Analytical Chemistry

DR. LEONARDO C. MEDINA, JR.

 Definition of Terms
 Conductance – measure of the ability of the
solution to conduct electricity.
 Equivalent Conductance – conductance of a
solution containing 1 gram equivalent of an
electrolyte, the solution being contained
between two plane electrodes 1 cm apart.
 Solubility – amount of solute that dissolves in a
given amount of solvent produce a saturated
solution.
 Henry’s Law – the weight of gas that
dissolves in a given amount of solvent is
directly proportional to the partial pressure
of the gas above the solution.
 Concentration – weight or volume of
solute present in a given amount of
solvent or solution.
 Debye Huckle Theory – There are
interionic attractions in solutions of
electrolytes so that the ions are not
completely independent of one another.
 Modern View of ionization
(Arrhenius)
 Electrolytes, when dissolved in H2O or other
ionizing medium, produced electrically charged
particles called ions.
 Electrolytes, in water solution, produce two
kinds of ions, cation (+) and anion (-). The
two type of charges occurs equivalent
quantities.
 Conductance of an electric current by a
solution is due to the presence of ions and the
extent of this conductivity is dependent upon
the number and kinds of ions between
electrodes.
 Ions are independent particles, which
have specific chemical properties of their
own.
 Electrolytes in water solution have a
greater effect upon the colligative
properties of the solution than those of
non-electrolytes.
 Electrolytes maybe divided into two:
strong electrolytes (completely ionized)
and weak electrolytes (with fewer ions).
 Acid- proton donor; Base – proton
acceptor.
Law of Mass Action (Gulberg and Waage) –
rate reaction is directly proportional to the active
masses (concentration) of the reacting substances.
Law of Chemical Equilibrium – the ration of
the product of the concentration of products to the
product of the concentration of reactants each
concentration raised to a power equal to the
number or coefficient of substances in the
equation is constant.
Le Chatelier’s Principle – When a stress is
applied to a system in equilibrium, the equilibrium
will shift in such a manner as to relieve or
neutralize the stress.
Protolysis – transfer of proton between acid and
base leading to the formation of new acid and
base.
Common Ion Effect – The ionization of a weak
electrolyte (weak acid or weak base) is markedly
decrease by adding to the weak electrolyte a salt
container one of the ions of the weak electrolyte.
Solubility Product Principle – In a saturated
solution of a fairly soluble electrolyte, the product
of the formal concentrations of the ions each ion
raised to the power equal to the number of times
it occurs in the formula, is a constant at a given
temperature.
 Werner’s Coordination Theory
 Certain metals exhibit two kinds of valency. The
principal or ionizable valency results in the formation
of simple salts. The auxiliary or non- ionizable valency,
which may be utilized after the principal valency has
been satisfied, is used to coordinate various groups
directly with central metal ion, that is to hold them
within a coordination sphere.
 Each metal ion has a fixed number of auxiliary
valences, resulting in a fixed coordination number. The
coordination number is frequently twice the principal
valency.
 The central metal ion may coordinate either neutral
molecules or negative groups. The charge on the
complexion is the sum of the charges on its
constituents.
 The auxiliary valences are directed in space.
Complex Ions – ions resulting from the union of
a simple ion with an atom, molecule or another
ion.
Kinds of Complexes:
 Ammonia complexes – Ag(NH3)2+
 Cyanide complexes – Ag(CN)2-
 Hydroxide complexes - Zn(OH)4-2
 Thiocyanate complexes - Ag(CNS) 2-
 Halide complexes - HgCl4-2
 Thio complexes - SbS3-3
 Hydrated Ions – Al(H2O)6+3
Salt Effect – Increases in the solubility of a
relatively insoluble salt and consequent increase in
the value for its solubility product, due to the
presence of either uncommon or common ions.
Chemical Kinetics – study of rate of reaction,
mechanism and how to control.
Colligative Property Law – increase in boiling
point, decrease in freezing point or vapor or direct
pressure or directly proportional to the molal
concentration of solution.
Hydrolysis – reaction between water and the ions
of a salt.
Degree of Hydrolysis – fraction of the total
amount of the ion that has reacted with water.
Saturated Solution – solution which contains
that amount of solute necessary to establish
equilibrium between the dissolved and undissolved
solute.
Unsaturated Solution – solution which is less
concentrated than a saturated solution.
Supersaturated Solution – solution which is
more concentrated than a saturated solution
 Analysis of Cations on basic
Constituents (Metals)
Cation Groups and Group Reagents:
Group Ions Group Ppt. –formed
Reagents by grp.
Reagent
Silver Group Ag+ HCl AgCl
Hg2+2 Hg2Cl2
Pb+2 PbCl2
II A Hg+2 H2S or HgS
Copper Pb+2 CH3CSNH2 PbS
Section Bi+2 (thioacetamide) Bi2S3
II B Cu+2 In 0.2 M HCl CuS
Aresenic Cd+2 CdS
Section As+3, As+5 As2S3
Sb+3, Sb+5 Sb2S3
Sn+2, Sn+4 SnS2
 Group Ions Group Ppt. –formed
Reagents by grp.
Reagent
III A Fe+2 H2S or FeS
Iron Fe+3 CH3CSNH2 FeS
Section Ni+2 In NH 4OH NiS
III B CO+2 COS
Amphoteric Mn+2 MnS
Section Al+3 Al(OH) 3
Cr+3 Cr(OH) 3
Zn+2 Zns
IV Ba+2 (NH4) 2 CO3 BaCO3
Alkaline Sr+2 SrCO3
Earth Group Ca+2 CaCo3
V Mg+ No group
Alkali K+ reagent
Group Na+ (Special tests.)
NH4
FLAME TEST: Use Pt wire. Clean with
concentrated HCl and heat until it imparts
no color to flame. Dip clean wire in sample
and ignite.
 Ba+2 yellowish green
 Li+, Sr+2 crimson
 Ca+2 brick red
 Na+ golden yellow
 K+ violet (blue or cobalt glass)
 Cu+2 green
 As+3 pale blue
 Sb+3 slight greenish
QUALITATIVE
ANALYSIS
 1. Separation of Cations into Groups
Solution
Solution containing
containing
Group
Group I-V
I-V
Cations
Cations

HCl

PRECIPITATE CENTRIFUGATE
Chlorides
Chlorides Cations
Cations
of
of of
of
Group
Group II Cations
Cations Group
Group II-V
II-V
CH3CSNH2 (HCl)

PRECIPITATE CENTRIFUGATE
Sulfides
Sulfides
of Cations
Cations
of
Group of
of
Group II Cations
II Cations
Group
Group III-V
III-V
CH3CSNH2 (NH3)

CENTRIFUGATE PRECIPITATE
Cations
Cations Sulfides
Sulfides and
and Hydroxides
Hydroxides of
of
of
of Group
Group III
III Cations
Cations
Group
Group IV-V
IV-V
(NH4)2HPO4

CENTRIFUGATE PRECIPITATE
Cations
Cations Phosphates
Phosphates
of
of of
of
Group
Group VV Group
Group IV
IV Cations
Cations
 2. Separation of Group I Cations
AgCl
AgCl (white)
(white)
Hg
Hg22Cl
Cl22 (white)
(white)
PbCl
PbCl22 (white)
(white)

hot water

CENTRIFUGATE PRECIPITATE
Pb+2
Pb +2 AgCl
AgCl // Hg
Hg22Cl
Cl22
Confirmatory
Confirmatory TestTest
Reagent:
Reagent: KK22CrO
CrO44 NH3
Result:
Result: formation
formation of
of yellow
yellow
precipitate
precipitate of
of PbCrO
PbCrO44

CENTRIFUGATE PRECIPITATE
Ag++
Ag HgNH
HgNH22Cl Cl // Hg
Hg
in
in the
the form
form of [Ag(NH33))22]]++
of [Ag(NH Confirmatory
Confirmatory Test
Test
Confirmatory
Confirmatory Test
Test Reagent: SnCl
Reagent: SnCl22
Reagent: HNO
Reagent: HNO33 Result
Result:: gray
gray mixture
mixture ofof Hg
Hg22Cl
Cl22
Result:
Result: formation
formation of
of white
white (white)
(white) and
and Hg
Hg (black)
(black)
precipitate of AgCl
precipitate of AgCl
 3. Separation of Group II Cations
3.1 Separation into Subgroups
As
As22S
S33 (yellow)
(yellow) As
As22S
S55 (yellow)
(yellow)
Sb
Sb22S
S33 (orange-red)
(orange-red) Sb
Sb22S
S55 (orange)
(orange)

KOH

CENTRIFUGATE PRECIPITATE
Group
Group IIA IIA Group
Group IIB
IIB
HgS
HgS Bi
Bi22SS33 As
As+3
+3 As+5
As+5
PbS
PbS CdS
CdS Sb +3 Sb
Sb+3 Sb+5
+5

CuS
CuS Sn +2 Sn
Sn+2 Sn+4
+4
 3.2 Separation of Group IIA Cations
HgS
HgS
HNO3
Bi
Bi22SS33
PbS
PbS

CdS
CdS
CuS
CuS PRECIPITATE CENTRIFUGATE
H2SO4
HgS
HgS Pb
Pb+2+2, Cu+2
, Cu+2,,
Confirmatory
Confirmatory Bi ,, Cd
Bi +3
+3
Cd+2
+2

Result
Result
Reagent: CENTRIFUGATE PRECIPITATE
Reagent: SnCl
SnCl22
(After dissolving
(After dissolving
in Bi+3
Bi +3, Cd+2
Cu+2
, Cd+2,, Cu +2 PbSO
PbSO44
in aqua
aqua regia)
regia)
Result: Confirmatory
Confirmatory
Result: gray
gray
mixture Test
Test
mixture ofof
Hg
Hg22Cl
Cl22 (white)
(white) Reagent: K
Reagent: K22CrO
CrO44
(After
(After
and
and Hg
Hg (black)
(black)
acidificati
acidificati
on
on with
with
CENTRIFUGATE PRECIPITATE acetic
acetic
[Cu(NH
[Cu(NH33))44]]+2
+2
acid)
acid)
[Cd(NH Bi(OH)
Bi(OH)33
[Cd(NH33))44]]+2
+2
Result:
Confirmatory
Confirmatory Tests
Tests Confirmatory
Confirmatory Result:
[Cu(NH Result formation
formation
[Cu(NH33))44]]+2
+2 Result
(deep
(deep blue)
blue) Reagent: of
of yellow
yellow
Reagent:
Reagent
Reagent:: [Fe(CN)
[Fe(CN)66]]-4-4 precipitate
precipitate
Na
Na22SnO
SnO22
Result
Result:: formation
formation of
of reddish-brown
reddish-brown precipitate
precipitate of
of of
of PbCrO
PbCrO44
Cu Result:
Result:
Cu22[Fe(CN)
[Fe(CN)66]]
formation
formation of
of
[Cd(NH
[Cd(NH33))44]]+2
+2 black
black
Reagent
Reagent:: CHCH33CSNH
CSNH22 precipitate
precipitate of
of
Result
Result:: formation
formation of
of yellow
yellow precipitate
precipitate of
of CdS
CdS bismuth
bismuth metal
metal
 3.3 Separation of Group IIB Cations
As
As+3
+3 As
As+5
+5
Sb +3
Sb+3 Sb +5
Sb+5
Sn
Sn+2
+2 Sn
Sn+4
+4

3F HCl

As
As22SS33
SnS
SnS22
Sb
Sb22SS33

conc HCl

PRECIPITATE CENTRIFUGATE

As
As22SS33 // As
As22SS55 Sn
Sn+2
+2,, Sb
Sb+3
+3
Confirmatory
Confirmatory Result
Result
Reagent:
Reagent: AgNO
AgNO33
(After
(After dissolving
dissolving inin HNO
HNO33and and buffered
buffered divide into two fractions
with C22H
with C H33OO22––))
Result:
Result: reddish
reddish brown
brown precipitate
precipitate of of
Ag33AsO
Ag AsO44
FIRST PORTION SECOND PORTION

Sn
Sn+2+2 Sb+3
Sb +3
Confirmatory
Confirmatory Test
Test Confirmatory
Confirmatory Test
Test
Reagent : HgCl
Reagent: HgCl22 Reagent: Sn
Reagent: Sn metal
metal
(After
(After reduction
reduction to
to Sn
Sn using
using Result: formation
Result: formation of
of black
black
Mg)
Mg) metallic antimony
metallic antimony
Result
Result:: mixture
mixture of
of Hg
Hg22Cl
Cl22
(white)
(white) or Hg (black) due
or Hg (black) due to
to
oxidation
oxidation ofof Sn
Sn
4. Separation of Group III Cations
4.1 Separation into Subgroups

Al(OH)
Al(OH)33 gelatinous
gelatinous white
white Fe
Fe22S
S33
(black)
(black)
MnS
MnS (pink)
(pink)
Cr(OH)
Cr(OH)33 gelatinousgrayish
gelatinousgrayish green
green ZnS
ZnS
(white)
(white)
NiS
NiS (black)
(black)
CoS
CoS (black)
(black)

CENTRIFUGATE PRECIPITATE

Group
Group IIIA
IIIA Group
Group IIB
IIB
[Al(OH) ]
[Al(OH)44] ––
Fe(OH)
Fe(OH)33 Co(OH)
Co(OH)22
[Zn(OH)
[Zn(OH)33]]–– Ni(OH)
Ni(OH)22 MnO(OH)
MnO(OH)22
CrO –2
CrO44–2
 4.2 Separation of Group IIIA Cations
1. CH3COOH
[Al(OH)44]]––
[Al(OH) 2. NH3
[Zn(OH)
[Zn(OH)33]]––
CrO –2
CrO44–2

Ba(CH3COO)2
PRECIPITATE CENTRIFUGATE

Al(OH)
Al(OH)33 CENTRIFUGATE PRECIPITATE
(white)
(white)
Confirmatory
Confirmatory
[Zn(NH33))44]]+2
[Zn(NH +2
BaCrO
Test
Test BaCrO44
Confirmatory
Confirmatory Test Test
Reagent:
Reagent: Confirmatory
Confirmatory Test
Test
Reagent: CH
Reagent: CH33CSNH
CSNH22 Reagent : H O
aluminum
aluminum Reagent: H22O22
Result: formation
Result: formation of of Result
Result:
Result: formation
formation of
of white
Result::
white precipitate
precipitate formation
red
red precipitate
precipitate (red
(red formation of
of
ZnS,
ZnS, after
after
color
color adsorbed
adsorbed by by blue color that
blue color that
acidification
acidification with
with
white
white precipitate)
precipitate) disappears
disappears
acetic
acetic acid
acid rapidly
rapidly
 4.3 Separation of Group IIIB Cations
Group
Group IIB
IIB
Fe(OH)
Fe(OH)33 Co(OH)
Co(OH)22
Ni(OH)
Ni(OH)22 MnO(OH)
MnO(OH)22

dissolve in concentrated HCl

Co+2
Co +2 Mn+2
Mn +2

Confirmatory
Confirmatory Test Test Confirmatory
Confirmatory TestTest
Reagent: NH
Reagent: NH44CNS CNS Reagent: NaBiO
Reagent: NaBiO33
Result:
Result: formation
formation of
of blue
blue complex
complex of
of Result:
Result: appearance
appearance of of purple
purple color
color
––
[Co(CNS)
[Co(CNS)44] ] –2
–2 due
due to
to oxidation
oxidation to
to MnO
MnO44

Fe+3 +2
Fe +3 Ni
Ni+2
Confirmatory
Confirmatory TestTest Confirmatory
Confirmatory Test Test
Reagent:
Reagent: NHNH44CNS
CNS Reagent:
Reagent: C C44H
H88OO22NN22
Result:
Result: appearance of
appearance of blue-green
blue-green color
color (dimethylglyoxime)
(dimethylglyoxime)
(thiocyanate
(thiocyanate added
added inin excess)
excess) Result:
Result: formation
formation of of red
red precipitate
precipitate of
of
Ni(C H O N )
Ni(C44H77O22N22)22
 5. Separation of Group IV Cations
MgNH
MgNH44POPO44 Ca
Ca33(PO
(PO44))22 PRECIPITATE
Sr
Sr33(PO44)22 Ba33(PO44))22
(PO ) Ba (PO CENTRIFUGATE
CaC
CaC22O O44
Mg
Mg+2+2
Confirmatory
Confirmatory Test Test
Confirmatory
Confirmatory Test
Test Test:
Test: Dissolve
Dissolve inin conc.
conc.
Reagent
Reagent:: KOH
KOH
CH3COOH / Result
HCl
HCl andand heat
heat in
in Bunsen
Bunsen
Result:: formation
formation of
of white,
white, flame
K2CrO4 gelatinous
gelatinous precipitate
precipitate that
that
flame
Result:
Result:imparts
impartsbrick
brickred
redcolor
color
adsorbs
adsorbs p-dinitro
p-dinitro
benzeneazoresorcinol
totothe flame
the flame PRECIPITATE
benzeneazoresorcinol
SrSO
SrSO44
PRECIPITATE CENTRIFUGATE Confirmatory
Confirmatory Test Test
Test:
Test: Dissolve
Dissolve in in
conc. HCl and
conc. HCl and heat heat
BaCrO
BaCrO44 Sr+2
Sr +2, Ca+2
Mg+2
, Ca+2,, Mg +2
in
in Bunsen
Bunsen flameflame
(yellow)
(yellow) CENTRIFUGATE Result:
Result: imparts
imparts crimson
crimson
Confirmatory
Confirmatory red color to the flame
red color to the flame
Result
Result
Ca+2
Ca +2
Mg+2
Mg +2
Test:
Test: CENTRIFUGATE PRECIPITATE
Dissolve
Dissolve
precipitate
precipitate Chromate
Chromate ions
ions Ba
Ba33(PO
(PO44))22
using
using conc.
conc. Sr
Sr33(PO
(PO44))22
HCl
HCl and heat
and heat Ca
Ca33(PO44))22
(PO
1. CH3COOH (conc.)
in
in Bunsen
Bunsen 2. (NH4)2SO4
flame
flame
Result:
Result:
imparts
imparts
yellowish
yellowish
green
green color
color to
to
the flame
the flame
 6. Separation of Group V Cations

Na
Na++,, KK++,, NH
NH44++

Na NH KK++
Na++ NH44++
Confirmatory Confirmatory Confirmatory
Confirmatory
Confirmatory Confirmatory Test Test
Test Test: To the Test
Test
Test Test: To the
Flame Flame
Flame Test:
Test: imparts
imparts
Flame Test:
Test: original
original solution,
solution,
imparts reddish-violet
reddish-violet color
color to
to
imparts yellow
yellow add
add KOH
KOH andand
color the
the Bunsen
Bunsen flame
flame
color to
to the
the cover
cover with
with watch
watch
Bunsen
Bunsen flame
flame glass
glass with
with
moistened
moistened redred
litmus paper.
litmus paper.
Result:
Result: red
red litmus
litmus
paper
paper turns
turns blue
blue
 Reaction to Show
Confirmation or
Identification Tests:
 I. Silver Group
 Pb+2 + K2CrO4 - - - -HAc- - - > PbCrO4 + 2 K+
yellow
 Ag(NH3) 2Cl + 2 HNO3 - - - - > AgCl + 2 NH4NO3
Green
 Hg2Cl2 + 2 NH3 - - - - > Hg + HgNH2Cl +NH4+ + Cl-
black white
2 HgCl2 + SnCl2 - - - - - - - > Hg2Cl2 + SnCl4
White
Hg2Cl2 + SnCl2 - - - - - - - > 2 Hg + SnCl4
black
 II. Copper Section
 HgS – HNO3-> Hg+2 - - SnCl2> Hg2Cl2 + Hg (gray or black)

 PbSO4- - NH4Ac- - - PbCrO4- - -(yellow)

K2CrO4
 2 Bi(OH)3 + 3 Na2SnO2 - - -> 2 Bi + 3 Na3SnO3 + 3 H2O

 Cu (NO3) 2 + NH4OH - - - -> Cu(OH)NO3 + NH4SnO3

Cu(OH)NO3 + 3NH4OH + NH4NO3 - - - -> Cu(NH3) 4(NO3) 2 + H2O
deep blue solution
 Cd(NH3) 4+2 - - -KCN- -> Cd(CN) 4-2- - -H2O-> CdS (yellow)
 Arsenic Section
 As2S3 -HNO3-> H3AsO4-Mg(NO3) 2-> MgNH4AsO4 +2NH4NO3 + 3H2
3NH4OH white crystalline ppt.
H3AsO4 + 12 (NH4) 2MoO3 +21HNO3- > (NH4) 3AsO4. MoO3 +12H2O
yellow cryst. Ppt. +21NH4NO3
 2SbCl3 + 3H2S - -> Sb2S3 + 6HCl; SbCl3 + 3 Ag - -> Sb +3AgCl
orange ppt. Black
 Sn+2 - - HgCl2-> Hg2Cl2 + Hg (white or gray ppt.)
Sn-2- - H2S- -> SnS2 (yellow ppt.)
 III. Iron Section
 MnO2 - HNO3 - - -> Mn (NO3) 2 - - NaBiO3 - -> HMnO4 (purple or violet)
KNO2 HNO3

 Fe (OH)3 - - HCl - -> Fe (SCN) 3 blood red coloration

KSCN

 Co+2- -NH4SCN - - in - -> Co (CNS) 4-2 deep blue color

Amyl alc. Ether

 Ni+2 - - dimethylglyoxime - -> (C4H7O2N2) 2 Ni red ppt

NH3
 Amphoteric Section :
 Al (OH)3 -HCl -> Al+3-NH4OH -> Al(OH) 3 red(will absorb aluminum dye)
Aluminum

reagent

 CrO4-2 + BaCl2 - - - - -> BaCro4 + 2 Cl-

Yellow ppt.

 Zn (NH3) 4+2 - - - H+ - - ->Zn+2 - - H2S - - -> ZnS (white ppt.)

 IV. Alkaline Earth Group
 BaCO3 - - - HAc - -> BaCrO4 (yellow)
K2CrO4

 SrCO3 - - - HAc - - - -> SrSO4 (white crystalline ppt.)

(NH4)2SO4

 Ca+2 + (NH4)2C2O4 - - - -> CaC2O4 + 2 NH4+

white smoky ppt
 V. Alkali Group
 Mg+2 + 2OH- - - - - -> Mg (OH)2 - - titan - -> Mg (OH) 2 red lake
Yellow

 Na+ + ZN+2 + 3 UO2+2 + 6 H2O - - -> Na(UO2)3Zn (Ac)9 .6 H2O

Yellow crystalline ppt.

 2K+ + Na+ + Co (NO2) 6-3 - - - -> K2NaCo (No2)6 yellow ppt.

 NH4+ + OH- - - - -> NH3 + H2O red litmus to blue

* NH3 + 2Hgl-2 + 3OH- - - -> HOHgNHHgl + 2H2O + 7 I-

Light brown
 POINTERS CONSIDERED DURING
ANALYSIS OF UNKNOWN SOLUTION:
 Note color of solution- as preliminary evidence for the
presence of ions.
 Note color of flame tests
 Acidic sample – don’t predict the absence of any ion
 basic sample – indicate the presence of cations whose
hydroxides are soluble in water or those cations that
form amphoteric hydroxides.
 Remove interfering substances.
– organic matter – sugars, glycerin, lactates, citrates, tartrates.
– Anions – phosphates, fluorides and oxalates.
Anion Analysis (Non Metal Ions)
 Silver Group- Forms Ag+ salts insoluble in water and
dilute HNO3 but their barium, and calcium salts are
soluble.
Members: S-2, CN-, I-, Br-, Cl-
 Barium Group- forms insoluble Ba or Ca salts are
neutral or basic solution, but their Ag salts are readily
soluble HNO3
Members: So4-2, So3-2, CO3-2, C2O4-2, PO4-2, BO2-1, F-1
 Soluble Group- form Ag+, Ba+2 or Ca+2 salts which are
soluble in water
Members: C2H3O2-, ClO3, NO2-
Note: Preparation of solution for the anion
analysis
 Only cations of alkali metal maybe present
in the solution during analysis.
 All interfering cations and NH4+ must be
removed by boiling with Na2CO3.
Catons are separated by precipitating as
CO3-2, or basic carbonates, O-2 or OH- with
NaCO3.
 Incompatible Ions
 If cations which form insoluble salt with some
anions were previously found in solution, then
these anions with which they form insoluble
salts are absent un the solution for analysis
(for anions) and we may eliminate these anios.
 Is solution is acid it cannot contain significant
concentrations of SO3-2, S-2, CO3-2 or NO2- for it
would escape as SO2, H2S, CO2- or NO.
(eliminate these anions.)
 Good oxidants (strong oxidizing agent) interact
with good reductants (strong reducing agent)
if solution is acidic.
 Preliminary Tests For Anions:
 Test for strong oxidizers (oxidizing
agent)
 Test for strong reducers (reducing
agent)
 Advanced test for anions of the silver
group
 Advanced test for Barium group anions
 Advanced test for sulfur containing
anions
Specific Tests for
Anions:
 A. Silver Group
1. Sulfide
S-2 - H3O+-> H2S (Gives black stain of PbS when paper wet
with Pb (C2H3O2)2 is exposed.

Note: In presence of oxidizing agent (from preliminary test)

S-2 + Pb(C2H3O2) 2 + NaOH - - - ->PbS ( black precipitate)

2. Cyanide
Fe(CH) + 6CN- - - -> Fe(Cn)-4 + 2 OH-
Fe(CN)6-4 + 4 Fe+3 - - - -> [ Fe6 Fe(CN)6] 3
Halides – remove S-2 and CN-2 (if present)
before conducting the test for the
halides.
 I- + NaNO2 + HC2H3O2 - - CC l -> I2 (pink or violet color in CCl4
layer)
 Br- + HClO + H2SO4 - - CCl4 -> Br2 (ORANGE COLOR IN CCl4
LAYER)
 Cl- + AgNO3 - - HNO3 - -> AgCl ( white ppt. in absence of S-2,
CN-, Br- or I-

If Br- and I- are present, remove or destroy

first before testing for Cl
 B. Barium Group
 SO4-2 + BaCl2 - -HCl - ->BaSO4 (white precipitate)
 SO3-2 + BaCl2 + H2O2 - - HCl - -> BaSO4 (white precipitate)
 CO3-2 + H2O2 + H2SO4 - - HCl- -> BaCO3 (white turbidity ob Ba(OH)2
drop)
Drop on
Glass loop
 C2O4-2 + CaCl2 - HC2H3O2 -> CaC2O4 -H2SO4--> Decolorization of
White ppt. KmnO4 KMnO4

C2O4-2 + KmnO4 +Ba(OH22 - - -> BaCO3 (white turbudity in Ba(OH) 2

Drop on on glass loop + loss of color
glass loop of KMnO4 – Hanging drop test
 PO4-3 + (NH4)2MoO4 + HNO3 - - ->(NH4)3 PO4. 12MoO3 yellow ppt. of
ammonium phosphomolybdate, soluble in NH3, hence this test will not
come out if test solution is too basic

 BO2- - - turmeric pa- > pink color- - -> bluish green color
Per (moisten dried moisten with
With test paper NaOH
Solution)
Turmeric is a complex organic compound the color of which is destroyed by
oxidizing agent or reducing agent; it is water soluble.
SO2- +HCl - - -> residue – H2SO4 -> (CH3) BO3, an ester which
CH3OH imparts greenish color of the
flame.

 F- + H2SO4 - - -> HF which shows etching property,

 Soluble Group:
 C2H3O2- - - H2SO4- -> HC2H3O2 (vinegar odor)
- - - H2SO4- -> CH3COOC2H5, ethyl acetate (odor of
CH3CH2OH plastic baloon)

 ClO3- + NaNO2 + AgNO3 - - HNO3- -> AgCl curdy white ppt.

ClO3- + 3HNO2 + 3 H2O - - - - - - ->Cl- + 3NO3- + 3H3O+

 NO2- + NaOH + Devarda’s alloy - - ->NH3 - - Nessler’s- -> red

NO3- (Cu-Al-Zn) reagent ppt.
(K2Hgl4)
3NO2 + 3 H2O - - - -> NO + 2 H2O + 2 NO3-
3NO3- + 8 Al + 5 OH- + 18H2O - - - -> 3NH3 + 8Al(OH)4-
 a) NO2- - - - NH2CSNH2, thiourea->N2 - - FeCL3- -> red color shows NO2-
HC2H3O2 SCN HCl Fe(SCN)4- ,red complex

Note: If negative then what is present in the positive test for NO2- and NO3 is
NO3-
CS(NH2) 2 +HNO2 - - - -N2 +SCN- +H3O+ +H2O

B. Brown Ring test:

NO2- + FeSO4 + H2SO4 - - - -> Fe(NO)+2, brown color shows NO2-
At junction of the 2 layers (FeSO4 and
H2SO4)
 ANALYTICAL CHEMISTRY
 branch of chemistry that deals
with the analysis, identification,
separation and composition of matter
 Divisions of Analytical
Chemistry
 Quantitative Analysis
 determines the relative amount of
components in a given sample
 Qualitative Analysis
 reveals the nature and components of
a given sample
 Steps in a Typical Analysis
 Choose a Method
 accuracy of method
 economic factors
 complexity and components of the sample

 Acquire a Sample
 representative of the bulk sample
 Prepare a Laboratory Sample
 crushing and grinding
 cone and quarter method
 Prepare a Replicate Sample
 to ensure quality and reliability of results
 Prepare Solution of the Sample
 Choice of Solvents
– Water (with or without heating)
– Non-oxidizing acids (e.g. HCl)
– Oxidizing acids (e.g. HNO3, hot concentrated H2SO4)
– Aqua Regia (mixture of HCl and HNO3 in 3:1 ratio)
– Organic Solvents
– Molten Flux
 Acidic Flux (potassium pyrosulfate, K2S2O7, potassium bisulfate,
KHSO4 and boric acid)
 Basic Flux (sodium carbonate, Na2CO3)
 Oxidizing Flux (sodium peroxide, Na2O2)
 Eliminate Interferences
– Masking
– Precipitation
– Other methods such as chromatography,
electrodeposition, extraction, ion exchange
or volatilization
 Measure the Analyte in the Sample
 Calculate Results
 Evaluate Results
 Classification of Methods for
Quantitative Analysis
A. Classical Methods

 Gravimetric Method
 involves measurement of the mass of
a substance chemically related to the
analyte
 Volumetric Methods
 involves measurement of the volume
of solution that reacts completely with
the analyte in the sample
 B. Modern Methods
 Electroanalytical Method
 involves measurement of the electrical properties of
the analyte such as current, potential or quantity of
charge
 Spectroscopic Method
 involves measurement of the electromagnetic
radiation that either produced or resulted from its
interaction with the analyte
 Other methods that involves the measurement of the
properties of the analyte such as heat of reaction
(calorimeter), index of refraction (refractometer),
optical activity (polarimeter) or mass-to-charge ratio
(mass spectrometer)
 Classification of Methods
According to Sample Size
METHODS

ULTRAMICR
MICRO SEMI-MICRO MACRO
O

Mass < 1 mg 1–10 mg 10–100 mg > 100mg

Volume < 0.05 mL 0.05 mL–0.10 > 0.10 mL

mL
Classification of Analyte in a
Sample
PERCENTAGE IN
SAMPLE

Major Constituent > 1%

Minor Constituent 0.1 – 1%

Trace Constituent 0.001% - 0.1%

Ultratrace Constituent < 0.001%

 Classification of Reagents and
Chemicals
 Commercial or Technical Reagents
 reagents that undergo superficial purification and not directly
used for analysis
 United States Pharmacopoeia (USP Grade) / National Formulary
Reagents
 reagents used by pharmacist and unfit for analysis
 Chemically Pure (CP) Reagents
 reagents that are more refined compared to technical reagents
 Reagent Grade / Analytical Reagent (AR) / Certified Reagent
 reagents analyzed by the manufacturer with analysis found on
the label of the container (e.g. American Chemical Society
Reagents, ACS)
 Primary Standard
 chemicals with purity greater than 99.95%
 Concentrations of
Concentrated Acids and Bases
ACIDS % WEIGHT SPECIFIC GRAVITY MOLARITY
CH3COOH 99.7 1.05 17.4
HF 49.0 1.17 28.9
HCl 37.3 1.18 12.1
HBr 48.0 1.50 8.9
HI 47.0 1.50 5.5
HNO3 70.0 1.42 15.8
HClO4 70.5 1.67 11.7
H2SO4 96.5 1.84 18.1
H3PO4 85.0 1.70 14.7

ACIDS % WEIGHT SPECIFIC GRAVITY MOLARITY

NH3 29.0 0.90 15.3
KOH 45.0 1.46 11.7
NaOH 51.0 1.48 18.9
 SI Prefixes

PREFIX SYMBOL MULTIPLIER PREFIX SYMBOL MULTIPLIER

Y yotta- 1024 y yocto- 10–24
Z zetta- 1021 z zepto- 10–21
E exa- 1018 a atto- 10–18
P peta- 1015 f femto 10–15
T tera- 1012 p pico- 10–12
G giga- 109 n nano- 10–9
M mega- 106  micro- 10–6
k kilo- 103 m milli- 10–3
h hecto- 102 c centi- 10–2
da deca- 101 d deci- 10–1
 Fundamental Units of
Measurement
* Systemé International QUANTITY SI* UNIT AES** UNIT

d’ Unites length meter (m) foot (ft)

** American mass kilogram (kg) pound (lb)
Engineering System
time second (s)

temperature Kelvin (K) Rankine (R)

amount of
gram-mole pound-mole
substanc
(gmol) (lbmol)
e
electric
Ampere (A)
current
intensity of
candela (cd)
light
 Method of Expressing
Concentrations of Solutions
1. mass solute
% w
w   100%
mass solution

2. gram solute
% v w  100%
mL solution
3. volume solute
% v
v  100% proof  2% v v 
volume solution
4. mole fraction (X) 
mole solute
mole solute  mole solvent
5. Molarity (M)  mole solute
L solution

6. molarity (m) 
mole solute
kg solvent
mg solute μL solute
7. parts per million (ppm) = 
kg solution L solution
mg solute
 (for dilute aqueous solution)
L solution

8. parts per billion (ppb) =

μg solute

nL solute
kg solution L solution
μg solute
 (for dilute aqueous solution)
L solution
GRAVIMETRIC
ANALYSIS
 Types of Gravimetric Analysis
 Extraction Method
 the analyte in the sample is obtained using as
appropriate solvent and the residue from the solution,
after evaporation of the solvent, is chemically related
to the analyte
 Precipitation Method
 the analyte is converted into a sparingly soluble
solid, filtered, washed, dried or ignited and weighed
 Volatilization Method
 the sample is treated to yield a gas that is passed
in an absorbing medium; the analysis is based upon
the change in mass of the medium
 Common Steps in Gravimetric
Analysis
 weigh the sample
 solution of sample
 precipitation
 filtration and washing
 weigh the ignited or dried precipitate
 drying or ignition

0.875
0.875 1.369
1.369
gram
gram gram
gram
700
C
 Calculation in Gravimetric
Analysis
mass of weighed substance (ws)
% analyte in the sample =  GF 100%
mass of sample

Gravimetric Factor (GF)

molar mass of desired substance (M ds ) ds
GF = 
molar mass of weighed substance (M ws ) ws
ds
=molar ratio of the desired substance and weighed substance
ws
 Mechanism of Precipitation
Precipitates are formed by two different pathways:
 Nucleation
 very few atoms, ions, or molecules join
together to form a stable solid particle
 prevails at high relative supersaturation
 result in the formation of large number of
small particles
 Particle growth
 prevails at low relative supersaturation
 result in the formation of small number of
large particles
 Particle Size and Properties of
Precipitate
Types or Appearances of Precipitates
 colloidalprecipitate (sulfur)
 curdy precipitate (AgCl)
 fine crystals (BaSO4)
 coarse crystals (PbCl2)
 gelatinous precipitate (Al(OH)3)
 Crystalline Suspension
 temporary dispersions of particles in a liquid
medium with size ranging from 0.1 mm or
greater
 particles that settle readily and easily filtered
 Colloidal Suspension
 tiny particles with size ranging from 0.1
microns to 100 microns in diameter
 these particles do not settle readily and cannot
be filtered easily
Factors Affecting Particle Size
 Temperature
 Concentration of Reactants
 Solubility of Precipitate
 Mixing Rate of Reactants

Ideal Properties of Precipitate

 Can be easily filtered and washed free from impurities or
contaminants
 Has very low solubility to avoid losses during filtration
and washing
 Inert towards components of the atmosphere
 Has known composition after subjecting to appropriate
heat treatment
 Electrical Nature of Colloidal Suspension
 Suspensions, which are stable since these particles are either
positively or negatively charged, hence repel each other
 By heating, stirring and addition of electrolyte causes this
suspension to combine together and form a readily filterable solid
 This process of converting a colloidal suspension into a readily
filterable solid is called coagulation or agglomeration.
 Adsorption of Colloids
 Ions are attached directly to the solid surface and comprise the
primary adsorption layer
 The charge of this layer is dependent on the charge of the ion
present in excess
 A charged primary adsorption layer attracts excess oppositely
charged ions to form a secondary later or counter-ion layer
 These ions, held by electrostatic forces have higher mobility
compared to the ions in the primary layer
 The two layers, which constitute an electrical double layer,
prevent other particles to come close thus inhibits the formation of
larger aggregates
 Factors Affecting Adsorption of Ions
 Common Ion Effect. Precipitates have a tendency to adsorb
ions identical to it more than any other ions.
 Paneth-Fajans-Hahn Rule. In cases that there is more than one
ion adsorbed, the one having a lower solubility is adsorbed to a
greater extent.
 Extent of Ionization of the Contaminant. The degree of
adsorption increases as the ionization of the contaminant
decreases.
 Effect of Concentration. Greater adsorption of contaminant ion
increases as its concentration in the liquid phase increases
 Peptization of Colloids
 Process by which an agglomerated colloid return to it dispersed
state during washing due to leaching of electrolyte responsible for
its coagulation
 It is then necessary to wash the precipitate, not by pure water
but with a solution that contains an electrolyte which eventually
volatilize upon drying or ignition
Coprecipitation
 Phenomenon that arises when other soluble compounds
are detached out of solution by a precipitate
von Weimarn ratio (Relative Saturation)
Q _S
Relative Saturation 
S
whereQ concentration of the solute as precipitation begins
S solubility of the precipitate
 Large von Weimarn ratio results in the formation of a
colloidal precipitate
 Small von Weimarn ratio results in the formation of a
crystalline solid
Experimental Methods to Control Particle Size of Precipitate
In order to obtain low relative supersaturation and
form a crystalline precipitate accordingly, Q must be
minimized and S must be maximized. The following
methods are done to accomplish such conditions:
 Increase temperature during precipitation (to increase
solubility of the precipitate)
 Precipitate from dilute solutions
 Slow addition of precipitating agent with stirring
 Precipitate at low pH
Drying and Ignition of Precipitate
  After filtration, the precipitate is heated to
constant mass and weighed. The composition of the
weighed substance is known and is chemically related
to the analyte.
 Common Inorganic
Precipitating Agents
ELEMENT/ION WEIGHED ELEMENT/ION WEIGHED
PRECIPITATE SUBSTAN PRECIPITANT PRECIPITAT SUBSTAN PRECIPITANT
D CE ED CE
Cl AgCl Al Al2O3
Br AgBr AgNO3 Cr Cr2O3
NH3(aq)
I AgI Fe Fe2O3
SO4–2 BaSO4 BaCl2 Sn SnO2
As As2O3 Ba BaSO4
Bi Bi2S3 Cd CdSO4 H2SO4
Cd CdSO4 Sr SrSO4
H2S
Cu CuO Ca CaCO3
Sn SnO2 Mg MgCO3 (NH4)2C2O4
Sb Sb2O3 Zn ZnCO3
Mg Mg2P2O7 K H2PtCl6 K2PtCl6
(NH4)2HPO4
Zn Zn2P2O7 Hg HgS (NH4)2S
Volumetric Methods of Analysis

 Standard Solution – solution of known

concentration
 Standardization – process of determining
the concentration of an unknown solution
 Primary Standard – a substance of high
purity used for standardization
 Characteristics of a Good
Primary Standard
 High purity and high equivalent weight
 Stable towards air, high temperature and
humidity
 Soluble in water
 Conditions for a Volumetric
Analysis
 The reaction must be rapid and can be
represented by a simple balanced
equation
 The reaction must be complete and no
side reaction occurs
 An appropriate indicator must be
available in order to detect the end point
of the reaction
 Types of Titration

 Direct Titration – type of titration where the

analyte reacts with the standard solution
directly
 Back Titration – type of titration where an
excess standard solution is added and the
excess is determined by the addition of
another standard solution
 Replacement Titration – type of titration where
the analyte is converted to a product
chemically related to it and the product of such
reaction is titrated with a standard solution
 Acid–Base Titration
Concepts of Acids and Bases
 * hydronium ion,
BRONSTED
protonated water or LEWIS -
ARRHENI
US
solvated proton LOWRY

 ** hydroxide ion
Produces
Electron-
*H3O+
pair Proton
ACID in
accep donor
soluti
tor
on
Produces
Electron- Proton **HO–
BASE pair accepto in
Donor r soluti
on
 Strength of Acids and Bases

 Ionization Reaction – reaction involving

formation of ions
 Strong Acids/Bases – completely ionized in
solution
HCl + H2O  H3O+(aq) + Cl–(aq)
NaOH + H2O  Na+(aq) + HO– (aq)
 Weak Acids/Bases – partially ionized in solution
HF + H2O ↔ H3O+ (aq) + F– (aq)
NH3 + H2O ↔ NH4+(aq) + HO–(aq)
 Autoprotolysis of Water

 H 2O + H2O ↔ H3O+(aq) + HO–(aq)

KW = 1 x 10–14 at 25C
Strong Acids. HCl, HBr, HI, HClO4, HNO3,
H2SO4 (only on the first ionization)
Strong Bases. Bases of Group 1A and 2A
Weak Acids. HF, HCN, H2SO3, H3PO4 and
organic acids
Weak Bases. Ammonia and derivatives
 Calculation of pH

 Strong Acids: pH  - log Cacid 


 Strong Bases: pH  14  log n HO - C base 
 Weak Acids: pH  - 1 2 log K a Cacid 
C
when K
 1000
acid
a

1 log K C
 Weak Bases: pH  14  2 b base 
C
when K
 1000
base
b

 At 25C… pH + pOH = 14
 Hydrolysis of Salts

 Acid and base reacts to form salt and water. As

a general rule, salts coming from weak acids or
weak bases hydrolyze in water, that is, only the
strong conjugate hydrolyzes in water. An acidic
salt is formed from the reaction of a strong
acid and weak base. A basic salt results from the
reaction of a strong base and a weak acid. Thus,
a neutral salt is a product of the reaction
between a strong acid and a strong base.
 Hydrolysis Reaction of Salts
 Acidic Salt : NH4Cl
NH4+ + H2O ↔ H3O+ + NH3
KW
KH 
K NH3

 BasicSalt : NaCN
CN– + H2O ↔ HO– + HCN
KW
KH 
K HCN
 pH of Salts

 Acidic Salt :  Csalt 

pH  7  2 log 
1

 Kb 
when Csalt
 1000
KH

 Basic Salt :
 C salt 
pH  7  1 2 log  
when  Ka 
Csalt
 1000
KH
 Buffer Solutions

Solutions that contains weak acid or weak

base and its conjugate salt. These
solutions tend to resist changes in pH.
pH of a Buffer Solution
[acidic component]
pH  pK a  log
[basic component]
Henderson – Hasslebalch Equation
If Kb is given… pH  14  pK b  log
[acidic component]
[basic component]
 Primary Standards for Bases

 Benzoic Acid, C6H5COOH

 Oxalic Acid, H2C2O42H2O
 Potassium Biiodate, KH(IO3)2
 Potassium Hydrogen Phthalate (KHP),
C6H2(COOH)(COOK)
 Sulfamic Acid, (HSO3NH2)
Primary Standards for Acids
 Calcium Carbonate, CaCO3
 Mercuric Oxide, HgO
 Sodium Carbonate, Na2CO2
 Tris-hydroxymethylaminomethane
(THAM), (CH2OH) 3CNH2
 Indicators for Acid-Base
Titration
 Bromocresol Green
 pH Transition Range: 3.8 – 5.4
 changes from yellow to blue
 pKa = 4.66
 Bromothymol Blue
 pH Transition Range: 6.2 – 7.6
 changes from yellow to blue
 pKa = 7.10
 Methyl Red
 pH Transition Range: 4.2 – 6.3
 changes from red to yellow
 pKa = 5.00
 Methyl Orange
 pH Transition Range: 3.1 – 4.4
 changes from orange to yellow
 pKa = 3.46
 Phenolphthalein
 pH Transition Range: 8.3 – 10.0
 changes from colorless to pink
 pKa = 9.00
 Applications of Acid-Base
Titration
Kjeldahl Method (Determination of Organic Nitrogen)
Step 1. Digestion
 The sample is oxidized in hot, concentrated sulfuric acid,
H2SO4 and turns black…
To convert . . . Carbon and Hydrogen to . . . CO2
and H2O
To convert . . . Amides and Amines to . . . NH4+
To convert . . . Azo, Azoxy and Nitro Group to . . . N or
its oxide
 Catalysts
Potassium Sulfate (K2SO4) – increases the boiling point of
sulfuric acid
Mercuric Oxide (HgO) – increases the rate of reaction
Selenious Acid (H2SeO3) – best catalyst
Step 2. Distillation
 The oxidized solution is cooled and then treated with
NaOH to liberate ammonia
 gas:
NH4+ + HO-  NH3(g) + H2O
 Glass or Porcelain beads are added to avoid bumping
 In some modifications, hydrogen peroxide is added to
decompose organic matrix formed
 If mercuric oxide, HgO is used as a catalyst, it is
necessary to add sodium
thiosulfate, Na2S2O3 to precipitate mercuric sulfide, HgS.
Hg2+ + S2O3-2 + 2HO-1  HgS(s) + SO4-2 +
H2 O
 Standard

Step 3. Titration NaOH solution

1. Using an excess amount of

HCl…NH3Standard NH 3

NaOH solution
Excess HCl

Excess HCl
NH3 + HCl NH4Cl
The excess HCl is determined using a
standard NaOH solution
HCl + NaOH  NaCl + H2O
2. Ammonia distilled is collected in a boric
acid solution…
NH3 + H3BO3  NH4+ + H3BO3-2
Titrate the H3BO3–NH3 solution with standard
acid…
H2BO3-2 + H3O+  H3BO3 + H2O
Percentage Protein in the Sample
% protein = % N * f = 5.70 (cereals)
6.25 (meat products)
6.38 (dairy products)
Double Indicator Method (Mixture of Bases)
Mixture Na2CO3 and NaHCO3
CO -2
CO33-2

A V0→Ph

V0→MR
HCO
HCO33-- 1st
1st Endpoint
Endpoint HCO
HCO33--

A
B VPh→MR

CO
CO22

CO
CO22
2nd
2nd
Endpoint
Endpoint
 The first endpoint is detected by
phenolphthalein indicator and the second
endpoint by methyl red.
1 mmol Na 2 CO3 106.00mg Na 2 CO3
mg Na 2 CO3  2V0Ph (M HCl )  
2 mmolHCl 1 mmol Na 2 CO3
1 mmol NaHCO3 84.01mg NaHCO3
mg NaHCO3  VPhMR - V0Ph (M HCl )  
1 mmolHCl 1 mmol Na 2 CO3
1 mmol NaHCO3 84.01mg NaHCO3
mg NaHCO3  V0MR - 2V0Ph (M HCl )  
1 mmolHCl 1 mmol Na 2 CO3
Mixture of Na2CO3 and NaOH
NaOH
NaOH CO
CO33-2-2

B A V0→Ph

H
H22O
O HCO
HCO33-- 1st
1st Endpoint
Endpoint V0→MR

A VPh→MR

CO
CO22
2nd
2nd Endpoint
Endpoint

1 mmol Na 2 CO 3 106.00 mg Na 2 CO 3
mg Na 2 CO 3  2VPh  MR ( M HCl )  
2 mmol HCl 1 mmol Na 2 CO 3
1 mmol Na 2 CO 3 106.00 mg Na 2 CO 3
mg Na 2 CO 3  2V0 MR - V0 Ph ( M HCl )  
2 mmol HCl 1 mmol Na 2 CO 3
1 mmol NaOH 40.00 mg NaOH
mg NaOH  V0 Ph - VPh  MR ( M HCl )  
1 mmol HCl 1 mmol NaOH
1 mmol NaOH 40.00 mg NaOH
mg NaOH  2V0 Ph - V0 MR ( M HCl )  
1 mmol HCl 1 mmol NaOH
 Precipitation Titration

 One of the oldest analytical techniques

that started in the mid–1800’s. Silver
nitrate (AgNO3) is commonly employed in
such technique. Titration with AgNO3 is
often termed as argentometric titration.
 Indicators in Precipitimetry

The equivalence point can be observed by the following:

– formation of a colored secondary precipitate
 Mohr Method (K.F. Mohr, Germany, 1865)
Direct method for halides and cyanides
Titrant: Silver nitrate, AgNO3
Titration Reaction: Ag+ + Cl–1  AgCl(s)
white
Indicator: sodium chromate, Na2CrO4
Indicator reaction: 2Ag+ + CrO42-  Ag2CrO4(s)
red

Primary Standard for AgNO3: NaCl

Titration is carried out between pH of 7–10. Usually a low
concentration of chromate is desired to detect the end point clearly
since a chromate ion imparts an intense yellow color.
 – formation of a colored complexion
Volhard Method (Jacob Volhard, Germany, 1874)
Direct method for silver – Indirect method for Halides
Titrant: Potassium thiocyanate, KSCN
Direct Titration Reaction: Ag+ + SCN–1  AgSCN(s)
white
Indirect Titration Reactions: Ag+ + Cl–1  AgCl(s)
(s)
excess white
Ag+ + SCN–1  AgSCN(s)
white
Indicator: ferric alum
Indicator reaction: Fe+3 + SCN-1  Fe(SCN)2+
red

Titration is carried out in acidic condition to hasten precipitation

of ferric ion to its hydrated oxide form.
 – formation of a colored adsorption complex
Fajans Method (K. Fajans, Poland, 1874)
Titrant: Silver nitrate, AgNO3
Titration Reaction: Ag+ + Cl–1  AgCl(s)
white
Indicator: dichlorofluorescein, best for determination
of halides and cyanides
End point: color change from yellow to pink

Titration is carried out between pH of 4-7. Dextrin is

added to prevent excessive coagulation of the AgCl
precipitate.
 Complex Formation Titration

 Thistype titration is used for the

determinations of cations. Typical
reagents used are organic compounds
containing groups which are electron
donors and have the ability to form
multiple covalent bonds with the metal
ion.
 Determination of Cyanide by
the Liebig Method
 The titration is carried by the dropwise
addition of AgNO3 in a solution of a
cyanide forming a soluble cyanide complex
of silver: 2CN–1 + Ag+  Ag(CN) 2–1. The
endpoint of the titration is the formation
of a permanent faint turbidity: Ag(CN)2–1
+ Ag+  Ag [Ag(CN)2](s)
 Determination of Nickel
 An ammoniacal solution of nickel is treated with
a measured excess of standard cyanide solution
and the excess is determined by a standard
AgNO3 solution according to the reactions:
Addition of Excess Cyanide : Ni(NH3)6+3 +
4CN–1 + 6H2O Ni(CN)4–1 + 6NH4OH
Back Titration with Ag+ : 2CN–1 + Ag+ 
Ag(CN)2–1
Endpoint : Ag(CN)2–1 + Ag+  Ag[Ag(CN)2](s)
 Titration with
Ethylenediaminetetraacetic
Acid (EDTA)
 The structure suggests six potential sites (hexadentate)
for metal bonding: the four carboxyl groups and two
amino groups. Commercially, the free acid and the
dehydrate are available. Solutions of EDTA combines
with any metal ions in a 1:1 ratio. The indicator used for
titration is the Eriochrome Black T. For metal ion
detections, it is necessary to adjust the pH to 7 or above
so that the blue form predominates in the absence of a
metal cation. Generally, metal complexes with EDTA are
red as H2In–1. When an excess EDTA is added, the
solution turns blue according to the reaction:
MIn–1 + HY–3  HIn–2 + MY-2
red blue
 Direct Titration with Added Metal
Ions
 In the determination of Ca2+, small
amount of magnesium chloride is added to
EDTA. Initially, Ca+2 displaces Mg+2 in the
EDTA complex and the latter combines
with EBT producing a red complex. When
all the calcium is titrated, the liberated
Mg+2 is released, combined with the EDTA
and the endpoint is observed.
 Introduction to
Electrochemistry
 An oxidation/reduction reaction is one in which electrons are
transferred from one reactant to another. Oxidation reaction
involves an increase in the oxidation state of an element while
reduction reaction involves a decrease in the oxidation state.
Consider the reaction:
Ce4+ + Fe2+  Ce3+ + Fe3+
For oxidation reaction…LEORA
Loss of Electron(s), Oxidation, substance oxidized is the Reducing
Agent
For reduction reaction…GEROA
Gain of Electron(s), Reduction, substance reduced is the Oxidizing
Agent
 In this reaction, Ce4+ ion acquires an electron from Fe2+. Such
strong electron affinity for electrons makes Ce4+ an oxidizing agent
or an oxidant. On the other hand, Fe2+ readily gives its electron and
is a reducing agent or reductant
 Balancing Redox Reactions

 Step 1. Assign oxidation numbers of

each of the species in the reaction
MnO4-1 + NO2-1  Mn2+ + NO3-1 (acidic medium)

+7 -2 +3 –2 +2 +5 –2
Step 2. Write the half–cell reactions. Identify oxidation
and reduction reactions. If compounds are present in the
reaction, use the ions in the half–cell reaction
OXIDATION: NO2-1  NO3-1 + 2e
+3 +5
REDUCTION: MnO4-1 + 5e  Mn+2
+7 +2
Step 3. Balance the reaction by multiplying a factor so
that the number of electrons on both sides is the same.
OXIDATION x 5: 5NO2-1  5NO3-1 + 10e
+3 +5
REDUCTION x 2: 2MnO4-1 + 10e  2Mn+2
Step 4. Balance by adding H2O to the oxygen deficient side and
H+/OH- on the other side.
OXIDATION x 5:5NO2-1 + 5H2O  5NO3-1 + 10H++ 10e
+3 +5
REDUCTION x 2:2MnO4-1 + 16H+ + 10e  2Mn+2 + 8H2O
+7 +2
------------------------------------
2MnO4-1 + 5NO2-1 + 6H+  2Mn+2 + 5NO3-1 + 3H2O
 Electrochemical Cells

 Electrochemical cells has two electrodes, each are immersed in an

electrolyte solution. Salt bridges are used to prevent the
two solutions from mixing.
 The cathode in an electrochemical cell is the electrode where
reduction occurs. The anode, on the other hand, is where
oxidation occurs.
 A galvanic or voltaic cell is an electrochemical cell that stores
electrical energy. The reaction at the anode and the cathode
occurs spontaneously and allows flow of electrons from the anode to
the cathode with the aid of an external conductor.
 In contrast, an electrolytic cell requires an external source of
electrical energy to operate.
Schematic Representation of
Cells
Cu / Cu2+ (0.0200M) // Ag+
(0.0200M) / Ag
ANODIC REACTION
CATHODIC REACTION
 Electrode Potentials

An electrode potential is the potential of a

cell with the hydrogen electrode as the
anode. Standard Hydrogen Electrode
(SHE) is assigned a value of 0.000V at all
temperatures. The standard electrode
potential, E of a half reaction is the
electrode potential when the activities of
all reactants and products are unity (1 M
molar concentration and 1 atm partial
pressure).
Standard Reduction Potential

A positive value of the standard reduction

potential of an electrode implies that it
was used as cathode with the SHE as
anode. High positive value of a reduction
potential also indicates that the electrode
is a good oxidizing agent.
Thermodynamic Potential of an
Electrochemical Cell, Ecell
This potential can be computed at standard
conditions as follows:
Ecell = Ecathode – Eanode
 Effect of Concentration on
Electrode Potentials: Nernst
Equation
EE RT [C]c [D]d ...
ln a b
Nernst Equation
nF [A] [B] ...

At 25C… EE 0.0592 [C]c [D]d ...

log a b
n [A] [B] ...

where
R – gas constant, 8.314
T – temperature in Kelvin
n – number of electrons that appear in the
half-cell reaction
F – Faraday’s Constant, 96487.38
coul
mole e 
Oxidation–Reduction Titration

Permanganate Process (KMnO4)

In acidic medium…
MnO4–1 + 8H+ + 5e–  Mn2++ 4H2O
In basic/neutral medium…
MnO4–1 + 2H2O + 3e–  MnO2 + 4HO–
Standardization of KMnO4 solution
Indicator: self indicating
 Primary Standards

Against Na2C2O4
 Rxn: C2O4–2  2CO2 + 2e–
Against As2O3
 Rxn: As3 + 4H2O  H3AsO4 + 5H+ + 2e–
Against Ferrous solutions
 Rxn: Fe2+ +  Fe2+ + e–
Against pure Fe
 Rxn: Fe  Fe2+ + 2e–
 Applications of Permanganimetric
Titrations
Fe2+  Fe3+ + e-
Sn2+  Sn4+ + 2e-
NO2-  NO3- + 2e-
H 2O 2  O2 + 2e-
Mo3+  MoO42- + 3e-
Ti3+  TiO2+ + e-
Dichromate Process
Rxn: Cr2O72- + 6e–  2Cr3+
Indicator: sodium diphenylbenzidine sulfonate
barium diphenylamine sulfonate
Applications of Dichromate Process
 Fe2+  Fe3+ + e–
 U4+  UO22+ + 2e–
 Cu+  Cu+2 + e–
Iodometric Titration (Indirect Titration with Iodine)
Rxn: I2 + 2e –  2I–
Titrant: Na2S2O3
Indicator: starch
Primary Standard:
K2Cr2O7 (Cr2O7 – + 6I –  2Cr3+ + 3I2)
Titration Reaction:
2S2O3–2 + I 2  S4O6 –2 + 2I–