Analytical Chemistry

Scope
Solution Compositions
Acids and Bases
Gravimetric Analysis
Titrimetric Methods
Redox Reactions

Solutions

Solution Compositions

Units of Concentration

*Formality identical to molarity that is used for

solutions of ionic salts that do not exist as
molecule in solid or in solution.

Units of Concentration

Units of Concentration
Normality = f x Molarity
f:
for acids: no. of replaceable H+
for bases: no. of replaceable OHfor salts: net charge of an ion
for redox reactants: no. of electrons lost or gain

Units of Concentration
Mole fraction

Mole percent

Units of Concentration

Units of Concentration

1 ppm = 1 mg/L
1 ppb = 1 g/L
1 ppt = 1 ng/L

Example 1
What is the molarity of water at 40C?

Ans. 55.5 M

Example 2
The concentration of glucose in normal
spinal fluid is 75 mg/100 g. What is
the molal concentration?

Ans. 4.2 x 10-3 M

Example 3
A 34.00%-by-mass solution of H3PO4 in
water has a density of 1.209 g/cm3 at
200C. What is the molarity and
molality of this solution?

Ans: 4.19 M, 5.26 m

Example 4
The hardness of water (hardness count) is
usually expressed as parts per million
(by mass of CaCO3), which is equivalent
to milligrams of CaCO3 per liter of water.
What is the molar concentration of Ca2+
ions in a water sample with hardness
count of 175?
Ans. 1.75 x 10-3 M.

Acids and Bases

Arrhenius Theory
Bronsted-Lowry Theory
Lewis Theory

Acids and Bases

Arrhenius Theory of Acid and Bases:

An acid produces H+ and

a base produces OHin aqueous solutions.

Acids and Bases

Brnsted-Lowry Theory of Acid and Bases:

An acid is a proton donor, and

a base is a proton acceptor.

Acids and Bases

Brnsted-Lowry Theory of Acid and Bases:
*For every acid, there is a conjugate base and for every
base, there is a conjugate acid.

Acids and Bases

Brnsted-Lowry Theory of Acid and Bases:
Role of Solvent:
- Makes to act the substance to behave as an acid or base.

Amphoteric refer to a substance that can act as acid or base.

Acids and Bases

Brnsted-Lowry Theory of Acid and Bases:
Classification of Solvents:

1.
2.
3.
4.

Solvent
Protophilic (proton seeking)
Protegenic (proton generating)
Amphiprotic (both 1 & 2)
*Aprotic

Example
H2O, NH3
H2O,HOAc
H2O, EtOH
C6H6, CCl4

*independent of proton seeking and generating.

Acids and Bases

Lewis Theory of Acids and Bases
A Lewis acid is a species (an atom, ion or
molecule) that is an electron-pair acceptor.

A Lewis base is a species that is an electronpair donor.

Acids and Bases

Lewis Theory of Acids and Bases

Ligands molecules or ions that behave as

Lewis bases.

Acids and Bases

Lewis Theory of Acids and Bases

Strengths of Acids and Bases

STRONG

WEAK

Acids

Bases

Acids

Bases

HCl

LiOH

HF

NH3

HI

NaOH

HCN

Organic bases

HBr

KOH

H3PO4

Amines

HClO4

RbOH

H3BO3

HClO3

CsOH

H2CO3

HNO3

Mg(OH)2

H2SO3

HBrO3

Ca(OH)2

Carboxylic acids

*H2SO4

Ba(OH)2

Polyprotic acids

Strengths of Acids and Bases

*HClO4 , HBr, H2SO4, HCl and HNO3 are of

same strengths in water; but in glacial acetic
acid, their strengths are:
HClO4 > HBr > H2SO4 > HCl > HNO3
This phenomenon is known as levelling effect
of water.

p-Functions
p-Functions are a method of expressing
concentrations, especially very large or very small
values.
pH commonly known p-Function
- defined as negative logarithm of hydronium ion
concentration.
pH = - log[H3O+]

* pH can be less than 0 or greater than 14.

pH Calculations

pH Calculations
Other values of Kw...

pH Calculations
For strong acids, wherein water contributes to
H3O+ in solution;

I:
:
F:

H2O + H2O
55.5 M
55.5 M
-X
-X
55.5-X
55.5-X

H3O+ +
MSA
+X
MSA+ X

OH0
+X
X

pH Calculations
K w = [H3 O+ ] OH = 1 x 1014
14
K w = [MSA+ X] X = 1 x 10
X 2 + MSA X 1 x 1014 = 0
Then,
pOH = -log [X]
pH = 14 + log [X]

pH Calculations
For strong bases, wherein water contributes to
OH- in solution;

I:
:
F:

H2O + H2O
55.5 M
55.5 M
-X
-X
55.5-X
55.5-X

H3O+
0
+X
X

OHMSB
+X
MSB + X

pH Calculations

Example 5
What is the pH of 1 x 10 -8 HNO3 solution?

Ans. 6.98

Example 6
What is the pH of pure water at 50 0C?

Ans. 6.63

Example 7
How much water is to be added to 12 M HCl
in order to prepare 1600 mL solution of pH
= 1.50?

Ans. 1595.784 L

Example 8
Calcium hydroxide solution has a
concentration of 0.05 M. Calculate its
pH.

Ans. 13

Example 9
A solution is prepared by adding 125.0 mL of
0.025 M HNO3 to 150.0 mL of 0.020 M
HCl. Determine the concentration of pOH
of the resulting mixture.

Ans. 12.35

pH Calculations
For weak acids:

I:
:
F:

MWB
55.5 M
-X
-X
MWB X 55.5-X

0
+X
X

0
+X
X

pH Calculations
For weak acids:

pH Calculations
For weak bases:

I:
:
F:

MWB
55.5 M
-X
-X
MWB - X 55.5-X

0
+X
X

0
+X
X

pH Calculations
For weak bases:

pH Calculations
For weak acids and
acidic salt:
X 2 + Kx MK = 0
* K = Ka for Weak
acid
K = Kw/Kb for
Acidic salt
pH = -log [X]

For weak bases and

basic salt:
X 2 + Kx MK = 0
* K = Ka for Weak base
K = Kw/Kafor Basic
salt

pH = 14 + log [X]

pH Calculations
Percent Ionization
equilibrium concentration of ionized acid
initial concentration of acid

X 100

Example 10
Calculate the pH of a 0.010 M solution
of iodic acid (HIO3, Ka = 0.17).

Ans. 2.02

Example 11
What mass of benzoic acid, HC7H5O2 is
needed to dissolve in 350.0 mL of
water to produce a solution having a
pH of 2.85? Ka = 6.3 x 10-5.

Ans. 1.4 g

Example 12
Caproic acid, HC6H11O2, found in small
amounts in coconut and palm oils, is
used in making artificial flavors. A
saturated aqueous solution of the
acid contains 11 g/L and has pH =
2.94. Calculate the Ka for the acid.
Ans. 1.4 x 10-5

Example 13
What is the percent ionization of
propionic acid in a solution that is
0.45 M HC3H5O2? pKa = 4.89.

Ans. 0.53%

Example 14
What is the % ionization in 0.10 M NH3?

Ans. 1.33 %

Common Ion Effect

Common Ion Effect
Shift in equilibrium when one or more ions that
are part of the equilibrium are introduced from
an outside source.
reduction in the dissociation of the weak
electrolyte

Example 15
Calculate the [H3O+] in a 0.0045 M benzoic
acid (HC7H5O2) solution. Ka = 6.3 x 10-5.
Calculate the [H3O+] in a 0.0045 M benzoic
acid a solution which contains 0.001 M
NaC7H5O2.

Hydrolysis Reaction of Salts

Acidic Salt: NH4Cl
NH4+ + H2O
KH = KW /KNH3

Basic Salt: NaCN

CN- + H2O
KH = KW /KHCN

H3O+ + NH3

HO- + HCN

pH of Salts
pH of Salts
Acidic Salt: pH = 7 log[Csalt/Kb]
when Csalt/KH >>> 1000
Basic Salt: pH = 7 + log[Csalt/Ka]
when Csalt/KH >>> 1000

Example 16
What is the pH of an aqueous solution that
is 0.089 M NaOCl? pKa = 7.54

Ans. 10.24

Example 17
What weight (in grams) of NH4Cl is needed
to be dissolved in 200 mL of water to
provide a solution having a pH of 4.50?
Kb = 1.8 x 10-5

Ans. 19.2 g

Buffered Solutions
A buffered solution is one that resists a change in
pH when either hydroxide ions or protons are
added.

Buffered Solutions
Buffer Capacity
- refers to the amount of acid or base that a
buffer can neutralize before its pH changes.

Buffered Solutions

Buffered Solutions
pH of a Buffered Solution

or

Example 18
A buffered solution contains 0.25 M NH3
and 0.40 M NH4Cl. Calculate the pH.

Ans. 9.05

Example 19
How many mL of pure formic acid (s.g =
1.22) must be mixed to 325 mL of 0.0664
M NaOH solution to obtain a buffer
solution of pH 3.25? Ka = 1.7 x 10-4

Ans. 3.51 mL

Example 20
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

Ans. 9.02

Acid-Base Indicators
Acid-Base Indicator is a substance whose color depends
on the pH of the solution to which it is added.

Two forms of acid-base indicators:

1. Weak acid (represented by HIn.
2. Conjugate base (represented by In-.

HIn
+
acid color

H2O

H3O+ +

Inbase color

Acid-Base Indicators
HIn
+
acid color

H2O

H3O+ +

Inbase color

Acid-Base Indicators
Name

pH range

pKa

Color change

Thymolphthalein

1.70

1.2-2.8

R-Y

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-Purple

Thymol Blue

8.96

8.0-9.6

Y-B

Phenolphthalein

9.00

8.3-10.0

C-Pink

Thymolphthalein

10.0

9.4-10.6

C-B

Example 21
A particular indicator has a color red and a
color blue in its acid and base form
respectively. If this indicator has a Ka = 3
x 10-5 , by how much must the pH
change in order to change the indicator
from 75% red to 75% blue?
Ans. 0.95

Gravimetry

Gravimetry
Gravimetric Methods:
- are methods that depend upon measuring the
mass (i.e., gravity).

Gravimetry
Three types of gravimetric methods:
1) Volatilization Methods
2) Extraction Methods
3) Precipitation Methods

Gravimetry
Three types of gravimetric methods:
Volatilization Method
The analyte are volatilized at suitable temperature.
The volatilized species are collected.
The collected samples are weighed directly or weighed by difference.

Gravimetry
Three types of gravimetric methods:
Extraction Method
The analyte to be determined is extracted w/ appropriate
solvent.

The mass of the purified extract is related to

the amount of the analyte.

Gravimetry
Three types of gravimetric methods:
Precipitation Method
A sample is dissolved in an appropriate solvent.
The analyte is precipitated by a reagent that yields a sparingly
soluble product.
The precipitate is converted to a product of known composition by heat treatment.

Gravimetric Methods
Basic calculations:
Percentage of analyte in a sample is calculated
using a Gravimetric factor GF.

Gravimetric Methods
Basic calculations:

Example 22
A sample containing NaBr and KBr only
weighs 312.54 grams. The sample
was dissolved in water and treated
with excess AgNO3. The precipitate
formed was found to weigh 532.55
grams. Calculate % KBr in the
sample.
Ans. 49%

Example 23
A 0.1005 gram sample of an ionic
compound containing chloride ions
and an unknown metal is dissolved in
water and treated with an excess of
AgNO3. If 0.0445 g of AgCl
precipitate forms, what is the % by
mass of Cl- in the original compound?
Ans. 10.95%

Example 24
What weight of Mn ore should be taken
so that the percentage of MnO2 in the
ore would be twice the mass of
Mn3O4
precipitate
obtained
in
milligram?
Ans. 57.0 mg

Example 25
A 0.8715 gram sample containing chloride
and iodide ions gave a silver halide
precipitate which weighs 1.8561 grams.
This was heated with Cl2 gas to convert
silver iodide precipitate to AgCl. The
resulting precipitate weighs 1.7223 gram.
Calculate the percentage of chloride in
the sample.
Ans. 43%

Titrimetric Methods

Titrimetric Methods
Titrimetric methods are analytical procedures in
which the amount of an analyte is determined
from the amount of a standard reagent required
to react completley with the analyte.

Titrimetric Methods
Types:
1.
2.
3.
4.

Precipitimetry
Acidimetry/Alkalimetry
Compleximetry
Reductimetry/Oxidimetry

Titrimetric Methods
Standard Solution
- a reagent used to titrate the analyte.
It must:
1. Have a precisely known concentration.
2. Generally is added from a buret.

Titrimetric Methods
Standard Solution

Titrimetric Methods
Primary Standard

a
highly
purified
compound that serves
as a reference materials.

Titrimetric Methods
Primary Standard
It must have the ff. characteristics:
a. High purity
b. Stable in air
c. Absence of hydrated water molecules
d. Moderate cost and easy availability
e. Solubility in the titration solutions
f. Large formula weight (molecular weight)
*Compounds that do not meet all these criteria are called secondary standards.

Titrimetric Methods
Some commonly used Primary Standards:
For Bases:

Benzoic Acid, C6H5COOH (f = 1)

Oxalic Acid, H2C2O42H2O (f = 2)
Potassium Biiodate, KH(IO3)2 (f =1)
Potassium Hydrogen Phthalate (KHP),
C6H4(COOH)(COOK) (f =1)
Sulfamic Acid (HSO3NH2) (f =1)

Titrimetric Methods
Some commonly used Primary Standards:
For Acids:

Calcium Carbonate, CaCO3 (f = 2)

Mercuric oxide, HgO (f = 2)
Sodium Carbonate, Na2CO3 (f = 2)
Tris-hydroxymethylaminomethane (THAM),
(CH2OH)3CNH2 (f =1)

Example 26
How many grams of KHP are needed
to neutralize 167.33 mL of 0.99955 M
NaOH?

Ans. 34.157 grams

Example 27
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 6.12 ml of
acid (1mL = 4.1 mg NaOH). What is
the molarity of the NaOH solution?
Ans. 0.2151 M

Applications of Acid-Base Titration

1. Determination of Organic NitrogenKjeldahl Method
2. Double indicator method for mixture
of bases Warder Titration
3. Acid Number
4. Saponification Number

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+ + OHNH3(g) + H2O

Kjeldahl Method (Determination of Organic

Nitrogen)
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

Kjeldahl Method (Determination of Organic

Nitrogen)

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

Kjeldahl Method (Determination of Organic

Nitrogen)

Percentage Protein in the sample

%protein =%N * f
f = 5.70 (cereals)
= 6.25 (meat products)
= 6.38 (dairy products)

Example 28
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%

Example 29
A 7.443-gram sample beef was analyzed for its
N content and the liberated NH3 was
collected in a 43.25 mL of 0.4330 M HCl and
a 15.00 mL back titration with 0.0250 M
NaOH was required. Determine the % protein
in the sample using 6.25 as factor for meat
products.
a.12.44% b. 21.57% c. 32.54% d. 10.98%

Example 30
A 3000 mg sample of flour was taken through a
Kjeldahl method. Upon digestion, the
ammonia liberated was collected into 200 mL
of 0.995 M H3BO3 solution. If this solution
required 25.25 mL of 0.3315 M HCl for
titration to methyl red end point, what is the
percentage of protein in flour? Use 5.70 for
cereal products.
Ans. 22.27%

Example 31
A 500 mg sample of each mixture was
analyzed for its alkaline content using 0.1025
M HCl via double indicator method.
Mixture

V0->Ph

V0->MR

4.27

10.18

0.01

6.19

5.12

10.24

6.37

6.38

5.63

9.04

Determine the weight

compositions of each
mixture.

Acid Number
Acid number - mass (mg) of KOH that will neutralize
the acid produced fromwater degradative reaction of
one gram of fat or oil
Acid no. = (VxM)KOH X MW KOH
gram fat or oil

Saponification no.
Saponification no./Koettstorfer no. = mass of KOH reqd
to saponify 1 gram fat or oil

Sap. no. = (Vblank, mL Vsample, mL ) (MHCl)(56.10)

gram fat or oil
Molar mass of Fat or Oil. = 168,300
Sap. Value

Example 32
The saponification no. of triglycerides
is 200. The average MW of the
triglycerides is:

A. 200

B. 280

C. 600

D. 840

Precipitation Titrations
Common Technique:
Argentometric Titrations:
1. Mohr method
2. Volhard method
3. Fajans method

Method

Mohr

Titrant

Indicator

AgNO3

K2CrO4

Rxn : Ag ( aq ) Cl AgCl ( s ) 2 Ag ( aq ) CrO 4 2 ( aq ) Ag 2CrO 4( s )

KSCN
Backtitration :
Volhard

Ag ( aq ) Cl AgCl( s )

ferric alum, NH4Fe(SO4)212H2O

Fe 3 ( aq ) SCN 1 ( aq ) Fe( SCN ) 2 ( aq )

Ag ( aq ) SCN ( aq ) AgSCN ( s )

Fajans

Ag

( aq )

AgNO
3

Cl AgCl ( s )

Fluorescein
Dicholro-fluorescein
End point: greenish-yellow to
pink

Example 33
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

Ans. 13.43 %

Titration with EDTA

EDTA Ethylenediaminetetraacetic acid
combines w/ any metal ion in ratio of 1:1
Indicators:
1. Eriochrome Black T or Solochrome
2. Calmagite

Example 34
An EDTA solution was prepared by dissolving
the disodium salt in 1 L of water. It was
standardized using 0.5063 gram of primary
standard CaCO3 and consumed 28.50 mL
of the solution. The standard solution was
used to determine the hardness of a 2 L
sample of mineral water, which required
35.57 mL of the EDTA solution. The
concentration (ppm) in terms of CaCO3 is
Ans. 315.95 ppm

Example 35
The 300 mg sample of impure Na2SO4 (142.04)
was dissolved in sufficient water and the
sulfate was precipitated by the addition of
35.00 mL of 0.1022 M BaCl2. The precipitate
was removed by filtration and the remaining
BaCl2 consumed 6.79 mL of 0.2467 M EDTA
for titration to the Calmagite endpoint.
Calculate the purity of the sample.

Redox Reactions

Example 36
Balance the reaction:

NO 2 MnO4 NO3 MnO2

RULES:

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 zero.
The sum of oxidation number of elements in a polyatomic ion is the
charge of the ion

Example 37
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

Example 38
A sample of pyrolusite weighing 0.2400
gram was treated with excess KI. The
iodine liberated required 46.24 mL of
0.1105 M Na2S2O3 solution. Calculate %
MnO2 (86.94) in the sample.

a. 46.27% b. 30.85% c. 92.54% d. 76.12%

Example 39
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 K2Cr2O7 for titration to the
diphenylamine sulfonic acid endpoint.
Calculate % Fe3O4 (231.55 g/mol) in the ore
sample.
a. 15.05% b. 45.15% c. 90.30% d. 67.98%

Example 40
A 10.00 gram sample of cooked-ham was
pured 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.
Ans. 90 ppm

Masking
Example 41:
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.
Ans. 47.08% Cu, 3.48% Hg