Acids and Bases

:



1391

........................................................................................
3 .............................................................

1
 (1-1
.....................................................................................................
5 ....................
(1-2
.....................................................................................................
7 .................................
& Acids (1-3
Bases ................................................................................................ 8
(1-4 pH )Weak
11 ............................................................ ( Acid
(1-5 pH )Weak
13 ............................................................... ( Base
(1-6 pH )Conjugated acid-
15 ............................... (base
(1-7 pH
16 ..............................................
(1-8 )Indicator
19 .............................................................................. ( Solution
(1-9 )( : -
21 ................................................................
(1-10
)( 25 .............................................................................
(1-11
.................................................................................................
29
(1-12
49 ..................................................................
(1-13 Alkalinity :1
50 .......................................................................
2
 (1-14 )Buffer
60 ........................................................................ ( Solutions

:


.





-


.
- ASTM Standard method BP ...
-

.






.



5
3

.

...

.

.


) (
1
.
) pH ( .

. )(




. -
.
.

.
.

4
 (1-1
1325 . 1345
.
1348 .


. 1354
6) (

1357
.

:
(1 1358 .1360
(2 1366 .1368
(3 .1369
(4 1369
.1371
(5

58 .59
:
(1
.
(2 .
:
(1 1 2

.
(2 .
(3
.
(4 .
(5
.
(6
.
(7
.

5
- ) (ISI
. -


.

(1-2
) (Analytical Chemistry

) (Qualitative Analysis
) (Quantitative Analysis.
:
) (1
) (2
) (3
) (4
) (5
) (6

6
 ) (Classical Methods
) (Instrumental Methods .

.

.

(1-3 Acids & Bases

.
. 25oC
:
-
H2O H+ + OH

Autoprotolysation .

Autoprotolysis .

2C2H5OH C2H5OH2+ + C2H5O- K = 10-14.5

2NH3 NH4+ + NH2- K = 10-32

2H2SO4 H3SO4+ + HSO4- K = 10-3

:
1000 g
K H 2O
H OH

CM
n

m
M
18 g / mol
55.5 mol / L
H 2O V V 1L

7
 ]K. [H2O] = 10 -14 = [-OH][+H

]KW = 10 -14 = [-OH][+H

pH + pOH = 14

] [+H ] [-OH

10 -7
]= [-OH] = [+H

pH = -log[H+]= -log 10 -7 = 7

100oC
] [+H 6-10 pH 6 .
pH .

.
-
H2O +Q H+ + OH

pH amphiprotic :

1
pH pKs
2

Ks .

pH (1 .
1 1
pH Neutral H 2O pKs 14 7
2 2

1 1
pH Neutral NH 3 pKs 32 16
2 2

8
 pKa (2 5 2

pKb pKs (H2O) = 14) . pKs

((NH3) = 32

K a .K b K s pK a pK b pK s

pK b ( in H 2O ) pK s pK a 14 5 9

pK b ( in NH 3 ) pK s pK a 32 2 30

+H :

[H
]Total C ) pH log(C
C .
7-10 .

If C 0 pH log

pH log C
If 0

M pH (3 M 0.1 10
10-

.
H mol/L 10
7- +

0.1 .
pH log C log 0.1 1

mol/L 10-
+H 10
mol/L 7-10 .
pH log log 10 7 7

-OH :
[OH ] C ) pOH log(C

C .
7-10 .
If C/ 0
pH 14 log
) pH 14 log(C

9
 If 0 pH 14 log C

pH (4 ) (NaNH2 M 12-10
.
+ -
NaNH2 Na + NH2
pH 32 log C 32 log 10 12 20

(1-4 pH )(Weak Acid

HA )H+(aq) + A-(aq

Ka
A H

) (1
][HA

)(2
] [ A ] [ H

CHA :
]C HA [ A ] [ HA ]C HA [ H ] [ HA

] [ HA] C HA [ H )(3

2 3
:

Ka
H 2
[ H ]2 K a [ H ] K a .C HA 0 )(4

] C HA [ H

Ka K a2 4 K a .C
[H ]
2

10
 HA
:
C HA [ H ] C HA
Ka
H 2

H 2
K a .C HA
C HA
] [H C HA
<<

H ( K
1

a ) .C HA 2
)(5

) log-(5 ) (6 .

pH
1 1
pK a log C )(6
2 2

:
%90
K-
2
a

C 1
:

pH K a

C
+H .

K
a (1 pH
C
1 1 1
pHKa pK
Weak Acid a log C
C 2 100 2

1 Ka
K 10 K a 4 K a .C
2
MediumAcid
100] C
a
[H
2

K log C
pH
Strong Acid a 10
C

pH (5 ) (Hydrofluoric acid 1M
0.001M 5M-10 (Ka =10-3.2) .
a) C 1 M K a 10 3.2 10 3.2 0.01 Weak Acid
C 1

1 1 1 1
pH pK a log C 3.2 log 1 1.6
2 2 2 2
11
b)
K a 10 3.2 1 K
C 0.001 M 3 10 0.2 a 10 not Weak , not Strong
C 10 100 C

Ka K a2 4 K a .C 10 3.2 10 6.4 4 10 6.2 10 3.2 5.3 10 3.5

[H ]
2 2 2

C)
6 10 4 (3 5.3 10 4 ) 9.9 10 4
[H ] 4.95 10 4 pH 3.3
2 2

5 K a 10 3.2 Ka
C 10 M 5 101.8 10 Strong Acid
C 10 C

pH log C log 10 5 5

(Weak Base) pH ( 1-5

BOH B+(aq) + OH-(aq)

Kb
B OH

( 1)
[BOH ]

: CBOH
[ B ] [OH ] (2)

C BOH [ B ] [ BOH ] C BOH [OH ] [ BOH ]

[ BOH ] C BOH [OH ] (3)

3 2
:

Kb
OH 2
[OH ]2 K b [OH ] K b .C BOH 0
(4)

C BOH [OH ]

Kb K b2 4 K b .C
[OH ]
2

12
 BOH
:
C BOH [OH ] C BOH
Kb
OH
2

OH 2
K b .C BOH
C BOH
] [OH C BOH
<<

OH ( K .C
1

b BOH ) 2
)(5

) log-(5 ) (6 .
1 1
pOH pK b log C )(6
2 2

1 1
pH 7 pK a log C )(7
2 2

:
%90
:
Kb 2

C 1

pH K b

C
.

Ka
(1 pH
C

11 1
K7b
pHWeak pK a log C
Base
C 2 100 2

1 K b K b K b2 4 K b .C
Medium
[OH] 10Base
100 C 2

K b 14 log C
pH
Strong Base
10
C

13
 (1-6 pH )(Conjugated acid-base
HA Ca -A Cb
pH .
HA )H+(aq) + A-(aq

Ka
A H


][HA

[H ] K a
HA pH pK a log
] [ A
] [ A ][ HA

Henderson-Hasselbalch Equation .
)
( ] [HA] = [-A pH = pKa .
pH
:
1 1 ][ Base
pH ( pK a ( Acid ) pK a ( Base ) ) log
2 2 ] [ Acid

(1 ) ( .

(2 ) ( .

(3 ) (Non conjugated
) pKa(Base)>pKa(Acid.

(4 ) (Conjugated
.

14
 (1-7 pH

pH (6 M 0.1 M 0.3
.
HCl + CH3COONa NaCl + CH3COOH

0.1 mol 0.3 mol 0 mol 0 mol

0 mol 0.2 mol 0.1 mol

0.1 mol

:
] [ A 0.2
pH pK a log 4.7 log 5
][ HA 0.1

pH (7 mol 0.1 mol 0.2

.
-
HBO2 + CH3COO No Reaction

pKa (HBO2/BO2-) = 9.2

pKa (CH3COOH/CH3COO-) = 4.7

pKa (base) < pKa (base) :

.
1 1 [ Base] 1 1 0 .2
pH ( pK a ( Acid ) pK a ( Base ) ) log (9.2 4.7) log 7 .1
2 2 [ Acid ] 2 2 0 .1

pH (8 mol 0.1 mol 0.2

.
HCl + CH3COOH No Reaction

HCl +H
pH .
pH log C log 0.1 1

pH (9 mol 0.1 mol 0.3

.
HF + CH3COOH No Reaction
pKa (HF/F-) = 3.2
pKa (CH3COOH/CH3COO-) = 4.7
15
 . -
pH
.
1 1 1 1
pH pK a log(C ) 3.2 log(0.1) 2.1
2 2 2 2

pH (10 mol 0.2 mol 0.3

.
-
pKa (HBO2/BO2 ) = 9.2

pKa (NH4+/NH3) = 9.2

2
.
1 1 1 1
pH pK a log(C1 C 2 ) 9.2 log(0.2 0.3) 4.75
2 2 2 2
pH (11 0.1M .
Mannitol 1mol
pH . -
.

HBO2 / BO2 pKa 9.2

BO2 Ma Ma BO2 pK C 6.0

HBO2 )H+(aq) + BO2-(aq pKa = 9.2

1 1 1 1
pH pKa log C pH 9.2 log 0.1 5.1
2 2 2 2

BO2-(aq) + Ma MaBO2-
:.
MaBO2- BO2-(aq) + Ma Kc = 10-6

[ H ][ BO2 ]Total ][ BO2 ][ Ma

Ka [ BO2 ]Total [ BO2 (aq)] [ MaBO2 ] and K c
] [ HBO2 ] [ MaBO2

][ BO2 ][ Ma Ma
[ BO2 ]Total ( [ BO2 ] Free ) [ BO2 ]Total [ BO2 ] Free (1 )
Kc Kc
16
 [ BO2 ]Total [ BO2 ]Free
Ma
(1 )
Kc

[ H ][ BO2 ]Total [ H ][ BO2 ]Free

Ka Ka K a K a pK a pK a log
] [ HBO2 ] [ HBO2

Ma 1
1 1 6
10 6 pK a 9.2 6 3.2
Kc 10

1 1 1 1
pH pK a log C pH 3.2 log 0.1 2.1
2 2 2 2

(1-8 )(Indicator Solution

pH
. )(

17
 .
] [+H
] [+H pH
. HIn
) (Phenolphthalein
:
-
HIn H+ + In
Color Colorless
] [+H
.
.
] ) [+H ] ([-OH

.

H O :
3 In

K 1

HIn a

log- 2 3 . 3

Henderson-Hasselbalch .
H O K HIn
3

a
In

2

pH pK a log
In

HIn 3

In
-

10 HIn In

HIn
In
0.1
HIn
18
 . 10 1/0

Indicator pH Range = pKa 1

)( pH
pH
) (Methyl Orange .
pH 1/3 pH 5/4
. pH 1/3 5/4
)( .



)(Titrand -In +H

. %0.5- %0.1
.
.

.

-
pH

1/3-5/4 )Methyl
(Orange
2/4-3/6 )(Methyl Red
0/5-0/8
) 6/9 -0/8 )
(Purple (Phenolphthalein

19
 :

:

pH ) . -(
(1-9 )( : -

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

.
) (
.
.
.
.
) (
) (
. M 4 4
5/0 . 2
)2 = 4 0.5 .
( mol :
VM =
VN =

20

:

N acid (eq/L) V(mL) acid meq acid = meq base N base (eq/L) V (mL) base

)( ) N.V = N.V( :
.


.
) (Erlen meyer
.
.
) (Pipette .
) (Burette
. :
N1.V1 = N2.V2
.

:
-1
) ( .
.
-2
.
. )
( .

.

21
 -3 ) (Burette
) ( .
.
-4 .
-5
.
.
-6 0.1mL 0.1mL
0.1mL) .
0/15 15(.
-7
.
) ( .
)
(Pipette Filler . ) 20 (
) .

(.
-8
.
-9
.
-10 ( V1 ) .
-11
.
-12
.
-13 .
.
. )
(
.
.
22
 -14 .
) .( V2
-15 ) (
).( V= V2 V1
-16



.
-17
.

.
) (Neutralization .
) (
pH 7
.
.
-
:

( >= pH=7 .

( >= pH<7 .
)(Methyl Orange

( >= .
)pH>7(Phenolphthalein

( pH
7 . HCl NaOH
.
NaOH + HCl NaCl + H2O

23
 .
. H2O pH
-
H2O = H+ + OH .

+H -OH
KH2O = 10 -14 = [-OH][+H] : pH
7 .
( pH
7 HCl NH4OH
.
NH4OH + HCl NH4Cl + H2O
pH
.
NH4Cl + H2O NH4OH + H+ , Cl-

.
.
NH4OH = NH4+ + OH-
( pH
7 NaOH
.
CH3COOH + NaOH CH3COONa + H2O
CH3COONa + H2O CH3COOH + Na+ , OH-
CH3COOH = CH3COO- + H+

)(
.
-
. pH
.
).
(.

24

) ( .
) (.

pH .

(1-10 )(
* .
:
x 0 pH log C

0 x 1 ) pH logC (1 x

x 1 pH 7

x 1 )pH 14 log C( x 1

0.1M
.
pH

13

pHeq = 7

1
25 x
X=1
 pH
7 . )
pH (
.
.
) (
) . (
. .
.

(10 0.1M
pH )-4.4
(6.2 . )( .

10 .

: :

pH (1 x =0 pH = -log C = .
-log 0.1 = 1
pH .
pH 14 log C pH (2 x=2 )( x 1
= 13
(3 Alkalimetry pH) pHV(

pH .
pH

pHeq = 7
26
 pHV = 6.2

Loss Error
x

.
0 x 1 pH logC (1 x) 6.2 log C ( x) x 10 5.2
Error % x 100 10 5.2 100 10 3 0.001%

pH
10 -
.
pH 14 log C( x 1) or pH 14 log C( x) x 0.001 x% 0.1%

H+(aq) + )OH-(aq H2O

C 0 0

C-xC xC

0 xC-C
:

C )C-xC or C(1-x

100 y% = (1-x)100

(11 )(
) 0.1 (pHV pH
%1 .
pH .
.
1
( 0 x 1 pH logC (1 x ) 6.9 log C ) C 10 5
1
100
(x 1 pH 14 log C( x 1) 7.1 14 log C ) C 10 5
100

0.00001M
.
4 pH.
pH :
pH logC pH log 10 5 pH 5

pH 14 logC pH 14 log 10 5 pH 9

pH
pH= 9

27
 pH= 5

0.1M x (12
pHV pH
%1 .
0 x 1 pH logC (1 x) pH [log 0.1 log 0.01] 3
x 1 pH 14 log C( x 1) pH 14 [log 0.1 log 0.01] 11
0.1M
3 11 .
: 0.1M
3650mg/L.

(13 0.001M
pHV pH
%1 .
0 x 1 pH logC (1 x ) pH [log 0.001 log 0.01] 5
x 1 pH 14 log C( x 1) pH 14 [log 0.001 log 0.01] 9
0.001M
5 9 .

.

(1-11

28
 Acidimetry :
.

)HA + OH-(aq A-(aq) + H2O

0 0
C

C-CX CX CX

1 1
x0 pH pK a log C
2 2

x
0 x 1 pH pK a log
1 x

1 1
x 1 pH 7 pK a log C
2 2

x 1 )pH 14 log C( x 1

) (Equilibrium point -OH Cx-C C(x-

) 1.

pKa
:
pH (1 x=0.5 pH = pKa .
. pH 14 log
C( x 1
pH (2 x=2 )
(3 Acidimetry .
(4 ) = pH
pKa ( 4 0.1
pH %1
.

0.1
pH
pH %1
.

4 4

29
x
x = 0.5 x=2
 (14

HBO2 C = 0.01 pKa (HBO2/BO2-) = 9.2

CH3COOH C = 0.001 pKa (CH3COOH/CH3COO-) = 4.7

(
x 0.5 pH pK a 9.2
x 2 pH 14 log 0.01 12

2.8 .

x 0.5 pH pK a 4.7 (
x 2 pH 14 log 0.00111

6.3 .

(15 0.1M
pHV 6.2 10 .
) . 0.1M %0.6
pKa(Acetic acid) = 4.7(.
pH .
1 1
x 1 pH 7 4.7 log 0.1 8.85
2 2
pH
)( .
)HA + OH-(aq A-(aq) + H2O
0 0
C

C-CX CX CX

30
 .

x 1 1
0 x 1 pH pK a log ( 6.2 4.7 log () log ) 1.5
1 x x x
1
( ) anti log(1.5 ) 30 x 0.033 x% 3.3%
x

)( :
x 1 pH 14 log C( x 1) 10 14 log 0.1(x) x 0.001, x % 0.1%
.

(16 Ka C -
) . 0.1 pH
%1.

1 1
x 1 pH 7 pK a log C
2 2 .
pH V pH eq 0.1

1 1 x
7 pK a log C 0.1 pK a log
2 2 1 x
1 1 0.99 1 1
7 pK a log C 0.1 pK a log pK a log C 4.9 5
2 2 0.01 2 2
log K a log C 10 K a C 110
.
1 1
7 ) pK a log C 0.1 14 log C (x
2 2

1 1
7.1 pK a log C 12 log C pK a log C 10
2 2

log
K
log
10C


Ka
C

110
a
0.1M .
0.1M pKa 9
31
 9 . 0.01 0.001 pKa
8 7 ) .
( .

(1 pH
.
HA )H+(aq )+ A-(aq

Ka
A H

) (1
][HA

CHA :
] [ A ] [ H )(2
]C HA [ A ] [ HA ]C HA [ H ] [ HA

] [ HA] C HA [ H )(3

2 3
:

Ka
H 2
[ H ]2 K a [ H ] K a .C HA 0 )(4

] C HA [ H

Ka K a2 4 K a .C
[H ]
2

HA
:

32
 ]C HA [ H ] [ HA Ka
H 2

H 2
K a .C HA
C HA
<<C HA

] [H

H ( K
1

a ) .C HA 2
)(5

) log-(5 ) (6 .
1 1
pH pK a log C )(6
2 2

(2 )
equivalent point (
pH . )
( Conjugated base .
] [ A
pH pK a log
Henderson-Hasselbalch Equation ][ HA

] [HA] = [-A pH = pKa .

(3 equivalent point
) ( pH .

)A-(aq + H2O HA + OH-

Kb
HA OH
] [ A
) (1

] [ HA] [OH

-CA :
] C A [ A ] [OH ] [ A ] C A [OH

33
 Kb
OH 2

] C A [OH

-OH -A :
Kb
OH 2

C A

pH
pH pOH 14 K a .K b K
w
.

(4 equivalent point
pH
.

mL 50 0.1M phenolphthalein
0.1M pH .
pH . 1.75
5-10.
5 .
(1 mL 50 0.1M
.
5 1:
K a 1.75 10
1.75 10 4 0.01 Weak acid
C 0.1
1 1 1 1
pH pK a log C pH 4.75 log 0.1 2.88
2 2 2 2
mL 10 (2 0.1M .
pH . )Conjugated
( base .
10 mL 0.1 M 1 50 mL 0.1 M 10 mL 0.1 M 4
[ A ] M [ HA] M
60 mL 60 60 mL 60
1
] [ A
pH pK a log pH 4.75 log 60 4.16
][ HA 4
60
(3 15mL 0.1M
25mL . pH .
) ( Conjugated base -
.

25 mL 0.1 M 2. 5 50 mL 0.1 M 25 mL 0.1 M 2.5

[ A ] [ HA]
M M
75 mL 75 75 mL 75
2.5
] [ A
pH pK a log pH 4.75 log 34
75 4.75
][ HA 2.5
75
 pH = pKa.
(4 mL 50.
.
pH
3 .

)CH3COO-(aq + H2 O CH3COOH + )OH-(aq

Kb
CH 3COOH OH
] [CH 3COO

] [CH 3COOH ] [OH

:
[CH 3COO ] 0.05 [OH ] 0.05

Kb
OH 2

] C A [OH

-OH -A :
Kb
OH 2
pOH
1 1
pK b logC
C A 2 2
1 1 1 1
pOH pK b logC 9.24 log 0.05 5.27
2 2 2 2

pH pH pOH
14 K a .K b
Kw
.
pH pOH 14 pH 14 pOH 14 5.27 8.73

(5 mL 10 mL 60 .
equivalent point
pH .

35
 60 mL 0.1 M 50 mL 0.1 M 1
[OH ] M pOH 2
110 mL 110

pH pOH 14 pH 14 pOH 14 2 12
pH pH

.

(17 Oxalic acid Phosphoric acid

0.1M :
( mL 10 phenolphthalein mL 48
0.1N .
( mL 10
0.1N .

(1 .
pH (2
(3 .
(4 .
pH (5
(6 .
(7 .
H2C2O4 : pKa = 1.25 , 4.25
H3PO4 : pKa = 2.1 , 7.2 , 12.4

)O2(g) + 4e + 4H+(aq )2H2O(l

)H2C2O4(aq )2CO2(g) + 2e- + 2H+(aq

Phenolphthalein pHv = 9.5

)Alpha-naphtol pHv = 3.5(Red)-5(yellow

pH

-
OH
36
 13

-
PO43

Equivalent Point 12.4

-
HPO42 -
HPO42
-
HPO42
)
7.2
(pH=9.5

-
H2PO4
- 2
C2O4
4.25

-
-
HC2O4
H2PO4

2.1

H3PO4
-
HC2O4
1.25

H2C2O4

)V (NaOH
V (NaOH) = 48 mL
) (Equivalent Point pH=9.8 . pHeq
pHv = 9.5 .
1 1
pH eq ( pKa 3 pKa 2 ) (12.4 7.2) 9.8
2 2

.
1 1 1
pH v pK 1 log 9.5 7.2 log log 2.3 x 5 10 3
x x x

x 5 10 3 Re lative Error 5 10 3 100 0.5%

%0.1 %1
.

37


O2(g) + 4e + 4H+(aq) 2H2O(l)

2(C2O42- 2CO2 + 2e- )

4H+(aq) + C2O42-(aq) + O2(g) 2CO2(g) + 2H2O(l)

1 1
pH eq ( pKa 3 pKa 2 ) ( 7.2 2.1) 4.65
2 2

pH v pK log x 5 7.2 log x log x 2.2 x 6.3 10 3

x 6.3 10 3 Re lative Error 6.3 10 3 100 0.6 %

pH

-
OH

13

)
(pH=5
7.2
Equivalent Point = 4.65

-
H2PO4

2.1

V (NaOH)

38
 V (NaOH) = 11.5 mL

N acid Vacid N Base VBase

eq eq
( N acid 10 ( mL ) 0.1 ) ( ) 11.5 ( mL) N 0.115
L L

mol eq 32.7 g 1 mol mol

? ( ( H 3 PO4 ) 0.115 ) 0.042
L L 1eq 98 g L

.
2 mL 23
:
48 mL 23 mL 25 mL
mL 25 2
:

eq eq
( N acid 10 ( mL) 0.1 ) ( ) 12.5 ( mL) N 0.125
L L
mol eq 45 g 1 mol mol
? ( ( H 2 C2O4 ) 0.125 ) 0.0625
L L 1eq 90 g L
(18
0.1M :

( pHv = 4
( 0.1M
.pHv = 10
.
Al3+ + H2O Al(OH)2+ + H+ pKa = 5

2Al3+ + 3C2O42- Al2(C2O4)3 pK =11

H2C2O4 : pKa = 1.25 , 4.25

pH
-
OH 13

39
 pH )
(4
1 1 1 1
pH eq pKa log C 5 0.1 2
2 2 2 2
5
Equivalent Point

+
Al3

1
)V (base

pH 4 :
pHv pKa log x x anti log 1 0.1 Re lative erroe 0.1 100 10 %

pH
13

pH )
(10

4.25
pHeq= 8.6

)V (base

C (0.1) 3 K 10 5
1 1 10 8

K 10 13 pK 13
10
11 8
K 10

. -
.
C2O42- + H+ HC2O4-

pKa pH
4.25

40
 . +H
.
:
pHv pKa log x 10 13 log x x 0.001 x 0.001 x% 0.1 %
pH pH 2
8.75 pH
) 4(
% 0.1
%10 .
( :
Al3+ + H2O Al(OH)2+ + H+ pKa = 5

Le Chatelier

:

pK a pK a log pK a 5 8 13
(19 .
HCOOH + NH4Cl pKa(HCOOH/HCOO-) = 3.7

pKa(NH4+/NH3) = 9.2
pH 13

9.2

Junction = 5.5
3.7
x

(20 0.1M
.
HCOOH + CH3COOH pKa(HCOOH/HCOO-) = 3.7

pKa(CH3COOH/CH3COO-) = 4.7
pH 13

Junction = 8.3


41 .

x
 4.7

3.7

( 21
0.1m .

H3PO4/PO43- )pKa ( 2.1 7.2 12.4

H2CO3/CO32- )pKa(6.4 -10.2

H2CO3 + Heat CO2 + H2O

: pka 10.2 12.4

.

pH

12.4 PO43- HPO42-

CO32- HCO3-
10.
2

HPO42- H2PO4-
7.2

6.4 HCO3- H2CO3

Junction = 4.3

H2PO4- H3PO4
2.
1
1 1
pH eq ( pKaCarbonic acid pKa Phosphoric acid ) ( 6.4 2.1) 4.25
2 2
42
1
 ) (6.0-4.4
.
pH pK a log(x ) 4.4 6.4 log(x) x % 1%

HCl
.
.


.

pH 13

12.4

Junction = 5.2
7.2

x
1 1
pH eq ( pKa 2 pKa3 ) ( 7.2 12.4) 9.8
2 2

)H2PO4- (aq) + OH-(aq )HPO42-(aq

C 0 0 Concentration Balance
before Titration

C-xC xC xC Concentration Balance

After Titration

)HPO4- (aq) + OH-(aq )PO43-(aq

C 0 0 Concentration Balance
before Titration

)C-(C-xC xC-C xC-C Concentration Balance

After Titration

b x 1
pH pK a 3 log pH pK a 3 log ) pH pK a 3 log(x
a 2x

43
 pH pK a 3 log(x ) 10 12.4 log(x) x % 0.4%

-
)( ) (10mL

CO2
-
)(
.
) ( a mL
) ( b mL
. :
c= a-2b
N1V1=N2V2 2 -
.

(22 ) (Arsenic Acid )Arsenious

(acid 0.1M
pKa
.

pKa(H3AsO4) = 2.1- 6.7 11.2

pKa(H3AsO3) = 9.1- 12.1 13.4

H3AsO3 + Oxidant H3AsO4

pH

13

12.1

11.2

44
 9.1

6.7
)Equilibrium Point 1 (pH= 4.4
Suitable Junction
)(4.6

2.1
x

1 1
pH eq (1) ( pKa1 pKa 2 ) ( 2.1 6.7) 4.4
2 2

pKa

.
pH=4.4.

:
: ) (4.4- 2.8 pH=2.8-
4.4 .
: ) (4.8- 3.0
pH=3.0 4.8 .

.
pHv = 4.6 .
:

) pH pK a log(x

4.6 6.7 log(x) x 10 2.1 0.008 x% 0.8%

:
mL 10

.
mL 10
.

.

45
 (1-12

) pH log C ( x (1 :

pH 14 log C ( x) : (2
1
(pH pK a log )
x (3 :

pH 14 log C (x:
) (4

:
pH log C ) ( x (5

:
pH pK a ) log(x (6

1
pK a
pH : ( log
) (7
x

pH : log(
pK a 2 )x (8

)pH 14 log C (x (9 :

) pH log C ( x (10 :

) pH pK a log(x (11 :
) pH log C ( x (12 :
)pH 14 log C (x (13 :

) pH pK a log(x (14

:
(pH pK a log ) x (15

(1-13 Alkalinity :1

46
 pH 11

. pH 8 .

) P (Phenolphthalein

M )(Methyl Orange

M . Total Alkalinity .

:
.1
.
.2
.
.3

.4
.
.5

M=Total Alkalinity
.

(1 P=M

M
2P>M P (2
2

. M .

(M-P)2 . 2P-M

(3 P=0 . pH 3/8

. .

47
 2P<M - (4M
P
2
P . M-

(5 2P=M 2P.

Bicarbonate Carbonate Hydroxide Result of Titration

Alkalinity as CaCO3 Alkalinity as CaCO3 Alkalinity as CaCO3
M 0 0 P=0
M-P P 0 1/2M >P
2P<M
0 2P 0 1/2M=P
2P=M
0 )2(M-P 2P-M 1/2M<P
2P>M
0 0 M M=P

(1 pH ) Alkalinity (Pa=0
) (Conjugated pH Henderson-Haselbalch
. CO2 pH
TDS . CO2 )pH,
(-TDS, Temp, HCO3 Standard Methods CO2(4)-4500 Nomographic
. CO2 mg/L 8-7
H2CO3 mg/L 7-6 pH M-Alk. = 140
:
M
[ ])( mol / L
2.8 10 3
pH pK a1 log 50000 6.35 log 6.35 1.39 7.7
H 2 CO3 1.13 10 4
[ ( mol(2Pa<M
(2 pH ) Alkalinity ]/ L
62000
)pH (pH meter Pa M
9.9 )3 ppm(CaCO3 )10 ppm(CaCO3

.
)CO32- (aq) + H+(aq HCO3-
) (Conjugated pH Henderson-Haselbalch .
2Pa<M .
CO32- = Pa
HCO3- = M-P

48
 )Pa = 0.15 20 = 3 ppm (CaCO3
)M = 0.5 20 = 10 ppm (CaCO3
2Pa = 6 < M =10
Pa M Henderson-Haselbalch pH
pH pK a 2 log
[
Pa
50000
M Pa
]) ( mol / L
10 .3 log
.
6 10 5
10 .3 log 0.43 10.3 0.4 9.9
[ ] ( mol / L 1.4 10 4
50000

(3 pH Reaction ) Alkalinity (2Pa=M

)pH (pH meter Pa M

10.3 8 16

2Pa=M .
CO32- = 2Pa
HCO3- = 0
OH- = 0
:
)2Pa = 8 2 = 16 ppm (CaCO3

ppm :
)CO32- (aq) + 2H+(aq H2CO3

mol mg ) 1 meq(CaCO3 1 meq CO32 1 mmol CO32 1mol mol

? CO32 16 (CaCO3 ) 1.6 10 4
L L 50 mg (CaCO3 ) 1 meq (CaCO3 ) 2 meq CO32 1000mmol L

pH .
1 1 1 1
pH 7 pK a log C pH 7 10.3 log1.6 10 4 7 5.15 1.9 10.25
2 2 2 2
(4 pH ) Alkalinity (2Pa>M
)Pa = 160 ppm (CaCO3
)M = 180 ppm (CaCO3
pH .

[OH ] 2 P M 320 180 140 mg / L as CaCO3
mol mg ) 1 meq(CaCO3 1 meq OH 1 mmol OH 1mol mol
? OH 140 (CaCO3 ) 2.8 10 3
L L 50 mg (CaCO3 ) 1 meq (CaCO3 ) 1 meq OH 1000mmol L
pOH log [OH ] log 2.8 10 4 2.55 pH 11.45
: 140mg/L 0.0028mol/L-
0.1 0.01
.

(5 pH ) Alkalinity (Pa=M
pH s%1
mol 1 g NaOH 1000 mL ( So ln .) 1 mol NaOH 1mol OH mol
? OH 0.25
L )100 mL ( So ln . )1 L ( So ln . 40 g NaOH 1 mol NaOH L
: pH pH meter

pOH log.
[OH ] log 0.25 0.6 pH 13.4
Alkalinity pH
pH Alkalinity :
pH log . (1
pKa . (2
. (3
. (4
. (5
Pa ) 50mL ( . (6
(23
0.1M
.
49
 pH
13
H2O
-
OH 10.3
HCO3-
First Eq Piont Junction= 3.9
2- 6.3
CO3
H2CO3
Second Eq Piont
Junction =5.3
HCO3-

)V (acid
a mL

b mL

-OH .
:
b a D mL
a D C mL :

.
N1V1=N2V2
.
pHv
pHv .
1 1
pH ( pKa1 pKa2 ) (10.3 6.3) 8.3
2 2
1 1 1 1
pH pKa 2 log C 6.3 log 0.1 3.65
2 2 2 2

:
mL 10
. a
Basicity. .
mL 10 B
pH ) ( .
b . b-a
.
N1V1=N2V2 .
.

a

50
 NaOH
.
): (Error Calculation
pH=8
:
3 x 1 x 1
(pH pK a log ) 8 6.3 log 8 6.3 log
x2 x x

1
101.7 x 10 1.7 x 0.02 Additional Error % 2 %
x
:
)pH log C ( x 3 3.5 log 0.1( x ) x 0.003
Additional Error % 0.3 %

.
)OH-(aq) + H+(aq )H2O(l
C 0 0
C-xC xC

X=0 pH = 14 +logC

0<x<1 )pH = 14+ logC(1-x

1 1
X=1 pH 7 pK a 2 log C ])[pKa2(Carbonic acid=10.3 pH 11.5
2 2

)CO32-(aq) + H+(aq )HCO3-(aq

C xC
)C-(xC-C xC-C xC-C
2C-xC )C(x-1 )C(x-1

1<x<2 ] [CO32 2 x
pH pK a 2 log
pK a 2 log
] [ HCO3 x 1
1
x=2 pH ) ( pK a 2 pK a1
2
pH pK
-HCO3
.
(3.01 =aKp) dicA
HCO3
(3.6 =aKp) esaB

51
 )HCO3-(aq) + H+(aq )H2CO3 (H2O+CO2
C xC-C
)C-(xC-2C (xC-C)-C xC-2C
3C-xC xC-2C xC-2C

] [ HCO3 3 x
2<x<3 pH pK a1 log pK a1 log
] [ H 2 CO3 x2

1 1
x=3 pH pK a1 log C
2 2

)pH log C ( x 3
x>3

(24
Hot lime
soda .
.
pH T.H Pa M SiO2
10.3 56 8 16 1.0

:
.
2Pa=M
CO32- = 2Pa
HCO3- = 0
OH- = 0
:
)2Pa = 8 2 = 16 ppm (CaCO3

ppm
:
)CO32- (aq) + 2H+(aq H2CO3

mol mg ) 1 meq(CaCO3 1 meq CO32 1 mmol CO32 1mol mol

? CO32 16 (CaCO3 ) 2
1.6 10 4
L L 50 mg (CaCO3 ) 1 meq (CaCO3 ) 2 meq CO3 1000mmol L

1 pH 1
pH 7 .
pK
a log C
2
1 2
1
pH 7 10.3 log1.6 10 4 7 5.15 1.9 10.25
2 2 52
 (25
Zeolite
Condensate .

pH T.H Pa M SiO2
9.9 Nil )3 ppm(CaCO3 )10 ppm(CaCO3 0.3 ppm

Pa 0.02N
phenolphthalein M
Methyl Orange . mL 50-
.
pH pH meter
.

pH

pKa2 =10.3

HCO3-
First Eq Piont Junction= 3.9
2-
CO3 pKa1=6.3

H2CO3
Second Eq Piont
Junction =5.3
-
HCO3

a mL )V (acid

b mL

-
.
)CO32- (aq) + H+(aq HCO3-

eq
0.02 ( H 2 SO4 ) 0.15 mL
mol L ) 3 10 3 meq( H 2 SO4 1 meq CO32 1 mmol CO32
? CO32
L 50 mL 50 mL ) 1meq( H 2 SO4 1 meq CO32
1mol 1000 mL mol
6 10 5
1000 mmol
. 1
L L

- +
)HCO3 (aq) + H (aq H2CO3
eq
0.02 ( H 2 SO 4 ) 0.35 mL
mol L ) 7 10 3 meq( H 2 SO4 1 meq CO32 1 mmol CO32
? HCO3
L 50 mL 50 mL ) 1meq( H 2 SO 4 1 meq CO32
53
1mol 1000 mL mol
1.4 10 4
1000mmol 1L L
 ) (Conjugated pH Henderson-
Haselbalch .

] [CO32 6 10 5
pH pK a 2 log 10.3 log 10.3 log 0.43 10.3 0.4 9.9
] [ HCO3 1.4 10 4
:
.
2Pa<M
CO32- = Pa
HCO3- = M-P
Feed Water :
)Pa = 0.15 20 = 3 ppm (CaCO3
)M = 0.5 20 = 10 ppm (CaCO3

2Pa = 6 < M =10

ppm
:

mol mg ) 1 meq(CaCO3 1 meq CO32 1 mmol CO32 1mol mol

? CO32 3 (CaCO3 ) 2
6 10 5
L L 50 mg (CaCO3 ) 1 meq (CaCO3 ) 1 meq CO3 1000mmol L

:
mol mg ) 1 meq(CaCO3 1 meqHCO3 1 mmol HCO32 1mol mo
? HCO3 7 (CaCO3 ) 2
1.4 10 4
L L 50 mg (CaCO3 ) 1 meq (CaCO3 ) 1 meq HCO3 1000mmol L

Pa M Henderson-
Haselbalch pH .
Pa
[ ])(mol / L
6 10 5
pH pK a 2 log 50000 10.3 log 10.3 log 0.43 10.3 0.4 9.9
M Pa 1. 4 10 4
[ ]( mol / L
50000
pH
pH pH . 0.1
pH
:
) pH log a ( H (1 pH :

pH +H . )(activity
a C .

54
 -
.
0.504 Z i2
log i -
1
Zi
0.504- .
.

(2 0.02N
(3 .

.

(4 . mL 50
1mL.
(5
.
(6
pKa .
(7 pH.
(8 Metrohm Slope pH -0.95
1.03.

(1-14 Buffer Solutions

pH
.
(1
(2 -
.
] d [ H ] or [OH

d pH
pH

55

x

. x=0.5
pH= pKa .
pH
. .

x
0 x 1 pH pK a log
xam 1 x
0.5
x 0.5 pH pK a log pH pK a
1 0.5

x= 0.5 -
.
x
5.0 =x .

x
x= 0.5
.
x=0.5
.


.
.

(ASTM D 1126) .

56
 Tampon Buffer

b
pH pk a log
a

b
A B log
a

b
log A B
a

b
) anti log( A B
a

) A: pH ( ) B: pka ( ) :Z (A-B
b = aZ
= a + b
a b )
(
.

: 500mL 0.1F pH=9 NH4Cl

mL ) (N =13
+
NH4 /NH3 pKa =9.2 Mw(NH4Cl) = 53.5

57
 b b b
pH pk a log 9 9.2 log log 0.2
a a a

NH3 = 0.6NH4+
NH3 + NH4+ = 0.1 NH4+ = 1/16 M , NH3 = 3/80 M

NH4Cl = 1/16(mol/L) 53.5(g/mol) 500/1000 = 1.67g

3
500
NH 4 OH 80 1.44 mL
13

58