Chemical Technician Review

ANALTYICAL 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
GOLD BOOK
Applications of Analytical Chemistry
Types of Analysis
Types of Analysis
Steps in a Typical Analysis
■ Choose a Method
■ Acquire Sample
■ Prepare a Laboratory Sample
■ Prepare solution of sample
■ Eliminate Interferences
■ Measure analyte in Sample
■ Calculate Result
■ Evaluate Result
Steps in a Typical Analysis
■ Choose a Method
Technique – a chemical or physical principle that can be
used to analyze a sample.

Method – a means for analyzing a sample for a specific

analyte in a specific matrix.

Procedure – written direction outlining how to analyze a

sample.

Protocol – a set of written guidelines for analyzing a sample

specified by an agency
Steps in a Typical Analysis
■ Choose a Method
Steps in a Typical Analysis
■ Acquire Sample – representative of bulk
Steps in a Typical Analysis
■ Prepare a laboratory sample
Steps in a Typical Analysis
■ Prepare a replicate sample (WHY?!?!?!)
Steps in a Typical Analysis
■ Prepare a solution of sample
■ Choice of solvents
a. Water
b. Non oxidizing acid
c. Oxidizing acid
d. Aqua regia (1:3 HNO3-HCl)
e. Organic solvent
f. Molten flux
Steps in a Typical Analysis

■ Eliminate Interferences
a. Masking
b. Precipitation
c. Chromatography
Steps in a Typical Analysis
■ Measure analyte in sample
Steps in a Typical Analysis
■ Evaluate data
CONCENTRATION UNITS
Solution -- a mixture consisting of a solute
and a solvent

Solute -- component of a solution present in

the lesser amount

Solvent -- component of a solution present in

the greater amount

Concentration -- amount of a solute present

in a solution per standard amount of solvent
Weight/Weight Percent (w/w%)
■ This unit of concentration is often used for concentrated
solutions, typically acids and bases

grams of solute
w/w % = x 100
grams of solution
Molarity (M)
■ This unit of concentration relates the moles of solute
per liter of solution
moles of solute
Molarity =
L solution
■ Molarity is the most common concentration unit
involved in calculations dealing with volumetric
stoichiometry.
Normality (N)
■ unit of concentration expressed in equivalents per liter
solution.
■ An equivalent can defined as the number of moles of
"reactive units" in a compound

grams of solute
Normality =
equivalent weight of solute x L solution
Molality (m)

■ This unit of concentration relates the moles of solute per

kilogram of solvent.

moles of solute
Molality =
kg solvent
Parts per million (ppm)
■ It is often used to express the concentration of very dilute
solutions.
grams of solute
ppm = x 10 6

grams of solution
mg solute
ppm =
L solution
mg solute
ppm =
kg solution
Parts per billion (ppb)
grams solute
ppb = x 109
grams of solution

µg solute
ppb =
L solution
µg solute
ppb =
kg solution
Mole fraction (X) and mole percent (%X)
mol solute
Xsolute =
total moles of all components
mol solute
Xsolute% = x 100
total moles of all components
Dilution
consists of adding more solvent to a solution so that
the concentration of the solute becomes lower.
Dilution
The total number of solutes in the solution remains the
same after dilution, but the volume of the solution
becomes greater, resulting in a lower molarity, ppm,
mg/L, or % concentration.

C1V1 = C2V2
Practice Problem
Analyzing food contaminants
Convert the detection limit of the above analysis, 5 mg
kg−1 to units of:
(a) mg g−1
(b) µg g−1
(c) ppm (by mass)
Practice Problem
Compute the following:
1. Calculate the molarity of a solution that is 39.77 % H2SO4 by
mass. The density of the solution is 1.305 g/mL.
2. What is the molality of a solution that contains 128 grams of
CH3OH in 108 grams of water?
3. Calculate the weight percent of HCl in 3.20 M solution. The density
of the solution is 1.10 g/mL.
4. How many mL of a 0.300 M AgNO3 solution will it take to make
500 mL of a 0.100 M AgNO3 solution?
Practice Problem
Compute the following:
5. A saline solution, NaCl in water, is 0.92 % (m/v). How many grams
of NaCl are required to prepare 35.0 mL of this solution?
6. How many grams of sucrose must be added to 375 grams of water
to prepare a 2.75 % by mass solution of sucrose?
7. A solution contains 128 g of CH3OH and 108 g of water. What is the
mole fraction of CH3OH in the solution?
Practice Problems:
■ Prepare 1 liter of 1.00 M NaCl solution.
■ Calculate the amount of 1 M NaOH aqueous solution
needed to make 100 mL of 0.5 M NaOH aqueous solution.
■ What is the molar concentration of chloride ions in a
solution prepared by mixing 100.0 mL of 2.0 M KCl with
50.0 mL of a 1.50 M CaCl2 solution?
Classical Methods

GRAVIMETRIC METHOD VOLUMETRIC METHOD

■ deals with the measurement ■ measures the volume of

of the mass of a substance solution necessary to react
that is chemically related to completely with the analyte.
the analyte.
Gravimetric Analysis Method
1. The weight or the volume of the sample is
obtained.

2. The analyte is either physically separated

from the sample matrix or chemically altered
and its derivative is separated from the
matrix.

3. The weight of the separated analyte or its

derivative is obtained.
Gravimetric Methods that Involve
Physical Separation

1. LOD
2. LOI
3. ROI
4. Insoluble Matters
5. Particle Size analysis
Types of Gravimetric Analysis
■ EXTRACTION METHOD
■ PRECIPITATION METHOD
■ VOLATILIZATION METHOD
Extraction Method

■ The analyte in the sample is obtained using an appropriate

solvent. After the evaporation of solvent, the residue is
chemically related to the analyte.
Practice Problem
The method for fat determination of Whey Protein Concentrate by
extraction is indicated below:
Sample Preparation
A 5g sample will be weighed and put in a Fat extraction
flask. Dissolve the sample with approximate 20 mL of warm
water and mix thoroughly. Add ammonia and
phenolphthalein.

Condition the fat dish at constant temperature of 1500C for

30 minutes to 1 hour. Cool to room temperature and weight
the fat dish to constant reading
Extraction
Add 10 mL of reagent alcohol, mix well. Add 25 mL of diethyl ether. Mix
the flask and shake in the vortex, allow the organic solution to settle.
Pour the organic solution in the fat dish. Repeat the extraction for 3 times
with 25mL diethyl ether.
Put the fat dish in the oven to dry. Make sure the oven is covered. Once
organic solvent is completely evaporated, cool the fat dish and weigh
again the fat dish.
Based on the data obtained, compute the %Fat in the WPC sample
Mass of Fat Dish, initial 100.0596g

Mass of Fat Dish, final 100.2456g

pH of warm water 7.012

Density of water 1.001 g/mL
Sample weight of WPC 5.1234g
Precipitation Method
■ The analyte is converted into a sparingly soluble solid,
filtered, washed, dried or ignited and weighed.
■ Governed by Solubility Guidelines.
Solubility Guidelines
Practice Problem
Determine if the following are soluble in aqueous
solution or not
1. AgNO3 7. SrSO4
2. BaSO4 8. PbSO4
3. NaCl 9. Mg(CH3CO2)2
4. KNO3 10. AgBr
5. Ca(OH)2 11. Fe(OH)3
6. KI 12. MgI2
Solubility Equilibria
■ Equilibrium between a solid and its ions in solution
■ Ksp is the solubility product constant
■ Solids that classified as “insoluble” typically have
small Ksp’s
Practice Problem:
Write the solubility product constant expression for the
following:

1. Silver Phosphate
2. Cadmium Hydroxide
3. Silver Chromate
4. Silver Sulfide
5. Copper (I) Chloride
Practice Problem:
Using the solubility products for each of the following
salts, calculate their molar solubility in g/L

1. CuCl ; Ksp = 1.9 x 10-7

2. Cd(IO3)2; Ksp = 2.3 x 10-8
3. BaSO4; Ksp = 1.1 x 10-10
Practice Problem:
Will mixture precipitate if equal volumes of 3.0 x 10-3M Ba2+
and 2.0x10-3M CO32- is mixed? Ksp of BaCO3 = 5.0 x10-9
Mechanism of Precipitation
NUCLEATION
■ Very few atoms, ions, or
molecules joined together to
form a stable solid particle.
■ Prevails at HIGH Relative
Saturation.
■ Result in the formation of
LARGE NUMBER of SMALL
PARTICLES
PARTICLE GROWTH
■ Prevails at LOW Relative
Saturation.
■ Results in the formation of
SMALL NUMBER of LARGE
PARTICLES
Von Weirmann Ratio
■ Measures the Relative Saturation
𝑸−𝑺
𝑹𝒆𝒍𝒂𝒕𝒊𝒗𝒆 𝑺𝒂𝒕𝒖𝒓𝒂𝒕𝒊𝒐𝒏 =
𝑺
■ Where: Q concentration of the solute
S solubility of the precipitate

■ Large RS results in formation of COLLOIDAL PRECIPITATE

■ Small RS results in formation of CRYSTALLINE SOLID
Ideal Properties of Precipitate

■ Can easily be filtered and washed.

■ Very slow solubility to avoid losses during filtration.
■ Inert towards components of the atmosphere.
■ Has known composition after heat treatment.

Want to

Convert to
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
Steps in
Gravimetric
Analysis
Step 1
Sample dried, triplicate
portions weighed
Steps in
Gravimetric
Analysis
Step 2
Preparation of Solution
Steps in
Gravimetric
Analysis
Step 3
Precipitation
Steps in
Gravimetric
Analysis
Step 4
Digestion
Steps in
Gravimetric
Analysis
Step 5
Filtration
Steps in
Gravimetric
Analysis
Step 6
Washing
Steps in
Gravimetric
Analysis
Step 7
Drying or Igniting
Steps in
Gravimetric
Analysis
Step 8
Weighing
Steps in
Gravimetric
Analysis
Step 9
Calculation
Calculation in Gravimetric Analysis

𝒘𝒕. 𝒐𝒇 𝒑𝒓𝒆𝒄𝒊𝒑𝒊𝒕𝒂𝒕𝒆 𝒙 𝑮𝑭
% 𝒂𝒏𝒂𝒍𝒚𝒕𝒆 𝒊𝒏 𝒕𝒉𝒆 𝒔𝒂𝒎𝒑𝒍𝒆 = 𝒙 𝟏𝟎𝟎%
𝒘𝒕. 𝒐𝒇 𝒔𝒂𝒎𝒑𝒍𝒆

𝒎𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒂𝒏𝒂𝒍𝒚𝒕𝒆 𝑿 𝒂𝒏𝒂𝒍𝒚𝒕𝒆

𝑮𝑭 = 𝒙
𝒎𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 𝒐𝒇 𝒑𝒓𝒆𝒄𝒊𝒑𝒊𝒕𝒂𝒕𝒆 𝒀 𝒑𝒓𝒆𝒄𝒊𝒑𝒊𝒕𝒂𝒕𝒆
Practice Problem: Indicate the Gravimetric
Factor for the following:

Substance Sought Substance Weighed

Br AgBr
FeS2 BaSO4
Bi Bi2O3
UO2 U3O8
CoSiF6 . 6H2O H2 O
F CeF3
Practice Problem: Indicate the Gravimetric
Factor for the following:

Analyte Precipitate
P Ag3PO4
K2HPO4 Ag3PO4
Bi2S3 BaSO4
Al Al2S3
Br AgBr
CaMg(CO3)2 CO2
Practice Problem
644 mg of a sample contains Mg ( AW= 24 ) has been
dissolved in water . The magnesium content of the sample is
precipitated as MgNH4PO4 .6H2O and ignited and weighed as
Mg2P2O7 ( MW = 222 ) . If this weight is 290 mg , calculate the
percentage of Mg in the sample?
Practice Problem
0.4 g of an impure reagent of KCl ( MW = 74.5 ) is dissolved
and an excess of AgNO3 solution is added . As a result of this
0.7332 g of AgCl ( MW = 143.5 ) precipitate is formed .
Calculate the percentage purity of KCl reagent?
Acid and Bases

BRONSTED-
LEWIS ARRHENIUS
LOWRY
Produces
Electron-pair
ACID Proton donor *H3O+ in
acceptor
solution
Produces
Electron-pair Proton
BASE **HO– in
donor acceptor
solution
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 D H3O+(aq) + F–(aq)
NH3 + H2O D NH4+(aq) + HO–(aq)
Strength of Acids and Bases
■ Strong Acids. HCl, HBr, HI, HClO4, HNO3, H2SO4 (only on the
first ionization)
■ Strong Bases. NaOH, KOH, Ba(OH)2

■ Weak Acids. HF, HCN, H2SO3, H3PO4 and organic acids

■ Weak Bases. Ammonia and derivatives
Practice Problems:
Which of the following are conjugate acid-base pairs?
a. HCl, NaOH
b. H2O, OH
c. H2SO4, SO42-
d. H2SO3, HSO3-
e. HClO4, ClO3-
f. H3C-NH2, H3C-NH3+
Autoprotolysis of Water
H2O + H2O D H3O+(aq) + HO–(aq)
KW = 1 x 10–14 at 25°C
At 25°C… pH + pOH = 14

Temperature, 0C Kw

0 0.114 x 10-14
25 1.01 x 10-14
50 5.47 x 10-14
75 19.9 x 10-14
100 49 x 10-14
 Calculation of pH
■ pX = p-function of [X] concentration
■ pH = p-function of [H+] concentration
Calculation of pH
 Calculation of pH
■ Strong Acids: pH = - log [nHacidCacid ]

■ Strong Bases: [
pH = 14 + log n HO - C base ]
■ Weak Acids: pH = - 2 log [K a Cacid ]
1 Cacid
Ka
>> 1000

■ Weak Bases: pH = 14 + 1 2 log [K b Cbase ] C ba se

Ka
>> 1000
Hydrolysis of Salts
■ Acid and base reacts to form salt and water. As a general
rule, salts coming from weak acids or weak bases hydrolyze
in water, that is, only the strong conjugate hydrolyzes in
water.

■ An acidic salt is formed from the reaction of a strong acid

and weak base.
■ A basic salt results from the reaction of a strong base and a
weak acid.
■ Thus, a neutral salt is a product of the reaction between a
strong acid and a strong base.
Hydrolysis Reaction of Salts

■ Acidic Salt : NH4Cl KW

NH4+ + H2O D H3O+ + NH3 KH =
K NH3

■ Basic Salt : NaCN KW

CN– + H2O D HO– + HCN KH =
K HCN
pH of Salts
é Csalt ù
■ Acidic Salt : pH = 7 - 2 log ê
1
ú
ë K b û

é Csalt ù
pH = 7 + 2 log ê
1
ú
■ Basic Salt : ë K a û

Csalt
When: >>> 1000
KH
Practice Problem
Determine the pH of the following solutions:
a. 0.06 M HCl
b. 0.02 M H2SO4
c. 0.5 M NaOH
d. 0.1 M Hypochlorous acid, K = 3.5 x 10-8
e. 5 M aqueous ammonia, Kb = 1.8 x 10-5
f. 0.5 M NaHCO3, Ka1 of Carbonic acid is 4.3 x 10-7
Buffer Solutions
■ Solutions that contains weak acid or weak base and its
conjugate salt.
■ These solutions tend to resist changes in pH.
■ Henderson Hasslebach Equation:

[acidic component]
pH = pK a - log
[basic component]
 Practice Problem
A buffer solution was made by dissolving 10.0 grams of
sodium acetate in 200.0 mL of 1.00 M acetic acid. Assuming
the change in volume when the sodium acetate is not
significant, estimate the pH of the acetic acid/sodium acetate
buffer solution. The Ka for acetic acid is 1.7 x 10-5
Practice Problem
A 1 L solution containing 0.100 moles of HC2H3O2 and 0.100
moles of C2H3O2 forms a buffer solution, pH = 4.74. What is
the pH after 0.020 moles of NaOH are added?
Practice Problem
Calculate the pH of the resulting solution when 20 mL of
0.100 M HCl was titrated with the following volumes of 0.100
M NaOH.
1. 0 mL of 0.100 M NaOH added
2. 10 mL of 0.100 M NaOH added
3. 20 mL of 0.100 M NaOH added
4. 20.02 mL of 0.100 M NaOH added
Practice Problem
Calculate the pH of the resulting solution when 50 mL of
0.100 M NH3 was titrated with the following volumes of 0.100
M HCl. (Kb, NH3 = 1.75 x 10–5)
1. 5 mL of 0.100 M HCl added
2. 50 mL of 0.100 M HCl added
3. 55 mL of 0.100 M HCl added
Volumetric Methods of Analysis
Volumetric Methods of Analysis
■ Standard Solution – solution of
known concentration

■ Standardization – process of
determining the concentration of
an unknown solution

■ Primary Standard – a substance

of high purity used for
standardization
Characteristics of a Good Primary
Standard
■ High purity and high equivalent weight
■ Stable towards air, high temperature and humidity
■ Soluble in water
Conditions for a Volumetric Analysis

■ The reaction must be rapid and can be represented by a

simple balanced equation

■ The reaction must be complete and no side reaction occurs

■ An appropriate indicator must be available in order to detect

the end point of the reaction
Types of Titration
■ Direct Titration – type of titration where the analyte reacts
with the standard solution directly

■ Back Titration – type of titration where an excess standard

solution is added and the excess is determined by the
addition of another standard solution

■ Replacement Titration – type of titration where the analyte

is converted to a product chemically related to it and the
product of such reaction is titrated with a standard solution
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
Practice Problem
Calculate the molarity of NaOH solution if 18.25 mL was used
to titrate 0.4815 gram of primary standard KHP
Practice Problem
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 5.12 mL of acid (1mL = 3.1 mg Na2O). What is the
normality of the NaOH solution?
Indicators for Acid-Base Titration
Bromocresol Green
■ pH Transition Range: 3.8 – 5.4
■ changes from yellow to blue
■ pKa = 4.66

Bromothymol Blue
■ pH Transition Range: 6.2 – 7.6
■ changes from yellow to blue
■ pKa = 7.10
Indicators for Acid-Base Titration
Methyl Red
■ pH Transition Range: 4.2 – 6.3
■ changes from red to yellow
■ pKa = 5.00

Methyl Orange
■ pH Transition Range: 3.1 – 4.4
■ changes from orange to yellow
■ pKa = 3.46
Indicators for Acid-Base Titration

■ Phenolphthalein
■ pH Transition Range: 8.3 – 10.0
■ changes from colorless to pink
■ pKa = 9.00
 For the ff titrations, state what indicator
is suitable for them:
Titration pH @ Indicator
Equivalence
Point
Strong Acid with Strong Base

Strong Base with Strong Acid

Weak Acid with Strong Base

Weak Base with Strong Acid

Combining Ratios, f
■ N=fM
■ Useful in stoichiometric calculations especially in
REDOX titrations.
Acids
Acid Combining Ratio
HnM n
R(COOH)n n
HSO3NH2 1
KH(IO3)2 1
Bases
Base Combining Ratio
M(OH)n n
NH3 1
R(NH2)n n
HgO 2
MCO3 2
THAM 1
Kjeldahl Method
■ Determination of Organic Nitrogen

Steps
1. Digestion
2. Distillation
3. Titration
Digestion
■ Sample is oxidized in hot concentrated sulfuric acid
To convert C and H to CO2 and H2O
To convert amides and amines to NH4+
To convert azo, azoxy, nitro group to N or its oxide

Catalyts
K2SO4 increase boiling point of the acid
HgO increase rate of reaction
H2SeO3 best catalyst
 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

Distillation
■ 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.
Titration
1. Using an excess amount of HCl…
NH3 + HCl ® NH4Cl

The excess HCl is determined using a standard NaOH solution

HCl + NaOH ® NaCl + H2O
Titration
2. Ammonia distilled is collected in a boric acid solution…
NH3 + H3BO3 ® NH4+ + H2BO3-2

Titrate the H3BO3–NH3 solution with standard acid…

H2BO3-2 + H3O+ ® H3BO3 + H2O
Percentage Protein in the Sample
% protein = % N * f

f = 5.70 (cereals)
6.25 (meat products)
6.38 (dairy products)
Practice Problem
A 0.7535g sample of wheat flour was analysed by the Kjeldahl
method. The ammonia (NH3) formed by addition of
concentrated base after digestion with H2SO4 was distilled into
25.00mL of 0.06211M HCl. The excess HCl was then back-
titrated with 9.95 mL of 0.03512 M NaOH. Calculate the mass
of nitrogen in the sample in grams. Given that proteins are
5.70% nitrogen by mass, calculate the percentage protein in
the flour.
Practice Problem
Calculate the percentage of acetic acid (60 g/mol) in a sample
of vinegar from the following data:
Sample 15.00 grams
Vol NaOH used 43.00 mL
Vol H2SO4 (0.600N) 2.50 mL
1.00 mL = 0.0315 g H2C2O4 . 2H2O (126 g/mol)
Precipitation Titration
■ 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.
Precipitation Titration
Method Mohr Volhard Fajans
Introduced by K.F. Mohr, Germany, 1865 Jacob Volhard, Germany, K. Fajans, Poland, 1874
1874
Reaction formation of a colored formation of a colored formation of a colored
secondary precipitate complexion adsorption complex
Purpose Direct method for halides Direct method for silver Direct method for halides
and cyanides Indirect method for Halides

Titrant Silver nitrate, AgNO3 Potassium thiocyanate, Silver nitrate, AgNO3

KSCN
Indicator sodium chromate, Na2CrO4 ferric alum dichlorofluorescein, best for
determination of halides
and cyanides
Indicator 2Ag+ + CrO42- ® Fe+3 + SCN-1 ® Fe(SCN)2 color change from yellow to
reaction Ag2CrO4(s) red pink
red
Primary for AgNO3: NaCl for AgNO3: NaCl
standard
Precipitimetry
Precipitant Combining Ratio
AgNO3 1
KSCN 1
Halide 1
Practice Problem
A 106.4 mg of sample of a pesticide was decomposed by the
action of sodium biphenyl in toluene. The liberated chloride ion
was titrated with 23.28 mL of 0.03337 M AgNO3 using an
adsorption indicator. Express the result of this analysis in
percent aldrin, C12H8Cl6 (364.92 g/mol)
Practice Problem
A mixture of LiCl (42.39 g/mol) and BaBr2 (297.22 g/mol)
weighing 600 mg is treated 45.15 mL of 0.2017M AgNO3 and
the excess is found to require 25.00 mL of 0.100M KSCN for
back titration, using ferric alum as indicator. What is the
percentage of BaBr2 in the sample?
Practice Problem
A 3.095 g sample containing KCl, KClO4 (138.55 g/mol) and
inert materials was dissolved in sufficient water to give 250
mL solution. A 50.00 mL aliquot required 13.97 mL of
0.08551M AgNO3 to titrate the Cl–. A second 50.00mL was
treated with V2(SO4)3 to reduce ClO4– to Cl–:
ClO4– + 4V2(SO4)3 + 4H2O ® Cl– + 12SO4–2 + 8VO2+ + 8H+
Titration of the reduced sample required 40.12 mL of the
AgNO3 solution. Calculate the percentage of ClO4– (99.45 g/mol)
in the sample.
Titration with 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 dihydrate
are available. Solutions
of EDTA combines with
any metal ions in a 1:1
ratio.
Titration with EDTA
■ The indicator used for titration is the Eriochrome Black Tâ.

■ 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.
Titration with EDTA
■ Generally, metal complexes with EDTA are red and indicated
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
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 displace 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.
Chelating Agent
Chelating Agent Combining Ratio
EDTA 1
Practice Problem
The zinc in a 755.6–mg sample of a foot powder was titrated
with 21.27 mL of 0.01645 M EDTA. Calculate the % Zn (65.37
g/
mol) in the sample.
Practice Problem
The sulfate in a 247.1 mg sample was precipitated as BaSO4
by addition of 25.00 mL of 0.03992 M BaCl2. The precipitate
was removed by filtration and the remaining BaCl2 consumed
36.09 mL of 0.02017 M EDTA for titration to the Calmagite
endpoint. Calculate the % SO3 in the sample.
Practice Problem
A 328.4 mg sample of brass (containing lead, zinc, copper and
tin) was dissolved in nitric acid. The sparingly soluble SnO2 ×
4H2O was removed by filtration and the combined filtrate and
washings were then diluted to 500.0 mL. A 10.00 mL aliquot
was suitably buffered; titration of the lead, zinc and copper in
this aliquot required 37.56 mL of 0.002500 M EDTA. The
copper in a 25.00 mL aliquot was masked with thiosulfate; the
lead and zinc were then titrated with 27.67 mL of the EDTA
solution. Cyanide ion was used to mask the copper and zinc in
a 100-mL aliquot; 10.80 mL of EDTA solution was needed to
titrate the lead ion.
Redox (Oxidation – Reduction)
Reactions
oxidation-reduction reactions are family of reactions that are concerned
with the transfer of electrons between species.
Redox (Oxidation – Reduction)
Reactions
■ The compound that loses an electron is said to be oxidized,
■ the one that gains an electron is said to be reduced.

■ A compound that is oxidized is referred to as a reducing agent,

■ a compound that is reduced is referred to as the oxidizing agent.
 Rules in Assigning Oxidation Numbers
■ 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 its charge.
■ An atom in its free or elemental form, the oxidation number is equal to zero.
■ For any monoatomic ion, the oxidation number equals the charge.
■ Metals have positive oxidation numbers like 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 (–1) and superoxides (–½)
■ The oxidation number of hydrogen is +1 except in hydrides (–1) Fluorine has oxidation number equal to –1.
The other halogens have an oxidation number equal to –1 except when combined with oxygen, they have
positive oxidation numbers
■ 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 its charge.
Practice Problem
Determine the oxidation number of the underlined elements in
each of the following compounds:
a. H2CO3
b. N2
c. Zn(OH)42-
d. NO2-
e. LiH
f. Fe3O4
Practice Problem
Identify the species being oxidized and reduced in each of the
following reactions:
a. Cr+ + Sn4+ → Cr3+ + Sn2+
b. 3 Hg2+ + 2 Fe (s) → 3 Hg2 + 2 Fe3+
c. 2 As (s) + 3 Cl2 (g) → 2 AsCl3
Practice Problem
Would you use an oxidizing agent or reducing agent in order for
the following reactions to occur?
a. ClO3- → ClO2
b. SO42- → S2-
c. Mn2+ → MnO2
d. Zn → ZnCl2
Guidelines for balancing Redox reaction equations:
— Identify the elements that are oxidized and reduced by examining
their Oxidation states
— Write the oxidation and reduction half-reactions and Balance Half
Reaction Equations.
— In an acidic and basic solution, use H+ and H2O to balance the charges and other atoms.
— In a basic solution, neutralize H+ with OH-. .
Remember: What you add to the left side of the equation should also be added to the other side.
— Add the two half-reactions algebraically such that the electrons in
the two half-reaction equations cancel completely. Cancel other
species such as H+, OH-, and H2O common to the two sides, if
necessary.
— Check your equation and make certain that numbers of atoms and
charge are equal on both sides.
Practice Problem
Balance the following redox reactions:
1. H2C2O4 + MnO4- → CO2 + Mn2+ (acidic)
2. Bi(OH)3 + SnO22- → SnO32- + Bi (basic)
Oxidation–Reduction Titration
Permanganate Process (KMnO4)
■ In acidic medium…
MnO4–1 + 8H+ + 5e– D Mn2+ + 4H2O
■ In basic/neutral medium…
MnO4–1 + 2H2O + 3e– D MnO2 + 4HO–

■ Standardization of KMnO4 solution

■ Indicator: self indicating
Permanganate Process
Primary Standards
■ Against Na2C2O4
Rxn: C2O4-2 D 2CO2 + 2e–
■ Against As2O3
Rxn: As3+ + 4H2O D H3AsO4 + 5H+ + 2e–
■ Against Ferrous solutions
Rxn: Fe2+ D Fe3+ + e–
■ Against pure Fe
Rxn: Fe D Fe2+ + 2e–
Applications of Permanganimetric
Titrations
■ Fe2+ D Fe3+ + e–
■ Sn2+ D Sn4+ + 2e–
■ NO2– D NO3– + 2e–
■ H2O2 D O2 + 2e–
■ Mo3+ D MoO42– + 3e–
■ Ti3+ D TiO2+ + e–
Dichromate Process
■ Rxn: Cr2O72- + 6e– D 2Cr3+

Indicator: sodium diphenylbenzidine sulfonate

barium diphenylamine sulfonate
Endpoint: change of color from green to violet
Applications of Dichromate Process

■ Fe2 D Fe3+ + e–
■ U4+ D UO22+ + 2e–
■ Cu+ D Cu+2 + e–
Iodometric Titration (Indirect Titration
with Iodine)
Rxn: I2 + 2e– D 2I–
■ Titrant: Na2S2O3
■ Indicator: starch
■ Primary Standard:
K2Cr2O7 (Cr2O7-2 + 6I– D 2Cr3+ + 3I2)
■ Titration Reaction:
2S2O3-2 + I2 D S4O6-2 + 2I–
Iodimetric Titration (Direct Titration with
Iodine)
■ Titrant: I2 in KI (I2(s) + I– D I3–)
■ Indicator: Starch
■ Titrant Reaction: I3– + 2e– D 3I–
Reductors
■ When metal concerned exist in two
oxidation states, they are pre-
reduced before the treatment.

Jones Reductor
■ Composed of a vertical tube filled
with amalgamated zinc
Walden Reductor
■ Metallic silver is being used
Redox
Oxidants Combining Ratio
KMnO4 Acidic 5
Neutral/Basic 3
K2Cr2O7 6
I2 2
Ce4+ 1
MnO2 2
KBrO3 6
Redox
Reductants Combining Ratio
FeSO4 (Fe2+) 1
Fe metal 2
As2O3 4
Na2C2O4 2
I3 - 2
Na2S2O3 1
Practice Problem
What is the molarity of a KMnO4 solution standardized against
0.0127 gram Na2C2O4 (134 g/mol) requiring 37.6 mL of the
solution in acidic medium?
Practice Problem
A sample of iron ore weighing 214.6 mg was dissolved in acid
and passed through a Jones reductor. The resulting solution
21.27 mL of 0.01436 M K2Cr2O7 for titration to the
diphenylamine sulfonic acid endpoint. Calculate % Fe3O4
(231.55 g/mol) in the ore sample.
Practice Problem
A sample of pyrolusite weighs 0.2400 gram and contains
92.50% MnO2. The iodine liberated from KI by the MnO2 is
sufficient to react with 46.24 mL of Na2S2O3 solution. What is
the molarity of the thiosulfate solution?