K E N N E T H

Analytical Chemistry
Kenneth Soriano, EIT, AMIChemE
 Course Outline

• Solutions and Their

Concentrations
• Gravimetric Analysis
• Acid – Base Equilibria
• Volumetric Analysis
 O

O Solutions and Their

Concentrations
O

OH
Aspirin

O OH

Stearic Acid
 Molarity (M)

• Molar concentration is the number of that

species that is contained in 1L of the
solution
 Part per Million (ppm)

• For very dilute solutions, parts per million

(ppm) is a convenient way to express
concentration
 Parts per Million (ppm)

• A handy rule in calculating parts per

million is to remember that for dilute
aqueous solutions whose densities are
approx. 1.00 g/mL,
Parts per Billion (ppb)
 Normality (N)

• is the number of equivalents that is

contained in 1L of the solution
Normality
 O O

H
Gravimetric
H H Analysis O
Anthraquinone
OH
O
Progesterone

H H

O
Testosterone
 Gravimetric Analysis

• Gravimetric Method of Analysis – deals

with the measurement of the mass of a
substance that is chemically related to the
analyte.
Basic Steps on Precipitation Method
• Sample is dissolved in an appropriate
solvent.
• A precipitant is used to convert the analyte
into a sparingly soluble precipitate.
• The precipitate is converted into a product of
known composition by a suitable heat
treatment.
• The percentage of the analyte in the sample
is calculated using the gravimetric factor (GF)
Gravimetric Analysis

WT.
SAMPLE
Prepare Solution of the Sample
• Choice of Solvent
Water ( w/ or w/o heating)
Non-Oxidizing Acids
Oxidizing Acids (HNO3)
Aqua Regia (3:1 HCl:HNO3)
Fluxing Agents
Acid: K2S2O7 Redox: Na2O2
Basic: Na2CO3
 EXCESS
DISSOLVED
PRECIPITATING
SAMPLE
AGENT
 Precipitation of Analyte
Elements / Ion Precipitating Final/Ignited
Precipitated Agent Form
Cl, Br, I AgNO3 AgCl, AgBr, AgI
Fe, Al ,Cr NH3 Fe2O3 , Al2O3 , Cr2O3
Mg NH4 HPO4 Mg2P2O7
K H2PtCl6 K 2PtCl6
Ni Dimethylglyoxime Ni – DMG
CaC2O4 - 110°C
Ca (NH4)2C2O4 CaCO3 - 500°C
CaO - 800°C
PRECIPITATION
OF THE
ANALYTE
FILTRATION
AND
IGNITION
OF THE
PRECIPITATE
Gravimetric Analysis

WT.
FINAL FORM
Calculations
 Example
• A 0.5662-g sample of an ionic compound
containing chloride ions and an unknown
metal is dissolved in water and treated
with an excess of AgNO3. If 1.0882 g of
AgCl precipitate forms, what is the percent
by mass of Cl in the original compound?
ANS. 47.54%
 Example 1
The aluminum in a 759.08 mg of impure
aluminum sulfate sample was precipitated
as Al(OH)3 and ignited at 1100°C to yield a
precipitate of Al2O3 weighing 387.953 mg.
Express the result of analysis in terms of
%Al.
a. 27.05% b. 13.53%
c. 18.67% d. 23.29%
 Example 2
• A 250 mg sample containing 45% MgCO3
and 55% CaCO3 was ignited producing
CO2 as decomposition product. Assuming
that the decomposition reaction is
complete, what is the change in weight of
a NaOH solution used to absorb CO2
ANS. 119.21 mg
 Example 3
• What weight of an impure NaCl sample
must be taken for analysis so that the
weight of AgCl precipitate obtained in mg
will be equal to the %Cl in the sample?

ANS. 24.73 mg
 Example 4
• A sample containing NaBr and KBr only
weighs 253.02 mg. The sample was
dissolved in water and treated with excess
AgNO3. The precipitate formed was found
to weigh 429.85 mg. Calculate the %NaBr
in the sample.
ANS. 49%
 Example 5
• A 0.6407-g sample containing chloride and
iodide ions gave a silver halide precipitate
weighing 0.4430 g. This precipitate was
then strongly heated in a stream of Cl2 gas
to convert the AgI to AgCl; on completion
of this treatment, the precipitate weighed
0.3181 g. Calculate the percentage of
chloride and iodide in the sample.
Ans. 4.72% Cl- and 27.05% I-
 O O

H
Acid – Base
H H Equilibria O
Anthraquinone
OH
O
Progesterone

H H

O
Testosterone
 Arrhenius Acids and Bases

• Arrhenius defined acids as substances

that ionize in water to produce H+ ions and
bases as substances that ionize in water
to produce OH- ions.
ARRHENIUS ACID ARRHENIUS BASE
Produces H3O+ in sol’n Produces OH- in sol’n
 Arrhenius Acids and Bases
• Monoprotic Acid - each unit of the acid
yields one hydrogen ion upon ionization
 Arrhenius Acids and Bases
• Diprotic Acid - each unit of the acid gives
up two H+ ions, in two separate steps
 Arrhenius Acids and Bases
• Triprotic Acid - which yield three H+ ions,
are relatively few in number
Arrhenius Acids and Bases
 Strength of Acids and Bases
• Classification of Electrolytes
STRONG
1. Inorganic acids such as HNO3,
HClO4 , H2SO4 (only on first
ionization) , HCl, HI, HBr, HClO3,
HBrO3
2. Alkali and Alkaline-Earth (Grp I and 2. Most organic acids ( ex. HC2H3O2
II) hydroxides - KOH, NaOH,
LiOH, RbOH, Mg(OH)2, Ba(OH)2 ,
Ca(OH)2
3. Most Salts
WEAK
1. Many inorganic acids, including HF
HCN, H2CO3, H3BO3, H3PO4, H2S,
H2SO3
acetic acid, HCOOH formic acid)
3. Ammonia and most organic bases
4. Halides, cyanides, and
thiocyanates of Hg, Zn, and Cd
 Bronsted-Lowry
Acids and Bases
• Brønsted acid is a substance capable of
donating a proton, and a Brønsted base is
a substance that can accept a proton.
BRONSTED ACID BRONSTED BASE
Proton Donor Proton Acceptor
 Bronsted-Lowry

HCl : Proton Donor (H+)

H2O: Proton Acceptor
 Bronsted-Lowry

• An extension of the Brønsted definition of

acids and bases is the concept of the
conjugate acid-base pair, which can be
defined as an acid and its conjugate
base or a base and its conjugate acid.
Conjugate means
“joined together”
 Bronsted-Lowry

• The conjugate base of a Brønsted acid is

the species that remains when one proton
has been removed from the acid.
• Conversely, a conjugate acid results from
the addition of a proton to a Brønsted
base.
 Bronsted-Lowry
• Every Brønsted acid has a conjugate
base, and every Brønsted base has a
conjugate acid. For example, the chloride
ion (Cl- ) is the conjugate base formed
from the acid HCl, and H3O+ (hydronium
ion) is the conjugate acid of the base H2O.
Bronsted-Lowry
Bronsted-Lowry
Bronsted-Lowry
 Lewis Acids and Bases

• Lewis base as a substance that can

donate a pair of electrons. A Lewis acid
is a substance that can accept a pair of
electrons.
LEWIS ACID LEWIS BASE
Electron Pair Acceptor Electron Pair Donor
Lewis
Autoprotolysis of Water
Autoprotolysis of Water
• In 1 L, or 1000 g, of water, there are 1000
g/(18.02 g/mol), or 55.5 moles, of water.
Therefore, the “concentration” of water, or
[H2O], is 55.5 mol/L, or 55.5 M. This is a
large quantity compared to the
concentrations of other species in solution
(usually 1 M or smaller), and we can
assume that it does not change
appreciably during the course of a
reaction.
Autoprotolysis of Water
Ion Product Constant
p Function
Whenever [H+] = [OH-], the aqueous solution
is said to be neutral.
 Example

At 100°C, what is the neutral pH of water?

pH of Strong Acid
pH of Strong Acid

B
 pH of Strong Acid
• Neglecting contribution of H2O to H3O +
function……….
C
 pH of Strong Acid
• pH of 1 x 10-7 M HCl
• Using C…………... pH = ?
• Using A and B…… pH =?

• pH of 1 x 10-10 M HCl
• Using A and B…….pH =?
 pH of Strong Acid
• Alternative Formula:
D

E
pH of Strong Base

G
 pH of Strong Base
• Calculate the pH of 1 x 10^-8 M NaOH
• Calculate the pH of a 0.02 M Ba(OH)2
solution
• The pH of a Ba(OH)2 solution is 10.0.
What is the H+ concentration?
Weak Acid
Acid Ionization Constant (Ka)
Percent Ionization
 Example
Calculate the pH of a 0.036 M nitrous acid
(HNO2) solution and calculate the %
ionization. Ka = 4.5 x 10^-4

The pH of a 0.10 M solution of formic acid

(HCOOH) is 2.39. What is the Ka of the
acid?
 Example
• A 0.03 M HClO2 solution is 10.0% ionized.
Calculate Ka

• Ka for HC2H3O2 is 1.75 x 10-5. What is the

pH of a 0.003 M solution?
Weak Base
Weak Base
 Example
• Calculate the pH of a 0.08 M NH3 solution.
Kb = 1.8 x 10-5
 Common-Ion Effect
• Common Ion Effect
• *is the shift of equilibrium caused by the
addition of a compound having an ion in
common with the dissolved substance
• *reduction in the ionization of the weak
electrolyte
 Example
• Ex. Calculate the [H3O+] in a 0.005 M
HC2H3O2 solution. Ka = 1.8 x 10-5

• Ex. What is the [H3O+] in a 0.005 M

HC2H3O2 which contains 0.001 M
NaC2H3O2?
An important relationship between the acid
ionization constant and the ionization
constant of its conjugate base can be
derived as follows, using acetic acid as an
example:
• The conjugate base, CH3COO-1, supplied
by a sodium acetate (CH3COONa)
solution, reacts with water according to the
equation
 Hydrolysis Reaction of Salts
• Acidic Salt: NH4Cl
NH4+ + H2O H3O+ + NH3 KH = KW/KNH3
• Basic Salt: NaCN
CN- + H2O HO- + HCN KH = KW/KHCN
 pH of Salts
Acidic Salt:
when Csalt/KH >>> 1000

Basic Salt:
when Csalt/KH >>> 1000
 Example
What is the pH of the resulting solution
made by mixing 25 mL of 0.1 M HCl and
15 mL of 0.1 M NaOH?

What is the pH of 0.256 M NH4Cl? Kb of NH3

= 1.8 x 10-5?
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
 What mass in grams of NaC2H3O2 must be
dissolved with 500 mL of 0.100 M acetic
acid to make 2L of buffer solution of pH =
5? Ka = 1.8 x 10-5
a. 2.28 g b. 7.19 g c. 7.38 g d. 2.12 g
What is the pH of the resulting solution
made by mixing 5 mL of 0.2178 M HCl and
15 mL of 0.1156 M NH3? Kb = 1.8 x 10-5?
a. 9.49 b. 11.00 c. 9.02 d. 12.74
 What volume of 0.200 M HCl must be
added to 80 mL of 0.150 M NH3 to
produce a 2L buffer solution with a pH of
8.00? Kb of NH3 = 1.8 x 10-5
a. 3.2 mL b. 9.6 mL c. 28.8 mL d. 56.8 mL
 O O

H
Volumetric Analysis
H H O
Anthraquinone
OH
O
Progesterone

H H

O
Testosterone
Volumetric Methods of Analysis measures
the volume of solution necessary to react
completely with the analyte
 Volumetric Analysis
Standard Solution – solution of known
concentration
 NaOH
PELLETS
 Volumetric Analysis
• Primary standard –
a substance
of high purity
 Volumetric Analysis
• Characteristics of a Good Primary
Standard
High purity and high molecular weight
Stable towards air, high temperature and
humidity
Soluble in water
Readily available and fairly inexpensive
 Primary Standards for Bases
• Benzoic Acid, C6H5COOH (1 OH-)
• Oxalic Acid, H2C2O4∙2H2O (2 OH-)
• Potassium Biiodate, KH(IO3)2 (1)
• Potassium Hydrogen Phthalate (KHP),
C6H4(COOH)(COOK) (1)
• Sulfamic Acid (HSO3NH2) (1)
 Primary Standards for Acids
• Calcium Carbonate, CaCO3 (2 H+)
• Mercuric oxide, HgO (2)
• Sodium Carbonate, Na2CO3 (2)
• Tris-hydroxymethylaminomethane
(THAM), (CH2OH)3CNH2 (1)
Standardization – process of determining
the concentration of an unknown solution
 Volumetric Analysis
• Conditions for Volumetric Analysis
The reaction must be rapid and can be
represented by a simple balanced equation.
The reaction is complete and no side reaction
occurs.
An appropriate indicator must be available in
order to detect the end point of the reaction
 NaOH
Solution
V mL = ?

DISTILLED
WATER

DISSOLVED
KHP
(known amount)
INDICATOR
(Ph)
(1-2 drops)
Record the volume
of NaOH consumed

END POINT
Very Light Pink
Solution
 Example
In a titration experiment, a student finds
that 23.48 mL of a NaOH solution are
needed to neutralize 0.5468 g of KHP.
What is the concentration (in molarity) of
the NaOH solution?
 Example
How many grams of KHP are needed to
neutralize 18.64 mL of a 0.1004 M NaOH
solution?
 Types of Titration
Direct Titration – the analyte reacts with
the standard solution directly

Back Titration – an excess standard

solution is added and the excess is
determined by the addition of another
standard solution
 Types of Titration
• 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
 Example
In standardizing a solution of NaOH against
1.431 gram 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 c. 0.7831
b. 0.2044 d. 0.2598
 Kjeldahl Method
(Determination of Organic Nitrogen)
Step 1. Digestion
The sample is oxidized in hot, concentrated
sulfuric acid, H2SO4 and turns black. . .
Step 2. Distillation
The oxidized solution is cooled and then
treated with NaOH to liberate ammonia
gas: NH4+ + HO- NH3(g) + H2O
Step 3. Titration
Using an excess amount of HCl. . .
NH3 + HCl NH4Cl
The excess HCl is determined using a
standard NaOH solution
HCl + NaOH NaCl + H2O
Using Excess HCl – Back Titration
(a) mmol excess reagent added
- (b) mmol excess reagent reacted w/ back
titrant
(c) mmol excess reagent reacted w/
analyte
Ammonia distilled is collected in a boric acid
solution. . .
NH3 + H3BO3 NH4+ + H2BO3-1
Titrate the H3BO3-NH3 solution with standard
acid. . .
H2BO3-1 + H3O+ H3BO3 + H2O
 Using excess H3BO3 acid –
Replacement Titration

*data about boric acid – IRRELEVANT

• Percentage Protein in the sample
%protein =%N * f = 5.70 (cereals)
= 6.25 (meat products)
= 6.38 (dairy products)
 A 5.8734-gram sample beef was analyzed
for its N content and the liberated NH3 was
collected in a 50.00 mL of 0.4691 M HCl
and a 12.55 mL back titration with 0.0256
M NaOH was required. Calculate the
percentage protein in the beef sample.
a.17.32% b. 5.54% c. 34.64% d. 11.08%
A 2060 mg sample of flour was taken
through a Kjeldahl procedure and the
ammonium produced was distilled into 100
mL of 0.1006 M H3BO3 solution. If this
solution required 34.7 mL of 0.174 M HCl
for titration to methyl red end point, what is
the percentage of protein in flour? Use
5.70 for flour. Ans. 23.89%
 A 758-mg sample of full cream milk was
analyzed by the Kjeldahl method; 38.61
mL of 0.1078 M HCl were required to
titrate the liberated ammonia. Calculate
the % N in the sample.
a.12.04% b. 7.69% c. 15.59% d. 10.93%
 Double Indicator Method
 Mixture of NaOH, Na2CO3 or NaHCO3
• Hargis
 Double Indicator Method
 Mixture of NaOH, Na2CO3 or NaHCO3 - no
more than two of these three constituents
can exist in appreciable amount in any
solution
 Double Indicator Method
 Mixture of NaOH, Na2CO3 or NaHCO3
• Skoog
Na2CO3 and NaHCO3
Na2CO3 and NaOH
Double Indicator Method (Mixture of Bases)

A sample that may contain NaOH,

Na2CO3, NaHCO3, and inert matter alone
or in compatible combination is titrated
with 0.1000 N HCl with phenolphthalein as
the indicator and the solution became
colorless after the addition of 48.8 mL.
Methyl orange is then added and 14.55
mL more of the acid are needed for the
color change. If the sample weighs 2.345
grams, it contains
a. 5.842% NaHCO3 and 6.577% Na2CO3
b. 6.577% Na2CO3 and 5.842% NaOH
c. 65.77% Na2CO3 and 5.842% NaHCO3
d. 65.77% Na2CO3 and 5.842% NaOH
• A sample consisting of Na2CO3, NaHCO3
and inert matter weighs 1.179 grams. It is
titrated with 0.100 N HCl with
phenolphthalein as the indicator, and the
solution became colorless after the
addition of 24.00 mL. Another duplicate
sample was titrated with HCl using methyl
orange as indicator. It required 50.25 mL
of the acid for the color change. What is
the percentage of NaHCO3 in the
sample?
 Precipitation
• The titrant forms an insoluble product with
the analyte. An example is the titration of
chloride ion with silver nitrate solution to
form silver chloride precipitate. Again,
indicators can be used to detect the end
point, or potential of the solution can be
monitored electrically.

•
 Precipitation
• One of the oldest analytical techniques
that started in the mid-1800’s. Silver
nitrate (AgNO3) is commonly employed in
such technique. Titration with AgNO3 is
often termed as argentometric titration.
 Indicators in Precipitimetry
Formation of a colored secondary precipitate
Mohr Method (K.F. Mohr, Germany, 1865)
Direct Method for halides and cyanides
Titrant: Silver Nitrate, AgNO3
Titration Reaction: Ag+ + Cl- → AgCl(s) white
Indicator: sodium chromate, Na2CrO4
 MOHR METHOD
Indicator Reaction:
2Ag+ + CrO42- → Ag2CrO4(s) red
Primary Standard for AgNO3: NaCl
Titration is carried out between pH of 7-10.
Usually, a low concentration of chromate
is desired to detect the endpoint clearly
since a chromate ion imparts an intense
yellow color.
 MOHR METHOD
What is the molar concentration of AgNO3
solution standardized against 712 mg
primary standard NaCl (58.45 g/mol)
requiring 23.8 mL of the solution for
titration?
a. 0.5027 M b. 0.5118 M
c. 0.5263 M d. 0.5329 M
 MOHR METHOD
A 1.500-gram sample of impure AlCl3 was
dissolved in water and treated with 45.32
mL of 0.1000 M AgNO3 using Mohr
method. Determine its purity as %AlCl3
(133.33)
a. 40.28% b. 13.43%
c. 4.48% d. 27.36%
 VOLHARD METHOD
Formation of colored complexion
Volhard Method (Jacob Volhard, Germany,
1874)
Direct method for silver - Indirect method
for halides
Titrant: Potassium thiocyanate, KSCN
Titration is carried out in acidic condition to
hasten precipitation of ferric ion to its
hydrated oxide form.
 VOLHARD METHOD
Direct Titration Reaction:
Ag+ + SCN-1 → AgSCN(s) white
Indirect Titration Reaction:
Ag+(excess) + Cl-1 → AgCl(s) white
Ag+ + SCN-1 → AgSCN(s) white
Indicator: ferric alum
Indicator Reaction:
Fe+3 + SCN-1 → Fe(SCN)+2 red
Chloride in a brine solution is determined
by the volhard method. A 10.00-mL aliquot
of the solution is treated with 15.00 mL of
standard 0.1182 M AgNO3 solution. The
excess silver is titrated with standard 0.101
M KSCN solution, requiring 2.38 mL to
reach the red Fe(SCN)2+ end point.
Calculate the concentration of chloride in
the brine solution, in g/L. Ans. 5.434 g/L
 FAJANS METHOD
Formation of a colored adsorption complex
Fajans Method (K. Fajans, Poland, 1874)
Titrant: Silver nitrate, AgNO3
Titration Reaction: Ag+ + Cl-1 AgCl(s) white
Indicator: dichlorofluorescein, best for
determination of halides and cyanides
End point: color change from yellow to pink
 FAJANS METHOD
• Titration is carried out between pH of 4-7.
Dextrin is added to prevent excessive
coagulation of the AgCl precipitate.
 COMPLEXOMETRIC
The titrant is a reagent that forms a water-
soluble complex with the analyte, a metal
ion.
The titrant is often a chelating agent (a
type of complexing agent that contains two
or more groups capable of complexing with
a metal ion). The reverse titration may be
carried out also.
 COMPLEXOMETRIC
Ethylenediaminetetraacetic acid (EDTA) is
one of the most useful chelating agents
used for titration. It will react with a large
number elements , and the reactions can
be controlled by adjustment of pH.
Indicators can be used to form a highly
colored complex with the metal ion.
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 in detections, it is necessary to
adjust the pH to 7 or above so that the
blue form predominates in the absence of
a metal cation. Generally, metal
complexes with EDTA are red as H2In-1.
When an excess EDTA is added, the
solution turns blue according to the
reaction:
MIn-1 + HY-3 → HIn-2 + MY-2
wine red royal blue
 Example
What volume of 0.0305 M EDTA is needed
to titrate the Ca in 178.56 mg of CaCO3?
a.58.54 mL b. 29.27 mL
c. 43.91 mL d. 14.64 mL
Aluminum is determined by titrating with
EDTA:
Al3+ + H2Y2- → AlY- + 2H+
A 1.00 g sample requires 20.5 mL EDTA
for titration. The EDTA was standardized
by titrating 25.0 mL of a 0.100 M CaCl2
solution, requiring 30.0 mL EDTA.
Calculate the percent Al2O3 in the sample.
Ans. 8.71%
• A masking agent is a complexing agent
that reacts selectively with a component in
a solution to prevent that component from
interfering in a determination.
 A 1.509-g sample of a Pb/Cd alloy was dissolved
in acid and diluted to exactly 250.0 mL in a
volumetric flask. A 50.00-mL aliquot of the diluted
solution was brought to a pH of 10.0 with an
NH4+/NH3 buffer; the subsequent titration involved
both cations and required 28.89 mL of 0.06950 M
EDTA. A second 50.00 mL aliquot was brought to
a pH of 10.0 with an HCN/NaCN buffer, which also
served to mask the Cd2+; 11.56 mL of the EDTA
solution were needed to titrate the Pb2. Calculate
the percent Pb and Cd in the sample. Ans. 55.16%
Pb and 44.86% Cd
 Determination of Cyanide by
the Liebig Method
• The titration is carried by the drop wise
addition of AgNO3 in a solution of a
cyanide forming a soluble cyanide
complex of silver:
2CN- + 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(CN2)](s)
 Example
A 500-mg sample containing NaCN
required 23.50 mL of 0.1255 M AgNO3 to
obtain a permanent turbidity. Express the
result of this analysis as % CN-.
a. 15.34% b. 23.01%
c. 17.25% d. 30.67%
 Determination of Nickel
An ammoniacal solution of nickel is treated
with a measured excess of standard cyanide
solution and the excess of standard AgNO3
solution according to the reactions:
Addition of Excess Cyanide:
Ni(NH3)6+3 + 4CN-1 +6H2O → Ni(CN)4-1 +6NH4OH
Back Titration with Ag+:
2CN-1 + Ag+ → Ag(CN)2-1
Endpoint:
Ag(CN)2-1 + Ag+ Ag[Ag(CN)2](s)
 Example
A 750.25-mg of alloy nickel was dissolved
and treated to remove the impurities. The
ammoniacal solution was treated with 50 mL
of 0.1075 M KCN and the excess cyanide
required 2.25 mL of 0.00925 M AgNO3.
Determine %Ni in the alloy.
a. 20.86% b. 37.69%
c.10.43% d. 41.27%
 REDOX TITRATION
• Reduction-Oxidation. These “redox”
titrations involve the titration of an
oxidizing agent with a reducing agent, or
vice versa.
 OXIDANT

OXIDANT Combining Ratio, also (f)

KMnO4 (a) 5
KMnO4 (b,n) 3
K2Cr2O7 6
I2 2
MnO2 2
 REDUCTANT
REDUCTANT Combining Ratio, also (f)
Na2C2O4 (C2O4-2) 2
FeSO4 (Fe+2) 1
Na2S2O3 1
KI 1
Fe metal 2
As2O3 4
H2O2 2
Cu+ 1
What is the molarity of a KMnO4 solution
standardized against 1.356 gram Na2C2O4
(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
The percentage of MnO2 in a 500 mg
sample which after the addition of 80.00
mL of 0.1056 M FeSO4 solution required
8.50 mL of 0.0867 M K2Cr2O7 is
a. 33.52% b. 35.00%
c. 17.50% d. 67.04%
A 240-mg sample of pyrolusite was treated
with excess KI. The iodine liberated
required 46.24 mL of 0.1105 M Na2S2O3
solution. Calculate the % MnO2 in the
sample.
a. 46.27% b. 30.85%
c. 92.54% d. 76.12%
A sample of iron ore weighing 385.6 mg
was dissolved in acid and passed through
a Jones reductor. If the resulting solution
required 52.36 mL of 0.01436 M K2Cr2O7
for titration, calculate % Fe3O4 (231.55
g/mol) in the ore sample.
a. 15.05% b. 45.15%
c. 90.30% d. 67.98%
A 0.200-g sample of pyrolusite is analyzed for
manganese content as follows. Add 50.0 mL of
a 0.100 M solution of ferrous ammonium sulfate
to reduce the MnO2 to Mn+2. After reduction is
complete, the excess ferrous ion is titrated in
acid solution with 0.0200 M KMnO4, requiring
15.0 mL. Calculate the percent manganese in
the sample as Mn3O4 (only part or none of the
manganese may exist in this form, but we can
make the calculations on the assumption that it
does). Ans. 66.74%
A hydrogen peroxide solution is analyzed
by adding a slight excess of standard
KMnO4 solution and back-titrating the
unreacted KMnO4 with standard Fe+2
solution. A 0.587-g sample of the H2O2
solution is taken, 25.0 mL of 0.0215 M
KMnO4 is added, and the back-titration
requires 5.10 mL of 0.112 M Fe2+ solution.
What is the percent H2O2 in the sample?
Ans. 6.13%
A sample of a pyrolusite weighs 0.5000 g.
To this is added 0.6674 g of As2O3 and
dilute acid. After solvent action has
ceased, the excess three-valent arsenic is
titrated with 45.00 mL of 0.1000 N KMnO4.
Calculate the oxidizing power of the
pyrolusite in terms of percentage MnO2.
Ans. 78.19%