.

-1
.

1-1

)H 2 O(l) / OH (aq

H2O

H
O
)H 2 O(l
3
)(aq
/ :

) H 2 O (l) H 2 O(l) H 3O (aq) OH (aq

H
O
.
OH
:

e
3 q

Ke pKe pK e log K e:
+H3O -OH .
-2-1 .

OH
:
. pH < 7 H 3O

OH
:
. pH > 7 H 3O

OH
:
. pH = 7 H 3O
: pHpH

14

H3O
OH

H3O
OH

0
H 3O
OH

 -2 KA / .

-1-2 .
HA (aq) H 2 O(l) A H3O :
:
:
A H 3O

K A KA .
HA

)(aq

)(aq

K A 10 pK A

pKA -HA/A pK A log K A :

pKA / ) 3 . (79
:

BH H 2 O B H 3O
: BH+/B +BH

: BH+/B B H3O :
KA
BH
-2-2 pH . pKA
/ A/B
A H 2 O B H 3O
B H3O
B H3O
B :

KA
log K A log
pK A log
log H 3O
A
A
A
B

pH pK A log
A

pK A log
pH
A

 -3-2 K .
- A1 A1/B1 B2 : A2/B2
) A1(aq) B2(aq) B1(aq) A 2(aq

A 2 :
B
H
O

B1 A 2
K
1
3
pK A1 pK A 2

A1
K
*
K 10
K

K
K A2
A1
A1 B2
B2 H3O
KA1 KA2 A1/B1 .A2/B2 pKA1 = -logKA1 . pKA2 = -logKA2

-3 .

-1-3 .
. pH

)HA (aq) H 2 O(l) A (aq) H3O(aq

AH C
:
:

xf
n f (H 3O ) H 3 O f V
10 pH

x max
n0
CV
C
3-1

A1 A2 . C
A1 A2 1 A1
2 A2 ). (1 > 2
10 pH

pH1 A1 pH2 ) A2 : (pH1 < pH2:

C

 KA .
- K AH K A :

A . H 3 O

q

AH q

K Q r,q

-3-2 K
. K = KA KA .
:
C A1 A2 1 > 2
) KA1 > KA2 ( pKA1 < pKA2 . pH1 < pH2
:

KA

pKA

)C(mol

pH

A1 :

6,3.10-5

4,20

10-2

3,1

13%

A2 :

1,8.10-5

4,75

10-2

3,4

4%

A1 . A2 -1-3 .
. pH

B C B(aq) H 2 O(l) BH (aq) OH (aq):

:

Ke
xf
n f (OH ) OH f V
K e pH

10

x max
n0
C
CV

C H3O
f

 B1 B2 . C
B1 B2 1 B1
2 B2 ). (1 > 2
K e pH

pH1 B1 pH2 ) B2 : (pH1 > pH210 :

C
KA .
BH . OH

q
q
K Q r,q
K B : B q
Ke
K

KA

BH . OH
H 3 O
Ke
q
q

K
KA
B q . H3O
q

-3-2 K
K
KA K A e :
K
KA .
:
C B1 B2 1 > 2
) KA1 < KA2 ( pKA1 > pKA2 . pH1 > pH2
:

KA

pKA

)C(mol

pH

B1 :

2,0.10-11

10,7

10-2

11,4

25%

B2 :

6,3.10-10

9,20

10-2

10,6

4%

B1
B2

 -4 .

-1-4 .
-2-2 / A/B :
B
pH pK A log
A
:
B 0
B A :
log
pH = pKA A
B

log
pH > pKA 0 : B A .
:
A
B 0
B

A
log

: .
:
pH < pKA A
pH

pH = pKA

B A

A B

A B

A/B

NH 4 / NH 3 : pKA = 9,2
NH 4 pH < 9,2
NH 3 pH > 9,2

 NH 4 NH 3
NH 3
NH 4
pH
pK A 9, 2
0
14
NH 4 / NH 3
-2-4 .
A . B
A

A
:
A B
B

B
:
A B

%
100

%CH 3COO

80

A B
%CH 3COOH

60

pK A

40
20

0
0 1 2 3 4 5 6 7 8 9 10 11

CH3COOH/CH3COO
-3-4 .
-HIn/In HIn -In
-HIn/In pKAi HIn

)HIn (aq) H 2 O(l) In (aq

) H 3O(aq
:

HIn In
pH = pKAi HIn -In .
In
HIn 1
HIn 10
log
log
1
HIn

In
In
HIn

B
A :

pH pK A log

pK Ai pH 1

pH pK Ai 1

 In
-In
10
HIn

B
A :

pH pK A log

pH pK Ai 1

In
log
1
HIn
pH pK Ai 1

: : BBT

pH

HIn

pK Ai 1

-5 .

pK Ai

In

pK Ai 1

B
A
A .
B .
- : 1 .
-1-5 .
- )(
.
-2-5 .
HA H3O Cl
OH

) ( OH H3O 2H 2 O :
HA RCOOH OH
) ( OH AH A H 2 O :
-3-5 .

Na OH

) +H3O ( OH H3O 2H 2 O :
B ) +H3O
( H 3O B H 2 O BH :
-4-5 .
) (-Na+ + OH VB = 5 ml CB = 20 mmol.l-1 CH3COOH VA = 20 ml . CA = 10 mmol.l-1
pH ) pHf = 4,8 (VA + VB
. :
.

CH 3COOH OH
CH 3COO H 2 O

0
xf

0
xf

n 0 OH

n 0 AH

n 0 AH x f n 0 OH x f

 n 0 HA C A .VA 2.104 mol : -OH n 0 OH 104 mol:

xf :
n f (OH ) n 0 (OH ) x f :
): nf(OH-
. VA VB

n 0 OH C B .VB 104 mol

x max

) x f n 0 (OH ) n f (OH
) n f (OH ) n f (OH
OH

f
VTOT
VA VB
Ke
n f (OH )
. VA VB

H 3 O

n f (OH ) OH

1014
n f (OH ) 4,8 . 5 20 .103 1,57.1011 mol
10

xf :
x f 104 1,57.1011 104 mol
xf
-

1 :
x max
1 .

-6
-1-6 ). (1

4,60
pH-mtre
CH3COOH
CA VA = 20 ml

)(-Na+ + OH
-CB = 20 mmol.l

 pH :

dpH
dVB

.E

)(1
) pH f (VB

pH
10

pH E

) (T1
)(T

) (T2

4
2

)VB (ml
14

12

10

VB,E

-2-6 .
CH3 COOH OH CH 3COO H 2 O : CA .VA CB .VB,E 10 ml :
n 0 (CH 3 COOH) n E (OH ) : E
3
VB,E
3 10.10
CA CB
CA 20.10
102 mol.l1
3
VA
20.10

-7

VB,E

-1-7 ). (2
VB = 10 ml NH3 CB
) (-H3O+ + Cl CA = 10-2 mol.l-1 pH
) (2 .


dpH
dVB

)(2
pH
) pH f (VA
) (T1

10

)(T
) (T2

.E

8
6
4
2

)VA (ml
28

pH E

24

20

16

12

VA,E
-2-7 .

NH 3 H 3 O NH 4 H 2 O : CB .VB CA .VA,E 20 ml :
n 0 (NH 3 ) n E (H 3O ) : E
3
VA,E
20.10
CB CA
CA 102
2.102 mol.l1
3
VB
10.10

-8 .

VA,E

-1-8 .
) (T1 ) (T2 )) pH = f(V ) (1 ) ((2 ) (T ) (T1 ) (T2 ) (T1
) (T )) pH = f(V ) (1 ). ((2
) (T2

 -2-8 :
dpH
g(V
)

B ). (1

dVB
dpH
g(V
)

A ). (2

dVA
dpH
E

dV
-3-8 .
)
( .
pHE ) (

.

:

) (1 pHE = 8,3 10 8,1 - ) (2 pHE = 5,6 6, 2 4, 2

 9 100

10 100

 11 100

12 100

 12 100

13 101

 13 101