Physical chemistry

Physical chemistry is the study of macroscopic, atomic,

subatomic, and particulate phenomena in chemical systems in
terms of physical laws and concepts. It applies the principles,
practices and concepts of physics such as motion, energy, force,
time, thermodynamics, quantum chemistry, statistical mechanics
and dynamics.
Physical chemistry, in contrast to chemical physics, is
predominantly (but not always) a macroscopic or supra-
molecular science, as the majority of the principles on which
physical chemistry was founded are concepts related to the bulk
rather than on molecular/atomic structure alone; for example,
chemical equilibrium, colloids.
Some of the relationships that physical chemistry strives to
resolve include the effects of:
1. Intermolecular forces on the physical properties of
materials (plasticity, tensile strength, surface tension in
liquids).
2. Reaction kinetics on the rate of a reaction.
3. The identity of ions on the electrical conductivity of
materials.
4. Surface chemistry and electrochemistry of membranes.

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.

London dispersion forces

Otherwise known as quantum-induced instantaneous
polarization or instantaneous dipole-induced dipole forces, the
London dispersion force is caused by correlated movements of
the electrons in interacting molecules. The electrons, which
belong to different molecules, start "feeling" and avoiding each
other at the short intermolecular distances, which is frequently
described as formation of "instantaneous dipoles" that attract
each other.
Debye (induced dipole) force
The induced dipole forces appear from the induction (also
known as polarization), which is the attractive interaction
between a permanent multipole on one molecule with an
induced multipole on another. This interaction is called Debye
force after Peter J.W. Debye.
Dipole-dipole interactions
Dipole-dipole interactions are electrostatic interactions of
permanent dipoles in molecules. These interactions tend to align
the molecules to increase the attraction (reducing potential
energy). An example of dipole-dipole interactions can be seen in
hydrogen chloride (HCl): The positive end of a polar molecule
will attract the negative end of the other molecule and cause
them to be arranged in a specific arrangement. Polar molecules
have a net attraction between them. For example HCl and
chloroform (CHCl3)

Keesom interactions (named after Willem Hendrik Keesom) are

attractive interactions of dipoles that are Boltzmann-averaged
over different rotational orientations of the dipoles. The energy
of a Keesom interaction depends on the inverse sixth power of
the distance, unlike the interaction energy of two spatially fixed
dipoles, which depends on the inverse third power of the
distance.
Often, molecules have dipolar groups within them, but have no
overall dipole moment. This occurs if there is symmetry within
the molecule, causing the dipoles to cancel each other out. This
occurs in molecules such as tetrachloromethane. Note that the
dipole-dipole interaction between two atoms is usually zero,
because atoms rarely carry a permanent dipole. See atomic
dipoles.
Hydrogen bonding
A hydrogen bond is the attractive interaction between a
hydrogen atom and an electronegative atom, such as nitrogen,
oxygen, or fluorine. The hydrogen bond is often described as a
strong electrostatic dipole-dipole interaction. However, it also
has some features of covalent bonding: It is directional, stronger
than a van der Waals interaction, produces interatomic distances
shorter than sum of van der Waals radii, and usually involves a
limited number of interaction partners, which can be interpreted
as a kind of valence.

Intermolecular hydrogen bonding is responsible for the high

boiling point of water (100 °C) compared to the other group 16
hydrides that have no hydrogen bonds. Intramolecular hydrogen
bonding is partly responsible for the secondary, tertiary, and
quaternary structures of proteins and nucleic acids. It also plays
an important role in the structure of polymers, both synthetic
and natural.

 Chemical kinetics

Reaction rate tends to increase with concentration - a

phenomenon explained by collision theory.

Chemical kinetics, also known as reaction kinetics, is the study

of rates of chemical processes. Chemical kinetics includes
investigations of how different experimental conditions can
influence the speed of a chemical reaction and yield information
about the reaction's mechanism and transition states, as well as
the construction of mathematical models that can describe the
characteristics of a chemical reaction. In 1864, Peter Waage and
Cato Guldberg pioneered the development of chemical kinetics
by formulating the law of mass action, which states that the
speed of a chemical reaction is proportional to the quantity of
the reacting substances.
Chemical kinetics deals with the experimental determination of
reaction rates from which rate laws and rate constants are
derived. Relatively simple rate laws exist for zero-order
reactions (for which reaction rates are independent of
concentration), first-order reactions, and second-order reactions,
and can be derived for others. In consecutive reactions the rate-
determining step often determines the kinetics. In consecutive
first-order reactions, a steady state approximation can simplify
the rate law. The activation energy for a reaction is
experimentally determined through the Arrhenius equation and
the Eyring equation. The main factors that influence the reaction
rate include: the physical state of the reactants, the
concentrations of the reactants, the temperature at which the
reaction occurs, and whether or not any catalysts are present in
the reaction.
Factors affecting reaction rate
Nature of the reactants

Depending upon what substances are reacting, the reaction rate

varies. Acid/base reactions, the formation of salts, and ion
exchange are fast reactions. When covalent bond formation
takes place between the molecules and when large molecules are
formed, the reactions tend to be very slow. Nature and strength
of bonds in reactant molecules greatly influences the rate of its
transformation into products. The reactions which involve lesser
bond rearrangement proceed faster than the reactions which
involve larger bond rearrangement.
Physical state

The physical state (solid, liquid, or gas) of a reactant is also an

important factor of the rate of change. When reactants are in the
same phase, as in aqueous solution, thermal motion brings them
into contact. However, when they are in different phases, the
reaction is limited to the interface between the reactants.
Reaction can only occur at their area of contact, in the case of a
liquid and a gas, at the surface of the liquid. Vigorous shaking
and stirring may be needed to bring the reaction to completion.
This means that the more finely divided a solid or liquid
reactant, the greater its surface area per unit volume, and the
more contact it makes with the other reactant, thus the faster the
reaction. To make an analogy, for example, when one starts a
fire, one uses wood chips and small branches—one doesn't start
with large logs right away. In organic chemistry, On water
reactions are the exception to the rule that homogeneous
reactions take place faster than heterogeneous reactions.
Concentration

Concentration plays a very important role in reactions, because

according to the collision theory of chemical reactions,
molecules must collide in order to react together. As the
concentration of the reactants increases, the frequency of the
molecules colliding increases, striking each other more
frequently by being in closer contact at any given point in time.
Think of two reactants being in a closed container. All the
molecules contained within are colliding constantly. By
increasing the amount of one or more of the reactants it causes
these collisions to happen more often, increasing the reaction
rate.
Temperature

Temperature usually has a major effect on the rate of a chemical

reaction. Molecules at a higher temperature have more thermal
energy. Although collision frequency is greater at higher
temperatures, this alone contributes only a very small proportion
to the increase in rate of reaction. Much more important is the
fact that the proportion of reactant molecules with sufficient
energy to react (energy greater than activation energy: E > Ea) is
significantly higher and is explained in detail by the Maxwell–
Boltzmann distribution of molecular energies.
The 'rule of thumb' that the rate of chemical reactions doubles
for every 10 °C temperature rise is a common misconception.
This may have been generalized from the special case of
biological systems, where the Q10 (temperature coefficient) is
often between 1.5 and 2.5.
A reaction's kinetics can also be studied with a temperature
jump approach. This involves using a sharp rise in temperature
and observing the relaxation rate of an equilibrium process.
Catalysts

Generic potential energy diagram showing the effect of a

catalyst in an hypothetical endothermic chemical reaction. The
presence of the catalyst opens a different reaction pathway
(shown in red) with a lower activation energy. The final result
and the overall thermodynamics are the same.

A catalyst is a substance that accelerates the rate of a chemical

reaction but remains chemically unchanged afterwards. The
catalyst increases rate reaction by providing a different reaction
mechanism to occur with a lower activation energy. In
autocatalysis a reaction product is itself a catalyst for that
reaction leading to positive feedback. Proteins that act as
catalysts in biochemical reactions are called enzymes.
Michaelis-Menten kinetics describe the rate of enzyme mediated
reactions. A catalyst does not affect the position of the
equilibria, as the catalyst speeds up the backward and forward
reactions equally.
In certain organic molecules, specific substituents can have an
influence on reaction rate in neighbouring group participation.
Agitating or mixing a solution will also accelerate the rate of a
chemical reaction, as this gives the particles greater kinetic
energy, increasing the number of collisions between reactants
and therefore the possibility of successful collisions.
Pressure

Increasing the pressure in a gaseous reaction will increase the

number of collisions between reactants, increasing the rate of
reaction. This is because the activity of a gas is directly
proportional to the partial pressure of the gas. This is similar to
the effect of increasing the concentration of a solution...
Equilibrium
While chemical kinetics is concerned with the rate of a chemical
reaction, thermodynamics determines the extent to which
reactions occur. In a reversible reaction, chemical equilibrium is
reached when the rates of the forward and reverse reactions are
equal and the concentrations of the reactants and products no
longer change. This is demonstrated by, for example, the Haber–
Bosch process for combining nitrogen and hydrogen to produce
ammonia. Chemical clock reactions such as the Belousov–
Zhabotinsky reaction demonstrate that component
concentrations can oscillate for a long time before finally
attaining the equilibrium.
Free energy
In general terms, the free energy change (ΔG) of a reaction
determines whether a chemical change will take place, but
kinetics describes how fast the reaction is. A reaction can be
very exothermic and have a very positive entropy change but
will not happen in practice if the reaction is too slow. If a
reactant can produce two different products, the
thermodynamically most stable one will generally form except
in special circumstances when the reaction is said to be under
kinetic reaction control. The Curtin–Hammett principle applies
when determining the product ratio for two reactants
interconverting rapidly, each going to a different product. It is
possible to make predictions about reaction rate constants for a
reaction from free-energy relationships.
The kinetic isotope effect is the difference in the rate of a
chemical reaction when an atom in one of the reactants is
replaced by one of its isotopes.
Chemical kinetics provides information on residence time and
heat transfer in a chemical reactor in chemical engineering and
the molar mass distribution in polymer chemistry.
Applications
The mathematical models that describe chemical reaction
kinetics provide chemists and chemical engineers with tools to
better understand and describe chemical processes such as food
decomposition, microorganism growth, stratospheric ozone
decomposition, and the complex chemistry of biological
systems. These models can also be used in the design or
modification of chemical reactors to optimize product yield,
more efficiently separate products, and eliminate
environmentally harmful by-products. When performing
catalytic cracking of heavy hydrocarbons into gasoline and light
gas, for example, kinetic models can be used to find the
temperature and pressure at which the highest yield of heavy
hydrocarbons into gasoline will occur.

 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.