Analytical Chemistry

Introduction
 Classification of Analytical
Methods
Classical methods
• gravimetric
• titrimetric
Instrumental methods
• spectroscopy
• electroanalytical
• chromatography
 Five Generations of Instruments
First-generation Systems
• manual & visual interaction between
instrument and analyst
• examples:
– burets
– mechanical balances
– Dubusque colorimeter
 Five Generations of Instruments
First-generation Systems
Manual

manipulation Instrument
Analyst or
Process
Direct

results
 Five Generations of Instruments
Second-generation Systems
• analyst interacts with knobs & switches &
results are displayed on analog meters &/or
strip chart recorders
Examples:
• Beckman DU, DU-2, & DB-G
Spectrometers & pH meter
• B & L Spectronic 20 & 21
 Five Generations of Instruments
Second-generation Systems
Manual

manipulation Instrument
Analyst or
Process
Indirect Direct
Output
Device
results
results
 Five Generations of Instruments
Third-generation Systems
• microcomputers interfaced to existing
instruments to log & process data
Examples:
• Pet computer interfaced to Spectronic 20
and pH meters
 Five Generations of Instruments
Third-generation Systems
Operating
Control Instructions
Computer
(External)
Raw
Analyst Data Instrument
Processed
Data or
Process
Indirect Output Direct
results Device results
 Five Generations of Instruments
Fourth-generation Systems
• miniaturized computers integral component
( microprocessor)
Examples:
• B & L Spectronic 2000
• Varian 3700 GC
• PE FTIR
• Hitachi FT-NMR
• Buck AA
 Five Generations of Instruments
Operating
Fourth-generation Systems Instructions

Commands
Instrument
Control or
Analyst
Computer Process

Indirect Output
results Device Processed
output Output signals
signals
 Five Generations of Instruments
Fifth-generation Systems
• dedicated computers
Examples:
• Waters & PE HPLC
• HP 8452As and 8453As UV-Vis Spectrometers
• HP GCD-Plus GC/MS
• Buck IR
• PE FTIR
• Anasai FT-NMR
 Five Generations of Instruments
Fifth-generation Systems
Raw data
Instrument or Process
Machine-level commands

Control Diagnostics Data

Processed data Processing
(Information)
High-level
commands Intelligent System

Integrated
Computers Output
User Interface
Device
User-level Explanation
commands (Knowledge)
Analyst
Types of Instrumental Methods
 Instruments for Analysis
Components of a typical instrument
Electrical
Meter
or
or
mechanical Scale
Analytical input
Input signal
signal Output
Signal transducer Signal Recorder
signal
generator or processor
detector

12.301

Digital
unit
 4 Basic Components of
Instruments for Chemical Analysis
• signal generators
• detectors (input transducers)
• signal processors (circuits & electrical
devices)
• readout devices
Some Examples of Instrument Components
 Types of Data Domains
analog
– information is encoded as the magnitude of
some electrical quantity
time
– information stored as the time relationship of
signal fluctuations
digital
– information is in one of two conditions
 Selecting an Analytical Method
Defining the problem:
1. What accuracy and precision are required?
2. How much sample is available?
3. What is the concentration range of the analyte?
4. What components of the sample will cause
interference?
5. What are the physical and chemical properties of
the sample matrix?
6. How many samples are to be analyzed?
 Numerical Criteria for Selecting
Analytical Methods

1. Precision
2. Bias
3. Sensitivity
4. Detection Limits
5. Concentration Range
6. Selectivity
 Other Characteristics to Be
Considered in Method of Choice
1. Speed
2. Ease and Convenience
3. Cost and availability of instrument
4. Per-sample cost
Figures of Merit for Precision of Analytical Methods
 Bias
Bias =  - xi
where  => population mean
("most popular value")
xi => true concentration
 Sensitivity
2 factors limiting sensitivity:
• slope of calibration curve
– steeper slope, greater sensitivity
• reproducibility of measurements
– equal slope, better reproducibility, greater
sensitivity
 Sensitivity
IUPAC defined calibration sensitivity
S = mc + Sbl
where S => measured signal
c => concentration of the analyte
Sbl => instrumental signal for blank
m => slope of calibration line
ignores precision
 Sensitivity
analytical sensitivity => 
 = m/ss
where ss =>standard deviation of the signals
advantages:
- relatively insensitive to amplification factors
- independent of units
disadvantage:
- standard deviation of signal can vary with
concentration
 Detection Limit
minimum concentration or weight of analyte
that can be detected at a known confidence
level
 Detection Limit
minimum distinguishable analytical signal => Sm
Sm = Sbl + ksbl
where Sbl => mean blank signal
k => some multiple (normally 3)
sbl => absolute standard deviation of the blank
measure 20-30 blanks over extended period of
time to determine Sbl and sbl
detection limit => cm = (Sm - Sbl)/m
Applicable Concentration Range
Concentration Range

LOL
Instrument response

LOQ => limit of quantitative

measurement

LOQ LOL => limit of linear

response
Useful range

Concentration
 Selectivity
degree to which a method is free from
interference by other species contained in
the matrix
S = mAcA + mBcB + mCcC + Sbl

where S => analytical signal

cA, cB, cC=> concentrations of A, B, and C,
mA, mB, cC => calibration sensitivities of A, B, and C,
respectively, slope of calibration curve
Sbl => instrumental signal of blank
 Selectivity
kB,A = mB/mA and kC,A = mC/mA
where kB,A => selectivity coefficient for B
with respect to A
kC,A => selectivity coefficient for C
with respect to A
yielding
S = mA(cA + kB,AcB + kC,AcC) + Sbl