INTRODUCTION:

ANALYTICAL CHEMISTRY

1.1 Types and steps in analysis

1.2 Review the terms: moles, molarity and concentration.
Other expressions of concentration: % (w/w), % (v/v),
ppm, ppt, ppb
1.3 Calculations involving different expressions of
concentrations

What is analytical chemistry???

is concerned with the chemical characterization of matter
and the answer to two important questions:

What is it
(qualitative)

How much is it
(quantitative)

Analytical chemistry provides the methods and tools needed for

insight into our material worldfor answering four basic
questions about a material sample:
What?
Where?

How much?
What arrangement, structure or form?

 Deals with the identification of elements, ions, compounds

present in a sample (what is it)
Qualitative tests may be performed by selective chemical
reactions or with use of instrumentation
May be achieved by a number of strategies. Some examples are:
- sample preparation, eg extraction, precipitation
- instrumentation (selective detectors)
- target analyte derivatization
- chromatography, which provides powerful separation

Quantitative
Deals with the determination of how much of one or more
constituents is present ( how much is it)
For quantitative analysis, a history of the sample composition
will often be known

The analyst will have performed a qualitative test prior to

perform the more difficult quantitative analysis

Difference between qualitative and quantitative

analysis:
Qualitative analysis seeks to establish the
chemical composition in a sample
Quantitative analysis seeks to establish the
amount of the content, such as element or
compound in a sample

1. DEFINING THE PROBLEM what do we really need to

2.
3.

4.
5.
6.
7.

know
SELECT A METHOD
OBTAINING A REPRESENTATIVE SAMPLE we cant
analyze the whole thing
PREPARING THE SAMPLE FOR ANALYSIS it probably
needs to be altered
PERFORMING ANY NECESSARY CHEMICAL SEPARATIONS
PERFORMING THE MEASUREMENT you decide the
method
CALCULATING THE RESULTS AND REPORTING THE
DATA this is the whole object

Table 1.1 Steps in an analysis

1.

DEFINING THE PROBLEM what do we really

need to know

- must know what information is needed, by whom,

for what purpose, and what type of sample is to be
analyzed.
- the way you perform an analysis will depend on
your experience, the equipment available, the cost
and the time involved
- the analyte is the substance analyzed for. Its
concentration is determined
- once the problem has been defined, the following
steps can be started

2. SELECT A METHOD
- Factors to select a method:

sample type
size of sample
sample preparation needed

- analytical methods are often classed according to

size of sample. The analysis may be classed as
meso, semimicro or ultramicro
- table 1.2 gives approximate classifications according
to sample weight or volume

Table 1.2 Classification of analytical methods according to size

of sample

3. OBTAINING A REPRESENTATIVE SAMPLE we

cant analyze the whole thing
- the material to be sampled may be solid, liquid or

gas. It may be homogeneous or heterogeneous in

composition
the gross sample consists of several portions of
the material to be tested
the gross sample must be reduced in size to obtain
a laboratory sample
the laboratory sample is a small portion of this,
made homogeneous
the analysis sample is that actually analyzed

4. PREPARING THE SAMPLE FOR ANALYSIS it

probably needs to be altered
-

the first step in analyzing a sample is to measure the amount

being analyzed (e.g volume or weight of sample)
solid samples usually must be put into solution
usually replicate samples are taken for analysis
the pH of the sample solution will usually have to be adjusted
once a sample is in solution
it is important to prepare and analyze replicate blanks,
particularly for trace analyses
a blank consists of all chemicals is the unknown and used in
an analysis in the same amounts (including water) run
through the entire analytical procedure

5. PERFORMING ANY NECESSARY CHEMICAL

SEPARATIONS
- to eliminate interferences
- to provide suitable selectivity in the measurement
- to preconcentrate the analyte for more sensitive or
accurate measurement
- it is preferable to separate the analyte away from
the sample matrix, in order to minimize losses of
the analyte
- separation steps may include precipitation, extraction
into an immiscible solvent, chromatography, dialysis
and distillation

6. PERFORMING THE MEASUREMENT you decide

the method
- gravimetric analysis usually involves the selective
separation of the analyte by precipitation, followed by
the very nonselective measurement of mass
- in volumetric or titrimetric analysis, the analyte reacts
with a measured volume of reagent of known
concentration, in a process called titration
- instrumental techniques are used for many analyses
and constitute the discipline of instrumental analysis

..cont
- instruments are more selective and sensitive than
-

volumetric and gravimetric methods. But they may be

less precise
the instrumentation must be calibrated
calibration is accomplished by preparing a series of
standard solutions of the analyte at known
concentrations
a calibration curve is the instrument response as a
function of concentration
table 1.3 compares various analytical methods with
respect to sensitivity, precision, selectivity, speed and
cost

Table 1.3 Comparison of different analytical methods

7. CALCULATING THE RESULTS AND REPORTING

THE DATA this is the whole object
- the analyst must provide expert advice on the
significance of a result
- the analyst should critically evaluate whether the
results are reasonable and relate to the analytical
problem as originally stated

 The mole (mole) is the SI unit for the amount of a chemical species.

A mole (mol) is an amount of substance that contains as many elementary

units (atoms, molecules and formula units) as there are atoms in exactly
12 gram of the carbon-12 isotope
A mole of molecules is Avogadro's number of molecules.

Avogadro's number is the number of 12C atoms in12.0000 g of

has been experimentally determined to equal 6.022 x 10 23.

12C

and

1 mol of any chemical species contains 6.022 x 1023 of that species.

Moles =

mass
molar mass (RMM)

Mass

Moles x molar mass

(RMM)

Concentration
(gdm-3)
Moles

Molarity x Molar mass (RMM)

(moldm-3)
Molarity x Volume(L)
(moldm-3)
Concentration(gdm-3), molarity(moldm-3),
molar mass (RMM)

Moles, molarity, volume

Molarity (M) : No of moles of the solute in 1L of solution.

M = no.mol solute
no.L solution
Eg: Calculate the molar concentration of ethanol in aqueous
solution that contains 2.30 g C2H5OH (46.07 g/mol) in 3.50L of
solution.
no. mole C2H5OH = 2.30 g
= 0.4992 mol
46.07 g/mol

Molarity =

0.04992 mol
3.5 L

= 0.0143 M

Normality (N) = The number of equivalents

Volume of solutions.

An equivalent represents the mass of material

(the moles) of the a species that take part in a
reaction the reaction unit.
eg. In acid-base reaction the reaction unit is the
number of H+
In redox reaction the reaction unit is the
number of electrons

The normality of a solution is a multiple of

the molarity of the solution
Generally, the normality of a solution is just
one, two or three times the molarity.
CaCl2
Eg:

Ca2+ + 2Cl0.5 M CaCl2 = 1 N CaCl2

1.4 M CaCl2 = 2.8 N CaCl2

N = n M (where n is an integer)

For an acid solution, n is the number of H+ provided

by a formula unit of acid.
example: A 3 M H2SO4 solution is the same as a 6 N
H2SO4 solution.
For a basic solution, n is the number of OH- provided
by a formula unit of base.
example: A 1 M Ca(OH)2 solution is the same as a 2N
Ca(OH)2 solution.
REMEMBER! The normality of a solution is NEVER
less than the molarity

Molality (m) : No of moles of the substance per

kilograms of the solvent.
m = no.mol solute
kg solvent
Unit: mol/kg

What is the molarity of a solution of 0.60 g

NaCl in 100 mL of solution?
Given, MW NaCl = 58.5g/mol.

Answer: 0.102 mol/L

Typical seawaters contain sodium chloride,

NaCl as much as 2.7 g per 100 mL.
(a) What is the molarity of NaCl in the saline
water ?
(b) The MgCl2 content of the saline water is
0.054 M. Determine the weight (grams) of
MgCl2 in 50 mL of the saline water ?

(a) What is the molarity of NaCl in the saline

water ?
- MW of NaCl = 22.99 + 35.54 = 58.44 g/mol
- No.of mol of NaCl in 100 mL saline water
= 2.7 g
= 0.0046 mol
58.44 g/mol

- Molarity of saline water = mol

volume
= 0.046mol
100/1000 L
= 0.46 M

(b) The MgCl2 content of the saline water is 0.054 M.

Determine the weight (grams) of MgCl 2 in 50 mL
of the saline water ?

MW of MgCl2 = 24.30 + 2(35.45) = 95.20 g/mol

Weight of in 50 mL of saline water
= (M x V) x RMM
= 0.054 M x (50/1000) x 95.20 g/mol
= 0.26 g

Concentration can be described in term of %

concentration:
1. Percent weight/weight (% w/w)
2. Percent weight/ volume (% w/v)
3. Percent volume/volume (% v/v )

1. Percent weight/weight (w/w %)

Weight solute
X 100
Weight solution
2. Percent weight/ volume ( w/v%)
Weight solute
X 100
Volume solution

3. Percent volume/volume ( v/v% )

Volume solute X 100
Volume solution

1. - Percent weight/weight (w/w % )is used to

express the concentration of commercial
aqueous reagents.

- Example: HNO3 is sold a 70% solution. It

means the reagent contains 70 g pure
HNO3 per 100 g solution.
- HCl is sold as 37 % solution. It means for
every 100 g solution there is 37 g pure
HCI.

- Percent weight/ volume w/v % is used to

indicate the composition of dilute
aqueous solution of solid reagents.

- Example: 5 % aqueous silver nitrate refers

to solution prepared by dissolving 5 g of
silver nitrate in sufficient water to give
100 mL of solution.

- Percent volume/volume ( v/v% ) is used to

specify the concentration of a solution
prepared by diluting a pure liquid with
another liquid.

- Example: A 5 % aqueous methanol solution

means 5 mL of methanol dissolve in
enough distilled water to make 100 mL
solution.

Example:
What is the w/v % of protein when 1.25 g of
protein is dissolved in 250 mL of solution.
w/v % =

Weight of solute

x 100

Volume of solution
= 1.25 g x 100 = 0.5 %
250 mL

 Parts per thousand (ppt), part per million (ppm)

and part per billion (ppb)
For samples that contain smaller amount of
component the concentration is expressed in
terms of ppt, ppm or ppb.

ppt =

grams of analyte
X 103
grams of sample

ppm =

grams of analyte X 106

grams of sample

ppb =

grams of analyte
grams of sample

X 109

ppt

w/w
v/v
w/v
g/g x 103 mL/mL x 103 g/mL x 103
mL/L
mg/g
mg/mL
L/mL
g/kg
g/L

factor

103

g/g x 106 mL/mL x 106 g/mL x106

mg/kg
L/L
mg/L
ppm g /g
nL/mL

106

g/g x 109 mL/mL x 109 g/mL x 109

g /L
nL/L
ppb g /kg

109

Examples:
1. What is the w/v in ppm of sodium in a solution
containing 2.500mg of Na+ in 500 mL of
solution.

ppm (w/v)= mg of analyte = 2.500 mg = 5 ppm

0.5L
L of solution
ppm (w/v) = g of analyte
mL of solution
-3g
2.500
x
10
=
500 mL
= 5 ppm

X 106
X 106

2. An analysis for cadmium in water give a value

of 1.20 ppb (w/v). What mass of cadmium is
contained in 1.00 L water?
ppb = g/mL x 109

xg
X 109 = 1.20
103 mL
x g = 1.2 x 103
109
x = 1.2 x 10-6 g
= 1.2 g

3. Determine the ppm of ferrous ion, Fe2+, in a

solution known to be 1.2 10-6 M Fe3(PO4)2.8H2O
(RMM=501.61)

solution
1. Convert from molarity (mol/L) to concentration
(g/L)
g/L = mol/L X RMM

g/L = 1.2 x 10-6 x 501.61

= 6.019 x 10-4 g/L
2. Convert from g/L to ppm
ppm = g/mL X 106

6.019 x 10-4 g/L = 6.019 x 10-4 g/103 mL x 106

= 0.6019 ppm

4. Describe the preparation of 1L 0.1 M HCl

from concentration HCl 37% w/w and with
density 1.18 g/mL
conc. HCI
37 % w/w

= 1.18 g/mL

1L
0.1 M HCI

Steps:
Using 2 formula:
1.

Molarity (concentrated) = percentage (%) x ( /RMM) X 1000

2.

M1V1 (concentrated) = M2V2 (diluted)

1.

Molarity (concentrated), M1
= 37/100 x (1.18 /36.5) x 1000
= 11.96 mol/L

2.

M1V1(conc) = M2V2(diluted)
M1 = 11.96
M2 = 0.1
V1 = ??
V2 = 1
11.96 (V1) = 0.1(1)
V1 = 0.1 (1) = 8.36 x 10-3 L
11.96
= 8.36 mL

 Pipet accurately 8.36 mL into a 1 liter volumetric

flask which has already contained a small amount of
distilled water and dilute to mark

How many milliliters of concentrated sulfuric acid,

94.0% (g/100 g solution), density 1.831 g/cm3, are
required to prepare 1 L of 0.100 M solution?

Answer: 5.69 mL

1.

Molarity (concentrated), M1
= 94/100 x (1.831 /98) x 1000
= 17.56 mol/L

2.

M1V1(conc) = M2V2(diluted)
M1 = 17.56
M2 = 0.1
V1 = ??
V2 = 1
17.56 (V1) = 0.1(1)
V1 = 0.1 (1) = 5.69 x 10-3 L
17.56
= 5.69 mL

 Pipet accurately 5.69 mL into a 1 liter volumetric

flask which has already contained a small amount of
distilled water and dilute to mark

5. Describe the preparation of a 250 mL 50

ppm solution of AgNO3 from solid chemical.
50 ppm
1L
1000 mL
250 ml

=
=
=
=
=
=

Remember
50mg/L
ppm = mg/L
50mg
50mg
250 mL x 50 mg/1000 mL
12.5 mg
0.0125g

Weigh accurately 0.0125 g AgNO3, dissolve in

small amount of water, transfer to a 250 ml
volumetric flask and dilute to mark.

6. Descripe the preparation of 0.5 L 50 ppm of Clfrom solid KCl.

50 ppm Cl- = 50 mg Cl- in 1 L

Remember
ppm = mg/L

1 L = 50 mg
0.5 L = 0.5 x 50 = 25 mg Clmol of Cl- = 25 x 10-3 g / 35.5
= 7.04 x 10-4 mol
mol of KCl = mol of Cl( KCl K+ + Cl-)
mol KCl = 7.04 x 10-4 mol
mass of KCl = 7.04 x 10-4 X RMM KCl
= 7.04 x 10-4 x 74.5
=0.0524 g
0.0524 g of KCl is weighed, dissolved in a small amount
of distilled water, transfered into a 500 mL volumetric
flask and diluted to mark.

7. How many gram of Ba(NO3)2 is needed to

prepare a 50 mL solution containing 100
ppm NO3-?
Remember
ppm = mg/L

100 ppm NO3- = 100 mg NO3- in 1000 mL

1000 mL = 100 mg
50 mL = 50 x 100 / 1000
= 5 mg = 0.005 g NO3Ba(NO3)2 Ba2+ + 2NO3-

Mol of NO3 = 0.005 g/ 62 gmol-1 = 8.06 x10-5 mol

. Cont

Ba(NO3)2 Ba2+ + 2NO3-

2 mol of NO3= 1 mol Ba(NO3)2

8.06 x 10-5 mol NO3- = 4.03 x 10-5
8.06 x10-5 mol NO3- contain in 4.03 x 10-5 mol
of Ba(NO3)2
mass of Ba(NO3)2 needed
= mol Ba(NO3)2 x RMM Ba(NO3)2
= 4.03 x 10-5 x 261 g/mol = 0.011 g

A solution contains 118.5 g KI per liter

solution. Calculate the concentration in
(a) % (w/v)
(b) % (w/w)
Given the density of the solution at 25oC
is 1.078 g/mL.

(a) Volume percent, % (w/v) = mass of solute (g) x 100

volume of solution(ml)
= 118.5 g
x 100
1000 mL
= 11.85% (w/v)
(b) weight percent, % (w/w) = mass of solute (g)
mass of solution (g)
= 118.5 g
x
1mL
x
100
1000 mL
1.078 g
= 10.99% (w/w)

x 100

An aqueous solution contains 56 ppm SO2.

Calculate the molarity of the solution.

Solution:

Remember
ppm = mg/L

MW of SO2 = 32 + 2(16) = 64 g/mol

56 ppm = 56 mg/L = 56 x 10-3 g/L
64 gmol-1
= 8.75 x 10-4 mol/L
Remember
mol/L = g/L RMM