PHYSICAL

CHEMISTRY
Physical Chemistry,fieldofsciencethat applies the laws of physics to
elucidate the properties of chemical substances and clarify the
characteristics of chemical phenomena. The term physical chemistry is
usually applied to the study of the physical properties of substances,
such as vapor pressure, surface tension, viscosity, refractive index,
density, and crystallography, as well as to the study of the so-called
classical aspects of the behavior of chemical systems, such as thermal
properties, equilibria, rates of reactions, mechanisms of reactions, and
ionization phenomena (see Chemical Reaction; Heat; Heat Transfer;
Ionization). In its more theoretical aspects, physical chemistry
attempts to explain spectral properties of substances in terms of
fundamental quantum theory; the interaction of energy with matter;
the nature of chemical bonding; the relationships correlating the
number and energy states of electrons in atoms and molecules with
the observable properties shown by these systems; and the electrical,
thermal, and mechanical effects of individual electrons and protons on
solids and liquids.

PHYSICAL
CHEMISTRY
Physical Chemistry,fieldofsciencethat applies the laws of physics to
elucidate the properties of chemical substances and clarify the
characteristics of chemical phenomena. The term physical chemistry is
usually applied to the study of the physical properties of substances,
such as vapor pressure, surface tension, viscosity, refractive index,
density, and crystallography, as well as to the study of the so-called
classical aspects of the behavior of chemical systems, such as thermal
properties, equilibria, rates of reactions, mechanisms of reactions, and
ionization phenomena (see Chemical Reaction; Heat; Heat Transfer;
Ionization). In its more theoretical aspects, physical chemistry
attempts to explain spectral properties of substances in terms of
fundamental quantum theory; the interaction of energy with matter;
the nature of chemical bonding; the relationships correlating the
number and energy states of electrons in atoms and molecules with
the observable properties shown by these systems; and the electrical,
thermal, and mechanical effects of individual electrons and protons on
solids and liquids.

HISTORICAL
DEVELOPMENT
Theearliestphaseof the development of physical
chemistry as a specialized field of study was
devoted to investigating the problem of chemical
affinities, or the widely varying extents and
degrees of vigor with which various substances
react with each other. Common examples are the
easy corrosion of iron compared to gold, and the
fact that oxygen supports combustion but
nitrogen does not.

HISTORICAL
DEVELOPMENT
Theearliestphaseof the development of physical
chemistry as a specialized field of study was
devoted to investigating the problem of chemical
affinities, or the widely varying extents and
degrees of vigor with which various substances
react with each other. Common examples are the
easy corrosion of iron compared to gold, and the
fact that oxygen supports combustion but
nitrogen does not.

HISTORICAL
DEVELOPMENT
19TH CENTURY
Itwasfirstassumedthat rapid reactions were those
that proceeded to completion. It was soon realized,
however, that these were determined independently;
the degree of completeness of a reaction is
determined by its so-called equilibrium constant, a
concept introduced in 1864 by the Norwegian
chemists Cato Maximilian Guldberg and Peter Waage,
whereas the rate of a reaction is determined by the
intimacy of contact between the reactants, the
presence or absence of a catalyst (see Catalysis), and
other variables.

HISTORICAL
DEVELOPMENT
TH
Dalton proposed his atomic theory
19TheBritishchemistJohn
CENTURY

in 1803 and it was placed on a firm footing in 1811 when

the Italian physicist Amedeo Avogadro made clear the
distinction between atoms and molecules of elementary
substances. About the same time, the concepts of heat,
energy, work, and temperature began to be clarified and
made more precise. The first law of thermodynamics,
according to which heat and work are mutually exactly
interconvertible, was first clearly stated by the German
physicist Julius Robert von Mayer in 1842. The second law of
thermodynamics, according to which spontaneous processes
occur with an increase in the degree of disorder in the
system, was enunciated by the German mathematical
physicist Rudolf Julius Emanuel Clausius and the British
mathematician and physicist William Thomson, later Lord
Kelvin, in 1850-51. See Atom; Thermodynamics.

HISTORICAL
DEVELOPMENT
TH
Dalton proposed his atomic theory
19TheBritishchemistJohn
CENTURY

in 1803 and it was placed on a firm footing in 1811 when

the Italian physicist Amedeo Avogadro made clear the
distinction between atoms and molecules of elementary
substances. About the same time, the concepts of heat,
energy, work, and temperature began to be clarified and
made more precise. The first law of thermodynamics,
according to which heat and work are mutually exactly
interconvertible, was first clearly stated by the German
physicist Julius Robert von Mayer in 1842. The second law of
thermodynamics, according to which spontaneous processes
occur with an increase in the degree of disorder in the
system, was enunciated by the German mathematical
physicist Rudolf Julius Emanuel Clausius and the British
mathematician and physicist William Thomson, later Lord
Kelvin, in 1850-51. See Atom; Thermodynamics.

HISTORICAL
DEVELOPMENT
19TH CENTURY

Thesedevelopmentsmade it possible to begin to

interpret the properties of gases, which represent
the simplest states of matter, in terms of the
behavior of their individual molecules. In the
period 1860-75, Clausius, the Austrian physicist
Ludwig Boltzmann, and the British physicist
James Clerk Maxwell showed how to account for
the ideal gas law in terms of a kinetic theory of
matter (see Gases). From this beginning have
flowed all the subsequent insights into the
kinetics of reactions and the laws of chemical
equilibrium.

HISTORICAL
DEVELOPMENT
TH
19Importantcontributions
CENTURY
to the field of physical chemistry were

made toward the end of the 18th century by the French chemist
Comte Claude Louis Berthollet, who studied the rate and
reversibility of reactions, and the Anglo-American physicist
Benjamin Thompson who attempted to deduce the mechanical
equivalent of heat. In 1824 the French physicist Nicolas Lonard
Sadi Carnot published his studies of the correlation between
heat and work, which established him as the founder of modern
thermodynamics, and in 1836 the Swedish chemist Jns Jakob
Berzelius assessed the role played by catalysts in accelerating
reactions. The application of the first and second laws of
thermodynamics to heterogenous substances in 1875 by the
American mathematical physicist Josiah Willard Gibbs and his
discovery of the phase rule laid down the theoretical basis of
physical chemistry. The German physical chemist Walther
Hermann Nernst, who in 1906 enunciated the third law of
thermodynamics, also made a lasting contribution to the study

HISTORICAL
DEVELOPMENT
19TH CENTURY
TheDutchphysicalchemist Jacobus Hendricus van't
Hoff, generally regarded as the father of chemical
kinetics, initiated the foundation of stereochemistry in
1874 with his work on optically active carbon
compounds and three-dimensional and asymmetrical
molecular structures. Three years later, he related
thermodynamics to chemical reactions and developed
a method for establishing the order of reactions. In
1889 the Swedish chemist Svante August Arrhenius
investigated the speeding of chemical reactions with
increase in temperature and enunciated the theory of
electrolytic dissociation, known as Arrhenius's theory.

HISTORICAL
DEVELOPMENT
20TH CENTURY
Thedevelopmentofchemical kinetics has
continued into the 20th century with the
contributions to the study of molecular
structures, reaction rates, and chain
reactions by physical chemists such as Irving
Langmuir of the United States, Jens Anton
Christiansen of Denmark, Michael Polanyi of
Great Britain, and Nikolay Semenov of the
Soviet Union, and important basic research
continues today.

HISTORICAL
DEVELOPMENT
20TH CENTURY
In1923theAmericanchemist
Gilbert
Newton Lewis further clarified the principles
of chemical thermodynamics enunciated by
Gibbs.

HISTORICAL
DEVELOPMENT
TH
20
CENTURY
Thegreatwatershedperiod
for the development of

physical chemistry was 1900-30. In 1897 the German

physicist Max Planck had proposed that energy in certain
systems is quantized, or occurs in discrete units or
packages, just as matter occurs in discrete units, the
atoms. In 1913, the Danish physicist Niels Bohr showed
how the concept of quantization served fully to explain
the spectrum of atomic hydrogen. In 1926-29, the
Austrian physicist Erwin Schrdinger and the German
physicist Werner Heisenberg developed the picture of the
wave function, a mathematical expression incorporating
the wave-particle duality of electrons, and showed how
to calculate useful properties from this formula. From
these beginnings, modern concepts of the structures of
atoms and the nature of the bindings between atoms

SUBDIVISIONS OF
PHYSICAL CHEMISTRY
Themainsubdivisions of the study of physical
chemistry are chemical thermodynamics;
chemical kinetics; the gaseous state; the liquid
state;
solutions;
the
solid
state;
electrochemistry;
colloid
chemistry;
photochemistry;
and
statistical
thermodynamics.

CHEMICAL
THERMODYNAMICS
Thisbranchstudiesenergy in its various forms
as related to matter. It examines the ways in
which the internal
energy,
degree of
organization or order, and ability to do useful
work are related to temperature, heat absorbed
or evolved, change of state (for instance, from
liquid to gas, gas to liquid, or solid to liquid),
work done on or by the system in the form of
the flow of electrical currents, formation of
surfaces and changes in surface tension,
changes in volume or pressure, and formation
or disappearance of chemical species.

CHEMICAL KINETICS

Thisfieldstudiesthe rates of chemical processes as a function

of the concentration of the reacting species, of the products of
the reaction, of catalysts and inhibitors, of various solvent
media, of temperature, and of all other variables that can affect
the reaction rate. It is an essential part of the study of chemical
kinetics to seek to relate the precise fashion in which the
reaction rate varies with time to the molecular nature of the
rate-controlling intermolecular collision involved in generating
the reaction products. Most reactions involve a series of
stepwise processes, the sum of which corresponds to the
overall, observed reaction proportions (or stoichiometry) in
which the reactants combine and the products form; only one
of these steps, however, is generally the rate-controlling one,
the others being much faster. By determining the nature of the
rate-controlling process from the mathematical analysis of the
reaction kinetics and by investigating how the reaction
conditions (for instance, solvent, other species, and
temperature) affect this step, or cause some other process to
become the rate-controlling one, the physical chemist can

GASEOUS STATE

GASEOUS STATE
Thisbranchisconcerned with the study of the properties of gases,
in particular, the law that interrelates the pressure, volume,
temperature, and quantity of a gas. This law is expressed in
mathematical form as the equation of state of the gas. For an
ideal gas (that is, a hypothetical gas consisting of molecules
whose dimensions are negligibly small, and which do not exert
forces of attraction or repulsion on each other), the equation of
state has the simple formula: PV = nRT, where P is pressure, V is
volume, n is the number of moles of the substance, R is a
constant, and T is the absolute (or Kelvin) temperature. For real
gases, the equation of state is more complicated, containing
additional variables due to the effects of the finite sizes and force
fields of the molecules. Mathematical analysis of the equations of
state of real gases permits the physical chemist to deduce much
about the relative sizes of molecules, as well as the strengths of
the forces they exert on each other.

LIQUID STATE
Thisfieldstudiesthe properties of liquids,
in particular, the vapor pressure, boiling
point, heat of vaporization, heat capacity,
volume
per
mole,
viscosity,
compressibility, and the manner in which
these properties are affected by the
temperature and pressure at which they
are measured and by the chemical nature
of the substance itself.

SOLUTIONS
Thisbranchstudiesthe special properties
that arise when one substance is dissolved
in another. In particular, it investigates the
solubility of substances and how it is
affected by the chemical nature of both
the solute and the solvent. It also involves
the study of the electrical conductivity and
colligative properties (the boiling point,
freezing point, vapor pressure, and
osmotic
pressure)
of
solutions
of
electrolytes, which are substances that
yield ions when dissolved in a polar

SOLID STATE

Thisbranchdealswith the study of the internal

structure, on a molecular and atomic scale, of
solids, and the elucidation of the physical
properties of solids in terms of this structure. This
includes the mathematical analysis of the
diffraction patterns produced when a beam of X
rays is directed at a crystal. By using this
method, physical chemists have gained valuable
insights into the packing arrangements adopted
by various types of ions and atoms. They have
also
learned
the
symmetries
and
crystallographies of most solid substances as well
as their cohesive forces, heat capacities, melting
points, and optical properties.

ELECTROCHEMISTRY
Thisbranchisconcerned with the study of chemical
effects produced by the flow of electric currents
across interfaces (as at the boundary between an
electrode and a solution) and, vice versa, the
electrical effects produced by the displacement or
transport of ions across boundaries or within gases,
liquids, or solids (see Electricity). Measurements of
electrical conductivity in liquids yield insights into
ionization equilibria and the properties of ions. In
solids, such measurements provide information about
the states of the electrons in crystal lattices and in
insulators, semiconductors, and metallic conductors.
Measurements of voltages (electric potentials) yield
knowledge of the concentrations of ionic species and
of the driving forces of reactions that involve the gain
or loss of electrons from a variety of reactants. See

COLLOID
Thisbranchstudiesthe
nature and effects of
CHEMISTRY
surfaces and interfaces on the macroscopic
properties of substances. These studies involve
the investigation of surface tension, interfacial
tension (the tension that exists in the plane of
contact between a liquid and a solid, or between
two liquids), wetting and spreading of liquids on
solids, adsorption of gases or of ions in solution
on solid surfaces, Brownian motion of suspended
particles, emulsification, coagulation, and other
properties of systems in which tiny particles are
immersed in a fluid medium. See Colloid.

PHOTO CHEMISTRY

Thisbranchconcernsthe study of the effects resulting

from the absorption of electromagnetic radiation by
substances, as well as the ability of substances to emit
electromagnetic radiation when energized in various
ways. When X radiation interacts with matter, electrons
may be ejected from their places in the interiors of
atoms, ions, or molecules, and measuring the energies
of these electrons reveals much about the nature of the
electron arrangement within the atom, ion, or molecule.
Similarly, investigation of the absorption of ultraviolet
and visible light discloses the structure of the valence,
or binding electrons (see Ultraviolet Radiation);
absorption of infrared radiation provides information
about the vibrational motions and binding forces within
molecules; and absorption of microwaves permits
scientists to deduce the nature of the rotational motions
of molecules, and from this the exact geometries

PHOTO CHEMISTRY
The study of the interaction of electromagnetic
radiation with matter, when that interaction does
not result in chemical changes, is often
designated as spectrochemistry, and the term
photochemistry is then used only for those
interactions that produce chemical changes.
Examples of photochemistry (that is, lightinduced) reactions are the fading of dyes when
exposed to sunlight, the generation of vitamin D
in the human skin by sunlight, and the formation
of ozone in the upper atmosphere by the
ultraviolet radiation from the sun.

STATISTICAL
THERMODYNAMICS AND
Thisbranchisconcerned with the calculation
the internal MECHANICS
energy, degree of order

of
or
organization (entropy), ability to do useful work
(free energy), and other properties, such as the
equations of state of gases, the vapor pressures
of liquids, the molecular shapes adopted by
polymer chains, and electrical conductivities of
ionic solutions. These calculations are based on a
model of the individual molecule or ion and the
mathematical techniques of statistical analysis,
which permit the mutual interactions of large
numbers of randomly arranged particles to be
evaluated.

CURRENT STATUS

Physicalchemistryand chemical physics

are vigorously active fields of research in
chemistry today. Electrochemistry, colloid
chemistry, and photochemistry are of
great importance in many phases of
modern industry. The current computer
and
communication
revolutions,
for
example, could not have occurred without
the special chemicals, crystals, and
devices developed in the course of
research in these branches of physical
chemistry.

CURRENT
STATUS
Intheareaoffundamental
research,
as
distinguished from applied research, the greatest
emphasis today is on the theoretical analysis of
spectra of all kinds, ranging from the X-ray region
of the electromagnetic spectrum to the radio-wave
region (see Spectroscopy; Spectrum). Emphasis is
also placed on the application of quantum and
wave mechanics to elucidate the principles of
molecular binding and structure. Valuable insights
into these questions have been gained by studying
the properties of substances under conditions of
both
extremely
high
and
extremely
low
temperatures and pressures as well as under the
influence of strong electrical, magnetic, and