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? How much is

it?
(Qualitative) (Quantitative)
- identifies the elements - determines the relative
and compounds present in amounts of the components
a sample presence
 QUALITATIVE VS.
QUANTITATIVE
Qualitative Quantitative
 Deals with the identification of  Deals with the determination of how
elements, ions, compounds present in much of one or more constituents
a sample (what is it) (how much is it)
 Performed by selective chemical  A history of the sample composition
reactions or with use of will often be known
instrumentation
 The analyst will have performed a
 Achieved by a number of strategies. qualitative test prior to perform the
Some examples are: more difficult quantitative analysis
 Sample preparation, e.g
extraction, precipitation
 Instrumentation (selective
detectors)
 Target analyte derivatization
 Chromatography, which provides
powerful separation
 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 carbon-
12 isotope
 A mole of molecules is Avogadro’s number of molecules
 Avogadro’s 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
Avogadro’s 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 = 0.4791 mol

58.44 g/mol

Molarity = 0.47909 mol

1L
= 0.4791 M
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

Remember!!
Molarity = 0.05 mol • convert volume
0.4 L to L or dm3
= 0.125 M
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.
Weight percent (w/w) = weight solute (g) x 100 To express the
weight of sample (g) concentration of
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

ppm and ppb for solid diluting a pure liquid

with another liquid

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.