09-Sep-21

Chapter 3
Instrument methods of analysis

Assoc. Prof. Nguyen Phuoc Dan

Instrument methods of analysis

✓ Instrument methods of analysis is used widely in monitor quality of air,
underground water, surface water and soil pollution
✓ Analysis instrument can be used immediately in research area or areas
need to check environmental quality
✓ pH meter and spectrometer are invented in many centuries ago and now
become common in testing and monitoring environmental quality

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111Optical method

Optical method
➢ Optical method measure the results of interactions between radiant energy and
matter. The energy of a photon related to its wavelength λ as follows:
h : Planck constant, h = 6,63.10-34 J.s = 6,63.10-27 erg.s
ℎ𝑐 c : photon velocity, c = 3.1010 cm/s
𝐸=
𝜆 λ : photon wavelength

➢ Optical methods of analysis are designed to measure the ability of a material or

solution to absorb radiant energy or emit radiation or to disperse or scatter radiation.

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Optical method

1.Absorption method
➢ When a source of radiant energy, such as beam of white light, is
passed through a solution, the emergent beam will be lower in
intensity than entering.
➢ If the solution does not contain suspended particles that scatter
light, the reduction in intensity is due primarily to absorption by the
solution.
➢ The use of a spectrophotometer is to determine the extent of
absorption of various wavelengths of visible light by a given solution
➢ All instruments designed to measure the absorption of radiant
energy have the basic components of: energy source, energy
spreader, sample holding and energy detector.

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1.Absorption method

Diagram of UV-Vis spectrophotometer

1.Absorption method Parameters in environmental engineering

Sample Indicator Wavelength (nm)
Gas
As Dietyldithiocacbaminat Ag 538
HCHO p-rosanilin 570
H2S FeCl3, dimetyl-p-phenylendiamin 670
NH3 Nessler (K2HgI4) 450
NO, NO2 Acid sunfanilic, N-1-Naphtyll-etilendiamin-2HCl 550
Solution
Al brompirogalol 623
Cl- Hg(SCN)2 480
Cr (VI) Diphenylcacbazit 540
Cu Disunfonat battocuproin 480
Fe o-phenalthrolin 510
NO3-, NO2- Sunfanilamit, N-1-naphtyl-etilendiamin-2HCl 520
Phenol Basic ferixyanua, 4-amin-antipirin 460,510

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Emission method
▪ Many metallic element, when subjected to suitable excitation, will emit radiation of
characteristic wavelengths.
▪ Under properly controlled conditions, the intensity of the emitted radiation at some particular
wavelength can be correlated with a quantity of the element present.

▪ The widely used methods includes:

✓ Atomic Emission Spectroscopy
✓ Atomic Absorption Spectroscopy
✓ Inductively Coupled Plasma Spectroscopy
▪ The instruments for Emission methods contains: light
source, prism and slit

Atomic Emission Spectroscopy Emission method

➢ This method in its simplest form as a flame photometer is used in water analysis for
determining the concentration of alkali and alkaline-earth meals such as sodium,
potassium and calcium.
➢ The spectrum for each metal is different and its intensity depends upon the
concentration of atoms in the flame, the method of excitation used and the after-
history of the excited atoms.

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Emission method

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Atomic Absorption Spectroscopy Emission method

▪ This method has gained wide application of trace quantities of most elements in water such as
copper, iron, magnesium, nickel and zinc.
▪ The similarity between this and flame photometry is it also uses a flame unit, a prism and a detector.
▪ The advantage of atomic absorption spectroscopy is that it is quite specific for many elements that
give poor results with the flame photometer.

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Inductively Coupled Plasma Spectroscopy Emission method

➢ In the ICP method, a stream of argon gas flows through
three concentric quartz tube, which are surrounded by a
water-cooled induction coil that is powered by a radio-
frequency generator to form a strong magnetic field.

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Electrical methods
of analysis

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Electrical methods of analysis

▪ Electrical methods of analysis make use of the relationships between
electrical and chemical phenomena and is particularly useful in
water chemistry.
▪ The pH meter is probably the most widely used electrical method of
analysis along with modern instruments used to determine
conductivity, TDS and DO concentration.
▪ There are different types of electrical methods:
▪ Potentiometric Analysis
▪ Polarographic Analysis
▪ Conductimetry Analysis
▪ Coulometry Analysis

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Potentiometric Analysis
Electrical methods of analysis
➢ The measurement of the potential of an electrode can permit the calculation of the activity or
concentration of a component of the solution.
➢ Nernst equation gives the relationship between the relative potential of an electrode and the
concentration of a corresponding ionic species.
Where
Eo: oxidation-reduction potential of the system
E = Eo +
RT a
ln oxh = Eo +
RT f
ln oxh
 
Oxh R: gas constant
zF akh zF  
fkh Kh T: absolute temperature
F: Faraday constant
z: number of electrons in the electrode reaction
aoxh, akh: is activity of the oxidation, reduction substances
foxh, fkh: is activity coefficient of the oxidation, reduction
substances
[oxh], [kh]: is concentration of oxidation, reduction
substances
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Potentiometric Analysis
▪ Potentiometric methods are based on measurements of the potential of
electrochemical cells in the absence of appreciate currents
▪ Basic components:
▪ A reference electrode: give reference for potential measurement,
▪ Indicator electrode: Where species of interest is measured,
▪ Potential measuring device

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Potentiometric Analysis
➢ Determine the Cl- in the solution using potentiometric analysis:
AgCl + e- → Ag + Cl-

RT
ECl = EClo + ln Cl − 
zF

➢ Cl- concentration is determined based on the potential of the electrodes:

RT
E = EClo − ESCE + ln Cl − 
zF

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Potentiometric Analysis

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Metal electrode
➢ A metal electrode consists of a metal in contact with its ions in solution.
➢ Type1: This electrode consists of a metal electrode immersed in a solution of its
soluble salt Mn+
▪ Present: M/([Mn+])
▪ Reaction: M - ne- → Mn+

➢ Type 2: This electrode consists of a metal electrode cover by its insoluble salt MA
and immersed in a solution contains An- ions → to determine concentration of ion
An-

▪ Present: M,MA↓/An-
▪ Reaction: MA + ne- → M + An-

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Oxidation-reduction electrode
➢ This electrode consists of a nonreactive electrode immersed in a solution of ions in both reduced
and oxidized form.
➢ Pt electrode in solution consists of FeCl3 and FeCl2
▪ Present: Pt/Fe3+, Fe2+
▪ Reaction: Fe3+ + e- → Fe2+

𝐹𝑒 2+
𝐸𝑖𝑛𝑑 = 𝐸 𝑜 − 0.0592 𝑙𝑜𝑔
𝐹𝑒 3+

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Electrode with metal contacting slightly soluble salt

➢ This electrode consists of a metal in contact with one of its slightly soluble salts,
while the salt, in turn, is in contact with a solution containing a common anion.
➢ The calomel electrode consists of Hg, calomel (Hg2Cl2) and KCl
▪ Present: Hg/Hg2Cl2/KCl
▪ Reaction: Hg+ + Cl- → ½ Hg2Cl2 + e-
➢ This electrode is used to determine the concentration of salt in the solution

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➢
Glass electrode
This glass electrode is used universally for measurement of pH.
➢ Glasses with different compositions selectively develop potentials with different ions.
➢ Glass electrodes are commercially available for measuring concentration of the following io
ns: Na+ , K+ , NH4+ and Ag+

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Types of electrode

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Types of electrode

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Types of electrode

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https://youtu.be/P1wRXTl2L3I
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https://www.youtube.com/watch?v=PBTn4gTEbkU&t=132s
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Membrane electrode
➢ This electrode contained a thin membrane placed between the standard solution inside and the s
olution of interest.
➢ Membrane electrodes are generally divided into four classes:
▪ Glass electrodes
▪ Liquid membrane electrodes
▪ Gas-permeable membranes electrodes
▪ Crystalline membrane electrodes

➢ The glass electrodes are widely used for pH measurement

Membrane Crystalline LaF3 Crystalline Ag2S Glass Liquid

electrodes

MeasureS2- and Measure Na+ Measure Ca2+

Use Measure F-
Ag+ and H+ and K+
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Membrane electrode

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Liquid membrane electrode

➢ Liquid membrane electrodes provide a means for
direct potentiometric determination of the
activities of several polyvalent cations such as Ca2+
and Mg2+.
➢ The liquid is an organic compound that is
immiscible in water and contains functional groups
that can exchange with ions from solution.
➢ When placed in a solution, the ion for which the
electrode is developed exchanges with ions within
the water-liquid exchanger interface and
establishes a potential that is measured.

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Crystaline membrane electrode

➢ This electrodes contain a solid membrane (other than glass) between the sample and a
reference solution that is selective for anions.
➢ The membranes generally consists of a sparingly soluble salt of the anion of interest.
➢ The downside of this type of electrode is its little electrical conductivity at room temperature.
To improve the electrical conductivity, a small amount of crystal lattice monovalent ions is
often added to the solution to increase the mobility of the solid phase. F- ions is used (in the
rare fluoride), Ag+ (Ag and Ag2S in halogenur), Cu + (in Cu2S).
➢ LaF3 is an ideal substance for crystal membrane electrode that is used for the determination of
F-.

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Gas-permeable membrane probes

➢ These probes consist of a pH electrode and a reference electrode immersed together in a solution
retained by a gas permeable membrane.
➢ Analyzed gas includes NH3 and CO2
➢ Any gas that forms a weak acid or base in water can be analyzed with gas permeable membrane
probes, including HCN, HF, H2S, SO2 và NO2.
➢ Probes used in Environmental engineering to measure
▪ Concentration of O2 in aeration tank
▪ Residuals of Cl2 and F2
▪ CO, NOx, SOx

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3. Chromatographic
Methods

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Chromatographic Methods
Chromatography is the general term
used to describe the set of different
procedures used to separate
components in a mixture based upon
their relative affinity for partitioning
between different phases

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Chromatographic • Chromatographic instruments are now widely used in the

environmental engineering and science fields
→ Permit rapid quantitative measurements to be made of
Methods
•
chemicals present in complex mixtures and at concentrations in
the ppb or pg/L range and lower
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https://youtu.be/SnbXQTTHGs4

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Chromatographic Methods
• For example, carbon dioxide is more soluble in water than methane, so if both gases were
present in a sample of air that was brought into contact with water
• → Carbon dioxide would partition more strongly into the water than would methane
• → This property, which is different for different molecules, can be used to bring about their
separation

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Chromatographic Methods
Two different phases are generally used in modern chromatography to effect separation of a mixture one
is the stationary phase and the other the moving phase.
− Stationary phase may be either a liquid or a solid
− Moving phase may be either a liquid or a gas.
• When the mobile phase is a gas, the procedure is termed gas chromatography
• when it is a liquid, it is called liquid chromatography

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Chromatographic Methods

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Gas chromatophy
Chromatographic Methods
• Gas chromatography entails the vaporization of a liquid sample followed by the separation of the
various gaseous components formed so that they can be individually identified and quantitatively
measured

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Gas chromatophy
• The gas cylinder contains a carrier gas such as
hydrogen, helium, or nitrogen, which is continuously
swept through the chromatographic column
• A small sample for analysis is injected, usually with a
syringe, into the sample port where it is flash-
evaporated to convert its components into a gaseous
state
• The constantly flowing stream of carrier gas carries the
gaseous constituents through the chromatographic
column. The gases travel through at different rates, so
they emerge from the column at different times
• Their presence in the emerging carrier gas is detected
by chemical or physical means
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Gas chromatophy
• The response of the detector is fed into a recorder, perhaps after electronic integration
→ This process will produce a typical chromatogram.

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Gas chromatophy
▪ Each peak represents a specific chemical compound or a mixture of compounds with the same rate of
movement through the column.
▪ The time for each compound to emerge from a given column is a characteristic of the compound and is
known as its retention time.
▪ The area under the peak is proportional to the concentration of the compound in the sample.

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Gas chromatophy
https://youtu.be/cBXgSPO3pzw

https://youtu.be/ZpPzImDSfqc

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High-Performance Liquid Chromatography (HPLC)

• HPLC is especially useful for separating nonvolatile species and those that are thermally unstable
→ Extends the range of compounds that can be separated for analysis beyond that possible with gas
chromatography.
• Among the compounds that can be separated by this procedure are amino acids, proteins, nucleic acids,
hydro- carbons, fatty acids, carbohydrates, phenols, a great variety of inorganic substances,…

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High-Performance Liquid Chromatography (HPLC)

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High-Performance Liquid Chromatography

• One or more solvent reservoirs hold degassed and
prefiltered solvent, which is pumped through the
column system at pressures up to 400 atm.
• A pulse damper is used to even the flow rate
• A pre-column or guard column is used to increase the
life of the analytical column by removing particulates
and contaminants from the solvent
* Sometimes the guard column is used after sample
injection to remove undesirable contaminants that it may
contain

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High-Performance Liquid Chromatography

• The sample is introduced into the system either with a syringe or more generally with a sampling loop,
and as it is pushed through the analytical column by the solvent, separation of components occurs.
• A suitable detector for the species of interest is used at the column exit, and the response is stored,
integrated, and recorded.
• The waste solvent is collected for safe disposal

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https://youtu.be/eCj0cRtJvJg

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Question
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Assignment
1. List the physical properties of elements or compounds that can be used as the basis
for an instrumental measurement.
2. What different kinds of interactions between radiant energy and materials or
solutions are optical methods designed to measure?
3. Why cannot a single instrument be used to measure absorbance at all
wavelengths?
4. What wavelength range is characteristic of (a) visible radiation, (b) ultraviolet
radiation, and (c) infrared radiation? Which range is characterized by (d) the highest
radiation energy and (e) the lowest radiation energy?
5. List at least six different substances in water that can be determined by
potentiometric analysis.

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Assignment
6. What are four different kinds of membrane electrodes end what is the principle
behind the operation of two membrance electrodes in the lecture?
7. Give the basic concept behind chromatographic analysis?
8. What is the difference between gas chromatography, liquid chromatography, and
gas-liquid chromatography?
9. What are the basic components of a chromatographic system?
10. What is a necessary property of a compound for it to be analyzed by gas
chromatography?
11. What advantage does high-performance liquid chromatography have over gas
chromatography? What is one of HPLC’s major limitations, and how has this
limitation been overcome in gas chromatography?
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