CHM256

CHAPTER 1: INTRODUCTION TO
ANALYTICAL CHEMISTRY

OUTLINE
1. Types and steps in analysis
2. Review the terms: moles, molarity and
concentration. Other expressions of
concentration: % (w/w), % (v/v), ppm,
ppt, ppb
3. Calculations involving different
expressions of concentrations

LESSON OUTCOMES
Differentiate between qualitative &
quantitative analysis
Explain the steps involve in quantitative
analysis
Calculate the concentration of solution
Explain the preparation of solution

IMPORTANCE OF ANALYTICAL
CHEMISTRY
Applied throughout industry, medicine and all the
sciences.
Used to collect necessary data to solve problems in
many fields of science such as: Chemistry, Biology,
Environmental Studies, Agriculture, Medicine, Materials
Science, Archeology, Forensic Science, Geology,
Physics, Engineering, etc

INTRODUCTION
Concerned with the chemical
characterization of matter and the answer
to two important questions:
Analytical
chemistry

What is it?
(Qualitative)
- identifies the elements
and compounds present in
a sample

How much is
it?
(Quantitative)
- determines the relative
amounts of the components
presence

QUALITATIVE VS.
QUANTITATIVE
Qualitative

Quantitative

Deals with the identification of

elements, ions, compounds present in
a sample (what is it)

Deals with the determination of how

much of one or more constituents
(how much is it)

Performed by selective chemical

reactions or with use of
instrumentation

A history of the sample composition

will often be known

Achieved by a number of strategies.

Some examples are:
Sample preparation, e.g
extraction, precipitation
Instrumentation (selective
detectors)
Target analyte derivatization
Chromatography, which provides
powerful separation

The analyst will have performed a

qualitative test prior to perform the
more difficult quantitative analysis

METHODS OF
CHEMICAL ANALYSIS
To estimate the concentration of an analyte may require

both measurement of the mass or volume of the sample

and some physical quantity that is related to the
concentration of the element or compound.

This quantity can be classified as:

1. Gravimetric mass of a precipitate
2. Volumetric volume of a titration
3. Electroanalytical voltage, current, amount of charge
4. Spectroscopic absorbance, fluorescence, emission
5. Miscellaneous radioactivity, reaction rate, refractive
index

STEPS IN QUANTITATIVE
ANALYSIS
Select method / Choosing method
Acquire sample
Processing sample
Eliminate interferences
Calibrating and measuring concentration
Calculate results
Evaluate results

CHOOSING A METHOD
1. The selection process is the level accuracy
required
2. Economic factors is the number samples that will
be analyzed
3. Complexity of the sample and the number of
components in the sample always influence the
choice of method to some degree.
4. Sample preparation needed
Analytical methods are often
classed according to size of
sample (meso, semimicro,
ultramicro)

ACQUIRING THE SAMPLE

Performed on a sample that has the same composition
as the bulk of material from which it was taken
When the bulk is large and heterogeneous, great effort is
required to get representative sample
i. The gross sample consists of several portions of
the material to be tested
ii. The laboratory sample is small portion of this made
homogenous
iii. The analysis sample is the sample that actually
analyzed
The most difficult step and the source of greatest error
Sampling (the process of collecting a
small mass of material whose
composition accurately represent the
bulk of the material being sampled)

PROCESSING THE
SAMPLE
Preparing laboratory samples
SOLIDS grinding, mixing, storage to avoid changes
(water content, oxidation). Selecting the subsamples
for analysis
LIQUIDS solvent and analyte evaporation, settling
of solids storage to minimize chemical changes
(refrigeration, freezing, deoxygenate, dark)
Usually replicate samples
Replication improves the quality of the results and
provides a measure reliability
Preparing solutions: physical and chemical changes how to dissolve the sample ? (acid, base, oxidant,
reductant, organic solvent)

ELIMINATING
INTERFERENCES
Perform any necessary chemical separation
Impurities may contribute to (or decrease) the
spectroscopic signal used to calculate the
concentration [e.g. Si produces the same blue colour
as PO43- with molybdenate reagent]

Interference species that causes an

error in an analysis by enhancing or
attenuating (making smaller) the
quantity being measured

CALIBRATING AND
MEASURING
CONCENTRATION

Instrumentation must be calibrated

Calibration is accomplished by
preparing a series of standard
solutions of the analyte at known
concentrations.
Accurate standards are usually
used to plot a calibration line [e.g.
Absorbance vs. Concentration]
Standard compounds used to make
the calibration solutions must be
chemically stable [e.g. metals
should not oxidize, salts should not
gain or lose water]

CALCULATING RESULTS
Concentration of unknown samples is calculated using
the calibration line equation
These computation is also based on the raw
experimental data collected in the measurement step,
the characteristic of the measurement instruments, and
stoichiometry of the analytical reaction
The analyst must provide expert advice on the
significant of a result
The analyst should critically evaluate whether the
results are reasonable and relate to the analytical
problem as originally stated

EVALUATING RESULTS
to estimate whether results are reliable or not
Precision is estimated using the standard deviation or
standard error using replicate measurements (measure of
how closely individual measurements agree with one
another)
Accuracy is best evaluated by including some verified
standard materials close in nature and composition to the
unknown samples (how closely individual measurements
agree with the correct, or true value)
Important in analytical chemistry and
is referred to as quality control or
quality assurance

REVIEW THE TERMS

The mole (mol) 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 grams of the carbon12 isotope
A mole of molecules is Avogadros number of molecules
Avogadros number is the number of 12C atoms in 12 g of 12C
and has been experimentally determined to equal 6.022 x
1023
1 mol of any chemical species contains 6.022 x 1023 of that
species
Molar mass is the mass in grams of 1 mole of a substance

RELATIONSHIP BETWEEN
MOLE AND NUMBER OF
ENTITIES
1 mole of atoms/molecules/ions of any element will contain
Avogadros number of atoms/molecules/ions or 6.022 x 1023
atoms/molecules/ions of that element.
For example:
1 mol of Mg atom contain 6.022 x 1023 Mg atom
1 mol of H2O molecules contain 6.022 x 1023 H2O molecules
1 mol of Na+ ions contain 6.022 x 1023 Na+ ions

FORMULA!!
Number of entities = number of moles x 6.022 x 1023
1. Calculate the number of atoms in 1 mol of aluminium atoms
(6.02 x 1023)
2. Calculate the number of atoms in 0.5 mol of aluminium
atoms (3.02 x 1023)
3. If a container has 12.0 x 1023 atoms of magnesium,
determine number of moles of magnesium atoms (2.0
moles)
4. How many molecules of CO2 are found in 3.5 moles of CO2?
(2.1 x 1024)
5. How many Cl- ions are present in 0.25 moles of CaCl2?
(3.0 x 1023)

MOLE VS. MILIMOLE

1. Calculate the number of moles for 3.4 g of carbon atoms

(0.28 moles)
2. What is the mass of 0.30 moles of CH4? (4.8 g)
3. How many moles of Cl- is present in 0.34 moles of CaCl2?
(0.68 moles)
4. What is the mass of H in 2.5 moles of H2O? (5.0 g)
5. What is the mass of O in 3.0 moles of CO2? (96.0 g)

WHAT IS SOLUTION
CONCENTRATION?
Concentration is the amount of solute in a given volume of
solution.
Solution
: A homogenous mixture of two or more
substances, consisting of solvent and
solute
Solute
: The substance present in a smaller
proportion of the solution. It can be
solid, liquid or gas.
Solvent
: A substance that generally a liquid
present in the larger proportion of the
solution.
Water is considered a universal solvent for most solutions.

DENSITY AND SPECIFIC

GRAVITY OF SOLUTION
Density of a substance is the mass per unit volume. In
SI unit, density is expressed in unit of kg per liter,
(kg/L) or in metric system the unit use is gram per
milliliter, (g/mL)
Density of water = 1 g/ mL
Specific gravity is the ratio of the mass of an equal
volume of water at 4oC.
Specific gravity is dimensionless.

MOLARITY / MOLAR
CONCENTRATION
Molarity : no of moles of the solute in 1 L (dm3) of solution
Molar mass (atomic mass) - the mass of 1 mole of a
substance in unit gram. (Unit for molar mass is g/mol)
Unit for Molarity (mol/L)

FORMULA!!
M = no of mol of solute
volume of solution (L)

or
M = no of mmol of solute
volume of solution (mL)

EXAMPLES
Calculate the molar concentration of ethanol in aqueous
solution that contains 2.30 g C2H5OH (46.07 g/mol) in 3.50
L of solution
No of mole C2H5OH = 2.30 g
= 0.4992 mol
46.07 g/mol
Molarity = 0.04992 mol
3.5 L
= 0.0143 M

TRY THIS!!
1. Sea water contains roughly 28.0 g of NaCl per liter.
What is the molarity of sodium chloride in sea water?
No of mole NaCl = 28.0 g
58.44 g/mol
Molarity = 0.47909 mol
1L
= 0.4791 M

= 0.4791 mol

2. What is the molarity of 5.30 g of Na2CO3 dissolved in

400.0 mL solution?
No of mole Na2CO3 = 5.30 g

= 0.05 mol

106 g/mol
Molarity = 0.05 mol
0.4 L
= 0.125 M

Remember!!
convert volume
to L or dm3
1 L = 1000 mL
1 dm3 = 1000 cm3

MOLALITY
Number of moles of solute that dissolved in 1000 g of solvent, m
Preferred expression of concentration involving colligative
properties (b.p elevation, freezing point depression, osmotic
pressure)
Unit for molality (mol/kg)

FORMULA!!

m = no of mol of solute
1 kg of solvent

EXAMPLES
If you have 10.0 grams of Br2 and dissolve it in 1.00 L of
cyclohexane, what is the molality of the solution? The
density of cyclohexane is 0.779 kg/L at room temperature.
Mol of Br2

= 10 g
= 0.063 moles Br2
(159.8 g/mol)

Next, convert the volume of solvent to the weight of solvent

using the density
= 1.00 L x 0.779 kg/L = 0.779 kg
Now just divide the two to get the molality
Molality, m =
0.063 moles Br2
0.779 kg cyclohexane
= 0.080 molal

TRY THIS!!
1. A sulfuric acid solution containing 571.4 g of H2SO4 per
liter of solution has a density of 1.329 g/cm3. Calculate
the molality of H2SO4 in this solution

No of mol H2SO4 =

571.4 g
(98.0768 g/mol)

= 5.826 mol

Mass of solvent
1 L of solution = 1000 mL = 1000 cm3
1.329 g/cm3 times 1000 cm3 = 1329 g (the mass of the entire
solution)
1329 g - 571.4 g = 757.6 g = 0.7576 kg (the mass of water in the
solution)
Molality, m = 5.826 mol / 0.7576 kg = 7.690 m

PERCENTAGES
Concentration can be described in term of %
concentrations
% concentrations (% w/w, w/v, v/v),
Number of parts in 100 parts, eg. Gram of A in 100
grams of sample.
% of A =

number of parts of A
x 100
number of parts of sample

%(w/w)
Percent weight in weight concentration i.e. weight in 100 g of
sample.
To express the
Weight percent (w/w) =
weight solute (g) x 100
concentration of
weight of sample (g)
commercial aqueous
reagents

% w/v
Percent weight in volume concentration i.e. weight in 100 ml of sample.
Weight percent (w/v) = weight solute (g)
x 100
volume of sample (L)
To indicate the
composition of
dilute aqueous
solution of solid
reagents

% v/v
Percent volume in volume concentration i.e. volume in 100 ml of sample.
Weight percent (v/v) = volume solute (mL) x 100
To specify the
volume sample (mL)
concentration of a
solution prepared by
diluting a pure liquid
with another liquid

ppm and ppb for solid

and liquid

ppm = parts per million (106)

ppb = parts per billion (109)
ppt = part per trillion (1012)
parts of a substance present in one million (or 1 billion) parts of
solvent (water)
If we use gram as the unit, 1ppm means we have 1 g of
substance in 1,000,000 g solvent.

ppm, ppt, ppb

ppt = grams of analyte x 103
grams of sample
ppm = grams of analyte x 106
grams of sample
ppb = grams of analyte x 109
grams of sample
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
0.5 L
ppm (w/v) = g of analyte x 106
ml of solution
= 2.5 x 10-3g
x 106
500mL
= 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

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)

4. Describe the preparation of 1L 0.1 M HCl

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

Using 2 formula:
1. Molarity (concentrated) = percentage (%) x (density/RMM) X 1000
2. M1V1 (concentrated) = M2V2 (diluted)

5. Describe the preparation of a 250 mL 50 ppm solution

of AgNO3 from solid chemical.

6. Describe the preparation of 0.5 L 50 ppm of Cl- from solid KCl.

7. How many gram of Ba(NO3)2 is needed to prepare a 50 mL

solution containing 100 ppm NO3-?

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?

SELF TEST
1. Define:
a) Parts per million
b) Molality
c) Molarity
d) Percentage
2. Calculate the number of mole in the following:
i) 250 ml, 0.150 M HCl (Ans: 0.0375 mole)
ii) 6.72 liter H2 at STP. (Ans: 0.3 mole)
Hint: 1 mol of H2 at STP contain 22.4 L

3. How many mole of solute present in the following

solutions:
i) 16.3 liter solution 0.113 M (Ans: 1.8419 mole)
ii) 15.6 ml solution 0.025 M (Ans: 0.0039 mole)
4. Calculate the molar concentration of ethanol in an aqueous
solution that contains 2.30 g of C2H5OH (46 g/mol) in 3.5 L
of solution (Ans: 0.0143 M)
5. Calculate the molarity of 15.0 g ammonia in 750 mL
solution. (Ans: 1.1765 M)
6. Briefly explain how to prepare the following solutions; 500
mL 6.50 % (w/v) aqueous ethanol, C2H5OH.