The gas laws started to evolve in 1643 with the invention of the barometer and continued until 1873 with the van der Waals equation. Note that this is well before the birth of the modern atomic theory. The gas laws led to numerous concepts including the mole, temperature, formula weight, absolute zero, kinetic energy, and stoichiometric coefficients. This brief history highlights some of the early pioneers.
Barometer
Evangelisto
Torricelli (1608-1647)
Torricelli served as Galileo's secretary (1641-1642)
and succeeded him as court mathematician to
Grand Duke Ferdinando II. Torricelli used mercury to
make the first barometer in 1643.
Mercury is more than 13 times as dense as water; a
water barometer would require a tube more than 30
feet long. Under standard conditions at sea
level, the height will be 29.92 inch or 760 millimeters. The invention
of the barometer allowed Boyle to discover the relationship between
pressure and volume. (Torricelli
letter to Michelangelo concerning the Barometer)
Boyle's Law: P1V1=P2V2
Robert
Boyle (1627-1691)
Boyle had the good fortune to have Robert
Hooke as an assistant and together they made an air pump. Recognizing
its scientific possibilities, Boyle conducted pioneering
experiments in studying the role of air in combustion,
respiration, and the transmission of sound.
In 1662, Boyle published what is now known as Boyle's
law: At constant temperature the volume of a
gas is inversely proportional to the pressure.
Boyle was aware that a gas expands when heated but no
temperature scale existed and he
could not determine the relationship between "hotness"
and volume.
Amontons' Law: P1T2=P2T1
Guillaume
Amontons (1663-1705)
Amontons developed the air thermometer--it relied
on increase in volume of a gas with temperature
rather than the increase in volume of a liquid. Amontons failed to discover
Charles' law for the same reason as Boyle: a temperature scale did not
exist. Using the air thermometer,
Amontons (1702) devised a method to measure change in temperature
in terms of a proportional change in pressure. Although
Amontons' law became the most obscure of
the gas laws, it was this work that eventually led to the
concept of absolute zero
in the 19th century.
As a consequence of becoming deaf as a young boy, Amontons
worked on inventions to benefit
the deaf. One of his inventions, the first
telegraph, relied on a telescope, light,
and several stations to transmit information over
large distances. Although not adopted
in Amontons lifetime, the ideas were later refined
and put into use.
Kinetic Theory of Gases
Daniel
Bernoulli (1700-1782)
Bernoulli studied medicine at the insistence of
his father Johann Bernoulli, chair of mathematics
in Basel Switzerland. However the younger bernoulli became interested
in his father's theories of kinetic
energy and even applied these theories to his doctoral dissertation
on the mechanics of breathing. While practicing
medicine in Venice, Bernoulli published his first
mathematical work consisting of four separate parts: (1) Probability,(2)
flow of water from a hole in a container, (3)
the Riccati differential equation, and (4) a geometry
question concerning figures bounded by two arcs of a circle. These paperswon
him a position at the influential Academy of Sciences
in St. Petersburg, Russia. At the academy Bernoulli
lectured in medicine, mechanics, and physics. He developed
what is nowcalledBernoulli's principle: The pressure
in a fluid decreases as its velocity increases.
The modern kinetic
molecular theory of gases essentially started with Bernoulli's suggestion
in 1734 that the pressure exerted by a gas on the
walls of its container is the sum of the many
collisions by individual molecules, all moving independently of each other.
Bernoulli derived the basic
laws for the theory of gases and gave, although not in full detail, the
equation of state discovered by van der Waals a century later.
Temperature Scale
Measurement of temperature has developed relatively
recently in human history. The invention of the thermometer is generally
credited to Galileo
who developed the first known thermometer (1592) based
on the expansion/contraction of air. German
physicist Fahrenheit
made a mercury
thermometer (1714) ranging from the freezing of
water (32°) to body temperature (96°). Swedish astronomer
Celsius
(1742) devised a scale ranging from the boiling of
water (0°) to the freezing of water (100°)--this
inverted scale (centigrade) gained widespread use and in 1948 the name
was changed to Celsius. In 1848 British physicist
William
Thomson (Lord Kelvin) proposed a system using
degree Celsius but starting at zero Kelvin (-273°C).
Charles' Law: V1T2=V2T1
Jacques
Charles (1746-1823)
The physical principle known as Charles'
Law states that the volume of a gas equals a constant
value multiplied by its temperature as measured on the Kelvin scale. The
law's name honors the pioneer balloonist Jacques Charles,
who in 1787 did experiments on how the volume of gases depended on temperature.
The irony is that Charles never published the work for which he is remembered,
nor was he the first or last to make this discovery. In
fact, Amontons had done the same sorts of experiments
100 years earlier, and it was Gay-Lussac in 1808 who
made definitive measurements and published results showing thatevery gas
he tested obeyed this generalization.
Law of Combining Volumes

Joseph
Gay-Lussac (1778-1850)
Gay-Lussac carefully investigated the ratio of the volume
of hydrogen gas that combined with a given volume
of oxygen gas to form water. He found the oxygen could combine with exactly
twice its own volume of hydrogen. There were similar simple volumetric
ratios for other reactions between gases and if the
product of the reaction was also a gas, it filled a volume
simply related to those of the combining gases.
Gay-Lussac combined research with his passion of hot
air balloons. Because nitrogen is lighter than oxygen,
Gay-Lussac reasoned there might be proportionately less oxygen in
the air at higher elevations. To find out, in 1802
he went up in a balloon to 23,000 feet (a record for 50 years). He found
the proportions nearly the same.
Law of Partial Pressures: PT
= P1 + P2 + P3
+ ...
John
Dalton (1766-1844)
Dalton's law of partial pressures was stated by John
Dalton in 1801: The total pressure of a mixture of
gases is equal to the sum of the partial pressures of the
individual component gases. The partial pressure is the pressure
that each gas would exert if it alone occupied the
volume of the mixture at the same temperature.
Avogadro's Principle

Amedeo
Avogadro (1776-1856)
After practicing law for three years, Avogadro began
to study mathematics and physics. Eventually he was
appointed Professor of Natural Philosophy at the College of Vercelli. Based
on the work of Gay-Lussac, all gases when subjected to an equal rise in
temperature expand by the same amount, Avogadro published
an article (1811) stating that at the same temperature and pressure, equal
volumes of different gases contain the same number of molecules.
The science community was not ready to accept such a radical idea and Avogadro's
Principle went ignored for the next 50 years. Avogadro's work was
finally recognized when countryman Stanisalo
Cannizaro presented the work at a Conference in 1860. Today,
one mole (6.022E23) is called Avogadro's number. At
the time Avogadro's principle was becoming acceptable, Bernoulli's 1738
kinetic model of tiny gas molecules
moving about in otherwise empty space was also reexamined; our modern view
of gases began to emerge in 1860.
Graham's Law of Effusion: u1/u2
= (m2/m1)½

Thomas
Graham (1805-1869)
Graham was professor of chemistry at University
College in London and later became Master of the
Mint. He is best known for Graham's law (1846) which states that
the rate of effusion of a gas
is inversely proportional to the square root of its molecular weight. Graham
also devised the technique known as dialysis to separate
colloids from crystalloids and coined many of the
terms used in colloid chemistry.
Molecular Speed: u = (3RT/M)½
James
Clerk Maxwell (1831-1879)
Maxwell treated gases statistically (1866) and formulated
what has become known as the root-mean-square
molecular equation (u = [3RT/M]½).
This represents a relationship between
molecular mass, average speed, and temperature (R is the familiar gas constant).
Because two gases with two different masses
must have the same average kinetic energy at the sametemperature,
the heavier gas molecules must possess lower average speed.
On another front, Maxwell's mathematical equations expressing
the behavior of electric and magnetic
fields are considered one of great achievements of
the 19th century.
Boltzmann Distribution
Ludwig
Boltzmann (1844-1906)
The distribution of velocities among molecules of a gas
was first developed by Maxwell (1859) and later generalized
by Boltzmann (1871). The Maxwell-Boltzmann theory explained the gasl
aws in terms of the motion of individual molecules. Previously it
was assumed heat flowed from hot to cold. The
Maxwell-Boltzmann theory treated molecules at high temperature as havinga
high probability of moving toward those at low temperature. Consider the
distribution of velocities for oxygen at 25°C
shown in the figure: Boltzmann worked out a statistical approach
to show more molecules moving at 400 m/s than at any
other speed. This type of curve is called a Maxwell-Boltzmann distribution.
All systems observed to date appear to obey the distribution law.
van der Waals Equation: (P +
a/V2)(V-b) = RT

Johannes
van der Waals (1837-1923)
van der Waals began as an elementary school teacher (1856-1861)
but continued with his studies of
math and physics. At age 36 (1873) van der Waals obtained his doctorate
and published the famous equation:
(P + a/V2)(V-b)
= RT [for a = b = 0, the equation
becomes PV =RT] The equation considers
the specific volume of gas molecules and predicts critical temperature
for condensation. The equation also assumes a force (van der Waals
forces) between molecules. In
1910 van der Waals awarded Nobel Prize for Physics.