CHAPTER 1

FUNDAMENTALS
OF ANALYTICAL
CHEMISTRY
 TODAYS’ CLASS OUTLINE
 Classification of Chemistry
 Define Analytical chemistry

 The scope of the course

 Common languages of analytical

chemistry
 Selecting an analytical method

 Concept of Analytical perspective

 Basic equipments and instrumentation

 Units for expressing concentration

 Preparing solutions

 Standardization and calibration

05/22/2025 2
 CHEMISTRY
 Chemistry is the study of matter, including its
composition, structure, physical properties, and
reactivity
 For simplicity chemistry is classified into

 Organic chemistry
 Inorganic chemistry
 Physical chemistry
 Biochemistry

Analytical chemistry

05/22/2025 3
 WHAT IS ANALYTICAL CHEMISTRY?
 Analytical
chemistry is branch of
chemistry responsible for
characterizing the composition of
matter, both
 Qualitatively
(what is present?) and
Quantitatively (how much is present?)
 And,
 Improving established methods,
 Extending existing methods to new types of
samples, and
 Developing new methods for measuring
chemical phenomena
05/22/2025 4
Generally, therefore,
Analytical chemistry is defined
as chemical discipline that
gains information on the
chemical composition and
structure of substances,
particularly on the type of
species, their amount,
possible temporal and
spatial changes, and
structural
05/22/2025 relationships5
 THE SCOPE OF THE COURSE
 Analytical techniques that are responsible
for separation, identification, and
quantification of the chemical components
of natural and artificial materials.
 Qualitatively (what is present?) and
What did you eat today?

 Quantitatively (how much is present?)

How much of water, carbohydrate, protein, vitamins,

minerals did
you intake?
05/22/2025 6
 COMMON LANGUAGES OF ANALYTICALCHEMISTRY
Analyte – The component of interest in the
sample
 Matrix – Components of the sample other

than the analyte of the interest. i.e the

remainder of the sample.
 Analysis - is the process that provides

chemical or physical information about the

analyte
 Analyzing a sample generates a

chemical or physical signal that is

proportional to the amount of analyte in
the sample.
A method is the application of a
05/22/2025 7
 Qualitative analysis
An analysis in which we determine the
identity of the constituent species in a sample
Quantitative analysis
An analysis in which we determine how much
of a constituent species is present in a sample
Characterization analysis
An analysis in which we evaluate a sample’s
chemical or physical properties
Fundamental analysis
An analysis whose purpose is to improve an
analytical method’s capabilities

05/22/2025 8
 SELECTING AN ANALYTICAL METHOD
 In choosing a method some or all of the
following
criteria should be considered:
 Accuracy is how closely the result of an

experiment agrees with the “true” or expected

result.
 Accuracy can be expressed by an absolute

error, e
or as a percentage relative error,
%er

05/22/2025 9
 SELECTING AN ANALYTICAL METHOD
 Precision- when a sample is analyzed several
times, the individual results are rarely the
same. Instead, the results are randomly
scattered. Precision is a measure of this
variability. The closer the agreement between
individual analyses, the more precise the
results.

05/22/2025 10
SELECTING AN ANALYTICAL METHOD
 Sensitivity - The ability to demonstrate that two
samples have different amounts of analyte is an
essential part of many analyses. A method’s
sensitivity is a measure of its ability to establish that
such differences are significant.
 Specificity - An analytical method is specific if its
signal depends only on the analyte.
 Selectivity is a measure of a method’s freedom
from interferences
 Scale of operation - Three potential
limitations:
 The amount of sample available for the analysis,
 The expected concentration of analyte in the
samples,
05/22/2025 11
 The minimum amount of analyte that produces a
 ANALYTICAL PERSPECTIVE

5. Propose a 1. Identify and

solution define
problem

2. Design the
4. Analyze the experimental
experimental data Feedback procedure
loop

3. Conduct
experiment

05/22/2025 12
 ANALYTICAL PERSPECTIVE
 STEP 1 Identify and define the
problem
 Determine type of information needed
 Qualitative – What is present in a sample?
 Quantitative – How much is present?

 Characterization – Characterizing the chemical

and
physical properties
 Fundamental – improving the existing

methodology
 Identify context of the problem

05/22/2025 13
 ANALYTICAL PERSPECTIVE
 STEP 2 Design the experimental
procedure
Establish design criteria
Identify interferents
Select method
Establish validation criteria
Establish sampling strategy

05/22/2025 14
 ANALYTICAL PERSPECTIVE
 STEP 3 Conduct an experiment and gather
data
 Calibrate instruments and equipment
 Standardize reagents
 Gather data
 STEP 4 Analyze the experimental data
 Reduce or transform data,
 Analyze statistics,
 Verify results
 Interpret results
 STEP 5 Propose a solution to the problem
 Conduct external evaluation
05/22/2025 15
 BASIC EQUIPMENTS IN ANALYTICAL
CHEMISTRY
 Equipments for measuring mass ---
Analytical balance

05/22/2025 16
 BASIC EQUIPMENTS IN ANALYTICAL
CHEMISTRY
 Equipments for measuring Calibration
volume mark

Beake Measuring Volumetric

Transfer
r cylinder flask
Pipet

05/22/2025 17
 BASIC LAB-WARES AND EQUIPMENTS IN
ANALYTICAL CHEMISTRY
 Equipments for measuring
volume

Measuring Droplets (pastor Manual Automatic

pipette pipette) syringe syringe
05/22/2025 18
 BASIC LAB-WARES AND EQUIPMENTS IN
ANALYTICAL CHEMISTRY
 Equipments for drying and
calcination

Oven ( 110-140 Muffle (>200

05/22/2025 oC) oC) 19
 BASIC LAB-WARES AND EQUIPMENTS IN
ANALYTICAL CHEMISTRY
 Desiccators -After drying or decomposing a
sample, it should be cooled to room
temperature in a desiccators to avoid the re-
adsorption of moisture.

 Refer Chapter 2 of Skoogs’“ Fundamental of

analytical
chemistry”
05/22/2025 20
 BASIC TOOLS OF ANALYTICAL CHEMISTRY
1. Basic equipments and instrumentation
2. Units for expressing concentration
3. Preparing solutions
4. Standardization and calibration

05/22/2025 21
 UNITS OF EXPRESSING CONCENTRATION
 Concentration is a general measurement
unit stating the amount of solute present in
a known amount of solution

05/22/2025 22
 UNITS OF EXPRESSING CONCENTRATION
 Common units for reporting
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓
concentration
Molarity 𝑠𝑜𝑙𝑢𝑡𝑒 M
𝑁𝑢𝑚𝑏𝑒𝑟𝑙𝑖𝑡𝑒𝑟𝑠𝑜𝑓𝑜𝑓𝐸𝑊𝑠
Normality 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
N
𝑙𝑖𝑡𝑒𝑟𝑠𝑀𝑜𝑙𝑒𝑠 𝑜𝑓
𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Molality 𝑠𝑜𝑙𝑢𝑡𝑒 m
𝑔 𝐾𝑔
𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑜𝑓
𝑠𝑜𝑙𝑣𝑒𝑛𝑡
100𝑔 𝑜𝑓
Weight % %w/w
𝑚𝑙 𝑜𝑓
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑠𝑜𝑙𝑢𝑡𝑒
Volume % %v/v

100𝑚𝑙g of𝑜𝑓
solute
100 ml
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Weight to volume % %w/v
g of solute
solution
106 g
Parts per million ppm
g of solute
solution
109 g
Parts per billion ppb

solution
05/22/2025 23
 UNITS OF EXPRESSING CONCENTRATION
 Molarity is the concentration of a particular
chemical species in solution. It is the number of
moles of solute per liter of solution (M)

𝑀𝑜𝑙𝑒𝑠 𝑜𝑓
Molarity(M) 𝑠𝑜𝑙𝑢𝑡𝑒𝑜𝑓
𝑙𝑖𝑡𝑒𝑟𝑠
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
Example:-
1. Calculate the molarity of a potassium dichromate solution
prepared by placing 9.67 g of K2Cr2O7 (294.2 g/mol) in a 100
ml volumetric flask, dissolving, and diluting to the
calibration mark.
2. Calculate the molar concentration of ethanol in an aqueous
solution that contains 2.3g of C2H5OH in 3.5L of solution.
05/22/2025 24
 UNITS OF EXPRESSING CONCENTRATION
 Weight, Volume, and Weight-to-Volume

𝑔 𝑜𝑓
Ratios

Weight 𝑠𝑜𝑙𝑢𝑡𝑒
100𝑔 𝑜𝑓
%w/
𝑚𝑙 𝑜𝑓
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
% w
Volume 𝑠𝑜𝑙𝑢𝑡𝑒
100𝑚𝑙 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
g of
solute
100 ml
Weight to %v/v
% %w/
solution
volume
v
%
05/22/2025 25
UNITS OF EXPRESSING CONCENTRATION
 Examples:
1. 10 ml of ethanol (C2H5OH) is added into 100ml
volumetric flask and diluted to the calibration
mark. Calculate the concentration of ethanol in
V/V %.
2. A 250.0-mL aqueous solution contains 45.1
mg of a pesticide. Express the pesticide’s
concentration in weight/volume percent.
3. A catalyst Pd/Al2O3 contains 5 w/w % nominal
loading of Pd. Calculate the amount of
Pd(CH3COO) 2 needed to prepare 1 g of this
catalyst.
4. A solution of 1.5% w/v NH4NO3, contains
05/22/2025 26
 UNITS OF EXPRESSING CONCENTRATION
 Parts per million (ppm) and Parts per
billion (ppb)

g of
10solute
6 g solution
Parts per million
g of
solute 10
ppm
9
Parts per billion ppb

g solution

05/22/2025 27
UNITS OF EXPRESSING CONCENTRATION
 Parts per million (ppm) and Parts per billion (ppb)
 For extremely dilute solutions, we approximate the
density of an aqueous solution as 1.00 g/mL, then
solution concentrations can be expressed in ppm or ppb
using the following relationships.

 Example-
A 250.0-ml aqueous solution contains 45.1 mg of a
pesticide.
Express the pesticide’s concentration in parts per million,
and
05/22/2025 28
 There fore , we express ppm
concentration in a variety of units
depending on what we need to use. But
they are all interrelated.

Example , Dissolved O2 in water shows a

concentration of 250 mL of water At SATP and 2.2
mg of O2. What is the concentration in ppm?

ppm concentration = 1 mg = 2.2 mg = 8.8

mg/L = 8.8 ppm
1L 0.25 L
05/22/2025 29
 UNITS OF EXPRESSING CONCENTRATION
 Examples on interchanging units
 A concentrated solution of aqueous ammonia is
28.0% w/w NH3 and has a density of 0.899 g/ml.
What is the molar concentration of NH3 in this
solution?
 Commercially available concentrated hydrochloric
acid is 37.0% w/w HCl. Its density is 1.18 g/ml.
Using this information calculate
(a) the molarity of concentrated HCl, and
(b)the mass and volume (in ml) of solution containing
0.315
moles of HCl.
 The concentration of lead in an industrial waste
stream is
0.28 ppm. What is its molar concentration?
 Refer more examples from Skoogs’ “
05/22/2025 30
1. Basic equipments and
BASIC TOOLS OF ANALYTICAL CHEMISTRY
instrumentation
2. Units for expressing concentration
3. Preparing solutions
4. Standardization and calibration

05/22/2025 31
 PREPARING SOLUTIONS
 Material needed to prepare a
solution
 For more accurate measurements
Volumetric
Measuring
flasks
Pippe

 For approximate
measurements

Beake
r
Measuring
cylinder
05/22/2025 32
 PREPARING SOLUTIONS
 There are two methods for preparing solutions
 Stock Solutions
 A stock solution is prepared by weighing out an
appropriate portion of a pure solid or by measuring out
an appropriate volume of a pure liquid and diluting to a
known volume.
 Example
 Describe how you would prepare the following three
solutions in volumetric flask:
 500 ml of approximately 0.20 M NaOH using solid NaOH
 1 L of 150.0 ppm Cu2+ using Cu metal
acial acetic
acid;
 2 L of 4% v/v acetic acid using concentrated gl

05/22/2025 33
 PREPARING SOLUTIONS
 Preparing Solutions by Dilution
 Dilutions
The process of preparing a less concentrated
solution from a more concentrated solution.
 You dilute a solution whenever you add solvent to a
solution. Adding solvent results in a solution of lower
concentration.
 For example, if there are 20 grams of salt (the solute)

dissolved in 1 litre of water (the solvent), this solution has

a certain salt concentration.
 If one adds 1 litre of water to this solution the salt

concentration is reduced. However The diluted solution

still contains 20 grams of salt/(0.171 moles of NaCl).
 You can calculate the concentration of a solution

following a dilution by applying this equation:

05/22/2025 34
 PREPARING SOLUTIONS
 Preparing Solutions by Dilution
 Solutions with small concentrations are often prepared by
diluting a more concentrated stock solution. A known
volume of the stock solution is transferred to a new
container and brought to a new volume. Since the total
amount of solute is the same before and after dilution, we
know that
COVO=CdVd
 Example
 A laboratory procedure calls to prepare 250 ml of 10M
NH3 solution from concentrated NH3 (14.8M). What
volume do you need to take from the concentrated
solution?

05/22/2025 35
 CALIBRATION AND STANDARDIZATION
 Calibration is a comparison between
measurements

 Calibration: Determines the relationship

between the analytical response and the analyte
concentration.
 Usually accomplished by the use of chemical
standards
 Standardization is the process of developing
and
implementing technical standards.

05/22/2025 36
STANDARDIZATION AND CALIBRATION
Standard solution:
 A standard solution (standard titrant) is a
reagent of known concentration.
 It plays a central role in all analytical methods of
analysis. The ideal standard solutions for a
titrimetric method will;
 be sufficiently stable so that it is necessary to
determine its concentration only once:
 react rapidly with the analyte so that the time
required
between additions of reagent is minimized
 react more or less completely with the analyte so
that satisfactory end points are realized and
 undergo a selective reaction with the analyte that
can be described by a balanced equation.
05/22/2025 37
 STANDARDIZATION AND CALIBRATION
Determination of specific
analyte concentration in
solution
There are several ways to determine specific
analyte concentration of a sample: The
unknown analyte response is compared with
chemical standards:
 the titration procedures
 the direct comparison technique

05/22/2025 38
 STANDARDIZATION AND CALIBRATION
1.Determination of Analyte’s
concentration by reacting with
the
standard solution
(titration)
Example - The titration of strong acid
HCl with strong base NaOH, a
standard solution of sodium
hydroxide is used to determine the
amount of HCl present. (we will deal
about this in Chapter 4.

05/22/2025
HCl + NaOH 39
 STANDARDIZATION AND CALIBRATION
2. Determination of analyte’s
concentration by direct comparison
 Some analytical procedures compare the property
of the analyte with that of a standard.
Color of the analyte (CuNO3)2) in Standard colors obtained by multiple dilutions of
the pure (CuNO3)2)
sample

05/22/2025 40
 STANDARDIZATION AND CALIBRATION
External standard calibration method
 An external standard is prepared separately from the sample
 They are used to calibrate the instrument and procedure
when there are no interference effects from matrix
components in the analytes solution.
 Steps to follow
1. A series of such external standards containing the
analyte in known concentrations is prepared.
2. Then a calibration curve is prepared by plotting the data
or by fitting them to a suitable mathematical equation,
such as the linear relationship used in the method of
least square.
3. The next step is the prediction step, in which the response
signal obtained for the sample is used to predict the
unknown analyte concentrations from the calibration
curve or best fit equation.
05/22/2025 41
 STANDARDIZATION AND CALIBRATION
Determination of analyte’s concentration by
direct comparison-----External standard
calibration method;

Color of the analyte (CuNO3)2) in the Standard colors obtained by multiple dilutions of pure
sample (CuNO3)2)

?
05/22/2025 M 42
 STANDARDIZATION AND CALIBRATION
 If you measure the absorbance (signal related
to the intensity of the color which directly
proportional to amount of Cu2+) of the standard
solutions prepared

Sstd=mCstd + b
m=slope of the
line b=the y
intercept

05/22/2025 43
 LINEAR REGRESSION-FINDING THE LEAST
SQUARE LINE
 When a calibration curve is a straight-line, we
represent it using the following mathematical
equation
 Y = mx + b
 where
 y is the signal, Sstd, and
 x is the analyte’s concentration, Cstd.
 The constants b is the calibration curve’s expected y-
intercept
 m is the expected slope
 Because of uncertainty in our measurements, the best
we can
do is to estimate values for m and b.
 The goal of a linear regression analysis is to
05/22/2025 44
determine the best estimates for the
 FINDING THE LEAST SQUARE LINE
Finding the least square line and estimate the slope and y
intercept
Example
 The table below represents the calibration data's for the

determination of isooctane in hydrocarbon mixture. Carryout a

least square analysis of the experimental data provided in the
table.
 In doing so, calculate the slope, intercept, and define the least square
line,
Conc X 0 0.1 0.2 0.3 0.4 0.5

Area Y 0 12.36 24.83 35.91 48.79 60.42

05/22/2025 45
 FINDING THE LEAST SQUARE LINE

7
0

6
0

5
Signal- Peak

4
0
area

3
0

2
0

1
0

0
0 0. 0. 0.3 0. 0.
1 2 5 6
0.4

05/22/2025 Concentration 46
 FINDING THE LEAST SQUARE LINE
The idea is to find the best equation of the line that fits
7
the data
0

6
0
Signal- Peak area

5
0

4
0
Y = mx + b
3
S pk = mConc +
(Spk)

0
b
2
0

1
0

0
0 0. 0. 0.3 0.4 0.
1 2 0.5 6

05/22/2025
Concentration - 47
 FINDING THE LEAST SQUARE LINE
 The closer the data points are to the line predicted
by a least-square analysis, the smaller are
residuals.
 How good is our prediction?

 An important quantity called coefficient of

determination
(R2)

R2= 1- (SSres/SStot)

05/22/2025 48
 FINDING THE LEAST SQUARE LINE
 The following standardization data were provided
for a series of external standards of Cd2+

Ca 15.4 30.4 44.9 59 72.7 86

Smeas
4.8 11.4 18.2 26.6 32.3 37.7

 Estimate the slope and y intercept and find the

least
square line by using linear regression analysis.

05/22/2025 49