oduction to Analytical Chemi

Dr T. E. Geswindt
Office F43
[email protected]

Skoog, West, Holler and Crouch, Fundamentals of Analytical Chemistry, 9 th edition, Chapter 8
 ANALYTICAL CHEMISTRY

Studies and uses instruments (or

methods i.e. “wet chemistry”) to
separate (& refine), identify
(characterize) and quantify matter
(chemical compounds/elements)

Skoog, West, Holler and Crouch, Fundamentals of Analytical Chemistry, 9 th edition, Chapter 8
 Aims
• Definitions associated with analysis: analyte,
matrix, replicates, accuracy, precision, standard
sample, and sampling.

• Types of errors associated with analysis

• Challenges experienced when analyzing real as
compared to standard samples
• Thinking process in choosing an analytical
method
• Dissolution of an inorganic sample
What is Analytical Chemistry?
CHEMISTRY of Quantitative and
It is the
Qualitative Analysis
quantitative qualitative
Analysis involves both quantitative and
the amount of (a) particular
qualitativecomponent(s).
aspects.
the chemical identity of (a)
Quantitative – the amount of (a) particular
component(s).
component(s).

quantitative
Qualitative qualitative
– the chemical identity of (a)
component(s).
TYPICAL REAL LIFE ANALYTICAL
QUESTIONS
1)Determine the concentration
alcoh of
in blood? ol
arse
2) Determine the concentration
nic of
in water? pestic
ide
3) Determine the concentration of
sample analyte
Identify the
in fruits? , and
matrix in each case.
What aspects of analysis is required?
Procedures in Analysis
include
Selecting a method

Sampling

Sample work-up/clean-up
Dissolution, Chelating,
Derivatisation, Filtration

High resolution separation

Detection

Data processing
 TYPES OF SAMPLES and their
characteristics
Real sample
• High complexity
• Heterogeneous
• Problems with volatility, solubility, stability (e.g. speciation)
• Time consuming
• Expensive

Standard sample
• Homogeneous
• Solubility is predictable
• No interferences
• Tools are available
 POSSIBLE SOURCES OF SAMPLES
Animal tissue

River effluent

Rocks/ores

ambient air in a polluted city/

Platinum group metal deposits on roads (due to
catalytic converter deposition)

glass

rubber
The following may result in sample loss,
error in the result and has implications on
quality control or the feedback processes.
Volatility

Heterogeneity

Kinetic/ Thermodynamic
Stability

Solubility
If a sample is not soluble, we probably need to:
• Decompose it at high temperature
• Use a combination of concentrated reagents
(e.g. Au dissolution)
In the process of decomposing and
using concentrated reagents:
• Sample will be lost in the process
• Possible interference from reagents (matrix effects)
• Ionic composition will be modified

If the target analyte is a metal for

example, we would need to deal with
interferences by using a sample work-up
step
Examples of possible approaches:
What constitutes a good analysis?
Good Analysis = Selectivity + Chemical
Knowledge + Time Management
Methodology
Manipulation
For a real life samples: Determines delivery

There are no standard methods of analysis

ing e m o
n
ien ng
Complexity is unknown

th iti
ed ssi
t!
is tu
Complexity increases the number of

i
In
variables

r
Variables affect the sample
Variables affect the performance of the
Initially our analysis considered only the
target analyte BUT owing to the complexity
of the sample, these considerations may be
compounded.
We have to consider:

Systematic error – measurements of the same nature

would vary in a predictable manner
Consider Analysis of Calcium carbonate with a
Flame Emission photometer
• Variables
• Dissolution by fusing at high temperature
• Large excess reagent used in the process

1) Physical loss of sample;

2) Fuel to air ratio on intensity of Ca emission
line
3) Position of the flame with respect to slit
4) Preparation of standards

a. Water quality
b. Volumetric aspects
c. Complexity
d. Viscosity
WE ARE REQUIRED TO MEASURE
CONCENTRATION
PROCESS

Choose a method

Prepare a sample

Conduct analysis

Evaluate the
concentration

Report the data

 What are the processes
involved in analysis?
Sample preparation - low resolution separation.

Separation - high resolution.

Detection - sensitivity.

Data processing
 Choice of Analytical method
Method should be based on the background
knowledge

In Addition to:
Expected concentration
Required accuracy
Possible interference/components
present
Number of samples to be analyzed
These requirements will determine
the:

METHODOLOGY,
Sample preparation technique
Sample work-up

These aspects should address:

1. Components
2. Concentration
3. Time required for the process
4. Sampling
 SAMPLING and SAMPLE
HANDLING
The process by which a representative
sample/fraction is acquired is termed
SAMPLING.

• most difficult step in the entire process.

• limits accuracy of a procedure.

• necessarily involves statistics:

- since conclusions are drawn about a much larger
 SAMPLING
Sample must be representative of the bulk
material/population
The reliability of
Solubility an analytical
Homogeneity process will not
exceed that of
Physical state (solid, gas, liquid)
the sampling
step.
Statistical goals of sampling:
- a mean value that is an unbiased estimate
of the population.
 IDENTIFY THE
POPULATION
Random sampling

consid
COLLECT A GROSS
SAMPLE
er the
errors
Random sampling

REDUCE THE
Reduce size =
GROSS SAMPLE TO
and
A LABORATORY
homogeniz
A chemist carries 3-6 portions of a sample
through an entire analytical procedure.
PORTIONS = REPLICATES
Replicates - each portion should be of equal
mass or volume and be representative of
the bulk.
Variation in each replicate will give rise to
replicates uncertainty
increased implies the need
. for an average or
specifically for a mean or median value to be
calculated.
MEAN
- is used a central value and is more
reliable than an individual result.
- analysis of variation in data allows us to
estimate uncertainty associated with
central value.

MEDIAN
- Replicate data arranged in increasing/decreasing order
(value).
- There should be an equal number of data either side of
the median.
PRECISION
- Describes the reproducibility of measurements
i.e. how close measurements are to each other.
- 3 terms that describe the precision of replicate
measurements
- Standard deviation
- Variance
- Coefficient of Variance => describes the difference
between i and

ACCURACY
- Is the closeness of the measurement to the
true/accepted value – expressed by the error.
-
Absolute Error (E)
E = i - , where = the accepted/true value

Relative ERROR (δ)

- more useful than absolute error.
- reported as a the percent relative error or as PPT
(parts per thousand).
δ = (or 1000 if reported as ppt)

Low A Low Low A high High A Low High A High

 Types of Errors in Chemical Analyses
Random (Indeterminate) Error
• data scattered more/less around the mean value

Systematic (determinate) Error

• causes mean to differ from accepted value
• all results are either too high or too low
• introduces bias in measurements

Gross Error
• YOU!!!
• are large errors resulting values that too high or too
low (not all data)
• leads to outliers (this should be determined to be an
outlier, i.e. Q-test)
 SYSTEMATIC ERROR
Sources of Systematic Errors
Instrumental errors
=> non-ideal instrument behaviour
=> bad calibration
=> wrong conditions of use
Method errors
=> non-ideal chemical or physical
behaviour of analyte.
Personal errors
=> carelessness, inattention and personal
limitations
 How can we best deal with systematic
errors?
Instrument: we need to continuously calibrate, not over
trust measurements
Personal: some self-discipline is required
Method: Choose an appropriate one (avoid colour changes
if you are colour blind, e.g. titrations)
Consider systematic method errors
a) Analysis of standard samples
• Use standardized reference material (SRM) or
Certified reference material (CRM)
b) Independent analysis
• Seek an opinion (reliable and independent)
 INORGANIC (non-biological ) SAMPLES
GROSS sample
- is a replica of the entire mass of material
- corresponds both chemically and in particle size
distribution
- gross sample weight is limited to what is necessary for
convenience and economy
- the weight is determined by the uncertainty that can be
tolerated between composition of the gross sample and
the entire populous
- the degree of heterogeneity of the whole sample
- level of the particle size at which heterogeneity begins
- For instance: gases and liquids are heterogeneous
at the molecular level => require only small
SAMPLING HOMOGENEOUS SOLNS. (liquids
and gases)
1. samples should be stirred prior to mixing.
2. several portions taken for large volumes of solns.
3. industrial liquids and gases sampled through
continuous flow.
4. might need to sample at different levels for large
volumes.
SAMPLING PARTICULATE
5. special devices are required SOLIDS
for industrial
1. effluent.
sampling bulky particulate material is difficult.
2. difficult to acquire a random sample.
3. usually carried out mechanically.
SAMPLING METALS and ALLOYS
1. generally, chips removed from a metal surface
not representative of entire bulk and solid from
interior must be sampled.
2. obtained by sawing, milling and drilling.
3. drillings are usually melted down and poured
onto deionised-distilled water for granulation
(sponge).
PREPARATION OF A LABORATORY SAMPLE
a. Reduction of gross sample to a finely ground
homogeneous laboratory sample is accomplished
by: crushing, grinding, sieving, mixing and
dividing the sample for weight reduction
(halving)
b.CRUSHING
A statistically and GRINDING
significant number (lab. samples)
of particles
should be retained after each division.
- Avoid excessive grinding since it results in:
• loss of volatile compounds
• oxidation of certain species [Fe2+ → Fe3+ + e-]
• loss or gain in water content
• loss of sample (dust)
• (NB! Beware of complexes interacting mechanochemically)
 CRUSHING and GRINDING (lab. samples)
contin’d
- Intermittent screening of sample increases the
efficiency of grinding
- May lead to contamination of sample from wear
of grinding surfaces
 MIXING SOLID (lab. samples)
- Essential that solid samples are thoroughly mixed
- Mixing is done by rotation or ball milling

Decomposing and Dissolving the sample

The correct choice among the various reagents and
techniques for decomposing and dissolving
analytical samples can be critical to the success of
the analysis.
General considerations
Choosing a solvent: - possible interferences are
introduced on dissolution.
- consider the purity of reagents when dealing with
Aqueous reagents for Dissolving or
Decomp. the sample
- Hot aqueous strong acids: HNO3, HCl, H2SO4 and
HClO4
-Decomposing using
Oxidizing Mixtures: inorganic
Aqua acids3;in
Regia (HCl:HNO 3V:1V)
-open vessels
Hydrofluoric acid (HF)
Acids used in their concentrated forms
a)HF, HCl, HNO3, H2SO4, HClO4
b)Oxidizing mixtures: H2SO4, HF, HClO4 combinations
Consider the acids individually
1) HCl: excellent for inorganic, but very poor for organic

2) HNO3: dissolves all common metals except Al and Cr

HNO3 + Br2 + H2O2 is used for organic dissolution, for
trace metal analysis (wet ashing). Process converts
organics into CO2 + H2O. Volatilization prevented by use
of closed vessels
3) H2SO4: dissolves and decomposes many organic
compounds - wet ashing
4) Oxidising mixture – aqua regia HCl, HNO3 + Br2/H2O2
rather dangerous mixture
5) HClO4: hazardous when hot
6) HF: mostly used for the dissolution of silicate rocks and
 Decomposition by FLUXES
• Fluxes are used when samples decompose slowly
or very little
• A Flux is an Alkali-metal salt:
- Added in 10 times excess
- Fused at between 300 to 1000°C
- The are
• Fluxes product (thebecause:
avoided melt) is dissolved in H2O
• Large quantities of flux are required.
• High salt content may hamper subsequent
analysis.
High temperature ignition in Air/O2

Microwave digestion with acids in a

closed vessel
i) recent development
ii) not always successful

Dry ashing for organics: oxidation of

organics in air
i) Carried out in a crucible, oxidize to CO2
ii) Dissolution of non-volatiles before analysis
BIOLOGICAL
SAMPLES
 Sample Preparation for Biological Samples
(organic analytes)
Pesticides
Example triazines:
What is the source of sample?
Where should we sample?
What are the expected concentrations?
In what form will we find the target analytes?
If it involves human consumption, then we need to take urine
samples.

Possible analytical techniques:

-HPLC
 So for a Pesticide (triazine in this case)

Degradation product e.g., 4-nitrophenol, 4-

chlorophenol

Human consumption

Adverse effects

Europe 0.1 μg/L of drinking water

EPA 3 μg/L

Phenols + pesticides: 0.5 μg/L, need

Time distribution in analysis
Analysis 6%
Collection 5%
Data management 27%
Sample processing 61%
Workflow diagram for chromatographic analysis
Sampling: Collection and Storage
Sample preparation: Extraction, Collection,
Concentration, Isolation
Analysis: Identification
Sources of Error
Sample handling 30%
Operator 19%
Columns 11%
Calibration 9%
Instrument 8%
Chromatography 7%
Sample introduction 6%
Evaluation 6%
Contamination 4%

Possibilities;
-use biological recognition elements example;
enzymes and antibodies

Important steps
Sampling
Sample preparation
Sample work-up
Usual sample preparation steps
-filtration
-liquid-liquid extraction manual steps involved
-solid phase extraction
Requirements for a method
-simplicity
-cost should be minimal
-speed
-precision
-recovery
-reliability
-reproducibility and repeatability
-robustness
-solvent consumption
-environmental compatibility
-user friendliness
In our mind
-analyte?
-analyte concentration?
-matrix?
-technique?
-sample size?
 EXTRACTION METHODS
The extent to which solutes are distributed between
immiscible solvents differ from one species to the
next and is exploited for separation.
The Distribution Coefficient
- Is an equilibrium constant that describes the distribution
of solute between two immiscible solvents.
For solute A dissolved in an aqueous soln. when the
aqueous soln. of A is shaken with an organic solvent, say
hexane, then
[A(or
A(aq)
Kd [A(aq
g)]
A(org)
Activity of A in
each case
Where Kd, the equilibrium constant, is the
distribution coefficient. The activities are approx.
equal to molar concentrations of A.

different states of
In the case of
aggregation in soln.

xAy(aq) [A(org
yAx (org)
Kd [A(aq)
)]
y

= ]x
Then
 The Distribution Ratio

For simple systems such as, A(aq) A(org) the

distribution coefficient
Kd = the distribution ratio (D).
C(or
C(a
g)
Where D =
q)
 TYPES of EXTRACTION PROCEDURES
Simple Extraction
- Soln. containing analyte is extracted successively using
up to 6 portions of fresh solvent.
- An ordinary separating funnel is used with either the
original soln. or the extract retained for completing the
analysis.
- Distribution ratio is favourable , in fact about 5 to 10
times better.
Exhaustive Extraction
- Permits the separation of components of a mixture that
have relatively unfavourable distribution ratios (<1)
from those having ratios approaching 0.
Counter-current Fractionation
- Permits the separation of components with nearly
identical partition ratios. Fractionation occurs by a
counter-current scheme in which distribution between
fresh portions of the two phases occurs in a series of
Modern methods
discrete steps.
• Accelerated solvent extraction
• Automated soxhlet extraction
• Supercritical fluid extraction
• Microwave assisted solvent extraction
• Pressurised hot water extraction
• Solid phase extraction
• Solid phase microextraction
• Stir bar extraction, sonication
Typical matrix compounds
Biological: protein, fatty acids, peptides

Soil samples: humic acids

 SOXHLET EXTRACTION
- Sample sizes range between 1 and 10 g.
- Solid samples are ideally suited.
- Able to achieve ca 99 % extraction.
Limitations
- Large volumes of solvent.
- Long extraction times.
- Difficult to automate.
1)Extraction solvent
2)Round bottom flask
3)Soxhlet adaptor
4)Condensed solvent
5)Sample matrix
6)…
7)…
8)Expansion adaptor
fitting
9)Condenser
10)Water inlet
11)Water outlet
 Liquid-liquid Extraction

- Based on partitioning between an aqueous and an organic solvent

layer.
- Layers are arranged based on the density, with the more dense layer
below and the less dense layer above.
- Shake, and release gas pressure (in case of ether).
- Decant or tap-off aqueous layer.
- Can be tedious, time consuming, sample losses may occur and
requires large volumes of solvent.
Liquid-liquid extraction
 Extracting semi-volatile organics
Ultrasonic extraction
Process
• uses ultrasonic vibration to facilitate contact between
sample and solvent
• rather fast, 3 min extractions uncommon
• extraction not too efficient
• possible to degrade samples
-optimal conditions
Solvent
operating conditions
• can handle small sample size
• typical solvents
- acetone-hexane
- acetone-methylene chloride
 After extraction
- filtration
- centrifugation
Ultrasonic extraction Vs Soxhlet
Less popular
Requires less sample
Sequential extractions possible
Generally has better attributes

Fast, though not efficient and has the potential to

degrade the sample
 Supercritical Fluid Extraction

• A substance that has a temperature above its critical

temperature and a pressure above its critical pressure. A
density near its liquid density is supercritical fluid.
• Tc > 31° and Pc > 72.9 bar.

critical point
Pressure/bar

SOLID LIQUID

Fluid

Triple point GAS

Temperature/°C
Properties of a supercritical fluid
High diffusivity
>> than a liquid
=> able to penetrate the matrix.
Low viscosity
=> exerts minimal surface tension
= better mass transfer

Supercritical solvent is able to dissolve different

compounds depending on the exact conditions of T and
P above Tc and Pc.
SUPERCRITICAL CARBON DIOXIDE
CO2 Most commonly used :
- Non toxic
- Non Flammable
- Available in High purity
- Relatively Low critical T and P
- Versatile
- Fast
- Green
- Clean
- Wide range of analysis
- Limited by sample size
- An alternative is H2O (pressurised Hot water
extraction)
 ACCELERATED SOLVENT EXTRACTION

Pressurised liquid/fluid extraction

• Uses pressurised solvents @ elevated temperature and

pressure for extraction
(100 < P < 140 atm; 100 °C < T< 180 °C).
• Affects sample, solvent and the solvent-sample
interaction.
• Deeper matrix penetration.
• Changes sample solubility (increase).
• Solvent viscosity and surface tension is reduced.
• Multiple solvents can be used but has poor selectivity.
Typical ASE
sequence
1)Load cell
2) Fill with solvent
(0.5- 1 min)
3) Heat and
pressurize (5 min)
4) Static extraction
(5 min)
5) Flush with solvent
(5 min)
 Advantages of ASE
o Minimal solvent use
o Fast extraction
o Fully automated
o User friendly
o Easy method development
o Variety of solvents to choose from
o Low cost per sample,
o Universal method

Major Limitation
Poor selectivity
 MICROWAVE ASSISTED EXTRACTION
Used for solid and semi-solid matrices

Simultaneous heating of sample and solvent.

Should monitor temperature and pressure.
Solvent choice adds selectivity.
Capable of being run under high-throughput conditions.

Poor
selectivity
 SOLID PHASE EXTRACTION (SPE)

A sample preparation technique with principles similar to

those of HPLC for selective adsorption of analytes or
interferences from complex matrices
Used for sample clean-up or analyte concentration
preceding LC, GC, IC or other techniques
Cost effective alternative to or replacement for LLE
(productivity,
solvents, waste)
 Solid Phase Extraction vs Liquid-liquid
Extraction
• Improved throughput
• Decrease in use of organic solvents
• Decrease in generation of waste
• Higher and more reproducible recoveries
• Cleaner extracts
• No emulsions formed
• Tunable selectivity (different phases)
• Readily automated
• Solvents have to immiscible (during extraction from
aqueous medium)
• Should not form emulsions
 Typical applications of SPE
1) sample clean-up
a. remove column killers
b. clean-up before LC-MS / LC (combined with general
detection)
c. pharmacokinetic studies
2) Trace enrichment
a. environmental analysis
b. biological samples
c. concentrate analytes for better sensitivity
3) Desalting
4) Sample preservation
 SOLID PHASE MICROEXTRACTION (SPME)

• Uses fused silica fibre coated with a non-volatile polymer

to extract organic analytes directly from aqueous
samples or from the headspace above the sample.
• The analyte partitions between the fibre and the liquid
phase.
• The analytes are then desorbed thermally in a heated
injector of a GC instrument.
• The techniques involves sample and sample pre-
concentration in a single step .
 SOLID PHASE EXTRACTION
• Is an extraction method that uses a solid phase and a
liquid phase to isolate one, or one type, of analyte from
solution.

• It is used to clean up a sample before using

chromatographic or other analytical methods to quantify
ADVANTAGES
the DISADVANTAGES
amount of analyte(s) in the sample.
Greater selectivity Wide range of chemistries
High recoveries Choice of solvent
Good reproducibility Wide range of pH conditions
Low solvent Many steps and method
consumption development time
Greater cost per sample
 [PtCl6]2-

[RhCln(H2O)6-n]3-n (n = 4 – 6)
 In what form do we conduct SPE?

Cartridge, disk or pipette tips consists of the same

material.
Disks
• Higher flow rate than cartridges
• Small particles allow rapid mass transfer
• Less channelling effects
• Prone to plug at high flow rates
• Available in a limited range
• Significantly more expensive
• Shorter extraction times
• Larger surface area per unit bed
• Used for passive sampling
Cartridge

• Easily prepared in the laboratory

• Easy to scale-up for larger volume samples
• Prone to channeling or clogging
• Easily affected by matrix
• Less amenable to miniaturization
Pipette tips

• No vacuum manifold
required
• Flow can be bidirectional
• Disposable, no
carryover/contamination
• Recommended for small
samples
 Steps involved in Solid Phase Extraction
STEP STEP STEP STEP
1 pre-
Sample 2
Conditioning 2a
Equilibration 3
load sample
treatment - add solvent - treat - introduce
- pH adjustment onto sorbent sorbent with sample
- Centrifugation material a solution
- Filtration similar to
- Dilution sample TYPES OF
- Buffer addition SORBENT
STEP STEP - Silica gel
4 5 - Polymer
Washing Elution
based PS-
- Remove - Remove
DVB resins
interfering analyte with - Alumina –
components carefully inorganic
selected oxide
solvent particles
-
 STEP STEP
1 2
Conditioning Sample (analyte matrix)
Solvent

SORBENT
BED
 STEP
3

SORBENT
BED +
analyte
matrix

Sample
liquid
 STEP STEP
4 5
Wash Solvent Eluting Solvent

SORBENT
BED

Impurities or anal
analyte
 Typical SPE Chemistries

1) Non-polar (reverse phase)

alkyl C1, C2, C3 etc
aromatic phenyl
polymeric PS-DVB (polystyrene–
divinylbenzene)
2) Polar (normal phase)
silica gel
alumina
3) Anion exchange silica
4) Cation exchange
5) Mixed mode phases
6) Speciality phases
THE REAL SITUATION DURING OPTIMIZATION
Analyte

Recovery/ Concentration
Extraction mechanism

Sorbent Matrix
Clean-up

Solvents also play an important role

Once the method is developed, it should be
VALIDATED
 Advanced SPE techniques

• Matrix solid phase dispersion (MSPD)

• QuEChERS (quick, easy, cheap, effective, rugged and safe)
approach
• Supported liquid-liquid extraction
• Multimodal extractions
• Column switching/on-line SPE
• Special phases (MIPs, RAMs)
• Multiple affinity removal system (MARS)
• Solid phase microextraction SPME
• Single drop microextraction SDME
• In-tube microextraction
Dispersive SPE: QuEChERS (quick, easy, cheap,
effective, rugged and safe)
-created to facilitate the rapid screening of large numbers of food
and agricultural samples for pesticide residues

Principle
-Mix sorbent with sample and conduct extraction. Applicable to solid
samples with semi-volatile analytes

Summary of the process

1. Shake sample with solvents and salts
2. Centrifuge for 1 min
3. Mix a portion with sorbent
4. Centrifuge
5. Analyse
Solid phase SPME
microextraction SPME fiber

-Created specifically for

volatile organics
-solventless extraction
method
-uses fused silica fiber
coated with thin film of
sorbent

SPME: 2 step process

-tip of a silica fiber is

chemically modified
Mode of sampling with
SPME
1. Within sample
2. Head space
3. Within sample with a
membrane
Sampling
-silica fiber is pushed
out of the needle
-immersed into sample
-after a while it is
withdrawn and
-used to inject directly
into GC
 Atomic Absorption Spectroscopy
(AAS)
• Principle of AAS

• Instrumentation
• One of the more common techniques used to detect
metals in samples.

• Reliable and simple to use.

• Can be used to analyse about 60 elements.

• Used for both qualitative and quantitative purposes, i.e.

determination of concentration.
• The first AA spectrophotometer was used in
Australia, at the CSIRO by Alan Walsh.

• Built by a Dutch company.

Elements detectable by AAS
• The sample is atomized (turned into gas) in an atomizer, the atoms are able to absorb
radiation at a specific frequency.

• Atomic Absorption spectroscopy quantifies the absorption of the ground state atoms in
gaseous state.

• Both ultraviolet and visible light produce transitions to higher electronic energy levels.

• Analyte concentration is determined from the amount of adsorption of atoms in the

ground state.

• Concentration measurements are usually determined from a working curve after

calibrating the instrument using a set of standards of known concentration.
Schematic of an AAS
Light Source

• Hollow cathode tube, by far most common.

• It contains a tungsten anode and a hollow

cylindrical cathode made of the element to be
determined.

• These are sealed in glass tube containing an

inert gas such as Argon or Neon.

• Each element has its own unique lamp that

must be used for that analysis.
 Quartz window

Pyrex body

Anode

Cathode
Nebulizer
• aspirates liquid at a controlled rate.

• Creates a fine aerosol spray for introduction into the

flame.

• Mixes the aerosol with the fuel and oxidant for

introduction into flame.
Nebulizer
Atomizer
• Elements to be analysed need to atomized
(atomic state).

• Atomization is the separation of particles into

molecules and breaking molecules into atoms.
The analyte is therefore exposed to high
temperatures in a flame or graphite furnace.
Flame atomizer
• For a flame we mix a fuel with and oxidant.

• Mostly we use an air-acetylene flame but we

also use a nitrous oxide-acetylene.

• Liquid or dissolved samples are typically used

with a flame atomizer.
Graphite tube atomizer
• Uses a graphite coated tube to atomize the
sample.

• In GFAAS, samples are deposited in a small

graphite coated tube which then can be heated
to vaporise and atomize the sample.

• The graphite tubes are heated using a high

current power supply.
Monochromator
• Important part of the AA spectrometer. It is used
to separate out the thousands of lines.

• A Monochromator is used to select the specific

wavelength of light which is absorbed by the
sample, and excludes the unwanted
wavelengths.

• The selection of the specific light allows the

determination of the selected element in the
presence of others.
Detector
• The light selected by the Monochromator is
directed onto the detector that is typically a
photomultiplier tube whose function is to
convert the light signal into an electrical signal
proportional to the light intensity.

• The processing of the electrical signal is fulfilled

by a signal amplifier. The signal could be
displayed for readout, or further fed into the
data station for printout by the requested
format.
Calibration curve
• A calibration curve is used to determine the
concentration of an unknown element in
solution. The instrument is calibrated using
several standard solutions of known
concentration. The absorbance of each solution
is measured and plotted versus the known
concentration.

• The sample with unknown concentration of the

element is fed into the instrument and the
absorbance is measured. The concentration is
determined from the curve.
Applications
• Determination of small quantities of metals.

• Environmental studies: drinking water, ocean

water, soil.

• Food industry.

• Pharmaceutical industry.