Αναλυτική Χημεία

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.35
1: .37
1.1 .37
1.2 .38
1.3 .42
1.4 .43
: & .50
3: .77
3.1 .77
3.2 .77
3.3 . .78
3.4 .80
3.5 ( )80
3.6 .80
3.7 .81
: & .84
4: -.118
4.1 Arrhenius.118
4.2 Brnsted Lowry.118
4.3 - Lewis.120
4.4 Brnsted -Lowry.120
4.5 .121
Page 1
Generated by ABC Amber LIT Converter, http://www.processtext.com/abclit.html
4.6 - pH..121
4.7 .123
4.8 .123
4.9 .125
-: & .128
6: .169
6.1 .169
6.2 .169
6.3 .170
6.4 .171
: & .174
7: .210
7.1 .210
7.2 .210
7.3 .211
7.4 .211
7.5 .212
7.6 .213
7.7 .214
7.8 .215
: & .218
8: .262
Page 2
8.1 .262
8.2 .264
8.3 .265
8.4 .267
8.5 .268
8.6 EDTA..269
8.7 .270
8.8 EDTA..271
: & .275
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C
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Page 18
1.
G. Schwedt ( . ),
, . , , 1999.
2.
. . . . , , ,
, 1992.
3.
D. Skoog, D. West, F. Holler, S. Crouch, Analytical Chemistry - an introduction,

7thEd,Saunders College Publishing,Fort Worth, 2000.
4.
.. , . . .. ,
- , ,
, 2000.
5.
.. , .. , . - , ,
, , 1998.
6.
. , , , , 2, , 2001.
7.
. , , ,
1996.
8.
D. Harvey, Modern Analytical Chemistry, McGraw-Hill, Boston, 2000.
9.
D. Rafferty and S. Robers (ed.), Problem Solving in Analytical Chemistry, Royal Society
ofChemistry, London 1998.
10.
. , ,
, 18 , 2001.
11.
. , , , , 2000.
12.
J. Tyson, Analysis- What Analytical Chemists Do, Royal Society of Chemistry,

Cambridge ,1997.
Page 19
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Page 23
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Page 26
10.
Cl-: Mohr, Volhard, Fajans
( .202).,
(ASTM, BS.).
11. (G. Atkinson,

J. Chem. Educ. 1982, 59, 201-202) .
.
Page 27
11.

.
1.4 . 10-15.

, ..ASTM (American Society for Testing Materials), BS (British
Standards).
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0,2ppm.
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Page 28
5. .
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Page 29
100mg
100mg
50mg
( ) 30mg

15mg 50Kg .
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1.
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3.
4.
5.
14.
10 .
UV,
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Page 30
aA + bB
cC + dD :
[ ] .
mol/L, atm., ,
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( ), ( So)
( Go): Go=- RTln K= -2,303 RT log K , Go= - S
Le Chatelier
(, , )
.

.
3.2
,
., Le Chatelier.
Page 31
KCl (s)
K+ (aq)+ Cl- (aq) HCl( Cl-).
3.3 . .

.
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, ( ) ( c),
.

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( )
:
1.
H2O, w
2.
, s
3.
, a

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DebyeHuckel
, . ,
,
.

, c.
( I)
:
I=1/2 ( c1 Z12+ c2 Z22 +)
, c1, c2, .. 1,Z2, 1, 2, .
Page 32

.
( ) :
=c
, , Z
. Debye -Huckel:
i = i, Zi = i
= , i=

(1
= 10-10m).
Debye-Huckel :
<0,2
25C
1 i3
Huckel:
, Debye
( )
, mn, :
= ( m. Bn)1/m+n
Debye-Huckel mBn 25C :
, , ,
.
i 11 .
Debye-Huckel
, < 0,01.
:
Page 33
1.
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<1.
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0-50C( ).
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8.

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CN-,
:
HCN + H2O
H3O + CN-
Ag + CNNi2++ 4CN-
AgCN (s)
Ni(CN)42-
3.4
H ( ),
, (
).
aA + bB
:
cC + dD ,
Page 34

. ,
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3.5 ( )
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:
1[K1] + 2[K2] + = 1[1] + 2[2] +
, [K1] 1 1 , , [1]
1 1 .
3.6

.
, , ,
.
0,025 H3PO4
: P =
P . ,
0,025 = [H3PO4] + [2P4-] + [P42-] + [P43-]
3.7
Page 35

:
1.
2.
3.
4.
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Page 36
Page 37
&
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2.
0-0,1 ;
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1
( H2SO4).
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Page 38
. .
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3.1 45 ).
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1 c. Debye-Huckel:
3. ( Ko)
:
.HCN ( aq )+H2O ( l )
H3O ( aq )++CN- ( aq )
.NH3 ( aq )+H2O ( l )
NH4 ( aq)++ OH ( aq )
.PbI2(s) + S2- (aq)

.BaCO3 (s)+2H3O +(aq)
PbS (s)+ 2I (aq)

Ba (aq)2++ H2CO3 (aq)+ 2H2O (l)
Page 39
3.
HCN= 1,
() , .
,
, 55,5 .
. :

, ..
4.
. Mg2+ Ba2+;.
. + 900 pm, - 350 pm;
4.
. 3.1 ( . 45) Mg2+
8 5 Ba2+.
. () Ba2+ 56 12 Mg2+

.
Page 40
. .
5.
3O+ 0,01
HCl 0,04 KClO4. pH .
5.
:
I=1/2 ( c1 Z12+ c2 Z22 +)
I= 1/2 {[3+](+1)2+ [Cl-](-1)2+ [K+](+1)2+ [ClO4-](-)2}=

= 1/2 (0,01.1 + 0,01.1 + 0,04.1 + 0,04.1) = 0,05
3.1 ( . 45) 3+= 0,86.
3+=0,86.0,01=8,6 10-3
pH = -log 8,6 .10-3 =3-log8,6=3-0,934=2,07
6.
. 0,2 KNO3
. 0,2 K2SO4 . 0,05 NaCl
.0,025 CuCl2
6.
:
I=1/2 ( c1 Z12+ c2 Z22 +)
:
) I= 1/2 {[+](+1)2+ [3-](-1)2}= 1/2 (0,2.1 + 0,2.1 ) = 0,2
Page 41
) I= 1/2 {[+](+1)2+ [S42-](-2)2}= 1/2 (0,4.1 + 0,2.4 ) = 0,6

) I= 1/2 {[Na+](+1)2+ [Cl-](-1)2}= 1/2 (0,05.1 + 0,05.1 ) = 0,05
) I= 1/2 {[Cu+](+2)2+ [Cl-](-1)2}= 1/2 (0,025.4 + 0,05.1 ) = 0,075
7.

NaCl 0,001 M.
7.
:
I=1/2 ( c1 Z12+ c2 Z22 +)
I= 1/2 {[Na+](+1)2+ [Cl-](-1)2}= 1/2 (0,001.1 + 0,001.1 ) = 0,001
Debye Huckel:
:
-log Na+= 0,51(+1)20,001 =0,016., Na+=0,964
Cl-=0,964.
8.

1,0 10-3 1,0 10-1.

. Fe3++ SCN. H2PO4-+ H2O

.PO43-+ H2O
.Hg2++ 2Cl-
Fe(SCN)2+
HPO42-+ H3O+
HPO42-+ OHgCl2
8.
. =1,0 10-3
-logFe(SCN)2+=0,51. 2210-3Fe(SCN)2+= 0,862
Page 42
-logFe3+=0,51.3210-3 Fe3+= 0,716

-logSCN- =0,51.1210-3 SCN-= 0,964
K={[Fe(SCN)2+].Fe(SCN)2+}/ {[Fe3+]Fe3+[SCN-] Fe3+-} =
f{Fe(SCN)2+/Fe3+.SCN-}= f. 1,249
=1,0 10-1
f =0,801. K
-logFe(SCN)2+=0,51. 2210-1Fe(SCN)2+= 0,226
-logFe3+=0,51.3210-1 Fe3+= 0,035

-logSCN- =0,51.1210-3 SCN-= 0,690
K={[Fe(SCN)2+].Fe(SCN)2+}/ {[Fe3+]Fe3+[SCN-] Fe3+-} =
f{Fe(SCN)2+/Fe3+.SCN-}= f. 9,358 f=0,107. K
f> f,
Fe3++ SCNFe(SCN)2+ .
. : K= a. 0,862 K= a. 0,226,
a> a. :
H2PO4-+ H2O
HPO42-+ H3O+
. : K= h. 1,161 K= h. 4,45. h< h
.
. : K= s. 0,801 K= s. 0,108. s> s
.
9.
; O
, 0 0,1 :
.
.
. .
9.
Page 43
. ( 3.1 . 45 46)
10.
10.
, ..
, ..
, .
( )
. . H2O B.
BaSO4C. .
,
. ( 4, . 49 ).
11. pH 0,0010 ) ) 0,050
K2SO4. a : 6,0.10-5.
Page 44
11.
) < 10-3, 3+= C6H5COO-1
, C6H5COOH= 1,
() , .
, ,
, .
,
:

C6H5COOH +H2O
/mol L-1
0,001
C6H5COO- +H3O+
0,001x
x
x
: (0,001x)0,001
K= Ka= x2/ 0,001 = 6,0.10-5
x = 2,4 .10-4M
, pH =3,6
). :
= [0,10(+1)2+ 0,050(-2)2] = 0,15
Debye-Huckel
:3+= C6H5COO-= 0,63
, K =([H3O+]H3O+.[C6H5COO-] C6H5COO-)/([C6H5COOH] C6H5COOH)= a.

H3O+. C6H5COOa= 6,0. 10-5/ (0,63.0,63) =1,5.10-4
:
Ka= 2/ (0,001) =1,5 .10-4
= 3,9 .10-4M
, pH = 3,4.
12. H2SO4,
HSO4- SO42-.
Page 45
12.
.
.
: 1[K1] + 2[K2] + = 1[1] +
2[2] +
, [K1] 1 1 , , [1]
1 1 .
:
[3+]= [SO4-] +2[SO42-] + [OH-]

.
( . 50)
13. 3+, -, Ca2+, HCO3-,
CO32-, Ca(HCO3)+, Ca(OH)+, K+ ClO4-.
13.
:
1[K1] + 2[K2] + = 1[1] + 2[2] +
, [K1] 1 1 , , [1]
1 1 .
,
[3+] + 2[Ca2+] + [K+] + [Ca(OH)+]+[Ca(HCO3)+]= [-] + [ClO4-] + [HCO3-] + 2[CO32]
Page 46
( . 50)
14. P 0,0100 a3PO4.
14.
:
P = P
, 0,0100= [H3PO4] + [2P4-] + [P42-] + [P43-]
( . 51)
15. Mg Br 0,200 MgBr2 )
MgBr2 Mg2+ Br- )
MgBr+.
15.
)

molMg: 0,200= [Mg2+]
mol Br : 0,400 = [Br-]
) MgBr2 MgBr+.
molMg: 0,200= [Mg2+] +[MgBr+]
mol Br : 0,400 = [Br-] +[MgBr+]
( . 51 52)
16. :
. 0,100 HF
. 0,100M NaH2PO4
.0,100M CH3COONa
Page 47
16.
)0,100 HF
: [3+] = [F-] + [OH-]
: 0,100 = [3+] + [HF] + [OH-]
F: 0,100 = [F-] +[HF]
)0,100NaH2PO4
: [3+] + [Na+]= [H2PO4-] + 2[HPO42-] + 3[PO43-]+[OH-]
Na: 0,100 = [Na+]
P: 0,100 =[H2PO4-] +[HPO42-] +[PO43-] +[H3PO4]
)0,100CH3COONa
: [3+] + [Na+]= [CH3COO-] +[OH-]
Na: 0,100 = [Na+]
C: 0,200 =2[CH3COO-] + 2[CH3COOH]
17. pH 0,010 M NaH
0,0040 Ca(NO3)2. pH,
.
17.
:
= [0,010(+1)2+ 0,010(-1)2+0,0040(+2)2+ 0,0080(-1)2] =0,022
Debye-Huckel
:H-= 0,84
Page 48
,pOH=-log-=-log.c =-log 0,84 .0,010 =2,08pH=11,92

- pOH=-log c-=-=-log 0,010 =2,00
pH=12,00.
4.1 Arrhenius
Arrhenius:

, +.
, -.

, :
++ -
.
, , , , ,
- .
4.2 Brnsted Lowry

BrnstedLowry:
( )
( )
Page 49
4.1 Bronsted Lowry.
Brnsted - Lowry, :
1.
Brnsted - Lowry
Arrhenius, ,
, , ..
3 Cl .
2.
, .
, .
, . ,
.
:
+ +
- , -,
- .
, , :
++
:
+
- ++
. .
3.

. ,
Page 50
HCl (
).
, .
4.
: +
- + +
()

. ,
.
Brnsted Lowry ,
, ,
. ,
, .
, , ,
. , ,
, .
5.
. ,
, .
4.3 - Lewis
Lewis, ,
(+).
Lewis ( )
(o ).
Lewis (
).
Lewis (
) .
Lewis : Lewis,
: + : [:]
Page 51

( ).
Lewis :
,
.. AlCl3 [AlCl3+ :Cl-AlCl4-]
, .. Cu2+ [Cu2++ 4 :NH3Cu(NH3)42+].

.
, .. Ni [Ni+:CO:Ni(CO)4 ]
8 , ..SiF4
[SiF4+2 :F-SiF62-]
,
..O=SO[O=S-O+:OH-HSO3-]
Lewis,
, .. ,
.
Lewis.
4.4 Brnsted -Lowry

Brnsted Lowry
+ +, .
( +)
.. +
-+ +
(
).
(
) .
Arrhenius ( Ka Kb)
-,
Brnsted Lowry.
4.5
1.
Page 52

, . ,
.
.
.
2.
. ,
. ,
.
3.
(),
:
,
-, +.
,
. : -CH3<H-2< -H< H-F
,
-, , +.
,
. : HF < HCl < HBr < HI.

. ()
, .
, - .
:
C6H5- < -NH2< -OH < -I < -Br < -Cl < -F < -CN < -2.
- .
. ,

.
:
NH3>PH3>AsH3>SbH3>BiH3,
.
Page 53
4.6 - pH

, :
H2O
H2O
H3O+
OH-

Kw .
Kw= [H3O+] [ OH- ]
Kw, . .,
. 25 C :
Kw= 10-14 (25C )
: [3+][-] = 10-14( 25oC)
[3+] = [-] = 10-7
: [3+] > 10-7
() : [3+] < 10-7
3+Sorensen 1909
pH:
pH = - log [H3+] pH = - log [H-]
:
:
pH + pOH = 14 ( 25oC)
pH = 7
pH < 7
pH > 7
Page 54
pH , ,
, . , ,
. pH
pH. -
pH
pH. pH .
,
.. Cl CN,
, . , ,
, [ 3+] . , [
3+] HCl > [ 3+] HCN . , pH
. .
, .
4.7

.
. , ,
3+ -. ,
(3+) (-) , ,

3+( .. Cl) ,
3+,
, .. HCl+H2O Cl-+ 3+
3+,
3+ .
.
, -(.. )

- , .. 2-+ 2 - + .
Page 55

LiOH
NaOH
HCl
KOH
HBr
RbOH
HI
CsOH
H2SO4(

)
HNO3
HClO4
R4NOH (R.. (CH3)4NOH

.
E
(Mg, Ca, Sr, Ba)
,
.
HClO3
HBrO3
4.8
, :
HA + H2O
H3O++ A-
Page 56
2,
55,5 . ( Ka)
, .
, Ka
. Ka ,
, ,
.
, :
:
B + H2O
HB++ OH-
Kb . ,
Kb .
Ostwald
:
Ka= 2 c/(1- )
Kb= 2 c/(1- )
Ostwald. O
,
.

Ka= 2 c
Kb= 2 c
( K)
.
Ka Kb
:
+ 2
3++ - (1)
- :
Page 57
-+ 2
+ -
(2)
(1) Ka , (2) Kb -.
:
aHA. KbA - = Kw

. , -
Brnsted Lowry:
+

.
.
4.9
pH
.
, pH .
(0,1- 1 )
, ( /-) (
/ +).

Henderson-Hasselbalch pH
:
..
/ - :
.
.
.
.
Page 58
+ (aq)
,
- ,
.
Henderson-Hasselbalch []/[H] [BH+] / [B] pH . ,
pH,
[-]/[H] [BH+] / [B] , .

pH. mol
pH .

, [-]/[H] [BH+]/[B].

1 0,1. ,
pH p Ka 1 p Ka +1 pOH p Kb1 p Kb +1 .
pH=p Ka. pH=p Kb,
.

/- .. HF/ NaF:
1. .. HF NaF
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 NH3
y mol HCl, y < x.
,
, .

, :
Page 59
1. .. , .
2.
pH ( , , ,
.). .
3. , , .
,
. ,
.
4: &
-: &
1. a 1,0 10-7mol L-1.

pH 0,10;
. 1,0
. 2,0
. 3,0
. 4,0
. 5,0
1.
:
HA +H2O
/mol L-1
0,10
0,10x
H3O+
+ A-
: (0,10x)0,10
Page 60
, Ka= x2/ 0,10= 1,0.10-7
x = 1,0 .10-4M pH =4,0
2. pH 0,20 mol
( a=1,010-4,8mol L-1) 0,020 mol 1,0
L ;
. 2,8
. 3,8
. 4,8
. 5,8
6,8
2.
: C= 0,20/1,0 mol/ L=0,20
C= 0,020/1,0mol/L=0,020
Henderson-Hasselbalch pH :
pH = -log 1,0.10-4,8+log 0,020/0,20 =4,8 1 =3,8

.
( . 80)
3. 1,0 ( b=1,0 10-5mol L-1) 1,0

pH :
. 3,0
. 5,0
. 7,0
. 9,0
. 11,0
3.
Page 61
: [3] = 0,50 [4
Cl] = 0,50 M. Henderson-Hasselbalch pH:
,
C= [3] = 0,50 , C=[4Cl] = 0,50 M p Ka= 14,0 - p Kb =
= 14,0 + log1,0 10-5= 14,0 5,0 =9,0
,pH =9,0 +log(0,50/0,50) =9,0
.
( . 80)
6. HCl 0,10M pH 1,0. 1:10, pH

2,0. , 1:106, pH 7,0.
;
.
. HCl 100% .
. pH +
. HCl + .
. + H3O+
. Cl1,010-7M , pH
.
4.
. . HCl 100%.
. , pH +( . 68).
. , HCl + ,
. pH 1:106
Page 62
( c=10-7M) 7,0 7,0 . pH

HCl 2:
: [3+] = 10-7+ x [OH-] = x

x <10-7. , 10-7+ x ?
10-7, x 10-7. x
Kw :
Kw= [H3+] [OH-] = 10-14 x (10-7+ x) = 10-14 x = 0,62 10-7
[H3+] = 10-7+ 0,6 10-7= 1,6 10-7
pH = 7,0 log1,6 =6,8
. , + H3O+.
.
. , Cl10-7M , HCl (
) pH .
7. SO2 H2SO3
: H2SO3 ( aq )+H2O ( l )
H3O+ ( aq )+HSO3- ( aq )
Ka=10-2
SO2, [H2SO3]: [HSO3-] = 1, [H3O+]
= [H2O]. Ka
, 55molL-1,
[H3O+] =5,5 10-1M [H3O+]10-0,4M. , pH0,4.

o; .
. [H2O ] =1M
. [H2SO3]: [HSO3-] SO2
. [H2SO3]: [HSO3-] 1
. Ka .
.
Page 63
5.
. . 1M, 55
. . [H2SO3]: [HSO3-]
SO2. [HSO3-] [3+] / [H2SO3] Ka.
. . [H2SO3]: [HSO3-] (..
) 1.
. . . .
, = Ka / [2].
[H2SO3]: [HSO3-] = 1 [H3O+] = KapH =2
6.
:2H2O
H3O++ OH
;
.
. pH
. .. .
6.
. ,
Le Chatelier, .
. pH (.. )
, (3+).
. ( .. ) ,
, .
Page 64
7.
. pH-p Ka :
. 50%
. 90%
. 99%
. .
7.
. :
HA +H2O
/mol L-1
H3O++A-
0,5 c
0,5 c
0,5 c
=0,5c.0,5c/ 0,5c =0,5c
0,5 c
0,5 c
0,5 c
,pH-p Ka= -log 0,5c + log 0,5c =0
. :
HA +H2O
/mol L-1
H3O++A-
0,9 c
0,9 c
0,9 c
=0,9c.0,9c/ 0,1c =0,9c.9
0,1 c
0,9 c
0,9 c
,pH-p Ka= -log 0,9c + log 0,9c.9=log9
Page 65
HA +H2O
/mol L-1
H3O++A-
0,99 c
0,99 c
0,99 c
0,01 c
=0,99c.0,99c/ 0,01c =0,99c.99
0,99 c
0,99 c
,pH-p Ka= -log 0,99c + log 0,99c.99=log99

. 99,999%
() pH-p Ka=log99999
8.
H2SO4 0,1M HCl 0,1M ;
pHH2SO4 0,05M;
. 1
. 1
. 1.
8.
(pH) (mole..NaOH
) H2SO40,1M
HCl0,1M pHH2SO4 5M
:
H2SO4+ H2O H3O+
+ HSO4-
/mol L-1
0,05
0,05
0,05
0,05
0,05
0,05
Page 66
HSO4-+H2O
H3O++SO42-
/mol L-1
0,05
0,05
0,05-x
0,05+x
x
x
pH = -log (0,05+x)
x<0,05
pH > 1.H .
9.
.
. . ;
;
. ;
9.
. , Ka
(
).
( . 100). ,
, 3+,

3+ .
(100%)
. . ,
. , (..
)
.
.
Page 67
10.
pH 7-8.
.
pH ,
pH .
. ,
pH .
. ; pH
;
. pH [CO32-] [HCO3-]
0,0030 0,96.
a = 4,8 10-11 HCO3
10.
. Al2(SO4)3 2Al3++ 3SO42Al3+ + 3H2O
Al(OH)3 (s) + 3H+
. HCO3-/CO32- :
HCO3-+ H2O
CO32- + H3O+
c= c,
] = [CO32-] pH = p Ka
[HCO3-
( .82).
. Henderson-Hasselbalch pH:
pH1= p Ka+log 0,003

pH2= p Ka+log 0,96
pH = pH2- pH1= log 0,96-log0,0030 = log 0,96/0,0030 =2,5
Page 68
11.
pH 7,35 7,45.
.
. + ( aq ) pH 7,4.
.
pH HCO3-. HCO3 pH, .
11.
)pH = 7,4 [H+ (aq)]= 10-7,4= 4,0 10-8M
) pH
, , .
H2CO3/HCO3-,
:
H2CO3 +H2O
HCO3- + H3O+
(i) , 3+
HCO3-, :HCO3+ H3O+H2CO3+ H2O. H3O+ ,
pH .
pH
(7,35 7,45). ,
.
(ii) , -
H2CO3,
:H2CO3 + OH-H2O + HCO3-. pH
.
pH 7,6
. , pH .. 7,7-7,8,
.
12.
Brnsted-Lowry.
:
CH3COOH
1,8.10-5
Page 69
ClCH2COOH
1,4.10-3
Cl2CHCOOH
3,3.10-2
Cl3CCOOH
2,0.10-1
12.
- ,
-.
:CH3COOH < ClCH2COOH < Cl2CHCOOH < CCl3COOH.
( .100 101)
13.
:
. K+, Cu2+
. Fe2+ , Fe3+
. Al3+ , Ga3+
13.
. :
19+:[r]
29Cu2+: [Ar]3d9
Cu2+
+. Cu2+ ( Lewis)
+.
. Fe3+ Fe2+ .
. Al3+ Ga3+ .
Page 70
( . 63 64)
14.
) CH3COOH a =1,8.10-5, w
1,0.10-14 25 C. b CH3COO) 25 C
p Kb
4,75
()
3,38
9,40
14.
. Ka Kb :
a b= w
: b = w / a = 1,0 10-14/ 1,8 10-5= 5,6 10-10
. (CH3NH2) CH3- + ,
+, (
p Kb).
(C6H5NH2) C6H5- - ,
+, (
p Kb ).
( .100 101)
Page 71
15.
Lewis:
. Mn2+
. CH3NH2
. H2NOH
. SO2 (g)SO2 (g)+ BF3 (g) O2S:BF3 (s)
. Zn(OH)2 Zn(OH)2 (s)+ 2OH- [Zn(OH)4]2-
15.
) Lewis
Mn2+ ( aq ).

.
)CH3NH2
.
) .
)SO2 (g), .
Lewis.BF3 (g) .
) OH-
. Zn(OH)2 ,
.
( . 63 64)
16.
. CH3CH3(), CH3CH2OH ( ), CH3CH2OCH2CH3(),

. (OH)2S=O ( ), (OH)2S(=O)2( )
Page 72
16.
) ,
-, +. ,
:
CH3CH2O-H > CH3C-H3
CH3CH2O-H > CH3CH2OCH2C-H3
- ,
C-.: CH3CH2OCH2C-H3> CH3C-H3
) (=) - ,
-. : (OH)2S(=O)2 > (OH)2S=O
17.
H2S 2. H2S
61 C.
Cl H2S Cl.
;
17.
() (HCl
), . H2S,
2S ( )
2
.
18.
(
) :
(J mol-1)
HCl
NaOH
-57,1
HCl
KOH
-57,2
Page 73
HNO3
NaOH
-57,3
HNO3
KOH
-57,3
CH3COOH
NaOH
-55,2
HCl
NH3
-55,2
18.
n ,
. ,
HCl (aq)+ NaOH (aq)NaCl (aq)+ H2O (l) n= - 57,1 kJ
HNO3 (aq)+ KOH (aq)KNO3 (aq)+ 2 (l) n= - 57,3 kJ

( ) :
H+ (aq)+ OH- (aq)H2O (l) n=- 57,1 kJ

( ) .
.. CH3COOH (aq)+ NaOH (aq)CH3COONa (aq)+ H2O (l) n= -55,2 kJ
19.
(NH4)2SO4 K2SO4. 0,225g
NaOH. 15,7
mL HCl 0,100 mol/L. %
(NH4)2SO4.
19.
Page 74
mol(NH4)2SO4 0,225g.
:
(NH4)2SO4 (aq)+ NaOH (aq)Na2SO4Cl (aq)+ 23 ( g )+ 2H2O
mol
2mol
3+HCl4Cl
2mol 2mol
, 2 = (15,7/1000).0,100 =7,85 10-4mol(NH4)2SO4 7,85 10-4.132 =0,104g
0,225g 0,104g(NH4)2SO4
100g
= 46,2 %w/w(NH4)2SO4
20.
Tollens
.
. Ag+ Ag ,
.
Tollens.
, .
;
1. .
2. Ag+
3. .
4.
5. Ag ,
6. .
Page 75
20.
6.1
,
() .
,
.
:
,
. , ,
.
, ,
.

.
6.2
.
1.
:
. ,
. ,
2. -
.
:
Page 76
. , KMnO4
. , J2
. , J3.
.
,
EDTA.
4.
.
AgNO3, .
.
1.
2.
.
1.
2.
3.
4.
.
1.
2.
, ,
, .,
.
6.3
: .
Page 77
:
.
.
.
:
,
, .
NaOH, , CO2
.
: (.. 0,1 % )
, .
:
.
: .
: () ,
.
:
(.. 1 mL) .
:
, () .
:
. ,
. .
: .
, .
:
.
,
, .. .
: .
,
,
.
:

.
Page 78
(indirect titration):

.
:
,
.
: .. pH,
( ),
, .
.
,
.. pH.
: ,
.
6.4
1.

, .
2.
1,
.
3. ( )
4.
, ( Erlenmeyer)
.
,
.
5. -
Page 79
6: &
: &
1. ;
;
1.
,
() .
,
.
:
,
. , ,
.
:
1.
(0,1%)
.
2.
3.
4.
,
.
, :
Page 80
1.
2.
3.
,
.
2. ;
; .
2.
.
.

1. : . ,
. , .
.
2. : . ,
KMnO4, . , J2 .
, J-.
C .
3.
. ..
EDTA.
4.
.
AgNO3, .
.
Page 81
1.
2.
.
1.
2.
3.
4.
.
1.
2.
3.
;

; ,
, , .. ;
3.
.. pH,
( )
, .
.
,
, .. pH.
Page 82
. NaOH 0,1 M HCl.

.
:
1.

.
2.

.
3.

,
.
4.
. (eq)

;
(.. ) .
. (1);
Page 83
4.
. : 1eq= 1mol / n
,n= + ( ) n = -
+ ( )
n = , (
).
. : 1eq= 1mol / n ,
n = .
COOH
:
i) HCOOH ( ):
HCOOH + NaOHHCOONa + H2O
1eqHCOOH= 1mol / 1 ii)
HCOOH ():
5HCOOH + 2KMnO4+ 3H2SO45CO2+ K2SO4+ 2MnSO4+ 8H2O
1eqHCOOH= 1mol / 2
. ()
1L.
(1) 1
.
5.
. .
. .
. .
. .
. .
. .
Page 84
5.
.
, .
eq=eq

. ,
. ,
,.. .
.
.

.

.
.
,..Na2CO3(aq).

,
, .
NaOH, , CO2
.
.
.
(.. 0,1 % )
, .
. .. () mole
1 L .
() eq 1
L .
Page 85
=n.M (n 4).
.

.

,
.
6.
. 500,00mLAgNO30,0750 M AgNO3.
. 1,00LHCl0,315 HCl 6,00 M
. 600,0mL +0,0825 4[Fe(CN)6]
. 2,00LHClO40,120 60 %w/w HClO4 =1,60g mL-1.
. 500,00 mL Cl 0,200M (38,32 %w/w=1,19 g
mL-1).
6.
. 1L 0,0750mol AgNO3
0,5 L
x;
x = 0,0380 molAgNO3 , mAgNO3= 0,0380 (108+14,0 +3.16,0)

=0,0380 . 170 = 6,46gAgNO3
, 6,46 g AgNO3
500 mL ( ).
. .
:
C1. V1 = C2.V2 , 6,00. V1= 0,315
.1,00 V1= 0,0530L =53,0 mL

, 53,0mL
1,00L
Page 86
. 1,00L 0,0825mol+
0,600L
x;
x = 0,0500 mol + 0,0500/ 4 = 0,0120mol 4[Fe(CN)6]

, m4[Fe(CN)6]= 0,0120(4.39,1+55,8+ 6. 12,0+ 6. 14,0) =0,0120. 368 = 4,42 g
, 4,42 g4[Fe(CN)6]
600 mL.
. 100/ 1,60 = 62,5 mL 60 g 60 /100,5= 0,60 mol HClO4
1000mL
x;
x = 9,60 molHClO4 9,60

:
C1. V1 = C2.V2 , 9,60. V1=
0,120 .2,00 V1= 0,025 L =25,0 mL

, 25,0mL
2,00L
. 100/ 1,19 = 84,0 mL 38,32 g 38,32 /36,5= 1,05mol HCl
1000mL
x;
x = 12,5 molHCl 12,5

:
C1. V1 = C2.V2 , 12,5. V1=
0,200.500 V1= 8,00 mL

, 8,00mL
500,00 mL
7.
.Na2CO3 HCl HCO3.Na2C2O4 KMnO4 CO2

. 3PO4 NaOH PO42. 3PO4 NaOH 2PO4-
Page 87
.NaHCO3 H2CO3 CO32-
7.
. :CO32- + + HCO3,1 eq =1mol / 1
. :C2O42- 2CO2+2e,1 eq =1mol / 2
. :PO43- + + H PO42,1 eq =1mol / 1
. :PO43- + 2+ H2PO4,1 eq =1mol / 2
. :HCO3- + +
H2CO3 ,1 eq =1mol / 1
HCO3- CO32- + +
,1 eq =1mol / 1
8.
0,3367 g Na2CO3 28,66mL

H2SO4
, :CO32- + 2 +CO2+ H2O
H2SO4.
8.
Na2CO3+ H2SO4 Na2SO4+CO2+ H2O
:molNa2CO3/ molH2SO4 = 1: 1
, 0,33687 / 106,0= 28,66 .10-3.c c = 0,111 M
9.
Page 88
. Cl,
Na2CO3 Cl.
. Na2C2O4( )
KMnO4, Cl H2SO4.
9.
. Na2CO3
HCl. HCl
. , HCl .
. KMnO4 HClCl2.,
Na2C2O4 . ,
Na2C2O4 .
10.
4,476 g SO2
22, :
SO2 (g) +22 (aq) H2SO4 (aq)
25,00 mL NaOH 0,0093 M H2SO4
NaOH 13,33mL HCl 0,01007 M.
. S ppm.
10.
, mol S .
:
eq =eq
, eqHCl + eqH2SO4=eqNaOH
molesHCl + 2. molesH2SO4=molesNaOH
Page 89
13,33 . 10-3. 0,01007 + 2 =25,00.10-3.0,0093
= 0,049 .10-3mol S
(moles H2SO4=moles S) m s
=0,049 .10-3.32 = 1,584 10-3g
4,476g 1,584 10-3g S
106
=354
354ppm. S.
11.
0,3396 g 96,4 % w/w Na2SO4 37,70

mL BaCl2, :
Ba2+ (aq) + SO42- (aq) BaSO4 (s)

BaCl2.
11.
Ba2+ (aq) + SO42- (aq) BaSO4 (s)
:molBaCl2/ molNa2SO4= 1: 1
, 37,70 10-3c =0,964 .0,3396 / 142c = 0,06115 M
12.
. 0,100 EDTA mg /mL
. 0,0500 MnO4 mg Fe2O3/mL
12.
:

(.. 1 mL) . K2Cr2O7
1,267 mg Fe / mL 1mL K2Cr2O7 1,267 mg Fe.
Page 90
. 1 mL 0,100 M EDTA 0,100mmol EDTA

0,100mmolBa2+(
Ba2++EDTABa2+- EDTA)0,100mmolBa 0,100 .153mg BaO. 0,100
M EDTA15,3mg /mL
. 1 mL 0,0500 MMnO40,0500 mmolMnO4
0,250mmol Fe3+( MnO4-+ 8H++ 5Fe2+Mn2++ 5Fe3++ 4H2O ) 0,250/2mmolFe2O3
0,250/2 .160mg Fe2O3. 0,0500 MMnO4 20,0 mg
Fe2O3/mL
13.
0,500 g Na2CO3 50,0 mL HCl 0,100
( ).
CO2 aOH
0,100 . 5,60 mL .
% w/w Na2CO3.
13.
, mol Na2CO3
:
eq = eq
, eqNa2CO3+ eqNaOH =eqHCl
2. molesNa2CO3+molesNaOH =molesHCl
2 +5,60. 10-3. 0,100 =50,00.10-3.0,100
= 2,22 .10-3mol Na2CO3
mNa2CO3=.2,22. 10-3.106 = 0,235 g

0,500g 0,235 g Na2CO3
100
=47,1
47,1% w/w Na2CO3.
Page 91
14.
,
Fe2+.
K2Cr2O7 0,0150 . 1,68 g
35,6 mL , % w/w
Fe2O3.
14.
, mol Fe2O3
:
Fe3++ e- Fe2+
2x mol
2x mol
6 Fe2++ Cr2O72-+ 14 H+6 Fe3++ 2Cr3++ 7H2O

2x mol 2x/6 mol
2x/6 mol = 35,6 10-3. 0,015
x = 1,60 10-3mol Fe2O3 1,60 10-3.160 = 0,256 g Fe2O3
1,68 g 0,256 g Fe2O3

100g
=15,2
15,2% w/w Fe2O3.
15.
2,5000 g Kjeldahl . To
NaOH.
50,00 mL
H2SO40,30 M. NaOH
0,60 . 28,50 mL
. (%
w/w) .
15.
Page 92
, mol N
:
eq = eq
,
eqN3+ eqNaOH
molesH2SO4
=eqH2SO4
molesNH3+molesNaOH
=2.
+28,50.10-3.0,60 =2.50,00.10-3.0,30 =12,90 .10-3mol
NH312,90 .10-3mol m =12,90 .10-3.14,01 = 0,1807 g

2,5000g 0,1807g N
100
=47,1
7,23% w/w N.
16.
Br- BrO3 Br- Br2.
Vogel: .
BrO3-.
10 mL 10% 2 ..
.
, -.
, .
. ;
.
;
16.
)
(moleq)
.
Page 93
) .
, : (i)
,(ii) ,(iii)
,(iv)
(v)
, .. .
17.

;
17.
,
:
1.
.,
,
.
2.
3.
,
.
4.
,..
.
5.
,
.
18.
.
.
.
.
18.
. ,
. , ,
.. , .
Page 94
. (Ca2+,
Mg2+ ) .
7.1
:
. ,
+ (aq)+ - (aq)
2 ( l)

:
1.
2.
3.
4.
, .
5.
,
, . ,
,
. ,
.
7.2
Page 95
,
.
pH .
:
pH < p KIn1, In ( )
pH >p KIn+1 , In-( )
pH, p KIn .
- :
pH , pH

.
, 50,00 mL CH3COOH 0,100 M
NaOH 0,100M . ,
, pH , pH
( 7.1).
7.1: 50,00mL CH3COOH,

NaOH 0,100 M.

, pH
.
7.3
Page 96
pH
. ,
,
. ,
.
,
( 7.2).
7.2 :: ,pH ,:
, pH / V ,: , 2pH / V2
7.4
. ,

. ,
.
,
7.3.
,..H3BO3,
pH .
7.3 :: ,:
. .
Page 97
7.5
- HCl
NaOH( 7.4).
:
1.
pH 3+.
2.
, . pH
. , pH =7.
:eq HCl = eq NaOH.
3.
pH OH-.

, 7.4.
pH ,
. ,
HCl 0,1 MNaOH 0,1 M ( ).
pH ,
. , HCl
0,0005 MNaOH 0,001 M
( ).
Page 98
7.4 . 50mL 0,05 M HCl 0,1 NaOH .

50 mL 0,0005 M HCl 0,001 NaOH.
7.6
,
CH3COOH NaOH( 7.5)
7.5. 50 mL CH3COOH 0,10 M NaOH 0,10 . 50 mL CH3COOH 0,001 M

NaOH 0,001 .
:
1.
pH
(CH3COOH)
2.
, NaOH
/NaOH. To pH
Henderson Hasselbach.
3.
.
: eq CH3COOH = eq NaOH.
pH CH3COONa.
Page 99
4.
pH NaOH.

7.5,
,
, .. .
CH3COOH 0,10 M NaOH 0,10 M ,
pH
. ,
( , 7.5),
.
7.7
( ).
( ) , p K,
( 7.6). ,
.
( ) .. Ka <10-10
.. C <10-6M. ,
Ka C 10-9.
7.6 . .
0,100 50mL
NaOH 0,100 M.. 50,0mL 0,100
HCl 0,100 M.
7.8
Page 100
.
. ,
.
Ka1/ Ka2<104,
.
, .
(COOH)2 a1= 5,60. 10-2 a2= 5,42.10-5. ,
Ka1/ Ka2 104,
Ka1. CH2A>10-9 Ka2. CHA->10-9.
3PO4 a 1= 7,11. 10-3, a2= 6,32.10-8 a3=7,1.10-13
( 3+) pH =
(p Ka1+p Ka2)/2, ( 3+)
pH = (p K a2+p Ka3)/2.
7.7 ()
(). ( a1/ a2<104)
:HOOC-COOH+NaOH
HOOC-COONa + H2O . ,
pH ,
.
:HOOC-COONa + NaOHNaOOC-COONa + H2O
, .
a1/a2
.
. ,
(a3=7,1.10-13),
.
Page 101
7.7 25,00mL0,100 NaOH 0,100M.

A.H3PO4 B. (COOH)2.
1.

7thEd,Saunders College Publishing,Fort Worth, 2000.
2.
.. , . . .. ,
- , ,
, 2000.
3.
.. , .. , . - , ,
, , 1998.
4.
D. Harvey, Modern Analytical Chemistry, McGraw-Hill, Boston, 2000.
7 : &
: &
1. 50,0mL CH3COOH 0,100 M

NaOH0,100
Page 102
1.
. pH .
. , 50,00mLa0,100
M, 50,00mL.
. ,
, pH
CH3COOH-CH3COONa. pH Ladder (
). pH 5,0mL 45, 0mL.
. , pH NaOH.
pH 75,00 mL 100,00 mL.
.
.
. , .
Page 103
2. CO2
. HCl;
CO2HCl , -78C -85C,.
2.
CO2 CO2 (q) H2CO3 (q).
C2. To CO2 Van der Walls,
. , HCl
H3O+ Cl- .
3. HCl H3PO4 NaOH 0,100 M. To
35,00 mL NaOH,
Page 104
.
50,00 mL NaOH,
. mmol.
3.
mmolHCl mmolH3PO4.
H3PO4 . ,
meqHCl+meqH3PO4=meqNaOH
.1+ .1=0,100.35,00
+= 3,50 (1)

+ H3PO4 .
( . 128, 7.1). :
mgeqHCl+mgeqH3PO4=mgeqNaOH
.1+.2=0,100.50,00
, H3PO4 ,
+2= 5,00 (2)
, = 2,00mmolHCl = 1,50mmolH3PO4
4.
HCl 0,100 N (
) : 0,1383 g Na2CO3
25,00 mL ( ).
HCl 0,100 N,
( ), 27,30 mL .
HCl; ,

Na2CO3 106,0.
Page 105
4.
..(Molarity) Cl 0,100 ,
.
: Na2CO3+2HCl2NaCl+ CO2+ H2O
:molNa2CO3: molHCl=1:2
0,1383/ 106,0: 0,1. V= 1:2 V= 0,02609 L 26,09mL
:
. = / =26,09/27,30
, . = 0,9557.
5.
(CaCO3) .
.

, .
.
1,24 g 50,0 mL HCl 0,500 . HCl
23,7 mL NaOH 0,200 .
. mol HCl .
. CaCO3.
5.
xmol CaCO3 1,24 g .
:
CaCO3 + 2HCl CaCl2+ CO2+ H2O
x mol
2x mol
NaOH + HCl NaCl + H2O
Page 106
x mol
x mol
, :
moles HCl CaCO3+moles HCl NaOH =
moles HCl
, 2x +23,7. 10-3.0,200 = 50,0.10-3. 0,500 x =10,13 10-3 mol
. , mol HCl :2x=20,26 10-3mol
. 1,24g 10,13 10-3 mol10,13 10-3 . 101,1g CaCO3
100 g
, CaCO3.: 82,58%w/w
6.
Ka 1,00.10-7.
pH 0,100;
. 1,00
. 4,00
. 2,00
. 3,00
. 5,00
6.
:
HA (q) +H2O (l)

/ molL-1
0,100
x
A- (aq) +H3O+ (aq)
0,100-x
Page 107
a=x2/0,100 = 1,00.10-7
0,100-x0,100 , a/c < 0,01
,: x = 1,00. 10-4.,pH =4,00.
.
7.

0,200 ( Ka=1,00. 10-5) NaOH 0,200 M;
. (pH 8,0-9,8)
. (pH 9,3-10,5)
. (pH 6,8-8,2)
. (pH 6,0-7,6).
7.
: moles HA = moles NaOH.
, VmL HA 0,200 M VmL NaOH 0,200 M,
:
NaOH (aq)
H (aq)
/ mmol
0,200. V
0,200. V
0,200. V
0,200. V
Na (aq)+H2O (l)
0,200. V
-
0,200. V
pH Na
:[Na] = 0,200.V/2V = 0,100
A- (aq)
+ H2O(l)
HA (aq) + OH- (aq)
Page 108
/molL-1
0,100
x
0,100-x
b=x2/0,100= 1,00.10-9
: x = 1,00. 10-5. ,pOH =5,00pH =9,00.

,
pH (8,0-9,8) pH
.
H2SO4 SO3 100% H2SO4

. 1,00g H2SO4 50,0mL

NaOH 1,00, 21,4 mL.
SO3.
8.
8.
x mol SO3 molH2SO4 1g .
, x.80,1 + .98,1 =1
(1)
:
SO3 + 2NaOH Na2SO4+ H2O
x mol 2x mol
H2SO4 +2NaOH Na2SO4 + 2H2O
mol
2 mol
Page 109
, :
molesNaOH SO3+ molesNaOH H2SO4 =
moles NaOH
, 2x +2 = 21,4.10-3. 1,00
(2) 1 2 , x
=2,76 10-3 mol
1,00g .H2SO4 2,76.10-3 mol2,76.10-3. 80,1g SO3
100 g
, H2SO4 SO3.: 22,1%w/w

9. 1,00 ,
1,00 . :
1.
2.
3. .
9.
1. ,
( 1,00 KOH) , pH
Page 110
7, ( )
.
2. ,
10mL ( 20mL
).
3. ,
( 1,00 3) , pH
7, ( )
.
10.
. NH4Cl ; .. NH4Cl 0,10
pH=5,1 298 (NH3 p Kb=4,7600);
. pH NH30,20 298.
. HCl 0,20 : i) NH30,20
ii) NaOH 0,20 .
.
.
. ,
, .
. pH 30,0 mL CH3COOH 0,100 M
20,0 mL NaOH 298 ( a=1,8.10-5 CH3COOH).
HCl CH3COOH .
10.
. NH4Cl , :
NH4Cl4++Cl- 4+
4+ (aq)+ H2O(l)
/molL-1
3 (aq)
+ 3+ (aq)
0,10
Page 111
0,10-x
x
a= x2/ 0,100 = 1,00.10-14+4,76 x = 10-5,12pH =5,12.
. :
3 (aq)+ H2O(l)
/molL-1
H4+ (aq) + OH- (aq)
0,20
0,20-x
x
x
b= x2/ 0,20 = 1,00.10-4,76 x = 2,0 10-5,76pOH =5,76-log2= 5,76-0,301 = 5,46 pH =
14,0-5,46 = 8,54.
.
1.
i)pH.= -log 0,2 = 0,70
pH.
5,1
pH.pH3= 8,5
ii)
pH.= -log 0,2 = 0,70

pH.
7,0
pH.= 14-log 0,2 = 13

.
. HCl 3(
) 4Cl-NH3.

HCl aOH, pH
HCl.,
( ), pH
NaOH.
Page 112
, . 84-86.
. :
CH3COOH (aq)+NaOH (aq)
(l)
/ mmol
3,00
2,00
2,00
2,00
CH3COONa (aq)+H2O
2,00
1,00
2,00
CH3COOH -CH3COONa pH
Henderson Hasselbalch.
C.= [CH3COONa] =2,00/50,0 C.= [CH3COO] =1,00/50,0
pH = pKa + log C./C.= 5,0 log1,8 + log2,00 = 5,05
:
HCl (aq) + NaOH (aq)
/ mmol
3,00
2,00
2,00
2,00
NaCl (aq)+H2O (l)
2,00
1,00
2,00
pH
HCl: C.= [Cl] =1,00/50,0 pH =-log1,00/50,0 =1,70
11.
pH 50,0 mL HCOOH 0,10
KOH 0,10 M:
. 0,0 mL
. 10,0 mL
. 30,0 mL
. 48,0 mL
. 50,0 mL
. 51,0 mL
. 60,0 mL.
. ( KaHCOOH = 1,80.10-4)
Page 113
11.
. 0,0 mL
HCOOH(q)+H2O (l)
/ molL-1
COO- (aq)+H3O+ (aq)
0,10
0,10-x
a=x2/0,10 = 1,80.10-4
: x = 4,24. 10-3. ,pH =2,37

. 10,0 mL
COOH (aq)
+ KOH (aq)
/ mmol
5,00
1,00
1,00
1,00
COOK (aq)+H2O (l)
1,00
4,00
1,00
, COOH -COOK opH
Henderson Hasselbalch:
pH= p Ka+
log([HCOO-]/[HCOOH]) = 3,75 + log 1/4 = 3,15

. 30,0 mL
COOH (aq)
+ KOH (aq)
COOK (aq)+H2O (l)
/ mmol
5,00
3,00
3,00
3,00
3,00
2,00
3,00
Page 114
, COOH -COOK opH

pH= p Ka+
. 48,0 mL
COOH (aq)
+ KOH (aq)
/ mmol
5,00
4,80
4,80
4,80
COOK (aq)+H2O (l)
4,80
0,20
4,80
, COOH -COOK pH
pH= p Ka+
. 50,0 mL
COOH (aq)
+ KOH (aq)
/ mmol
5,00
5,00
5,00
5,00
COOK (aq)+H2O (l)
5,00
5,00
pH COO
: 5,00./100,00 = 0,0500
COO- (aq)+ H2O(l)
COOH (aq)+ OH- (aq)
Page 115
/molL-1
0,0500
0,0500-x
h=x2/0,0500= 10-14/1,80. 10-4
: x = 1,67. 10-6. ,pOH =5,78pH =8,22.

. 51,0 mL
COOH (aq)
(aq)+ H2O (l)
+ KOH (aq)
/ mmol
5,00
5,10
5,00
5,00
COOK
5,00
0,100
5,00
pH OH: [] =0,100 / 101= 9,90
10-4 pOH =3,00pH
=11,00
. 60,0 mL
COOH (aq)
+ KOH (aq)
/ mmol
5,00
6,00
5,00
5,00
COOK (aq)+H2O (l)
5,00
1,00
5,00
pH OH: [] =1,00 / 110= 9,0910-3
pOH =2,04pH =11,96
.
Page 116
12.
CH3CH(OH)COOH. 10,0 mL NaOH 0,050
:
NaOH/mL
pH
0,00
2,50
2,00
3,10
4,00
3,40
6,00
3,70
8,00
3,90
10,0
4,10
12,0
4,40
14,0
4,70
16,0
9,10
18,0
11,6
20,0
11,8
.
.
.
.
Page 117
. mol L-1 g mL-1

. a , .
12.
. .

: .
NaOH,
NaOH pH .
. pH
8 ( ).

( 7.1 .128)
.
( . 116). , , 15,5mL
NaOHpH =8,2.
Page 118
, ( ) :
mmol =mmol NaOH c.10,0 =0,050 .15,5c = 0,078 M (
mol L-1)
Mr =90,08,
g mL-1 0,078. 90,08 .10-3= 7,03 10-3g mL-1.
. pH
( ) :
CH3CH(OH)COOH(q)+H2O (l)
CH3CH(OH)COO(aq)+H3O+ (aq)
/
mol L-1
0,078
0,078-x
pH =2,5x =10-2,5
a=x2/0,078-x= 10-5/(0,078 10-2,5)=1,33 10-4

13.
0,106 g Na2CO3 0,0860 g NaHCO3
HCl 0,100 M. mL ;
Page 119
. ( pH 8,0-9,8).
. ( pH 3,1- 4,4).
: MrNa2CO3= 106,0 MrNaHCO3= 84,02
13.
:
0,106/ 106,0 = 1,00 .10-3 mol Na2CO3 0,0860/ 84,02 = 1,02 .10-3 mol NaCO3
. ( pH
8,0-9,8) :
Na2CO3 + HCl
/ mmol
NaCl
+ NaHCO3
1,00 .10-3 1,00 .10-3
1,00 .10-3
, 0,100 . V=1,00 .10-3 mol HCl V= 10,0 mL
1,00 .10-3
. (
pH 3,1- 4,4) :
Na2CO3 + 2HCl
/ mmol
2NaCl
+ 2
1,00 .10-3 2,00 .10-3
2,00 .10-3
NaCO3 + HCl
/ mmol
+ CO2
NaCl
1,00 .10-3
+ CO2
+ 2
1,02 .10-3 1,02 .10-3
1,02 .10-3 1,02 .10-3

, 0,100 . V=3,02 .10-3 mol HCl V= 30,2 mL
Page 120
14.
NaOH,
NaHCO3 Na2CO3. 25,00 mL HCl
0,1202 :
. ( pH :8,0- 9,8)
. (3,8- 5,4).
.

mg/mL.
1
HCl (
V)
2 HCl (
mL
V)
mL
22,42
22,44
15,67
42,13
29,64
36,42
16,12
32,23
0,00
33,33
14.
NaOH NaHCO3 Na2CO3
.

, :
NaHCO3+ NaOHNa2CO3+ 2
:i) NaOH ii)
Na2CO3iii) NaHCO3iv) NaOH-Na2CO3v) NaHCO3- Na2CO3
: 1)
: 8,0- 9,8 2) : 3,8- 5,4
Page 121
HCl: V V
.
1: HCl1 ()
2 ( )
V V
V
= V>0
V =2 V

NaOH
Na2CO3
V > V= 0
NaHCO3
V <2 V
NaOH - Na2CO3
V >2 V
NaHCO3- Na2CO3
.
: + ClNaCl +H2O mmol NaOH =
mmol HCl ( 1 2)=0,1202.22,43 = 2,695
, 2,696 .40,00/25,00 = 4,314mg NaOH /mL
B. B NaHCO3
Na2CO3. :
Na2CO3+ ClNaHCO3+ NaCl (1)
Na2CO3+2Cl2NaCl +CO2+2 NaCO3+ClNaCl +CO2+2 (2)
mmol Na2CO3= mmol HCl(1) =0,1202.15,67 = 1,884
2mmol Na2CO3+mmol NaHCO3= mmol HCl(2) = 0,1202.42,13
=5,064 , B : 1,884 .106,0 /25,00 = 7,986mg
Na2CO3/mL 5,064 2.1,884 =1,296mmol NaHCO31,296.84,02/25,00 = 4,356mg
NaHCO3/mL
. 1 NaHNa2CO3.
:
Na2CO3+ ClNaHCO3+ NaCl
NaO + ClNaCl+ 2(1)
Na2CO3+ 2Cl2NaCl +CO2+2 NaO + ClNaCl+ 2 (2)
Page 122
,mmol Na2CO3+ mmol NaOH = mmol HCl(1)=0,1202.29,64= 3,563

2mmol Na2CO3+ mmol NaOH = mmol HCl(2)=0,1202.36,42= 4,378
, 0,815 .106,0 /25,00 = 3,456mg
Na2CO3/mL 2.3,563- 4,378 =2,748mmol NaH2,748 .40,00 /25,00 = 4,397mg
NaO/mL
. 1 Na2CO3.
:
Na2CO3+ ClNaHCO3+ NaCl (1)
Na2CO3+ 2Cl2NaCl +CO2+2 (2)
,mmol Na2CO3= mmol HCl(1)=0,1202.16,12=1,938
2mmol Na2CO3 = mmol HCl(2)=0,1202.32,23=3,874
, 1,938 .106,0 /25,00 = 8,217mg Na2CO3/mL
3,874/2 .106,0 /25,00 = 8,213mg Na2CO3/mL
: 8,217 + 8,213 / 2 = 8,215mg Na2CO3/mL
. V > V= 0 1
NaCO3. 2 :
NaCO3+ClNaCl +CO2+2 (2)
,mmol NaCO3 = mmol HCl(2)=0,1202.33,33=4,006
, 4,006 . 84,02/25,00 = 13,46mg NaCO3/mL
.. , .. , . - , ,
, , 1998, . 178-189.
15.
HCl, H3
PO4 NaH2PO4. 25,00 mL NaOH
Page 123
0,1200 : . ( pH
3,85,4) . (9,3-10,5)
.
mg/mL.
1
NaOH(
V.
2 NaOH ( V)
)
mL
mL
18,72
23,60
7,93
7,95
0,00
16,77
13,12
35,19
13,33
26,65
15.
: NaOH,
NaHCO3 Na2CO3( 14) : HCl, H3PO4
NaH2PO4.

, :
NaH2PO4+ HClNaCl +H3PO4
:i)HCl ii)H3PO4iii)NaH2PO4 iv)
HCl-H 3PO4 v)H3PO4- NaH2PO4.
: 1)
: 3,8- 5,4 2) : 9,3-10,5
NaOH: V. V
.
2: NaOH1 (
) 2 ( )

V V
Page 124
V = V
HCl
V =2 V
H3PO4
V> V =0
NaH2PO4
V<2 V
HCl-H3PO4
V > 2 V
H3PO4-NaH2PO4
. V<2 V 2
HClH3 PO4. :
HCl+NaOH NaCl+ 2 H3PO4 +NaOHNaH2PO4+H2O (1)
HCl+NaOH NaCl+ 2 H3PO4 + 2NaOHNa2HPO4+ 2H2O (2)
,mmol
HCl
mmolH3PO4
mmol
NaOH(1)=0,1200.18,72=2,246 mmol HCl + 2mmolH3PO4 = mmol

NaOH(2)=0,1200.23,60=2,832
A :
2,832- 2,246 = 0,5860 mmolH3PO4 0,5860.97,99 /25,00 = 2,297mgH3PO4/ mL
2,246-0,5860 =1,660mmolHCl 1,660.36,46 /25,00 = 2,421mgHCl/ mL
. V = V 2
HCl. :
HCl+NaOH NaCl+ 2 (1 2)
,mmol HCl = mmol NaOH( 1 2)=0,1200.7,94=0,953
:0,953 .36,46 /25,00 = 1,39mgHCl/ mL
. V> V =0 2
NaH2PO4. :
NaH2PO4 +NaOH Na2HPO4+ 2 (2)
,mmolNaH2PO4 = mmol NaOH(2)=0,1200.16,77=2,012
Page 125
:2,012 .120,0 /25,00 = 9,658mgNa2HPO4/ mL

. V > 2 V 2 H3PO4
NaH2PO4. :
H3PO4 +NaOHNaH2PO4+H2O (1)
H3PO4+2NaOHNa2HPO4+2H2O NaH2PO4+NaOHNa2HPO4+ 2 (2)
mmolH3PO4 = mmol NaOH(1)= 0,1200.13,12=1,574
2mmolH3PO4 +mmolNaH2PO4 = mmol NaOH(2)=0,1200.35,19=4,223
:
1,574 .97,99 /25,00 = 6,169mgH3PO4/ mL
4,223-2.1,574 =1,075mmolNaH2PO4 1,075 .120,0 /25,00 = 5,160mgNaH2PO4/ mL
. V =2 V 2
H3 PO4. :
H3PO4 +NaOHNaH2PO4+H2O (1)
H3PO4+2NaOHNa2HPO4+2H2O (2) mmolH3PO4
= mmol NaOH(1)= 0,1200.13,33=1,600
2mmolH3PO4 = mmol
NaOH(2)=0,1200.26,65=3,198
:
1,600 .97,99 /25,00 = 6,271mgH3PO4/ mL(1)
3,198 /2=1,599mmolH3PO4 1,599 .97,99 /25,00 = 6,267mgH3PO4/ mL(2)
: 6,269mgH3PO4/ mL
.. , .. , . - , ,
, , 1998, . 190-196.
16.
50,00mL NaOH
0,04166
, .
. Ladder .
Page 126
. (C6H8O7) g
/100mL
: p Ka1= 3,13 p Ka2=4,76 p Ka3= 6,40.
16.
) 3. Ladder
:
) Ka1/ Ka2<104 Ka1/ Ka3<104

( . 137-138).
,
.,
: 3 +3NaOHNa3+ 3H2O

( . 116). , ,
17,62 mL NaOH.
Page 127
:
3mmol = mmol NaOH =0,04166.17,62=0,7340
(0,7340 /3).192,1 = 47,00mg 0,04700g
50,00mL 100,0mL 2.0,04700g= 0,09400g
.
17.
,
C6H4N2O2S, SO2
SO2 22 H2SO4.
NaOH ,
. ,
0,5136 g , 48,13 mL a 0,1251.
17.
x mmol (C6H4N2O2S) .
x mmolSO2 x mmol
H2SO4.
NaOH
:
H2SO4+2NaOHNa2SO4+2H2O
,mmoles NaOH=2mmolesH2SO4=2x =0,1251.48,13
x =3,0105 mmol
0,5136 g 3,0105. 168,18mg 0,50631 gC6H4N2O2S
Page 128
100 g
95,58 %w/w (
C6H4N2O2S)
18.

Kjeldahl .
(0,9814g) ,
4+.To NH4+ NaOH 3.
3 50,00mL HCl 0,1047 M. HCl
() NaOH0,1183
. 22,84mL
. %w/w ,
6,38g.
18.
x mmol () 0,9814g .
x mmol4+ x mmol 3.
()
HCl 0,1047 MNaOH0,1183
:
HCl +NH3NH4Cl HCl+NaOHNaCl + H2O
:mmoles NaOH + mmoles NH3= mmolesHCl
, 0,1183 .22,84 +x = 0,1047.50,00 x = 2,53303 mmol N2,53303 .14,01 mg
N2,53303 .14,01 6,38 10-3= 0,226412g
0,9814 g 0,226412g
100 g
23,1 % w/w
Page 129
8.1

( - Lewis),
,
( Lewis). , .
.
.
Lewis.
d ,
. .
.
.

, Lewis.
.

.

. : 2, 3, 4, 5, 6, 8 12.
6, 4 2.
.
,
Lewis : n++ m (:L) [Lm]n+
, n+: ,L: m: .

().
,
, . ,

.

, CN-, 2, 3.,

, .

.
Page 130
,
.
.
.

(en):
, .
, [Co(en)3]3+.

, EDTA4-.
,
, .
EDTA .
To EDTA
1:1.

IUPAC ,
:
1.

.
Page 131
2.
, 8.1.
,
-, - .
3.

.
4.
,
, ,
.
:
[Co(NH3)3Cl3] ()
4[Fe(CN)6] ()
[Co(H2N-CH2-CH2-NH2)3]2+ ().

.

:
1.
1. .

, .. [Cr(NH3)6][Fe(CN)6] [Fe (NH3)6][ Cr (CN)6]
1. .
, .. [Co(NH3)4Cl2]NO2
[ Co(NH3)4Cl2]+ NO2 [Co(NH3)4NO2]Cl2 [Co(NH3)4NO2]2+
2Cl1. .
, .. [Co(NH3)5(NO2)]Cl2
[ Co(NH3)5(NO)]Cl2
2.
2.
.
, cis,
trans.
Page 132
2.
, .
8.2
H ( Kinst)

..Cu(NH3)42+
Cu2+ + 4 NH3
Kinst= [Cu2+ ][NH3]4/ [Cu(NH3)42+]

H (Kf) o
.
.
..Cu2+ + 4 NH3
Cu(NH3)42+
Kf= [Cu(NH3)42+] / [Cu2+ ][NH3]4

: Kf . Kinst= 1
,
Kinst,
Kf .
()
.

,
, Ladder [Cd(NH3)4]2+
(
)
. EDTA,
1:1, Ladder Ca2+ Mg2+ .
8.3
Page 133

. :
1.
2.
3.
.
.
4.
.
, ,
.. , .

EDTA, EDTA.
EDTA :
1.EDTA 4. ,
EDTA pH . , pH =3 6 3-,
(pH = 10-14) 4-.
Ladder EDTA:
Page 134
: EDTA pH . ,
mol EDTA .
2.
EDTA, Y4-,
1:1. Kf,
4-. ,
EDTA (3-, 22-, 4-), , pH .
Kf, : Kf = Kf.4
, 4 molEDTA 4-, 4=[4-] /[EDTA]
EDTA , 4-.
, Kf, pH . ,
pH.
KfEDTA-M,
pH .
pH ,
o , .
3.
EDTA, Na2H2.22,
.
EDTA, 4 .
Page 135
4.
EDTA ,
.
8.4
8.1
:
. , ,
n+.
. ,
n-4 n+EDTA.
. ,
n-4, EDTA
n+ n-4EDTA.
8.1
.
8.5
.
,
, pM ,
.
,
pM ,
.
Page 136
8.2.
Ca2+EDTA.
. Kf -EDTA

, ( 8.3).
. pH
pH .
pH ,
8.4. pH. ,
pH ,
.
Page 137
8.3.
.
8.4. pH Ca2+ 0,100 M

EDTA 0,100 M.
8.6 EDTA
EDTA
, Kf.
Page 138
100,0mL Ca2+0,100 M
EDTA0,100 pH = 10, Kf= 1,8.1010.
pCa : . 0,000mL,. 50,0mL,.100,0mL .
150,0 mL EDTA.
1.
EDTA pCa =-log [Ca2+] = -log1,00.10-1= 1,00
2.
, EDTA
Ca2+. pCa ( ) Ca2+.

Ca2+ CaY4- .
50,0 mL EDTA : pCa = 1,48
3.
100,0 mL EDTA Ca2+ Ca4- ,

pCa = 5,77
4.
150,0 mL EDTA Ca2+ Ca4, EDTA pCa = 9,95
8.7

-In, .
-In In,
. ,
, ,
pH.
,
, .
.
8.1:
Page 139
pKa
/
H2In- /
Eriochrome Black T
p Ka2= 6,3
HIn2- /
p Ka3=11,6
Murexide
p Ka2= 9,2
p Ka3=10,9
In3- /
H4In- /
H3In2
H2In3
8.8 EDTA
EDTA:
1.
pH
EDTA. Kf,
-EDTA ,
.
. ..
, ,
. Mg2+, Ca2+, Pb2+, Ni2+,
Fe3+.
2.
, ..
Kf , .
EDTA,
.Zn2+. :
mol Mn++ mol Zn2+ = mol EDTA
Co2+, Mn2+, Al3+.
3.
Page 140
,
.
.Mg-EDTA, :
Mg-EDTA + n+M-EDTAn-4+ Mg2+
Mg2+ EDTA, : mol
n+= Mg2+= mol EDTA.
4.
, ,
. SO42-
Ba2+ pH=1. ,
EDTA. EDTA . g2+ .,
mol EDTA= mol Ba2++ mol Mg2+ mol Ba2+=mol SO42-.
CO32-, CrO42-, S2-, SO42-.
5.

.
, Mg2+Al3+,
Al3+, F-, AlF63+.
Mg2+ EDTA.
5.

7thEd,Saunders College Publishing, Fort Worth , 2000.
6.
.. , . . .. ,
- , ,
, 2000.
7.
.. , .. , . - , ,
, , 1998.
8.
. . , ,
, ,1983.
Page 141
9.
. , , , , , 1997.
10.
. , , , 1996.
11.
.. , . . , ...
, , , 1992.
12.
D. Harvey , Modern Analytical Chemistry, McGraw-Hill, Boston , 2000
8 : &
: &
1.
;
1.

. ,
, ,
.

.
2.
MgY2- ;
2.

Mg2+. .
Page 142
.
,
.
3.0,100 L EDTA0,0104 M
Ca2+ Mg2+ , 31,5mL .
0,100L SO42-,
Ca2+ CaSO4 , Mg2+
18,7mL EDTA0,0104 M.
Ca2+ Mg2 mg/L.
3.
xmmolCa2+ mmolMg2+ 0,100 L.
mmol
Ca2++mmol
Mg2+=mmol
EDTA
x+=31,5.0,0104=0,328
, : mmol Mg2+= mmol EDTA
, =18,7.0,0104 =0,194 mmol Mg2+ x=0,134 mmolCa2+
, 1,94 mmol L-1 1,94. 24,305 = 47,1 mg L-1Mg2+
1,34 mmol L-1 1,34. 40,080 = 53,7 mg L-1Ca2+
4.
25,00mL ( Cl) i2+ 25,00mL EDTA0,05283
. NaOH pH pH = 5,5
CH3COOH - CH3COONa.
Zn2+0,02299 M, 17,61mL
().
Ni2+.
4.
Page 143

: mmol EDTA = mmol Zn2+ + mmol Ni2+ 25,00. 0,05283
=17,61. 0,02299 + 25,00. CNi2+ , CNi2+ = 0,03664 M
5.
50,0mL Cd2+ 5,00 .10-3M
EDTA 0,0100 pH =10 NH30,010 M.
5.
. pCd .
. Cd2+, 25,0mL EDTA 0,0100 M,
25,0mL.
. ,
, pCd Cd2+.
pCd 5,00mL 10,0 mL.
. , pCd
Cd2+-EDTA. pCd 30,0 40,0 mL.
.
. .
, .
Page 144
6. Co(NH3)5(SO4)Br ,
. :
. .
. () AgNO3 ,
BaCl2 .
. () AgNO3 , BaCl2
.
.
Page 145
6.

.
() [Co(NH3)5(SO4)]Br :
Ag+ (aq)+ Br- (aq)AgBr (s)
() [Co(NH3)5Br](SO4)
: Ba2+ (aq) + SO42- (aq)BaSO4 (s)
7.
7.
, .

.
(
), .
8.
(
);
.C6H5NH2
.NH4+
.CH3NH2
.NH3
.C2H4(NH2)2
Page 146
8.

.
. Lewis.
Lewis , ,
(4+),
( ) .
(C6H5NH2,CH3NH2, NH3) (C2H4(NH2)2) .
9.
.(C2H5)O
.H2NCH2CH2NH2
9.
() ,
,
.
(C2H5)O,

, .
Page 147
, H2NCH2CH2NH2(en)
.
, [Co(en)3]3+.
, ( ,
)
.
10.
0,0100 g AgCl 50,00 mL 0,300 M NH3,
[g(NH3)2]+, :
g (aq)++ 2NH3 (aq)
[g(NH3)2]+ (aq)
(mol L-1) Ag+.

inst , 6,80.10-8.
10.
[g (aq)+] = (0,0100/ 143,321) : 0,05000 =1,395 10-3
:
g+ (aq)
/molL-1
+ 2NH3 (aq)
1,395 10-3
0,300
2x
[g(NH3)2]+ (aq)
x
1,395 10-3-x 0,300-2x
,
( Kf =1/ Kinst= 1,471 .107)
1,395 10-3 0,300-20,300
f =1,395.10-3/ [Ag+].0,3002=1,471 . 107 [g+] =1,054 10-9M
11.
50,00 mL
Sr2+0,0100M EDTA 0,020 M. pH =11.
pSr : .0,00 mL, .10,00 mL, .
24,00 mL, .24,90 mL, .25,00 mL, . 25,10 mL, . 26,00 mL .30,00 mL. KfSr2+
EDTA=3,67.108
Page 148
11.
5.
EDTA pSr
=-log [Sr2+] = -log0,0100= 2,00
6.
, EDTA
Sr2+. . 10,00 mL EDTA:
Sr2+
+ EDTA
/ mmol
0,500
0,200
0,200
0,200
Sr4-
0,200
0,300
0,200
: [Sr2+] = 0,300 mmol/60,00 mL= 5,00 10-3M pSr =-log 5,00.10-3= 2,30
. 24,00 mL EDTA:
Sr2+
+ EDTA
/ mmol
0,500
0,480
0,480
0,480
Sr4-
0,480
0,0200
0,480
: [Sr2+] = 0,0200 mmol/74,00 mL= 2,70 10-4M pSr =-log 2,70.10-4= 3,57
Page 149
. 24,90 mL EDTA:
Sr2+
+ EDTA
/ mmol
0,500
0,498
0,498
0,498
Sr4-
0,498
0,00200
0,498
: [Sr2+] = 0,00200 mmol/74,90 mL= 2,67 10-5M

pSr =-log 2,67.10-5= 4,57
. 25,0 mL EDTA:
Sr2+
+ EDTA
/ mmol
0,500
0,500
0,500
0,500
Sr4-
0,500
-
0,500
[Sr4- ] = 0,500/75,00=0,00667
pSr2+
:
Sr2+
+ EDTA
Sr4-
/
x
x
0,00667-x0,00667
Kf= 0,00667/x2= 3,67.108., x =4,263.10-6
[Sr2+] =4,263.10-6 pSr =-log4,263.10-6 = 5,37
. 25,10 mL EDTA:
Page 150
Sr2+
+ EDTA
/ mmol
0,500
0,50 2
0,500
0,500
Sr4-
0,500
-
0,0020
0,500
[Sr4- ] = 0,500/75,10=0,00666 [EDTA] = 0,0020/75,10 = 0,0000266 M

pSr2+
:
Sr2+
/
Sr4-
+ EDTA
x+0,00002660,0000266
0,00666-x0,00666
Kf= 0,00666/x. 0,0000266= 3,67 108., x =6,822.10-7

[Sr2+] =6,822.10-7 pSr =-log6,822.10-7= 6,17
. 26,00 mL EDTA:
Sr2+
+ EDTA
/ mmol
0,500
0,520
0,500
0,500
Sr4-
0,500
-
0,0200
0,500
[Sr4- ] = 0,500/76,00=0,00658 [EDTA] = 0,0200/76,00 = 0,000263 M
Page 151
pSr2+
:
Sr2+
Sr4-
EDTA
/
x
x+0,0002630,000263
0,00658-x0,00658
Kf= 0,00658/x. 0,000263= 3,67 108., x =6,817.10-8
[Sr2+] =6,817.10-8 pSr =-log6,817.10-8= 7,17
. 30,00 mL EDTA:
Sr2+
+ EDTA
/ mmol
0,500
0,600
0,500
0,500
Sr4-
0,500
-
0,100
0,500
[Sr4- ] = 0,500/80,00=0,00625 [EDTA] = 0,100/80,00 = 0,00125 M

pSr2+
:
Sr2+
EDTA
Sr4-
/
x
x+0,001250,00125
0,00625-x0,00625
Kf= 0,00625/x. 0,00125= 3,67 108., x =1,362.10-8
[Sr2+] =1,362.10-8 pSr =-log1,362.10-8= 7,87
Page 152
12. EDTA 0,1000 M mg mL-1CaCO3.
12.

, , (.. 1 mL).EDTA

1:1.
:mmoles Ca2+= mmoles
EDTA ,mmoles/mL Ca2+= mmoles/ mL EDTA mmoles
/ mL CaCO3= mmoles / mL EDTA = 0,1000 mmol / mL
, EDTA 0,1000 M mg mL-1CaCO3
0,1000. 100,088 =10,01 mg / mL CaCO3
13.

EDTA. 100 L KOH
2,00 . EDTA 0,00122
M, . 0,203 mL EDTA,
mg L-1 meq L-1.
Page 153
13.
:mmolesCa2+= mmolesEDTA
,mmolesCa2+=0,00122.0,203 = 0,248.10-3 [Ca2+] =
0,248.10-3/ 100.10-6= 2,48mmol / L 2,48. 40,080 = 99,4mg / L 2,48.2 =4,96meq /L
14.
Ca2+ Mg2+
. 100,0 mL 23,00 mL
EDTA 0,0100 pH =10. 100,0 mL
aOH Mg2+ Mg(OH)2
EDTA 0,0100 pH=13,0. , 16,00 mL.

Fo(mg CaCO3/100mL) Do(mgCaO /100mL).
14.
, x mmolesCa2+ mmoles Mg2+ 100 mL .
mmolesCa2++
mmoles
Mg2+=mmolesEDTA x + = 23,00.0,0100 =0,230mmol

, : mmolesCa2+=
mmolesEDTA x= 16,00.0,0100 =0,160mmol
Fo: 0,23.100,088 mg
CaCO3/100mL = 23,0 Fo
Do: 0,23.56,079 mg CaO/100mL =
12,9 Do
Page 154
1
1
DAC: Division of Analytical Chemistry
FECS:Federation of European Chemical Societies
Page 155

What is Analytical Chemistry ?
Analytical Chemistry is what analytical chemists do
C. N Reiley (1925-1981)
FisherAnalyticalChemistryAward.
Page 156
,
: ,
, ,
.
Page 157
:
. :- ( m > 100mg), -(m = 10-100mg),
-(m = 1- 10mg) - (m < 1mg)
. :
.
.. ,
, , .

, ,
.
,
, in Vivo.

(hyphanated instruments) .

:
( ),
50% .
:
-
( )
Page 158
: ,
( ).
:
.
Page 159
: , Ni
.

1
: .
(official)
.

: .
:
1.
2. .. IUPAC
3.
4.
Page 160
5.
6.
7.
8.
9.
10. -
11.
12.
13. .
,
, , .
: : , ,
, .
APHA: American Public Health Association, ASTM: American Society for Testing Materials
,EPA: Enviromental Protection Agency

Page 161
: .
: , .
: .
, ( ),
.
: ,
.
s (standard deviation) RSD
(relative standard deviation).
Page 162
: ,
: .
: S = dP / dX
,
P: :
, .
.
, .
:
( ).
Page 163
:
() ().
: , ..
.
:
, .. 1,10
,
.
: ,
( ).
Page 164
: .

,
.
: : )
) )
) .
) ).
: , .,

.
Page 165
: ,
,..
.
:
. (
standards) .
, .
:
, .. , ,
, .
:
, , .
Page 166
1

.
, .

.

( , , , ).

-
( )
:
-
( )
Page 167
Al3+ .
: Al3+
.

1
:
, ,
. ,
.
Page 168
,
.
.

( L
mL) . ,
,
,. .

Page 169
,
, ,
1.7.
1.7 : 1. , 2. .

1
:
1.
2. .
Page 170
3.
.

, ,
SO2, .

(.. 61% , 6%).
Page 171
:HCl, HNO3H2SO4 , , ,
, . HClO4H3PO4.
3
3

. ,
.
, ,
, .
( ) .
. ,
.
,
Page 172
( ), (.. ,
, ) .
.
: .

(
) .. 2 (g)+ 3H2 (g)
2NH3 (g)
3
(
)
.. CaCO3 ( s )
CaO ( s )+CO2 ( g )
Page 173
CaCO3,CaO CO2.

3

:
(g)+ (g)
(g)+ (g)

Kc . .

., c
,
c
.
Page 174
3

, . ,
= -
: > 0, : < 0

3

S
, ( S=
S.S.).
.
, .
: .

3

Page 175
G
, .
G< 0 . G> 0
G= 0

3
HenryLouis Le Chatelier:
(1850-1936). , . Le
Chatelier , .
, , ,
.
.
Page 176
3
:
: ( )
. . H2O .
BaSO4C. .
Page 177
, Fe(SCN)2+ KNO3,
, :
Fe(SCN)2+
Fe3++SCN
3
:
.

.
Page 178
3
:
:
.

, , .
,
, + - , .
Debye-Huckel.

Page 179
,
, ,
.
0, 1 c
: H2SO4
( ).
.

3
:
Page 180
2, 3+, -,ClO4-, Fe(CN)63-,

CN-, Fe3+, Mg2+ , CH3OH, HCN, NH3NH4+.
.
:
[3+] + 3[Fe3+] + 2[Mg2+ ] + [NH4+]=
[-] + [ClO4-] + 3 [Fe(CN)63-] + [CN-]

Page 181
Svante Arrhenius(1859 -1927)

. 1903
.
:
Cleve, ( )

.
!!! .
, , , ..
rrhenius,
, , .

4
Johanes Brnsted(1879 -1947) .

.
. 1947,
, .
Page 182
Thomas Lowry(1874-1936) , .
Brnsted Lowry, ,
.
, +,
, . ,
, ,..
3+. 3+
, ,
. . 52+ 94+.
Page 183
Lewis(1875-1946) .
.
Lewis.

(D2 2 2).
HCl
HBr
HI
H2SO4( )
HNO3
HClO4
Page 184
LiOH
NaOH
KOH
RbOH
CsOH
R4NOH (R,.. (CH3)4NOH )
(Mg, Ca, Sr, Ba) ,
.
4
Kw ,
pH : 1) 2)
.
/C
Kw
Page 185
0,114x10-14
25
1,01 x10-14
50
5,47 x10-14
100
49
x 10-14
S.P.L. Sorensen(1868 -1939). .

Carlsberg. 1909 pH (-)
.
, . Sorensen
,
.
Page 186
: pH .
CH3OH+CH3OH
CH3OH2+ +CH3O HCOOH+HCOOH
HCOOH2++HCOONH3+ NH3
NH4++NH2-
Page 187
(.. ) .
, .
Page 188
1. 0,1 , 1 - ? 1
c-x? c ( x ).
2. Ka c ,
:
Ka/ c 0,01, 1 - ? 1 c-x? c
4
-
Page 189
,
p Ka=2,97 4,58
Page 190
:
.
: pH .
Page 191
:
[-] / [H].
.
. ,
eq=eq
Page 192
Page 193
1. (0,1%) .
2. .
3. .
4. .
1.
2.
3.
,
.
Page 194
.
. (.. ),
.
.
. .. .
. ,
.
Na2CO3( ), K2Cr2O7, 3
Na2C2O4( ), AgNO3( )
CaCO3( ).
. ,
. ,
.
.
. .. .
Page 195
6
NaOH 0,1 M HCl.

:
1.

.
2.

.
3.

,
, .

6
Page 196
:
0,1mL. A ,
, .. 23,20 23,25
23,25mL 23,25mL.
0,2mL,
.
6
.
.
.
.
Page 197
7
7

, .
,
.
(Cl) .
Na2CO3, .
(NaOH) CO2
, . ,
,
. ,

.
Page 198
O ,
, .
:
pH :
pH, .

pH
.
( )
:
1.
. pH = 7.
2. .
, , pH< 7.
3. .
, pH > 7.
Page 199

:
,
.

. ,
2 ,
.
, , 5 10-4.
:
Ka1>> Ka2 >> Ka3 .
:
1.
2.
3.
, .
4.
5.
Page 200
7.1:

8
8
:[g(NH3)2]+[Cu(H2)4]2+ :[Fe(CO)5]
[Pt(NH3)2Cl2].
Page 201
M. Tassaert 1798,
Co(NH3)63+.
SO42-PO43- , S6+, P5+
O2- , .
3BrCl
OH-
CN
CO32
C2O42
NH3
en
C2H5N
edta
H2O
-( -)
Page 202
: .
. .
[Ag(NH3)2]+
[Ni(CN)4]2
[Co(NH3)6]3+
chelates
.
Page 203
To EDTA
: Mn2+-EDTA
nEDTA.2H2O.

()
:
M+L
ML
Kf1= [ML] / [M][L]
M L+ L
ML2
Kf2= [ML2] / [ML][L]
M L2+ L
ML3
Kf3= [ML3] / [ML2][L]
M Ln-1+ L
MLn
Kfn= [MLn] / [MLn-1][L]
Page 204
Ladder Cd2+ - NH3:
, ,
.
LadderCa2+Mg2+ EDTA:
Page 205
EDTA 4 :
4
++3-
Ka1= 1,0.10-2
3Y-
++22-
Ka2= 2,2.10-3
2Y2-
++3-
Ka3= 6,9.10-7
Y3-
++4-
Ka4= 5,5.10-11
EDTA, Y4-,
: EDTA-M
pH.
pH EDTA, Y4-.
Page 206
pH.
: pH
EDTA, 0,01 .
50,0 mL EDTA:
Ca2+
/ mmol
10,0
+ EDTA
Ca4-
5,0 0
Page 207
5,00
5,0 0
5,0 0
5,00
5,0 0
: [Ca2+] = 5,00 mmol/150,0 mL = 0,0300 M pCa =-log 3,00.10-3= 1,48
100,0 mL EDTA Ca2+ Ca4- :

Ca2+
+ EDTA
/ mmol
10,0
10,0
10,0
10,0
Ca4-
10,0
10,0
[Ca4- ] = 10,0/200,0 =0,0500 pCa2+
:
Ca2+
+ EDTA
Ca4-
/
x
x
0,0500-x0,0500
Kf= 0,0500/x2= 1,8.101. , x =1,70.10-6, [Ca2+] =1,70.10-6 pCa =log1,70.10-6 = 5,77
Page 208
150,0 mL EDTA Ca2+ Ca4, EDTA:

Ca2+
+ EDTA
/ mmol
10,0
15,0
10,0
10,0
Ca4-
10,0
5,00
10,0
[Ca4- ] = 10,0/250,0 = 0,0400 [EDTA] = 5,00/250,0= 0,0200M
pCa2+ :
Ca2+
+ EDTA
Ca4-
+ 0,02000,0200
0,040 0-0,0400
Kf= 0,0400/.0,0200 = 1,80.1010. , =1,10.10-10 [Ca2+] =1,10.10-10
pCa =-log1,10.10-10 = 9,95
:
1.
M-In In.
2.
,
.
Page 209
3.
-In ,

M-L. :
-In + HL
H-In + M-L
.
ML 10-100 -In.
4.
L In .
5.
, pM
, .
: .
Eriochrome Black T,
.
.

Page 210
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D. Skoog, D. West, F. Holler, S. Crouch, Analytical Chemistry - an introduction,

D. Harvey, Modern Analytical Chemistry, McGraw-Hill, Boston, 2000.

J. Tyson, Analysis- What Analytical Chemists Do, Royal Society of Chemistry,

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11. (G. Atkinson,

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K+ (aq)+ Cl- (aq) HCl( Cl-).

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.PbI2(s) + S2- (aq)

PbS (s)+ 2I (aq)

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I= 1/2 {[3+](+1)2+ [Cl-](-1)2+ [K+](+1)2+ [ClO4-](-)2}=

. 0,2 K2SO4 . 0,05 NaCl

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) I= 1/2 {[+](+1)2+ [S42-](-2)2}= 1/2 (0,4.1 + 0,2.4 ) = 0,6

-log Na+= 0,51(+1)20,001 =0,016., Na+=0,964

. Fe3++ SCN. H2PO4-+ H2O

-logFe(SCN)2+=0,51. 2210-3Fe(SCN)2+= 0,862

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-logFe3+=0,51.3210-3 Fe3+= 0,716

-logFe(SCN)2+=0,51. 2210-1Fe(SCN)2+= 0,226

-logFe3+=0,51.3210-1 Fe3+= 0,035

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:3+= C6H5COO-= 0,63

, K =([H3O+]H3O+.[C6H5COO-] C6H5COO-)/([C6H5COOH] C6H5COOH)= a.

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