210

Volumetry

Volumetry

Dr. Supaporn Sangsrichan

For Student 2011

(Standard
Solution)

(titration)

(titration)

(end point)





(indicator)

(equivalence point)

(equivalence point)





(titration error)

T
S

= X

((titrant))
(titration)

CV
CV
t
0

Cs Ct

Cs Ct

T Vt


Vs + Vt

Cs =

Cs0 Vs
Vs Vt

.. (2)

Ct =

C 0t V t
Vs V t

.. (3)
6

X=

C
C

= (X-1)
= 100 (X-1)

. (4)

t
% titration error = C 1 100
s

X 1
X = 1

X 1

(5)

V endpt V eq.pt
x 100 (6)
=
V eq.pt

(Standard Solution)

1.
(Direct method)

(Direct method)

(Indirect method)
9

10

1 AgNO3
0.1500 M 250 ..
(Ag =107.9, N=14.01, O=16.00)

2.
(Indirect method)

11

 2


1.5301 M

H2SO4

250 ..
0.2000 M H2SO4

13

3 HCl conc.

0.1 M 500mL
38%w/w d=
1.188 g/mL MW= 36.45

(Standard solution)

1.
(Primary standard solution)

(solute)


4

(

)

1.
2.

Na2CO3 , H2C2O4 .2H2O KH(C8H4O4)

17

18

 4 NaOH (M)



KHP 0.7546 g NaOH
40.50 mL

2.

(Secondary standard solution)









NaOH , KMnO4 HCl

(Standardization)
19

1.

(Visual Method
chemical indicator method)

(Detection of end point )

(The titrant serves as its own indicator)

(visual observation)

(electrical methods)

KMnO4
MnO4-

Mn2+

21

-
(Acid-Base indicators, HIn)
- (Acid-Base indicators, HIn)
-

HIn + H2O

22

H3O+ + In

pH =

pH

23

pH = pKIn 1

24

pH pKIn -1

pH pKIn +1

14
13
12 pH = 7.0
11
10
9
pH 876
5
4
3
2
1
0

pKIn -1 < pH < pKIn +1

pH 6.0 - 7.6




pH 7.6
pH 6.0
pH > 6.0 < 7.6

NaOH (mL)

25

27

HNO3

H+ + NO3-

CaOH2

Ca2+ + 2OH-

28

100%

H+ + ClO4-

26

HClO4

PP
BB
MO

29

HClO(aq) + H2O

ClO-

(aq)

+ H3O+

NH3(aq) + H2O

NH4+(aq) + OH-

HClO(aq) + C2H5OH

ClO-(aq) + C2H5OH2+

NH3(aq) + C2H5OH

C2H5O-

+ NH4+
30

 (monoprotic acid
dissociation)

H+ 1

H2S
HS-

H+ + HS
H+ + S2-

HCOOH (aq)
CH3COOH (aq)

H2CO3
HCO3-

H+ + HCO3H+ + CO32-

HCOOH CH3COOH

H+(aq) + HCOO-(aq)
H+ (aq) + CH3COO- (aq)

(polyprotic
dissociation )

H+ 3 H3 PO4 ,
H3PO3

acid

1
1 H+
H+
2 H2CO3 , H2S , H2C2O4
31

HClO(aq) + H2O
Ka

ClO=

H+ + H2PO4H+ + HPO42H+ + PO43-

+ H3O+

32

[H3O+][ClO-] [HClO][OH-]
.
[HClO]
[ClO-]

= [H3O+][OH-]

[H3O+] [ClO-]

HClO

H3PO3
H2PO4HPO42-

Ka . Kb

= Kw

[HClO]

ClO-(aq) + H2O
Kb

(aq)

(aq)

+ OH-

Ka.Kb = Kw

[HClO] [OH-]

= 1x10-14

[ClO-]
33

0.0500
M 50 mL NaOH 0.1000 M

pH + pOH = 14

34

2. pH

pH = -log[H3O+]
1. pH

3. pH NaOH ??

4. 0.1 mL

CH3COOH (Ka=1.75x10-5)
0.1000 M 50.00 mL NaOH 0.1000 M

1. pH

1

HOAc + H2O

OAc- + H+

39

1. pH

2

[H3O+]

HOAc + H2O

OAc- + H+

2.
NaOH 10.00 mL
CH3COOH CH3COONa

3.

4. 50.10 mL

CH3COONa OAc- + H2O

HOAc + OH-

CH3COO- NaOH

44

45

CH3COOH 0.1 M 10 mL NaOH 0.1 M

[OH ]

14
13
12
K
[Salt] 11
10
Ka
9
pH 876
5
4
3
2
1
0
w

46

Ka

8.7

PP
BB
MO
NaOH (mL)

47

48

NH3 0.1 M
14 10 mL HCl 0.1 M
[H ]

13 pH = 5.3
12
11
Kw
[Salt]10
Kb
9
pH 876
5
4
3
2
1
0

PP
BB
MO

HCl (mL)

49

HCO3-

CO32-(aq) + H2O
-

[HCO3 ][OH - ]
Kb1
2[CO 3 ]

Kb 2

H2CO3

[H 2 CO 3 ][OH - ]
[HCO 3 ]

Kb1

Na2CO3 (0.05 M) 10 mL HCl 0.1 M

+ OH-

14
13
12
11
10
9
pH 876
5
4
3
2
1
0

+ OH-

(aq)

Kw 1.00x10 -14

2.25x 10 -8
Ka2 4.45x10 7

H2CO3

CO32-(aq) + 2H2O
Kb

(aq)

Kw 1.00x10-14
Kb1

2.13x 10-4
Ka 4.69x1011

HCO3-(aq) + H2O

[H 2CO3 ][OH - ]2

(aq)

+ 2OH-

Kb Kb1.Kb2

[CO32- ]

2.13x10

x 2.25x108 4.79x10-12

51

H2PO4- (aq)

H3PO4(aq) + H2O

[H 3 O ][H 2 PO 4 ]
[ H 3 PO 4 ]

H2PO4-(aq) + H2O
[H 3 O ][HPO 4 ]

[ H 2 PO 4 ]

HPO42-(aq) + H2O

Ka 3

HCO3-

H2CO3

HCl (mL)

52

H2PO4-

H3PO4(aq) + H2O

Ka1 7.11x 10-3

HPO42-

PO43

PP
BB
MO

H3O+

(aq)

+ H3O+

(aq)

+ H3O+

H2PO4-(aq) + H2O

HPO42-

(aq)

+ H3O+

H3PO4(aq) + 2H2O

HPO42-

( )
(aq)

+ 2H3O+

2-

Ka 2

CO32-

Ka 1

50

2-

Ka 2 6.32x 10-8
(aq)

Ka1.Ka 2

+ H3O+

[H 3O ]2 [HPO 4 ]
[H 3 PO 4 ]

H3PO4(aq) + 3H2O

7.11x10 -3 x 6.32x 10 -8 4.49x10 -10

PO43-

(aq)

+ 3H3O+

3-

[H 3O ][PO 4 ]
2
[HPO 4 ]

Ka 3 4.5x 10-13

53

Ka1.Ka2 .Ka3 7.11x10-3 x 6.32x10-8 x 4.5x10-13 2.0x10-22

54


(polyprotic)

(Redox indicator)

55

(Disappearance of the color of the substance titrated)

(Formation of a second precipitate of color
different from the main precipitate)

2Cu(NH3)42+ + 7CN- + H2O

56

Cl-

(aq)

2Cu(CN)32- + 2NH4+
+ 6 NH3+ CNO-

2Ag+

+ Ag+(aq)

(aq)

+ CrO42-(aq)

AgCl(s)

Ag2CrO4

(s)

57

(Formation of a soluble product of distinctive color)

+ SC
SCN-

Fe3+

SCN

(Adsorption indicator)

Ag+

58

AgSCN
SC

(Fajans method)

[FeSCN]2+

59

60

10


Fajans Method

(Titration to first turbidity)

Indicator: Fluorescein, Rhodamine

Dichlorofluorescene, C19H9O3Cl2COOH; HDf

(Liebig)

Secondary adsorption, counterion

Na+
Na+
Na+ Cl-

Df-

Cl
AgCl
Cl-

ClNa+

Cl-

Ag+

Na+

Na+

Ag+

Ag+

Na+

Cl-

Df-

Df-

Na+

Cl-

Df-

2CN-

Ag+
Ag+
Df-

Ag+

Na+

Df-

AgCl
Ag+

Primary adsorption

AgCN2-

+ Ag+

Ag+

AgAgCN2

Df-

Df
61

62

NaCl AgNO3, Dichlorofluorescein

(Completion of precipitation or clear point method)

(Electrical methods)

63

64

(Amperometry)

(Potentiometry)

( electrode)

(equivalence point)

(Conductometry)
(conductance)

65

(polarographic cell)


(Coulometry)
(C l
t )


(electrolysis)







Q = it
66

11

2.

5.





*



*

3
3.

6.
(indicator blank)

1.

1 (0.1%)

4.

*



*
67

7.

68


3

Molarity
+ bB

product

A (g)
A (g/mol)

aA

Volumetric calculation

A(mmol) V(mL) x C A (mmol A/mL)

A(mol) V(L) x C A (mol A/L)

(1)

(2)
(3)

V =
CA=

69

Molarity
aA

1.


20.00 cm3 NaOH 0.1000 M
40.50 cm3

product

+ bB

70

A a

B b

M A xVA a

M B xVB b
M A xVA M B xVB

b
a

(1)

(2)

71

12

2.
92.5mg Calcium perchlorate 0.0500 M
19.90 cm3

3. 50.0 mL Ba(OH)2
0.01963 M




29.71 mL

HCl
Ba(OH)2
H+ + OH-

H+ + ClBa2+ + 2OHH2O

2mol HCl
1mol Ba(OH) 2
74

2mol HCl
1mol Ba(OH) 2

Oxidation-Reduction reaction

=a/b

M A xVA M B xVB

a
b

1.
2.
3.
4
4.
5.

76

4. 0.2121 g Na2C2O4 (134.00 g/mol)

KMnO4 43.31 mL
M

Half Oxidation

Half Reduction

13

Redox

80

Back Titration
A
A

excess

+ B

products

+ C

products

Normality
+A

. no. eq. wt

excess

no. meq. wt

B
MA x VA

= N x V (dm3)
= N x V (cm3)

NA x VA
MC x VC

MB x VB

= formula weight

eq. wt

MA x VA

MC x VC

no of H+

mg B

==

NB x VB

NA

MW B
81

g
equivalent weight

82

Redox
eq. wt

= formula weight

eq. wt

no of H+

formula weight

Oxidation no.

2CN-

+ 2Ag+

eq. wt KCN
2CN-

= formula weight KCN

+ Ag+

eq. wt KCN

C2O42- + 2 MnO4- +16H+

Ag[Ag(CN)2]

+3

Ag(CN)2

+ 2 Mn2+

+8H2O

+4

+1
+7
eq. wt MnO4- =

= formula weight KCN

10 CO2

-5

+2

formula weight MnO4-

2
83

84

14

Fe2+

Cr2O72-

Fe3+

Back Titration

Cr3+

A
A

+ B

products + A

+ C

products

excess

excess

B
NA x VA

85

MA x VA

NC x VC

MC x VC

mg B
eq. wt. B
mg B
MW. B

86

3. MnO2
FeSO4
Fe2+

K2Cr2O7
MnO2 200 mg
50.0
cm3 0.100 N Fe2+ 16 cm3 0.0830 N
K2Cr2O7

15