9

(gravimetric analysis)


2 (precipitation)
(volatilisation)


BaSO4
BaCl2
ZZ
X
Ba2+(aq) + SO42-(aq) YZ
Z BaSO4(s)

9.1

(introduction period)


(nuclei) (nucleation)
4

(colloidal particle)
1-100 nm
(growth)

224

( surface)

2
1)

( colloidal
aggregate)
2)

(fine crystal)

(crystalline aggregate)
(coarse crystal)
3
1)

( 10-6-10-4mm)
1.1) ( sol)

(curdy precipitate) AgCl

1.2) ( gel)

(gelatinous precipitate) Al(OH)3 Fe(OH)3

(gelatin) (jelly)
2)
1mm

3)

225

crystalline precipitate

BaSO4,CaCO3
PbCl2

9.1

9.1
T unsatulation region
S solubility curve

226

Q Q


Q S Q-S

9.2

(Von Weimarn)

(relative supersaturation)

Q
S

Q S
S

....

Q S
S

Q S
S

Q S
S

9.3

(contamination)

227

2
(contamination by true precipitation)
(contamination by coprecipitation)
9.3.1

Ksp
2
1) (simultaneous precipitation)

2) (postprecipitation)

Ksp

CdS CuS HgS
ZnS

9.3.2

228

3
(surface adsorption) (occlusion)
9.3.2.1

(isomorphous)
(isomorphism) MgKPO4 MgNH4PO4
K+ NH4+
Mg2+ MgNH4PO4
K+ NH4+
MgNH4PO4 MgKPO4 BaSO4 Pb2+
BaSO4 BaSO4
PbSO4 BaSO4

9.3.2.2

BaSO4 BaCl2
BaSO4 Ba2+
Cl-

Cl- NO3 - ClO4 - NO3-
Ba(NO3)2 BaCl2 Ba(ClO4)2


CrO42-

229

1)

2)

3) (degree of dissociation)

As2S3 H2S AsO33-
S2- S2- H+ H2S

4)

1)

2)

3)

4)

5)

230

6)

7)
9.3.2.3

BaSO4
BaCl2

SO42- SO42-
Na+ Na2SO4 BaCl2
Na+ SO42- Ba2+ BaSO4
Na2SO4 Na2SO4

9.4

9.4.1

1) Q-S

2)
Q-S
3) ( ) Q-S
(S)

231

9.4.2

(digestion)



9.4.3

(reprecipitation)

9.4.4

(washing)

(mother liquour)
1)
1.1)
1.2)

2)
3)
peptization
4)

9.5

(precipitating agent)

232

9.5.1

(hydrous oxide)
9.1

NH3(aq)

Be
Al
Sc
Fe
In
U
Zn
Ge
As
Mg
Ca
Mn
Zn
Sr,Cd,Pb,Ba,W

Be hydrous oxide
Al hydrous oxide
Sc hydrous oxide
Fe hydrous oxide
In dysrous oxide
(NH4)2U2O7
ZnS
GeS
As2S3
MgNH2PO4
Ca3(PO4)2
MnNH4PO4.H2O
ZnNH4PO4.H2O

BeO
Al2O3
Sc2O3
Fe2O3
In2O3
U3O8
ZnO
GeO2
As2O3
Mg2P2O7
CaSO4
Mn2P4O7
Zn2P4O7
sulphates

H2S

(NH4)2HPO4

H2SO4
HCl

Ag
Si
Cl
Br
I
Nb
Si
SO42-

AgNO3

HClO4
BaCl2

9.5.2

Sr,Cd,Pb,Ba W
sulphates
AgCl
Si(silici acid)
AgCl
AgBr
AgI
Nb2O5
SiO2
BaSO4

AgCl
SiO2
AgCl
AgBr
AgI
Nb2O5
SiO
BaSO4

1)

5 6
( chelate complex)

233

Mn+ +nHX

MXn

nH+

8- (oxine)
Mg Al
Pd Ni Pd
Ni
110C
2)

( sodium tetraphenylboron) ( C6H5)4B-Na+
K+ NH4+
Hg(II),Rb Cs
(Phenylarsonic acid)
+4 Zr4+,Hf4+,Ti4+,Th4+ Sn4+
(benzidine) H2NC6H4C6H4NH2

H2N

NH2

(H2NC6H4)2.H2SO4

234

9.2

8-hydroxyquinoline

dimethylglyoxime

sodium tetraphenylboron

benzidene
cuferron

-benzoin oxime (cuproin)

tetraphenylarsonium chloride

20 pH

Ni2+ Pd2+

K+ NH4+
Hg2+ Rb+
SO42-

Cu
Mo Ni,Nb Ta

ReO4MoO4-,HgCl42-,CdCl42-,ZnCl42-

9.6

1)

2)

3)

4)

5)

235

9.7

1)

2)

3)

4) HCl
NaOH
5)

6)
1-2

7)
AgCl CaC2O4
Fe(OH)3.xH2O

Fe2O3
8)



HNO3 () AgCl
HNO3 (), NH3,
9) 110-120oC 1-2

CaC2O4.H2O

236

10)
11)

1.

2.

3.

4.

5.

6.

7.

9.2

237

9.8

(volatillisation)


NaHCO3 H2SO4
ZZ
X
NaHCO3(aq) + H2SO4(aq) YZ
Z CO2(g) + H2O(l)+NaHSO4(aq)

2
1)

2)

1)

CO2
NaOH
2NaOH

CO2
Na2CO3

H2 O

N2

CO2

CO2

NaOH

CaSO4

CaSO4

9.3

(Skoog,West%Holler,1997,p.72)

238

2) H2S

3) C H
CO2 H2O
4) (caustic alkali)
NH3
NH3
5) H2SO4 HF SiF4
SO2

SiO2 + 4HF

SiF4

2H2O

9.3

CO32
SO32
2S

F SiO2

Si
HF
H3BO3
H2SO4

CO2

Ba(OH)2(aq)+CO2(g)=BaCO3(s)+H2O

SO2

SO2(g)+H2O2(aq)=H2SO4(aq)

H2S

Cd2+ + H2S(g)=CdS(s)+2H+

H2SiF6

SiF4

B(OCH3)3

MeOH
Cr2O72NH4

As2O3

HCl
NaOH
HCl

CrO2Cl2
NH3
AsCl3

( , 2542, 472)
9.9

239

aA

bB

cC

dD

D A

A
wtA

=
=

1
a

fwA
fwD
d
a
fwA
wtD x

d
fwD

(gravimetric
factor)

S
BaSO4
wtS
wtBaSO4

fwS
fwBaSO4

BaSO4 S
wtS

fwS
fwBaSO4

wtBaSO4

fwS
fwBaSO4

Mg

Mg2P2O7 2 Mg Mg

wtMg
wtMg2P2O7

2fwMg
fwMg2P2O7

wtMg

wtMg2P2O7

2fwMg
fwMg2P2O7

9.4

240

9.4

KClO4 K

fwK
fwKClO4
fwK2O
2fwKClO4
3fwFe
fwFe3O4
2fwFe3O4
3fwFe2O3
2fwFe
fwFe2O3
fwKAlSi3O8
3fwSiO2

KClO4 K2O
Fe3O4 Fe
Fe2O3 Fe3O4
Fe2O3 Fe
SiO2 KAlSi3O8

A =
A 100

% A

wtA
100
wtSample

9.1 200.0mL Ca
CaC2O4 26.6002g
CaO 26.7134g Ca 100 mL
CaO
=
26.7134-26.6002 = 0.1132g

molCa
molCaO

molCa

wtCa
fwCa

wtCa

=
=
=

Ca 200

mL

1
1
wtCaO
fwCaO
wtCaO
fwCaO
fwCa
fwCaO
40.08
0.1132g
56.08
0.0809g
wtCaO

0.0809g

241

Ca 100

mL

=
=

0.0809g 100mL
200mL
0.0404g

9.2 382.5mg
AgNO3 AgCl 523.5mg

Cl-

=
=
=

%Cl-

=
=

fwCl
fwAgCl
35.45
523.5mg
143.33
129.48mg
129.48mg
100
382.5mg
33.85%
wtAgCl

9.3 482.5mg MgCl2 NaCl

MgNH4PO4 1050oC
Mg2P2O7 321.2mg Mg

wtMg =
=
=
%Mg

=
=

2fwMg
fwMg2P2O7
2 24.31
321.2mg
222.57
70.17mg
70.17mg
100
482.5mg
14.54%
wtMg2P2O7

9.4 1.1324g HCl

Fe2O3.xH2O NH3
Fe2O3 0.5394g 1)%Fe 2)%Fe3O4

1) %Fe
wtFe

=
=
=

2fwFe
fwFe2O3
2 55.847
0.5394g
159.69
0.3773g
wtFe2O3

242

%Fe

=
=

0.3773g
100
1.1324g
33.32%

2) %Fe3O4
wtFe3O4

=
=
=

%Fe3O4

=
=

9.10

2fwFe3O4
3fwFe3O4
2 231.54
0.5394g
3 159.69
wtFe2O3

0.5214g
0.5214g
100
1.1324g
46.04%

1) (speed)

2)(sensitivity)



0.1%
3)(accuracy)
1%

0.2%

243

4)(selectivity)

100%
9.11

9.11.1

9.5

Be,Al,Fe
Zn
Mg
Cd,Pb,Ba
Ag
Cl
SO42PO43-

NH3(aq)
H2S
(NH4)3PO4
H2SO4
HCl
AgNO3
BaCl2
MgCl2

9.11.2

1)

2)
silicotungstic acid

244

9.12

245

9.13

1)
2)
3)
4)
5)
2.
3.
4.

5.
6.
7.
8.
9.
10.

11. 0.1803g Pb3O4
PbSO2 0.2378g Pb3O4 Pb

12. 0.5095g Fe2O3 Al2O3

0.1187g (Fe2O3 Fe
Al2O3 ) Fe
Al
13. 0.4828g NaCl KCl 2
AgNO3 AgCl 1.1280g
NaCl KCl
14. CaO CaCO3
5% CaCO3
CaO + CO2
CaCO3
1.

246

.(2533). 1. :
.
.(2526)..:
.
. 1. :

.
.(2546). - -
. :.
.(2543).. .
.
.(2542)..:
.
.(2536). 1. :
.
Christian,G.D.(2004).Analytical Chemistry.(6th ed.).
United States of America:John Wiley & Sons,Inc.
Harris,D.C.(1999).Quantitative Chemical Analysis.
(5th ed.).New York:W.H.Freeman & company.
Skoog,D.A.,West D.M.,& James F.H.(1997).Fundamentals of
Analytical Chemistry.(7th ed.).Fort Worth:Harcourt
College Publishers.