Lecture 1 INTRODUCTION TO INSTRUMENTAL

ANALYSIS

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OUTLINE:
CLASSIFICATION OF ANALYTICAL METHODS
TYPES OF INSTRUMENTAL METHODS
INSTRUMENTS FOR ANALYSIS
SELECTING AN ANALYTICAL METHOD
CALIBRATION OF AN INSTRUMENTAL METHODS

INTRODUCTION

Problem set:
1-4, 1-9, 1-10, 1-11

Classical vs Instrumental
Qualitative instrumental analysis is that measured property that indicates
presence of analyte in matrix
Quantitative instrumental analysis is that magnitude of measured property
that is proportional to concentration of analyte in matrix
Species of interest
All constituents including analyte.
Often need pretreatment - chemical extraction, distillation,
separation, precipitation

CLASSIFICATION OF ANALYTICAL METHODS

CLASSICAL:
Qualitative - identification by color, indicators, boiling points,odors
Quantitative - mass or volume (e.g. gravimetric, volumetric)
INSTRUMENTAL:
Qualitative - chromatography, electrophoresis and identification by measuring
physical property (e.g. spectroscopy, electrode potential)
Quantitative - measuring property and determining relationship to concentration
(e.g. spectrophotometry, mass spectrometry). Often, same instrumental
method used for qualitative and quantitative analysis.

INTRODUCTION

PROPERTY

EXAMPLE METHOD

Radiation Emission

Emission spectroscopy - fluorescence,

phosphorescence, luminescence

Radiation Absorption

Absorption spectroscopy spectrophotometry, photometry, nuclear

magnetic resonance, electron spin
resonance

Radiation Scaterring

Turbidity, Raman

Radiation Refraction

Refractometry, interferometry

Radiation Diffraction

X-ray, electron

Radiation Rotation

Polarimetry, circular dichroism

TYPES OF INSTRUMENTAL METHODS

PROPERTY

EXAMPLE METHOD

Electrical Potential

Potentiometry

Electrical Charge

Coulometry

Electric Current

Voltammetry - amperometry, polarography

Electrical Resistance

Conductometry

Mass

Gravimetry

Mass-to-charge Ratio

Mass spectrometry

Rate of Reaction

Stopped flow, flow injection analysis

Thermal Characteristics

Thermal gravimetry, calorimetry

Radioactivity

Activation, isotope dilution

Often combined with chromatographic or electrophoretic methods

TYPES OF INSTRUMENTAL METHODS

Block diagram
for the overall
process of
instrumental
measurement.

Example:
spectrophotometry
Instrument:
spectrophotometer
Stimulus:
monochromatic light energy
Analytical response:
light absorption
Transducer:
photocell
Data:
electrical current
Data processor:
current meter
Readout:
meter scale

INSTRUMENTS FOR ANALYSIS

DATA DOMAINS: way of encoding analytical response in electrical or non-electrical

signals.
Interdomain conversions transform information from one domain to another.

Detector : device that indicates change in environment

Transducer : device that converts non-electrical to electrical data
Sensor : device that converts chemical to electrical data

INSTRUMENTS FOR ANALYSIS

NON-ELECTRICAL DOMAINS

ELECTRICAL DOMAINS

Physical (light intensity, color)

Current (Analog)

Chemical (pH)

Voltage (Analog)

Scale Position (length)

Charge (Analog)

Number (objects)

Frequecy (Time)
Pulse width (Time)
Phase (Time)
Count (Digital)
Serial (Digital)

Time:
Analog:
Digital:

Parallel (Digital)

vary with time (frequency, phase, pulse width)

continuously variable magnitude (current, voltage, charge)
discrete values (count, serial, parallel, number*)

INSTRUMENTS FOR ANALYSIS: DOMAINS

Advantages:
(1) easy to store
(2) not susceptible to
noise

DIGITAL BINARY DATA

What accuracy is required?

How much sample is available?
What is the concentration range of the analyte?
What components of the sample will cause interference?
What are the physical and chemical properties of the sample
matrix?
How many samples are to be analyzed?

DEFINING THE PROBLEM

Performance Characteristics: Figures of Merit

How to choose an analytical method? How good is measurement?
How reproducible? - Precision
How close to true value? - Accuracy/Bias
How small a difference can be measured? - Sensitivity
What range of amounts? - Dynamic Range
How much interference? - Selectivity

SELECTING AN ANALYTICAL METHOD

INDETERMINATE OR RANDOM ERRORS

FIGURES OF MERIT: PRECISION

DETERMINATE ERRORS (operator, method, instrumental)

FIGURES OF MERIT: ACCURACY

(larger slope of calibration curve m, more sensitive measurement)

FIGURES OF MERIT: SENSITIVITY

Signal must be bigger than random noise of blank

FIGURES OF MERIT: DETECTION LIMIT

At detection limit we can say confidently analyte is

present but cannot perform reliable quantitation
Level of quantitation (LOQ): k=10
Limit of linearity (LOL): when signal is no longer
proportional to concentration

FIGURES OF MERIT: DYNAMIC RANGE

No analytical method is completely free from

interference by concomitants. Best method is more
sensitive to analyte than interfering species
(interferent).

k's vary between 0 (no selectivity) and large number

(very selective).
FIGURES OF MERIT: SELECTIVITY

Basis of quantitative analysis is magnitude of measured

property is proportional to concentration of analyte

CALIBRATION METHODS

CALIBRATION CURVES (WORKING or ANALYTICAL)

SAMPLE PROBLEM:

SAMPLE PROBLEM

SAMPLE PROBLEM

Calibration Curves:
several standards containing exactly known
concentrations of the analytes are introduced into the
instrument and the response is recorded.

CALIBRATION OF INSTRUMENTAL METHODS

STANDARD ADDITION METHOD

An internal standard is added in constant amount to

samples, blanks, and calibration.
The analyte to internal standard signal as a function of
the analyte concentration is determined.
The ratio for the samples is then used to obtain their
analyte concentrations from a working curve.

INTERNAL STANDARD METHOD

TRANSFORMATION OF ALKENES AND ALKYNES

TRANSFORMATION OF ALKENES AND ALKYNES

TRANSFORMATION OF ALKENES AND ALKYNES

TRANSFORMATION OF ALKENES AND ALKYNES

TRANSFORMATION OF ALKENES AND ALKYNES