Instrumental Analysis

Analytical chemistry / Instrumental Analysis

Instrumental Analysis
Definition of Analytical chemistry: the science dealing with the
methods used to obtain the chemical composition of a sample.
Definition of Instrumental Analysis: a science that exploit the
physical properties of an analyte to obtain information, both qualitative
and quantitative.

Chemical composition is determined


qualitatively: answers what is present?

quantitatively: answers how much each component is present?

The purpose of this course is to present an overview of all important

aspects related to basic and advanced instrumental techniques:

Separation techniques – chromatography

Identification techniques – UV-VIS, FT-IR, MS, NMR

Advanced characterization techniques – imaging, isotopic
distribution related, on-site, etc.
Analytical methods of analysis:
A. Classical(wet-chemical methods)

Separation of analytes - extraction, distillation, precipitation (precipitation),
filtration (filtering), etc.

Qualitative Analysis - boiling point, freezing point, color, odor, density,
reactivity, refractive index, etc.

Quantitative Analysis - gravimetric and volumetric analysis
B. Instrumental Methods of Analysis

Separation of analytes

by size 
by change of chemical state

filtration 
precipitation

dialysis 
ion exchange

size exclusion chromatography 
electrodeposition

by mass / density 
volatilization

centrifugation 
by partitioning between phases

by change of physical state 
extraction – ex. SPE

distillation 
chromatography

sublimation 
LC

recrystalization 
GC

SFC

Characterization of pure compounds - UV-VIS, FT-IR, MS, NMR
Advanced methods
 Instrumental Analysis
some background knowledge needed ...

ORGANIC CHEMISTRY
INORGANIC CHEMISTRY

BIOCHEMISTRY

ANALYTICAL CHEMISTRY
PHYSICS

MATHEMATHICS
 ORGANIC CHEMISTRY
deals almost with carbon containing compounds
with covalent bounds between atoms
From alchemy to the science of chemistry

Friedrich Wöhler 1828

1953 - Stanley Lloyd Miller

highlights the formation of organic compounds
(2% amino acids) from gases
 From atom scale to elementary particles
Fundamental interactions

Gravitational interaction - governs the motion of planets, solar systems, all matter

Electromagnetic interaction - is the force that governs the movement of electrons in
orbits around the nuclei

Weak Nuclear Interaction - is the force that holds protons and neutrons together,
forming the nuclei of atoms

Strong Nuclear Interaction - is the force that holds quarks in protons and neutrons
ELEMENTARY PARTICLES
IN PHYSICS
Atoms and elementary particles
- proton and neutron -
Atoms and elementary particles
- string theory -
Electromagnetic radiation
Electromagnetic radiation
Electromagnetic radiation
 Electromagnetic radiation

Bioelectromagnetics1 is the study of the interactions and effects of EM radiation on living

organisms. The effects of electromagnetic radiation upon living cells, including those in humans,
depends upon the radiation's power and frequency. For low-frequency radiation (radio waves to
visible light) the best-understood effects are those due to radiation power alone, acting through
heating when radiation is absorbed. For these thermal effects, frequency is important as it affects
the intensity of the radiation and penetration into the organism (for example, microwaves penetrate
better than infrared). It is widely accepted that low frequency fields that are too weak to cause
significant heating could not possibly have any biological effect.[45]

Despite the commonly accepted results, some research has been conducted to show that weaker
non-thermal electromagnetic fields, (including weak ELF magnetic fields, although the latter does
not strictly qualify as EM radiation[45][46][47]), and modulated RF and microwave fields have
biological effects.[48][49][50] Fundamental mechanisms of the interaction between biological
material and electromagnetic fields at non-thermal levels are not fully understood.[45]

The World Health Organization has classified radio frequency electromagnetic radiation as
Group 2B - possibly carcinogenic.[51][52] This group contains possible carcinogens such as lead,
DDT, and styrene. For example, epidemiological studies looking for a relationship between cell
phone use and brain cancer development, have been largely inconclusive, save to demonstrate
that the effect, if it exists, cannot be a large one.

At higher frequencies (visible and beyond), the effects of individual photons begin to become
important, as these now have enough energy individually to directly or indirectly damage biological
molecules.[53] All UV frequences have been classed as Group 1 carcinogens by the World Health
Organization. Ultraviolet radiation from sun exposure is the primary cause of skin cancer.[54][55]
Ionizing radiation
The periodic system of elements
Isotopes
Atomic number Z
Mass number A
Molecular mass M
 Atomic orbitals

Physicists and chemists use a standard notation to indicate the electron configurations of atoms and molecules. For
atoms, the notation consists of a sequence of atomic subshell labels (e.g. for P the sequence 1s, 2s, 2p, 3s, 3p) with the
number of electrons assigned to each subshell placed as a superscript. For example, H has one electron in the s-orbital
of the first shell, so its configuration is written 1s1. Li has two electrons in the 1s-subshell and one in the (higher-energy)
2s-subshell, so its configuration is written 1s2 2s1 (pronounced "one-s-two, two-s-one"). P (atomic number 15) is as
follows: 1s2 2s2 2p6 3s2 3p3.
 Atomic orbitals - Quantum numbers
Because of the quantum mechanical nature of the electrons around a nucleus, atomic orbitals can
be uniquely defined by a set of integers known as quantum numbers. These quantum numbers
only occur in certain combinations of values, and their physical interpretation changes
depending on whether real or complex versions of the atomic orbitals are employed.

The quantum numbers, together with the rules governing their possible values, are as follows:


The principal quantum number n describes the energy of the electron and is always a positive
integer. In fact, it can be any positive integer, but large numbers are seldom encountered. Each
atom has, in general, many orbitals associated with each value of n; these orbitals together are
sometimes called electron shells.


The azimuthal quantum number ℓ describes the orbital angular momentum of each electron and
is a non-negative integer. Within a shell where n is some integer n 0, ℓ ranges across all (integer)
values satisfying the relation 0 ≤ ℓ ≤ n 0 − 1. For instance, the n = 1 shell has only orbitals with ℓ
= 0, and the n = 2 shell has only orbitals with ℓ = 0, and ℓ = 1. The set of orbitals associated with
a particular value of ℓ are sometimes collectively called a subshell.

 The magnetic quantum number, mℓ describes the magnetic moment of an electron in an arbitrary
direction, and is also always an integer. Within a subshell where ℓ is some integer ℓ 0, mℓ ranges
thus: − ℓ0 ≤ mℓ ≤ ℓ0

source: en.wikipedia.org
Atomic orbitals - Quantum numbers

s-type drum modes

p-type drum modes

d-type drum modes

Atomic orbitals

Erwin Schrödinger

1887-1961
 Atomic orbitals – electronic configuration

Pauli exclusion principle

An orbital can contain 0, 1 or 2 electrons. In a 2-electron orbital, they are always of opposite spin.

(two or more identical fermions - particles with half-integer spin - cannot occupy the same
quantum state within a quantum system simultaneously)

Hund's rule of maximum multiplicity

Excepting s orbitals, the electron occupation of the upper
orbitals follows the rule of occupying degenerate levels
by one electron before the formation of electron pairs.

(for a given electron configuration, the lowest energy

term is the one with the greatest value of spin
multiplicity)
Molecules – neutral group of two or more atoms held together
by chemical bonds
(covalent links between atoms - molecules are distinguished
from ions by their lack of electrical charge)
 Formation of molecular orbitals
Molecular orbitals arise from allowed interactions between atomic orbitals, which are allowed if the symmetries
(determined from group theory) of the atomic orbitals are compatible with each other. Efficiency of atomic orbital
interactions is determined from the overlap (a measure of how well two orbitals constructively interact with one
another) between two atomic orbitals, which is significant if the atomic orbitals are close in energy. Finally, the number
of molecular orbitals formed must be equal to the number of atomic orbitals in the atoms being combined to form the
molecule.
 Formation of molecular orbitals
Bonding, antibonding, and nonbonding Mos

When atomic orbitals interact, the resulting molecular orbital can be of

three types: bonding, antibonding, or nonbonding.

Bonding MOs:

Bonding interactions between atomic orbitals are constructive (in-phase)
interactions.

Bonding MOs are lower in energy than the atomic orbitals that combine
to produce them.

Antibonding MOs:

Antibonding interactions between atomic orbitals are destructive (out-of-
phase) interactions, with a nodal plane where the wavefunction of the
antibonding orbital is zero between the two interacting atoms

Antibonding MOs are higher in energy than the atomic orbitals that
combine to produce them.

Nonbonding MOs:

Nonbonding MOs are the result of no interaction between atomic orbitals
because of lack of compatible symmetries.

Nonbonding MOs will have the same energy as the atomic orbitals of one
of the atoms in the molecule.
Formation of molecular orbitals
Formation of molecular orbitals
- orbital hybridization -
sp3
Formation of molecular orbitals
- orbital hybridization -
sp2
Formation of molecular orbitals
- orbital hybridization -
sp
Electronegativity, polarization of
covalent bonds
Intermolecular forces

Van der Waals interactions

Dipole-dipole interactions

Ion-dipole interactions

Hydrogen bonding
Hydrogen bonding
Dipole-dipole interactions
Ion-dipole interactions
Van der Waals interactions