .
,
8, .. 7 6,
.
2,3-.
C*
, :
I II .
III IV. , I III,
.
22-0188-02.indd 210
5/11/2013 11:37:20
211
(
) ,
. ,
.
,
. ,
.
, ,

. , :
,
, , .
C*,
,
. C
,
.
2,3-.
.
I II . III IV
, , .
.
, 2,3- ,
.
,
C*, ,
2.
,

.
22-0188-02.indd 211
5/11/2013 11:37:20
212
5.4
:
. 2-
. 2,3-
. 2,4-
. 3-
*
. CH3CHCH2CH2CH3

Br
*
C, .
* *
*
C, 22 = 4 .
. CH3CHCHCH2CH3

Br Br
*
*
*
. CH3CHCH2CHCH3
C

, 3 .
Br
Br

. CH3CH2CHCH2CH3
,

,
Br

.

:
. 2-
. 2,3-
. 2,4-
. 3-
(. 2, . 4, . 3, . 1)
22-0188-02.indd 212
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213

( > C = C <) ()
(). ()

.

.
A 2-, .
H
CH 3
C=C
CH 3
CH 3
C=C
CH 3
H
, ( )
, cis ,
( ) , trans.
> C = C <
C
.
5.22 .
cis-1,2 trans-1,2 .
, , cis
trans. 2--2-,
CH3C=CHCH2CH3
Cl

.
,
,

.
cis - trans

.
.
Cl
CH3
C=C
Cl
CH2CH3
CH3
C=C
CH2CH3
H

,
.
22-0188-02.indd 213
5/11/2013 11:37:22
214
Z

. 1--1--2-- CClBr = CHF
:
H
F
C=C
Cl
Br
Br
C=C
Cl
cis, trans. ,
,
. , 1, 2 1,
2 C
. 1
,
(1 ) 2
(2 ). ,
1
2. : 1 9F, 2 , 1 35Br, 2 17Cl.
1 1 , ( Zusammen = ),
,
( Entgegen = ). :
H
(1) F
C=C
Z
CI
Br (1) (1) F
C =C
E
Br (1)
CI
5.5
;
:
. CH2 = CCl2 1,1-
. CHCl = CHCl
1,2-
(), C
, .
(), C
.
C5H10
.
22-0188-02.indd 214
5/11/2013 11:37:23
215
5.3

:
.
:
, .
.
:
, , , ,
- - .

,

. , ,
,
.

( < 0).

r2 ,

.

:
1. > C = C <
.. CH2 = CH2 + Br2 CH2BrCH2Br
, r2 ,
r2 Br2, ,
. r2
. , r2
,
r2 .
HBr

CH3CH=CH2 + HBr
CH3CHCH3
r
CH3CH2CH2Br
,
, Markovnikov.
1. r2

.
2. .
3. Br2 ,

1,2-.
22-0188-02.indd 215
5/11/2013 11:37:24
216
Markovnikov:

(
+) .
:
. HCl 1-
. HBr 2--2-
2. C C

,
, ,
. ,
,
, .
,
Markovnikov. ,
, ,
.
Vladimir Markovnikov
(1837-1904).
.
,

.
5.6
HC CH + 2
Pt Pd
i
H2C=CH2
+H2
CH3 CH3
Cl
CH3C CH +HCI
CH3C=CH2
H3CCCH3
Cl

HC CH + HOH
+HCI

,
,
.
Cl

H2SO4 / Hg
CH3CHO
HgSO4

CH2=CH-OH ()
.
HCl 2O
.
,
C
C,
,
.
22-0188-02.indd 216
9/4/2014 12:21:07
217
3. :
C=O

, . , , .

+ -
:
:
+
+ -
C = O + HA
C OH
A
,
, :
H
H
R
C=O >
R
C=O >
Ph
C=O >
Ph
C=O >
Ph
C=O >
Ph
C=O
R- (CH2+1-) Ph- (C6H5-).

:
1. 2
C=O + H2
COH
H
2. HCN
-
2-:
C OH + 2H2O
C OH + NH3
CN
COOH
3. Grignard ,
, .
Franois Grignard
RMgX
Grignard .
Franois Grignard (18711935).

.

1900. 5 200

.

1912.
22-0188-02.indd 217
5/11/2013 11:37:24
218
Grignard : R-(MgX)+
> C = :
+
- +
C = O + RMgX
C OMgX
R
Grignard

-
.. CH3MgCl
, :
OMgX
C
OH
C

CvH2v+1 -
+ Mg(OH)X
R
= 1 CH3-
:
.
. ,
(HCHO) RMgX
RCH2OH, (R1CH=O)
R1
R1
CH OH,
C = O
R
R2
R1
RCOH
R2
= 3 CH3CH2CH2-
= 3 (CH3)2CH-
= 4 CH3CH2CH2CH2-
= 4 (CH3)2CHCH2-
= 4 (C3)3C-
. (
).
. Grignard Mg
RX .
RX + Mg
= 2 CH3CH2-
= 4 (CH3CH2)(CH3)CH-
RMgX
,
RMgX ,
Grignard: RMgX + HOH RH + Mg(OH)X

, :
C=C + xY
CC
22-0188-02.indd 218
5/11/2013 11:37:25
219

(.. 2, HCl, ) ,
.
:
1.
.. 1- NaOH,
HBr .
CH2CHCH3 + NaOH
| |
H Br
CH2=CHCH3+NaBr + -
2.
HCl 1,1-
1,2- .
CH3CH2CHCl2 + 2NaOH
CH3CHClCH2Cl + 2NaOH
CH3C CH + 2NaCl + 2H2O

3.
CH2CHCH3
CH2=CHCH3 + H2O
| |
H
170 C
H2S4.
Saytseff.
Saytseff,
,
,
.
, HBr 2-
2-.
2
Alexander Zaitser
Saytseff (1841-1910).

.

.
CH3CHCHCH3 + NaOH
| |
H r

CH3CH=CHCH3 + NaBr + -

HBr 2-
2--2--;
22-0188-02.indd 219
5/11/2013 11:37:25
220

.
: - + - - + -

.
:
1. (RX) ,
+-.
R+X- + +- R + A X

, :
ROH
RNH2
RX
RC=CR
RCN
RR
RCOOR
,
C-.
: RI > RBr > RCl > RF.
:
. NaOH
, ..
CH3CH2CI + NaOH CH3CH2OH + NaCl
. (KCN)
(RCN),
.
RX + KCN RCN +
RCN + 22O +- RCOOH + 3
. (RONa)
. RX
RONa (R R), , ..
CH3Cl + CH3CH2ONa NaCI + CH3OCH2CH3
. 3 , ..
CH3CH2CI + 2 CH3CH2NH2 + HCl
. , ..
CH3Cl + CH3COONa CH3COOCH3 + NaCl
. , ..

CvH2v+1Cl
NaOH
HCl ,
CvH2v+1Cl NaOH
-Cl
- .

RCN

-,
.. CH3CN .

RNH2 ,

, .. CH3NH2
.

HCI

CH3CH2NH3+Cl-.

.
CH3Cl + CH3C CNa CH3C CCH3 + NaCl
22-0188-02.indd 220
5/11/2013 11:37:25
221
2. (ROH)
(-) Cl
SOCl2.
ROH + SOCl2 RCl + SO2 + HCl
To (RCl) ,
(SO2, HCl) .
3.

R-C-OR + H-OH R-C-OH + ROH

,
(.. H2SO4).
,
() ().

sp2 (
).
,

vo
.
120.
4.

, ,
. .
CH4 :
CH4 + Cl2
CH3Cl + HCl
Cl2
CH2Cl2 + HCl
Cl2
CH2Cl3 + HCl
Cl2
CCl4 + HCl
5.

.
.

p

- .

- p

,

,

.
22-0188-02.indd 221
5/11/2013 11:37:25
222
5.23 Kekul ( ).
(
) .

( ).

.
.

3 H2SO4 (
).
2
FeX3 3.

H2SO4.
RX
AlX3 ,
RCOX AlX3.

. ,
, . (..
), (.. )
, ().
.
, :
----...
Polymers, : .
.
12 .

:
R-O-O-R. R-O-O-R +
RO-M-M...M-OR

,
( ) .
.
, ,
.

22-0188-02.indd 222
5/11/2013 11:37:26
223
,
: ,
.
:
. CH2 = CH : CH2 = CH-,
.
:
CH2=CH
(-CH2-CH-)
5.1
CH2=CH-A
ch3-
Cl-
CH2=CH2
(CH2CH2)
CH3CH=CH2
(CH2CH)
CH2=CHCl
(CH2CHCl)
ch3
,
(CHCH2)
CH=CH2
CN-
ch2=chcn
(CH2CH)
(orlon)
CN

.
22-0188-02.indd 223
5/11/2013 11:37:26
224
. 1,4
.
:
CH2=CCH = CH2
(CH2C = CHCH2)v
5.2 o
1,4 CH2= C CH = CH2
2--1,3

CH3- CH2= CCH=CH2
ch3
(CH2C=CHCH2)v
ch 3
2--1,3
CH2=CCH=CH2
Cl
(CH2C=CHCH2)v
Cl
Cl-
1,3-
ch2=ch ch=ch2
(CH2CH=CHCH2)V
Buna
Cis ,
trans ,
.
.

.
.
, .. 1,3 Buna
,
, . ,

.
,
.
(1,3-
) Buna S
( Bu na Na
S ).
1,3- (CH2 = CH-CN)
Buna .
22-0188-02.indd 224
5/11/2013 11:37:26
225
-
-

. :
.
.
:
C
:
C-O, C-N, C-X
C-H.
C
:
C-
C-O, C-N, C-X.

, , , ,
- .
r2 :
-2
-1

CuO ( )

Cu ( ).
-1
CH2 = CH2 + r2 CH2Br-CH2Br

C .. = -2 -1 Br .. = 0 -1.
CH2 = CH2 ,
C-Br.
-
:
1.
(
C-H) ( C-O),
:
RCH2OH
+[]
-H2O
RCHO
+[]
RCOOH
(
C-H):
R1
R2
+[O]
CH OH
-H2O
R1
R2
C=O

n4 K2Cr2O7. (nO4)
n2+. (K2Cr2O7)
(Cr 3+). nO4

K2Cr2O7 (
).
22-0188-02.indd 225
5/11/2013 11:37:27
226
K2Cr2O7
. ,
K2Cr2O7.

( ).

.
2.

(nO4 K2Cr2O7),
, :
1. Fehling ( ),
Cu2+
Cu2O, :
2+
1+
RCHO + 2CuSO4 + 5NaOH RCOONa + Cu2O +2Na2SO4 +3H2O

2. To Tollens, AgNO3,
, Ag+ Ag,

().
1+
0
+
RCHO + 2AgNO3 +33 2 RCOONH4 + 2Ag +24O3

.
3.
() .
+2
+4
HCOOHCO2
COONa
C2
COONa
C2 ( Ca(H)2,
:

Tollens
.

.
5.24 To CO2 .
22-0188-02.indd 226
5/11/2013 11:37:27
227
- ,
,
.
..
:
. 1 1
(.. Na ) .. = 1. C,
.
. 1 ,
.. = 2.
5.7
. RCH2OH RCOOH nO4 H2SO4
5RCH2OH + 4KMnO4 + 6H2SO4 5RCOOH + 4MnSO4 + 2K2SO4 + 112O
4x5
5x4
RCH2OH RCOOH
.. = 4, 2 1
(2 + 2 = 4).
. RCH2OH RCOOH K2Cr27 H2S4
6+
3+
3RCH2OH + 2K2Cr27 + 8H2S4 3RCOOH + 2Cr2(S4)3 + 2K2S4 + 11H2

4x3
3x4
RCH2OH ..
C -1. 2 RCHO, ..
C +1, ,

, .. = 2.

RCHO (.. C: +1)
RCOOH
(.. C: +3) .. 2,

.
RCH2OH RCOOH ..,

, 4.
. HCOOH C2 nO4 H2SO4
2+
7+
4+
2+
5HCOOH + 2KMnO4 + 3H2SO4 5CO2 + 2MnSO4 + K2SO4 + 82O

2x5
5x2
.. C HCOOH CO2 2.
. (COONa)2 CO2 nO4 2SO4
COONa
5
+ 2KMnO4 + 8H2SO410CO2 + 2MnSO4 + K2SO4 + 5Na2SO4 + 8H2O
COONa
.. (COONa)2 2,
2 Na.
22-0188-02.indd 227
5/11/2013 11:37:27
228
. RCHO RCOOH ( RCOONa)
Fehling (CuSO4 + NaOH).
2+
1+
RCHO + 2CuSO4 + 5NaOH RCOONa + Cu2O + 2Na2SO4 + 3H2O

2x1
1x2
. RCHO RCOOH ( RCOONH4)

AgNO3.
1+
RCHO + 2AgNO3 + 33
+H2O
RCOONH4 + 2Ag + 24O3
2x1
1x2
3.

, , , ,
.. CH3C N + 22 CH3CH2NH2
-
, Brnsted - Lowry,
, .
.
,
. , a,
. , ,
. :
RCOOH

1. Na
2. Na2CO3 K2CO3
3. Na
C6H5OH
4. 3
RCCH

1. Na
1. Na
2. Na
ROH
1. Na
:
RCOOH >C6H5OH >ROH>RC CH
22-0188-02.indd 228
9/4/2014 12:22:24
229
,
.
.
RCOOH + H2O RCOO- + H3O+
+ 2
+ 3 +

RCOOH + NaOH RCOONa + 2O
Na
+ aOH
+ 2
Brnsted - Lowry :
B
C65
R2
RC C
R-

RO-
RCOO-
.
CH3NH2 + HCl CH3NH+3Cl
ch3ch2
NH + HCl
ch 3ch2
ch2+ ch2
ch3ch2
NH2+Cl-
22-0188-02.indd 229
5/11/2013 11:37:28
230

.

.
() .
:
+ + :
+ + ,
.

.
,
.
.
()
.

. , HCl
H Cl
. /
Cl
Cl
Cl
Cl

. ..

( ).
( ) (
)
.

.
CH4, :
22-0188-02.indd 230
5/11/2013 11:37:28
231
H
H + C H
H C
,
.

.
. /
HCl -Cl ,
:
-
H+ + Cl
H CI
, ,

. ,

.
, CH3Cl :
-
CH3+ + Cl
CH3 CI
CH3+ .
CH3MgCl:
CH3 MgCl
CH3- + MgCl+
CH3- .

( )
+1.

( ) -1.

-, .. CH3CH2+
.

-, ..CH3C2.
22-0188-02.indd 231
5/11/2013 11:37:28
232
,

.
. .

,

().
,
.
,

. .. 3:

H

N H
:
NO2+, SO3 , R+

:
OH-, CN-, NH3 , R-
F3
F
f

F
,
, .
,
.
22-0188-02.indd 232
Lewis

-

Lewis, :

: .
5/11/2013 11:37:28
233
.

.
,
(Cl-Cl).

.

Cl2
Cl + CH4 HCl + CH3

CH3 + Cl2 CH3Cl + Cl
2Cl

( ).
:

. .

:

Cl + Cl Cl2

Cl + CH3 CH3Cl
CH3 + CH3 CH3 CH3
To
.
:
CH2Cl2
CHCl3
CCl4
.

.
SN2.
180
,
. .. - ()
CH3Br:
+
Br
Br
H
H C O-H
H
_
H
C
H
_
22-0188-02.indd 233
5/11/2013 11:37:29
234
SN1
. ,
( )
. ..
CN- () (CH3)3C-Br:
CH3
CH3 C+
CH3
CH3
CH3
+ CN
CH3 C
CN
CH3
CH3 C
CH3
+
+ Br
Br
CH3 C
CH3
CH3
.

:
HNO3+ H2SO4 HSO4- + NO2+ + H2O

O2+, :
O2N
H
+
NO2

, C- :
O2N
H
+
NO2
+ H+
.

, .. HCl
CH2 = CH2.
:
HCl (+). ()
- ,
C-, ,
.
22-0188-02.indd 234
5/11/2013 11:37:29
235
H
CH2
CH3
CH2
CH2
+ Cl-
+
, , ,
,
. .
Cl-
, - C-Cl,
Cl-.
CH3
Cl-
CH2Cl
CH2 +
CH3
.
> C =
() (). ,
C = C , ,
:
+
C=O

C .
C,
() ,
.
+

, :
+
C= +
O
C
22-0188-02.indd 235
5/11/2013 11:37:29
236
+
+ -
HCN, :
CH3
C = O + HCN
H
CH3
H
CH3
H
OC
+ H+
CN
+ H+
CN
CH3
H
C
CN
R(MgX)+, :
CH3
CH3
CH3
CH3
22-0188-02.indd 236
C = O + RMgX
O+ MgX+
R
CH3
CH3
CH3
H
+ MgX+
MgX
C
5/11/2013 11:37:29
237
5.4

,
.

.
.

.
I.

.
5.8
, .
CH2 = CH2
CH3COOH

. .

.
H
CH3CH2OH
CH2 = CH2 + 2
ch3cooh + h2o
CH3CH2OH + 2[]
+
5.9

,

, ..
n4 , [],

2.
CH3CH = CH2
CH3 - C CH
To ,
.

NaOH.
:
ch3ch=ch2 + CI2
CH3CHch2
CI
ch3chch2
Cl
Cl
+ 2NaOH
CI
22-0188-02.indd 237
5/11/2013 11:37:29
238
5.10
2- 1-
;
CH3CH2CH2OH
CH3CHCH3

1 2.
2-
.
1-.
CH3CH2CH2OH
2SO4
ch3ch=ch2 + 2
ch3ch=ch2 + 2
+
CH3CHCH3
1. , .
2. 1-
1-.
3. 1-
1-.
II.

( ).
22-0188-02.indd 238
5/11/2013 11:37:29
239
,
-,
.

.
. .

,
Na NaOH
.
Na2CO3 + RH
RCOONa(s) + NaOH(s)
, , .

:
.
CH3
CHOH
0
CvH2v+1
.
CH3
CO
0
CvH2v+1
Cl2, r2 I2 NaOH .
:
CH3
CHOH + 42 + 6NaOH
CvH2v+1
CHX3 + CvH2v+1COONa + 5NaX + 5H2

X = Cl, Br, I
22-0188-02.indd 239
5/11/2013 11:37:29
240
:
1. .
CH3
CH3
C + 2
C=O + 2
CvH2v+1
CvH2v+1
2. .
C3
CH3
C=O + 32
C=O + 3
CvH2v+1
CvH2v+1
3. -CX3 --
(CHX3).
OC3
C=O + OH
C=O + CHX3
CvH2v+1
CvH2v+1
, :
CH3
C=O + 3Cl2 + 4NaOH
CHCl3 + CvH2v+1COONa + 3NaCl + 3H2O
CvH2v+1
, (CHI3)
.
5.11
.
CH3CH2OH CH4
,

.
CH3COONa
.
CH3CH2OH + 2[O]
CH3COOH + H2O
CH3COOH + NaOH
CH3COONa + NaOH
22-0188-02.indd 240
CH3COONa + 2O
CH4 + Na2CO3
5/11/2013 11:37:29
241
5.12
CH3CH = CH2
CH3COOH

. ,
2- .
CH3CH=CH2 +
CH3CHCH3
OH
CH3CHCH3 + 4I2 + 6NaOH
CH3 + CH3COONa + 5NaI + 5H2O
OH
CH3COONa + HCI
CH3COOH + NaCl
1.
1-
.
2. 1-
.
.
,

, :
i)
RCN + KCl
RCl + KCN
+
RCOOH + 3
RCN + 22

ii)
,
,
-.
R
R
C= + HCN
R
|
RCCN
|
OH
+22
H+ OH-
R
|
RCCOOH + NH3
|
OH
22-0188-02.indd 241
5/11/2013 11:37:29
242
5.13
CH2 = CH2 CH3CH2COOH

.
CH2 = CH2 + HCI CH3CH2Cl
CH3CH2Cl + KCN CH3CH2CN + KCl
CH3CH2CN + 2H2O
h+
OH-
5.14
CH3CH2COOH + NH3

2- ( ).
CH3CH2OH CH3CHCOOH
-
CH3CHCN HCN
, .
CH3CHO + H2O
CH3CH2OH + [O]
ch3chcn
CH3CHO + HCN
ch 3chcn
OH
+ 2H2O
OH
+
-
CH3CHCOOH
+ 3
1. 1-
.
2. 2-
2--2- .
22-0188-02.indd 242
5/11/2013 11:37:29
243
.

,
.
i) Wurtz:
2RX + 2Na
RR + 2NaX
ii) :
CuCl
HC CH + HC CH
NH4CI
CH2 = CH - C CH

,
.
iii) Grignard.
5.15
.
;
CH2 = CH2
CH3CH2CH2CH3
.
Wurtz.
CH3CH2Br
CH2 = CH2 + HBr
2CH3CH2Br + 2Na
CH3CH2CH2CH3 + 2NaBr
5.16
CH3CH2OH
2-.
; CH CH CHCH
CH3CH2OH
3
2
3
OH
2- CH3CH2MgCl CH3CHO,
.
CH3CH + H2
CH3CH2H + ||
CH3CH2Cl + S2 + HCl
CH3CH2OH + SOCl2
CH3CH2Cl + Mg
CH3CH2MgCl
22-0188-02.indd 243
5/11/2013 11:37:30
244
CH3
H
CH3
C=O + CH3CH2MgCl
CH3CHCH2CH3
OMgCl
OMgCl
H
CH3CHCH2CH3
+ H 2O
OH
CH2CH3
+ Mg(OH)Cl
1.
2,3-.
2.
2,3--2-.
.

,
:
i)
,
.
HC CH + Na NaC CH +
2 2
H C CNa + RX HC CR + NaX
HC CR + Na NaC CR +
1
H
2 2
NaC CR + RX R CR + NaX
ii)
RC = + CaCO3
(RCOO)2Ca
iii) Grignard
5.17

1-.
HC CH
22-0188-02.indd 244
CH3CH2C CH
5/11/2013 11:37:30
245

.

1
HC CH + Na HC Na + H2
2
HC CH + H2
CH2 = CH2
CH2 = CH2 + HCl CH3CH2Cl

HC CNa + CH3CH2Cl HC CCH2CH3 + NaCl
5.18

2-.
HC CH
CH3CHCH3
OH

.
.
HC CH + 2
Hg2+
CH3CHO
2CH3COOH + Ca(OH)2
(CH3COO)2Ca
CH3COCH3 + H2
Ni
[]
CH3COOH
(CH3COO)2Ca + 2H2O
CaCO3 + CH3COCH3
ch 3chch 3
OH
1.
3-.
2.
3-.
22-0188-02.indd 245
5/11/2013 11:37:30
246
-
,
()
.
,
: ,
, .. ,
,
.
,
.

(, - , - ,
- , - ),
- .
I. Br2 CCl4
, :
C=C
+ Br2
C C
Br Br

.
II. RC CH
CuCl RC CCu.
RC CH + CuCl + 3 RC CCu + NH4Cl
R-C CH
. ,
2 Na
RC CH.
22-0188-02.indd 246
5/11/2013 11:37:30
247
5.19

.
;
CuCl,
, :
HC CH + 2CuCl + 23 CuC CCu + 2N4Cl
( ,
). ,
r2 CCl4. ,
CH2 = CH2, .
CH2- CH2
ch2=ch2 + Br2
Br
Br
1. C 4H 6.
, ,
;
2.
.
;
-
1. ,
(Na).
2, .
ROH + NaRONa + H2
, .
2.
,
(
). ,
.
KMnO4. ,

n4, .
3. :
CvH2v+1CHOH
CH3
22-0188-02.indd 247
5/11/2013 11:37:31
248
,
. ,
I2 + NaOH
( ), :
CvH2v+1CHOH
CH3

, CH3CH2OH, .
5.20
C4H10O
Na .
;
C4H10O C4H9OH (4
) (3 ). Na
4 C4H9OH.
,
-2- ( ):

CH3
ch3Cch3
OH
5.21
:
1-, 2-, , 2--1-.
.
(1, 2, 3 4)
:
. 1, 3 4 .
. 3 .
. 4 ,
NaOH.
,
.
() 2
.
, . 2
(CH3CH2OCH3).
22-0188-02.indd 248
5/11/2013 11:37:31
249
() 3
. .
3 2--1- (CH2 = CHCH2OH).
() 4
.
,
2- . 4 2-
1 1-.
1.
-1- 2-;
2. C38O.
,
;
NaOH ;
3. : ,
.
.
,
;
-

,
.
1. ,
. ,
.
Tollens ( ).

RCHO + 2CuS4 + 5NaOH RCOONa + Cu2 + 2Na2S4 + 3H2O
To
Cu2O.
AgNO3
RCHO + 2AgNO3 + 33 + 2ORCOONH4 + 2Ag + 2NH4NO3
To Ag
( ).
2. :
RCCH3
22-0188-02.indd 249
5/11/2013 11:37:31
250
,
. , I2 + NaOH
, (CHI3),
.
,
.
5.22
C5H10O.
.
.
, .
,
:
ch3cc 3h7
ch3ch2cch 2ch3
, . ,
. , ,
3-.
ch 3ch2cch 2ch3

1. () C3H6. ()
AgNO3 Ag.
(A);
2. () C5H12O :
() ()
,
. ;
-

.
CH2O2.
, :
, ,
..
22-0188-02.indd 250
5/11/2013 11:37:31
251
1. ,
. , ,
, ,
,
. , .

.
CO2, . ,
.
2.
, ,
. ,
.
,
.
3. ,
( )
.

NaOH :
RCOOR + NaOHRCOONa + ROH,

.
5.23
C4H8O2. ,
.
, .
,
. .

. ,
, .
,

. , ,
(HCOOH).
, .
1- 2-. ,
, (),
.
2- . ,
22-0188-02.indd 251
5/11/2013 11:37:31
252
2-.
:
HCOOCHCH3
CH3
1. :
) ;
) ;
) ;
2. C4H8O2. . , . ;
ROH, ArOH RCOOH

.
2ROH + 2Na 2RONa + 2
,
a 2 10-16. ,
pH 7.
C6H5OH
a C6H5OH 10-10. a
C6H5OH a1 H2CO3,
10-6, a
RCOOH, 10-5.
5.24
1 2
CH3COOH C6H5OH.
.
.
2 , 1
. ;
CH3COOH
:
CH3COONa + 2 + CO2
CH3COOH + NaHC3

. 2
CH3COOH 1
C6H5OH.
22-0188-02.indd 252
9/4/2014 12:23:49
253
5.25
1-.
;
NaOH.
( ),
. 1-.
C6H5OH + NaOH
C6H5ONa + 2O
1-
C6H5OH .
;
22-0188-02.indd 253
5/11/2013 11:37:31
...

(2-) ,

. ,

.
Fischer
,

.
:
CHO
H C OH

ch2oh
I
CHO
OHCH
ch2oh
II
I Fischer D
Dextrum=,
, II
L Laevus=,

.
22-0188-02.indd 254
CHO
*CHOH
ch2oh

,
.
CHO
CHO

HO C H
HO C H
H C OH
HO C H
ch2oh
ch2oh
L-
D-

R S , Emil Fischer (18521919)
.
.
Fischer :
To D L

( Fischer)
.
, D
L
- -.
,
D L -
-, .
CH
HCH
ch3
CH
HC2
ch3
L-
D-
D L,
R S,
. , D
, .. D-(+) ,
D , .. D-(-) .
5/11/2013 11:37:32
255
1. () s-s, s-p p-p

.
.
2. () p-p
( )
.
3. ( )

( ).
4.
, CH4, CH2=CH2 CH CH. ,
5. ()
, .
6.
.
7. ( )
.
, .
.

C
.
8.
R S.

.

(+) (-).

.
C*,

2. ,
.
22-0188-02.indd 255
5/11/2013 11:37:32
256
9.
,
.
( ) cis - trans
.
10.
.
11.
, , , ,
- .
12.
,
.
13. ,
.
().
.
14.
( )
+1, .. CH3+.

( )
-1, .. CH3-.
15.
,

().
16.
( ).

.
17.

.
18.
.

(.. ).
22-0188-02.indd 256
5/11/2013 11:37:32
257
19. ,
.
20. -
Br2 CCI4.
21. RC CH
Na CuCl + 3.
22.
Na.
23.
.
24. ,
, .. NaHC3.
25. ,

. ,
.
R S
cis - trans
22-0188-02.indd 257
5/11/2013 11:37:32
258
- -

1. ;
2. ;
3. () ;
4. () ;
5. ;
6. ;
7. ;
8. ;
9. ;
10. ;
11. R S ;
12. ;
13. ;
14. ;
15. ;
16. ;
17. cis - trans
;
18. ;
19.
;
20. ;
21. ;
22-0188-02.indd 258
5/11/2013 11:37:32
259
22.
;
23. ;
24. ;
25. ;
26. ;
27. .
28. .
29. .
30. ;
31.

;
32. ;
33. ;
34.
;
35. RC CH
;
36.
;
37. ;
38. ;
39. ,
22-0188-02.indd 259
5/11/2013 11:37:32
260
-
.
40.
HCl Cl2;
* 41. p
;
42. .
.
.......................... ..............
.
. ...........................
......... .
. p , ..............,
.............................. .
. . ..........................
s p
................... sp,
..........
43. . sp
sp ;
. sp2
sp2 ;
. sp3
sp3 ;
* 44. CH3CH2Cl ()
()
() .
* 45. :

H
C=C

Cl
* 46. , H-C C-Cl.
5 , 1
3 , 2
47.
.
. CH4 () ,
sp3 s .
. CH2=CH2
() () .
. C- () .
22-0188-02.indd 260
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261

. CH3Cl () C-
() C-Cl.
48. (I)
, ,
.
I
II
BeH2
sp2
BCl3
sp3
CCl4
sp
49. :
. CCl3COOH
. CH2BrCOOH
. CH2ClCOOH
. CF3COOH
.
50. :
.
.........
.
. ..................
............. ...................
. ....................
.............
. ........................................
......................... .
. .................... .........................
.............. .
51.
.
. 2-
. 3-
. 3-
. 3-
52. 2--1-
R S .
* 53. 200 mL 16 g
10 cm,
+6.
. ;
. 200 mL 10 g
( ), ,
,
;
. +75, . -3,75
22-0188-02.indd 261
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262
* 54. -24,
+32. 2 g ,
20 mL, 10 cm,

+0,4.
.
1 g A, 1 g B
* 55.
:
.
.
.
.
. .
56. .. C5H11OH
.
57.
.
.
,
.
.
,
.
.
.
.
.
58. 2,3,4-
.
,
.
* 59.

.
4 , 2 4
3,4--, 3
60. ()
(II).
I
22-0188-02.indd 262
2,3-
2,3,4-
2,4-
2-
2--2-
3-
5/11/2013 11:37:32
263
61.
, , , :
CH3CH=CHCH3(A) + 2
CH3CH=CHCH3+ HCl
CH3CH=CHCH3+ HCl
CH3CH=CHCH3 + Cl2 E
* 62. .
.. C5H10Cl2.
. , ,

.
* 63. 3--2- .
64. C4H7Cl
cis - trans
.
.
65.
C4H8 2, Br2, HCl 2O.
,
.
66.
C4H6 2, HCl 2O.

.
67. A, , .
. A + HCl CH3CHCH3

Cl
. + Cl2

. + NaOH
CH CH + ....
68.
C3H6O HCN
CH3MgBr.
2O.
* 69.
, , , .
. A + HCN,
+ 2 2 O C H 3 C HCO O H + 3

. + CH 3 MgBr ,
+ H 2 C H 3 C H 2 O H +. . . . .
22-0188-02.indd 263
9/4/2014 12:24:28
264
* 70. C4H9OH
,
Grignard.
* 71.
C4H9Cl,
NaOH
.
72.
, , .

CH3CH2CH2OH + NaCl
A + NaOH
+ CH3CH2Cl CH3-O-CH2CH3 + NaCl
+ KCN CH3CHCH3 + KCI
CN
73. C4H10O :
. nO4 H2SO4
. K2Cr2O7 H2SO4.
,
.
74. :
. nO4 H2SO4,
. ,
. AgNO3.
75.
nO4 H2SO4.
. HCOOH . (COOH)2 . HCOONa . (COONa)2
76.
NaOH.
.
.
.
77.
C2H7N HCl.
78. :
. . ............. HCl,
. ............
. ............ . ............................
. ..............
.
........................ HCl ...................
............................
* 79. :
2, 2, CH4 C2H6.
22-0188-02.indd 264
5/11/2013 11:37:33
265
* 80. :
CH3Br, CH3CH2MgBr HBr.
81. (I)
(II).
I
CH3
II
+
CH3
CH3
Cl2
82.
: 3, -, CH3+, CH3-, AICI3, NH2- , O2+.
83. HCl .
84. HCN .
. -
85. .
.
. 1-
2-.
. 1-
1-.
86. A, , .

+ CH3ONa

B + NaCl

+SOCl2
+ KCN
A
CH3CHCH3
+ KCl

Cl

+ NaOH
+ NaCl + H2O
* 87. : . 1-
, . 2-
.
* 88. CH3CH2OH :
.
. 2-
.
.
* 89. , HCN, :
. 2- . . 2-
.
.
. 3-.

22-0188-02.indd 265
5/11/2013 11:37:33
266
90. :
.
. 4--2-.
91. : 1- 1-.
;
92. , :
C4H6 () + CuCl + 3 + ...
C5H8 (B) + Na H2 + ...
+ 2
93. () C5H12O :
. 2.
. .
.
94. :
1-, 2- .
.
,
;
* 95.
.

C4H9cl
(A)
+NaOH
/
C4H9OH
()
I2 + aOH
* 96.
.
C5H10O (A) + CuS4 + NaOH
+ 2 + NaOH
* 97. , , ,
.
CH3MgBr + C3H6(A) C4H9OMgBr(B)
+ 2 + Mg(OH)Br
+ KMn4 + H2S4 C4H8O() + ....
98. A, ,
: C5H10O2 ()+ NaOH +
(s) + NaOH(s) CH4 + Na2CO3

+ 2 + NaOH
* 99. , , ,
.
C4H8O2 + NaOH +
+ KMnO4 + H2SO4 + ...
+ HCI + NaCl
22-0188-02.indd 266
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267
* 100. C7H14O2
,
. ,
.
;
CH3CH2COOCHCH2CH3
CH3

** 101.
(C5H10O2) :

. , , , .
.
i, ii, iii iv.
** 102. () (C6H6O)x. 4,71 g
() 200 g ()
-20 C
-21,2 C. :

. (),
() Kf = 4,8 C/m.

.
().

. () r2
CCl4 NaOH
C6H5ONa. (A);
* 103. ,
A, ,
:
A(C4H6)
+ H2O
+ CuCl + NH3

+ I2 + KOH
+ HCN
22-0188-02.indd 267
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268
104.
.

C6H5Br + Mg
A + CH3CHO
+H2O
+ Mg(OH)Br
* 105. ,
, , , :

A (C3H7Cl)
+NaOH

+I2 + KOH
+2Cr27 (H+)
+HCN
+H2O
* 106. ,
, , ,
.

A (C6H12O2)
+2O
B (C2H4O2) +
+l2 + KOH
+KMnO4 (H+)
+HCN
** 107. C11142.
NaOH
C7H5O2Na C4H10O.
NaOH .
. :

. A, , .

. o .

. :

i. nO4 H2SO4.

ii. 2 + .

* 108. , 1 6,
: , -1, , , .
, .
. 3, 5 6
.
. 2, 4 5
.
. 6 .
. 4 ,
.
22-0188-02.indd 268
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269
* 109.
1- 2--3-.
, , , , .

CH3CH2CH2OH
2Cr2O7 H+
A
SOCI2
A+E
KOH
H2O
HCl
Mg
2--3-
* 110. , 70,
. . ;
;

* 111.
, .
. ,
3 g , , , 19,7 g .
, .
A: CH3CH2 X,
: CH3CH(OH)CH3
6 g ,
* 112.
60 13,2 g CO2 7,2 g 2O.
. ;
. ,
; ,
,
;
. 0,2 ,
H2SO4, 12 g ;
. 60 g 1 mol , mol
; ;
4.
. ; Grignard;
. CH3CH(OH)CH3
. 0,4 L, . 66,67%
** 113. 88
, .
. ,

;
. () .
: COOCH(CH3) 2
22-0188-02.indd 269
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270
. , .
, ,
. ;
. ;

-
41.
96. CH3CH2COCH2CH3
43. . 180, . 120, . 109,5
97. A: CH3CH2CHO
47. . , . , . , .
: CH3CH2CHCH3
49. > > >
OH
51. . .
98. CH3COOCHCH3
53.
ch3
57. . , . , . , .
99. CH3COOCH2CH3
61. (2) (2) (4) (3)
101. A: CH3CH2CN
OH
67. A: CH3CH=CH2
E: CH3-C-COOH
: CH2=CH2
69. A: CH3CHO, : HCHO
72. A: CH3CH2CH2Cl,
B: CH3ONa
: CH3CHCH3

Cl
86. A: CH3CHCH3
OH
B: CH3CHOCH3
ch3
92. . CH3CH2C CH
CH3
: CH3CH2COOCH2CH3
103. A: CH3CH2C CH
B: CH3CH2COCH3
104. : C6H5CH(OH)CH3
105. A: CH3CHCH3
Cl
106. A: CH3COOCHCH2CH3
ch3
OH
. CH3CH2CH2C CH
E: CH3CH2CCN

OH
ch3
93. CH3CH2CCH3

CH3 107. A: C6H5COOCHCH2CH3
CH3
95. A: CH3CH2CHCH3
109. A: CH3CH2CHO
Cl

: CH3CH=CH2

22-0188-02.indd 270
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22-0188-02.indd 271
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:
, O C O
().
:

.

.
Pauli:

.
: 5f.
.
Heisenberg:

(p=m u) , ..
.
: .
Li, Na, , Rb, Cs, Fr.
:
( < 1).
:
. Be, Mg, Ca, Sr,
Ba, Ra.
, *C:
.
: o
.
:
.
: ( )
.
,

, .. 90-99% .
:
.
:
.
: .
:
, CHO, .
:
CvH2v+1OH.
: 17 .
F2, Cl2, r2, I2, t.
:
.
:
()
, .
:
( Brnsted - Lowry):
.
Brnsted-Lowry ():
-
.
: ,
22-0188-02.indd 272
5/11/2013 11:37:34
( - ):

pH .
: , ,

.
:
() ,
.
:
.
:

.
:

.
:

,
.
:

.
() :

2.
: 18
.
He, Ne, r, Kr, Xe Rn.
: ( ) ( )

.
:
V
,
.
(G):
G = - TS
.
:

. :
:
.
(g) + e- (g)-, < 0
():

,
.
(g) +(g) + e-, i 1 = > 0
: , , .
H = U + P . V
:
, ,
.
:
.
22-0188-02.indd 273
5/11/2013 11:37:34
():

.
():
.
VSEPR: ,
,
,
.
:
RCOOH.
:
4f .
:
CN.
, , :
,
.
: , = 1,
.
:

.
:
.
:
.
Hund:
, spin .
:

.
:

Schrdinger (n),
(l)
(ml). ,
spin,
(spin).
:
,
.
:

.
: Brnsted-Lowry .
:
.
:

.
() :
p-p (
) .
- (pH):
. pH = -log[H3O+]
: pH .
:
22-0188-02.indd 274
5/11/2013 11:37:34
,
.
: , .. OH-,
CN -, , .. 2O, 3,

.
:

pH ,
.

.
aufbau)
, .. s, p, d f.
: ( )

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

.
.
:
, Kb.
:
, a.
:
.
:
d .
:

.
:

( ,
22-0188-02.indd 275
5/11/2013 11:37:34

Pauli

Bohr
Brnsted - Lowry

Grignard

220
223
218
220
223
215
224
217
23
239
24
32
203
63
102
223
243
223
13
100
242
163
166
213
133
84
217
124
191
190
19
246
133, 136
97
119
133
84
98

210

169

169

169

209

75

203

202

33

69
72

203

216

217, 218

199

115

64

231

167

170

166

25

19

35
Lewis
36

232

234

173

63

189
VSEPR
41

136

100

98

99

105

127

201
22-0188-02.indd 276
5/11/2013 11:37:34

Hund
Markovnikov

Saytseff

spin

(1)
(2)
Ostwald

pH

213
128
26
216
36
219
169
224
224
224
231
231
19
19
19
20
20
217
28
211
190
30
177
63
72
112
127
230
127
237
31
63
29
106
223
222
223
222

Bohr

Daniell
Leclanch

s
p
d
f

223
223
208
209
13
235
232
173
173
133
111
201
201
201
19
166
175
209
101
101
33
177
63
63
63
246
27
27
28
28
13
194
193
20
20
19
202
63
22-0188-02.indd 277
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Arrhenius Svante
Atkins P.W.
Bohr Niels
Brnsted Johanes
Clausius Rudolf
De Broglie Louis
Einstein Albert
Fischer Emil
Gibbs Josiah Willarl
Grignard Franois
Hawking Steven
99
74
13
100
69
17
47
254
75
217
47
Hiessenberg W.
Hund Friedrich
Lewis Gilbert
Lowry Thomas
Markovnikov Vladimir
Nerst Walter
Ostwald Wilhelm
Planc Max
Pauli Wolfrang
Schrdinger Erwin
Saytseff Alexander
17
26
101
100
216
171
112
16
23
17
219
22-0188-02.indd 278
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22-0188-02.indd 279
5/11/2013 11:37:34
22-0188-02.indd 280
5/11/2013 11:37:34

( )
22-0188-02.indd 281
C
Al
Ag
Ca
Ba
Br
S
I
K
Sn
Mn
Mg
Pb
Na
Ni
O
Si
Fe
Hg
H
F
P
Cu
Cl
Cr
Zn
14
12
27
108
40
137
80
32
127
39
119
55
24
207
23
59
16
28
56
201
1
19
31
63,5
35,5
52
65
5/11/2013 11:37:34
22-0188-02.indd 282
5/11/2013 11:37:35
22-0188-02.indd 283
5/11/2013 11:37:35
22-0188-02.indd 284
5/11/2013 11:37:35
22-0188-02.indd 285
5/11/2013 11:37:35
22-0188-02.indd 286
5/11/2013 11:37:35
22-0188-02.indd 287
5/11/2013 11:37:35
22-0188-02.indd 288
21/2/2014 1:45:21

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1

4.1 .................................................................................................................. 163

5.1 - - .................... 189

Niels Bohr (1885-1962).

Max Planck (1858-1947).

(l) n, 0, 1, 2, ... (n - 1).

spin (ms) +1/2 -1/2,

Fe: 1s2 2s2 2p6 3s2 3p6 3d6 4s2

6C, 9F, 10Ne, 15.

Lewis : HBrO, SF6,

7,77 . 1014 s-1

59.  Rb (=37) Na (=11)

w = -20 kJ, q = +50 kj.

U = q + w = -20 kJ + 50 kJ = +30 kJ.

Josiah Willard Gibbs (1839

: C3C2(g) CH3CHO(g) + H2(g)

G : 2(g) + 2(g) 2(g) G

G : 2MgO(s) 2Mg(s) + O2(g),

Gf, NaCl = -384,05 kJ mol-1.

NH4NO3(s) NH+4 (aq) + NO3-(aq)

16.  : Mg + 2HCl MgCl2 + 2

COCl2(g) H2O2(l) H2O(l)

. G = 70,02 kJ, . 739K

Svante Arrhenius (1859 - 1927).

Johanes Brnsted (1879 1947).

Thomas Lowry (1874-1936).

.. [3+] = 10-5 M, [3+] [-] = 10-14

[-] > 10-7 [3+] < 10-7

[3+] [-] = Kw = 10-14

[3+] = 10-7 = [-]

[3+] > 10-7 M > [OH-]

[3+] < 10-7 M < [OH-]

S.P.L. Srensen (1868

pH < 7 < pOH

pH > 7 > pOH

3.9 pH : . Mg(OH)2 . - CH3COOH.

HCl + H2O H3O+ + Cl0,01

pH HBr 8,1 g/L;

3O+ HCl 10-7 ;

H2O + H2O 3O+ +

: [3O+] = 10-7 + x [-] = x .

0,99 1, a = 10-6. , [3O+] = 10-4

0,1 - x 0,1 x = 10-5 = [3O+] pH = 5.

- 3 0,1 NH4Cl 0,02 ,

[3+] << co [3+] << c.

[H3O + ][A ] x(c + x)

[-] << c [OH-] << c.

HCI NaCl + H2O

pOH = pKb + log

HCOOH 0,2 / HCOO0,4

pH CH3COOH 0,5 CH3COONa 0,9 ,

HCl 0,2 500 mL

1 L 3 0,2 N4Cl 0,4

[3O+] = 10-9 , [3O+] = 1,5 10-9

pH 6,6-8,2. pH < 6,6

[-] > 10 [],

[Ag+][Cl-] = 210-6 210-6 = 410-12 2

AgCl 10-5 mol/L.

, s = [My+]x [Ax-]y = (xs)x (ys)y = xxyy sx+y

. (s) Ag2CrO4 2O.

Ks = [Ag+]2[CrO42-]= (2s)2 s = 4 10-12 s = 10-4 mol L-1

, [Ag+]2[CrO42-] = Ks (0,1 + 2 s1)2 s1 = 4 10-12.

Ca(NO3)2 0,01 1 L, NaF.

59. Rb (=37) Na (=11)

16. : Mg + 2HCl MgCl2 + 2

53. 5 L NaCl 0,1 . pH ;

54. pH NH4Cl 0,1 ;

55. 200 mL 2O 1,36 g HCOONa. pH

* 56. 10 L CH3COONa 1 p = 10 90 L 2O.

57. 0,1 (I) pH

. N3 0,1 NH4Cl 0,2

* 86. 400 mL 3 0,1 NH4Cl 0,1

93. 1 L BaSO4 0,00256 g

94. CaF2 100 L 2O;

* 95. +- Na+A- 0,1

. 1 L NaA 0,1 1 L MgCl2

* 118. To pH RCOONa 0,1

** 124. 1 L AgCl Ag2Cr4 : [Ag+] = 10-4 , [Cl-] = 10-6 , [Cr42-] = 8 10-4 .

** 125. [Cl-] = 10-2 [Br-] = 10-3 .

26. Ag(s) Ag+(aq)