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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.

Henrys

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 Chateliers 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.

Werners 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
Reagents

Ppt. formed
by grp.
Reagent

Group

Ions

Silver Group

Ag+
Hg2+2
Pb+2

HCl

AgCl
Hg2Cl2
PbCl2

II A
Copper
Section
II B
Aresenic
Section

Hg+2
Pb+2
Bi+2
Cu+2
Cd+2
As+3, As+5
Sb+3, Sb+5
Sn+2, Sn+4

H2S or
CH3CSNH2
(thioacetamide)
In 0.2 M HCl

HgS
PbS
Bi2S3
CuS
CdS
As2S3
Sb2S3
SnS2

Group

Ions

Group
Reagents

Ppt. formed
by grp.
Reagent

III A
Iron
Section
III B
Amphoteric
Section

Fe+2
Fe+3
Ni+2
CO+2
Mn+2
Al+3
Cr+3
Zn+2

H2S or
CH3CSNH2
In NH 4OH

FeS
FeS
NiS
COS
MnS
Al(OH) 3
Cr(OH) 3
Zns

IV
Alkaline
Earth Group

Ba+2
Sr+2
Ca+2

(NH4) 2 CO3

V
Alkali
Group

Mg+
K+
Na+
NH4

No group
reagent
(Special tests.)

BaCO3
SrCO3
CaCo3

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
Li+, Sr+2
Ca+2
Na+
K+
Cu+2
As+3
Sb+3

yellowish green
crimson
brick red
golden yellow
violet (blue or cobalt glass)
green
pale blue
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
of
of
Group
Group II Cations
Cations

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

Sulfides
Sulfides
of
of
Group
II
Group II Cations
Cations

CENTRIFUGATE
Cations
Cations
of
of
Group
Group IV-V
IV-V
(NH4)2HPO4

CENTRIFUGATE
Cations
Cations
of
of
Group
Group VV

PRECIPITATE
Phosphates
Phosphates
of
of
Group
Group IV
IV Cations
Cations

CENTRIFUGATE
Cations
Cations
of
of
Group
Group III-V
III-V
CH3CSNH2 (NH3)

PRECIPITATE
Sulfides
Sulfides and
and Hydroxides
Hydroxides of
of
Group
Group III
III Cations
Cations

2. Separation of Group I Cations


AgCl
AgCl
Hg
Hg22Cl
Cl22
PbCl
PbCl22

(white)
(white)
(white)
(white)
(white)
(white)
hot water

CENTRIFUGATE
+2
Pb
Pb+2
Confirmatory
Confirmatory Test
Test
Reagent:
Reagent: K
K22CrO
CrO44
Result:
Result: formation
formation of
of yellow
yellow
precipitate
precipitate of
of PbCrO
PbCrO44

PRECIPITATE
AgCl
AgCl // Hg
Hg22Cl
Cl22
NH3

CENTRIFUGATE
Ag
Ag++
in
in the
the form
form of
of [Ag(NH
[Ag(NH33))22]]++
Confirmatory
Confirmatory Test
Test
Reagent:
Reagent: HNO
HNO33
Result:
formation
of
Result:
formation
of
precipitate
of
AgCl
precipitate of AgCl

PRECIPITATE

white
white

HgNH
HgNH22Cl
Cl // Hg
Hg
Confirmatory
Confirmatory Test
Test
Reagent
:
SnCl
Reagent: SnCl22
Result
Result:: gray
gray mixture
mixture of
of Hg
Hg22Cl
Cl22
(white)
(white) and
and Hg
Hg (black)
(black)

3. Separation of Group II Cations


3.1 Separation into Subgroups
As
As22S
S33
Sb
Sb22S
S33

(yellow)
(yellow)
(orange-red)
(orange-red)

As
As22S
S55
Sb
Sb22S
S55

(yellow)
(yellow)
(orange)
(orange)

KOH

CENTRIFUGATE
Group
Group IIA
IIA
HgS
HgS Bi
Bi22SS33
PbS
PbS CdS
CdS
CuS
CuS

PRECIPITATE
Group
Group IIB
IIB
+5
As
As+5
+3 Sb
+5
Sb
Sb+3
Sb+5
+2 Sn
+4
Sn
Sn+2
Sn+4

+3
As
As+3

3.2 Separation of Group IIA Cations


HgS
HgS
Bi
Bi22SS33
PbS
PbS
CdS
CdS
CuS
CuS

HNO3

PRECIPITATE

CENTRIFUGATE

H2SO4

+2, Cu+2
Pb
Pb+2
, Cu+2,,
+3
+3
+2
Bi
Cd+2
Bi ,, Cd

HgS
HgS
Confirmatory
Confirmatory
Result
Result
Reagent:
Reagent: SnCl
SnCl22
(After
dissolving
(After dissolving
in
in aqua
aqua regia)
regia)
Result:
Result: gray
gray
mixture
mixture of
of
Hg
Cl22 (white)
(white)
Hg22Cl
and
and Hg
Hg (black)
(black)

CENTRIFUGATE

PRECIPITATE

+3, Cd+2
+2
Bi
Bi+3
, Cd+2,, Cu
Cu+2

CENTRIFUGATE
+2
[Cu(NH
[Cu(NH33))44]]+2
+2
[Cd(NH
[Cd(NH33))44]]+2
Confirmatory
Confirmatory Tests
Tests

+2
[Cu(NH
[Cu(NH33))44]]+2

(deep
(deep blue)
blue)

Reagent
Reagent:: [Fe(CN)
[Fe(CN)66]]-4-4
Result
Result:: formation
formation of
of reddish-brown
reddish-brown precipitate
precipitate of
of

Cu
[Fe(CN)66]]
Cu22[Fe(CN)

+2
[Cd(NH
[Cd(NH33))44]]+2

Reagent
Reagent:: CH
CH33CSNH
CSNH22
Result
Result:: formation
formation of
of yellow
yellow precipitate
precipitate of
of CdS
CdS

PRECIPITATE
Bi(OH)
Bi(OH)33
Confirmatory
Confirmatory
Result
Result
Reagent:
Reagent:
Na
Na22SnO
SnO22
Result:
Result:
formation
formation of
of
black
black
precipitate
precipitate of
of
bismuth
bismuth metal
metal

PbSO
PbSO44
Confirmatory
Confirmatory
Test
Test
Reagent:
Reagent: K
K22CrO
CrO44
(After
(After
acidificati
acidificati
on
on with
with
acetic
acetic
acid)
acid)
Result:
Result:
formation
formation
of
of yellow
yellow
precipitate
precipitate
of
of PbCrO
PbCrO44

3.3 Separation of Group IIB Cations


+3
As
As+3
+3
Sb
Sb+3
+2
Sn
Sn+2

+5
As
As+5
+5
Sb
Sb+5
+4
Sn
Sn+4

3F HCl
As
As22SS33
SnS
SnS22
Sb
Sb22SS33
conc HCl

PRECIPITATE

CENTRIFUGATE

As
As22SS33 // As
As22SS55
Confirmatory
Confirmatory Result
Result
Reagent:
Reagent: AgNO
AgNO33
(After
(After dissolving
dissolving in
in HNO
HNO33and
and buffered
buffered
with
H33O
O22))
with C
C22H
Result:
Result: reddish
reddish brown
brown precipitate
precipitate of
of
Ag
AsO44
Ag33AsO

+2,, Sb
+3
Sn
Sn+2
Sb+3

divide into two fractions

FIRST PORTION
+2
Sn
Sn+2
Confirmatory
Confirmatory Test
Test
Reagent
:
HgCl
Reagent: HgCl22
(After
(After reduction
reduction to
to Sn
Sn using
using
Mg)
Mg)
Result
Result:: mixture
mixture of
of Hg
Hg22Cl
Cl22
(white)
or
Hg
(black)
(white) or Hg (black) due
due to
to
oxidation
oxidation of
of Sn
Sn

SECOND PORTION
+3
Sb
Sb+3
Confirmatory
Confirmatory Test
Test
Reagent:
Reagent: Sn
Sn metal
metal
Result:
Result: formation
formation of
of black
black
metallic
antimony
metallic antimony

4. Separation of Group III Cations


4.1 Separation into Subgroups
Al(OH)
Al(OH)33

gelatinous
gelatinous white
white
(black)
(black)

Cr(OH)
Cr(OH)33

gelatinousgrayish
gelatinousgrayish green
green
(white)
(white)

CENTRIFUGATE
Group
Group IIIA
IIIA

[Al(OH)
]
[Al(OH)44]
[Zn(OH)
[Zn(OH)33]]
2
CrO
CrO442

Fe
Fe22S
S33
MnS
MnS

(pink)
(pink)
ZnS
ZnS

NiS
NiS
CoS
CoS

(black)
(black)
(black)
(black)

PRECIPITATE
Group
Group IIB
IIB
Fe(OH)
Co(OH)
Fe(OH)33
Co(OH)22
Ni(OH)
MnO(OH)
Ni(OH)22
MnO(OH)22

4.2 Separation of Group IIIA Cations


[Al(OH)
[Al(OH)44]]
[Zn(OH)
[Zn(OH)33]]
2
CrO
CrO442

1. CH3COOH
2. NH3

Ba(CH3COO)2
PRECIPITATE

Al(OH)
Al(OH)33
(white)
(white)
Confirmatory
Confirmatory
Test
Test
Reagent:
Reagent:
aluminum
aluminum
Result:
Result: formation
formation of
of
red
red precipitate
precipitate (red
(red
color
color adsorbed
adsorbed by
by
white
white precipitate)
precipitate)

CENTRIFUGATE

CENTRIFUGATE
+2
[Zn(NH
[Zn(NH33))44]]+2
Confirmatory
Confirmatory Test
Test
Reagent:
Reagent: CH
CH33CSNH
CSNH22
Result:
Result: formation
formation of
of
white
white precipitate
precipitate
ZnS,
ZnS, after
after
acidification
acidification with
with
acetic
acetic acid
acid

PRECIPITATE
BaCrO
BaCrO44
Confirmatory
Confirmatory Test
Test
Reagent
:
H
O
Reagent: H22O22
Result
Result::
formation
formation of
of
blue
color
that
blue color that
disappears
disappears
rapidly
rapidly

4.3 Separation of Group IIIB Cations


Fe(OH)
Fe(OH)33
Ni(OH)
Ni(OH)22

Group
Group IIB
IIB
Co(OH)
Co(OH)22
MnO(OH)
MnO(OH)22

dissolve in concentrated HCl

+2
Co
Co+2

Confirmatory
Confirmatory Test
Test
Reagent:
NH
CNS
Reagent: NH44CNS
Result:
Result: formation
formation of
of blue
blue complex
complex of
of
2
2
]
[Co(CNS)
[Co(CNS)44]

+3
Fe
Fe+3
Confirmatory
Confirmatory Test
Test
Reagent:
Reagent: NH
NH44CNS
CNS
Result:
appearance
Result: appearance of
of blue-green
blue-green color
color
(thiocyanate
(thiocyanate added
added inin excess)
excess)

+2
Mn
Mn+2
Confirmatory
Confirmatory Test
Test
Reagent:
NaBiO
Reagent: NaBiO33
Result:
Result: appearance
appearance of
of purple
purple color
color

due
due to
to oxidation
oxidation to
to MnO
MnO44

+2
Ni
Ni+2
Confirmatory
Confirmatory Test
Test
Reagent:
Reagent: C
C44H
H88O
O22N
N22
(dimethylglyoxime)
(dimethylglyoxime)
Result:
Result: formation
formation of
of red
red precipitate
precipitate of
of
H
O
N
)
Ni(C
Ni(C44H77O22N22)22

5. Separation of Group IV Cations


MgNH
MgNH44PO
PO44 Ca
Ca33(PO
(PO44))22
Sr
(PO
)
Ba
(PO
Sr33(PO44)22 Ba33(PO44))22

CH3COOH
K2CrO4

PRECIPITATE
BaCrO
BaCrO44
(yellow)
(yellow)
Confirmatory
Confirmatory
Result
Result
Test:
Test:
Dissolve
Dissolve
precipitate
precipitate
using
using conc.
conc.
HCl
and
HCl and heat
heat
in
in Bunsen
Bunsen
flame
flame
Result:
Result:
imparts
imparts
yellowish
yellowish
green
green color
color to
to
the
flame
the flame

CENTRIFUGATE

+2
Mg
Mg+2
Confirmatory
Confirmatory Test
Test
Reagent
Reagent:: KOH
KOH
Result
Result:: formation
formation of
of white,
white,
gelatinous
gelatinous precipitate
precipitate that
that
adsorbs
adsorbs p-dinitro
p-dinitro
benzeneazoresorcinol
benzeneazoresorcinol

PRECIPITATE
CaC
CaC22O
O44
Confirmatory
Confirmatory Test
Test
Test:
Test: Dissolve
Dissolve in
in conc.
conc.
HCl
HCl and
and heat
heat in
in Bunsen
Bunsen
flame
flame
Result:
Result:imparts
impartsbrick
brickred
redcolor
color
totothe
flame
the flame

CENTRIFUGATE
+2, Ca+2
+2
Sr
Sr+2
, Ca+2,, Mg
Mg+2

CENTRIFUGATE
CENTRIFUGATE
Chromate
Chromate ions
ions

PRECIPITATE
Ba
(PO44))22
Ba33(PO
Sr
Sr33(PO
(PO44))22
Ca
(PO
Ca33(PO44))22

+2
Ca
Ca+2

+2
Mg
Mg+2

1. CH3COOH (conc.)
2. (NH4)2SO4

PRECIPITATE
SrSO
SrSO44
Confirmatory
Confirmatory Test
Test
Test:
Test: Dissolve
Dissolve in
in
conc.
HCl
and
heat
conc. HCl and heat
in
in Bunsen
Bunsen flame
flame
Result:
Result: imparts
imparts crimson
crimson
red
color
to
the
flame
red color to the flame

6. Separation of Group V Cations


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

Na
Na++
Confirmatory
Confirmatory
Test
Test
Flame
Flame Test:
Test:
imparts
imparts yellow
yellow
color
color to
to the
the
Bunsen
Bunsen flame
flame

NH
NH44++
Confirmatory
Confirmatory Test
Test
Test:
To
the
Test: To the
original
original solution,
solution,
add
add KOH
KOH and
and
cover
cover with
with watch
watch
glass
glass with
with
moistened
moistened red
red
litmus
paper.
litmus paper.
Result:
Result: red
red litmus
litmus
paper
paper turns
turns blue
blue

K
K++
Confirmatory
Confirmatory
Test
Test
Flame
Flame Test:
Test: imparts
imparts
reddish-violet
reddish-violet color
color to
to
the
the Bunsen
Bunsen flame
flame

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

Hg2Cl2 + 2 NH3 - -

+NH4+ + Cl-

Green

- - > Hg + HgNH2Cl

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


NH3

red ppt

Amphoteric Section :

Al (OH)3 -HCl -> Al+3-NH4OH -> Al(OH) 3 red(will absorb aluminum dye)
Aluminum
reagent

CrO4-2 + BaCl2 - - - - -> BaCro4 + 2 ClYellow 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


Yellow

red lake

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

NH4+

yellow ppt.

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

* NH3 + 2Hgl-2 + 3OH- - - -> HOHgNHHgl + 2H2O + 7 ILight 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 dont 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-, ClBarium 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 OHFe(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 layer)


Br- + HClO + H2SO4 - LAYER)
Cl- + AgNO3 - - HNO3 CN-, Br- or I-

- CC l -> I2 (pink or violet color in CCl4


CCl4 -> Br2 (ORANGE COLOR IN CCl4
-> AgCl ( white ppt. in absence of S-2,

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
KMnO4
White ppt. 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
plastic baloon)
CH3CH2OH

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


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

NO2- + NaOH + Devardas alloy - - ->NH3 - - Nesslers- -> red


(Cu-Al-Zn)
reagent
ppt.
NO3(K2Hgl4)
3NO2 + 3 H2O - - - -> NO + 2 H2O + 2 NO33NO3- + 8 Al + 5 OH- + 18H2O - - - -> 3NH3 + 8Al(OH)4-

a) NO2- - - - NH2CSNH2, thiourea->N2 - - FeCL3- -> red color shows NO2HC2H3O2


SCN
HCl Fe(SCN)4- ,red complex

Note: If negative then what is present in the positive test for NO2- and NO3 is
NO3CS(NH2) 2 +HNO2 - - - -N2 +SCN- +H3O+ +H2O
B. Brown Ring test:
NO2- + FeSO4 + H2SO4 - - - -> Fe(NO)+2, brown color shows NO2At 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

Mass
Volume

ULTRAMICR
O

MICRO

SEMI-MICRO

MACRO

< 1 mg

110 mg

10100 mg

> 100mg

< 0.05 mL

0.05 mL0.10
mL

> 0.10 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

yotta-

1024

yocto-

1024

zetta-

1021

zepto-

1021

exa-

1018

atto-

1018

peta-

1015

femto

1015

tera-

1012

pico-

1012

giga-

109

nano-

109

mega-

106

micro-

106

kilo-

103

milli-

103

hecto-

102

centi-

102

da

deca-

101

deci-

101

Fundamental Units of
Measurement
* System International
d Unites
** American
Engineering System

QUANTITY

SI* UNIT

AES** UNIT

length

meter (m)

foot (ft)

mass

kilogram (kg)

pound (lb)

time

second (s)

temperature

Kelvin (K)

Rankine (R)

amount of
substanc
e

gram-mole
(gmol)

pound-mole
(lbmol)

electric
current

Ampere (A)

intensity of
light

candela (cd)

Method of Expressing
Concentrations of Solutions
1.

mass solute

100%
mass solution

2.

gram solute
% v
100%
mL solution

3.

volume solute
100%
% v
volume solution

4.

mole fraction (X)

proof 2% v v

mole solute
mole solute mole solvent

5. Molarity (M) mole solute


L solution

6.

mole solute
molarity (m)
kg solvent

7.

mg solute
L solute
parts per million (ppm) =

kg solution L solution

8.

mg solute
(for dilute aqueous solution)
L solution

g solute
nL solute
parts per billion (ppb) =

kg solution L solution
g 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
gram
gram

700
C

1.369
1.369
gram
gram

Calculation in Gravimetric
Analysis
% analyte in the sample =

mass of weighed substance (ws)


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
ws

=molar ratio of the desired substance and weighed substance

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
colloidal

precipitate (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
PRECIPITATE
D

WEIGHED
SUBSTAN
CE

Cl

AgCl

Br

AgBr

AgI

SO42

BaSO4

As

PRECIPITANT

ELEMENT/ION
PRECIPITAT
ED

WEIGHED
SUBSTAN
CE

PRECIPITANT

Al

Al2O3

Cr

Cr2O3

Fe

Fe2O3

Sn

SnO2

As2O3

Ba

BaSO4

Bi

Bi2S3

Cd

CdSO4

Cd

CdSO4

Sr

SrSO4

Cu

CuO

Ca

CaCO3

Sn

SnO2

Mg

MgCO3

Sb

Sb2O3

Zn

ZnCO3

Mg

Mg2P2O7

H2PtCl6

K2PtCl6

Zn

Zn2P2O7

Hg

HgS

(NH4)2S

AgNO3
BaCl2

H2S

(NH4)2HPO4

NH3(aq)

H2SO4

(NH4)2C2O4

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

AcidBase Titration

Concepts of Acids and Bases

* hydronium ion,
protonated water or
solvated proton
** hydroxide ion

LEWIS

ACID

BASE

Electronpair
accep
tor
Electronpair
Donor

BRONSTED
ARRHENI
US
LOWRY

Proton
donor

Produces
*H3O+
in
soluti
on

Proton
accepto
r

Produces
**HO
in
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 1014 at 25C
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
Acids: pH - log Cacid
Strong Bases: pH 14 log n HO - C base
pH - 1 2 log K a Cacid
Weak Acids:
C
1000
K
when
1 log K C
pH

14

b base
2
Weak Bases:
C
1000
K
when
At 25C pH + pOH = 14
Strong

acid

base

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

Basic

CN

Salt : NaCN
+ H2O HO
KW
KH
K HCN

+ HCN

pH of Salts

Acidic Salt :

Csalt
pH 7 2 log

Kb

when

Csalt
1000
KH

Basic Salt :
when

C
salt
pH 7 1 2 log

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
pH pK

log

[acidic component]
[basic component]

Henderson Hasslebalch Equation


If Kb is given

[acidic component]
pH 14 pK b log
[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 . . . CO2
To convert . . . Carbon and Hydrogen

and H2O

To convert . . . Amides and Amines


To convert . . . Azo, Azoxy and Nitro Group

its oxide

to . . . NH4+
to . . . N or

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
NaOH solution

Step 3. Titration
1. Using an excess amount of
NH
HClNH3Standard
NaOH solution
Excess HCl
Excess HCl
+ HCl

NH3
NH4Cl
The excess HCl is determined using a
standard NaOH solution
HCl
+ NaOH

NaCl
+ H2O
3

2. Ammonia distilled is collected in a boric


acid solution
NH3 + H3BO3 NH4+ + H3BO3-2
Titrate the H3BO3NH3 solution with standard
acid
H2BO3-2 + H3O+ H3BO3 + H2O

Percentage Protein in the Sample

% protein = % N * f =

5.70
6.25
6.38

(cereals)
(meat products)
(dairy products)

Double Indicator Method (Mixture of Bases)


Mixture Na2CO3 and NaHCO3
-2
CO
CO33-2

V0Ph

A
1st
1st Endpoint
Endpoint

HCO
HCO33--

V0MR

HCO
HCO33--

VPhMR

B
CO
CO22
CO
CO22

2nd
2nd
Endpoint
Endpoint

The first endpoint is detected by


phenolphthalein indicator and the second
endpoint by methyl red.
mg Na 2 CO3 2V0Ph (M HCl )

1 mmol Na 2 CO3 106.00mg Na 2 CO3

2 mmolHCl
1 mmol Na 2 CO3

1 mmol NaHCO3 84.01mg NaHCO3

mg NaHCO3 VPhMR - V0Ph (M HCl )


1 mmolHCl
1 mmol Na 2 CO3
1 mmol NaHCO3 84.01mg NaHCO3

mg NaHCO3 V0MR - 2V0Ph (M HCl )


1 mmolHCl
1 mmol Na 2 CO3

Mixture of Na2CO3 and NaOH


NaOH
NaOH

CO
CO33-2-2

H
H22O
O

V0Ph

HCO
HCO33--

1st
1st Endpoint
Endpoint
VPhMR

CO
CO22

mg Na 2 CO 3 2VPh MR ( M HCl )

2nd
2nd Endpoint
Endpoint

1 mmol Na 2 CO 3 106.00 mg Na 2 CO 3

2 mmol HCl
1 mmol Na 2 CO 3

mg Na 2 CO 3 2V0 MR - V0 Ph ( M HCl )

1 mmol Na 2 CO 3 106.00 mg Na 2 CO 3

2 mmol HCl
1 mmol Na 2 CO 3

1 mmol NaOH 40.00 mg NaOH

1 mmol HCl
1 mmol NaOH
1 mmol NaOH 40.00 mg NaOH

- V0 MR ( M HCl )
1 mmol HCl
1 mmol NaOH

mg NaOH V0 Ph - VPh MR ( M HCl )


mg NaOH 2V0 Ph

V0MR

Precipitation Titration
One

of the oldest analytical techniques


that started in the mid1800s. 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+ + Cl1 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 710. 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+ + SCN1 AgSCN(s)
Indirect Titration Reactions: Ag+ + Cl1 AgCl(s)
(s)

excess

Ag+ + SCN1 AgSCN(s)

white
white

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+ + Cl1 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


This

type 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: 2CN1 + Ag+ Ag(CN) 21. The
endpoint of the titration is the formation
of a permanent faint turbidity: Ag(CN)21
+ 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 +
4CN1 + 6H2O Ni(CN)41 + 6NH4OH
Back Titration with Ag+ : 2CN1 + Ag+
Ag(CN)21
Endpoint : Ag(CN)21 + 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 H2In1. When an excess EDTA is added, the
solution turns blue according to the reaction:
MIn1 + HY3 HIn2 + 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 reactionLEORA
Loss of Electron(s), Oxidation, substance oxidized is the Reducing
Agent
For reduction reactionGEROA
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


+7 -2

(acidic medium)

+3 2

+2

+5 2

Step 2. Write the halfcell reactions. Identify oxidation


and reduction reactions. If compounds are present in the
reaction, use the ions in the halfcell 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
RT [C]c [D]d ...
EE
ln a b
nF [A] [B] ...

At 25C

Nernst Equation

0.0592
[C]c [D]d ...
EE
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
coul
F Faradays Constant, 96487.38
mole e

OxidationReduction Titration
Permanganate Process (KMnO4)
In acidic medium
MnO41 + 8H+ + 5e Mn2++ 4H2O
In basic/neutral medium
MnO41 + 2H2O + 3e MnO2 + 4HO

Standardization of KMnO4 solution

Indicator: self indicating

Primary Standards
Against Na2C2O4
Rxn: C2O42 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+
Sn2+
NO2H 2O 2
Mo3+
Ti3+

Fe3+ + eSn4+ + 2eNO3- + 2eO2 + 2eMoO42- + 3eTiO2+ + e-

Dichromate Process
Rxn: Cr2O72- + 6e 2Cr3+
Indicator: sodium diphenylbenzidine sulfonate
barium diphenylamine sulfonate

Applications of Dichromate Process

Fe2+
U4+
Cu+

Fe3+
UO22+
Cu+2

+
+
+

e
2e
e

Iodometric Titration (Indirect Titration with Iodine)


Rxn: I2 + 2e 2I
Titrant: Na2S2O3
Indicator: starch
Primary Standard:
K2Cr2O7 (Cr2O7 + 6I 2Cr3+ + 3I2)
Titration Reaction:
2S2O32 + I 2 S4O6 2 + 2I