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Chemical and Physical Principles Analytical Chemistry

114
ANALYTICAL CHEMISTRY
Analytical Chemistry
Branch of Chemistry that deals with the analysis, identification, separation and
composition of matter
Involves methods used to identify the substances that are present in a sample
(qualitative analysis) and the exact amount of the identified substances
(quantitative analysis)
Quantitative Methods of Analysis
A. Classification of Methods of Analysis
1. Classical methods
a. Gravimetric method measurement of the mass of a substance that is
chemically related to the analyte
b. Volumetric method measurement of the volume of solution necessary to react
completely with the analyte
2. Modern methods
a. Spectroscopic method measurement of the electromagnetic radiation
produced by the analyte or its interactions with it
b. Electroanalytic Method involves measurement of the electrical properties of
the analyte such as current, potential or quantity of charge
3. Other methods 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)
B. Typical Steps in Analysis
1. Selection of an appropriate method
In the selection of method of analysis, it is necessary to consider the level of
accuracy, complexity and component of the sample, availability of equipment
and trained personnel and the time of analysis
Standard procedures are usually available from literature such as Chemical
Abstracts, Analytica Chimica Acta, Applied Spectroscopy, Journal of the
Association of Analytical Chemists, etc.
2. Obtaining a representative sample
The American Society for Testing and Materials (ASTM), National Bureau of
Standards (NBS) and Association of Official Analytical Chemists (AOAC) are
such a few organizations that impose standard sampling procedures for
analysis of some samples
Three steps are generally followed in obtaining samples: obtaining a gross
sample, obtaining a laboratory sample and obtaining an analysis sample
A gross sample is obtained from a bulk sample and obtained in such a manner
that it is considered a representative of the bulk sample
A laboratory sample is a fraction of the gross sample weighing several grams
wherein further reduction to few milligrams results into an analysis sample
Chemical and Physical Principles Analytical Chemistry
115
3. Measurement of the sample
First step in preparing a sample involves measurement of either mass or
volume
Solid samples are dried in an oven usually from 110C-120C for about 1-2
hours and cooled in a dessicator; analysis is said to be done in a dry basis.
Samples that decompose upon heat treatment are analyzed on a wet basis or
as-received basis
Replicate samples are taken for analysis to ensure accuracy of the method used
and quality of the results. Results obtained from these replicate samples are
treated using various statistical tests to establish reliability
Table 1. Classification of analysis based on sample size
Method Sample Mass Sample Volume
macro more than 100 mg more than 0.100 mL
semi-micro 10 mg 100 mg 0.050 mL to 0.100 mL
micro 1 10 mg less than 0.050 mL
ultra-micro less than 1 mg
4. Preparation of a solution of the sample
Most methods are designed to process liquid samples specifically solutions,
since these samples are homogenous and are easy to handle
The following solvents are commonly employed in preparation of the solutions
of the sample:
a. Water. Samples of soluble salts readily dissolve in water at room
temperature and heating may be done to facilitate dissolution of the sample.
b. Non-oxidizing acids. In many instances, some portion of the sample will
not dissolve in water and usually the addition of acids render the sample
soluble. Hydrochloric acid is a typical non-oxidizing acid along with dilute
sulfuric and perchloric acid.
c. Oxidizing acids. For more stubborn samples, hot, concentrated sulfuric
acid, nitric acid and aqua regia are used. Aqua regia is a mixture of
hydrochloric acid and nitric acid in 3:1 volume ratio. Hydrofluoric acid is
also used for dissolving silicate ores.
d. Fluxing agents. Samples which were not dissolved in aqueous solvents are
usually fused with a molten solvent called flux. Fluxing agents may be
classified as acidic (K
2
S
2
O
7
, KHF
2
and B
2
O
3
), basic (Na
2
CO
3
, K
2
CO
3
,
NaOH or KOH) and oxidizing (Na
2
O
2
). Fusion is done by mixing a finely
ground sample with the solid flux in an inert crucible and heated until the
flux melts.
Reagents and chemicals used in the laboratory are classified as follows:
a. Commercial or technical reagents. Reagents that undergo superficial
purification and not directly used for analysis
b. United States Pharmacopoeia (USP Grade) or National Formulary
Reagents. Reagents used by pharmacists and unfit for analysis
c. Chemical Pure (CP) reagents. Reagents that are more refined compared to
technical reagents
d. Reagent grade or analytical reagent (AR) or certified reagent. Reagents
analyzed by the manufacturer with the analysis found on the label of the
container
e. Primary standard grade. Chemicals with purity greater than 99.95%
Chemical and Physical Principles Analytical Chemistry
116
There are several ways of expressing concentration of a particular species in
solution. The following are most commonly used to express concentrations of
solutions:
a. Weight percent usually used to express concentration of commercial
aqueous reagents
100%
solution of weight
solute of weight
wt
wt
%
,
_

b. Volume percent commonly used to specify the concentration of a pure


liquid compound diluted with another liquid
100%
solution of volume
solute of volume
vol
vol
%
,
_

For alcoholic beverages, percentage of alcohol is usually expressed in


terms of proof as follows:
1
]
1

,
_

vol
vol
% 2 proof
c. Weight/volume percent used to indicate the concentration of a solid
reagent in a dilute aqueous solution
100%
(mL) solution of volume
(gram) solute of weight
vol
wt
%
,
_

d. Mole fraction (x) commonly used in unit operations to express


concentrations of solute present in a stream of gas or liquid
solvent of mole solute of mole
solute of mole
x
+

e. Molality (m) temperature-independent concentration term used


conveniently in physicochemical measurements of colligative properties of
solutions
(kg) solvent of kilogram
(mol) solute of mole
m
f. Molarity (M) most commonly used in titration and denotes the amount
of solute, in moles, dissolved in a solvent and diluting to a final volume of
1L in a volumetric flask
(L) solution of volume
(mol) solute of mole
M
Formality (F) concentration term identical to molarity commonly used
for solutions of ionic salts that do not exist as molecule in solid or in
solution
g. Normality (N) once popular unit of concentration still used by some
chemists
(L) solution of volume
(eq) solute of equivalent
N
Chemical and Physical Principles Analytical Chemistry
117
An equivalent represents the mass of material providing Avogadros
number of reacting units. The number of equivalents is given by the
number of moles multiplied by the number of reacting units per molecule
or atom.
f
MW
m
EW
m
solute of equivalent
where m = mass of solute [g], EW = equivalent weight [g-equiv
1
], MW =
molar mass [g-mol
1
] and f = molar equivalent [equiv-mol
1
]
Therefore, normality (N) is related to molarity (M) according to the
following equation:
L
eq
L
mol
mol
eq
M f N
1
]
1

1
]
1

1
]
1


Table 2. Molar equivalents of solutes
Nature of solute Molar equivalent
acid number of replaceable H
+
base number of equivalent HO

salt net charge of an ion


oxidant gain of electron
reductant loss of electron
h. p-function - used to express concentrations at a magnitude of 10
n
where n
is any integer less than zero defined as follows:
, ) } , ) x x f p log
where x = concentration of the species in molarity, M
5. Treatment of the sample
Some samples has to be reduced or oxidized prior to analysis or sometimes
treated to become colored or converted to a form that it can be readily
volatilized
More often, the accuracy of an analysis is affected by the presence of
unwanted components called interferences
Interferences can be eliminated by converting it into non-interfering form by a
process called masking. Typical masking procedure may be done by
converting the interference into a stable complex ion that does not react with
the reagents added to the sample
Some separation processes are commonly employed to isolate the analyte from
the interferences such as precipitation, electrodeposition, extraction, ion
exchange, volatilization and chromatography
6. Measurement of the analyte
Using classical methods of analysis, results can be accurate up to a few parts
per thousand or better, requires relatively large amount of sample and usually
applied to measurement of major constituents in a sample
Instrumental methods are generally more sensitive and selective. Analysis is
rapid, automated and capable of measuring more than one analyte at a time;
however, these techniques are more expensive than classical methods.
Chemical and Physical Principles Analytical Chemistry
118
Table 3. Classification of constituents in a sample
Component Relative Amount
major greater than 1.00%
semi-micro 0.10% 1.00%
micro 0.001% 0.10%
ultra-micro less than 0.001%
7. Calculation of results and reporting of data
Results of analysis can be expressed depending on the nature of analyte
a. Solid Samples. Calculations on solid samples are based on mass. The most
common way of expressing results in a macro determination is by % mass
or % weight
100%
sample wt.
analyte wt.
wt
wt
%
,
_

Table 4. Concentrations of analyte in solid samples in trace concentrations


Unit Definiton Unit
parts per
thousand
3
10
sample gram
analyte gram
wt
wt
pt
,
_

sample kg
analyte g
or
sample g
analyte mg
parts per
million
6
10
sample gram
analyte gram
wt
wt
ppm
,
_

sample kg
analyte mg
or
sample g
analyte g
parts per
billion
9
10
sample gram
analyte gram
wt
wt
ppb
,
_

sample kg
analyte g
or
sample g
analyte ng
b. Liquid Samples. Similarly, concentrations of solid or liquid analytes in
liquid samples obtained from a macro analysis is usually expressed as %
weight by volume or % volume by volume defined as follows:
100%
sample mL
analyte gram
vol
wt
%
,
_

or 100%
sample volume
analyte volume
vol
vol
%
,
_

Table 5. Concentrations of analyte in liquid samples in trace concentrations


(wt/vol and vol/vol)
parts per
million
6
10
sample mL
analyte gram
vol
wt
ppm
,
_

sample L
analyte mg
or
sample mL
analyte g
parts per
billion
9
10
sample mL
analyte gram
vol
wt
ppb
,
_

sample L
analyte g
or
sample mL
analyte ng
parts per
trillion
12
10
sample mL
analyte gram
vol
wt
ppb
,
_

sample L
analyte ng
or
sample mL
analyte pg
parts per
million
6
10
sample vol
analyte vol
vol
vol
ppm
,
_

sample L
analyte L
or
sample mL
analyte nL
parts per
billion
9
10
sample vol
analyte vol
vol
vol
ppm
,
_

sample L
analyte nL
or
sample mL
analyte pL
Chemical and Physical Principles Analytical Chemistry
119
Gravimetric Methods of Analysis
A. Types of Gravimetric Analysis
1. 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
2. Precipitation Method. The analyte is converted into a sparingly soluble solid,
filtered, washed, dried or ignited and weighed
3. 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
B. Gravimetric Factor and Precipitating Agents
1. Calculation in gravimetric analysis
To calculate the amount of analyte in the sample
100% GF
sample of mass
form final of mass
analyte %
Gravimetric Factor (GF)
ratio molar
form final mol
analyte mol
form final of mass molar
analyte of mass molar
GF

,
_


y
x
2. Precipitating agent
An ideal precipitating agent must give an insoluble product that has the
following properties:
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
Table 6. Precipitating agents used in precipitation gravimetry
Species
Precipitated
Final Form Precipitant
Species
Precipitated
Final
Form
Precipitant
Cl AgCl
AgNO
3
Al Al
2
O
3
NH
3
Br AgBr Cr Cr
2
O
3
I AgI Fe Fe
2
O
3
SO
4
2
BaSO
4
BaCl
2
Sn SnO
2
As As
2
O
3
H
2
S
Ba BaSO
4
H
2
SO
4
Bi Bi
2
S
3
Cd CdSO
4
Cd CdSO
4
Sr SrSO
4
Cu CuO Ca CaCO
3
(NH
4
)
2
C
2
O
4
Sn SnO
2
Mg MgCO
3
Sb Sb
2
O
3
Zn ZnCO
3
Mg Mg
2
P
2
O
7
(NH
4
)
2
HPO
4
K H
2
PtCl
6
K
2
PtCl
6
Zn Zn
2
P
2
O
7
Hg HgS (NH
4
)
2
S
C. Theory of Precipitation
1. Properties of precipitates
a. Particle size. Solid particles formed from precipitation may vary accordingly:
Colloidal 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
Chemical and Physical Principles Analytical Chemistry
120
Crystalline particles with size ranging from 100 microns or greater; these
particles settle readily and easily filtered
Particle size is usually affected by temperature, concentration of reactants,
solubility of precipitate and mixing rate
b. Appearance. Precipitates may appear to be colloidal (S) , curdy (AgCl), fine
crystal (BaSO
4
), coarse crystal (PbCl
2
) or gelatinous (Al(OH)
3
)
c. Relative supersaturation (von Weimarn ratio)
S
S Q
ation supersatur relative

where Q = concentration of the solute as precipitation begins and S = solubility


of the precipitate
In order to obtain low relative supersaturation and form a crystalline
precipitate, Q must be minimized and S must be maximized. The following
methods are done to accomplish such conditions:
increase the temperature during precipitation (to maximize S)
precipitate from dilute solution (to minimize Q)
slow addition of precipitating agent with stirring (to minimize Q)
2. Mechanism of precipitation
Precipitation is assumed to occur in two ways:
a. Nucleation
Prevails at high relative supersaturation
Results in the formation of large number of small particles
b. Particle growth
Prevails at low relative supersaturation
Results in the formation of small number of large particles
3. Colloidal precipitates
a. Electrical nature of colloidal suspensions
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
b. 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
layer 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
Counter
Ion
Layer
Primary
Adsorption
Layer
Chemical and Physical Principles Analytical Chemistry
121
c. Factors affecting adsorption
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
Volumetric Methods of Analysis
A. Important Terminologies
1. Standard solution solution of known concentration
2. Standardization process of determining the concentration of an unknown
solution
3. Primary standard a substance of high purity used for standardization
4. Secondary standard compound whose purity was established by a chemical
analysis and serves as reference material for volumetric analysis
5. Equivalence point point in titration where the amount of titrant added is
chemically equivalent to the analyte in the sample
6. End point an observable change in a titration process which estimates the
equivalence point
7. Titration error the difference between the actual volume of titrant required to
reach the end point and the theoretical volume of titrant required to reach the
equivalence point
B. Conditions for a Volumetric Analysis
1. The reaction must be rapid and can be represented by a simple balanced equation
2. The reaction must be complete and no side reaction occurs
3. An appropriate indicator must be available in order to detect the end point of the
reaction
C. Characteristics of a Good Primary Standard
1. High purity and high equivalent weight
2. Stable towards air, high temperature and humidity
3. Soluble in water
D. Types of Titration
1. Direct Titration type of titration where the analyte reacts with the standard
solution directly
2. Back Titration type of titration where an excess standard solution is added and
the excess is determined by the addition of another standard solution
3. 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
Chemical and Physical Principles Analytical Chemistry
122
E. Acid-Base Titration
1. Theories of acids and bases
Theories Acid Base
Arrhenius theory
Svante August Arrhenius (1859-1927)
substances that
dissociate in aqueous
solution to form
a
H
3
O
+
substances that
dissociate in aqueous
solution to form
b
HO

Brnsted-Lowry theory
Johannes Nicolaus Brnsted (1879-1947)
Thomas Martin Lowry (1874-1936)
proton donor proton acceptor
Lewis theory
Gilbert Newton Lewis (1875-1946)
species that accepts
lone pair electrons
species that donates
lone pair electrons
a
hydronium ion, protonated water or solvated proton
b
hydroxide ion
2. Autoprotolysis or self-ionization reactions
Involves spontaneous reaction of molecules producing a pair of ions
Protic solvents have reactive H
+
and undergo autoprotolysis
H
2
O + H
2
O H
3
O
+
+ HO

14.0 pK
C 25
auto

NH
3
+ NH
3
NH
4
+
+ NH
2

8 . 9 2 pK
C 25
auto

CH
3
COOH + CH
3
COOH CH
3
COOH
2
+
+ CH
3
COO

5 . 14 pK
C 25
auto

CH
3
OH + CH
3
OH CH
3
OH
2
+
+ CH
3
O

7 . 16 pK
C 25
auto

CH
3
CH
2
OH + CH
3
CH
2
OH CH
3
CH
2
OH
2
+
+ CH
3
CH
2
O

1 . 19 pK
C 25
auto

In these reactions, a molecule (or an ion) can act as an acid and as a base and is
termed as amphoteric
Other similar terms are:
Amphipatic compounds are those that possess both hydrophilic and
lipophilic properties
Amphiprotic species are amphoteric molecules that can either accept or
donate a proton
Ampholytes are amphoteric molecules that contain both acidic and basic
groups and commonly exist as zwitterions at a certain pH range
Table 7. Ion product constants for water
T,C K
W
10
14
T,C K
W
10
14
T,C K
W
10
14
0 0.11 20 0.69 40 2.84
5 0.19 25 1.00 45 3.86
10 0.30 30 1.45 50 5.18
15 0.46 35 2.05 100 49.87
Concentrations are expressed in molarity using density of water at each temperature. Source: W.L. Marshall and
E.U. Franck, Ion Product of water Substance, 0-1000C, 1-10,000 Bars, J. Phys. Chem. Ref. Data 10(2), 1981, pp.
295-304.
3. Strength of acids and bases
Strong Weak
Acids Bases Acids Bases
HCl
HBr
HI
HNO
3
HClO
4
1
H
2
SO
4
LiOH
NaOH
KOH
RbOH
CsOH
2
R
4
NOH
carboxylic acids
polyprotic acids
metal cations
ammonia
amines
1
only the first ionization is complete; dissociation of the second proton has an equilibrium constant of 1.2 10
2
2
quaternary ammonium hydroxide; hydroxide salt of an ammonium cation
Chemical and Physical Principles Analytical Chemistry
123
4. Calculation of pH
At 25C, the ion product constant for water, K
W
is equal to 1.00 10
14
At this temperature 14 pOH pH pK
W
+
For a dilute solution at 25C in which the contribution of water to the amount
of H
3
O
+
and HO

in solution and the correction due to activity coefficients are


negligible, the following formulas can be used to calculate the pH:
a. Strong acids (SA) and strong bases (SB)
HA + H
2
O H
3
O
+
(aq)
+ A

(aq)
(SA): }
SA
M log pH
MOH M
+
(aq)
+ HO

(aq)
(SB): }
SB
M log 14 pH +
b. Weak acids (WA) and weak bases (WB)
HA + H
2
O H
3
O
+
(aq)
+ A

(aq)
(WA): }
WA a
2
1
M K log pH
B + H
2
O BH
+
(aq)
+ HO

(aq)
(WB): }
WB b
2
1
M K log 14 pH +
c. Hydrolysis of salts
As a general rule, salts coming weak acids or weak bases hydrolyze in water,
that is, only the strong conjugate hydrolyzes in water
Acidic salt (AS) is formed from the reaction of a strong acid and weak base
HCl
(aq)
+ NH
3(aq)
NH
4
+
(aq)
+ Cl
1
(aq)
SA WB SCA SCB
Since only the strong conjugate hydrolyzes in water
NH
4
+
(aq)
+ H
2
O NH
3(g)
+ H
3
O
+
(aq)
] [NH
] O ][H [NH
K
K
K
4
3 3
b
W
h
+
+
(AS):
1
]
1


b
AS
2
1
K
M
log 7 pH
Basic salt (BS) is formed from the reaction of a strong base and weak acid
NaOH
(aq)
+ HCN
(aq)
Na
+
(aq)
+ CN
1
(aq)
+ H
2
O
SB WA WCB SCA
Since only the strong conjugate hydrolyzes in water
CN
1
(aq)
+ H
2
O HCN
(g)
+ HO
1
(aq)
] [CN
] [HCN][HO
K
K
K
1
1
a
W
h

(BS):
1
]
1

+
a
BS
2
1
K
M
log 7 pH
Neutral salt (NS) is formed from the reaction of a strong base and strong acid
Salts from weak acid and weak base (WAB) will have the following
hydrolytic equilibrium expressed by the equation
NH
4
+
(aq)
+ CN
1
(aq)
+ H
2
O NH
4
OH + HCN
] O [H ] [NH ] [CN
] OH [HCN][NH
K K
K
K
2 4
1
4
b a
W
h
+
(WAB):
1
]
1


b
a W
2
1
K
K K
log pH
Amphoteric salts (HA
1
or HA
2
)ionize as a weak acid and also a Brnsted
base that hydrolyzes
H
3
A + H
2
O H
3
O
+
+ H
2
A
1
K
a1
H
2
A
1
+ H
2
O H
3
O
+
+ HA
2
K
a2
HA
2
+ H
2
O H
3
O
+
+ A
3
K
a3
}
a2 a1
2
1
1
2 a1
1
2 a2 a1 a1 W
2
1 1
2
K K log
] A [H K
] A [H K K K K
log A H of pH

'

+
+

}
a3 a2
2
1
2
a2
2
a3 a2 a2 W
2
1 2
K K log
] [HA K
] [HA K K K K
log HA of pH

'

+
+

Chemical and Physical Principles Analytical Chemistry


124
Table 8. Ionization constants of weak acids and bases
Weak acids Formula K
a1
K
a2
K
a3
Acetic CH
3
COOH 1.75 10
5
Benzoic C
6
H
5
COOH 6.30 10
5
Hydrocyanic HCN 7.20 10
10
Hydrofluoric HF 6.70 10
4
Hydrogen sulfide H
2
S 9.10 10
8
1.20 10
15
Oxalic HOOCCOOH 6.50 10
2
6.10 10
5
Phosphoric H
3
PO
4 1.10 10
2
7.50 10
8
4.80 10
13
Phosphorus H
3
PO
3 5.00 10
2
2.60 10
7
Sulfuric H
2
SO
4 1.20 10
2
Sulfurous H
2
SO
3 1.30 10
2
5.00 10
6
Weak bases Formula K
b1
K
b2
Ammonia NH
3 1.75 10
5
Aniline C
6
H
5
NH
2 4.00 10
10
Diethyl amine (C
2
H
5
)
2
NH 8.50 10
4
Dimethyl amine (CH
3
)
2
NH 5.90 10
4
Ethyl amine C
2
H
5
NH
2 4.30 10
4
Methyl amine CH
3
NH
2 4.80 10
4
THAM (CH
2
OH)
3
CN 1.20 10
6
Triethyl amine (C
2
H
5
)
3
N 5.30 10
4
Trimethyl amine (CH
3
)
3
N 6.30 10
5
Ethylenediamine H
2
NC
2
H
4
NH
2 8.50 10
5
7.10 10
8
Zinc hydroxide Zn(OH)
2 4.40 10
5
d. Buffer solutions
Solution that has the ability to resist changes in hydrogen ion concentration
upon the addition of small amounts of acid or base (buffer action)
Usually consists of a mixture of weak acid (HA) and its conjugate salt (A
1
)
or of a weak base (B) and its conjugate salt (BH
+
)
Henderson-Hasselbalch equation
] H [M
] H ][M [H
K
acidic
basic
A
+
+ +

] [M
] [M
log pK pH
basic
acidic
A

] HO [M
] HO ][M [HO
K
1
basic
1
acidic
1
B

] [M
] [M
log pK pK pH
basic
acidic
B W

Buffer capacity or buffer intensity or buffer index is the number of moles of
strong acid or strong base for a liter of solution to cause a unit change in pH
}
}
}
} pH d
C d
pH d
C d

B HA

where C
HA
and C
B
= number of moles per liter of strong base or strong acid,
respectively to cause d[pH]. For a buffer solution containing weak acid and
its conjugate salt with concentrations greater than 0.001 M, the buffer
capacity is estimated as
1
1
A
HA
A
HA
C C
C C
2.303

Chemical and Physical Principles Analytical Chemistry


125
To account for the contribution of water to either H
3
O
+
or HO
1
in solution, use the
following scheme:
5. Commercial concentrated acids and bases
Acids %wt
Specific
Gravity
Molarity Bases %wt
Specific
Gravity
Molarity
HAc 99.7 1.05 17.4 NH
3
29.0 0.90 15.3
HF 49.0 1.17 28.9 KOH 45.0 1.46 11.7
HCl 37.3 1.18 12.1 NaOH 51.0 1.48 18.9
HBr 48.0 1.50 8.9
HI 47.0 1.50 5.5
HNO
3
70.0 1.42 15.8
HClO
4
70.5 1.67 11.7
H
2
SO
4
96.5 1.84 18.1
H
3
PO
4
85.0 1.70 14.7
6. Primary standards for acid-base titration
a. Acidic substances for standardizing basic solutions
Name Formula
Molar
Mass
Molar
equivalent
Benzoic acid C
6
H
5
COOH 122.125 1
Potassium hydrogen bis(iodate) KH(IO
3
)
2
389.915 1
Potassium hydrogen o-phthalate C
6
H
4
(COOH)(COOK) 204.22 1
Sulfamic Acid HSO
3
NH
2
97.09 1
b. Basic substances for standardizing acidic solutions
Name Formula
Molar
Mass
Molar
equivalent
Sodium Carbonate Na
2
CO
3
105.989 2
Mercuric Oxide HgO 216.59 2
Sodium tetraborate decahydrate Na
2
B
4
O
7
10H
2
O 204.22 2
Tris(hydroxymethyl)aminomethane (CH
2
OH)
3
CNH
2
121.137 1
7. Indicators for acid-base titration
Common Name pKa
pH transition
Range
Color change
methyl orange 3.46 3.1-4.4 r-y
bromocresol green 4.66 3.8-5.4 y-b
methyl red 5.00 4.2-6.3 r-o
bromothymol blue 7.10 6.2-7.6 y-b
m-cresol purple 8.32 7.6-9.2 y-p
phenolphthalein 9.00 8.3-10.0 c-r
thymolphthalein 10.0 9.4-10.6 c-b
thymol blue
1.70 1.2-2.8 r-y
8.96 8.0-9.6 y-b
Indicator pH range is pK
a
1 and the appropriate indicator for an acid-base
titration is one with pK
a
close to the equivalence point pH
0 MK K
2
+ x x
, ) x log 14 pH +
, ) x log pH
weak base (WB)
basic salt (BS)
weak acid (WA)
acidic salt (AS)

'

BS
AS
WB
WA
/K K
/K K
K
K
K
A W
B W
B
A
0 K M
W
2
+ x x
strong base (SB)
strong acid (SA)
Chemical and Physical Principles Analytical Chemistry
126
8. Applications of acid-base titration
a. Determination of nitrogen Kjeldahl Method
Developed by Johan Gustav Christoffer Kjeldahl (1879-1900) in 1883
Step 1: Digestion
involves oxidation of the sample with hot and concentrated sulfuric acid to
convert the carbon and hydrogen to CO
2
and H
2
O, respectively and the
nitrogen (amides or amines) to NH
4
+
for inorganic nitrates and nitrites, sample is reduced to NH
4
+
using either
Devarda alloy (50% Cu-45% Al-5%Zn) or Arnds alloy (60% Cu-40% Mg)
HgO and H
2
SeO
3
are added as catalyst while K
2
SO
4
is added to increase
the boiling point of the solution
Step 2: Distillation
The oxidized solution is treated with NaOH to liberate NH
3
gas
NH
4
+
(aq)
+ HO
1
(aq)
NH
3(g)
+ H
2
O
(l)
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 Na
2
S
2
O
3
to precipitate mercuric sulfide
Hg
2+
(aq)
+ S
2
O
3
-2
(aq)
+2HO
-1
(aq)
HgS
(s)
+ SO
4
-2
(aq)
+ H
2
O
(l)
Step 3: Titration
Ammonia gas is collected in an known excess of standard HCl and the
excess is titrated with a standard solution of NaOH using methyl red or
bromocresol green as indicator (back titration)
NH
3(g)
+ HCl
(aq)
NH
4
Cl
(aq)
HCl
(aq)
+ NaOH
(aq)
NaCl
(aq)
+ H
2
O
(l)
The distillate can also be collected using excess of boric acid and the
resulting solution is titrated using standard HCl (replacement titration)
NH
3 (g)
+ H
3
BO
3 (aq)
NH
4
+
(aq)
+ H
2
BO
3
-2
(aq)
H
2
BO
3
-2
(aq)
+ HCl
(aq)
H
3
BO
3(aq)
+ Cl
1
(aq)
+ H
2
O
(l)
For conversion of nitrogen content to protein content of selected food
products, the following factors apply:
Table 9. Jones factor for protein conversion
Animal origin Vegetable origin
Food Factor Food Factor Food Factor
Eggs 6.25 Barley 5.83 Wheat
Meat 6.25 Corn 6.25 Whole kernel 5.83
Milk 6.38 Oats 5.86 Bran 6.31
In general Rice 5.95 Beans
Cereals 5.70 Rye 5.83 Castor 5.30
Meat Products 6.25 Sorghums 6.25 Soybean 5.71
Dairy Products 6.38 Peanuts 5.46 Velvet 6.25
Source: Food and Agriculture Organization of the United Nations - http://www.fao.org/docrep/006/y5022e/y5022e03.htm
b. Double indicator method for mixture of bases Warder Titration
The presence of hydroxide, carbonate and bicarbonate in water is also
referred to as alkalinity which is a measure of the acid-neutralizing capacity
of water
One method requires titration of the mixture to reach the phenolphthalein
endpoint with the volume recorded as V
0-Ph
. On the same solution, methyl
red is then added and an additional volume is required to reach the end point
recorded as V
Ph-MR
Chemical and Physical Principles Analytical Chemistry
127
Another method requires two duplicate samples. One sample is treated with
phenolphthalein and the other with methyl red. Volumes of titrant required to
reach the phenolphthalein and methyl red endpoints are recorded as V
0-Ph
and
V
0-MR
, respectively.
m-Cresol purple can also be used to detect phenolphthalein alkalinity (P)
while bromocresol green or methyl orange for the total alkalinity (T)
Table 10. Alkalinity relationships
Result from titration NaOH Na2CO3 NaHCO3
V
0-Ph
> V
Ph-MR
V
0-Ph
V
Ph-MR
2V
Ph-MR
0
V
0-Ph
< V
Ph-MR
0 2V
0-Ph
V
Ph-MR
V
0-Ph
V
0-Ph
= V
Ph-MR
0 2V
0-Ph
= 2V
Ph-MR
0
V
0-Ph
0 ; V
Ph-MR
> 0 0 0 V
Ph-MR
V
0-Ph
> 0 ; V
Ph-MR
0 V
0-Ph
0 0
Note: If analysis involves measurement of volume due to total alkalinity (V0-MR), use the
conversion: VPh-MR = V0-MR V0-Ph
The following relationship can be summarized using the following diagram:
c. Acid number or acid value
Defined as the mass (mg) of KOH that will neutralize the acid produced from
water degradative reaction of one gram of fat or oil
oil or fat of gram
)(56.10) )(M (V
number Acid
KOH
mL
KOH

d. Saponification number or Koettstorfer number


+ 3 KOH +
OH H
2
C
CH
H
2
C OH
HO
R
1
COOK
R
2
COOK
R
3
COOK
H
2
C
HC
H
2
C OOCR
3
OOCR
2
OOCR
1
Defined as the mass (mg) of KOH required to saponify one gram of fat or oil
Can be used to determine the approximate molar mass of fat or oil
The sample is refluxed with ethanolic KOH and the resulting solution is
titrated with standard HCl
oil or fat of gram
)(56.10) )(M V (V
Value Sap
HCl
mL
samplel with
mL
blank

Value Sap
8,300 6 1
Oil or Fat of Mass Molar
Chemical and Physical Principles Analytical Chemistry
128
F. Precipitation Titration
1. Important terminologies
Saturated solution solution that contains the maximum amount of solute
dissolved in a given amount solvent at a specific temperature
Solubility the maximum amount of solute dissolved in a given solvent at a
specific temperature
Solutions that contain dissolved solute less than the maximum are called
unsaturated while those that contain dissolved solute more than the maximum
are called supersaturated solutions
2. Solubility rules for ionic compounds in water at 25C
Soluble compounds Insoluble compounds
All nitrates, bicarbonates, chlorates
and compounds containing alkali
metal ions and ammonium ion.
All carbonates, phosphates, chromates
and sulfides except that of alkali metal
ions and ammonium ion
All halides except that of Ag
+
, Hg
2
2+
and Pb
2+
All hydroxides except that of alkali
metal ions and Ba
++
All sulfates except that of Ag+, Ca
++
,
Sr
++
, Ba
++
and Pb
++
3. Solubility product constant (K
SP
)
Consider an aqueous saturated solution of a sparingly soluble salt represented by
the equation:
A
x
B
y (s)
x A
+y
(aq)
+ y B
x
(aq)
The equilibrium constant for this reaction would be:
] B A [
] [B ] [A
K
y(s) x
(aq)
x
(aq)
y
eq
y x +

However the concentration of the solid A


x
B
y
in the solution will be constant (the
ratio of the number moles of A
x
B
y
and the volume of the solid is constant). Thus,
y x
] [B ] [A ] B A [ K K (aq)
x
(aq)
y
y(s) x eq SP
+

Table 11. Solubility product constants at 25C
COMPOUND KSP COMPOUND KSP
AgCl 1.82 10
10
Mg(OH)
2
7.10 10
12
AgBr 5.00 10
13
Ca(OH)
2
6.50 10
6
AgI 8.30 10
7
PbCl
2
1.70 10
5
BaCO
3
5.00 10
9
PbI
2
7.90 10
9
Ba(IO
3
)
2
1.57 10
9
Hg
2
Cl
2
1.20 10
18
Al(OH)
3
3.00 10
34
Hg
2
Br
2
5.60 10
23
CaCO
3
(calcite) 4.50 10
9
Hg
2
I
2
4.70 10
29
4. Argentometric titrations
One of the oldest analytical techniques that started in the mid1800s
Silver nitrate (AgNO
3
) is commonly used as titrant and the end point are
observed as follows:
a. Formation of a secondary colored precipitate Mohr method
Developed by Karl Friedrich Mohr (1806-1879) in 1865
Titrant: AgNO
3
Titration reaction: Ag
+
(aq)
+ Cl
1
(aq)
AgCl
(s)
white
Chemical and Physical Principles Analytical Chemistry
129
Indicator: K
2
CrO
4
Indicator reaction: 2Ag
+
(aq)
+ CrO
4
2
(aq)
Ag
2
CrO
4(s)
yellow red
In practice, the indicator concentration is kept between 0.002 M to 0.005 M
Titration is done at a pH of 8 to avoid precipitation of silver as hydroxide
(above pH of 10) and eliminate formation of HCrO
4
1
(below pH of 6) which
results to consumption of more titrant
Usually a low concentration of chromate is desired to detect the end point
clearly since a chromate ion imparts an intense yellow color
b. Formation of a colored complex Volhard method
Developed by Jacob Volhard (1834-1910) in 1874
Titrant: KSCN
Back titration: Ag
+
(aq)
+ Cl
1
(aq)
AgCl
(s)
excess white
Ag
+
(aq)
+ SCN
1
(aq)
AgSCN
(s)
white
Indicator: ferric alum, NH
4
Fe(SO
4
)
2
12H
2
O
Indicator reaction: Fe
+3
(aq)
+ SCN
1
(aq)
Fe(SCN)
+2
(aq)
red
Titration is done in acidic medium using HNO
3
with indicator concentration
of about 0.01 M
For the titration of chloride, the resulting precipitate is filtered off before the
back titration since it reacts with the titrant and is more soluble than AgSCN
For the titration of iodide, the indicator is not added until all iodide is
precipitated since the dissolved iodide is oxidized by the ferric ion
c. Formation of a colored adsorption complex Fajans Method
Developed by Kazimierz Fajans (1887-1975) in 1926
Titrant: AgNO
3
Titration reaction: Ag
+
(aq)
+ Cl
1
(aq)
AgCl
(s)
:Cl
1
. . . . DCF
1
excess white greenish-yellow
Indicator: fluorescein, dichlorofluorescein or eosin
Indicator reaction: Ag
+
(aq)
+ Cl
1
(aq)
AgCl
(s)
:Ag
+1
:DCF
1
excess white pink
Before the equivalence point, chloride anion adsorbs to the precipitate in the
primary adsorption layer and drives the adsorption dye anion away by
electrostatic repulsion and the dye imparts a greenish-yellow color in
solution
As soon as the equivalence point is just exceeded with the presence of excess
silver ion, this ion now adsorbs to the precipitate in the primary adsorption
layer where the oppositely-charged adsorption dye anion adsorbs to the
counter-ion layer and imparts a pink color in solution
For titration of chlorides, fluorescein may be used at an optimum pH range
between 7-10 while dichlorofluorescein is used in acidic solution of pH
greater than 4.4
For bromides, iodides and thiocyanates, eosin is used for titration in acidic
medium of pH between 1-2 imparting magenta color at the end point
Dextrin is added to prevent excessive coagulation of the AgCl precipitate
Chemical and Physical Principles Analytical Chemistry
130
G. Complexation Titration
1. Important terminologies
Ligand molecule or ion which possesses at least one unshared pair of electron
capable of forming coordinate covalent bond with an ion
Coordination complex or metal complex formed when a metal ion is bonded to
monodentate ligands
Chelate complex formed when a metal ion is bonded to a polydentate ligand
Chelants chemicals that form soluble complex molecules with a metal ion
which results to inactivation of the ions ability to react with other elements to
produce precipitates
2. Titration methods involving complexes
a. Determination of cyanide Liebig method
The titration is carried by the dropwise addition of AgNO
3
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)
b. Determination of nickel
An ammoniacal solution of nickel is treated with a measured excess of
standard cyanide solution:
Ni(NH
3
)
6
+3
+ 4CN
1
+ 6H
2
O Ni(CN)
4
1
+ 6NH
4
OH
The excess cyanide is determined according to the Liebig method
c. Titration with ethylenediaminetetraacetic acid (EDTA)
The structure suggests six potential sites (hexadentate) for metal bonding
the four carboxyl groups and two amino groups
Reagents for EDTA titration
Free acid, H
4
Y can be used as a primary standard when dried for
several hours from 130C to 145C and dissolved completely with small
amount of base
Disodium EDTA dihydrate, Na
2
H
2
Y2H
2
O analytical reagent grade is
commercially available and usually dried at 80C for 24 hours
NH
3
-NH
4
Cl buffer solution (pH = 10) prepared from 17.5 grams of
NH
4
Cl and 142 mL of concentrated NH
3
and
Indicators for EDTA titration
Eriochrome Black T or Solochrome used for titrations with pH more
than 6.5 since it polymerizes in strongly acidic solutions; color changes
between pH range of 7-11 from royal blue to wine red;
Calmagite similar to EBT but color change is sharper and its aqueous
solution is stable; used for titration at pH = 10 using NH
3
-NH
4
Cl buffer
Solutions of EDTA combines with any metal ions in a 1:1 ratio
N
H
2
C C
O
N
C
H
2
C
O
M
H
2
C
H
2
C
H
2
C
H
2
C
C
O
C
O
O
O
O
O
HO
C CH
2
N
H
2
C
C OH
O
CH
2
H
2
C N
CH
2
C
OH
O
H
2
C C
OH
O
O
+ M
+n
Chemical and Physical Principles Analytical Chemistry
131
Types of EDTA titration
Direct titration solution containing the metal cation is buffered to the
desired pH and titrated directly with EDTA using auxiliary complexing
agent such as citrate, tartrate or triethanolamine to avoid precipitation of
the metal as hydroxide
Back titration in the absence of metal indicator, the solution is treated
with excess EDTA, buffered to the desired pH and the excess is
determined using standard solution of either sulfates or chlorides of zinc
or magnesium
Replacement titration applied for cations that do not react with the
metal indicator like Ca
+2
; in the determination of Ca
+2
, small amount of
magnesium chloride is added to EDTA where Ca
+2
initially displaces
Mg
+2
in the EDTA complex and displaced Mg
+2
combines with EBT
producing a red complex; when all the calcium is titrated, the liberated
Mg
+2
is released, combines with EDTA and the endpoint is observed
with the formation of blue uncomplexed indicator
H. Oxidation-Reduction Titration
1. Important terminologies
Oxidation process which involves increase in oxidation state as a result of loss
of electron
Reduction process which involves decrease in oxidation state as a result of
gain of electron
Disproportionation process in which an element in an intermediate oxidation
state yields products in both lower and higher oxidation states
Oxidant or oxidizing agent substance that accepts electron and undergoes
reduction
Reductant or reducing agent substance that donates electron and undergoes
oxidation
2. Oxidation numbers and balancing oxidation-reduction reactions
a. Rules in assigning oxidation numbers
An atom in its free or elemental form has oxidation equal to zero
For monoatomic ions, the oxidation number is equal to its charge
Metals have positive oxidation number such as alkali metals (+1), alkaline
earth metals (+2), aluminum (+3), zinc (+2) and silver (+1)
Nonmetals usually have negative oxidation numbers:
Oxygen is usually 2, except in peroxides (2) and superoxides (1)
Hydrogen is usually +1, except in hydrides (1)
Fluorine has 1 oxidation state; other halogens are usually in the 1
oxidation state, except when combined with oxygen, they are positive;
when different halogens are bound to each other, 1 is assigned to the
more electronegative halogen
The sum of oxidation number of elements in a compound is equal to zero
The sum of oxidation number of elements in a polyatomic ion is equal to the
charge of the ion
b. Balancing oxidation-reduction reactions
A reaction is balanced when the number of atoms of each element and the
net charge on both sides are equal
Chemical and Physical Principles Analytical Chemistry
132
Step 1: Assign oxidation numbers to each of the species in the reaction
NO2
1
+ MnO4
1
NO3
1
+ MnO2
+3 2 +7 2 +5 2 +4
Step 2: Identify oxidation and reduction reactions and indicate the number of
electrons lost or gained, respectively
Oxidation: NO2
1
NO3
1
+ 2e
+3 +5
Reduction: MnO4
1
+ 3e MnO2
+7 +4
Step 3: Balance the reaction by multiplying a factor on both sides of the
reaction so that the numbers of electrons on both reactions are the same
Oxidation 3: 3 NO2
1
3 NO3
1
+ 6e
+3 +5
Reduction 2: 2 MnO4
1
+ 6e 2 MnO2
+7 +4
3 NO2
1
+ 2 MnO4
1
3 NO3
1
+ 2 MnO2
Step 4: Balance the charges (by adding H
+
or HO

) and number of hydrogen


and/or oxygen atoms (by adding H
2
O) on both sides of the equation
In acidic medium, add H
2
O to the oxygen-deficient side and supply H
+
to
balance the hydrogen
3 NO
2
1
+ 2 MnO
4
1
+ 2 H
+
3 NO
3
1
+ 2 MnO
2
+ H
2
O
In basic medium, balance assuming reaction was in acidic medium.
Neutralize H
+
by adding HO
1
on both sides of the reaction and simplify
3 NO
2
1
+ 2 MnO
4
1
+ 2 H
+
+ 2 HO
1
3 NO
3
1
+ 2 MnO
2
+ H
2
O + 2 HO
1
3 NO
2
1
+ 2 MnO
4
1
+ 2 H
2
O 3 NO
3
1
+ 2 MnO
2
+ H
2
O + 2 HO
1
3 NO
2
1
+ 2 MnO
4
1
+ H
2
O 3 NO
3
1
+ 2 MnO
2
+ 2 HO
1
3. Standard electrode potential
The potential of a half-cell reaction with the standard hydrogen electrode (SHE)
used as anode when the activities of all reactant and products are taken as unity,
that is, 1M concentration and 1 atm partial pressure
Usually listed as standard reduction potential (
red
) where a positive value
implies that the electrode was used as a cathode and the SHE as anode
High value of a reduction potential indicates that the electrode is a good
oxidizing agent
Nernst equation
Formulated by Walther Hermann Nernst (1864-1941)
Accounts for the effect of concentration on electrode potentials
For a half-cell reduction reactionOx Red + ne

Ox
Red
Red Red
a
a
ln
nF
RT

where
Red
= actual cell potential [V],
Red
= standard reduction potential [V],
R = 8.314 J-mol
1
-K
1
, T = temperature [K], n = number of electrons that
appear in the half-cell reaction [mol], a = activity [ ] and F, Faradays
constant = 96485.3399 coul-(mol e

)
1
At 25C and for a given cell
Q log
n
0.05916

cell cell

where Q = reaction quotient [ ]
Chemical and Physical Principles Analytical Chemistry
133
The equilibrium constant and the standard electrode potential are related as
follows:
V 0.05916
n
K log

(T = 298.15 K, = 0 and Q = K)
4. Oxidation-reduction titration methods
a. Auxiliary oxidants and reductants
Pre-reductants
Jones reductor - consists of zinc metal treated with 2% solution of HgCl
2
(amalgamated zinc) and used to reduce Fe
+3
(Fe
+2
), Cu
+2
(Cu), TiO
+2
(Ti
+2
), UO
2
+2
(U
+3
or U
+4
) and Cr
+3
(Cr
+2
)
Walden reductor - consists of a column filled with silver metal or an
insoluble salt of silver and does not reduce Fe
+3
and TiO
+2
Na
2
SO
3
, NaHSO
3
, or SnCl
2
Pre-oxidants
NaBiO
3
, (NH
4
)
2
S
2
O
8
, K
2
S
2
O
8
, Br
2
, Cl
2
, Na
2
O
2
or H
2
O
2
b. Permanganate titration
Titration is carried out in acidic medium using sulfuric acid
In the presence of HCl, titrant is consumed to oxidize Cl
1
Acidic and basic solutions of KMnO
4
are less stable than neutral ones and
kept in dark-colored bottles to avoid decomposition
Titrant: KMnO
4
Half-cell reactions:
acidic medium MnO
4
1
+ 8H
+
+ 5e

Mn
+2
+ 4H
2
O
basic medium MnO
4
1
+ 2H
2
O + 3e

MnO
2
+ 4HO

Primary standards:
As
2
O
3
H
3
AsO
3
+ H
2
O H
3
AsO
4
+ 2H
+
+ 2e

Na
2
C
2
O
4
C
2
O
4
2
2CO
2
+ 2e

Fe metal Fe Fe
+2
+ 2e

FeSO
4
(en)SO
4
4H
2
O Fe
+2
Fe
+3
+ e

Indicator: self-indicating
Endpoint: pale pink color that persists for 30 s
c. Dichromate titration
Titration is carried out in acidic medium only
Titrant is stable towards light and less easily reduced in the presence of
organic matter compared to permanganate
Titrant: K
2
Cr
2
O
7
Half-cell reaction: Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
+3
+ 7H
2
O
Primary standards:
Fe metal Fe
(s)
Fe
+2
+ 2e

FeSO
4
(en)
2
SO
4
4H
2
O Fe
+2
Fe
+3
+ e

Indicator: sodium diphenylamine sulfonate


N-phenylanthranilic acid
Endpoint: first appearance of blue-violet
Chemical and Physical Principles Analytical Chemistry
134
d. Cerium (IV) titration
Titration is carried out in acidic medium using sulfuric acid at concentrations
0.5 M or higher
In the presence of HCl, titrant is consumed to oxidize Cl
1
Titrant: Ce(SO
4
)
2
and (NH
4
)
4
[Ce(SO
4
)
4
]2H
2
O
Half-cell reaction: Ce
+4
+ e

Ce
+3
Primary standard: As
2
O
3
Half-cell reaction: H
3
AsO
3
+ H
2
O H
3
AsO
4
+ 2H
+
+ 2e

Indicator: ferroin / N-phenylanthranilic acid


End point: orange-red to pale blue / yellowish-green to purple
e. Iodimetry: Direct titration with iodine
Titration is carried out in neutral, weak alkaline or weak acidic solutions
Titrant: I
2
dissolved in concentrated solution of KI
Half-cell reaction: I
3
1
+ 2e

3I
1
Primary standard: As
2
O
3
Half-cell reaction: H
3
AsO
3
+ H
2
O H
3
AsO
4
+ 2H
+
+ 2e

Indicator: Starch solution


Endpoint: Formation of intensely blue-colored complex
f. Iodometry: Indirect titration with iodine
The analyte is an oxidizing agent which reacts with I
1
added to the solution
in excess to liberate I
2
equivalent to the amount of analyte present
Titrant: Na
2
S
2
O
3
Half-cell reaction: 2S
2
O
3
2
S
4
O
6
2
+ 2e

Primary standard: KIO


3
or K
2
Cr
2
O
7
Half-cell reaction: 2IO
3
1
+ 12H
+
+ 10e

I
2
+ 6H
2
O
Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
+3
+ 7H
2
O
Indicator: Starch solution
Endpoint: Color change from blue to colorless
g. Summary of oxidants and reductants used in titration
Oxidants Half-cell reaction (V)
Combining
ratio
KMnO
4
(acidic) MnO
4
1
+ 8H
+
+ 5e

Mn
+2
+ 4H
2
O 1.51 5
KMnO
4
(basic) MnO
4
1
+ 2H
2
O + 3e

MnO
2
+ 4HO

1.695 3
MnO
2
MnO
2
+ 4H
+
+ 2e

Mn
+2
+ 2H
2
O 1.23 2
K
2
Cr
2
O
7
Cr
2
O
7
2
+ 14H
+
+ 6e

2Cr
+3
+ 7H
2
O 1.33 6
Ce(SO
4
)
2
Ce
+4
+ e

Ce
+3
1.61 1
I
2
in KI I
3
1
+ 2e

3I
1
0.5355 2
I
2
(satd) I
2
+ 2e

2I
1
0.5345 1
I
2
(aq) I
2
+ 2e

2I
1
0.6197 1
KIO
3
2IO
3
1
+ 12H
+
+ 10e

I
2
+ 6H
2
O 1.20 5
Reductants Half-cell reaction (V)
Combining
ratio
As
2
O
3
H
3
AsO
3
+ H
2
O H
3
AsO
4
+ 2H
+
+ 2e

0.559 4
Na
2
C
2
O
4
C
2
O
4
2
2CO
2
+ 2e

0.49 2
Fe metal Fe Fe
+2
+ 2e

0.440 2
FeSO
4
Fe
+2
Fe
+3
+ e

0.771 1
Na
2
S
2
O
3
2S
2
O
3
2
S
4
O
6
2
+ 2e

0.08 1
Chemical and Physical Principles Analytical Chemistry
135
C C C C
I Br
5. Application of oxidation-reduction titration
a. Iodine number of oils and fats
Measure of the degree of unsaturation of fats or oils
Expressed as the number of centigrams of iodine absorbed by 100 grams of
fat or oil
Sample is dispersed in chloroform, treated with solution of iodine
monochloride in glacial acetic acid (Wijs solution) and allowed to react in
the dark for 30 min
+ IBr (excess) + IBr (unreacted)
KI is added to liberate the unreacted iodine and titrated with standard
Na
2
S
2
O
3
solution
IBr (unreacted) + KI I
2
+ KBr
, ), )
(g) sample mass
M V V
Number Iodine
mg 10
cg 1
I mmol 1
I mg 53.80 2
O S Na 2
I 1
O S Na
blank mL,
O S Na
sample mL,
O S Na
2
2
3 2 2
2
3 2 2 3 2 2 3 2 2

b. Peroxide value of oils and fats


Measure of the extent of oxidative rancidity of fats and oils during storage
Expressed as the number of milliequivalent or millimole of peroxide per
kilogram of sample
Sample is dissolved in a mixture of chloroform and acetic acid (2:3), bubbled
with nitrogen gas to remove remaining oxygen and treated with excess KI to
liberate iodine
2 I
1
+ RO
2
H + H
2
O ROH + 2 HO
1
+ I
2
, ), )
(kg) sample mass
M V V
Value Peroxide
3 2 2
3 2 2
3 2 2 3 2 2 3 2 2
O S Na mmol 1
O S Na meq 1
O S Na
blank mL,
O S Na
sample mL,
O S Na

c. Dissolved oxygen (DO) Winkler Method


Measure of the amount of oxygen dissolved or carried in a given medium
Measure of the ability to oxidize organic impurities in a body of water
Sample is treated with manganese (II) hydroxide which is converted to a
brown precipitate of manganese (III) hydroxide in the presence of oxygen
4 Mn(OH)
2
+ O
2
+ 2 H
2
O 4 Mn(OH)
3
Alkaline iodide-azide solution is added and the precipitate is then dissolved
in concentrated H
3
PO
4
to release the iodine
Mn(OH)
3
+ I
1
+ 3H
+
Mn
+2
+ I
2
+ 3 H
2
O
, ), )
(L) sample volume
M V
oxygen Dissolved
2
2
3 2 2
2
3 2 2 3 2 2 O mmol 1
O mg 32
O S Na mmol 4
O mmol 1
O S Na
mL
O S Na

d. Chemical oxygen demand (COD)


Measure of the amount of oxygen necessary to oxidize all the organic
material in a water sample
Expressed as milligrams of oxygen required for oxidation per liter of sample
Sample is refluxed in the presence of HgSO
4
, Ag
2
SO
4
/H
2
SO
4
solution and a
known excess amount of standard K
2
Cr
2
O
7
solution and back titrated with
standard (NH
4
)
2
Fe(SO
4
)
2
solution
Chemical and Physical Principles Analytical Chemistry
136
, ), )
(L) sample volume
M V V
COD
2
2
7 2 2
2
2
7 2 2
2 2 2
O mmol 1
O mg 32
O Cr K mmol 4
O mmol 6
Fe mmol 6
O Cr K mmol 1
Fe
sample mL,
Fe
blank mL,
Fe

+ + + +
Molecular Absorption Spectrometry
A. Absorption Process and Beer-Lambert Law
If a beam of light passes through a glass container filled with liquid, the emergent
radiation is always less powerful than that entering
Consider a block of absorbing matter where a beam of monochromatic radiation of
radiant power, P
0
strikes the surface perpendicularly and passes through the length
of the material, b
The emergent or transmitted radiation will
always have less radiant power, P than the
entering or incident radiation
The fraction of incident radiation transmitted by
the solution, P/P
0
is called transmittance and
related to absorbance according to the equation:
0
P
P
log T log A
where A = absorbance, T = transmittance, P
0
=
incident radiant power [W], and P = transmitted
radiant power [W]
Beer-Lamberts law states that the absorbance
is directly proportional to the concentration of the absorbing species and to the
path length
bc
P
P
log T log A
0

where = molar absorptivity [L-mol
1
-cm
1
], b = path length [cm] and c =
concentration [mol-L
1
]
B. Quantitative Analysis
1. Standard addition method
Involves addition of several increments of a standard solution to aliquots of
samples of the same size and the resulting solution upon adding the color
development reagent is then diluted to a fixed volume (V
T
) and measured for its
absorbance
Assume several identical aliquots of the unknown solution of volume V
x
were
treated with several increments of standard solution of volume V
s
of known
concentration C
s
and diluted to a fixed final volume V
T
.
If each of these solutions were assumed to obey Beers law, the absorbance (A
S
)
of each solution is described by:
b m + + +
S X X S S
T
X X
T
S S
s
C C kV C kV
V
C bV
V
C bV
A
where k = b/V
T
, m = kV
S
and b = kC
X
V
X
P0 P
b
dx
Po P
Chemical and Physical Principles Analytical Chemistry
137
2. Analysis of mixtures
The total absorbance of a solution at a given wavelength is equal to the sum of the
absorbances of the components in the mixture
At
1
:
y y x x 1
bC bC A
1 1
+
At
2
:
y y x x 2
bC bC A
2 2
+
3. Photometric titration
Plot of absorbance versus volume of titrant where the curves consist of two
straight line regions with different slopes
The end point is the intersection of the extrapolated linear regions
REVIEW QUESTIONS AND PROBLEMS
1. All of the following is used as a hygroscopic material in desiccators except
a. CaSO
4
b. Mg(ClO
4
)
2
c. P
2
O
5
d. H
2
SO
4
2. Analytical methods classified as micro analysis uses sample mass ranging from
a. < 1 mg b. 1-10 mg c. 10-100 mg d. > 100 mg
3. Chemical which are tested by the manufacturers showing the actual percentages of
impurities and labeled on the containers are called __________.
a. reagent grade chemicals
b. analytical reagent
c. certified reagent
d. all of these
4. Vessels intended to contain definite volumes of liquid at a certain temperature
usually 20C are labeled as follows except
a. TC b. C c. In d. TD
5. What proportion by weight of Na
2
C
2
O
4
(134) to KHC
2
O
4
H
2
C
2
O
4
(218.2) that must
be mixed in a solution so that the normality of the resulting solution as a reducing
agent is three times the normality as an acid?
a. 0.33 b. 0.65 c. 1.54 d. 3.07
Chemical and Physical Principles Analytical Chemistry
138
6. Platinum crucibles can be used for the following processes without significant loss
except
a. Fusion with sodium carbonate, borax or alkali bifluorides
b. Evaporation with hydrofluoric acid
c. Ignition of oxides of Ca and Sr
d. Heating with sulfides
7. What volume of water must be added to concentrated HCl solution to prepare 100
mL 0.955 M HCl solution?
a. 7.9 mL b. 15.8 mL c. 46.0 mL d. 92.1 mL
8. What grade of water as defined by the British Standard 3978 is suitable for the
determination of trace quantities which can be prepared by the distillation of de-
ionized water?
a. Grade 1 b. Grade 2 c. Grade 3 d. Grade 4
For numbers 9 to 11
A 20% wt/wt aqueous solution of NaCl (58.45) at 25C has a density of 1.145 g-mL
1
.
Express the amount of solute in this solution as follows:
9. % wt/vol
a. 17 b. 19 c.21 d. 23
10. molarity (M)
a. 0.98 b. 1.96 c. 3.92 d. 5.88
11. molality (m)
a. 3.42 b. 5.13 c. 6.84 d. 8.56
12. The following describes colloidal suspensions formed during precipitation except
a. These particles are almost invisible to the naked eye
b. They settle readily from a given solution
c. They are not easily filtered
d. none of the these
13. A 1.5176 g sample of a CaCO
3
was dissolved in an acidic solution. The calcium was
precipitated as CaC
2
O
4
H
2
O (146.11) and the ignited precipitate at 230C was found
to weigh 0.8249 g. What is the percentage of CaO (56.08) in the sample?
a. 20.9% b. 23.8% c. 41.8% d. 47.6%
For numbers 14 to 16
To a solution containing a precipitate of PbS, an excess of H
2
S was added.
14. What is the ion present in the primary adsorption layer?
a. Pb
+2
b. H
+
c. S
2
d. HO

15. The charge of this layer is __________.


a. negative b. positive c. neutral d. any of these
16. The ion present in the counter ion layer is __________.
a. Pb
+2
b. H
+
c. S
2
d. HO

17. A mixture containing FeCl


3
(162.20) and AlCl
3
(133.33) only weighs 750.8 mg. The
chlorides were precipitated using ammonia and ignited to Fe
2
O
3
(159.69) and Al
2
O
3
(101.96), respectively. The oxide mixture weighs 351.3 mg. Calculate the percentage
of Al (26.98) in the sample.
a. 15.5% b. 41.2% c. 43.3% d. 58.8%
Chemical and Physical Principles Analytical Chemistry
139
18. Which of the following does not describe the correct way to wash precipitates?
a. Minimum volume of washing liquid must be used to wash the precipitate
b. Wash with small portions of washing liquid
c. For very soluble precipitates, ionic salts containing common ion must be
added to the washing liquid
d. Gelatinous precipitates requires more washing than crystalline precipitates
19. What weight of Mn ore should be taken so that the percentage of MnO
2
(86.94) in
the ore would be twice the mass of Mn
3
O
4
(228.82) precipitate obtained in
milligram?
a. 19.0 mg b. 38.0 mg c. 57.0 mg d. 76.0 mg
20. Process by which an agglomerated colloid return to it dispersed state during washing
due to leaching of electrolyte responsible for its coagulation
a. nucleation b. coagulation c. agglomeration d. peptization
21. A 5.488-gram sample containing MgCl
2
(95.21) and NaCl (58.45) was dissolved in
sufficient to give 1L solution. Analysis of chloride content of a 250 mL aliquot
resulted in the formation of 2.462 gram AgCl. The magnesium in a second 100 mL
aliquot resulted in the formation of 0.2610 gram of Mg
2
P
2
O
7
(222.53) after treatment
with (NH
4
)
2
HPO
4
. Determine the percentage of NaCl in the sample.
a. 12.7% b. 23.2% c. 36.1% d. 40.7%
22. It is the expressed as the volume of a solution chemically equivalent to a mass of a
solid reagent
a. titer b. aliquot c. molarity d. ppm
23. What is the extent of ionization of the second proton of 0.5 M H
2
SO
4
at 25C?
a. 1% b. 2% c. 4% d. 8%
24. Which of the following aqueous solutions of the same concentration will have the
largest pH value at 25C?
a. NH
3
b. KCl c. NH
4
Cl d. NaF
25. Which of the following solutions at 25C will have the lowest pH value?
a. 0.15 M Na
2
SO
4
(K
A2
of H
2
SO
4
= 1.2 10
2
)
b. 5.2 10
8
M HCl
c. 0.05 M NaCN (K
A
of HCN = 6.2 10
10
)
d. 0.01 M NH
4
Cl (K
A
of NH
4
+
= 5.6 10
10
)
26. Which of the following acid-base pairs will result in the formation of a buffer
solution when titration is done before the equivalence point?
a. NaOH and HCl
b. KOH HNO
3
c. NH
3
HBr
d. all of these
27. What volume of 0.1025 M HCl must be added to 15.64 mL of 0.0956 M NH
3
to
produce a solution of pH = 9.00?
a. 5.3 mL b. 7.3 mL c. 9.3 mL d. 11.3 mL
28. Which of the following statements is not correct?
a. The buffer capacity is always a positive number
b. The larger the buffer capacity, the more resistant the solution is to pH change
c. In general, alkaline buffering capacity is maximum over a pH range of pK
b
1
d. The acid buffering capacity is maximum at pH equal to pK
a
Chemical and Physical Principles Analytical Chemistry
140
29. What concentration of acetic acid is needed to prepare a buffer solution with pH =
4.50 and a buffer capacity of 0.10 M-pH
1
?
a. 0.067 M b. 0.122 M c. 0.174 M d. 0.225 M
30. Approximately how many grams of NH
4
Cl (53.45) should be dissolved in a liter of
0.125 F NH
3
to reduce the concentration of hydroxide ions to one-thousandth of its
original value?
a. 79.1 g b. 62.5 g c. 11.7 g d. 7.91 g
31. The conjugate base of H
2
PO
4
1
is __________
a. HPO
4
2
b. PO
4
3
c. H
3
PO
4
d. P
2
O
5
For numbers 32 to 35
Calculate the pH of the resulting solution when 25.0 mL of 0.100 M H
2
C
2
O
4
was treated
with the following volumes of 0.100 M NaOH:
32. 0 mL
a. 1.26 b. 2.84 c. 4.07 d. 5.12
33. 15 mL
a. 1.57 b. 1.71 c. 1.86 d. 2.04
34. 25 mL
a. 1.44 b. 2.88 c. 5.76 d. 6.64
35. 49.9 mL
a. 4.39 b. 7.39 c. 8.37 d. 12.18
For numbers 36 to 38
The acid dissociation constant of acetic acid in methanol is 3.02 10
10
. Calculate the pH
of the following solutions in acetic acid:
36. 0.035 MCH
3
COOH
a. 3.10 b. 5.49 c. 6.90 d. 8.51
37. 0.035 MCH
3
COOH + 0.070 MCH
3
COONa
a. 4.44 b. 5.05 c. 9.22 d. 9.82
38. 0.035 MCH
3
COONa
a. 2.97 b. 4.32 c. 11.03 d. 12.38
39. In the standardization of an acid solution with primary standard sodium carbonate,
why is it necessary to boil the solution before completing the titration?
a. to eliminate the reaction product, carbon dioxide and carbonic acid
b. to destroy the buffering action of the resulting solution due to the presence of
carbonic acid and unreacted hydrogen carbonate
c. to achieve a sharper endpoint with methyl red indicator due to the large
decrease in pH
d. all of the these
40. Calculate the molarity of NaOH solution if 12.25 mL was used to titrate 0.2615 gram
of primary standard KHP.
a. 0.1045 b. 0.1354 c. 0.2509 d. 0.1697
Chemical and Physical Principles Analytical Chemistry
141
41. What is the best basis for choosing the right indicator for a given acid base titration
from among the following?
a. type of acid
b. type of base
c. pH at equivalence point
d. molarity of the acid or base
42. In standardizing a solution of NaOH against 1.431 grams of KHP, the analyst uses
35.50 mL of the alkali and has to run back with 8.25 mL of acid (1mL = 10.75 mg
NaOH). What is the molarity of the NaOH solution?
a. 0.2118 M b. 0.2044 M c. 0.7831 M d. 0.2598 M
43. In the titration of a weak acid with a strong base, which of the following is the best
indicator to be used?
a. bromocresol green
b. methyl orange
c. methyl red
d. phenolphthalein
44. A 0.2055-g sample of calcite (impure CaCO
3
) is treated with 27.18 ml of 0.0712 N
HCl and the excess is found to require 5.44 ml of 0.0869 N NaOH for back titration.
Calculate the percentage purity of calcite in terms of % wt/wt CaCO
3
(100).
a. 17.8% b. 35.6% c. 53.4% d. 71.2%
45. Process of determining the nitrogen content of organic materials by mixing the
sample with powdered copper (II) oxide and ignited to a combustion tube giving
CO
2
, H
2
O, N
2
and small amounts of nitrogen oxides.
a. Kjeldahl Method
b. Dumas Method
c. Winkler Method
d. Wijs Method
46. A 640 mg sample of P
2
O
5
(141.94) contains some H
3
PO
4
(97.995) impurity. The
sample is reacted with water and the resulting solution is titrated with 0.867 M
NaOH requiring 20.7 mL to the thymolphthalein end point. Calculate the percentage
of impurity in the sample.
a. 0.90% b. 1.80% c. 2.70% d. 3.60%
47. In the titration of phosphoric acid, which of the following statements is true?
a. Titration curve contains three inflection points since it is a triprotic acid
b. Phenolphthalein indicator is used to detect the second end point.
c. It can be treated as a monoprotic or diprotic acid during titration
d. all of these
For numbers 48 to 50
A 500-mg sample of each mixture was analyzed for its alkaline content using 0.1025 M
HCl via double indicator method.
Mixture 1 2 3 4 5
V
0-Ph
(mL) 4.27 0.01 5.12 6.37 5.63
V
0-MR
(mL) 10.18 6.19 10.24 6.38 9.04
48. Which of the following mixtures contains NaHCO
3
?
a. Mixtures 2 and 4
b. Mixtures 4 and 5
c. Mixtures 3 and 4
d. Mixtures 1 and 2
49. Calculate the purity of the sample containing NaHCO
3
only.
a. 1.82% b. 5.22% c. 10.64% d. 11.13%
50. What is the % wt NaOH for the sample containing a mixture of NaOH-Na
2
CO
3
?
a. 1.82% b. 5.22% c. 10.64% d. 11.13%
Chemical and Physical Principles Analytical Chemistry
142
51. In the analysis of nitrogen using Kjeldahl Method, which of the following is added to
decompose organic matrices present in the sample?
a. H
2
SO
4
b. HgO c. K
2
SO
4
d. H
2
O
2
52. A 7.279-gram sample of meat was analyzed for its nitrogen content using Kjeldahl
Method. Upon digestion, the ammonia liberated was collected in 250 mL of 0.855 M
H
3
BO
3
. The resulting solution was titrated with 37.25 mL of 0.3122 M HCl using
mixed indicator. Determine the % protein in the sample using 6.25 as factor for meat
products.
a. 13.98% b. 2.24% c. 19.69% d. 3.14%
53. Which of the following is NOT used as primary standard for the standardization of
alkali solutions?
a. HgO b. H
2
C
2
O
4
c. HSO
3
NH
2
d. C
6
H
5
COOH
For number 54 and 55
A 1.05 gram sample of butter is refluxed with ethanolic KOH and required 10.4 mL of
0.1875 M HCl to reach the phenolphthalein end point. If blank determination required
27.7 mL of the same standard acid,
54. Calculate the saponification value
a. 45 b. 87 c. 125 d. 173
55. Assuming butter comprised mainly of fat, what is its molar mass?
a. 475 b. 970 c. 1445 d. 1940
56. Which of the following statements is true about precipitation titration?
a. In Volhard method, AgCl is more soluble than AgSCN thus requiring filtration
of AgCl prior to back titration
b. Titration involving adsorption indicators is slow but has wide range of
application
c. In Mohr titration, the concentration of the chromate ion in more basic
solutions is too low to produce the precipitate near the equivalence point
d. all of these
57. In the determination of chloride using Mohr method, what should be the theoretical
molar concentration of the chromate ion indicator given that K
SP
of Ag
2
CrO
4
is 1.1
10
12
?
a. 0.002 b. 0.004 c. 0.006 d. 0.008
58. Which of the following is not a correct analytical methodtitrant pair?
a. MohrAgNO
3
b. Fajans AgNO
3
c. Volhard AgNO
3
d. Liebig AgNO
3
59. A 1.500-gram sample of impure aluminum chloride was dissolved in water and
treated with 45.32 mL of 0.1000 M AgNO
3
using K
2
CrO
4
as indicator. Express the
analysis in %AlCl
3
(133.33).
a. 40.28% b. 13.43% c. 4.48% d. 27.36%
60. In Volhard Method, why is it necessary to carry out titration in acidic solution?
a. To prevent precipitation of iron as hydrated as hydrated oxide
b. To prevent formation of AgSCN precipitate
c. To prevent reduction of halide
d. To prevent precipitation of silver as hydrated as hydrated oxide
Chemical and Physical Principles Analytical Chemistry
143
61. A mixture of LiBr (86.845) and BaBr
2
(297.22) weighing 800 mg is treated 50.00
mL of 0.1879 M AgNO
3
and the excess is found to require 8.76 mL of 0.3179 M
KSCN for back titration, using ferric alum as indicator. What is the percentage of
BaBr
2
in the sample?
a. 67.95% b. 32.05% c. 35.62% d. 64.38%
62. In Mohr titration, which of the following statement is CORRECT?
a. The indicator is usually kept at a concentration of 0.2-0.5 M so as not to
obscure the red precipitate color
b. At low pH, part of the indicator is present as HCrO
4
1
and less Ag
+
are
required to reach the endpoint
c. At high pH, silver is precipitated as silver hydroxide thus produces error in the
amount of titrant added
d. all of these
63. A 750.25-gram alloy of nickel was dissolved and treated to remove the impurities. Its
ammoniacal solution was treated with 50 mL of 0.1075 M KCN and the excess
cyanide required 2.25 mL of 0.00925 M AgNO
3
. Determine % Ni (58.69) in the
alloy.
a. 20.86% b. 37.69% c. 10.53% d. 41.72%
64. Which of the following is true about Liebig method for determination of cyanide?
a. The titration process requires an indicator to signal the end of titration
b. The addition of excess amount of AgNO
3
produces an insoluble compound
c. A red complex of silver with cyanide is formed which signals the end of the
titration process
d. The ratio of silver to cyanide is 2:1 with a permanent faint turbidity as the
endpoint
65. A 500-mg sample containing NaCN required 23.50 mL of 0.1255 M AgNO
3
to
obtain a permanent faint turbidity. Express the result of this analysis as % CN

.
a. 15.34% b. 23.01% c. 17.25% d. 30.67%
66. Which of the following ions is best titrated with EDTA at minimum pH less than 7?
a. Ca
+2
b. Sr
+2
c. Mg
+2
d. Fe
+3
67. Which of the following affects the stability of metal complexes?
a. geometrical factors
b. macrocyclic effect
c. chelate effect
d. all of these
68. An EDTA solution was prepared by dissolving the disodium salt in 1L of water. It
was standardized using 0.5063 gram of primary standard CaCO
3
and consumed
28.50 mL of the solution. The standard solution was used to determine the hardness
of a 2L sample of mineral water, which required 35.57 mL of the EDTA solution.
Express the analysis in terms of ppm CaCO
3
.
a. 89 ppm b. 316 ppm c. 158 ppm d. 269 ppm
69. Which of the following statements is true?
a. Multidentate chelating agents form weaker complexes with metal ions
b. All metals can be determined with high precision and accuracy using
chelometric titration
c. Eriochrome black T gives a sharp endpoint for the titration of calcium
d. Ca-EDTA complex is more stable than Mg-EDTA complex
Chemical and Physical Principles Analytical Chemistry
144
70. The 300 mg sample of impure Na
2
SO
4
(142.04) was dissolved in sufficient water and
the sulfate was precipitated by the addition of 35.00 mL of 0.1022 M BaCl
2
. The
precipitate was removed by filtration and the remaining BaCl
2
consumed 6.79 mL of
0.2467 M EDTA for titration to the Calmagite endpoint. Calculate the purity of the
sample.
a. 80% b. 85% c. 90% d. 95%
71. A 0.8521 gram sample of an alloy was found to contain Cu (63.55) and Zn (65.41)
with small amounts of Pb (207.2) and Hg (200.59). The sample was dissolved in
nitric acid and diluted to 500 mL. A 10 mL aliquot was treated with KI to mask the
Hg and the resulting solution required 7.06 mL of 0.0348 M EDTA solution. A
second 25 mL aliquot was treated with ascorbic acid and the pH was adjusted to 2.00
to reduce Hg
+2
and the metallic Hg was removed from the solution. To this solution,
thiourea was then added to mask the Cu and the resulting solution required 8.58 mL
for titration. The lead ion was titrated in a 250 mL in the presence of NaCN to mask
Cu, Zn and Hg and required 3.11 mL for titration. Calculate the percentage of Cu
and Hg in the sample of alloy.
a. 47% Cu and 3% Hg
b. 44% Cu and 5% Hg
c. 53% Cu and 7% Hg
d. 56% Cu and 5% Hg
72. Commonly, the analyte in a sample is present in two different oxidation states. Pre-
reduction is then necessary before titration. One of the metallic reductors is zinc
soaked in a dilute solution of mercuric chloride. This reductor is known as
__________.
a. Walden reductor
b. Devarda Alloy
c. Lindlars catalyst
d. Jones reductor
73. At pH = 7 and a pressure of 1 bar, the potential for the half reaction, 2H
+
(aq)
+ 2e

H
2 (g)
is __________.
a. 0 V b. 0.414 V c. 0.828 V d. 1.255 V
74. Which of the following is false about iodine as an oxidizing agent in titration?
a. Standard iodine solutions have low smaller electrode potential
b. Sensitive and reversible indicators are readily available
c. Iodine is very soluble in water and losses are minimal
d. The solution lacks stability and requires regular standardization
75. What is the molarity of a KMnO
4
solution standardized against 1.356 gram Na
2
C
2
O
4
(134
g
/
mol
) requiring 25.1 mL of the solution in acidic medium?
a. 0.161 M b. 0.403 M c. 1.008 M d. 0.856 M
76. All of the following is used as oxidant in redox titrations except
a. KMnO
4
b. Cerium (IV) c. K
2
Cr
2
O
7
d. Iodide
77. A sample of iron ore weighing 385.6 mg was dissolved in acid and passed through a
Jones reductor. The resulting solution 52.36 mL of 0.01436 M K
2
Cr
2
O
7
for titration
to the diphenylamine sulfonic acid endpoint. Calculate % Fe
3
O
4
(231.55
g
/
mol
) in the
ore sample.
a. 15.05% b. 45.15% c. 90.30% d. 67.98%
78. A sample of pyrolusite weighing 0.2400 gram was treated with excess KI. The iodine
liberated required 46.24 mL of 0.1105 M Na
2
S
2
O
3
solution. Calculate % MnO
2
(86.94) in the sample.
a. 46.27% b. 30.85% c. 92.54% d. 76.12%
Chemical and Physical Principles Analytical Chemistry
145
79. Which of the following metal is not reduced by Walden reductor?
a. Cr b. Fe c. Cu d. V
80. A 10.00 gram sample of cooked-ham was pureed with 200 mL of water, filtered and
the resulting solution containing dissolved potassium nitrite was acidified. This
solution was treated with 25.00 mL of 0.00514 M KMnO
4
was back titrated with
14.97 mL of 0.01678 M FeSO
4
. Calculate the amount of nitrite (46.01) in ppm.
a. 450 b. 900 c. 1350 d. 1800
81. Which of the following is used as a pre-oxidant?
a. sodium bismuthate
b. ammonium peroxydisulfate
c. sodium peroxide
d. all of these
82. Which of the following statements is true on the determination of chemical oxygen
demand?
a. For solutions with high chloride content, addition of sulfamic acid is necessary
to eliminate the chloride interference
b. Chemical oxygen demand accounts for the oxygen demand of both
biodegradable and non-biodegradable oxidizable pollutants in a body of water
c. The interference caused by the nitrite ion is eliminated by the addition of
HgSO
4
which oxidizes this ion to its nitrate form
d. all of these
83. A 100 mL water sample was analyzed by Winkler Method. If 7.52 mL of 0.0124 M
Na
2
S
2
O
3
was used for titration, determine ppm O
2
in the water sample.
a. 2.8 b. 3.5 c. 6.4 d. 7.5
84. The following volumes of standard solutions containing 20 ppm Fe
+2
were added to
10-mL aliquot samples of waste water in 500-mL volumetric flasks. Excess
thiocyanates ion was added and the resulting solutions were diluted up to the mark
and the following absorbance were obtained in a 1.00-cm cell:
Volume of standards, ppm 0 5 10 15 20 25
Absorbance 0.095 0.281 0.433 0.628 0.806 0.972
Calculate the concentration of Fe
+2
in the waste water.
a. 5.5 ppm b. 8.3 ppm c. 11.0 ppm d. 16.5 ppm
85. A 500 mg sample of a solution containing cobalt (58.93) and nickel (58.69) was
dissolved and diluted to 50 mL. A 25 mL aliquot was treated with a complexing
agent to produce a colored complex and the volume was adjusted to 50 mL. The
following data were obtained for the simultaneous determination in a 1.00-cm cell:
Wavelength
(nm)
Molar absorptivity, [M
1
-cm
1
] Absorbance of
solution, A
Co Ni
510 36400 5520 0.815
656 1240 17500 0.314
Calculate the concentration of Co in the solution in ppm
a. 1172 ppm b. 1940 ppm c. 2142 ppm d. 2343 ppm