Physical Chemistry
Physical Chemistry
Physical Chemistry
History
The term "physical chemistry" was first introduced by Mikhail
Lomonosov in 1752, when he presented a lecture course entitled
"A Course in True Physical Chemistry before the students of
Petersburg University.
Modern physical chemistry originated in the 1860s to 1880s
with work on chemical thermodynamics, electrolytes in
solutions, chemical kinetics and other subjects. One milestone
was the publication in 1876 by Josiah Willard Gibbs of his
paper, On the Equilibrium of Heterogeneous Substances. This
paper introduced several of the cornerstones of physical
chemistry, such as Gibbs energy, chemical potentials, Gibbs
phase rule . Other milestones include the subsequent naming and
accreditation of enthalpy to Heike Kamerlingh Onnes and to
macromolecular processes.
The first scientific journal specifically in the field of physical
chemistry was the German journal, Zeitschrift für Physikalische
Chemie, founded in 1887 by Wilhelm Ostwald and Jacobus
Henricus van 't Hoff. Together with Svante August Arrhenius.
these were the leading figures in physical chemistry in the late
19th century and early 20th century. All three were awarded
with the Nobel Prize in Chemistry between 1901-1909.
Developments in the following decades include the application
of statistical mechanics to chemical systems and work on
colloids and surface chemistry, where Irving Langmuir made
many contributions. Another important step was the
development of quantum mechanics into quantum chemistry
from the 1930s, where Linus Pauling was one of the leading
names. Theoretical developments have gone hand in hand with
developments in experimental methods, where the use of
different forms of spectroscopy, such as infrared spectroscopy,
microwave spectroscopy, EPR spectroscopy and NMR
spectroscopy, is probably the most important 20th century
development.
Further development in physical chemistry may be attributed to
discoveries in nuclear chemistry, especially in isotope separation
(before and during World War II), more recent discoveries in
astrochemistry, as well as the development of calculation
algorithms in field of "additive physicochemical properties"
(practically all of physicochemical properties, as: boiling point,
critical point, surface tension, vapor pressure etc. - more than 20
in all, can be precisely calculated from chemical structure, even
if such chemical molecule is still non existent), and in this area
is concentrated practical importance of contemporary physical
chemistry.
Intermolecular force
Intermolecular forces are weak forces as compared to the
intramolecular forces. For example, the covalent bond present
within HCl molecules is much stronger than the forces present
between the neighbouring molecules. These forces are believed
to exist between molecules when they are sufficiently close to
each other. They are believed to consist of four types:
1. Dipole-dipole forces
2. Ion-dipole forces
3. Dipole-induced dipole force or Debye forces
4. Instantaneous dipole-induced dipole forces or London
dispersion forces.
Chemical kinetics
Surface science
Surface science is the study of physical and chemical
phenomena that occur at the interface of two phases, including
solid-liquid interfaces, solid-gas interfaces, solid-vacuum
interfaces, and liquid-gas interfaces. It includes the fields of
surface chemistry and surface physics. Some related practical
applications are classed as surface engineering. The science
encompasses concepts such as heterogeneous catalysis,
semiconductor device fabrication, fuel cells, self-assembled
monolayers, and adhesives. Surface science is closely related to
interface and colloid science. Interfacial chemistry and physics
are common subjects for both. The methods are different. In
addition, interface and colloid science studies macroscopic
phenomena that occur in heterogeneous systems due to
peculiarities of interfaces.
History
The field of surface chemistry started with heterogeneous
catalysis pioneered by Paul Sabatier on hydrogenation and Fritz
Haber on the Haber process. Irving Langmuir was also one of
the founders of this field, and the scientific journal on surface
science, Langmuir, bears his name. The Langmuir adsorption
equation is used to model monolayer adsorption where all
surface adsorption sites have the same affinity for the adsorbing
species. Gerhard Ertl in 1974 described for the first time the
adsorption of hydrogen on a palladium surface using a novel
technique called LEED. Similar studies with platinum, nickel,
and iron followed. Most recent developments in surface sciences
include the 2007 Nobel Prize of Chemistry winner Gerhard
Ertl's advancements in surface chemistry, specifically his
investigation of the interaction between carbon monoxide
molecules and platinum surfaces.
Surface chemistry
Surface chemistry can be roughly defined as the study of
chemical reactions at interfaces. It is closely related to surface
engineering, which aims at modifying the chemical composition
of a surface by incorporation of selected elements or functional
groups that produce various desired effects or improvements in
the properties of the surface or interface. Surface chemistry also
overlaps with electrochemistry. Surface science is of particular
importance to the field of heterogeneous catalysis.
The adhesion of gas or liquid molecules to the surface is known
as adsorption. This can be due to either chemisorption or by
physisorption. These too are included in surface chemistry.
The behavior of a solution based interface is affected by the
surface charge, dipoles, energies, and their distribution within
the electrical double layer.
Surface physics
Surface physics can be roughly defined as the study of physical
changes that occur at interfaces. It overlaps with surface
chemistry. Some of the things investigated by surface physics
include surface states, surface diffusion, surface reconstruction,
surface phonons and plasmons, epitaxy and surface enhanced
Raman scattering, the emission and tunneling of electrons,
spintronics, and the self-assembly of nanostructures on surface.
Analysis techniques
The study and analysis of surfaces involves both physical and
chemical analysis techniques.
Several modern methods probe the topmost 1–10 nm of the of
surfaces exposed to vacuum. These include X-ray photoelectron
spectroscopy, Auger electron spectroscopy, low-energy electron
diffraction, electron energy loss spectroscopy, thermal
desorption spectroscopy, ion scattering spectroscopy, secondary
ion mass spectrometry, and other surface analysis methods
included in the list of materials analysis methods. Many of these
techniques require vacuum as they rely on the detection of
electrons or ions emitted from the surface under study.
Moreover, in general ultra high vacuum, in the range of 10−7
pascal pressure or better, is necessary to reduce surface
contamination by residual gas, by reducing the number of
molecules reaching the sample over a given time period. At 0.1
mPa (10−6 Torr), it only takes 1 second to cover a surface with a
contaminant, so much lower pressures are needed for
measurements.
Purely optical techniques can be used to study interfaces under a
wide variety of conditions. Reflection-absorption infrared, dual
polarisation interferometry, surface enhanced Raman, and sum
frequency generation spectroscopies can be used to probe solid-
vacuum as well as solid-gas, solid-liquid, and liquid-gas
surfaces.
Modern physical analysis methods include scanning-tunneling
microscopy (STM) and a family of methods descended from it.
These microscopies have considerably increased the ability and
desire of surface scientists to measure the physical structure of
many surfaces. This increase is related to a more general interest
in nanotechnology.
Electrochemistry
Electrochemistry is a branch of chemistry that studies chemical
reactions which take place in a solution at the interface of an
electron conductor (a metal or a semiconductor) and an ionic
conductor (the electrolyte), and which involve electron transfer
between the electrode and the electrolyte or species in solution.
If a chemical reaction is driven by an external applied voltage,
as in electrolysis, or if a voltage is created by a chemical
reaction as in a battery, it is an electrochemical reaction. In
contrast, chemical reactions where electrons are transferred
between molecules are called oxidation/reduction (redox)
reactions. In general, electrochemistry deals with situations
where oxidation and reduction reactions are separated in space
or time, connected by an external electric circuit to understand
each process.