ANALYTICAL CHEMISTRY

Course Code: 0531 05 Chem -2103, Credits:02

Dr. Md. Ikram Hossain

Lecturer , Department of Chemical Engineering

Jashore University of Science and Technology, Jashore (7408)
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
COURSE CONTENT (as Summary)

Chapter 1. Introduction to Analytical Chemistry: analytical science, types of analysis: qualitative and quantitative analysis, analytical process,
choosing a method, validation of a method. Role of analytical chemistry. Reagents, classification of chemicals, Purification of substances, rules
of handling reagents and solutions. preparation and storage of standard solution ,cleaning and marking of glassware, analytical balance,
measuring volume, evaporating liquids, filtration and ignition of solids. Some important units of measurement. Laboratory note book,
Laboratory Safety.

Chapter 2: Sampling and sample preparation methodology: sample and sample types. Sampling and sampling methods for gas,liquids and
solids. Processing of sample, sample handling and treatment. Decomposition and dissolution of samples. Wet and dry ashing procedures.
Environmental sampling.
Chapter 3: Errors in measurements: Random and systematic errors. Precision and accuracy. Satistical treatment of data: Standard deviation,
variance, coefficient of variation. F-test, t-test, Q-test. The Gaussian distribution of deviations. Confidence level and limits. Propagation of
errors. Signal to noise ratio. Sensitivity and detection limits. Significant figure rules.

Chapter 4: Gravimetric methods of analysis: Conditions for analytical precipitation. Digestion of precipitates. Washing, filtration, drying and
igniting the precipitate. Homogeneous precipitation.

Chapter 5: Electro gravimetricmethods: Theory of electro-gravimetric analysis, Electrode reactions, Over potential, Completeness of
deposition, Electrolytic separation of metals, Character of the deposit, Electrolytic separation of metals with controlled cathode potential.

Chapter 6: Volumetric methods of analysis : Suitability of a reaction for use in volumetric analysis. Oxidation-reduction titrations, precipitation
titrations, redox indicators, adsorption indicators. Complexometric analysis. Formation constants of complexes. Chelates. EDTA titrations.
Effect of pH on EDTA equilibrium. Masking and damasking agents. Metal ion indicators. Potentiometric and conductometric methods of end
point determination.
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
Learning Objectives

After completing this chapter, you will be able to:

✓ Define analytical science and explain its role in research and industry.
✓ Differentiate between qualitative and quantitative analysis.
✓ Describe the analytical process and steps involved in method selection and validation.
✓ Identify types and classification of reagents and chemicals
✓ Apply rules for safe handling, purification, and storage of reagents and solutions.
✓ Use laboratory glassware and balances correctly for accurate measurements.
✓ Perform basic operations: filtration, evaporation, ignition of solids
✓ Use proper units and maintain a laboratory notebook accurately
✓ Follow laboratory safety rules and apply good laboratory practices (GLP)
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
Analytical science
➢ This is systematic study of the composition, structure, and properties of matter and
the methods used to obtain and interpret analytical data,
➢ It provides reliable chemical information for decision-making in research, industry,
health, and the environment,
➢ Integrates knowledge from chemistry, physics, biology, engineering, and data science;
So, A broader, interdisciplinary field that includes analytical chemistry but extends
beyond it.
➢ Focuses on the entire analytical process, from sampling and measurement to data
processing, automation, and quality assurance,
➢ Emphasizes modern technology, instrumentation, sensor systems, and data analytics

➢ Example: Designing a real-time sensor system for continuous air-quality monitoring

using analytical principles + engineering
Broadens the application of analytical chemistry to fields like public health,
environmental monitoring, and biopharmaceuticals. Often involves developing
new analytical methods and instruments.
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
Analytical Chemistry
❑ Analytical Chemistry deals with the chemical characterization of matter
✓ It answers two essential questions: As Everything is made of chemicals
What is it? → Qualitative Analysis (helps to identify)
How much is it? → Quantitative Analysis (measure them)

✓ Plays a vital role in all branches of chemistry, including:

•Agricultural – e.g., determining nitrogen in fertilizers
•Clinical – e.g., measuring blood glucose
•Environmental – e.g., detecting toxic gases in the air
•Forensic – e.g., detecting gunpowder residues
•Pharmaceutical & Manufacturing – ensuring drug purity and product quality
•Metallurgical – analyzing carbon content in steel
•Supports quality assurance and safety through accurate measurement.
•Ensures efficacy, safety, and compliance in chemical products and materials.

Late Charles N. Reilley said: “Analytical chemistry is what analytical chemists do”
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
Analytical Chemistry seeks ever-improved means of measuring the chemical composition
of natural and artificial materials, used to identify the substances that may be present in a
material and to determine the exact amounts of the identified substance.

Analytical chemists serve the needs of many fields:

✓ In medicine, analytical chemistry is the basis for clinical laboratory tests, which help
physicians diagnose disease and chart progress in recovery,
✓ In industry, analytical chemistry provides the means of testing raw materials and for
assuring the quality of finished products whose chemical composition is critical
✓ Many household products, fuels, paints, pharmaceuticals, etc., are analyzed by the
procedures developed by analytical chemists before being sold to the consumer,
✓ Environmental quality is often evaluated by testing for suspected contaminants using
the techniques of analytical chemistry.
✓ Nutritional value of food is determined by chemical analysis for major components such
as protein and carbohydrates, and trace components such as vitamins and minerals,
Indeed, even the calories in food are often calculated from its chemical analysis
✓ Analytical chemists also make important contributions to fields as diverse as forensics,
archaeology, and space science.
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
Chemical analysis….
A method of Separation, Identification and Quantification of different
components present in the given sample by using different analytical
techniques
Different types of chemical analysis -
Proximate Analysis?
✓ Proximate analysis is the process of determining the general composition
of a sample by measuring a few key parameters such as moisture, volatile
matter, ash, and fixed carbon (for fuels) or moisture, ash, crude protein,
fat, fiber, and, Nitrogen-free extract ,carbohydrates (for foods).

✓ Proximate analysis is important because it provides essential, quick, and

economical information about the composition and quality of a material —
whether it’s a fuel or a food product —Evaluation of Material Quality,
supporting for industrial, nutritional, and research applications..
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

Different types of chemical analysis -

Ultimate Analysis
✓ Ultimate analysis is the process of determining the elemental composition of a
material—especially fuels like coal, biomass, or petroleum products.
✓ It provides the percentage of individual elements such as carbon (C), hydrogen
(H), oxygen (O), nitrogen (N), sulfur (S), and sometimes ash.
✓ Accuracy is higher than Proximate Analysis
Importance of Ultimate Analysis
•Determination of Calorific Value
•Design of Combustion Systems
Essential for boiler and furnace design, as it tells how much air is needed for complete combustion.
•Pollution Control
Identifies sulfur and nitrogen contents, which help predict and control SO₂ and NOₓ emissions.
•Material Characterization
Provides detailed chemical information about the fuel for classification and comparison.
•Industrial Use
Used in energy generation, cement, steel, and power plants for selecting and blending fuels efficiently
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

Partial analysis,
✓ Which deals with the determination of selected constituents in the sample;
✓ Partial analysis is a limited or simplified form of analysis in which only
selected components of a material or mixture are determined—rather than
the full composition
✓ It provides specific information needed for a particular purpose without
performing a complete (proximate or ultimate) analysis
Key Features
✓ Involves determination of one or a few components (not all)
✓ Faster, simpler, and cheaper than full analysis
✓ Used when complete data are not necessary for decision-making
✓ Often used as a preliminary test before detailed analysis.

❖The component of interest in the sample is called the analyte, and the remainder of
the sample is the matrix.
 ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
Analytical process
The analytical process in chemistry can be considered as consisting of four principal
stages of operation
1. Sampling
2. Isolation (separation) of the desired constituent in a measurable state
3. Measurement of the desired constituent
4. Calculation and interpretation of the numerical data
1. Sampling
➢ First, step in any chemical analysis is procuring a representative sample to measure;
➢ Collecting a representative portion of material for analysis
Example 1: Suppose a chemist wants to determine the amount of arsenic in rice grown in a certain region. The
chemist collects rice grains from different fields, mixes them thoroughly, and analyzes a representative portion. This
ensures that the sample accurately represents the overall arsenic content in the region’s rice.

Example 12: In a fertilizer manufacturing plant, large shipments of phosphate rock arrive as raw material. Before
unloading the entire shipment, samples are taken from different parts of the cargo (top, middle, and bottom layers).
These samples are combined and mixed thoroughly to form a composite sample. A small portion of this composite is
analyzed to determine the phosphorus content and impurities (like silica or iron). This ensures the raw material meets
required specifications before it enters production.
Skoog, D. A. et al. Fundamentals of Analytical Chemistry,;Quantitative Chemical Daniel C Harris; Basic_Concepts_of_Analytical_Chemistry SM_Khopkar, Christian, G. D. Analytical Chemistry
 ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
2. Isolation (separation) of the desired constituent in a measurable state
➢ This step involves separating or isolating the component of interest (analyte) from the
rest of the sample matrix
➢ Removing interferences to obtain the analyte in a measurable form
➢ In the analysis of calcium in milk, the sample contains fat, protein, and other ions that
could interfere. To accurately measure calcium, the analyst first digests or precipitates
the milk sample to remove organic matter and isolate calcium as calcium oxalate,
which can then be measured accurately.
Classification of Separation Techniques- can be classified based on the principle or method used to
separate the analyte from the sample matrix
(i) Mechanical (or Physical) Separation Methods: These rely on physical properties such
as particle size, density, or phase to separate the desired component.
Examples:
Filtration- separating a solid precipitate from a liquid ( filtering calcium oxalate from
olution);
Centrifugation – separating components based on density differences (e.g., separating
plasma from blood)
Decantation – Pouring off a liquid after a solid has settled; Rice wash
Skoog, D. A. et al. Fundamentals of Analytical Chemistry,;Quantitative Chemical Daniel C Harris; Basic_Concepts_of_Analytical_Chemistry SM_Khopkar, Christian, G. D. Analytical Chemistry
 ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
2. Isolation (separation) of the desired constituent in a measurable state
2. Chemical Separation Methods
These involve chemical reactions that selectively convert the analyte or impurities into
different chemical forms that can be separated.
Examples:
✓ Precipitation – forming an insoluble compound of the analyte (e.g., precipitating
chloride as silver chloride).
✓ Extraction – transferring the analyte into another solvent where it is more soluble (e.g.,
extracting metal ions using organic solvents).
✓ Ion exchange – using resins to separate ions based on charge (e.g., separating cations
and anions in water).
3. Physicochemical (Instrumental) Separation Methods
Use both physical and chemical principles, often with instruments, to isolate and measure
Examples:
•Chromatography – separation based on differences in partitioning between stationary and mobile
phases (e.g., gas chromatography, HPLC).
•Electrophoresis – separation based on movement of charged particles in an electric field.
•Distillation – separation based on boiling point differences (e.g., separating ethanol from water).
Skoog, D. A. et al. Fundamentals of Analytical Chemistry,;Quantitative Chemical Daniel C Harris; Basic_Concepts_of_Analytical_Chemistry SM_Khopkar, Christian, G. D. Analytical Chemistry
 ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
3. Measurement of the desired constituent
➢ Once the analyte is isolated, it must be measured using a suitable method. The
measurement provides quantitative (how much) or qualitative (what is it) information
about the substance. This step can involve classical chemical methods or modern
instrumental techniques
Classification of Measurement Methods
Analytical measurements can be broadly classified into two main categories:
(i) Classical (Wet Chemical) Methods
Based on chemical reactions and manual operations without modern instruments
Type Principle Example
Gravimetric Measurement based on the mass of a pure Determination of sulfate as BaSO₄
Analysis compound formed from the analyte. by weighing the dried precipitate.
Volumetric Measurement based on the volume of a standard
Determining the acidity of vinegar
(Titrimetric) solution required to react completely with the
by titrating with NaOH.
Analysis analyte.
Determining carbon content by
Gasometric Measurement of volume of gas evolved or
measuring CO₂ evolved during
Analysis absorbed in a reaction.
combustion.
Skoog, D. A. et al. Fundamentals of Analytical Chemistry,;Quantitative Chemical Daniel C Harris; Basic_Concepts_of_Analytical_Chemistry SM_Khopkar, Christian, G. D. Analytical Chemistry
 ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
3. Measurement of the desired constituent
(ii) Instrumental (Modern) Methods: Rely on the measurement of physical or
physicochemical properties using scientific instruments. They are fast, sensitive, and
suitable for trace-level detection.
Category Measured Property Example Techniques Typical Use
Interaction of analyte with UV–Visible Spectrophotometry,
Determining metal ions,
Spectroscopic electromagnetic radiation Atomic Absorption Spectroscopy
organic functional groups,
Methods (absorption, emission, (AAS), Atomic Emission, IR
etc.
fluorescence) Spectroscopy
Electrical properties Measurement of ion
Electroanalytic Potentiometry (pH meter),
(potential, current, concentration (e.g., pH,
al Methods Conductometry, Voltammetry
resistance) chloride)
Differential distribution Separation and
Chromatograp
between stationary and Gas Chromatography (GC), HPLC quantification of mixtures
hic Methods
mobile phases (e.g., drugs, hydrocarbons)
Mass Mass-to-charge ratio of Identification of unknown
GC–MS, LC–MS
Spectrometry ions compounds
Thermogravimetric Analysis (TGA),
Thermal Change in mass or heat Studying decomposition,
Differential Scanning Calorimetry
Methods with temperature purity, thermal stability
(DSC)
Skoog, D. A. et al. Fundamentals of Analytical Chemistry,;Quantitative Chemical Daniel C Harris; Basic_Concepts_of_Analytical_Chemistry SM_Khopkar, Christian, G. D. Analytical Chemistry
 ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
4. Calculation and interpretation of the numerical data
➢ An analysis is not complete until the results have been expressed in such a manner
units (such as mg/L, % composition, or molarity) that the person for whom the results are
intended can understand their significance
➢ In recent years, greater attention has been paid to statistical techniques both in
development and in assessing the value of the final analytical results. This has led to
the establishment of a new branch of science termed Chemometrics
➢ In this final stage of the analytical process, where the raw measurement data obtained
from the experiment or instrument are processed mathematically to produce a
meaningful result (e.g., concentration, purity, percentage composition),
➢ Once the result is calculated, it is interpreted — that is, compared against:
Theoretical values; Specifications or standards Regulatory limits or tolerances;

This step converts numerical data into chemical understanding and decision-making —
for quality control, environmental safety, research conclusions, or industrial production.
Spectrophotometric measurements show that the absorbance corresponds to 0.015 mg/L of
copper in water, the analyst compares this result with environmental standards. For instance, if the
safe limit is 2.0 mg/L, the water is considered safe for drinking.
Skoog, D. A. et al. Fundamentals of Analytical Chemistry,;Quantitative Chemical Daniel C Harris; Basic_Concepts_of_Analytical_Chemistry SM_Khopkar, Christian, G. D. Analytical Chemistry
 ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

❑ Methods of Chemical analysis is mainly of two types

1. Qualitative chemical analysis

✓ Means to measure something by its quality rather than quantity

✓ Very often, we cannot use numbers or numerical expressions to describe
✓ Identification of atomic or molecular species or the functional groups in the
sample (What),
✓ Identification of a substances using characteristic such as color and solubility

❖ Identification of analysts, by using different types of analytical methods

Skoog, D. A. et al. Fundamentals of Analytical Chemistry,;Quantitative Chemical Daniel C Harris; Basic_Concepts_of_Analytical_Chemistry SM_Khopkar
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

1. Qualitative chemical analysis

o Inorganic Simple salt analysis and Mixture analysis for
identification of different anions and cations present in the given
unknown sample.
o Organic Compound analysis for identification of different functional
groups present in the given unknown compound

Potassium - Purple Sodium - Yellow Barium - Green

ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

2.0 Quantitative analysis –

Numerical information as to the relative amount of one or more of the components
(How much, Quantification)
➢ the sign (negative or positive)
➢ the magnitude
Both give the meaningful information.
CLASSIFICATION OF DIFFERENT ANALYTICAL TECHNIQUES
❑ Classical methods,
✓ Conventional type of methods for quantitative determination of analytes
✓ Consists of analytical techniques that use no electronic instruments other than
a balance.
✓ Usually relies on chemical reactions between the material being analyzed
(the analyte) and a reagent that is added to the analyte.
Like -Gravimetric, Volumetric, etc
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
CLASSIFICATION OF DIFFERENT ANALYTICAL TECHNIQUES
❑ Electrical methods of analysis
-Involve the measurement of current, voltage or resistance in relation to the
concentration of a certain species
Techniques under this general heading are
(i) Voltammetry
-measurement of current at a micro-electrode at a specified voltage
(ii) Coulometry
-measurement of current and time needed to complete an electrochemical reaction
or to generate sufficient material to react completely with a specified reagent
(iii) Potentiometry
-measurement of the potential of an electrode in equilibrium with an ion to be
determined
(iv) Conductimetry
-measurement of the electrical conductivity of a solution
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
CLASSIFICATION OF DIFFERENT ANALYTICAL TECHNIQUES
❑Optical methods of analysis
Dependent either upon
(i) Measurement of the amount of radiant energy of a particular wavelength absorbed
by the sample, or
(ii) The emission of radiant energy and measurement of the amount of energy of a
particular wavelength emitted.
➢ Absorption
-Methods are usually classified according to the wavelength involved as
(a)Visible spectrophotometry
(b)Ultraviolet spectrophotometry, and
(c) Infrared spectrophotometry.
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
CLASSIFICATION OF DIFFERENT ANALYTICAL TECHNIQUES
❑Optical methods of analysis
➢ Emission Methods
- Involve subjecting the sample to heat or electrical treatment, so that atoms are
raised to excited States causing them to emit energy: it is the intensity of this
emitted energy which is measured.
The common excitation techniques are:
(a) Emission spectroscopy, where the sample is subjected to an electric arc or
spark plasma and the light emitted
(b) Flame photometry, in which a solution of the sample is injected into a flame;
(c) Fluorimetry, An analytical method that utilizes ultraviolet light to excite
the sample and detects the fluorescence emitted during the return of the
sample to its ground state.
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
CLASSIFICATION OF DIFFERENT ANALYTICAL TECHNIQUES
❑ Nuclear radiation methods of analysis
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
CLASSIFICATION OF DIFFERENT ANALYTICAL TECHNIQUES
❑ Thermal methods of analysis
• Measured as a function of temperature
• Temperature is used as an independent variable while in some others as a dependent variable say time
• Helpful in interpreting the thermal behavior of the sample.
 Chapter 1. Introduction to Analytical Chemistry
CLASSIFICATION OF DIFFERENT ANALYTICAL TECHNIQUES
❑ Classification of Separation Methods
A. Classical methods
a) Precipitation
b) Distillation
c) Sublimation
d) Formation of complexes
B. Modern methods
i) Chromatography
ii) Solvent extraction
iii) Ion-Exchange
iv) Electrophoresis
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

On the basis of sample size, analytical methods are often classified as:

1. Macro, the analysis of quantities of 0.1 g or more;

2. Meso (semimicro), dealing with quantities ranging from 10-2 g to 10-1 g;
3. Micro, for quantities in the range 10-3 g to 10-2g;
4. Submicro, for samples in the range 10-4 g to 10-3g;
5. Ultramicro, for quantities below 10-4 g.

A major constituent is one accounting for 1- 100 per cent of the sample under
investigation;
A minor constituent is one present in the range 0.01-1 per cent; a trace constituent
is one present at a concentration of less than 0.01 per cent.
 Chapter 1. Introduction to Analytical Chemistry

Some of the major areas of application are listed below

(a) Fundamental Research

(b) Product Development
(c) Product Quality Control
(d) Monitoring and Control of Pollutants
(e) Assay
(f) Medical and Clinical Studies

Fifield1995-7
 Chapter 1. Introduction to Analytical Chemistry
Analytical problems and their solution (qualitative and quantitative)
1) Choice of Method
In the method selection, a compromise has to be reached between the sensitivity, precision and
accuracy desired of the results and the costs involved.
(2.) Sampling
Correct sampling is the cornerstone of reliable analysis. The analyst must decide in conjunction
with his technological colleagues how, where, and when a sample should be taken so as to be truly
representative of the parameter that is to be measured

(3) Preliminary Sample Treatment

For quantitative analysis, the amount of sample taken is usually measured by mass or volume.
Where a homogeneous sample already exists, it may be subdivided without further treatment. With main solids
such as ores, however. crushing and mixing are a prior requirement. The sample often needs additional
preparation for analysis, such as drying, ignition and dissolution.
 Chapter 1. Introduction to Analytical Chemistry
Analytical problems and their solution (qualitative and quantitative)

(4) Separations
A large proportion of analytical measurements is subject to interference from other
constituents of the sample.
Newer methods increasingly employ instrumental techniques to distinguish between
analyte and interference signals.
However, such distinction is not always possible and sometimes a selective chemical
reaction can be used to mask the interference.
(5) Final Measurement
This step is often the quickest and easiest of the seven but can only be as reliable as
the preceding stages. The fundamental necessity is a known proportionality between
the magnitude of the measurement and the amount of analyte present
 Chapter 1. Introduction to Analytical Chemistry

(6) Method of Validation

-To ensure that results yielded by a method are as accurate as possible, it is essential to validate the method by
analyzing standards which have an accepted analyte content, and a matrix similar to that of the sample. The accepted
values for these validated standards are obtained by extensive analysis, using a range of different methods.
Internationally accepted standards are available. In order to ensure continued accurate analysis, standards must be re-
analysed at regular intervals.

(7) The Assessment of Results

Results obtained from an analysis must be assessed by the appropriate statistical methods and their meaning
considered in the light of the original problem
 Chapter 1. Introduction to Analytical Chemistry

Requirements of the analysis determine the best method

Following design criteria considered :

I. Accuracy,
II. Precision,
III. Sensitivity,
IV. Selectivity,
V. Robustness,
VI. Scale of operation,
VII. Analysis time,
[Link] of equipment, and cost
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

I. Accuracy
Accuracy is how closely the result of an experiment agrees with the “true” or
expected result. We can express accuracy as an absolute error, e
e=obtained result−expected result
or as a percentage relative error, %er

obtained result−expected result

%er= ×100
expected result
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry

II. Precision,
When a sample is analyzed several times, the individual results vary from trial-to-trial. Precision is a measure
of this variability. The closer the agreement between individual analyses, the more precise the results.

✓ It is important to understand that precision does not imply accuracy. That the data in the upper half of Figure 1
are more precise does not mean that the first set of results is more accurate. In fact, neither set of results may
be accurate.

Figure 1 : Two determinations of the concentration of K+ in serum, showing the effect of precision on the
distribution of individual results. The data in (a) are less scattered and, therefore, more precise than the data in
(b).
ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry
Difference Between Accuracy and Precision

Accuracy Precision
Accuracy refers to the level of agreement Precision implies the level of variation
between the actual measurement and the that lies in the values of several
absolute measurement. measurements of the same factor.
Represents how closely the results agree Represents how closely results agree
with the standard value. with one another.
Multiple measurements or factors are
Single-factor or measurement.
needed.
It is possible for a measurement to be
Results can be precise without being
accurate on occasion as a fluke. For a
accurate. Alternatively, the results can be
measurement to be consistently
precise and accurate.
accurate, it should also be precise.
 Chapter 1. Introduction to Analytical Chemistry
Error
❑ Refers to the difference between true and measured value.
❑ The standard value can be obtained by following methods -
Absolute Error: The absolute error of a measurement is the difference between
the measured value and the true value. If the measurement result is low, the sign
is negative; if the measurement result is high, the sign is positive.
𝐸 = 𝑋𝑖 -𝑋𝑡

Relative Error
• Of a measurement is the absolute error divided by the true value.
• Can be expressed in percent, parts per thousand, or parts per million, depending
on the magnitude of the result.
𝐸 = 𝑋𝑖𝑋−𝑋𝑡*100%
𝑡
 Chapter 1. Introduction to Analytical Chemistry
Error
Classification of errors
Generally Chemical analyses are affected by two types of errors:
1. Systematic (or determinate) error, causes the mean of a data set to differ
from the accepted value.

There are several types of systematic errors: most important types are -
i. Personal errors and Operational errors
ii. Instrumental errors and reagent errors-
iii. Errors of methods
iv. Additive
v. Proportional error – error magnitude depends on the sample size
2. Random (or indeterminate) error, causes data to be scattered more or less
symmetrically around a mean value.
 Chapter 1. Introduction to Analytical Chemistry

1.0 Systematic (or determinate) error,

i) Personal errors and Operational Errors:
-the individual analyst is responsible for this. This type of errors may arise due to
the inability of the individual making observations. Some important personal errors
are:
a. Inability in judging color change sharply in visual titrations.
b. Error in reading a burette.
c. Mechanical loss of material in various steps of an analysis.
d. Failure to wash and ignite a precipitate properly.
e. Insufficient cooling of crucible before weighing.
f. Using impure reagents.
g. Ignition of precipitate at incorrect temperatures.
h. Errors in calculations.
 Chapter 1. Introduction to Analytical Chemistry

1.0 Systematic (or determinate) error,

ii. Instrumental errors and reagent errors-

Following factors are responsible for such errors:
a. Balance arms of unequal lengths.
b. Uncalibrated or improperly calibrated weights.
c. Incorrectly graduated burettes.
d. Attack of foreign materials upon glassware.
e. Loss in weight of platinum crucibles on strong heating.
f. Impure reagents.
Errors can be avoided by using calibrated weights, glassware and pure reagents.
 Chapter 1. Introduction to Analytical Chemistry

1.0 Systematic (or determinate) error,

iii. Errors of methods

These originate from incorrect sampling and from incompleteness of a reaction.
➢ In gravimetric analysis errors may arise owing to appreciable solubility of
precipitates, co-precipitation, and post-precipitation, decomposition, or volatilization
of weighing forms on ignition, and precipitation of substances other than the
intended ones.
➢ In titrimetric analysis errors may occur owing to failure of reactions to proceed to
completion, occurrence of induced and side reactions, reaction of substances other
than the constituent being determined, and a difference between the observed end
point and the stoichiometric equivalence point of a reaction.
 Chapter 1. Introduction to Analytical Chemistry

1.0 Systematic (or determinate) error,

IV. Additive
The error is constant in a series of determination of the result
Absolut vale of additive error is independent of the amount of the constituent
present in the determination e.g., loss in weight of a crucible adds error to the
weight of precipitate is ignited in it.
2.0 Random or Indeterminate Errors:
These errors are accidental and analyst has no control over them.
➢ These are random in nature and lead to both high and low result with equal
probability
➢ These cannot be eliminated or corrected and are the ultimate limitation on the
measurement.
➢ These can be treated by statistics repeated measurements of the same variable
can have the effect of reducing their importance.
 Chapter 1. Introduction to Analytical Chemistry
❑ Purification of substances
✓ For the identification of a compound, qualitative analysis of pure substance is required
✓ Need to purify the substance and then check its purity.
Several method
✓ Crystallization, Distillation, Sublimation, Differential Extraction, Chromatography etc.
available for purification of a compound
Sublimation-
Some solids can directly pass to the vapor state without going through the liquid phase
It is helpful in separating sublimable compounds from non-sublimable ones.

-Purification of camphor, naphthalene, anthracene, benzoic acid, Iodine and salicylic acid
etc containing non-volatile impurities.
 Chapter 1. Introduction to Analytical Chemistry
❑ Purification of substances
Crystallization
➢ Crystallization is the physical transformation (phase transition) of a liquid,
solution, or gas to a crystal, which is a solid with an ordered internal
arrangement of molecules, ions, or atoms.
➢ Used to separate a dissolved solid from a solution, when the solid is much
more soluble in hot solvent than in cold
➢ The solution is heated, allowing the solvent to evaporate to leave a saturated
solution behind
➢ Saturated solution is allowed to cool slowly and solids will come out of the
solution as the solubility decreases, and crystals will grow
Application of Crystallization:
•Purification of seawater
•Separation of alum crystals from impure samples
•In the pharmaceutical industry, crystallization is used as a separation and purification
process for the synthesis and isolation of co-crystals, pure active pharmaceutical
ingredients (API), controlled release pulmonary drug delivery, and separation of chiral
isomers.
 Chapter 1. Introduction to Analytical Chemistry
❑ Purification of substances

Simple Distillation
Separating mixtures based on differences in their volatilities in a boiling liquid mixture.

---Used to separate a liquid and soluble solid from a

solution (e.g. water from a solution of saltwater) or a pure
liquid from a mixture of liquids
---The solution is heated and pure water evaporates
producing a vapor which rises through the neck of the
round-bottomed flask
---The vapour passes through the condenser, where it
cools and condenses, turning into pure liquid H2O which is
collected in a beaker
After all the water is evaporated from the solution, only the
solid solute will be left behind
 Chapter 1. Introduction to Analytical Chemistry
❑ Purification of substances
Differential Extraction
➢ This method is used (purify) for immiscible liquids, that is, liquids that do not mix together
➢ Based on the difference in solubilities of the substance in different liquids
➢ For example, oil and water are immiscible.

The immiscible liquids are taken in a separating funnel and left undisturbed. After a while, they separate out
according to their specific gravities, with the heavier liquid at the bottom. Then they are later collected.

.
 Chapter 1. Introduction to Analytical Chemistry
❑ Purification of substances
Chromatography
➢ Based on the difference in rates of adsorption of the substance in a suitable
adsorbent.
➢ Types of chromatography such as paper chromatography, gas chromatography, column
chromatography, etc. The simplest is column chromatography

Method
A suitable adsorbent is packed into a column. This is known as the stationary phase.
Commonly used adsorbents are alumina (Al2O3), silica (SiO2), magnesium oxide (MgO) and
Fuller's earth. In column chromatography-

[Link] mixture of substance to be separated is dissolved in a suitable solvent and the solution is
poured on top of the column.
[Link] different components of the mixture get adsorbed in different parts of the column based
on their adsorptivity. The component to be with high adsorptivity is adsorbed at the top of the
column. The one with least adsorptivity is absorbed at the bottom of the column. Thus, different
bands of components are obtained based on their adsorptivity in the column.
 Chapter 1. Introduction to Analytical Chemistry
Column chromatography-
iii. The substances are then extracted using a suitable solvent. This is known as the mobile
phase. Commonly used solvents are petroleum ether, carbon tetrachloride, benzene,
alcohol, etc. The mobile phase is also known an eluent. The eluent dissolves and elutes out
the various components selectively. The weakest adsorbed component (the one with
least adsorptivity) is eluted out first. The component with maximum adsorptivity shows
minimum elution.
Stationary Phase
The substance on which the different components are adsorbed (adsorbent) is known as stationary phase. The
stationary phase may be a solid or a liquid but never a gas.
Mobile Phase
The substance which is used to extract the different components from the adsorbent is known as mobile phase. The
mobile phase may be a liquid or a gas but never a solid.

Types of chromatography Stationary phase Mobile phase

Column chromatography Solid Liquid

High performance liquid chromatography Solid Liquid
Thin layer chromatography (TLC) Solid Liquid
Gas chromatography: Gas
Liquid
a. Gas-liquid Gas
Solid
b. Gas-solid
 Chapter 1. Introduction to Analytical Chemistry
Column chromatography-
 Chapter 1. Introduction to Analytical Chemistry
❑ Rules for Handling Reagents and Solutions
➢ High-quality chemical analysis requires reagents and solutions of known purity
(A freshly opened bottle of a reagent-grade chemical can usually be used with confidence)

Rules to follow to prevent the accidental contamination of reagents and solutions

a) Select the best grade of chemical, -Pick the smallest bottle that is sufficient to do the job
2. Replace the top of every container immediately after removing reagent,
Do not rely on someone else to do so.
3. Hold the stoppers of reagent bottles between your fingers. Never set a stopper on a desk top
4. Never return any excess reagent to a bottle again, Unless specifically directed,
5. Never insert spatulas, spoons, or knives into a bottle that contains a solid chemical
6. Keep the reagent shelf and the laboratory balance clean and neat
7. Follow local regulations concerning the disposal of surplus reagents and solutions
 Chapter 1. Introduction to Analytical Chemistry
❑ Rules for Handling Reagents and Solutions
SOLIDS CHEMICALS

Figure 1: The transfer of a large amount of solid.

Figure 2: The transfer of a small amount of solid

Figure 3: Using a piece of weighing paper to transfer a solid.

 Chapter 1. Introduction to Analytical Chemistry
❑ Rules for Handling Reagents and Solutions
LIQUID CHEMICAL TRANSFER
 Chapter 1. Introduction to Analytical Chemistry

❑Cleaning and marking of of laboratory ware

➢ Chemical analysis is performed in a duplicate or triplicate way
--- Vessel containing a sample must be marked , identified easily
➢ Having small etched areas like Flasks, beakers, and some crucibles—
-Use semi permanent markings pencil
➢ Special marking inks are available for porcelain surfaces The marking is baked permanently into the glaze by
heating at a high temperature
➢ Every beaker, flask, or crucible that will contain the sample must be thoroughly cleaned before being used
➢ Apparatus should be washed with a hot detergent solution and then rinsed
—Initially with large amounts of tap water and finally with several small portions of deionized water
➢ Properly cleaned glassware will be coated with a uniform and unbroken film of water
---- Seldom necessary to dry the interior surface of glassware before use
 Chapter 1. Introduction to Analytical Chemistry
EVAPORATING LIQUIDS

--- A process by which a liquid or solid is transformed into vapor

--- Happens on the surface of liquids
---This process is said to involve a change in the state of matter of liquids
---The surrounding gas must not be saturated with the substance which is evaporating
--- Sometimes difficult to control because of the tendency of some solutions to overheat locally
---Unwanted substances can be eliminated during evaporation
--- Chemically its possible to enhance this process
--- Bumping is the sudden, often violent boiling tending to spatter solution out of its
container
---Wet ashing is the oxidation of the organic constituents of a sample with oxidizing reagents
 Chapter 1. Introduction to Analytical Chemistry

Analytical balance
➢ To measure masses with high accuracy

➢ An analytical balance has a maximum capacity that ranges from 1 g to several kilograms and
a precision at maximum capacity of at least 1 part in 105
➢ Macrobalance most common type of analytical balance with precision of 0.1 mg having load of
160 to 200 g
➢ A semimicroanalytical balance has a maximum load of 10 to 30 g with a precision of 0.01 mg
➢ A micro analytical balance has a maximum load of 1 to 3 g and a precision of 0.001 mg,
 Chapter 1. Introduction to Analytical Chemistry
Electronic Analytical Balance
➢ Pan rides above a hollow metal cylinder, surrounded by a coil that fits over the inner pole of a permanent magnet
➢ An electric current in the coil produces a magnetic field that supports or levitates cylinder, pan and indicator arm &
load on pan
➢ Current is adjusted so that the level of the indicator arm is in the null position when the pan is empty
➢ Placing an object on the pan causes the pan and indicator arm to move downward, thus increasing the amount of
light striking the photocell of the null detector
➢ The increased current from the photocell is amplified and fed into the coil, creating
a larger magnetic field, which returns the pan to its original null position
➢ Current required to keep the pan and object in the null position is
directly proportional to the mass of the object and is easily
measured, digitized, and displayed.

➢ A device such as this, in which a small electric current causes a

mechanical system to maintain a null position, is called a servo system

Figure1. Electronic analytical balance, Block diagram

ANALYTICAL CHEMISTRY Chapter 1. Introduction to Analytical Chemistry