T.E.T.Y.

124

2003

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

........................................................ 5
............................................................. 5
.................................................. 6
................................................................................. 6
............................................................................................................ 8
...................................................................................................... 8
..................................................................................................... 10
...................................................................................... 10
..................................................................... 10
.................................................................................................... 11
.......................................................................... 14
....................................................................................... 16
............................................................................................. 16
................................................................................................... 17
................................. 23
.................................................................... 25
..................................................................... 27
:
1: 33
2:
....................................... 38
3: ................................. 47
4:
.......................................................................... 51
5: ......................... 55
6: .. 60
7: 1 .................................... 67
8:
(TLC).......................................................... 73
. 78
- .................................................................. 79

()

Buchner



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2/3 .

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C

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( ), (0
C), (-10 C), (..
(-78 C), ),
.


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(..
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10

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( .

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, CaCl2, 2C3, P2O5, , , CaH2, ...

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( .. CaCl2)
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1 2 , ,
1 2,

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(KD) ,

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KD =


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.

11

 (
)
, KD .
,


.
:
S mL W0 g
V mL .

KD =

( )
( )

W0 g W1 g
, :
W0 W1
V

W1
g / mL ,
S
.

g / mL

:
W0 W1
W S W1 S
V
KD =
KD = 0
K D W1 V = W0 S W1 S
W1
W1 V
S
S
W1 (K D V + S) = W0 S W1 = W0
(K D V + S)

(1)

:
W1 W2
2

S
S
V

... W2 = W1
W2 = W0
KD =
W2

+
(K D V + S)
K
V
S
D

n :

Wn = W0
K D V + S

(2)

12

(2)

 Wn
0 W0, KD, S n

S
< 1

K
V
S

D

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,
2/3
( 1).
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1:

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.
NaCl
. NaCl

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13

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1)
2)
3)


4)

5)


Soxhlet,
.
Soxhlet
2, ,
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2: Soxhlet

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14



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15


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P = 1 Atm
, .

2 C.
.
,
(
).
,
Raoult
.
.

, +
% , 1.
tA
tB 20 %,
tM.
A ,
tC.
tB.

16

1:

.
.
, dT
dP, Clausius Clareyron:

dP
=
=
L
dT TV (V V S )

. VL
VS .
dP dT

. VL > VS (
) .
VL < VS ( )
.

, .

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,
(.. ).
.
,
.

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2 .

. .

.
2 C .

17



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()
() .
,
, .

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,
.
,

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.

. P = 1 Atm
. (P
= f(T)) 1.

( )
( ).
(
)
.

, P

1:

18

 :
)

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.
2. To

.

2:

,
2/3 .

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,
,
.
+ ,
. 3
.
t tA tB, ,
a2 2 .
= 30 % A, 70 % B = 70 % A, 30 % B
.
,
, .
,

. ,
.

19

tB

tA

3: -

tA ,
tB .
, :
)

Raoult
PA = PA XA,

PA , P
PA , P
XA , X

( XA

PB = PB XB

moles
)
moles A + moles

PA = nA RT
P = (nA+ nB) RT
n A
PA =
P = P

nA + nB
PB = XB P
P = PA+PB

X, XB .

20


,
, (
),
Raoult.

.
:
( 4).
C2H5OH
2 78,1 C 96 % C2H5OH 4 %
2, C2H5OH 78,3 C 2 100 C.
COOH (..= 101 C)
107 C.
.
)
)

4: ) )

( )

200 C ( )
.
200 C P = 760 mm Hg
90 C 20 mm Hg. 5

.
.

21

5:

( 6).

.

.

6:

22

1.
2.
3.

4.
5.
6.

7.
8.

9.

10.
11.
12.
13.
14.
15.

16.

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( )
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21.
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23. .

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1.

2.
3.
4.
5.

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24

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)

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25

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( 5-10
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26




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4 .
.

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.

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:
1) :

2) (x):
x=

xi
N

27

3) :
xi x
4) ():

=

xi x
N

5) (Sx):
.
Sx =

(xi x)2
N 1

.
.
+/-
:
+/- = t Sx
t Student-t .
t Student:
t Student

-1
1
2
3
4
5
6
7
8
9
10
15
20
30

=0,50
1,00
0,816
0,765
0,741
0,727
0,718
0,711
0,706
0,703
0,700
0,691
0,687
0,683
0,674

=0,80
3,08
1,89
1,64
1,53
1,48
1,44
1,42
1,40
1,38
1,37
1,34
1,32
1,31
1,28

=0,90
6,31
2,92
2,35
2,13
2,01
1,94
1,89
1,86
1,83
1,81
1,75
1,72
1,70
1,64

=0,95
12,7
4,30
3,18
2,78
2,57
2,45
2,36
2,31
2,26
2,23
2,13
2,09
2,04
1,96

28

=0,98
31,8
6,96
4,54
3,75
3,36
3,14
3,00
2,90
2,82
2,76
2,60
2,53
2,46
2,33

=0,99
63,7
9,92
5,84
4,60
4,03
3,71
3,50
3,36
3,25
3,17
2,95
2,85
2,75
2,58

=0,999
637,0
31,6
12,9
8,61
6,86
5,96
5,40
5,04
4,78
4,59
4,07
3,85
3,65
3,29

6) ( S x ):
.
Sx =

(xi x)2
N( N 1)

.
Q-Test
(xi) /
Q-Test ( )
.
Q-Test :

Q. =

x i x .
x max x min

xi =
x = ( )
xmax =
xmin =

Q Q
( ).

3
0,94

4
0,76

5
0,64

6
0,56

7
0,51

8
0,47

9
0,44

10
0,41

Q > Q Q Q .
Q-Test
.
.



.
.
4 5
(4,6732 g, ) 3
(4,67 g). .

.

29

 :
42,37
0,623

4
3

(.. 5,3810-3 3 5,38010-3 4
).

(

).
. 1,3590,05
1,360,05.
5 1
5 . .. 5,238
5,24, 9,672 9,67.
5 1
. 2,375 2,38, 6,945
6,94.

. 3,64 g 3
(3 6) (4) ,
.
(..
5,3810-3 8).


..

47+0,32 = 47
3,5+5,24 = 8,7
7,24+3,13 = 10,37

.
.
.. 56,238-56,232 = 0,006

.

.
..

2,195,372 = 11,76

30

 (least-squares method)

.

xi
i.

xi, i :
i = xi +
x,

x = 0.
.

i - i.
:
( i i ) 2

=0

( i i ) 2

=0

i =1

i =1

i =1
2

x i i x i i
=

N
N

N x i2 x i

i =1
i =1

i =1

i =1

i =1

i x i x i i i x i

= i =1

x i2

i =1

x i2

xi

i =1

31

i =1

i =1

 ( )
(r)

i =1

i =1

i =1

N x i i x i i
r=

2
2

N x 2 x N 2
i i i i
i =1 i =1
i =1
i =1

r .
r = 1 . r > 0,99 .


2

N i i
1 i =1
i =1
S =
2

2
2

N
x
x

i i
i =1

i =1

x i2

S = S i =1

( ) :
= + x t S x
t Student-t S
x
:

1
S = S x x i

N i =1

2
2

N
1
+
+
N x2 x
2 i i

N
i =1

i =1

90 % 95 %.

32

% ..
( ) NaHCO3 Na2CO3 ( )
.
NaHCO3 Na2CO3
aOH HCl .


.

,

(). .
(.. 2C3, ,
, , ,
(K2Cr2O7) ) , ,
,
, (
, , ).



/.


.


. 0.1 %.
:
1.
2. 35
45 mL .
.
3.
0,2 %.

33

 ,
, ,
.

:
1) /
. pH .

pH .

.
n
H+ + In


pH
, pH

pH.
pH=pK1.
( pK)
pH
. pH
.
pH 7,
pH 7
pH
7.
.
2)
.
3)
.
4) ( )
.
( ) (mol/L) ()
:
zpCxVx = zxCpVp

Cx = (zxCpVp)/(zpVx)

Cx : (mol/L)
Vx : (mL)
Cp : (mol/L)
Vp : (mL) ( )
zp,x : /

34


( ) / ,
().
.
(ml/Kg)
() :
Cxmx = Cpmp

Cx = (Cpmp)/mx

Cx : (mol/Kg)
mx : / (g)
Cp : (mol/ Kg)
mp : / (g) ( )
(I 0.1 mol/L)
mol/L.
:
.
/ .
(1 mg 0.001 mL)

1)
250 mL NaOH 0.2 .

NaOH .
NaOH .

CO2 . NaOH
. NaOH

.
aOH ,
20 mL HCl 0.1
30 mL ( 3 ).

, 0,02 mL.
NaOH,
.
,
:
N N
100
N

N .
0.1 %
35

 NaOH
( ) . , 20 mL
30 mL
3 .
,
.
: NaOH
. (

)
2) NaHCO3 Na2CO3
HCl 0.1 .
HCl
NaHCO3
Na2CO3. 10.00 mL / NaHCO3 Na2CO3,
, 100 mL
2 .
HCl.

() . HCl
.

- .
3 10 mL NaHCO3 Na2CO3
. ( g
mol) NaHCO3 Na2CO3
.

1.

2.

3.

4.

% %

36

100

-
-

()

. . p
pH. ,

pH
.

+ .

pH (
1).
.
( )

.
. + 1
2 1 atm. [2] = p(H2)
p(H2)=1atm.
:
2+ + 2e
ernst:
E. = E +

H2

2,3 R T
[H + ]2
log
nF
[H 2 ]

pH =0.
.
[+] ( [+]

37

)
:
E. = E +

2,3 R T
[H + ]2
log
nF
[H 2 ]

[+] (pH).
.
( ).
E = E
:
E. = E +

2,3 R T
[H + ]2
log

nF
[H 2 ]
=

2,3 R T
[H + ]2
log
nF
[H + ]2

= 0 :
= -0,059 log[H+] = 0.059 pH

pH p
.
( )

1
1 atm.
.
-
.


(Hg2Cl2). Hg2Cl2
.
:
2Hg + 2Cl

Hg2Cl2 + 2e

+
pH .
[Cl]
[KCl] .
KCl 0,242 V.
( pH)
38

 pH .

Li2O-BaO-La2O3-SiO2. H
+.
0,1
.
. +


H+ .
+
, [+].
[+] (pH) .

pH
.

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

:
H3O+

HA + H2O

(
) :
[H3O + ] [A ]

[HA]
( [2] a)
Ka

[3+] = a [HA]/[A]
log [H 3 O + ] = log K a log
: log [H3O+] = pH

39

[HA]
[A ]

 :
[HA]
[A ]

:
pH = pK a log

+ +

+
pH .
pH
1.
(
).

mL
1:

1 pH
.

.

. [] = [],
[]/[] = 1 log []/[] = 0.
[HA]
:
pH = pK a log
[A ]
p = pKa
(

40

 )

.
.
,
, .

pH

,
.
(Buffers)

pH
. H
(buffering capacity). pH,
,
( ) .

( ) ( )
( ).
: CH3COOH-CH3COONa
3-4Cl.

:
H3O+

HA + H2O

:
Ka

[H3O + ] [A ]

[HA]

[3+] = a [HA]/[A]
(
) [A] [] [HA] = ,
[3+] = a [HA]/[]
-log [3+] = -log a -log ([HA]/[])
pH = pa - log ([HA]/[])

pH = pa - log ([]/[])

[] =
[] =
41

 Henderson Hasselbalch
pH pKa, [] [].
:
pH = pb - log ([]/[])
[]=[] pH = pKa pH
pKa
.

.
p .

pH .

(buffer value) :
b
pH
b moles/L pH
pH . moles
pH
.
=

1.

5 mL
150 mL 45 mL .
aOH 0,1
.

(Buffer
standards pH7 pH4 pH9).
p :
1.
.
2.
.
. .
. .
. Buffer-standard (pH7).
3.
.
4.
p .
5.
7
6.
( 2, 2 5)
(pH4 pH9).
42


.
pH
. pH
NaOH.
aOH 0,5 mL,
pH
( ).
( NaOH
20 mL) NaOH 0,2-0,3 mL
pKa. 30 mL NaOH
0,5 mL
( NaOH 40-45 mL)
0,1 mL pH .
pH 2-3
2 mL .
,
.

1. pH
a .

.
( /) pH = f (VNaOH
ml). .
2 .

. NaOH
(V) .
V/2
pKa .
2. .
pH 0,5 mL

. 0,1 mL
. pH , pH/V (
pH
NaOH).
.

2.

43

 (mL)

2: pH/V V

3.
(2pH/V2)

3.
.

(mL)

3: 2pH/V2 V

44

4.
.. = g / V, (aOH)
5.

. uffers.
. pH 50 mL
40 mL 2P4 0,1 M 10 mL K2HPO4 0,1
M.
. 0,5 mL 0,1 aOH
10 mL pH .
. Cl 0,1
2P4 K2HPO4.
. pH
mmole .
.
, -, 50 mL
25 mL 2P4 0,1 M 25 mL
K2HPO4 0,1 M.
.

45

Ni2+
.

.
Ni2+ .

.

( ),
.

.


.. , ...

.
.
1: , .

Fe3+

NH3 (aq)

Fe(OH)3 (aq)

Fe(OH)3

Al3+

NH3 (aq)

Al(OH)3 (aq)

Al(OH)3

Ni2+

Ni(DMG)2 (aq)

Ni(DMG)2

Ca2+

C2O42-

CaC2O4 (aq)

CaC2O4/CaCO3/CaO

BaSO4 (aq)

BaSO4

SO4

2-

2+

Ba

(Cl, Br, I, F)
(SO42).

46

 :
..

+, Cl + Ag+, NO3

AgCl + + , NO3

2+ , SO42 + Ba2+, 2Cl

BaSO4 + 2a+ , 2Cl

T
.
, .

.

(bidentate ligand)
(multidentate ligand) .

. :
)
)

, ,
.



.

(colorimetric method)
.

/
/ :
)
)

.
.

H /
/
.
.
..
CO32 (aq) + 2H+ (aq)

H2O + CO2 (g)

NH4+ (aq) + OH (aq)

H2O + NH3 (g)

,
.

47


.
,

, .
(masking reagents).

.

Fe3+
.
Ni2+
(DMG) .
(DMG) :
H3C C NOH
H3C C NOH

. 1 %
DMG 95 % .
Ni2+ :
2 DMG + Ni2+

Ni(DMG)2

+ 2 H+

H 20 C 1,0 mg/L.
DMG ,
(
DMG Ni2+.
;).
.
.
Ni2+
.
.
Fe(II), Cu(II) Co(II) DMG
,
DMG
Ni(II).
(Pd(II)) , Bi(III),
DMG, , Pd(II)
, Bi(III)
Ni(II).

pH .

48


:
(50,00 mL 500 mL)
2 mL HCl (1:1)
200 mL.

.
.
. p
. .
70 C
70-80 mL
pH 8 9 ( p ).
1 min
.
8 mL NH4OH 4 5 mL DMG 1 % 95 %
, ( ).
Ni(DMG) Gooch .

.
,
.
Ni(DMG)
Gooch
.
( 1-2 NH4OH)
.
.
120 C,
.
.

49

( Ca2+
Mg2+)
.

.

.


.
EDTA .
EDTA :

EDTA :
1. To DTA
, 1:1.
2. -EDTA
, pH
, ..

50

3. EDTA ,
,
( Trilon B, Comlexone III, Chelation 3 ...).
4. -EDTA
.

,
, ...

.

.
:
1.
-.
2. - EDTA, DTA
-.
Eriochrome Black T ( Ind3-)
pH 10 Ind2
. 2+
Ind .
EDTA
.
Ind ( -EDTA
Ind)
( Ind2)
:
1. :
.
2. : EDTA
EDTA
.
.
3. :
EDTA

.
EDTA.
4. : +
EDTA.

.
.
, , ,

51

...
, ,
, :
(d)
10 mg CaO/1 L H2O
(F)
1 mg CaCO3/100 mL H2O
B = 1,7857

1 mg CaCO3/1 L H2O (ppm)
:
d < 7
d 7-14
d 14-21
d > 21

30 .
.

,

.
.

EDTA (22), Ind2- pH 10. pH
Ind2-
MgInd-
.
( 1),
MgInd-.
(
MgInd-) ( Ind2- pH 10)
:
2 2 2 (aq ) + Ca 2 + (aq ) + Mg 2 + (aq ) [CaY ]2 (aq ) + [ MgY ]2 (aq ) + 4 + (aq )
2 2 (aq ) + [ MgInd ] (aq ) [ MgY ]2 (aq ) + HInd 2 (aq ) + + (aq )

EDTA
.

52

 1: Ca2+-EDTA

: pH 10,
.
,
2Ind ( pH)
.

EDTA
37,225 g EDTA ( : 22 22),
70-80 C 2 .
(1 L),
0,1 EDTA.
To EDTA .
3-4Cl
6,75 g NH4Cl 57,0 mL NH3 1 L.
.
100,00 mL
10 mL (pH 10,
) (3-4 ).
50 C EDTA (
) .
3 .
50,00 mL (
3 ) 100,00 mL
( 3 ).
,
( )
.

53

.
.
Cu(II) Cu(I) I
2. 2


.

,
.
, Ce(IV),
, , Fe2+,
, S2O32.
, ,
...

.
.

0,5 V.
:
2

+ 2 e

2/ +0,5355 V,

.
()

(Na2S2O3), ().
54

+
2
( )

()

+
2S2O32
( )

3I

S4O62

(.. S2O32, As(III))
Cr(VI), Cu(II), NO2, IO4, H2O2 ...
,
.
a2S2O3.5H2O
.
(3) ( )
3
. :
3
I2

+
+

5I
2S2O32

6H+

32
2I

3H2

S4O62

.
S2O32 SO42
S2O32.


. ,
.

.

. .

10 mol/L.

.
55


.
:
)
)
) , ,
.
:
)
4I + 2 + 4H+
2I2 + 2H2O
)
)
)

Cu(II)
Cu2+/Cu+ (0.153 V)
[3]/ (0,536 V).
Cu2+
2Cu2+

5I

2CuI

[I3]

CuI
Cu2+/Cu+
Cu2+/Cu ( = 0,86 V).

5 min.
25 g a2S2O32 0,1 g a2CO3
.
pH

.
C2

H2O

S2O32

a2CO3

+
+

H+

H2CO3
HSO3

H+
CO2

56

H2O

HCO3

+
S0

2NaHCO3

 ( )
3,0 g 3 110 C .

1,2 1,5 g, 4 .
25 mL
. .

0,1 g 2-3 mL ,
50 mL (100 C)
. mL
.
.

3 g
. 250 mL
. 50 mL
(~
1g) () .
2Cu2+

4I

2CuI

I2

To (
) 0,1 .
I2

2S2O32

S4O62

2I

2,5 mL 3 250 mL.
3 g 25 mL . 2 mL Cl 6 M
.
(250 mL)
.


. 5 mL
()
-.

.

57

, , 50 mL a
0,1 . Na2S2O3
.

, Na2S2O3
. 3 mL
()
( ).
. 2 g KSCN.

[3]
S2O32 . Cu2I2
[3] .
Cu2I2 CuSCN
[I3] [2]
.
CuI

I2

SCN

CuSCN

[I3]

.
Na2S2O3 .
1 mL
.
KSCN, - .
.
Na2S2O3
.

.

1.

Cu(II)
.

2.

58

.
:
.

% .

.

.

.
,
, ,
NMR ESR, laser, .
,


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

. (R)
,
/ (UV/VIS) .

,

59

 , ,
.
Beer-Lambert :

I
1
A = log o = log = C d
I
T
Io :
I :
A :
T :
: /
C : moles/l
d :
Beer-Lambert

( ).
(C < 0.01 M)
C.
..
, ,

.


, .

.

Mn

< 2 % Mn. Mn
.



n2+ :
3n
2n2+

+
+

2NO3

8H+

5IO4

3H2O

3Mn2+
2MnO4
60

2NO
+

5IO3

4H2O
+

6H+

 3 3P4. H
(Mn2+) (MnO4)
KIO4
.

4 .

, .
0,1-2 %
MnO4.
CO2 :
C

+ 2S2O82

+ 2H2O

CO2

4SO42

4H+

T (4)2S2O8 Mn2+ nO4

(4)2S2O8
:
2S2O82 + 2H2O

+ 4SO42

4H+

Fe3+ 525 nm max

.
,
SO22, 2WO4 H3SbO4 ,
.
/

,

. :

( )
...

/
.

, /
.

61


(.. )
(.. ),
,
.
. ,
y ( )
/ .
.
,
, ,
, ,
. :
yi = a + b xi

.
..

(
(least-squares method) ).

.
MnO4.
pH
:
1) :

2) :

3) :

n4 + 8+ + 5e

Mn2+ + 4H2O

n4 + 4+ + 3e

Mn2 + 2H2O

n4 + e

Mn42

62




.
1. 500 mL 0,001
.
2.
50 mL 5,0 -5 , 1,0
-4 , 1,5 -4 2,0 -4 5,0 -4 .

() ,
, = f (C).

MnO4
1. ()
.
2. 7
480-570 nm
( ).
max
max.
3. max
.

.
4. ( ) max
.

MnO4
0,1 g
. 25 mL
50 mL 2 H2SO4. H
80 C.
n4
( )
. 3 .

63


1. Beer-Lambert
A = C d
2.

, Amax = f(C).
95 %.
.

( moles) ( mol/L)

.
3.
( moles)
( mol/L)
.
4.

MnO4 95 %.
.
5. % .. Mn .

64

 7
1

.


, , ...

.

.
Fresenius :
)


)

.
)

.
)

(NH4)2CO3.
)


.
.
1 .

65

Hg22+, Ag+, Pb2+, Bi3+, Cu2+, Cd2+

Hg2+, As3+, Sb3+, Sn4+, Co2+, Ni2+,
Mn2+, Fe3+, Al3+, Cr3+, Zn2+, Ba2+,
Sr2+, Ca2+, Mg2+, NH4+, Na+, K+
+ HCl

Hg2Cl2
AgCl2
PbCl2
I

CoS
NiS
MnS
FeS
Al(OH)3
Cr(OH)3
ZnS

Pb2+, Bi3+, Cu2+, Cd2+, Hg2+, As3+

Sb3+, Sn4+, Co2+, Ni2+, Mn2+, Fe3+
Al3+, Cr3+, Zn2+, Ba2+, Sr2+, Ca2+
Mg2+, NH4+, Na+, K+

Co2+, Ni2+, Mn2+, Fe3+, Al3+, Cr3+

Zn2+, Ba2+, Sr2+, Ca2+, Mg2+, NH4+
Na+, K+

PbS
Bi2S3
CuS
CdS
HgS
As2S3
Sb2S3
SnS2

Ba2+, Sr2+, Ca2+, Mg2+

NH4+, Na+, K+
BaCO3
SrCO3
CaCO3
Mg2+, NH4+, Na+, K+

1: .

66

 1 Ag+, Hg22+ Pb2+,

.
Ag+, Hg22+ Pb2+ ,
AgCl, , Hg2Cl2
PbCl2 ,
.
:
Ag+ + Cl

AgCl

Hg22+ + 2Cl

Hg2Cl2

Pb2+ + 2Cl

PbCl2

AgCl, PbCl2

:
AgCl2

AgCl + Cl
PbCl2 + 2Cl

PbCl4

.

.
PbCl2
.
PbCl2 ( )
Pb2+ 2CrO4 PbCrO4,
:
Pb2+ + CrO42

PbCrO4

Ag+ Hg22+
AgCl NH4OH
Ag(NH3)2Cl, :
AgCl + 2NH4OH

Ag(NH3)2Cl + 2H2O

67

 Ag+, Ag(NH3)2Cl AgCl (

) (HNO3) :
Ag(3)2+

Ag(NH3)2Cl

Ag+ + 23

2NH3 + 2+

2NH4+

Ag+ + Cl

AgCl

+ 2H3

AgCl + 2NH43

gCl NH4OH g2Cl2

g+:
g2Cl2 + 2NH4OH

Hg + HgNH2Cl + 2H2O + NH4Cl

68


(


).
10 mL 1
100 mL 10 mL .
2 mL Cl 6 . Ag+, Hg22+ Pb2+
.
AgCl, Hg2Cl2 PbCl2.
20 mL
100 mL.
1 mL 2CrO4 1
PbCrO4.
Pb2+
2CrO4.
AgCl g2Cl2.
2,5 mL 4 4 .
4
Hg22+.
3 4
( )
Ag+.
( 2)


.

69


HCl

( 2, 3, 4 5 )

: gCl, Hg2Cl2, PbCl2

2

: PbCl2

: Hg2Cl2, gCl

K2CrO4

NH4OH

PbCrO4

: Ag(NH3)2Cl

: Hg + HgNH2Cl

HNO3
AgCl

2: 1 .

70

(TLC)

.

.
.
Rf .

.

,
.

, ,
.
,

.

.
.

.
x,
:
Kx =

x C
=
x C

= 25 = 5.

71


.

.

.
.
(Martin & Synge)
Craig,
.
(n)
:
4t
n = r
w

tr
w ( ) ( 1).
To n ,
(column efficiency) , ,
...
n
.

(H H.E.T.P. = Height Equivalent to a Theoretical Plate):
L L w
H = =
n 16 t r

L .
.

1: .

72

 R (resolution) ,
tA tB wA wB :
R=

2(t A t B )
( wA + wB )

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

, ,
.
, .

.
,

, , , , ,
, ...
1:

-
( : )

-
( : )

&

--

73

 (Thin Layer Chromatography, TLC)

-
. (
),
.

,
... TLC
, , ,
.
( 100 ppm).
:
)
.
,
(
).
)
.
TLC Rf, .
Rf .
Rf, .
)
.
)

, ,
TLC.
)
.
TLC,

.
Rf.
)
.
, TLC

.
)
.
(.. 15 cm 15 cm),
.
10 mgr.
TLC, ,
, (Al2O3), silica gel
(SiO2), .

.
(.. , ), (.. ,
), (.. , ,
).
.
.
,
Van der Waals
, , , -

74

, ...
.


.

.
.

.
.
,
.

:


, Pasteur.
1 cm
. () ()

.
, 3 mm,
,

.
:
, 0,5 cm
,
.
(
2). .
70-80 % ,
.

2: TLC

75

 :
, UV (254 nm),
.
UV,
250-260 nm (.. , ).

, ,
.
,
UV, .
:

.

.
( 3).


.
.
Rf:
Rf
( 3)
. Rf
, ,
. Rf
, , ...
Rf .
Rf .
,
Rf (
3).
)
)

Rf1 = 0,5
Rf2 = 0,7
3: ) Rf ) .

76


,

. (),
.
4 , 4-,
:

4-

HO

CONH2

Rf .
()
() .

.
: ) 100 % ,
) 75 % 25 % , ) 50 % 50 % , )
25 % 75 % , ) 100 % )
.

, 50 mL 50
mL .
.

TLC.
, ,
.
77


:
1. , .. ,
, 1995.
2. , .. , ,
1992.
3. , .. , , 1989.
4. , . , , 1980.
5. , .. , , 1985.
6. , .. , , 1982.
7. , .. , ,
, 1987.
8. , .. , , 1993.
9. , .. , .. , ..
, , 1986.

:
1. Vogel, Practical A.I. Organic Chemistry, Longman, 1974.
2. Pavia, D. Lampman, G. Kriz, G. Jr. Introduction to Organic Laboratory Techniques,
Saunders, .
3. Skoog, D.A. West, D.M. Holler, F.J. Fundamentals of Analytical Chemistry, Saunders
College Publishing, Philadelphia, 1996.
4. Jeffery, G.H. Bassett, J. Medham, J. Denney, R.C. Vogels Textbook of Quantitative
Chemical Analysis, Longman, London, 1989.
5. Kunze, U.R. Grundlagen der Quantitativen Analyse, Thieme Verlag, Stuttgart, 1980.
6. Guebnitz, T. Haubold, G. Stoll, C. Analytisches Praktikum, Verlag Chemie,
Weinheim, 1993.
7. Jones, W.N. Stubbs, M.F. General Chemistry in the Laboratory, C.V. Mosby Co, St.
Louis, 1970.
8. Kennedy, S.E. Sparberg, E.B. Sterrett, F.S. Chemical Quantitative Analysis, Harper
and Row Publishers, New York, 1972.
9. Holderness, A. Lambert, J. The Essentials of Qualitative Analysis, Heinemann Books,
London, 1976.
10. Vogel, A.I. A Text-book of Quantitative Inorganic Analysis, Longman, London, 1975.
11. American Chemical Society, SAFETY in Academic Chemistry Laboratories, 4th ed.,
ACS Press, Washington DC, 1985.
12. Kanare, H.M. Writing the Laboratory Notebook, ACS Press, Washington DC, 1985.
13. Trelease, S.F. How to Write Scientific and Technical Papers, MIT Press, Cambridge
MA 1958.
14. Day, R.A. Underwood, A.L. Quantitative Analysis, 5th ed., Prentice-Hall, New Jersey,
1988.
15. Kennedy, J.H. Analytical Chemistry: Principles, 2nd ed., Saunders College Publishing,
New York, 1990.
16. Stoer, J. Bulirsch, R. Introduction to Numerical Analysis, 2nd ed., Springer Verlag,
New York, 1993.
17. Harris, D. C. Quantitative Chemical Analysis, 4th ed., W. H. Freeman and Company,
New York, 1995.
78

 1:

: .., , 1989.

2:

g
mL

100 g
100 mL

g
g
mg
mg
g

100 mL

1 L
1 mL
1 L
1 mL

mol
mmol
eq
meq
mol

1 L
1 mL
1 L
1 mL
1000 g

g/100 g
mL/100
mL
g/100 mL
g/L
mg/mL
mg/L
g/mL
mol/L
mmol/mL
eq/L
meq/mL
mol/1000 g

(% , w/w)
(% , v/v)
(%
, w/v)

(, M)
(, M)
(, N)
(, N)
(
1000 g , m)

: .., , 1989.

79

 3:
,

2,4-


()



-

pK

1,6
4,2
3,5
4,9
5,0
6,4
7,3
8,0
8,4
9,0
9,5
9,5

0,0-3,2
0,2-1,8
0,2-1,8
1,2-2,8
2,6-4,4
3,0-4,6
3,2-4,4

3,0-5,2
3,9-5,4
4,2-6,2
5,0-7,0
5,2-6,8
6,0-7,6
6,8-8,2
7,2-8,8
5,0-8,0
8,0-9,6
8,0-9,8
9,3-10,5
10,1-12,0
11,4-13,0
12,0-14,0

: .., , 1989.

80

 4:

2CO3
H+ + HCO3

HCO3
H+ + CO32

C6H5COOH
H+ + C6H5COO

+
H3BO3 H + H2BO3

H2SO4
H+ + HSO4

HSO4
H+ + SO42

H2SO3
H+ + HSO3

HSO3
H+ + SO32

NH4+
H+ + NH3

HCOOH H+ + HCOO

HNO2
H+ + NO2

H2C2O4 H+ + HC2O4

HC2O4
H+ + C2O42

CH3COOH CH3COO

H2C4H4O6
H+ + HC4H4O6

HC4H4O6 H+ + C4H4O62

H2S
H+ + HS

HS
H+ + S2

HCN H+ + CN

HF
H+ + F

HIO4 H+ + IO4

H2O2
H+ + HO2

HClO H+ + ClO

C6H5OH
H+ + C6H5O

+
H3PO4 H + H2PO4

H2PO4
H+ + HPO42

2
HPO4
H+ + PO43

H3PO3
H+ + H2PO3

H2PO3
H+ + HPO32

H2CrO4
H+ + HCrO4

HCrO4
H+ + CrO42

4,2 10-7 (1)

4,8 10-11 (2)
6,6 10-5
6,0 10-10
1 10-2 (1)
1,2 10-7 (2)
1,3 10-2 (1)
5,6 10-8 (2)
5,6 10-10
2,1 10-4
4,5 10-4
3,8 10-2 (1)
5,0 10-5 (2)
1,8 10-5
1,1 10-3 (1)
6,9 10-5 (2)
1,0 10-7 (1)
1,0 10-14 (2)
4 10-10
6,9 10-4
2,3 10-2
2,4 10-12
3,2 10-8
1 10-10
7,5 10-3 (1)
6,2 10-8 (2)
1 10-12 (3)
1,6 10-2 (1)
7 10-7 (2)
10-1 (1)
3,2 10-7 (2)

p
6,38
10,32
4,18
9,22
-2,0
1,92
1,89
7,25
9,25
3,68
3,35
1,42
4,30
4,74
2,96
4,16
7,00
14,00
9,4
3,16
1,64
11,62
7,49
10,0
2,12
7,21
12,0
1,80
6,2
1,0
6,49

: .., , 1989.

5:

C2H5NH2 + H2O
C2H5NH3+ + HO

+
NH3 + H2O NH4 + HO

C6H5NH2 + H2O
C6H5NH3+ + HO

(CH3)2NH + H2O (CH3)2NH2+ + HO

CH3NH2 + H2O
CH3NH3+ + HO

C5H5N + H2O C5H5NH+ + HO

(CH3)3N + H2O
(CH3)3NH+ + HO

N2H4 + H2O N2H5+ + HO

b
5,6 10-4
1,8 10-5
3,8 10-10
5,1 10-4
4,4 10-4
1,4 10-9
5,3 10-5
9,8 10-7

: .., , 1989.

81

pb
3,25
4,74
9,42
3,29
3,36
8,85
4,28
6,01

82

83