Language of Analytical Chemistry 21.8.2021

Satish Pradhan
Dnyanasadhana College, Thane
(Arts, Science & Commerce)
Department of Chemistry
M.Sc. Analytical Chemistry Sem-I
Language of Analytical Chemistry
Dr.G.R.Bhagure
11/9/2021 M.Sc. ANALYTICAL CHEMISTRY 1

1.1.1
• Analytical Perspective, Common analytical Problems, terms involved in Analytical
Chemistry(analysis, determination, measurement, techniques, methods, procedures
and protocol)
1.1.2
• An overview of analytical methods of analytical methods, types of instrumental
methods, instruments for analysis, data domains, electrical and non electrical domains,
detectors, transducers and sensors, selection of an analytical method, accuracy,
precision, selectivity, sensitivity, detection limit and dynamic range
1.1.3
• Errors, determinate errors, and Indeterminate errors, types of determinate errors,
tackling of errors.
1.1.4
• Quantitative methods of analysis: calibration curve, standard addition and internal
standard methods
1.1 Language of Analytical Chemistry (8L)

• 1.2 Quality in Analytical Chemistry (7L)
• 1.2.1 Quality Management Systems (QMS)
• Evolution and significance of Quality Management Systems ,
• Types of quality standards for Laboratories,
• Total quality management(TQM)
• Philosophy implementation of TQM (Reference of
Kaizen,six sigma approch & 5S)
• Quality Audits &reviews,
• Responsibility of Laboratory staff for quality and problems

1.2.2
• Safety in Laboratories
• Basic concepts of safety in Laboratories, Personal Protection
equipment (PPE) OSHA ,
• Toxic Hazard(TH) classifications, Hazardous Chemical Processes
including (processs calorimetry/thermal build up concepts)

1.2.3 Accreditations
• Accreditation of Laboratories, Introduction to ISO series,
Indian Government Standard
• (ISI, Hallmark, Agmark)
• 1.2.4 Good Laboratory Practices (GLP)
• Principle,Objective,OECD Guidelines,
• The USFDA 21 CFR 58, Klimisch score

Definition of Analytical Chemistry
Analytical Chemistry is branch
of chemistry which deals with the
study of theory and practice of
methods used to determine
composition of matter.

The Analytical
Perspective
What is the “analytical perspective”? Many
analytical chemists describe this perspective as
an analytical approach to solving problems.
Although there are probably as many
descriptions of the analytical approach as there
are analytical chemists, it is convenient for our
purposes to treat it as a five-step process:

The Analytical
Perspective
1. Identify and define the
problem.
2. Design the experimental
procedure.
3. Conduct an experiment, and
gather data.
4. Analyze the experimental data.
5. Propose a solution to the
problem.

1
• Determine the type of information needed
• Qualitative, Quantitative ,characterization or fundamental
2
• Identify interferent
• Select method
• Establish validation data
• Establish sampling strategy
3
• Calibrate Instruments and equipments
• Standerdise reagent
• Gather data
4
• Reduce or transform data
• Analyze statistics
• verify results
• Interpretate results
5 • Conduct external evaluation

Common Analytical
Modules
❖ Qualitative Analysis –
Identification of components
from a sample
❖ Quantitative Analysis -
Estimation of ‘how much’ of a
component is present
❖ Characterization Analysis
❖ Fundamental Analysis

• The Language of Analytical Chemistry
1
• Analysis: A process that provides chemical or physical information about the constituents
in the sample or the sample itself.
2
• Analyte's: The constituents of interest in a sample.
3
• Matrix: All other constituents in a sample except for the analyte's.
4
• Determination: An analysis of a sample to find the identity, concentration,
or properties of the analyte.
5
• Measurement: An experimental determination of an analyte’s chemical or
physical properties.

• The Language of Analytical Chemistry
6
• Technique: A chemical or physical principle that can be used to analyze a
sample.
7
• Method: A method is the application of a technique for the determination of a
specific analyte in a specific matrix.
8
• Procedure: Written directions outlining how to analyze a sample.
9
• Protocol: a protocol is a set of stringent written guidelines detailing the
procedure that must be followed if the agency specifying the protocol is to
accept the results of the analysis.
• Protocols are commonly encountered when analytical chemistry is used to
support or define public policy.

Analytical Methods
Chemical
methods
Physical
Methods

Physical Change
14
Physical Change
11/9/2021 M.Sc. ANALYTICAL CHEMISTRY

15
Chemical Change
Combustion of Fuel

Classification of
Chemical Methods of Analysis
Gravimetry
or
Gravimetric analysis
Volumetry
or
Volumetric analysis

Chemical
reaction /
change
Precipitation
Neutralization
Oxidation
Reduction
Complexation
17

Analytical
Technique
developed on
Precipitation
Reaction
Gravimetry
Metal ion
Non Metal
ion
Chemical Methods
18

Analytical
Technique
based on
Chemical
Reaction
Volumetry
Acid Base
Titration
Precipitation
Titration
Complexomet
ric Titrations
Redox
Titration
Chemical Methods
19

Technique
based on
Oxidation
Reaction
Elemental
Analyzer
Carbon
Hydrogen
Nitrogen
Sulphur
20

Classification of
Instrumental
methods
Optical methods
Electroanalytical
methods
Separation
methods
Miscellaneous
methods

Detector
Detector
Optical methods

Optical
Property
Absorption
Emission
Scattering
Fluorescence
Phosphorescence
Optical Activity
Optical
Methods
23

Optical
methods
Absorption
spectroscopy
Emission spectroscopy.
Atomic absorption
Spectroscopy.
Infrared Absorption
Spectroscopy
Fluorophotometry
Turbidimetry and
Nephelometry
Raman Spectroscopy

Technique based on the
Principles of Absorption
of Light
UV-Visible Spectroscopy
IR Spectroscopy
Atomic Absorption
Spectroscopy
25

Radiation Source Collimating Lens Filter Sample Cell Photocell Read Out Device
SINGLE BEAM COLORIMETER

O.2
Read out Meter Amplifier PMT Detector Sample Cuvette Grating
Collimating Lense
Radiation Source
27
SINGLE BEAM SPECTROPHOTOMETER

Grating Tungsten Lamp
Mirror Deuterium Lamp
Mirror
Mirror
Sample Cuvette
PMT Detector
Blank Cuvette
Read
Out
Meter
PMT Detector
28
DOUBLE BEAM SPECTROPHOTOMETER

0.25
Grating
Read Out
Amplifier
Sample Solution
Power
Supply
Rotating Chopper
Flame
Hollow
Cathode
Lamp
P.M.T.Detector
29
Robert Wilhelm Bunsen and Gustav Robert
Kirchhoff, both professors at the University of
Heidelberg, Germany.
The modern form of AAS 1950s by a team of
Australian chemists. They were led by Sir Alan Walsh
62 different
metals
Atomic Absorption Spectrophotometer

Principles of atomic Emission
of Light
Flame Emission
Spectroscopy
Photoemission or
Photoelectron spectroscopy
(ESCA )
Inductively Coupled
plasma Atomic
Emission Spectroscopy
30

Atomic
Spectroscopy
Emission Spectra
Absorption
Spectra
11/9/2021 31
M.Sc. ANALYTICAL CHEMISTRY

Prism Monochromator
Read Out
Amplifier
Sample Solution
Oxidant
Slit
Collimating
Mirror
P.M.T.Detector
Na, Mg, K, Li from
blood samples
32
Fuel
0.456
Flame Photometer

PMT Detector
33
Nebulizer
Amplifier
Computer System
Read out device
system
Monochromator
Plasma
60 metals can be
determined up
to 10 ppb
ICPAES
SPCTROMETER
Greenfield et al. developed plasma-based
instruments in the mid 1960s about the same
time flame-based instruments such as FAAS
and FAES (Chapter 2) became prominent
(Analyst, 89, 713-720, 1964).

Technique developed on
the Principles of Molecular
Emission of Light
Fluorescence
Spectroscopy
Phosphorence
Spectroscopy
34

U.V. Light &
visible light
Photocell
/PMT
detector
Primary filter Secondary filter
Read Out Device
Sample Cell
35
Single Beam Fluorimeter

Read Out Device
PMT detector
36
PHOSPHORIMETER

Technique based on
the Principles of
Scattering of Light
Turbidimetry
Suitable for Large
Particle size
Drinking water
Nephelometry
Suitable for
Small Particle
size
Medicinal
preparation
like saline, eye
drops
37

visible light
38
Read Out
Device
Filter
Sample Cell
Photocell Detector
TURBIDIMETER

visible light
39
Light
Trap
Nephelometer
Read Out Device
Sample Cell
Photocell Detector
Collimating Lens
Graduated Disc

Monochromatic
light nonlinear
40
Polarizer Sample Cell
Monochromatic light Analyzer
Polarimeter

Electrical
Property
Electrical
Conductivity
Emf Of Cell
Diffusion
Current
Electric Charge
Resistivity
Electrical
Impedance
41

Electrochemical
Methods
Electrical
Conductivity
Electrical
Conductivity
Meter
Emf Of Cell Potentiometer
pH pH meter
Diffusion
Current
Polorography
42

Principles of Electrolysis
Voltammetry
Electrogrvimetry
Polorography
Amperometry
43

•Separation
techniques
•Why separations
is essential ?
44

Classical
Separation
Technique
Based on solubilities
filtration,
precipitation,
crystallization
Based on
Volatility
distillation
Based on
Electrical effect
Electrophoresis
Based on Gravity: Centrifugation
Classical
Separation
Technique
45

Based on Retention
capacity of
stationary phase
Chromatography
Adsorption
Chromatography
Partition
Chromatography
46
Modern methods of Separation Techniques

Adsorption
Chromatography
TLC
GSC
ION Exchange
Size Exclusion
Chromatography
47

TLC: Application of sample and
development of Chromatogram by
Ascending way
High
Polar
48
Less
Polar

ION EXCHANGE CHROMATOGRAPHY
H+
H+ Na+
R
49

ION EXCHANGE CHROMATOGRAPHY
H+
OH-
Cl-
R
50

Partition
Chromatography
Paper
Chromatography
HPLC
GLC
51

Original
Line
Solvent Front
Solute front
Solute front
S
O
L
V
E
N
t
F
L
O
W
52
Separation in Paper Chromatography
Application of Sample

53
Solvent -1
Reservoir
Solvent -2
Reservoir
Mixing
Vessel
Degasser-1 Degasser-2
High Pressure
Pump
Differential Detector
Pressure
Gauze
Analytical
Column
Sample
Injection
Port
Flow
meter
Pre
Column
Fraction Collector
HPLC Instrument

*
* *
* *
*
*
Pressure regulator
and flow control
Sample Injection
port
column
Column oven
Recorder
Detector
54
GAS CHROMATOGRAPHIC INSTRUMENT
Retention time
Carrier Gas Most Volatile Least Volatile

•New Versions of
Chromatography
55

New Versions of
Chromatography
Fusion of Two
Technique
GC-MS
LC-MS
56
Separation, Identification,
Quantification and Determination
of Molecular weight

GC-MS

LC-MS

Thermal Methods
TGA
mass change versus
temperature or
time
Differential
Thermal Analysis
temperature
difference versus
temperature or time
Evolved Gas
Analysis
analysis of gases evolved
during heating of a
material, usually
decomposition products
Differential
Scanning
Calorimetery
heat flow changes
versus temperature
or time
59
Thermal stability of a
material

Substance
Chemical
Changes
Heated
Physical
Changes
Thermogravimetric
analysis
60

Technique
based on
Radioactivity
NAA
Archeology
Forensic Science
Geology
Semiconductor
Industry
Isotope Dilution
Technique
Clinical
Diagnosis
61

Types of Instruments
Property to be measured

Signal/Characteristic property Instrumental Methods
Emission of radiation Emission spectroscopy (X-ray, UV, visible,
electron, Auger); fluorescence,
phosphorescence, and luminescence
(X-ray, UV, and visible)
Absorption of radiation Spectrophotometry and photometry (X-ray, UV, visible, IR);
photoacoustic spectroscopy; nuclear magnetic resonance and
electron spin resonance spectroscopy
Scattering of radiation Turbidimetry; nephelometry; Raman spectroscopy
Refraction of radiation Refractometry; interferometry
Diffraction of radiation X-Ray and electron diffraction methods

Rotation of radiation Polarimetry; optical rotary
dispersion; circular dichroism
Electrical potential Potentiometry; chronopotentiometry
Electrical charge Coulometry
Electrical current Polarography; amperometry
Electrical resistance Conductometry
Mass-to-charge ratio Mass spectrometry
Rate of reaction Kinetic methods
Thermal properties Thermal conductivity and enthalpy
Radioactivity Neutron Activation and
isotope dilution methods

DATA
DOMAINS
Electrical
Domains
Non
Electrical
Domains
Detectors,
Transducers
Sensors

Data
domains
Information contained in
Chemical and physical
Characteristics of property of
interest is called as data
domain.
Ex. Current,
voltage

Domain
Electrical domain
Current, voltage, frequency,
charge, pulse width, are
called as electrical domain
Non-Electrical
domain
Physical and chemical property
, scale, position and number
are called as non electrical
domain

Information contained in
Chemical and physical
Characteristics of
property of interest
Nonelectrical domain
Information for human
Interpretation in terms of
property interest and
manipulation
Nonelectrical domain
Instruments converts
Transduction processing
Electric Domain

Classification of
Transducers
The input transducer
The input transducer is called the sensor,
because it senses the desired physical
quantity and converts it into another
energy form.
The output transducer
It converts information in electrical
domain to information in non-electrical
domain
Ex. Voltmeters, computer screens

Types OF
TRANSDUCERS
PHOTO
TRANSDUCERS
THERMAL
TTRANSDUCERS
BIOSENSOR

PHOTO TRANSDUCER
Photo transducer is device that converts
light energy into electrical energy are called
Photo- transducer

A
C
B
D D
(--)
G
+
PHOTOCELL DETECTOR
E-
G

Collector Anode
Photo Cathode
AMPLIFIER RECORDER
PHOTO TUBE DETECTOR
-

A SENSOR
• A sensor some time also
called as detector that
measures a physical
quantity and converts it
into signal which can read
by an observer

Thermal Transducer
Thermocouple
• Thermocouple sensor used for high temperature
measurement.
• Thermocouple converts temperature to an out put voltage
which can read by a voltammeter.
Hg
• Mercury in glass thermometer converts measured
temperature.
Uses
• Cars, Aero plane, Chemical plant ,Elevators, Doors ,
Manufacturing machine ,robotics.

Biological
Sensors:
• A biosensor is an analytical
device used for detection of
analyte that combines a
biological component with
a physiochemical detector.

• Thermal Transducers Infrared radiation generally does
not have sufficient energy:
• to produce a measurable current when using a photon
transducer. A thermal transducer, therefore, is used for
infrared spectroscopy. The absorption of infrared photons
by a thermal transducer increases its temperature,
changing one or more of its characteristic properties. The
pneumatic transducer, for example, consists of a small
tube filled with xenon gas equipped with an IR-
transparent

SIGNAL
PROCESSOR
• A device, such as a meter or
computer, that displays the
signal from the transducer in
a form that is easily
interpreted by the analyst.

Amplifier
Weak
Signal
Strong
Signal
Amplifier
An Electronic device that increases the
power of signal

Selection of Analytical method:
1 • Concentration of the component.
2 • The complexity of the materials/presence of interfering material
3 • The probable concentration of the species of interest
4 • Degree of Accuracy
5 • Sensitivity and detection limit
6 • Duration of an analysis
7 • Speed ,time and Cost of analysis
8 • Availability of equipments
9 • Skill person for handling the instrument
All the above factors should be taken into account
combinedly, to select the proper method.

Performance characteristics of analytical Method
:
1.Precision: It is the agreement between Individual observations of same
set.
2.Accuracy: It is defined as closeness of the observed value with the
true value.
3 Limit of detection(LOD): Minimum amount of concentration of a
component that can be detected with a given degree of confidence.
4.Limit of Quantification (LOQ): Minimum amount of concentration of a
component that can be estimated with a given degree of confidence is termed
as LOQ.

:
5.Limit of Linearity (LOL) : It is defined as maximum concentration
range up to which instrument is produces linear response.
6.Sensitivity: It is a measure of ability of method to discriminate
between two small concentration differences in the analyte.
7.Measurement of Sensitivity:
• It is measured in terms of slope of the calibration curve. If the slope is
greater sensitivity of the method is high and vise-versa.

:
8.Selectivity: It is defined as degree to which the
method is free from interferences from other
components present in the matrix.
9.Dynamic range:
• It is the concentration range from limit of
Quantification (LOQ) to Limit of Linearity (LOL).

Unit- 1.1.3 and
1.1.4
1.1.3 Errors,determinate
errors,and Indeterminate
errors,types of determinte
errors,takaling of errors.
1.1.4 Quantitative
methods of analysis:
calibration curve, standard
addition and internal
standard methods

1.1.3
•Errors, determinate
errors ,and
Indeterminate
errors, types of
determinate errors,
takaling of errors.

Any measurement involves the interaction of
following three components
Analyst
Sample
Method
90
ERROR

Observed
Value
True
Value
Error
Difference between
11/9/2021 91

Types
of
Error
Determinate
error
Determinate error are
those for which source
can be observed or
detected
Indeterminate
error
The error are for which
source can not be
observed or not detected
or can be pinpointed.
11/9/2021 92

Sr. No. Characteristics Determinate
error
Indeterminate Error
1 Origin Source can be observed No Source can be observed
2 Magnitude Large Small
3 Direction Unidirectional No direction
4 Reproducibility Reproducible Not Reproducible
5 Effect Affect the measurement No Affect on measurement
6 Remedy Minimization possible,
elimination in some cases
possible
No elimination
93

• The difference between
the measured value and
True value
• Absolute error= xi -T
Absolute
error
• Absolute error / True
value
• = xi –T/T
Relative
error
11/9/2021 94

• The error in which the absolute
error remains constant and the
relative error changes with the
change in sample size
Constant
errors
• The error in which the
magnitude of the absolute error
changes with change in sample
size but relative error remains
constant
Proportionate
errors
11/9/2021 95

Types of
Determinant
error
Instrumental
errors
Methodic errors
Operational
errors
Personal error
96

2
Addition of
excess amount
of titrant
3
Incomplete
reaction
4
Incomplete
decomposition
5
Co-
precipitation
and post Co-
precipitation
1
Solubility of
salt
Methodic
Errors
These
types of
errors
obtained
due to
classical
methods
as these
methods
involves
no. of
steps.
MnNH4PO4 ---- Mn2P2O7 +2NH3+H2O
97

Operational
errors
Weighing of the
hot crucible
Loss of
precipitate
during filtration
Blowing of last drop
of in the nozzle of the
precipitate
Improper
recording of the
instrument
Under washing
or over washing
of the ppt.
Ignorance of
temp.
98

Personal error:
The error due to physical
limitation of the analyst and
some time bias during
measurement are called as
Personal error.
Ex. Colourblindnees of the person
unable to detect end point .
11/9/2021 99

Minimization
of errors
Calibration of
apparatus and
Instruments
Running Blank
determination
Use of Independent
method of analysis
Running control
determination
Running Parallel
determination
standard addition
method
Internal standard
method
Amplification method
100

• Operational and instrumental error can
be minimized
Calibration of
apparatus and
Instruments
• Methodic and operational errors can be
minimized
Running Blank
determination
• Standard sub., Analysed and its result compared
with the true value
• Deviation of the obtained result from the true or
expected value will be measure of Methodic and
operational errors
Running of
control
determination
101

• Analysis of same sample by two method of analysis ,one
which will be chosen & results obtained can be compared.
• Methodic and operational errors can be different
Use of
Independent
method of analysis
• Analysis of same sample by two different method by same
analyst, or different .
• Methodic error will differ in two cases ,if same analyst
• Methodic and personal error will be differ in two cases if
different analyst.
Running Parallel
determination
• Sample is analysed alone then sample + standard substance analysed
• Methodic and operational errors will be same for two measurements
standard addition
method
102

• Fixed amount of reference material is added
to all standard solutions ,blank and sample .
• Ex. Na is added in the analysis of soil while
determining lithium
Internal
standard
method
• detector singles are amplified to rectify the
improper response of detector.
• With the knowledge of type of error analyst
can modify existing method, type of error
and magnitude.
Amplification
method
103

Methods of Quantitative
Analysis
Calibration Curve Method
Standard Addition Method
Internal Standard
Addition Method:-
11/9/2021 104

1.
Calibration
Curve
Method
A calibration curve is used to determine the
unknown concentration of an element in a solution.
The instrument is calibrated using several solutions
of known concentrations.
Physical property of each known solution is
measured
Physical property of an element in sample solution
is measured
calibration curve is obtained by plotting graph of
Physical property v/s concentration
unknown concentration of the element is then
calculated from the calibration curve
11/9/2021 105

•Physical
property
•--
Concentration-----------
Emission Intensity is Directly proportional
to concentration
11/9/2021 106

When Standard Addition
Method is useful
1.Sample composition is
unknown
2. Sample composition
affect on analysis
3. To nullify the effect of
Matrix
When Standard Addition Method

2.Standard
Addition
Method
Physical property of unknown (X) is first found out
against blank.
Then a series of standards having definite amount of
unknown (X) plus varying amount of standard are
prepared and diluted to same volume in each case .
Their Physical property is recorded by one by one
A graph of Physical property against concentrations
of standard (S) gives a linear curve.
The concentration of the unknown can be determined
by extrapolation of line which cuts to X axis.
11/9/2021 108

Sr.No. Volume of Sample
solution
Volume of Standard
solution
Physical
property
1 X 0
2 X S
3 X 2S
4 X 3S
5 X 4S
6 X 5S
11/9/2021 109

Concentration-----
Physical
property
--
Concentration of Unknown.
Method of Standard Addition Method:-
11/9/2021 110

When Standard Addition
Method is useful
1. The instruments
responses varies slightly
from run to run.
2. Such response are
difficult to control
3. When sample loss occur
during sample preparation
Internal Standard Addition Method

Internal
Standard
addition
Method
A series of standard solution containing the same elements as that present in
sample solution is prepared.
A fixed quantity of suitable internal standard is then added to each of
standard solutions, blank and sample solutions alike
Physical property of Each of above standard solutions and sample solutions is
measured
Physical property for each of above standard solution (Is) & (Ii) and
sample solution (Ix&Ii) are measured at different wavelength one
corresponds to element and other corresponds to the internal
standard.
The ratio of Physical property of the standard solutions to that of internal
standard (Is/Ii) are plotted against the concentration of standard solutions.
This gives a straight line from this curve concentration of sample solution
can be read by finding where the ratio (Ix/Ii) falls on concentration scale.
11/9/2021 112

Internal Standard Method:
Sr. No. Volume Of
Sample
Solution
Concentration
Internal
Standard
(ppm)
O.D.
1 Blank 5 0.02
2 sample 5 0.06
3 5 5 0.08
4 10 5 0.1
5 15 5 0.12
6 20 5 0.14

Concentration-----
Concentration of Unknown.
Internal Standard Method
114
Property of
Sample
Property of
Internal standard

Language of Analytical Chemistry 21.8.2021

Recommandé

Recommandé

Contenu connexe

Tendances

Tendances (20)

Similaire à Language of Analytical Chemistry 21.8.2021

Similaire à Language of Analytical Chemistry 21.8.2021 (20)

Dernier

Dernier (20)

Language of Analytical Chemistry 21.8.2021