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Analytical Chemistry 1
Analytical Chemistry 1
Definition of Terms
Henrys
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
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
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
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
(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)
(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
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
+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
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
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
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
Group
Group IIB
IIB
Co(OH)
Co(OH)22
MnO(OH)
MnO(OH)22
+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
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
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
yellow
+ 2 NH4NO3
Hg2Cl2 + 2 NH3 - -
+NH4+ + Cl-
Green
- - > Hg + HgNH2Cl
black
white
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.)
HNO3
red ppt
Amphoteric Section :
Al (OH)3 -HCl -> Al+3-NH4OH -> Al(OH) 3 red(will absorb aluminum dye)
Aluminum
reagent
V. Alkali Group
red lake
NH4+
yellow ppt.
Incompatible Ions
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
B. Barium Group
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.
Soluble Group:
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
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
Eliminate Interferences
Masking
Precipitation
Other methods such as chromatography,
electrodeposition, extraction, ion exchange
or volatilization
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%
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.
proof 2% v v
mole solute
mole solute mole solvent
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
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
0.875
0.875
gram
gram
700
C
1.369
1.369
gram
gram
Calculation in Gravimetric
Analysis
% analyte in the sample =
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
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
Temperature
Concentration of Reactants
Solubility of Precipitate
Mixing Rate of Reactants
Adsorption of Colloids
Ions are attached directly to the solid surface and comprise the
Peptization of Colloids
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
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
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
Types of Titration
AcidBase Titration
* 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
formation of ions
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
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
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]
[acidic component]
pH 14 pK b log
[basic component]
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
its oxide
to . . . NH4+
to . . . N or
Catalysts
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
% protein = % N * f =
5.70
6.25
6.38
(cereals)
(meat products)
(dairy products)
V0Ph
A
1st
1st Endpoint
Endpoint
HCO
HCO33--
V0MR
HCO
HCO33--
VPhMR
B
CO
CO22
CO
CO22
2nd
2nd
Endpoint
Endpoint
2 mmolHCl
1 mmol Na 2 CO3
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 HCl
1 mmol NaOH
1 mmol NaOH 40.00 mg NaOH
- V0 MR ( M HCl )
1 mmol HCl
1 mmol NaOH
V0MR
Precipitation Titration
One
Indicators in Precipitimetry
The equivalence point can be observed by the following:
formation of a colored secondary precipitate
white
red
excess
white
white
white
red
white
Determination of Cyanide by
the Liebig Method
The
Determination of Nickel
Titration with
Ethylenediaminetetraacetic
Acid
(EDTA)
The structure suggests six potential sites (hexadentate)
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
(acidic medium)
+3 2
+2
+5 2
Electrochemical Cells
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).
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
Primary Standards
Against Na2C2O4
Rxn: C2O42 2CO2 + 2e
Against As2O3
Rxn: As3 + 4H2O H3AsO4 + 5H+ + 2e
Against pure Fe
Rxn: Fe Fe2+ + 2e
Applications of Permanganimetric
Titrations
Fe2+
Sn2+
NO2H 2O 2
Mo3+
Ti3+
Dichromate Process
Rxn: Cr2O72- + 6e 2Cr3+
Indicator: sodium diphenylbenzidine sulfonate
barium diphenylamine sulfonate
Fe2+
U4+
Cu+
Fe3+
UO22+
Cu+2
+
+
+
e
2e
e