INTRODUCTION:

ANALYTICAL CHEMISTRY

Dr. Siti Hajar Alias

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? How much is it?

(qualitative) (quantitative)

Analytical chemistry provides the methods and tools needed for

insight into our material world for answering four basic
questions about a material sample:
v What? v How much?
v Where? v 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

Eg: Bau Lake remain Arsenic

1. DEFINING THE PROBLEM – what do we really need to
know
2. SELECT A METHOD
3. OBTAINING A REPRESENTATIVE SAMPLE – we can’t
analyze the whole thing
4. PREPARING THE SAMPLE FOR ANALYSIS – it probably
needs to be altered
5. PERFORMING ANY NECESSARY CHEMICAL SEPARATIONS
6. PERFORMING THE MEASUREMENT – you decide the
method
7. CALCULATING THE RESULTS AND REPORTINGTHE
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

Please give me environmental problem

that surround your life??
 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
can’t 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 of12C atoms in12.0000 g of 12C and

has been experimentally determined to equal 6.022 x 10 23.

• 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 isa multiple of
the molarity of the solution

Generally, the normality of a solution is just

one, two or three times the molarity.

CaCl2 Ca2+ + 2Cl-

Eg: 0.5 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 MgCl2 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

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

Weight solute X 100
Volume solution

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

Volume solute X 100
Volume solution
- 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 gx 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.

grams of analyte
ppt = X 103
grams of sample
grams of analyte X 106
ppm = grams of sample

ppb = grams of analyte X 109

grams of sample
 w/w v/v w/v factor
g/g x 103 mL/mL x 103 g/mL x 103
mg/g mL/L
ppt mg/mL 103
g/kg µ L/mL
g/L
g/g x 106 mL/mL x 106 g/mL x106
mg/kg µ L/L 106
ppm µ g /g mg/L
nL/mL
g/g x 109 mL/mL x 109 g/mL x 109
µ g /L 109
ppb nL/L
g /kg
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

L of solution 0.5L

ppm (w/v) = g of analyte X 106

mL of solution
= 2.500 x 10 -3g
X 106
500 mL
= 5 ppm
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 µg
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
1L
37 % w/w
0.1 M HCI
r = 1.18 g/mL
Steps:

Using 2 formula:

1. Molarity (concentrated) = percentage (%) x (r /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 = 50mg/L Remember

ppm = mg/L
1L = 50mg
1000 mL = 50mg
\ 250 ml = 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 Cl-
from solid KCl.
Remember
50 ppm Cl- = 50 mg Cl- in 1 L
ppm = mg/L
1 L = 50 mg
\ 0.5 L = 0.5 x 50 = 25 mg Cl-
mol 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 NO3-
Ba(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)2needed
= 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) x 100

mass of solution (g)
= 118.5 g x 1mL x 100
1000 mL 1.078 g
= 10.99% (w/w)
An aqueous solution contains 56 ppm SO2.
Calculate the molarity of the solution.
Remember
Solution: 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
TEST YOUR UNDERSTANDING

A solution contains Cu2+ ions at a

concentration of 3 x 10 -4 M. What is the
Cu2+concentration in ppm?

moles/L of Cu2+ = (3 x 10-4 mol x 63.55 g/mol)/L

moles/L of Cu2+ = 1.9 x 10-2 g/L
We want mg of Cu2+, so
moles/L of Cu2+ = 1.9 x 10-2 g/L x 1000 mg/1 g
moles/L of Cu2+ = 19 mg/L

moles/L of Cu2+ = 19 ppm

END OF CHAPTER 1