Physical and Chemical Principles Analytical Chemistry

C. ANALYTICAL CHEMISTRY
Analytical Chemistry branch of chemistry that deals with the separation, identification
and composition of matter.
Qualitative Analysis (what is present)
type of analysis that reveals the components of the sample
Quantitative Analysis (how much is present)
type of analysis that determines the amount of components present in a sample
Methods of Analyses
A. Classical Methods
1. Gravimetric Method deals with the measurement of the mass of a substance
that is chemically related to the analyte.
2. Volumetric Method measures the volume of solution necessary to react
completely with the analyte.
B. Modern Methods
1. Spectroscopic Method measures the electromagnetic radiation produced
by the analyte or its interactions with it.
2. Electroanalytic Method measures the electrical properties of the analyte
such as current (A), potential (V), resistance (), and amount of charge
(coul).
Quantitative Analysis
Gravimetric Method of Analysis
Basic Steps on Precipitation Method
1. Sample is dissolved in an appropriate solvent.
2. A precipitant is used to convert the analyte into a sparingly soluble precipitate.
3. The precipitate is converted into a product of known composition by a suitable heat
treatment.
4. The percentage of the analyte in the sample is calculated using the gravimetric
factor (GF):
wt. of precipitate GF
% analyte in the sample 100%
wt. of sample
molar mass of analyte x analyte
GF
molar mass of precipitate y precipitate

Volumetric Methods of Analysis

Standard Solution solution of known concentration
Standardization process of determining the concentration of an unknown solution
Primary Standard a substance of high purity used for standardization
Characteristics of a Good Primary Standard
1. High purity and high equivalent weight
2. Stable towards air, high temperature and humidity
3. Soluble in water
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.

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Physical and Chemical Principles Analytical Chemistry

Types of Titration
1. Direct Titration the analyte reacts with the standard solution directly
2. Back Titration an excess standard solution is added and the excess is
determined by the addition of another standard solution
3. Replacement Titration the analyte is converted to a product chemically related
to it and the product of such reaction is titrated with a standard solution

AcidBase Titration
Concepts of Acids and Bases
LEWIS BRONSTED-LOWRY ARRHENIUS
Electron-pair Produces *H3O+ in
ACID Proton donor
acceptor solution
Electron-pair Produces **HO in
BASE Proton acceptor
donor solution
* hydronium ion, protonated water or solvated proton
** hydroxide ion
Strength of Acids and Bases
Ionization Reaction reaction involving formation of ions
Strong Acids/Bases completely ionized in solution
HCl + H2O H3O+(aq) + Cl(aq)
NaOH + H2O Na+(aq) + HO(aq)
Weak Acids/Bases partially ionized in solution
HF + H2O H3O+(aq) + F(aq)
NH3 + H2O NH4+(aq) + HO(aq)
Autoprotolysis of Water
H2O + H2O H3O+(aq) + HO(aq) KW = 1 x 1014 at 25C
Strong Acids : HCl, HBr, HI, HClO4, HNO3, H2SO4 (only on the first ionization)
Strong Bases : Bases of Group 1A and 2A
Weak Acids : HF, HCN, H2SO3, H3PO4 and organic acids
Weak Bases : Ammonia and derivatives
Calculation of pH

Strong Acids : pH - log Cacid
Strong Bases : pH 14 log n HO -
C base
pH - 1 2 log K a Cacid
C acid
Weak Acids : when 1000
Ka
pH 14 1 2 log K b C base
C base
Weak Bases : when 1000
Kb
At 25C pH + pOH = 14
Hydrolysis of Salts
Acid and base reacts to form salt and water. As a general rule, salts coming from weak
acids or weak bases hydrolyze in water, that is, only the strong conjugate hydrolyzes in
water. An acidic salt is formed from the reaction of a strong acid and weak base. A
basic

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Physical and Chemical Principles Analytical Chemistry

salt results from the reaction of a strong base and a weak acid. Thus, a neutral salt is a
product of the reaction between a strong acid and a strong base.

Hydrolysis Reaction of Salts

Acidic Salt : NH4Cl
KW
NH4+ + H2O H3O+ + NH3 KH
K NH 3
Basic Salt : NaCN
KW
CN + H2O HO + HCN K H
K HCN
pH of Salts
C C
Acidic Salt : pH 7 1log salt when salt 1000
2
Kb KH
Csalt Csalt
Basic Salt : pH 7 1 2 log when 1000
Ka KH

Buffer Solutions
Solutions that contains weak acid or weak base and its conjugate salt. These solutions
tend to resist changes in pH.
pH of a Buffer Solution
[acidic component]
pH pKa log , Henderson Hasslebalch Equation
[basic component]
[acidic component]
If Kb is given pH 14 pK b log
[basic component]
Primary Standards for Bases
1. Benzoic Acid, C6H5COOH
2. Oxalic Acid, H2C2O4.2H2O
3. Potassium Biiodate, KH (IO3)2
4. Potassium Hydrogen Phthalate (KHP), C6H4(COOH)(COOK)
5. Sulfamic Acid (HSO3NH2)
Primary Standards for Acids
1. Calcium Carbonate, CaCO3
2. Mercuric Oxide, HgO
3. Sodium Carbonate, Na2CO3
4. Tris-hydroxymethylaminomethane (THAM), (CH2OH)3CNH2
Indicators for Acid-Base Titration
1. Bromocresol Green
pH Transition Range: 3.8 5.4
changes from yellow to blue
pKa = 4.66
2. Bromothymol Blue
pH Transition Range: 6.2 7.6

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Physical and Chemical Principles Analytical Chemistry

changes from yellow to blue

pKa = 7.10

3. Methyl Red
pH Transition Range: 4.2 6.3
changes from red to yellow
pKa = 5.00
4. Methyl Orange
pH Transition Range: 3.1 4.4
changes from orange to yellow
pKa = 3.46
5. Phenolphthalein
pH Transition Range: 8.3 10.0
changes from colorless to pink
pKa = 9.00
Applications of Acid-Base Titration
Kjeldahl Method (Determination of Organic Nitrogen)
Step 1. Digestion
The sample is oxidized in hot, concentrated sulfuric acid, H2SO4 and turns black
To convert . . . Carbon and Hydrogen to . . . CO2 and H2O
To convert . . . Amides and Amines to . . . NH4+
To convert . . . Azo, Azoxy and Nitro Group to . . . N or its oxide
Catalysts
Potassium Sulfate (K2SO4) increases the boiling point of sulfuric acid
Mercuric Oxide (HgO) increases the rate of reaction
Selenious Acid (H2SeO3) best catalyst
Step 2. Distillation
The oxidized solution is cooled and then treated with NaOH to liberate
ammonia
gas:
NH4+ + HO- NH3(g) + H2O
Glass or porcelain beads are added to avoid bumping
In some modifications, hydrogen peroxide is added to decompose organic
matrix
formed
If mercuric oxide, HgO is used as a catalyst, it is necessary to add sodium
thiosulfate, Na2S2O3 to precipitate mercuric sulfide, HgS.
Hg2+ + S2O3-2 + 2HO-1 HgS(s) + SO4-2 + H2O
Step 3. Titration
Standard
1. Using an excess amount of HCl
NaOH solution
NH3 + HCl NH4Cl
The excess HCl is determined using a standard NaOH solution
NH3 HCl + NaOH NaCl + H2O
2. Ammonia distilled is collected in a boric acid solution
NH3 + H3BO3 NH4+ + H2BO3-2

Excess HCl
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Physical and Chemical Principles Analytical Chemistry

Titrate the H3BO3NH3 solution with standard acid

H2BO3-2 + H3O+ H3BO3 + H2O
Percentage Protein in the Sample
% protein = % N * f = 5.70 (cereals)
= 6.25 (meat products)
= 6.38 (dairy products)

Double Indicator Method (Mixture of Bases)

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 V0-Ph. On the same solution, methyl red is then
added and an additional volume is required to reach the end point recorded as VPh-MR
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 V0-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)
Alkalinity relationships
Result from titration NaOH Na2CO3 NaHCO3
V0-Ph > VPh-MR V0-Ph VPh-MR 2VPh-MR 0
V0-Ph < VPh-MR 0 2V0-Ph VPh-MR V0-Ph
V0-Ph = VPh-MR 0 2V0-Ph = 2VPh-MR 0
V0-Ph 0 ; VPh-MR > 0 0 0 VPh-MR
V0-Ph > 0 ; VPh-MR 0 V0-Ph 0 0
Note: If analysis involves measurement of volume due to total alkalinity (V 0-MR), use the conversion: VPh-MR = V0-
MR V0-Ph

These relationships can be summarized using the following diagram:

Precipitation Titration
One of the oldest analytical techniques that started in the mid1800s. Silver nitrate
(AgNO3) is commonly employed in such technique. Titration with AgNO3 is often termed
as argentometric titration.
Indicators in Precipitimetry

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Physical and Chemical Principles Analytical Chemistry

The equivalence point can be observed by the following:

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Physical and Chemical Principles Analytical Chemistry

a. formation of a colored secondary precipitate

Mohr Method (K.F. Mohr, Germany, 1865)
Direct method for halides and cyanides
Titrant: Silver nitrate, AgNO3
Titration Reaction: Ag+ + Cl1 AgCl(s)
white
Indicator: sodium chromate, Na2CrO4
Indicator Reaction: 2Ag+ + CrO42- Ag2CrO4(s)
red
Primary Standard for AgNO3: NaCl
Titration is carried out between pH of 710. Usually, a low concentration of
chromate is desired to detect the end point clearly since a chromate ion imparts an
intense yellow color.
b. formation of a colored complexion
Volhard Method (Jacob Volhard, Germany, 1874)
Direct method for silver Indirect method for halides
Titrant: Potassium thiocyanate, KSCN
Direct Titration Reaction: Ag+ + SCN1 AgSCN(s)
white
Indirect Titration Reactions: Ag+ + Cl1 AgCl(s)
excess white
Ag+ + SCN1 AgSCN(s)
white
Indicator: ferric alum
Indicator Reaction: Fe+3 + SCN-1 Fe(SCN)2+
red

Titration is carried out in acidic condition to hasten precipitation of ferric ion to its
hydrated oxide form.
c. formation of a colored adsorption complex
Fajans Method (K. Fajans, Poland, 1874)
Titrant: Silver nitrate, AgNO3
Titration Reaction: Ag+ + Cl1 AgCl(s)
white
Indicator: dichlorofluorescein, best for determination of halides and cyanides
End point: color change from yellow to pink
Titration is carried out between pH of 4-7. Dextrin is added to prevent excessive
coagulation of the AgCl precipitate.

Complex Formation Titration

This type of titration is used for the determinations of cations. Typical reagents used
are organic compounds containing groups which are electron donors and have the ability
to form multiple covalent bonds with the metal ion.
Determination of Cyanide by the Liebig Method
The titration is carried by the dropwise addition of AgNO 3 in a solution of a cyanide
forming a soluble cyanide complex of silver: 2CN 1 + Ag+ Ag(CN)21. The endpoint of
the titration is the formation of a permanent faint turbidity: Ag(CN) 21 + Ag+ Ag
[Ag(CN)2](s)
Determination of Nickel

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Physical and Chemical Principles Analytical Chemistry

An ammoniacal solution of nickel is treated with a measured excess of standard

cyanide solution and the excess is determined by a standard AgNO 3 solution according to
the reactions:
Addition of Excess Cyanide : Ni(NH3)6+3 + 4CN1 + 6H2O Ni(CN)41 + 6NH4OH
Back Titration with Ag+ : 2CN1 + Ag+ Ag(CN)21
Endpoint : Ag(CN)21 + Ag+ Ag[Ag(CN)2](s)
Titration with Ethylenediaminetetraacetic Acid (EDTA)
The structure suggests six potential sites (hexadentate) for metal bonding: the four
carboxyl groups and two amino groups. Commercially, the free acid and the dehydrate
are available. Solutions of EDTA combines with any metal ions in a 1:1 ratio. The
indicator used for titration is the Eriochrome Black T . For metal ion detections, it is
necessary to adjust the pH to 7 or above so that the blue form predominates in the
absence of a metal cation. Generally, metal complexes with EDTA are red as H 2In1.
When an excess EDTA is added, the solution turns blue according to the reaction:
MIn1 + HY3 HIn2 + MY-2
red blue

Direct Titration with Added Metal Ions

In the determination of Ca2+, small amount of magnesium chloride is added to
EDTA. Initially, Ca+2 displaces Mg+2 in the EDTA complex and the latter combines with
EBT producing a red complex. When all the calcium is titrated, the liberated Mg +2 is
released, combined with the EDTA and the endpoint is observed.

Introduction to Electrochemistry
An oxidation/reduction reaction is one in which electrons are transferred from one
reactant to another. Oxidation reaction involves an increase in the oxidation state of an
element while reduction reaction involves a decrease in the oxidation state. Consider the
reaction:
Ce4+ + Fe2+ Ce3+ + Fe3+
4+
In this reaction, Ce ion
acquires an electron from For oxidation reactionLEORA
Fe2+. Such strong electron Loss of Electron(s), Oxidation, substance oxidized is
affinity for electrons makes the Reducing Agent
Ce4+ an oxidizing agent or an For reduction reactionGEROA
oxidant. On the other hand, Gain of Electron(s), Reduction, substance reduced is
Fe2+ readily gives its electron the Oxidizing Agent
and is a reducing agent or
reductant.

Balancing Redox Reactions

Step 1. Assign oxidation numbers of each of the species in the reaction
MnO4-1 + NO2-1 Mn2+ + NO3-1 (acidic medium)
+7 -2 +3 2 +2 +5 2
Step 2. Write the halfcell reactions. Identify oxidation and reduction reactions. If
compounds are present in the reaction, use the ions in the halfcell reaction
OXIDATION: NO2-1 NO3-1 + 2e
+3 +5
REDUCTION: MnO4-1 + 5e Mn+2
+7 +2
Step 3. Balance the reaction by multiplying a factor so that the number of electrons on
both sides is the same.

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Physical and Chemical Principles Analytical Chemistry

OXIDATION x 5: 5NO2-1 5NO3-1 + 10e

+3 +5
REDUCTION x 2: 2MnO4-1 + 10e 2Mn+2
+7 +2

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Physical and Chemical Principles Analytical Chemistry

Step 4. Balance by adding H 2O to the oxygen deficient side and H+/OH - on the other
side.
OXIDATION x 5: 5NO2-1 + 5H2O 5NO3-1 + 10H+ + 10e
+3 +5
REDUCTION x 2: 2MnO4-1 + 16H+ + 10e 2Mn+2 + 8H2O
+7 +2
------------------------------------
2MnO4-1 + 5NO2-1 + 6H+ 2Mn+2 + 5NO3-1 + 3H2O

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

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

Standard Reduction Potential

A positive value of the standard reduction potential of an electrode implies that it
was used as cathode with the SHE as anode. High positive value of a reduction potential
also indicates that the electrode is a good oxidizing agent.
Thermodynamic Potential of an Electrochemical Cell, Ecell
This potential can be computed at standard conditions as follows:
Ecell = Ecathode Eanode
Effect of Concentration on Electrode Potentials: Nernst Equation
RT [C]c [D]d ...
E E ln Nernst Equation
nF [A]a [B]b ...
0.0592 [C]c [D]d ...
At 25C E E log
n [A]a [B]b ...

where: R = gas constant, 8.314 J

K mol
T = temperature in Kelvin
n = number of electrons that appear in the half-cell reaction

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Physical and Chemical Principles Analytical Chemistry

F = Faradays constant, 96487.38 coul

mole e
OxidationReduction Titration
a. Permanganate Process (KMnO4)
In acidic medium MnO41 + 8H+ + 5e Mn2+ + 4H2O
In basic/neutral medium MnO41 + 2H2O + 3e MnO2 + 4HO
Standardization of KMnO4 solution
Indicator: self indicating
Primary Standards
1. Against Na2C2O4
Rxn: C2O4-2 2CO2 + 2e
2. Against As2O3
Rxn: As3+ + 4H2O H3AsO4 + 5H+ + 2e
3. Against Ferrous solutions
Rxn: Fe2+ Fe3+ + e
4. Against pure Fe
Rxn: Fe Fe2+ + 2e
Applications of Permanganimetric Titrations
1. Fe2+ Fe3+ + e
2. Sn2+ Sn4+ + 2e
3. NO2 NO3 + 2e
4. H2O2 O2 + 2e
5. Mo3+ MoO42 + 3e
6. Ti3+ TiO2+ + e
b. Dichromate Process
Rxn: Cr2O72- + 6e 2Cr3+
Indicator: sodium diphenylbenzidine sulfonate
barium diphenylamine sulfonate
Applications of Dichromate Process
1. Fe2+ Fe3+ + e
2. U4+ UO22+ + 2e
3. Cu+ Cu+2 + e
c. Iodometric Titration (Indirect Titration with Iodine)
Rxn: I2 + 2e 2I
Titrant: Na2S2O3
Indicator: starch
Primary Standard: K2Cr2O7 (Cr2O7-2 + 6I 2Cr3+ + 3I2)
Titration Reaction: 2S2O3-2 + I2 S4O6-2 + 2I

The Absorption of Radiation: Ultraviolet and Visible

If a beam of light passes through a glass container filled with liquid, the emergent
radiation is always less powerful than that entering. If the energy absorbed is greater for
some visible wavelengths than for others, the emergent beam will appear colored.

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Physical and Chemical Principles Analytical Chemistry

Beers Law
The absorption of radiant energy by matter can be described using Beers Law.
Consider a block of an absorbing material of concentration, c and thickness, b:

b P dP b
P ac 0 dx
o P
Po P P
ln abc
Po
Po
dx A log bc
P
1
A log bc
T

where: T = transmittance
A = absorbance
P = emergent radiation
= molar absorptivity
Po = entering radiation

REVIEW QUESTIONS AND PROBLEMS

1. All of the following is used as a hygroscopic material in desiccators except

a. CaSO4 b. Mg(ClO4)2 c. P2O5 d. H2SO4
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 c. certified reagent
b. analytical reagent d. all of these
4. What proportion by weight of Na2C2O4 (134) to KHC2O4H2C2O4 (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
5. 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
6. 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

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Physical and Chemical Principles Analytical Chemistry

7. 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 8 to 10
A 20% wt/wt aqueous solution of NaCl (58.45) at 25C has a density of 1.145 g-mL1.
Express the amount of solute in this solution as follows:
8. % wt/vol
a. 17 b. 19 c.21 d. 23
9. molarity (M)
a. 0.98 b. 1.96 c. 3.92 d. 5.88
10. molality (m)
a. 3.42 b. 5.13 c. 6.84 d. 8.56
11. 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
12. A 1.5176 g sample of a CaCO3 was dissolved in an acidic solution. The calcium was
precipitated as CaC2O4H2O (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%
13. A mixture containing FeCl3 (162.20) and AlCl3 (133.33) only weighs 750.8 mg. The
chlorides were precipitated using ammonia and ignited to Fe 2O3 (159.69) and Al2O3
(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%
14. 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
15. What is the extent of ionization of the second proton of 0.5 M H2SO4 at 25C?
a. 1% b. 2% c. 4% d. 8%
16. 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
17. 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 3O4 (228.82) precipitate obtained in
milligram?
a. 19.0 mg b. 38.0 mg c. 57.0 mg d. 76.0 mg
18. 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

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Physical and Chemical Principles Analytical Chemistry

19. Which of the following aqueous solutions of the same concentration will have the
largest pH value at 25C?
a. NH3 b. KCl c. NH4Cl d. NaF
20. Which of the following solutions at 25C will have the lowest pH value?
a. 0.15 M Na2SO4 (KA2 of H2SO4 = 1.2 102)
b. 5.2 108 M HCl
c. 0.05 M NaCN (KA of HCN = 6.2 1010)
d. 0.01 M NH4Cl (KA of NH4+ = 5.6 1010)
21. 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 c. NH3 HBr
b. KOH HNO3 d. all of these
22. 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
23. 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 pKb1
d. The acid buffering capacity is maximum at pH equal to pKa
24. Approximately how many grams of NH 4Cl (53.45) should be dissolved in a liter of
0.125 F NH3 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
25. The conjugate base of H2PO41 is __________
a. HPO42 b. PO43 c. H3PO4 d. P2O5
26. 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
27. 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
28. What is the best basis for choosing the right indicator for a given acid base titration
from among the following?
a. type of acid c. pH at equivalence point
b. type of base d. molarity of the acid or base
29. 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

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Physical and Chemical Principles Analytical Chemistry

30. 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 c. methyl red
b. methyl orange d. phenolphthalein
31. 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%
32. 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
CO2, H2O, N2 and small amounts of nitrogen oxides.
a. Kjeldahl Method c. Winkler Method
b. Dumas Method d. Wijs Method
For numbers 33 to 35
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
V0-Ph (mL) 4.27 0.01 5.12 6.37 5.63
V0-MR (mL) 10.18 6.19 10.24 6.38 9.04
33. Which of the following mixtures contains NaHCO3?
a. Mixtures 2 and 4 c. Mixtures 3 and 4
b. Mixtures 4 and 5 d. Mixtures 1 and 2
34. Calculate the purity of the sample containing NaHCO3 only.
a. 1.82% b. 5.22% c. 10.64% d. 11.13%
35. What is the % wt NaOH for the sample containing a mixture of NaOH-Na 2CO3?
a. 1.82% b. 5.22% c. 10.64% d. 11.13%
36. In the analysis of nitrogen using Kjeldahl Method, which of the following is added to
decompose organic matrices present in the sample?
a. H2SO4 b. HgO c. K2SO4 d. H2O2
37. 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
H3BO3. 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%
38. Which of the following is NOT used as primary standard for the standardization of
alkali solutions?
a. HgO b. H2C2O4 c. HSO3NH2 d. C6H5COOH
39. A 1.500-gram sample of impure aluminum chloride was dissolved in water and
treated with 45.32 mL of 0.1000 M AgNO3 using K2CrO4 as indicator. Express the
analysis in %AlCl3 (133.33).
a. 40.28% b. 13.43% c. 4.48% d. 27.36%
40. Which of the following is not a correct analytical methodtitrant pair?
a. MohrAgNO3 c. Volhard AgNO3
b. Fajans AgNO3 d. Liebig AgNO3

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Physical and Chemical Principles Analytical Chemistry

41. A mixture of LiBr (86.845) and BaBr2 (297.22) weighing 800 mg is treated 50.00 mL
of 0.1879 M AgNO3 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%
42. 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
43. 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%
44. 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%
45. 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
46. 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 CaCO3.
a. 89 ppm b. 316 ppm c. 158 ppm d. 269 ppm
47. 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
48. The 300 mg sample of impure Na 2SO4 (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%
49. 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 c. Lindlars catalyst
b. Devarda Alloy d. Jones reductor

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Physical and Chemical Principles Analytical Chemistry

50. At pH = 7 and a pressure of 1 bar, the potential for the half reaction, 2H+(aq) + 2e H2 (g) is __________.
a. 0 V b. 0.414 V c. 0.828 V d. 1.255 V
51. 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
52. What is the molarity of a KMnO 4 solution standardized against 1.356 gram Na 2C2O4
(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
53. All of the following is used as oxidant in redox titrations except
a. KMnO4 b. Cerium (IV) c. K2Cr2O7 d. Iodide
54. 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 2Cr2O7 for titration
to the diphenylamine sulfonic acid endpoint. Calculate % Fe 3O4 (231.55 g/mol) in the
ore sample.
a. 15.05% b. 45.15% c. 90.30% d. 67.98%
55. 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 2S2O3 solution. Calculate % MnO2
(86.94) in the sample.
a. 46.27% b. 30.85% c. 92.54% d. 76.12%
56. Which of the following metal is not reduced by Walden reductor?
a. Cr b. Fe c. Cu d. V
57. 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 KMnO4 was back titrated with
14.97 mL of 0.01678 M FeSO4. Calculate the amount of nitrite (46.01) in ppm.
a. 450 b. 900 c. 1350 d. 1800
58. Which of the following is used as a pre-oxidant?
a. sodium bismuthate c. sodium peroxide
b. ammonium peroxydisulfate d. all of these
59. A 100 mL water sample was analyzed by Winkler Method. If 7.52 mL of 0.0124 M
Na2S2O3 was used for titration, determine ppm O2 in the water sample.
a. 2.8 b. 3.5 c. 6.4 d. 7.5
60. 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 Molar absorptivity, [M1-cm1] Absorbance of
(nm) Co Ni solution, A
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

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