W

W
K

? ???

KKKKK

E F

K
K

K
K

W
KW .

W .
F

KE

KW .

W .
K

--

W
W

K .

K .
W
K
W
K??

--

WK

EF

EF

WK
K
WQualitative Analysis

FQualitative analysis

WKE
W .

KE

W .
KKKKK

WQuantitative Analysis

Quantitative analysis

Quantitative chemical analysisW

KQuantitative instrumental analysis

--

WQuantitative Chemical Analysis

W

+ X P

XReagentY

KP

E FX J

KVolumetric analysis

P X J
KGravimetric

WQuantitative Instrumental Analysis

FPhysical Properties

WKE
. Atomic Absorption Spectrometry

Physico-chemical Methods

K2CrO4Cr3+

KCrO42-

WK
W
--

K .

K .

K .

K .

K .

K .

WDefining the problem

K .

W .
KK

KK

KK

KK

W .
KK

KK

KK

KK

KK

WSampling

Bulk

HomogeneousKMaterial

--

Heterogeneous

KEKKKF

WWater sampling

WEKKKF-

450EPyrexF
K24

PTFE

Kpolytetrafluoroethylene

WE45F

KBiodegradation4
K

K(pH = 2)

WSoil sampling

E10FE30F

E2 1F

KPolyethylene
WSample preparation

110100WWeighingDryingK

KDesiccator 21

--

WSample ashingK

EF
WEF

700400WDry ashing

K24

WWet ashing

SulfuricNitric acid

WSample dissolutionK

W J

K
K

K(HCl-HNO3; 1:3)Aqua Regia

W
J

KK2S2O5
KNa2CO3

KNa2O2

WEliminating interferences

--

.
.Electrodeposition

Ion ExchangeChromatography .
KExtraction

KMasking .

WMeasurements

K .

K .

K .

W
.
KAutomatic methods

WCalculations and reporting data

Analyte

KRelative methodAbsolute method

Parts per percent

Kmillion

Replicate analysesE F

KMeanStandard deviation

KDeterminate errorRandom error





--

K
K K

K K
K K

K K

K K

K K

--

KEFEF

WEKKKF J

450 EPyrexF
K24

PTFEW

Kpolytetrafluoroethylene

WKE45F

KEbiodegradationF4
K

K(pH = 2)
K

--

F
KE

W
W

K .

K .

.
K

K .
K .

W
K
W
K??

Volumetric Analysis - An Introduction

WK

E

FW

KEF

W

KK

KK

:
()

:
)
(

WEquivalence pointEnd pointK

WEnd point

E F

WK
KEFK

KK

KpH-meterK

WEquivalence point

Stoichiometric

W
W

HCl + NaOH NaCl + H2O

KE1:1FNaOHHCl

W
W

2NaOH + H2SO4 Na2SO4 + 2H2O

FNaOHH2SO4
KE2:1

WK
K .
K .

KEF .
K .

W .
A+B C+D

WStandard solutionsK
W
KPrimary standardK

KSecondary standardK

WPrimary standard

K .

K .

K .
K .
K .

K .
W

Sodium carbonate, Na2CO3WK

KSodium tetraborate, borax, Na2B4O7.10H2OEF

WK

Oxalic acid, H2C2O4

KPotassium acid phthalate,KH(C8H4O4) C6H5COOH

WSecondary standard

EF

KStandardization

NaOH

KH2SO4NaOH

WK
EFW

EF

K
W

KAcid-base titrations .
KPrecipitation titrations .

KComplexometric titrations .

KOxidationreduction titrations .
WK
W J

Molecular weightK

Na = 23, C = 12, O = 16KNa2CO3W

MWNa2CO3 = (2 x 23) + 12 + (3 x 16)
MWNa2CO3 = 106 g/mol ELF

Number of molesK

KW
ZLZ

KW

WW
{ZLZ

{Z{LZ

W J

EF

E F

WEF
M1 V1 = M 2 V2

W
0.1FH2SO4NaOH10

W9E
K K

KNaOH K

W
WK
2NaOH + H2SO4 Na2SO4 + 2H2O
2mole : 1mole

WK
number of mmoles of NaOH 2
=
number of mmoles of H 2SO 4 1

M NaOH VNaOH 2
=
M H SO VH SO 1
2

M NaOH 10 2
=
0.1 9
1
0.1 9 2
= 0.18 M
M NaOH =
10 1

EFW
Acid-Base Titrations (Neutralization Titrations)

WK

KOH-H+
NaOH + HCl NaCl + H2O
Na+ + OH- + H+ + Cl- Na+ + Cl- + H2O

OH- + H+ H2O

W
KpHEFK

K
KpH-meter

WK

WArrhenius definition

Arrhenius J
KHydronium ion, H3O+

HCl + H2O Cl- + H3O+

Arrhenius

KOH-

NaOH Na+ + OH-

WBrnsted-Lowry definition

Brnsted and Lowry

W

KH+ J
H+

HA

A-

K J

H+

BH+

W
HA

BH+

A-

WLewis definition
W Lewis
Electron acceptor
KLewis acid

Electron donor
KLewis base

W
H3N: +

BF3 H3N+ + BF3

WK
pH

K
K
W

0.150HCl
KEF{

K10090605551504840200W

W
K0=NaOH
K0.1= HCl
pH = log[H + ]
pH = log(0.1)
pH = log(101 )
pH = (1) = 1

KNaOH20
Reacted HClmillimoles

KW

Reacted HCl (millimoles) = 20 0.1 = 2 mmoles

KHCl
no. of HCl mmoles = 0.1 50 = 5 mmoles

Wunreacted HCl mmolesEFHCl

no. of unreacted HCl mmoles) = 5-2 = 3 mmoles

WHCl
no. of mmoles
volume(ml)
3
Molar HCl =
= 0.04 M
70
Molar HCl =

WpH
pH = log(0.043)
pH = (1.37) = 1.37

pH = 14 pOHW W

pH

WEFNaOH

pH

20

40

60

80

100

14

14

12

12

10

10

(8.3-10)

(3.3-4.4)

2
0
0

20

40

60

( )

80

2
0
100

NaOHHClW

KEquivalence point

WK10.73.3

KMethyl OrangePhenolphthalein

K
WK
KEFW
CH3COOH + NaOH CH3COONa + H2O

14
12
10

pH

6
4
2
0
0

20

40

60

80

100

( )
W
E
F

WCH3COONa

CH3COONa + H2O

CH3COOH + Na+ + OH

EF10.77.7

K
WK
KEFW
NH4OH + HCl NH4Cl + H2O

12
10
8

pH

4
2
0
0

20

40

60

80

100

( )

H+NH4Cl
W

NH4Cl + H2O

NH4OH + H+ + Cl-

WK
KEFNH4OHCH3COOHW
CH3COOH + NH4OH CH3COONH4 + H2O

12
10

pH

6
4
2
0
0

20

40

60

80

100

( )

KMethylene blueNeutral blue

WK

WChemical equilibrium law

W
A + B

C + D

FDCEFBAW

KE

W
v1 = k1 x [A] x [B]
v2 = k2 x [C] x [D]

k2k1

Wv1 = v2
k1 X [A] X [B] = k2 X [C] X [D]

k1 [ C][ D ]
=
k2 [ A ][ B]

Kk2k1
KChemical equilibrium constant

W
aA + bB

cC + dD

Kdcba

W

[ C] [ D ]
K=
[ A ] [ B]
c

W
Le ChatelierK

KW
W

W
H+

HIn

EF

In-

EF

[H + ] [In ]
K In =
[H In ]

KOH-H+
W
KH+H+

KEFln-
H+
+ In EFH+EF
HIn

HInH+OH-

KEF
H+
+ In EFOH-EF
HIn

W
K

W
W

OHIn

OH-

In+

OH-H+W

In+ OHIn

In+OH-W

OHIn
K

W
K

WEF

2.9 4.0

Methyl yellow

3.1 4.4

Methyl orange

6.8 8.4

Phenol red

8.3 10.0

Phenolphthalein

7.2 8.8

Cresol red

W
Precipitation Titrations

WK

BAK
KC

A + B C + D

Silver nitrate, AgNO3

WSilver chloride, AgCl

AgNO3 + NaCl AgCl + NaNO3

WK
Mohr's W
K

KFajan's methodVolhard's methodmethod

WMohr's method

Chromate ion,CrO42-

K EF
KEF

Ag+

Cl-

CrO42-

KMohr's methodW

E F

K
EF
K

Ag+ + Cl- AgCl

(1)

EFEF

E2FE1F

2Ag+ + CrO42- Ag2CrO4

(2)

W
WpH = 7-8

K
.

2CrO42- + 2H+ Cr2O72- + H2O

K
K
K

Ag+ + OH- AgOH

WVolhard's method

Fe3+

EFThiocyanate ion, SCN-

K

W

KEF

SCN-

Ag+

Fe3+

KW

EFK
KAg+

SCN- + Ag+ AgSCN

(3)

Ag+K
WEFFe3+
Fe3+

+ SCN-

Fe(SCN)2+

(4)

KEFE3F

Chloride, Cl-Halides

KThiocyanate, SCN-Bromide, Br-

KECl-F

KEF

Ag+ EF + Cl- AgCl (s) + Ag+ EF

KK
KBack titration
W
SCN- + Ag+ EF AgSCN (s)

WEF

Fe3+

+ SCN- Fe(SCN)2+

W

W

F W

0.1234E
12.2E F

MillimolesK0.0930Molarity
K300

W
W

aA

EF

bB

EF
cC

EF

+ dA

()

EF

+
dA

EAF

()

WBA
Number millimoles A = ( volume A Molar A ) ( volume C molar C
Number millimoles B = number millimoles A

b
a

b
Number millimoles A atomic weight A 100
a
%B =
Sample weight

KWCWBWAW
W

Number millimoles AgNO3 = ( 40 0.1234 ) (12.2 0.093)

Number millimoles AgNO3 = 4.94 1.13
Number millimoles AgNO3 = 3.81 millimoles

W
1
1
Number millimoles Cl = 3.81 millimoles
Number millimoles Cl- = 3.81

W
3.81 35.4 100
300
% Cl = 44.96%
% Cl- =

WFajan's method
F
Fluorescein indicatorE

KEF

Ag+

In-

Cl-

KIn-

Cl-W

Adsorbed
KEF

Na+
-

Na+
-

Na+
-

Na+

Na+
-

Na+
-

Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl Cl

Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl-Ag+ ClCl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+

W
AgCl

Ag+
KEFIn-

In- In- In- In- In- In- In- In- In- In- In- In- In+

Ag Ag Ag Ag Ag Ag Ag Ag Ag Ag

Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl-Ag+ ClCl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+ Cl- Ag+

W
Reduction-Oxidation Titrations

WK

K
K
K

EFW

EFEFEFEF
EFW K

KEF

WOxidation and reductionK

WOxidation

Zno Zn2+ + 2e-

WReduction

Cu2+ + 2e- Cuo

WOxidizing and reducing agentsK

WOxidizing agent

Aox + ne- Ared

WReducing agent

Bred Box + ne-

WOxidation numberK

S2-Fe2+
WK

KS8P4,Ar, Cl2 K

(2-)K
K(1-)(Peroxides)

H2O, Fe2O3W(2-)

H2O2, Na2O2W(1-)

K(1-)(1+)K
H2S, NH3W(1+)

BaH2, LiHW(1-)

K
K

KClO4-Perchlorate Cl W

KCl=x
(4*-2) + x = -1
(-8) + x = -1
x = +7

KCr2O72-Dichromate Cr W

KCr=x

(2x) + (7*-2) = -2
2x 14 = -2
2x = -2 + 14
2x = +12
x = +6

Fe3+ Fe2+
Fe3+ + e- Fe2+

WHalf-equationsK
W

Cl2 ClCl2 2ClCl2 + 2e- 2Cl-

WPermanganate ion (MnO4-) J

MnO4- Mn2+
MnO4- + 8H+ Mn+2 + 4H2O
MnO4- + 8H+ + 5e- Mn+2 + 4H2O

WDichromate ion (Cr2O72-) J

Cr2O72- Cr3+
Cr2O7-2 + 14H+ 2Cr3+ + 7H2O
Cr2O7-2 + 14H+ + 6e- 2Cr3+ + 7H2O

W
WW

l2 lS2O32 S4O62l2 + 2e- 2l2S2O32- S4O6-2 + 2e-

(i)
(ii)

l2 + 2S2O32- S4O6-2 + 2I-

W(ii)(i)

MnO4- Mn2+
Fe2+ Fe3+

WW

MnO4- + 8H+ + 5e- Mn2+ + 4H2O

Fe2+ Fe3+ + e-

W
(i)
(ii)

W(ii)

5Fe2+ 5Fe3+ + 5e-

(iii)

W(iii)(i)
MnO4- + 5Fe2+ + 8H+ Mn2+ +5Fe3+ +4H2O

WW

MnO4- Mn2+
C2O42- CO2

MnO4- + 8H+ + 5e- Mn2+ + 4H2O

C2O42- 2CO2 + 2e-

W
(i)
(ii)

W(ii)(i)
-

2+

2MnO 4 + 16H + 10e 2Mn +8H2O

5C2O42- 10CO2 + 10e-

(iii)
(iv)

W(iv)(iii)
2MnO4- + 5C2O42- + 16H+ 2Mn2+ + 10CO2 + 8H2O

WW
2-

Cr2O7 Cr
Fe2+ Fe3+

3+

W
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
Fe 2+ Fe3+ + e-

(i)
(ii)

W(ii)

6Fe2+ 6Fe3+ + 6e-

(iii)

W(iii) (i)
Cr2O72- + 6Fe2+ + 14H+ 2Cr3+ + 6Fe3+ + 7H2O

WK
K{Ce4+{Fe2+100

KE F{{W

KNernst equation

RT [Ox ]
ln
nF [Re d ]b
a

E = E0 +

[Ox ]
0.0591
log
E=E +
n
[Re d]b
a

=[Ox]8.314 JK-1mol-1=R=E0=E

96485 C (coulombs)=F=[Red]

K=nlog2.303==ln(298)=T

W

Fe2+ Fe3+ + e- [E0 = 0.75V]
Ce4+ + e- Ce3+ [E0 = 1.45V]

W
[Fe3+]/[Fe2+]K
Fe3 +
0.0591

E = E0 +
log
1
1
1
Fe 2 +

[Ce4+]/[Ce3+] K
Ce 4 +
0.0591

0
log
=E +
1
2
1
Ce3 +

E1

[Fe3+]/[Fe2+]= 10/90, E1 = 0.69

[Fe3+]/[Fe2+]= 50/50, E1 = 0.75
[Fe3+]/[Fe2+]= 90/10, E1 = 0.81
[Fe3+]/[Fe2+]= 99/1, E1 = 0.87
[Fe3+]/[Fe2+]= 99.99/0.1, E1 = 0.93

EF
10
50
90
99
99.99

W
[Fe3+] = [Ce3+] [Ce4+] = [Fe2+]

E10 + E 02 0.75 + 1.45

=
= 1.10 V
2
2

K[Ce4+]/[Ce3+]Ce4+ J
E2

[Ce4+]/[Ce3+] = 0.1/100, E2 = 1.27

[Ce4+]/[Ce3+] = 1/100, E2 = 1.33
[Ce4+]/[Ce3+] = 10/100, E2 = 1.39
[Ce4+]/[Ce3+] = 90/100, E2 = 1.45

EF
100.1
101
110
190

WEF

1.5

E, Volt

1.3
1.1
0.9
0.7
0.5
0

20

40

60

80

100 120 140 160 180 200

Cerium (IV), mL

Ce4+W
WK
WPotassium permanganate

%2

StandardizationK

KFe2+
K

+2

MnO4 + 8H + 5e Mn + 4H2O

WK

WK
MnO4- + 2H2O + 3e- MnO2 + 4OH-

WK
MnO4- + e- MnO42-

K1500 .
K .

F

.
KE

K .

.
K

E F .
K

WCerium (IV)

W
Ce4+ + e-

Ce3+

Sn , H2O2 , Fe , V , Mo, W , Ti , U
K

WPotassium dichromate

K2Cr2O7

KEF

Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O

WPotassium bromate

KBrO3

WBr2

BrO3- + 5Br- + 6H+ 3Br2 + H2O

Br2

KBr
K

WKI

2I- + Br2 I2 + 2Br-

Na2S2O3

WIodine

Potassium iodide, KI

KWI3
I 2 + I-

I3-

WDirect methods (Iodimetric methods)

As(III)

SO32-H2SSn(II)Sb(III)

WIndirect methods (Iodometric methods)

KI

Aox + I- Ared + I2

KA

I2 + 2S2O32- 2I- + S4O62-

KCr3+Cu2+ClO-Br2Cl2Cr2O72-
W

Cr2O72-Cr3+0.2
EI-FKI

0.1S2O32-
K22.15

W
Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O
2I- I2 + 2e-

(i)
(ii)

W3C(ii)
Cr2O72- + 6I- + 14H+ 2Cr3+ + 3I2

(iii)

KKIEiiiF
W

2S2O32- S4O62- + 2eI2 + 2e- 2I-

(iv)
(v)

WEvFEivF
2-

2-

2S2O3 + I2 S4O6 + 2I

(vi)

W
2Cr3+ Cr2O72- 3I2 6S2O32Cr
2
1

3+

2-

: S2O3
: 6
: 3

KS2O32-
22.15
0.1
1000
moles = 2.215 103 moles

number of S2O32 moles =

number of S2 O32

KCr3+
1
number of Cr 3+ moles = number of S2 O32- moles
3
1
number of Cr 3+ moles = 2.215 10 3
3
3+
number of Cr moles = 7.38 104 moles

Cr 3+ (%) =
Cr

3+

Cr 3+

number of moles atomic weight 100

sample weight (g)

7.38 104 52.0 100

(%) =
0.2
(%) = 19.19%

WReducing agents and their applicationsK

K
W

WIron (II)

Fe2+Fe(NH4)2(SO4)2.6H2O

0.5F

KE

Fe2+

WPotassium thiosulfate

EFEF
K2S2O3

WS4O62-K
2S2O32- S4O62- + 2e-

WRedox titration indicatorsK

K W

WSelf indicator

KMnO4

WMn2+Fe2+

MnO4- + 8H+ + 5e- Mn+2 + 4H2O

EFFe2+EF

Mn2+MnO4-

MnO4-EFe3+Fe2+F

KMnO4-

WSpecific indicators

EFFe3+KSCN-

EFTi3+

Ti3+Fe(SCN)2-
WFe3+SCN-Fe3+
Fe (SCN)2+ Fe3+ + SCN-

E F

WTrue oxidation-reduction indicators

Inox + ne- Inred

EFEF

(II)10,1

K(Phen)3Fe2+

1.06 V

(Phen)3Fe3+ + e-

(Phen)3Fe2+ (E0 = 1.06 V)

EF
Fe2+KEEF

1.10 VE FCe4+
KEF(II)10,1
WEF

+1.1V

II{

+0.85V

+0.28V

E0In

W
Complexometric Titrations

WK
Complexing

agents
KELFLigands

M(H2O)n + L M(H2O)n-1L + H2O

KKMLn

K
EDTA

W K

Lewis acidK

KLigands Lewis base

WUnidentate ligands

: NH 3 H 2 O :

H3N: + M H3N: M

WBidentate ligands
K

EFEthylenediamine

KEF
Chelation

KChelating agents

H2

C H2

KEthylenediamineW

H2

C H2

N
H2
N C
Co

N C

H2

C H2

H2

WPolydentate ligands

Ethylenediamine tetraacetic acid

KEFEDTA

CH2COOH

HOOCCH2
N

CH2

CH2

N
CH2 COOH

HOOCCH 2

W

Coordination covalent bonds

KCarboxyl group, COOH

W K
EDTA .

KWEDTA .

M2+ + H2Y2- MY2- + 2H+

FNa2H2Y H4Y .
KEDTAE

CH2COONa

HOOCCH2
N

CH2

CH2

N
CH 2 COONa.2H2 O

HOOCCH 2

Na2H2YW
WEDTAK

EDTA
W

M2+ + H2Y-2 MY2- + 2H+

M3+ + H2Y2- MY- + 2H+

EFKpHEFEF

KKMY

KMYWEF

KMY
5.0 x 1010
4.9 x 108

Ca2+
Mg2+

KMY
4.2 x 1018
3.2 x 1016

Ni2+
Zn2+

KMY
1.0 x 1023
1.3 x 1025

Bi3+
Fe3+

MY

K Y

M + Y
H+}~
HY, H2Y,

MY

W Y
K
K

K
K

KFe3+Bi3+K

KBuffer solutions
WK

EDTA

K .

K .

K .

KEFEF .

WEriochrome black TK

KEFErio-T .
KNaH2D .

W .

OH

OH
N

NaSO3
NO2

Eriochrome black TW
WErio-TK
WEFpH = 10Erio-TEDTAMg2+
Erio-T .
W

HIn2- + Mg2+ MgIn- + H+

KEErio-TFMg2+
Mg2+ + H2Y2-

MgY2- + 2H+

KMgIn-
MgIn- + H2Y2- MgY2- + HIn2- + H+

K

EDTA
Erio-T

Mg2+

pH = 10

KpH = 10Erio-TEDTAMg2+W

WMurexide indicatorK
Ammonium salt of purpuric acid
W

K
KCalcichromeCalmagite

WEDTA K
WDirect titration

KEDTA

K EDTA EFEF

WBack titration

W
K .
K .

KEDTA .

K .

EDTA

KErio-TEDTA

K Zr4+

E 0.0502F10W

Zr4+

2.08E 0.0540FF
Kmillimoles

EDTA + Zr(IV) Zr-EDTA + EDTA EF

Bi3+ + EDTA EF Bi-EDTA

WW

Number of mmoles of Zr 4+ = number of mmoles of EDTA (before reaction) - number of millimoles of Bi 3+

Number of mmoles of Zr 4+ = (vol. of EDTA molarity of EDTA) - (vol. of Bi 3+ molarity of Bi 3+ )
Number of mmoles of Zr 4+ = (10.00 0.0502) - (2.08 0.0540)
Number of mmoles of Zr 4+ = 0.502 - 0.112
Number of mmoles of Zr 4+ = 0.39 mmoles

Concentration of Zr 4+ (mg) = 0.39 91.22

Concentration of Zr 4+ (mg) = 35.5 mg

WMixture titration

W

WK

PbBi

pH = 5
EF Bi pH =2
KPb

WMasking and demasking agentsK

CN-Cyanide ion, CN-

KPb, MgEFCo, Cu, Hg, Zn, Cd, Ni

K(CoFCoCN-Co, Mg
Co2+ + 4CN-

Co(CN)42-

Formaldehyde, HCHOMg
KCo

Co(CN)42- + 4H+ + 4HCHO Co2+ + 4HO.CH2CN

EF

K
K .

K .
K .
K .
1510 .
KK0.04

EF

0.150pH

K555050WNaOHK0.1
K

KK

KK

KK

EF

W
W .

KKKKKKKKKKKKKKKKKEFKKKKKKKKKKKKKKKKKKKKKKKKKEF

KKKKKKKKKKKKKKEF

KKKKKKKKKKKKKKKKKKKEFKKKKKKKKKKKKKKKEFKKKKKKKKKKKKKKKKKKKKKEF
KEF .
W .
KK
KK
KK

F .
KE

EF

W
K

KH2O2EFCr2O72-EFFe2(SO4)3EFKNO3EFFeCl3EF
W

N2O4 N2OEFOCl- ClO3-EFSO2 SO3EFMnO2 MnO4EF

Cr2O72- Cr3+
Fe2+ Fe3+

KEF

KEF
KI2EFEF

EF
W

KKKKKKKKKKKKKKKKKEF

KKKKKKKKKKKKKKKKKKKKKKEFKKKKKKKKKKKKKKKKKKEFK

KKKKKKKKKKKKKKKKKKKKKKKKKKEF
KKKKKKKKKKKKKKKKKKKKKKKKKKKKKKEF

EF

W .

K .
K .

KEF .
K .

K .

W .

K .
K .

K .
K .

.
KStoichiometric

K .
K0.06 .

EF
KpH = 1.00NaOH0 K
KpH = 1.09NaOH5
KpH = 7.00NaOH50
KpH = 11.68NaOH55

KKK

H+NH4Cl

NH4Cl + H2O

NH4OH + H+ + Cl-

pHK K
K

K
WCH3COONa

CH3COOH + Na+ + OH-

CH3COONa + H2O

EF

KKEFKEFKEFKEFKEFKEFK
WpH = 8K
K
.

CrO42- + 2H+ Cr2O72- + H2O

KK

Ag+ + OH- AgOH

K
KWWWK
KSCN- + Ag+ AgSCNK

KFe3+ + SCN- Fe(SCN)2+K

Fluorescein indicatorE
FK

KIn-

Cl-W

Adsorbed
K

AgCl

Ag+
KIn-

EF

K
K

KK
S = +6Fe = +3O = -2EFN = +5O = -2K = +1EFFe = +3Cl = -1EFK

KH = +1O = -1EFCr = +6O = -2EF

KEFEFEFEFK

KCr2O72- + 6Fe2+ + 2Cr3+ 7H2O + 6Fe3+K

EFEFEFK

KI

EF
KEFEFEFEFEFK
KCarboxyl group, COOHK
K
CH2COOH

HOOCCH2
N

CH2

CH2

CH2 COOH

HOOCCH 2

CH2COONa

HOOCCH2
N
HOOCCH 2

CH2

CH2

N
CH 2 COONa.2H2 O

KEFEF

Erio-TK
W

HIn2- + Mg2+ MgIn- + H+

KEErio-TFMg2+
Mg2+ + H2Y2-

MgY2- + 2H+

KMgIn-
MgIn- + H2Y2- MgY2- + HIn2- + H+

KEF

W
W
K .

K .

K .
K .

K .

W
K
W
K??

Gravimetric Analysis
WK

K
K

K
K

WK
W
WSample dissolution

K120100 J

K J

K J

W
K K
K K

K K
K K

WPrecipitation

WIgnitionDrying

120100

W
Fe(OH)3
K
Al(OH)3

KPrecipitated form

Al2O3Fe2O3

2Fe(OH)3 Fe2O3 + 3H2O

2Al(OH)3 Al2O3 + 3H2O

IgnitionE

Weighed

KAl2O3 Fe2O3Kform

WK
KEF K

K
K

K K

K K

WSolubility Product RuleK

W

K
AaBb

AaBb

aA

m+

n-

+ bB

WKEF


a

A m + Bn
K=
[ AaBb]

A m + Bn = K [ AaBb ]
a

(1)

(2)

kK AaBb

W[AaBb]

W(2)

a

A m + Bn = kK

(3)

Solubility product KspkK

Wconstant

Ksp = A m + Bn

(4)

WW

Ba(IO3)2

2+

Ba

+ 2IO3

WKsp

Ksp = [Ba2+] [IO3-]2

WAgClAgClSW

Ksp = 1.02 x 10-10

Ag+ = SCl- = SW
K sp = Ag + Cl
K sp = S S
K sp = S2
K sp = 1.02 1010 = S2
S = 1.02 1010 = 1.01 105 mol / L

WK
W

KBaSO4H2SO4
BaSO4
H2SO4

Ba2+ + SO422H+ + SO42-

Ba2+SO42-

KEF
W

KGravimetric factor

WGravimetric factor

WGravimetric factor (GF)

GF=

MW (or atomic weight) of analyte

MW of weighed substance

a
b

KWMW

KWanalyte

KWWeighed substance
KWa
KWb

KEF
WEF

AgCl
Cl-

2 Fe
Fe2O3

5 HgO
Hg5(IO6)2

AgCl

Cl-

Fe2O3

Fe3+

Hg5(IO6)2

HgO

W
Weight of analyzed substance (g) = GF weight of precipitate (g)

W
W

Weight % of analyzed substance =

GF weight of precipitate (g)

100
weight of sample (g)

(AgCl)0.204 W
0.535.5Cl143.3AgCl

35.5
143.3
GF = 0.2478

GF =

Weight of Cl- = 0.2478 0.204

Weight of Cl- = 0.05 g
Cl- (%) =

0.2478 0.204
100 = 10.11%
0.5

W
K .

K .
Ag2CrO4(S) .
KKsp = 1.9 x 10-12

Fe2O3Fe0.2010 .
KK0.1106

KEFEFEFEF K
K
KEF K

K
K(Filter)

K K

K
K

K7.8 X 10-5=S K
K38.49=0.07735= K

W
K
W
W

K
W
K

W
K?? K
K K

K K

WK

K
K

WSolubility product ruleK

KEF??

WCommon ion effectK

WEFAgCl

AgCl

Ag+ + Cl-

(1)

KNaCl

NaCl Na+ + Cl-

(1)

Cl-K

K

W

Pb(NO3)2PbI2S
KKsp(PbI2) = 1.4 X 10-8K0.1
W

0.1+S 0.1*
2S

+S
+2S

0.1
0.0

Pb2+
I-

K0.1S*
WKsp(PbI2)
Ksp = [Pb2+] [I-]2

WI-Pb2+Ksp

Ksp = (0.1)(2S)2 = 1.4 X 10-8
4S2 = 1.4 x 10-7
S2 = 3.5 x 10-8
S = 1.9 x 10-4 M

WFormation of precipitatesK

KKsp

A m + Bn > Ksp

Cl-Ag+E25FW

K1X10-4
W

K25KspAgCl = 1.7 x 10-10 EF

[Ag+] x [Cl-] = (1 x 10-4) x (1 x 10-4)
[Ag+] x [Cl-] = 1 x 10-8

KKspAgCl[Ag+] X [Cl-]
WPrecipitation of chlorides

KPb2+, Ag+, Hg22+W

KW

1.7x10-10EF
K1.7x10-10[Ag+] x [Cl-]

0.1HCl

KK0.01Cl

WK(Ag+, Cl-)

K(Ag+, Cl-) = [Ag+] x [Cl-] = 0.1 x 0.01

K(Ag+, Cl-) = 1 X 10-3

KK(Ag+, Cl-) > Ksp(AgCl)

WPrecipitation of sulfides

Cu2+, Cd2+, As3+, Sb3+,

Zn2+,
Sn4+, Hg2+,Bi3+

WH2SKMn2+, Co2+, Ni2+

2H+ + S2-

H2S

(1)

WH2S
[H + ]2 [S2 ]
K=
[H 2S]

(2)

1.1x10-22K

K0.125

[H ] [S ] = 1.1 10
K=
+ 2

[H ]

+ 2

22

0.1
[S2 ] = 1.1 10 23

W[S2-]

[S ] = 1.1 10
[H ]
2

+ 2

23

(3)

H+S2-

KH+

S2-

Ksp(CdS) = 1 x 10-28
Ksp(Bi2S3) = 1 x 10-97
Ksp(CuS) = 9 x 10-36
Ksp(HgS) = 4 x 10-53

KHCl
H2S
2H+ + S2HCl H+ + Cl-

(1)
(2)

H+HClLe Chatelier Principle

K EF

0.3KS2-

W(3)S2-KHCl

1.1 10 23
[S ] =
0.32
[S2 ] = 1.2 1022
2

K 1.0 x 10-4

WMSM2+

Ksp(MS) = [M2+] X [S2-]

Ksp(MS) = (1 X 10-4) X (1.2 x 10-22)
Ksp(MS) = 1.2 X 10-26

K1.2 X 10-26

W
S2-EF

Ksp(ZnS) = 1 X 10-21
Ksp(MnS) = 1.4 X 10-15
Ksp(NiS) = 3.0 X 10-19
Ksp(CoS) = 5.0 X 10-22

H+

WNH4OH + HN4Cl

WNH4OH

NH4OH

NH4+ + OH-

(1)

WH2S

H2S

2H+ + S2-

(2)

H+FH+NH4OH

(2)EOH-

S2-

F EF
K E

WPrecipitation of hydroxides

NH4OH + NH4ClKAl3+, Cr3+, Fe3+, Fe2+W

KOH-
WPrecipitation of carbonates

Ammonium carbonate

(Ca2+, Ba2+, Sr2+)

W

(NH4)2CO3

2NH4+ + CO32-

(1)

W
NH4Cl NH4+ + Cl-

(2)

CO32-NH4+(2)(1)

Ca2+ + CO32-

CaCO3

([Ca2+] X [CO32-] > Ksp(CaCO3))

Ba2+ + CO32-

BaCO3

([Ba2+] X [CO32-] > Ksp(BaCO3))

Sr2+ + CO32-

SrCO3

([Sr2+] X [CO32-] > Ksp(SrCO3))

MgCO3

([Mg2+] X [CO32-] < Ksp(MgCO3))

Mg2+ + CO32-

NH4+ + OH-

NH4OH

NH4Cl NH4+ + ClMg2+ + 2OH-

Mg(OH)2

[Mg2+] x (OH-]2 < KspMg(OH)2

WK

KKsp

A m + Bn < Ksp
K

W
K K

K K

K K

K K

WFormation of a weak electrolyte

KW

WAg3PO4AgNO3
2Na2HPO4 + 3AgNO3 Ag3PO4 + 3NaNO3 + NaH2PO4

WAg3PO4

3Ag+ + PO43-

Ag3PO4

PO43-W
Ag3PO4

WH3PO4H+

PO43- + 3H+

H3PO4

Ksp[Ag+]3 X [PO43-]PO43-

WKAg3PO4

Ag3PO4 + 3H+

3Ag+ + H3PO4

WFormation of a precipitate
K0.2KClAg3PO4W
KCl

3Ag+ + PO43-

Ag3PO4

KCl K+ + ClAg+ + Cl- AgCl

WNaIAgCl

Ag+ + Cl-

AgCl
Ag+ + I-

AgI

Ksp(8.5x10-17)KspWAgIAgCl

K(1.7 x 10-10)

WFormation of a complex ion

KAgClW

WHCl
AgNO3 + HCl AgCl + HNO3

AgCl

Ag+ + Cl-

WNH4OHAgCl

Ag+ + 2NH3

[Ag(NH3)2]+

NH4OH

NH3 + H2O

Ag+

WKsp

[Ag+] x [Cl-] < Ksp(AgCl)

WValence change of an ion

K
K

WEFW
S2-

WS

CuS

Cu2+ + S2-

3S2- + 2NO3- + 8H+

3S + 2NO + 4H2O

KAl(OH)3Ksp K

0.001 K

KEFEF K

KK

KK
KK

KKSpK

KKspK

K K

Ksp = [Al3+] X [OH-]3 K

KKsp[Ag+] X [Cl-] K
F[Ag+] X [Cl-]1.7 X 10-10KspEF

KKspE1.0 X 10-6
K K

K
K

KOH-

EFEFEFEF K
K

E25FKspWEF
Ksp

8.5X10-17
1.4X10-8
3.5X10-8
9.0X10-9
9.3X10-10
8.9X10-9
7.4X10-14
1.0X10-97
1.0X10-28
9.0X10-36
8.0X10-28
1.410-15
4.0X10-53
1.0X10-49
1.0X10-21
7.1X10-12
6.5X10-6
2.0X10-15
1.1X10-36
2.0X10-33
5.0X10-26
1.2X10-11
1.6X10-14
4.8X10-20
4.5X10-19
2.0X10-4
3.2X10-7
1.5X10-9
6.3X10-7
1.5X10-5
1.0X10-4
2.4X10-10
1.9X10-12
1.8X10-14
2.3X10-3

PbCl2
Hg2Cl2
AuCl2
AgBr
PbBr2
AgI
PbI2
MgCO3
CaCO3
SrCO3
BaCO3
PbCO3
Bi2S3
CdS
CuS
PbS
MnS
HgS
Ag2S
ZnS
Mg(OH)2
Ca(OH)2
Fe(OH)2
Fe(OH)3
Al(OH)3
Sn(OH)2
Mn(OH)2
Ni(OH)2
Cu(OH)2
Zn(OH)2
CaSO4
SrSO4
BaSO4
PbSO4
Ag2SO4
CaCrO4
BaCrO4
Ag2CrO4
PbCrO4
AgC2H3O2

1.7X10-10
1.6X10-5
2.0X10-18
3.2X10-25
5.0X10-15
2.1X10-6

AgCl

Be

9.01
12

Li

6.94
11

Na
22.99

Chemical symbol

Atomic weight

11

Non-metals

140.91

91

Pa

140.12

90

Th

Tc
Os

62

190.20

63

192.22

Ir

102.91
77

Ru Rh
101.07
76

Ni

64

195.08

Pt

106.42
78

Pd

58.69
46

238.03

92

144.24

237.05

Np

93

144.91

244.06

243.06

95

151.97

247.07

96

157.25

Cu

247.07

97

158.93

Tb

65

196.97

Au

107.87
79

Ag

63.55
47

Pu Am Cm Bk

94

150.36

Nd Pm Sm Eu Gd

61

262.12

186.21
107

Re

98.91
75

Co
58.93
45

28

IB
29

242.06

Cf

98

162.5

Dy

66

200.59

Hg

112.41
80

Cd

65.39
48

Zn

IIB
30

Al

Si
28.09
32

252.08

257.10

100

167.26

Er

68

207.20

Pb

118.71
82

Sn

72.61
50

70

208.98

Po

127.60
84

Te

78.96
52

Se

32.07
34

259.10

102

173.04

260.11

Lr

103

174.97

Lu

71

Ac

La

s
de

e
id
tin

ni
ha
t
n

Rn
222.02

At
209.99

Xe
131.29
86

I
126.90
85

Kr
83.80
54

Br
79.90
53

Ar
39.95
36

Cl
35.45
35

Ne
20.18
18

4.00
10

He

19.00
17

VIIA
9

Non-metals : - Metalloids or semimetals : - Metals :

- Alkaline metals :

258.10

101

168.93

Tm Yb

69

208.98

Bi

121.75
83

Sb

74.92
51

As

30.97
33

16.00
16

VIA
8

Es Fm Md No

99

164.93

Ho

67

204.38

Tl

114.82
81

In

69.72
49

Ga Ge

26.98
31

VA
7
14.01
15

Halogens : - Noble gases : - Transition metals : - Alkaline earth metals :

231.04

Pr

Ce

60

162.12

183.85
106

95.94
74

55.85
44

Fe

26

VIII
27

12.01
14

IVA
6

232.04

59

262.11

58

261.11

180.95
105

Ta

92.91
73

54.94
43

Mn

VIIB
25

Unq Unp Unh Uns

178.49
104

52.00
42

Cr

VIB
24

Nb Mo

50.94
41

VB
23

10.81
13

IIIA
5

0
2

**

**Ac

227.03

Ra

226.03

223.02

Fr

138.91
89

Hf

Ba *La

137.33
88

Cs

132.91
87

91.22
72

88.91
57

Sr

87.62
56

Rb

85.47
55

Zr

Ti

47.88
40

Sc

44.96
39

Ca

IVB
22

IIIB
21

40.08
38

Alkaliine Metals (Except H

Semimetals

---------------------------------Transition metals --------------------------------

24.31
20

Alkaline Earth Metals

Atomic number

Metals

39.10
37

22.99
19

Na Mg

IIA
4

1.01
3

IA
1

THE MODERN PERIODIC TABLE OF ELEMENTS

Halogens

Noble Gases

WEF

WEF

Anion
BrClFHIN3S2O2S2-

Anion
C2H3O2NH4+
CO32ClO3ClO2CrO42CNSCNCr2O72HCO3HSO4HSO3OHClONO3NO2C2O42ClO4MnO4PO43SO42SO32S2O32S4O62IO3IO4CNO-

Name of Anion

Bromide

Chloride

Fluoride

Hydride

Iodide

Nitride

Sulfide

Oxide

Phosphide

Name of polyatomic anion

Hydrogen carbonate or bicarbonate

Hydrogen sulfate or bisulfate

Hydrogen sulfite or bisulfite

Hydroxide

Hypochlorite

Nitrate

Nitrite

Oxalate

Perchlorate

Permanganate

Phosphate

Sulfate

Sulfite

Thiosulfate

Persulfate

Iodate

Periodate

Cyanate

Acetate
Ammonium
Carbonate
Chlorate
Chlorite
Chromate
Cyanide
Thiocyanate
Dichromate

Cation
Al3+
Ba2+
Bi3+
Cd2+
Ca2+
Cu+
Cu2+
Au3+
H+
Fe2+
Fe3+
Pb2+
Pb4+
Li+
Mg2+
Hg22+
Hg2+
Ni2+
K+
Ag+
Na+
Sr2+
Sn2+
Sn4+
Zn2+

Name of Cation
Aluminum
Barium
Bismuth
Cadmium
Calcium
Copper(I) or cuprous
Copper(II) or cupric
Gold(II1)
Hydrogen
Iron(II) or ferrous
Iron (III) or ferric
Lead(II) or plumbous
Lead(IV) or plumbic
Lithium
Magnesium
Mercury(I) or mercurous
Mercury(II) or mercuric
Nickel(II)
Potassium
Silver
Sodium
Strontium
Tin (II) or stannous
Tin(IV) or stannic
Zinc

WK

EF

K
W
K

3. G.D Christian: Analytical Chemistry, 5th edition, John Wiley &Sons, Inc,
International edition, 1994.
4. G.H. Jeffrey, J. Bassett, J. Mendham, R.C. Denney: Vogel's Textbook of
Quantitative Chemical Analysis, 5th edition, Longman Scientific & Technical,
1989.
5. D.A. Skoog, D.M. West and F.J. Holler, Analytical Chemistry An
Introduction, Saunders College Publishing 6th edition, International edition,
1994

- - ..................................................................................................
- - .................................................................................................................
- - ......................................................................................................
- - ................................................................................. W
- - .........................................................EFW
- - ..........................................................................................W
- - ...............................................................................W
- - .............................................................. W
- - ...................................................................................................... EF
- - ...................................................................................................... EF
- - ...................................................................................................... EF
- - ...................................................................................................... EF
- - ...................................................................................................... EF
- - ........................................................................................... EF
- - .......................................................................................... EF
- - .......................................................................................... EF
- - ........................................................................................... EF
- - ...........................................................................................EF
- - .............................................................................................................
- - ........................................................................................... Gravimetric Analysis
- - ...............................................................................................................
- - ....................................................................................................
- - ...........................................................................................
- - ...............................................................................................................
- - ....................................................................................................
- - .................................................................................................................... W